Cellulose and Fiber Science Developments: A World View 9780841203808, 9780841204379, 0-8412-0380-6

Table of contents :
Title Page......Page 1
Copyright......Page 2
ACS Symposium Series......Page 3
FOREWORD......Page 4
PdftkEmptyString......Page 0
PREFACE......Page 5
1 Recent Research and Technological Development of Cellulose in Japan......Page 6
1. Crystalline Structure of Cellulose and Cellulose Derivatives......Page 9
2. New Solvents for Cellulose......Page 14
3. Synthesis of Cellulose Derivatives......Page 16
4. Problems Related to Graft Copolymerization onto Cellulose and Cellulose Derivatives......Page 23
6. Cellulose Industries in Japan......Page 32
Literature Cited......Page 37
1. The concept of relationships between "fibrous materials and paper" in the course of the fundamental processes of paper converting and obtainment. Paper characteristics......Page 40
2.2. The behaviour of annual plants pulp undergoing the fundamental paper-converting operations......Page 43
2.3. Physical-mechanical properties of grades of paper with pulp addition from annual plants......Page 45
3.3. Characteristics of papers from beech pulps mixed up with spruce fir pulps......Page 48
3.4. Investigations on the ways of obtaining and using PPE as an adhesive in the mass......Page 52
4.1. General aspects of realizing the symbiosis among the components of the fibrous material......Page 61
4.2. Study of papers obtained from cyanoethylated pulp (22-25)......Page 62
4.3. Synthetic papers obtained from chemical fibres (synthetic and artificial)......Page 67
Conclusions......Page 70
Literature......Page 71
(1) Foamed Sheet Age (Up to 1967)......Page 73
(2) Film Base Type Synthetic Paper Age(from 1967 to 1970)......Page 74
2. Debut of Synthetic Pulp......Page 75
1. It is expected that Synthetic Pulp will be popular with users at large.......Page 76
c. Mineral Fiber Type......Page 78
d. Type of Forming by Absorption of Powder on the Surface of Pulp Fiber......Page 79
ABSTRACT:......Page 80
Introduction and Scope......Page 81
Newsprint from Pinus Radiata Plantations (Chile)......Page 85
Newsprint from Natural Coniferous Forests (Mexico)......Page 88
Newsprint from Eucalyptus (Brazil)......Page 90
Newsprint from Willow and Poplar (Argentina)......Page 94
Newsprint from Bagasse (Mexico and Peru)......Page 99
Bagasse Newsprint - Special Appendix......Page 108
Future Projects and Potential......Page 120
Newsprint Supply Situation and Perspectives......Page 128
SUMMARY......Page 132
Acknowledgments......Page 133
Eucalypts......Page 135
Basic Requirements of Papermaking Materials......Page 136
Post-War Technological Changes......Page 137
Possibilities for Utilizing Denser Woods......Page 139
Recent Research......Page 141
Abstract......Page 144
Literature Cited......Page 145
6 Technological Change in the Canadian Pulp and Paper Industry......Page 148
Refiner Mechanical Pulp......Page 152
Twin Wire Formers......Page 154
Continuous Digester......Page 155
Future Technology......Page 157
Literature Cited......Page 162
7 Recent Technical Developments in the Finnish Pulp and Paper Industry......Page 163
Conclusions......Page 170
Growth of pulp and paper industry......Page 172
Future shortage of pulp raw materials......Page 176
Pollution problems......Page 180
Conclusion......Page 184
9 Recent Developments in the Swedish Pulp and Paper Industry......Page 185
1) History of Cellulose Research in Switzerland......Page 196
2) History of "Swiss Cotton" Research and Development......Page 199
3) The Origin of Yarn Texturizing......Page 201
4) Recent Investigations of the Properties of Cross-linked Fabrics......Page 202
5) The Mechanism of Metal Ion Catalysis in the Cross-linking of Cotton......Page 209
Literature Cited......Page 215
I Novel Yarn Manufacture......Page 218
II Triacetate Polypropylene Carpet Fibers......Page 219
Ill Fluorochemical Fabric Finishes......Page 222
V Infrared Spectra of Monofilaments......Page 226
Acknowledgements......Page 230
1 - Introduction.......Page 231
2 - Texture Of Fibers.......Page 232
3 - Structure and Interactions in the Fiber.......Page 234
4 - Stress-Strain Behaviour.......Page 237
6 - Texture and Fatigue Behaviour.......Page 239
7 - Dyeing and Pore Size Distributions.......Page 244
8 - Discussion and Conclusions.......Page 245
LITERATURE CITED......Page 248
A New Process of Polyester Production from Terephthalic Acid and Ethylene Oxide......Page 251
High Modulus Vinylon (Vinal) Filament......Page 252
Flame Retardant Polyester Fiber (Heim)......Page 253
Electro-Conductive Fiber (Selmec)......Page 260
The Matrix-Fibril Bicomponent Fibers (Ecsaine, Clarino or Astrino)......Page 263
Emulsion Mix-Spinning of Polyvinyl Alcohol and Other Synthetic Polymers......Page 270
Acknowledgements......Page 274
Literature Cited......Page 275
C......Page 276
D......Page 277
F......Page 278
K......Page 279
N......Page 280
P......Page 281
R......Page 282
T......Page 283
Z......Page 284

Citation preview

Cellulose and Fiber Science Developments: A World View Jett C. Arthur, Jr., EDITOR Southern Regional Research Center, USDA

A symposium sponsored by the Cellulose, Paper and Textile Division at the 171st Meeting of the American Chemical Society New York, N . Y . , A p r i l 5-9,

1976

ACS SYMPOSIUM SERIES 50

AMERICAN

CHEMICAL

SOCIETY

WASHINGTON, D. C. 1977

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Library of Congress CIP Data Cellulose and fiber science developments. (ACS symposium series; 50 ISSN 0097-6156) (Monograph publishing on demand : Imprint series) Includes bibliographical references and index. 1. Paper making and trade-Congresses. 2. CelluloseCongresses. I. Arthur, Jett C. II. American Chemical Society. Cellulose, Paper, and Textile Division. III. American Chemical Society. IV. Series: American Chemical Society. A C S symposium series; 50. TS1080.C414 ISBN 0-8412-0380-6

676 ACSMC8

77-22540 50 1-287

Copyright © 1977 American Chemical Society A l l Rights Reserved. N o part of this book may be reproduced or transmitted in any form or by any means—graphic, electronic, including photocopying, recording, taping, or information storage and retrieval systems—without written permission from the American Chemical Society. PRINTED IN T H E UNITED STATES O F AMERICA

American Chemical Society Library 1155 16th St. N. W In Cellulose and Fiber Science Developments: A World View; Arthur, J.;

Washington, D.Society: C. 20038 ACS Symposium Series; American Chemical Washington, DC, 1977.

ACS Symposium Series Robert F. G o u l d , Editor

Advisory Board Donald G. Crosby Jeremiah P. Freeman E. Desmond Goddard Robert A. Hofstader John L. Margrave Nina I. McClelland John B. Pfeiffer Joseph V. Rodricks Alan C. Sartorelli Raymond B. Seymour Roy L. Whistler Aaron Wold

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

FOREWORD The ACS SYMPOSIUM a medium for publishin format of the SERIES parallels that of its predecessor, ADVANCES IN CHEMISTRY SERIES, except that in order to save time the papers are not typeset but are reproduced as they are submitted by the authors in camera-ready form. As a further means of saving time, the papers are not edited or reviewed except by the symposium chairman, who becomes editor of the book. Papers published in the ACS SYMPOSIUM SERIES are original contributions not published elsewhere in whole or major part and include reports of research as well as reviews since symposia may embrace both types of presentation.

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

PREFACE he centennial meeting of the American Chemical Society gave the Cellulose, Paper and Textile Division the opportunity to present a timely symposium on International Developments in Cellulose, Paper, and Textiles. Research scientists from academia, industry, and government, representing more than sixteen countries, presented significant research accomplishments in paper, wood, and cellulose chemistry and in cotton, wool, and textile fiber chemistry. In this volume, worl ments are contributed in three areas—cellulose, paper science, and fiber science—by investigators from Australia, Canada, Finland, France, Japan, Mexico, Rumania, Sweden, and Switzerland. Two companion volumes, "Cellulose Chemistry and Technology" and "Textile and Paper Chemistry and Technology" include other contributed manuscripts. I would like to thank the participants and the presiding chairmen of the world views sessions» particularly R. R. Benerito, C. Schuerch, K. Ward, Jr., R. L. Whistler, and J. J. Willard. Herman Mark kindly made significant remarks to open the Symposium. Southern Regional Research Center, USDA New Orleans, L A May 11, 1977

JETT

C.

ARTHUR,

vii

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

JR.

1 Recent Research and Technological Development of Cellulose in Japan KEI MATSUZAKI Faculty of Engineering, University of Tokyo, Hongo, Bunkyoku, Tokyo, 113 Japan

Production of chemica Japan changed as shown rayon reached to a maximum in 1937-38 and decreased to one twent i e t h during and after the second world war due to converting of the factories to munitions manufacturing and destruction. From around 1950, the production rapidly increased and the total production of c e l l u l o s i c fibers is ca. 500,000 tons/year for these ten years. In the field of c e l l u l o s i c f i b e r s , several companies stopped production of viscose rayon filament yarn and high tenaci t y yarn for t i r e cord and the output of those fibers decreased, while the output of cellulose acetate fibers and viscose rayon staples increased. The manufacturers of c e l l u l o s i c fibers and cellulose derivatives in Japan are l i s t e d in Tables I and II. Investigations on cellulose were active in 1930's and also after the second world war, especially on rayon fibers of new type such as polynosics and high tenacity rayon for t i r e cord, pulps for cellulose acetate, and c r y s t a l l i n e and supermolecular structure of cellulose. Most of companies, however, now stopped basic and application researches on c e l l u l o s e , although a large number of researchers in universities continue to work on c e l l u lose, especially, in Hokkaido University, Gumma University, University of Tokyo, Tokyo Institute of Technology, Shizuoka Univers i t y , Tokyo Metropolitan University, and Osaka City University. The number of a r t i c l e s related to cellulose and published in Japanese journals is ca. 200 for these ten years. Most of them were published in Sen-i Gakkaishi(J. of Soc. of Fiber Science and Technology, Japan, o r i g i n a l l y published in 1925 as J . Cellulose Institute). Kogyo Kagaku Zasshi(J. Chemical Society, Japan, Industrial Chemistry Section) which was united to Nippon Kagaku Kaishi now , also published a large number of papers together with Kobunshi Ronbunshu(J. High Polymer Society, Japan), Japan TAPPI and Mokuzai Gakkaishi(J. Wood Research Society, Japan). In addition, a considerable number of papers are published in foreign journals. Japan Tappi was established in 1947 just after the war. 3

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

C E L L U L O S E A N D FIBER

Table

i.

Manufacturers

Viscose rayon

of Rayons and C e l l u l o s e Acetate

Fibers

filaments;

Asahi Chemical Toray,

Ind.,

Kuraray,

Toyo Spinning,

Viscose rayon filaments Unitica.

for

Toray,

Unitica.

Teijin

tire

cord;

Teijin,

Toyo Spinning.

Viscose rayon s t a p l e s ; Mitsubishi

Rayon, Kanebo,

Toho Rayon,

Toyo Spinning,

Kuraray,

F u j i Spinning,

Nisshin Spinning,

Nitto

Daiwa Spinning,

Spinning, Kojin,

0m1 Kens hi

Spinning.

Toray Cuprammonium rayon; Asahi Chemical Acetate

fibers;

Mitsubishi

Acetate,

Daicel,

Asahi Chemical

Ind.,

Teij i η . The underlined manufacturers indicate those which stopped the production.

Table

II.

Cellulose

Manufacturers

Cellulose

Derivatives

nitrate;

Asahi Chemical Ind., Cellulose

of

Daicel,

Taihei Chemicals.

acetate;

Daicel,

Teijin,

Carboxymethyl Daiichi

Asahi Chisso.

cellulose; Kogyo Seiyaku,

Nichirin

Kagaku,

Daicel,

Adachi Koryo,

Sanyo

Kokusaku Pulp,

Shikoku Kasei,

Kyoto Gosei Kagaku. Methyl

cellulose;

Shin-etsu Kagaku, Hydroxyethyl

Matsumoto Yushi.

cellulose;

Fuji Chemical. Hydroxypropyl

cellulose;

Nippon Soda,

Shin-etsu

Hydroxypropyl methyl Shin-etsu

Kagaku.

cellulose;

Kagaku.

Hydroxy ι propyl methyl c e l l u l o s e Shin-etsu

phthalate;

Kagaku.

C e l l u l o s e acetate

SCIENCE

phthalate;

Wako Junyaku.

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

1.

1936

5

Cellulose in Japan

MATSuzAKi

1940

1945

1950

1955

1960

1965

1970

1975

Figure 1. Change of production of rayons and cellulose acetate fibers

Table

III.

Year Kogyo Kagaku Ζasshi

Number of

Articles

Published

Gakkaishi

Kobunshi Japan

Kagaku

TAPPI

Journals

65

66

67

68

69

70

71

72

73

74

75

3

5

7

3

4

5

10

-

-

-

-

37

2

5

4

5

16

Nippon Kagaku Kai s h i Sen-i

i n Japanese

Total

23

22

26

8

11

11

5

6

3

25

1

119

3

3

0

1

2

2

4

4

5

3

1

28

0

1

0

0

2

0

5

1

3

0

1

13

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

6

CELLULOSE

A N D FIBER

SCIENCE

Main thema of the investigations are the followings: Crystalline structure of cellulose and cellulose derivatives. Folding molecular structure of cellulose. New solvents for c e l l u l o s e . Synthesis of new cellulose derivatives. Fire-retarding effect of cellulose phosphate and i t s deriva­ tives. Effect of gamma-ray i r r a d i a t i o n or UV l i g h t on c e l l u l o s e , such as change of molecular weight, esr spectra and proper­ ties of irradiated products. Grafting of vinyl monomers onto cellulose and i t s derivatives by gamma-rays, UV l i g h t or with chemical catalysts or in the absence of catalyst.

1. 2. 3. 4. 5. 6. 7.

Some of the topics w i l l be discussed in the followings. 1.

Crystalline Structur Watanabe and Hayashi of Hokkaido Univ. proposed that the conformation of cellulose I i s different from that of cellulose II and that the differences in the conformation and the s t a b i l i t y is the cause of preservation and irreversibleness of c r y s t a l l i n e structure of cellulose I and cellulose II. At f i r s t , the c r y s t a l l i n e structure of cellulose t r i n i t r a t e (TNC) was investigated(l_,2). They proposed approximately 5 hel­ i c a l structure with a fiber period of 25.75A for TNC, although cellulose d i n i t r a t e obtained in a homogeneous reaction has a c r y s t a l l i n e s t r u c t u r e with a twofold screw axis and a f i b e r p e r i ­ od of 10.32A, same as other cellulose derivatives. Transforma­ tion of the twofold screw axis structure into 5 helical struc­ ture by t r i s u b s t i t u t i o n may be caused by twisting of pyranose ring in chair form to semi-boat form. The twisting may be re­ sulted by the bulkiness and repulsion between two nitro groups at 1*2 and Cg positions. The nitro groups which are o r i g i n a l l y in gauche conformation change into trans conformation. It was noted that natural cellulose always gives TNC with high c r y s t a l l i n i t y irrespective of sources, while cellulose II such as rayons even with high c r y s t a l l i n i t y ( F o r t i s a n ) gives TNC with low c r y s t a l l i n i t y ( 3 j . They proposed a bent-twisted structure which has no two­ fold screw axis for cellulose I I , as shown in Figures 3 and 4. Therefore, the structure of TNC obtained from cellulose II i s fundamentally 5 h e l i c a l , although i t i s incomplete(4). They analyzed c r y s t a l l i n e structure of cellulose II with the use of the bent-twisted conformation of molecule and obtained re­ l i a b i l i t y factor R = 0.265 for φ! =30° and φ =45° (5). This structure could explain i r spectra of cellulose II w e l l ; that i s , two intramolecular hydrogen bond absorptions due to 0j—>0ci> -CH symmetrical stretching vibration(parallel) and antisymmetrical stretching v i b r a t i o n ( a n t i p a r a l l e l ) . It i s well known that cellulose has cellulose III and IV modifications besides I and II. Mann et al.(6) found that OH v i 0

2

0

2

2

α

2

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

MATsuzAKi

Cellulose in Japan

O and Ο -» O are formed in (101 ) and (002) planes, alternatively. 2

e

β

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

s

8

CELLULOSE

A N D FIBER

SCIENCE

rations of cellulose III(or IV) change with the crystalline struc­ ture of cellulose(cellulose I or II) from which cellulose III(or IV) is derived. However, since X-ray diffractions are not clear­ ly different between cellulose III derived from cellulose I(designated as cellulose 1111 ) and that from cellulose II(cellulose 11111 ) , i t has not certainly been established that cellulose 1111 has a c r y s t a l l i n e structure different from that of cellulose

ιπ . π

Hayashi and Watanabe determined the ratio of meridional d i f ­ fractions (040)/(020) on cellulose III and cellulose IV as shown in Figure 5(7j. The ratio changed with the c r y s t a l l i n e structure of source cellulose but not with the c r y s t a l l i n i t y or orientation of c r y s t a l l i t e s . Therefore, cellulose III ι(or cellulose IVl) is a c r y s t a l l i n e modification of cellulose different from cellulose 11111 ( or cellulose IV j j ) , although they show similar equatorial diffractions. Various chemical reactions on cellulose I usually produce cellulose 1111 or cellulose IVj, and we obtain cellulose 111jj and cellulose IVjj from cellulose II. Interconversion between cellulose I, 111j and IVj or that between cellulose II, Ι Ι Ι π and IVιj is possible, but conversion of cellulose I family to c e l ­ lulose II family is only possible by dissolution and regeneration or mercerization(8), and i t is irreversible(Figure 6). In the est e r i f i c a t i o n such as acetylation and nitration or in the formation of addition compounds of cellulose I, molecular conformation of cellulose I is preserved and the regeneration results in cellulose

1(8-13).

The facts that the difference in molecular conformation is not reflected in equatorial diffractions as i l l u s t r a t e d in Figure 8 for cellulose t r i n i t r a t e , but reflected in meridional d i f f r a c ­ tions as already mentioned were ascertained by calculating d i f ­ fraction i n t e n s i t i e s . Thus, irreversibleness of cellulose I family to cellulose II family and preservation(or keeping memory) of each family struc­ ture during chemical reactions are caused by the molecular con­ formation of each family; that i s , the bent structure for c e l l u ­ lose I family and the bent-twisted structure for cellulose II fam­ i l y . They are not due to difference in the intermolecular hydro­ gen bonding systeig. In cellulose I, the distance between H-| and H 4 ' is only 1.85 Α(Φ,=Φ =34°) by the intramolecular hydrogen bond between Οβ-^Ο^·. This form is very unstable. Formation of c e l l u ­ lose II by twisting results in longer distance between H] and H 4 1 , thus giving a s t a b i l i z a t i o n energy of 2-3 kcal per glucose unit, which sums up to a large value for a molecule. It i s known that mercerization is a typical reaction of con­ version of cellulose I to cellulose II in fiber form. Merceriza­ tion of cellulose I under r e s t r i c t i o n of contraction or at high temperature to prevent swelling gives Na-cellulose I with ratio of meridional d i f f r a c t i o n s , (040)/(080) = 0 . 5 , whereas that of Na-cellulose I obtained from cellulose II is 0.02-0.05, irrespecΖ

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Cellulose in Japan

MATSuzAKi

Figure 4. Crystalline structure of cellulose II. Projection to (10Ί) plane. (-*) Hydrogen bonds in (101) plane; (=5) hydrogen bonds in (002) plane.

(040)

J

10

1

I

20

1

I

30 2 Θ (°)

I

(040)

I

I

40 10

I

I

I

20 2 θ

1

30 (·)

1

L

40

Figure 5. Crystalline modification of cellulose and meridional diffractions. R indicates the ratios of (020) to (040).

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

10

A N D FIBER SCIENCE

family I | family Π Meridional Diffract. Π TYPE I.HIi TYPE

/mJ

LU Û_ >\~

«

1

Figure 6. Transformation be­ tween cellulose modifications and classification of crystalline struc­ tures of cellulose based on the conversion

UNIT CELL (Equatorial Diffract)! I TYPE 1

CELLULOSE

Γ* Trinitrate I

Cell m

H Dinitrate I tiHCellll pTriacetatel

Cell I

Figure 7. Change of crystalline structure of cellulose in esterification in fiber j—HCelllEn form. ( ) Transformation of crystalline structure; ( ) heat-treatment Celinh Celll^ or swelling.

J Trinitrate Π -J

n

J

H Dinitrate π}-|^ C e l l l pTriacetatel p

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

1. MATSuzAKi

Cellulose in Japan

11

tive of the mercerization conditions(14). Therefore, there are two types of Na-cellulose I, that i s , Na-cellulose:Ii and Na-cellulose I χ χ . Although usual procedure for regeneration of Na-cel­ lulose Ij gives cellulose II, regeneration under l i t t l e swelling such as with hot water or with acetic acid gives cellulose I as i l l u s t r a t e d in Figure 9 for ramie. Na-cellulose I T is formed in the condition that cellulose is not strongly hydrated. Therefore, i t is deduced that for conversion of cellulose I conformation to cellulose II conformation, strong hydration of cellulose chains is necessary to give relaxation to intramolecular hydrogen bond­ ings. Therefore, mercerization or regeneration of Na-cellulose under strong swelling gives always cellulose II type structure. 2.

New Solvents for Cellulose

Recently, various kind l i q u i d N2O4 added with a l i t t l e amount of organic compounds by Fowler et a l . ( 1 5 ) , dimethyl sulfoxide(DMSO) added with a small amount of N0O4 by Williams(ll5) » pyridine-anhydrous chloral by Meyer(V7L liquid SO2 added with a secondary or tertiary amine by Hata et a l . ( 1 8 j , and dimethyl formamide(DMF) or dimethyl acetamide(DMAc) added with N2O4 or N0C1 by Schweiger(19-20). Nakao et al.(21,22) developed previous investigations in de­ t a i l as shown in Table IV and found several new solvents. They c l a s s i f i e d cellulose solvents into the following groups: (i) DMSO, DMF,DMAc and ethyl acetate added with a l i t t l e amount of N2O4. ( i i ) DMS0,DMF, formamide, a c e t o n i t r i l e , methylene chloride, e t c . , added with 3-30 moles of l i q u i d S02~amine(e.g., d i e t h y l amine) complex. ( i i i ) DMSO, DMF, DMAc and N-methyl-2-pyrrolidone added with an­ hydrous c h l o r a l . (iv) DMSO, DMF, DMAc and pyridine added with N0C1, or l i q u i d N0C1 added with a l i t t l e amount of polar organic solvents. Solvents such as DMSO and formamide added with S02-amine com­ plex, or DMSO, DMF and pyridine added with N2O4 not only dissolve cellulose in a few minutes, but the solution is stable and degra­ dation of cellulose is low especially at low temperatures lower than 50°C. The dissolution proceeds by cleavage of fibers and peeling-off from the fracture surface without appreciable swell­ ing usually observed in dissolution by aqueous solutions such as cuprammonium solution. It is also noted that at least 3 moles of reagents per glucose unit are necessary for dissolution of c e l l u ­ lose. Solvents added with S02~amine complex were investigated in detail(22). Thirty four solvents were found to dissolve natural cellulose but did not dissolve regenerated cellulose. The spec­ i f i c conductivities of complex solutions and cellulose solutions were determined, and the mechanism of dissolution was investiga­ ted. The complex formed between an amine and SO2 reacts with e e l -

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

12

CELLULOSE

Table

Cellulose sol vent

IV.

Solvents

SOg-amine

f o r Dissolving

Μ ­

g

r+ Ο φ —• 3 Φ

Sulfoxide Amide

DMSO DMF

Φ

3

TD

20

3 DMSO 50 14 DMF

DMAc

50 14 DMAc formamide 20 3 di ethyl Lactam

20

N0CU g

ο 3 — •σ Φ

Chloral

Φ

ο — φ

3 DMSO 3 DMF

_

n- 3 Φ ο 3 —

T3 Φ

3 DMSO 20 10 DMF 20

20 5

20 10 DMAc

20 10 20 10

5

^-butyro- 5 1actam £-capro1actam

Ami ne

50 30 pyri di ne 20 35

Nitrile

acetoni tri 1 e

pyri di ne 20 4 pyri di ne d - p i c o l i ne•20 5 3 - ρ i c ο 1 i η.20 e 7 20 15 acetoni t- 20 35 [aceto­ ri1e ni t r i 1 e ]

propionitrile

50 15 propionitrile

benzoni tri 1 e

50 25

Ester

50

ethyl acetate

methyl formate Lactone

Cyclic carbonate

5 [propi onitrile] [benzyl ni t r i l e ]

20

methyl 20 propi onat e

[

Cellulose.

20 20 5 DMAc 20

A N D FIBER SCIENCE

5 [ethyl acetate] 5

2C 8

f-Valero1 actone

50 20

/ - v a l ero- 5C 8 1actone

ï -butyro1actone

50 40

^-butyro- 5C 8 1actone

ethylene carbonate

50 30

propylene 5C 1 carbonate

propylene carbonate

50 30

] indicates

1iquid N0C1 .

mole i n d i c a t e s moles of reagents

per g l u c o s i d i c

# i n d i c a t e s cellophane is s o l . , but wood pulp is

unit. insol.

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

f

20

5

1. MATsuzAKi

13

Cellulose in Japan

l u i ose resulting three component complex of type II or III. The i r spectra of the cellulose solution is only overlapping of amineSO2 complex and c e l l u l o s e , and the absorption of OH groups of c e l lulose remains intact. Therefore, the formation of -0-S- bonds as is shown in IV or V i s not considered. Cell-OH

C e

ll-0

+ RN 3

H

SiC'

0

Cell-0-S0 H

Cell-0

2

+ R^H

+

S0

2

(IV)

(III)

Possible applications of new solvents of cellulose are investigated to some extent and suggested. (i) New solvents can dissolve blends of cellulose and synthetic polymers such as p o l y v i n y l chloride), polystyrene, polyacryl o n i t r i l e , etc. Blends of cellulose with cellulose acetate or cellulose nitrate are also dissolved. Films formed from blends of cellulose and poly(alkyl acrylate) are transparent and soft without addition of p l a s t i c i z e r . ( i i ) Grafted cellulose with vinyl polymers can be dissolved in the new solvents. Starch grafted with vinyl polymers also d i s solves. ( i i i ) Synthesis of cellulose derivatives with high degree of subs t i t u t i o n or homogeneous distribution of substituents w i l l be possible in the reaction in a homogeneous phase(e.g., synthesis of secondary cellulose acetate in one step). (iv) Production of f i l m s , f i b e r s , etc. from organic solutions of c e l l u l o s e , or blends, or grafted cellulose was suggested. It i s expected that those products may have special properties. 3.

Synthesis of Cellulose Derivatives

Synthesis of Unsaturated Acid Esters of Cellulose. General methods to synthesize cellulose esters are: (i) to treat cellulose with acid anhydride or acid chloride in the presence of a catalyst such as s u l f u r i c acid, perchloric a c i d , zinc chloride, or sodium acetate, or ( i i ) to treat cellulose with a mixture of the acid and t r i f l u o r o acetic acid anhydride or chloroacetic acid anhydride in the pres-

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

14

CELLULOSE

A N D FIBER

SCIENCE

ence of a catalyst. In our investigations(22,24) on the reaction of mixtures of α , β - u n s a t u r a t e d acid and acetic acid anhydride with c e l l u l o s e , i t was found that the substitution of unsaturated acid and acetic acid depends on the catalyst and the dissociation constants of the unsaturated acids. When s u l f u r i c acid i s the catalyst, strong acid such as ac r y l i c acid i s not introduced, whereas weak acids such as 3 , 3 dimethylacrylic acid are introduced more than acetic acid. In Table V, the results of e s t e r i f i c a t i o n of l i n t e r pulp(cellulose acetate grade) are shown. It shows that the ratios of unsaturat­ ed acid to acetic acid depend mainly on the pK of the unsaturat­ ed acids and do not depend on the composition of the mixed acids for e s t e r i f i c a t i o n . Rayon staple fibers treated with 40% potassium acetate as the catalyst were e s t e r i f i e dride, an unsaturated acid and potassium acetate in toluene at 120°C for 1-30 minutes. The results are shown in Figure 10. When the composition of cellulose mixed esters treated with the mixed acids of the same composition, e . g . , unsaturated acid/ace­ t i c acid anhydride = 1/1(by weight) is compared, i t i s seen that a c r y l i c acid is introduced more than 3,3-dimethylacrylic acid. This is quite opposite to the e s t e r i f i c a t i o n with s u l f u r i c acid as the catalyst. The relationship is shown in Figure 11. When s u l f u r i c acid i s the catalyst and the unsaturated acid is a stronger acid than acetic acid, the unsymmetrical anhydride formed by the reaction of the unsaturated acid with acetic acid anhydride, dissociates into an acetoxyl cation and an unsaturat­ ed acid anion. The acetoxyl cation produced mainly reacts with cellulose resulting in almost pure cellulose acetate. When the unsaturated acid is a weaker acid than acetic acid, such as β , β dimethylacrylic a c i d , dimethylacrylic acid cation i s mainly pro­ duced and attacks c e l l u l o s e . With potassium acetate as the catalyst, the dissociation of anhydride may be supressed by the presence of a large amount of s a l t and a nonpolar solvent(toluene), and the unsymmetrical anhy­ dride may d i r e c t l y be concerned with the e s t e r i f i c a t i o n . In this case, the composition of mixed acids affects the composition of cellulose esters, because the e s t e r i f i c a t i o n by acetic acid anhy­ dride and unsaturated acid anhydride also occurs and the ratio of the two anhydrides changes with the composition of the mixed ac­ ids. CrkCO. . CH C0 a

Q

CH = CHC00H 2

CH C0 CH =CHC0 3

+

C H 3

3

C Q

.°

v

CH -CHC0-°

V -

+

2

CH C0 3

C

H

3

CH =CHC00" 2

2

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

C

0

0

H

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

of

acid

56.0 46.7 48.0

0.8

acid

11.9

7,9

cellulose

„

b:

a

f \^

a

r « lb

a:

3,3-Dimethylacrylic acid

Crotonic

2g,

„

unsaturated

50.1

0.9

a

2g,

6.7

58.8

0.26

r

0.64

58.6

0.25

f \ lb

0.142 2.82 2.75

49.9 11.1 10.25

52.1 47.0

a c i d 0.4 m o l e s , 0.28

10.0

acid

anhydride 0.16 moles, 0.28

0.193

13.5

48.8

0.0941

0.0089

0.0103

(mol/mol)

acetic

2

a

o

f

4

0 . 2 nrl . 0.2 ml

5.12(25°C)

4.69(25°C)

4.43(25°C)

4.25(25°C)

H S0 2

K

acid

p

4

Anhydride

H S0 )

unsaturated acid

(cat;

and A c e t i c

0.028

52.7

60.0

59.8

acid(wU)

acetic

acetic

5hr

an U n s a t u r a t e d A c i d

59.1

2.1

0.74

acid(wU)

acid(wt%)

a

of

unsaturated

with Mixtures

acid(wt%)

2hr

Cellulose

acetic

of

unstaturated

Methacrylic a c i d
dioxane. The kind of vinyl monomers affected the radical decay in the order, methacrylic acid >methyl methacrylate = styrene. The rate of radical decay i s related to the a f f i n i t y of the solvents to cellulose fibers and the rate of penetration of solvents into f i b e r s . The preirradiated samples are capable of i n i t i a t i n g the graft copolymerization, while the unirradiated sample is not at a l l . Therefore, i t is concluded that the a b i l i t y of the samples preirradiated at room temperature to i n i t i a t e graft copolymerization is attributable to the cellulose radicals stable at room temperature. These radicals showing a singlet spectrum are believed to be alkoxy radicals at either C] or C4 position of the glucose unit resulted by the scission of glycosidic bonds. In order to verify the formation of alkoxy radicals by s c i s +

+

+

+

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

22

C E L L U L O S E A N D FIBER

_

S

S ο

120 100 80 60 AO

0

UT

1

R] 0]

UT

.1500

SCIENCE

R

2

0

2

R

0

3

R^

Ο4

R

2

0

2

R3 0

3

R4

O4

0

2

R

0

3

3

> 1000

Figure 18. Changes of mechanical erties of BIED-treated cotton fabrics by reduction and oxidation treatments. (A) Content of SS linkages; (B) flex abrasionS 300 ο 200resistance (untreated cotton 1880 cycles); (C) breaking strength retention; (D) i 100 0 warp wrinkle recovery, (O) dry, (Φ) < wet. (U) Untreated, (T) BIED-treated; (R) reduction, (O) oxidation.

U

Τ

R

1

0

1

R

2

3

TREATMENTS

2 min

10 min

30G

Figure 14. Decay of ESR spectra by warming the sam­ ples to room temperature and recorded at 77°K. (A) Wood cellulose irradiated with high-pressure mercury lamp for 60 min at 77 °K; (B) Fe -sensitized wood cellu­ lose irradiated with high-pressure mercury lamp for 60 min at 77 °K; (C) Fe -sensitized wood cellulose irradi­ ated with super high-pressure mercury lump for 90 min at77°K. 3+

3+

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

O4

1.

Cellulose in Japan

MATsuzAKi

TaWeVI

Reaction

of

Cotton

23

with

BIED

Branch

R e a c t i on

Total

time(hr)

combi ned (ccmoles/g)

BIED

Cross-

E f f i ciency

links ( i^mol es/g)

(%) 50

1

110

55

55

5

207

88

119

57

10

267

110

157

58

24

303

153

250

49

48

404

209

195

48

Table VII,

Mechanical

properties

of m o d i f i e d cotton

fabrics Breaki ng

Warp w r i n k l e

Sample

Treatment

SH

SS

(^tmoles/g )

recovery

strength

angle

retention (%)

dry

wet

Untreated

76

44

100

DMF-treated

72

46

99

73

47

97

104

111

57

reduced

II

-

BIED-treated •

0

reduced

733

0

70

67

73

23

328

lo9

115

48

oxidized

II

TableVffl. R e l a t i v e

signal

484

intensities

of c e l l u l o s e samples

i r r a d i a t e d with hi gh-pressure mercury

lamp at room

temperature.

Relative Sample

Number of s c i s s i on s ,

signal

i ntensi t y , a r b i t r a r y

units

mmole X

Untreated

1.0

Oximated

0.8

2.7

0.6

Swollen

3.0

4.2

11.5

3.1

9.0

15.3

Fe

+3

a:

sensitized

hard g l a s s , i r r a d i a t i o n

b: quartz

3.1

a

b

1.0

10

3

time 60 min.

glass, irradiation

time 30 min.

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

14.2 10.4

-

b

24

CELLULOSE

A N D FIBER

SCIENCE

sion of glycosidic bonds, cellobiose as a model compound of c e l ­ lulose was irradiated with l i g h t of wave length longer than 2800 A at 77°K for 2 hr. The esr spectra of the irradiated cellobiose and cellulose(soft wood dissolving pulp) are shown i n Figure 16. No radicals were detected on glucose under the same irradiation conditions. With l i g h t of wave length longer than 2200 A, r a d i ­ cals were formed on glucose, but the intensity was much stronger for cellobiose as shown in Figure 17. The reason for higher ac­ t i v i t y of cellobiose toward l i g h t than glucose i s attributed to the glycosidic bonds in the molecule. Paper chromatographic analysis of cellobiose irradiated with l i g h t of wave length longer than 2200 A at room temperature showed the presence of glucose. Figure 18 shows the esr spectra of cellulose samples treat­ ed with Ce+4, F e , Fe 3, and A g , and irradiated with a super high-pressure mercury lamp at 77°K for 90 minutes. Although there is a small differenc t i z e r s , i t is considered that their effects are nearly the same as those of Fe 3. Namely, these sensitizers contribute to the formation of radicals showing the singlet and t r i p l e t spectra. In the irradiation in a i r , hydroperoxide is generally form­ ed and the grafting reaction occurs by the decomposition of the hydroperoxides. We found, however, that hydroperoxide is not produced in the irradiation of cellulose in the air(43). The hydroperoxide of cellulose may be unstable and decompose rapidly into stable compounds. Therefore, in the graft copolymerization by the preirradiation in the a i r , the grafting occurs at trapped radicals as in the grafting in vacuum. It is noted that cellulose acetate forms hydroperoxide by the irradiation in the a i r and the degree of grafting and the total conversion of vinyl monomer(styrene) are proportional to 1/2 power of the concentration of hydroperoxide. Therefore, the grafting occurs at hydroperoxide groups formed in cellulose ace­ tate, although the i n i t i a t i o n efficiency is low. 0

+ 2

+

+

+

1

(2) Composition of Grafted Polymers(Branch Polymers). Grafting reaction is very often carried out in heterogeneous phase, espe­ c i a l l y in the reaction onto cellulose. In the heterogeneous grafting, when mixtures of vinyl monomers are grafted onto a trunk polymer, the monomer reactivity ratios π and r2 may be different from those in the ordinary copolymerization in l i q u i d phase. Sakurada et al.(44J investigated on the grafting of mix­ tures of styrene-acrylonitrile and butadiene-acrylonitrile onto viscose rayon. Odian et al.(45) investigated on the grafting of styrene-acrylonitrile onto cellulose acetate. In our i n v e s t i g a t i o n ( 4 3 j » mixtures of styrene-butyl acrylate were grafted onto viscose rayon and cellulose triacetate fibers. The comparison of the monomer reactivity ratios in the grafting with those in the ordinary copolymerization indicated that sty­ rène is contained in the grafted polymer more than in the ordinary copolymers, as shown in Table IX. The cause was explained by

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Cellulose in Japan

MATSuzAKi

ω 0

ifc

20 30 40 TIME (min)

50

60

Figure 15. Effect of various solvents on the decay of radicals produced by irradiation at room tempera­ ture. The F e *-sensitized sample was irradiated at room temperature for 30 min in quartz system. 3

Figure 16. ESR spectra of cellu­ lose and cellobiose irradiated with light of > 2800 Aat77°K

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

CELLULOSE

0

A N D FIBER

' IRRADIATION TIME (min)

Figure 17. Formation of radicals in glucose and cellobiose by irradiating with light of > 2200 A

Figure 18. ESR spectra of sensitized samphs irradiated with a super high-pressure mercury lamp at 77°K for 90 min

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

SCIENCE

1.

27

Cellulose in Japan

MATsuzAKi

Figure 19. Relationship between centration and the degree of grafting vs. peroxide concentration in graft copolymerization of styrene onto cellulose triacetate preirradiated with gamma rays in air at 0°C. Grafting conditions, 60°C, 20 hr.

Table

IX.

Monomer R e a c t i v i t y Acrylate Cellulose

Trunk P o l y m e r

R a t i o s of Styrene w i t h

in the G r a f t

and C e l l u l o s e

Copolymer

n-Butyl

C o p o l y m e r i z a t i o n onto Triacetate r

at r

$ t

50°C.

BuA

r

St^ BuA r

grafted

1 38 ± 0 01

0 22 ± 0 01

6 3

nongrafted

0 90 ± 0 03

0 40 ± 0 01

2 3

Cel1ulose

grafted

1 16

0 01

0 42

±

0 01

2 8

t r i acetate

nongrafted

1 08 ± 0 01

0 54

±

0 01

2 0

0 .76 ± 0 01

0 38 ± 0 01

2 0

Cel1ulose

±

AIBN-initiated copolymer

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

28

C E L L U L O S E A N D FIBER

SCIENCE

the adsorption of styrene or complex formation of styrene with radicals. (3)

Molecular Weight, Molecular Weight Distribution, and the Number of Grafted Polymers per Trunk Polymer. Since grafting reaction onto cellulose is usually carried out in heterogeneous phase, the termination is disturbed by the gel effect and the grafted polymer has higher molecular weight than the homopolymer. In homogeneous grafting onto cellulose derivatives dissolved in solvents, the molecular weight of the grafted polymer is not much different from that of the homopolymer. The molecular weight distribution of grafted polymers has been determined by several investigators. It was sometimes wide (46, £7) or i t had bimodal distribution(48). Our results(49) on the molecular weight distribution of polystyrene grafted onto cellulose triacetate showe the grafting the molecular weight distribution is similar to that of ordinary polystyrene. It is recognized that as the grafting proceeds, the molecular weight increases and the distribution becomes wider(Figure 20). As for the number of grafted chains per trunk polymer, Ikada et al.(50) showed that in the grafting reaction of styrene in methanol-water as solvent onto cellulose with simultaneous i r r a d i a t i o n , the number of branch molecules per trunk polymer is 0.915 after exhaustive extraction of unreacted cellulose and homopolystyrene. It is usually recognized that the number of grafted chains does not exceeds 1. New grafting methods which produce multi-branch grafted copolymers easily are expected to be developed. (4)

Stereoregularity of Polymers Formed in Graft Copolymerizat i o n . Since graft copolymerization onto s o l i d trunk polymers, especially onto f i b e r s , is a kind of organized polymerization in matrix, the structure of the polymers formed is expected to be different from those of the ordinary r a d i c a l - i n i t i a t e d polymers, because the s o l i d trunk polymers would give some influence on the molecular association and orientation of the monomers being polymerized. In our f i r s t report(51_), methyl methacrylate(MMA) and methac r y l i c acid were grafted onto various fibers such as nylon 6, cellulose triacetate fiber and polyester fiber with preirradiation techniques using gamma rays from a Co-60 source and the stereoregularity of the branch polymers isolated by acid hydrolysis was determined by proton NMR spectroscopy. The results i n d i cated that the stereoregularity of PMMA and poly(methacrylic acid) grafted onto viscose rayon and cotton was different from that of the polymers formed in ordinary radical polymerization. In the second report(52j, MMA was grafted onto viscose rayon, wood pulp, cellophane and p o l y v i n y l alcohol)(PVA). The stereoregularity of the polymers grafted onto rayon is different

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

1.

MATsuzAKi

Cellulose in Japan

29

from that of the polymers grafted onto wood pulp, mercerized wood pulp, cellophane and PVA films and powder. Recently, the stereoregularity of PMMA grafted onto various kinds of rayons, cotton 1 inters and mercerized cotton 1 inters was investigated in detail(53). The results shown in Table X i n d i cate that the stereoregularity of PMMA grafted onto ordinary v i s cose rayon filaments and staples and high tenacity viscose rayon staples of t i r e cord type is clearly different from that of the ordinary r a d i c a l - i n i t i a t e d polymers. Those rayons which give the different structures have high percentages of skin portion and the structure is different from that of polynosics and cuprammonium rayons. Therefore, i t is deduced that the polymerization in the skin structure affects the stereoregularity of polymers being polymerized. 5.

Application of Irradiatio

In the manufacturing of viscose rayons, aging of a l k a l i c e l lulose to lower the degree of polymerization of cellulose i s usually carried out. Imamura and Ueno(54) attempted to replace the aging of a l k a l i cellulose with i r r a d i a t i o n . Dissolving pulps were irradiated with gamma rays or electron beams in a range of 105 - 108 rad. The degree of polymerization and carbonyl and carboxyl contents after the irradiation depended on the total dose and not on the irradiation source. I r r a d i ation apparatus for large scale production of low DP pulps was investigated and among CO-60 gamma ray source, high voltage accelerator and low voltage accelerator, low voltage accelerator i s most suitable for industrial app1ication(55). Low DP pulps(DP 440) obtained by irradiation with gamma rays or electron beams were processed in viscose process without agi n g ^ ) . The analysis of the original and the irradiated pulps is shown in Table XI. The mechanical properties of rayon staples produced from the irradiated pulps are shown in Table XII. A l though they show tendency to have a l i t t l e low wet strength, wet elengation and knot strength, the difference is not appreciable. Pulps irradiated with electron beams showed the same results. 6.

Cellulose Industries in Japan

As for pulp and paper industries in Japan, Prof. Nakano w i l l write on the problems related to the industries. As for viscose process several companies already withdraw from the production and this tendency w i l l continue, because the increase of cost is expected due to the increase of prices of wood pulp and caustic soda, investment for pollution problems and the increase in labor wages. As a new product, Mitsubishi Rayon Co. i n s t a l l e d machines for production of viscose rayon spun bonds recently. The products are now being used for diaper l i n e n , l i n e r of paper table

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

39,5

7.1

H

I

4.1

4.1

6.3

36.6 39.2

Copper number

(%)

Number average DP

1.2

3.7

750

4.6

B-cellulose(%)

Original

92.0

Pentosan

G

5.3

5.3

36.6 37.6

58.1 57.1

H

A

X

G

4.4

H

4.2

3.8

1.8

3.7

3.7 1.9

3.6 1.2

465

7.9

4.9

8.3

776

87.5

I r r a d i ated

90.1

448

3.3

35.7 35.6

60.5 61.1

G

88.6

Original

Β

H

H

G

4.2

H

5.0

10.2

5.5

4.7 2.3

4.8 1.5

455

84.9 754

4.2

35.0

60.8

I r r a d i ated

4.9

37.2 32.5

57.9 62.5

G

88.2

Original

5.2

34.3 38.0

C

H

MERCERIZED ACID-HYDROCOTTON LYZED COTTON LINTER LINTER

61.5 56.8

COTTON LINTER

i r r a d i a t e d pulps

4.8

34.7 37.4

61.1 57.8

G

and gamma-ray

4.0

37.0 36.5

59.0 59.1

H

I r r a d i ated

A n a l y s i s of o r i g i n a l

5.5

36.7 39.9

G

59.3 54.5

H

t

HIGWENACITY RAYON STAPLE CUPRAMMONIUM RAYON (TIRE-CORD TYPE) (POLYNOSICS) FI LAMENT STAPLE

α-cellulose(%)

Pulps

G

ORDINARY VISCOSE RAYON STAPLE

STEREOREGULARITY OF P O L Y Î M E T H Y L METHACRYLATES) GRAFTED ONTO RAYONS AND COTTONS

59.2 54,6

H

T a b l e XI.

53,4

S

G

VISCOSE RAYON FI LAMENTS

T a b l e X.

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Properties

(g/d)

Tenacity-/ Wet {%)

1 .64

17. 4

(%) U)

jDry

[Wet (g/d)' (g/d)

Knot tenacity

Loop Tenacity

1 .81

1 .53

20. 4

68. 5

[Dry/Wet (%)

2. 31

(g/d)

Tenacity/ Wet

3.37

1 .72

2.06

1 .75

1 .62

1.55

16.5

14.6

67.8

2.23

3.29

1 .75

2.05

1 .77

23.3

22.5

60.1

1 .73 18.3

(g/d)

Elongation

1 .67 2.88

18.0

62.0

1.81

2.92

/ Dry

(d)

(g/d)

Fineness

(g/d)

Knot tenacity

( % )

Loop tenacity

/Dry Elongation^.

^Dry/Wet {%)

(g/d)

/ Dry

(d)

1 .65

1 .56

15.6

15.5

67.5

2.24

3.32

1 .76

2.03

1 .80

22.0

18.1

58.9

1 .68

2.85

1 .68

1 .60

1 .55

15.7

13.8

65.5

2.04

3.10

1 .77

1 .92

1 .82

19.9

17.2

59.2

1 .64

2.77

1 .64

Pulp Β Conven No-aging -tional

and n o - a g i n g v i s c o s e

of rayon s t a p l e f i b e r s

Pulp A Conven No-aging -tional

by c o n v e n t i o n a l

Comparison of p r o p e r t i e s

Fineness

Table XII.

1 .77

1 .62

15.6

14.5

68.5

2.31

3.37

1 .74

2. 09

20. 6 1 .81

61 . 7 17. 5

1 .79

2.90

1 .64

1 .58

1 .53

14.9

14.6

64.2

2.03

3.16

1 .78

1 .95

1.72

19.7

17.3

56.4

1 .63

2.89

1 .64

Pulp C Conven -tional No-aging

processes.

obtained

32

C E L L U L O S E A N D FIBER

0

2

4

6

SCIENCE

8

Molecular Weight (Μ) χ 10 Figure 20. Molecular weight distribution of grafted polystyrene formed in the copolymerization at 75°C

Ο G 20μ

260y

1 .1 m

fc

115 ml 8000 Fibers

Figure 21. Assembly of artificial kidney

•17 cm-

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

MATsuzAKi

Cellulose in Japan

STRAIN (%)

Figure 22. Stress-strain curves of hollow fibers

Cuprammonium

100

200

300

400 mmHg

MEAN TRANSMEMBRANE PRESSURE

Figure 23. Comparison of ultrafiltration rate

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

34

C E L L U L O S E A N D FIBER

SCIENCE

napkins, and packaging f r u i t s . Cuprammonium process increased i t s production steadily and developed several new products, such as a r t i f i c i a l kidney and spun-bonded fabrics. Asahi Chemical Industry Co. and Asahi Medi­ cal Co. developed a r t i f i c i a l kidney made of hollow fibers of cu­ prammonium rayon. The assembly is i l l u s t r a t e d in Figure 21. It is made of 8000 hollow fibers(each ca. 300 deniers), of which i n ­ side diameter is 260y. Cuprammonium rayon in Japan is manufac­ tured from cotton l i n t e r pulps. It has higher strength than re­ generated cellulose acetate hollow fibers as shown in Figure 22. It has higher rate of f i l t r a t i o n for water and urea, as shown in Figure 23. Especially, i t can be s t e r i l i z e d with ethylene oxide gas, permitting simple and short operations. Improved thrombogenicity permits less heparin dose and less residual blood after d i a l y s i s . Present production per month i s now 30,000 pieces. Asahi Medical Co. hollow cellulose acetate f i b e r s . They are used to prevent d i a l y ­ sis of cancer c e l l s and/or b a c i l l u s , but pass proteins of low molecular weight. The system is c l i n i c a l l y tested for reinfusement of a s c i t i c f l u i d . Cellulose derivative industries are developing steadily. Methyl cellulose(D.S. 1.8-2.0) i s mainly used for cement mortar and s t a b i l i z i n g agent for suspension polymerization of vinyl chloride and vinylidene chloride. Other uses are cosmetic. Most of hydroxypropyl methyl cellulose is used in the f i e l d same as methyl c e l l u l o s e , but a low viscosity grade is used in tablet coating. Hydroxypropyl methyl cellulose phthalate(hydroxypropyl 6-10%, methyl 18-22%, phthalate 27-35%) is used for enteric coating and photo-sensitive polymers. This polymer i s superior to cellulose acetate phthalate since the l a t t e r has tendency to produce ace­ t i c acid during preservation. Literature Cited 1. Watanabe, S., Hayashi, J., and Imai, K., J . Polym. Sci. (1968) C, 23, 809. 2. Hayashi, J., Imai, K., Hamazaki, T.,and Watanabe, S., Nippon Kagaku Kaishi(1973) 1582. 3. Watanabe, S., Imai, Κ., and Hayashi, J., Kogyo Kagaku Zasshi (1971) 74, 1420. 4. Hayashi,J., Imai, K., and Watanabe, S., Memoires of the Facul­ ty of Engineering, Hokkaido University (1972) 65, 97. 5. Watanabe, S., and Hayashi, J., Kogyo Kagaku Zasshi (1970) 73, 1890. 6. Marrinan, H . , and Mann, J., J . Polym. Sci.(1956) 21, 301. 7. Hayashi, J., Sueoka, Α., Ohkita, J., and Watanabe, S., Nippon Kagaku Kaishi(1973) 146. 8. Hayashi, J., Sueoka, Α., and Watanabe, S., Nippon Kagaku Kaishi(1973) 153. 9. Watanabe, S., Imai, Κ., and Hayashi, J., Kogyo Kagaku Zasshi

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

1.

MATSuzAKi

Cellulose in Japan

35

(1971) 74, 1427. 10. Hayashi, J., Sueoka, Α., and Watanabe, S., Nippon Kagaku Kai­ shi(1973) 160. 11. Hayashi, J., Imai,K., Hamazaki, T., and Watanabe, S., Nippon Kagaku Kaishi(1973) 1587. 12. Hayashi, J., Yamada, T., and Watanabe, S., Sen-i Gakkaishi (1974) 30, 190. 13. Hayashi, J., and Yamada, T., Nippon Kagaku Kaishi(1975) 544. 14. Hayashi, J., 33rd Autumn Meeting, Chemical Society, Japan at Fukuoka(1975). 15. Fowler, J r . , W.F., Unruh, C.C., Mc Gee, P.Α., and Kenyon, W. 0., J. Am. Chem. Soc.(1947) 69, 1636. 16. Williams, H.D., U.S.P. 3,236,669(1966). 17. Meyer, K.H., Studer, Μ., and van der Wyk, A.J.Α., Monatshefte (1950) 81, 151. 18. Hata, K. and Yokota, Κ., Sen-i Gakkaishi(1966) 22, 96. (1968) 24, 415, 420. 19. Schweiger, R.G., Chem. & Ind.(1969) 10, 296. 20. Schweiger, R.G., Tappi(1974) 57, 86. 21. Nakao, O., Sen-i to Kogyo(1971) 4, 128. 22. Yamazaki, S., and Nakao, O., Sen-i Gakkaishi(1974) 30, T234. 23. Matsuzaki, Κ., and Miyata, T., Sen-i Gakkaishi(1966) 22, 173. 24. Matsuzaki, Κ., and Miyata,T., Kogyo Kagaku Zasshi(1967) 70, 770. 25. Miyata,T., and Matsuzaki, Κ., Kogyo Kagaku Zasshi(1967) 70, 2192. 26. Schwenker, J r . , R.F., Lifland, L . , and Pacsu, E . , Textile Res. J.(1962) 32, 797. 27. Schwenker, J r . , R.F., and Lifland, L . , Textile Res. J.(1963) 33, 107. 28. Sakamoto, Μ., Takeda, J., Ojima, N . , and Tonami, H . , J. Polym. S c i . , A-1(1970) 8, 2139. 29. Sakamoto, Μ., Choi, S.-C., Murakami, J., Sato, T., and Teshirogi, T., Sen-i Gakkaishi(1974) 30, Τ 286. 30. Sakamoto, Μ., Cho, H . , Yamada, Y . , and Tonami, H., Colourage Annual(1971) 90. 31. Sakamoto, Μ., Cho, H . , Yamada, Y . , Ojima, N . , and Tonami, Η., Sen-i Gakkaishi(1974) 30, Τ 17. 32. Tesoro, G.C., Sello, S.B., and Willard, J.J., J. Appl. Polym. Sci.(1968) 12, 683. 33. Matsuzaki, K., Nakamura, S., Go, C., and Miyata, T., Sen-i Gakkaishi(1968) 24, 235. 34. Matsuzaki, Κ., Nakamura, S., and Tsukamoto, Η., Sen-i Gakkai­ shi(1970) 26, 560. 35. Berlin, Α.Α., and Makarova, T.A., J. Gen. Chem. (USSR)(1963) 21, 1267. 36. Tonami, H . , Sen-i Gakkaishi(1958) 14, 100. 37. Yoshimura, S., Sen-i Gakkaishi(1965) 21, 317, 358, 410, 419, 479, 553, 560. 38. Arthur, J r . , J.C., Mares, T., and Hinojosa, O., Textile Res.

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

36

C E L L U L O S E A N D FIBER

SCIENCE

J.(1966) 36, 630 and other papers. 39. Ogiwara, Y . , Hon, N-S., and Kubota, H . , J. Polym. S c i . , Polym. Chem. Ed.(1973) 11, 3243. 40. Ogiwara, Y . , Hon, N-S., and Kubota, H., J. Appl. Polym. Sci. 1974) 18, 2075. 41. Kubota, H . , Ogiwara, Y . , and Matsuzaki, K., J . Polym. Sci., Polym. Chem. Ed.(1974) 12, 2809. 42. Kubota, H., Ogiwara, Y . , and Matsuzaki, K., J. Appl. Polym. Sci.(1975) 19, 1291. 43. Matsuzaki, Κ., Nakamura, S., and Shindo, S., J . Appl. Polym. Sci.(1972) 16, 1337. 44. Sakurada, I . , Okada, T., Hatakeyama, S., and Kimura, F., J . Polym. Sci.(1964) C, No. 4, 1233. 45. Odian, G., Kruse, R.L., Kho, J.H.T., J. Polym. Sci. A-1(1971) 9, 91. 46. Huang, R.Y.M., and 7, 1393. 47. Huang, R.Y.M., and Chandramouli, P., J. Appl. Polym. Sci. (1968) 12, 2549. 48. Wellons, J.D., Schindler, Α., and Stannett, V . , Polymer(1964) 5, 499. 49. Matsuzaki, K., Komagata, H . , and Sobue, Η., Kogyo Kagaku Zasshi(1964) 67, 1949. 50. Ikada, Y . , Nishizaki, Y . , and Sakurada, I . , Bull. Inst. Chem. Research, Kyoto Univ.(1972) 50, 20. 51. Matsuzaki, K., Kanai, T., and Morita, N . , J. Appl. Polym. Sci. (1972) 16, 15. 52. Matsuzaki, Κ., and Kanai, T., J. Appl. Polym. Sci.(1976) 20, 2221. 53. Matsuzaki, Κ., and Kanai, T., unpublished results. 54. Imamura, R., Ueno, T., et al., Kamipa Gikyoshi(Japan Tappi) (1971) 25, 121, 242, 465, 512. (1972) 26, 164. 55. Makita, Μ., Sen-i Gakkaishi(1974) 30, Ρ 260.

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

2 The Relationships between Fibrous Materials and Paper Products. Concepts. Prospects CRISTOFOR I. SIMIONESCU Polytechnic Institute of Jassay, Romania

1. The concept o materials and paper processes of paper converting and obtainment. Paper characteristics For quite a long time, relations which can be established between pulp, as the original fibrous material, and paper, the end product of a series of intermediate technological processes, have been the intuitive concern of paper producers. Yet the detection of qualitative and especially quantitative relations apt to outline the reciprocal influences between the original properties of the cellulose fibrous material and those of the paper end product (physical, Theological, mechanical strength paper properties) is a matter of future achievement. In the course of paper-converting a series of operations and processes (which are sketched out in figure 1) come between pulp (the raw material) and paper (the end product). Modern technologies c a l l for an additional use of auxiliary (non-fibrous) materials having specific functions. The use of adhesives leads to a reevaluation of the above mentioned sketch of influences and thus we get a completed form (figure 2). From figure 2 we may infer that pulp is l i k e l y to be influenced by an addition of adhesives which, in their turn, exert an influence on the fundamental operations. However pulp has a decisive part in lending paper certain specific characteristics. Similar decisive actions are brought forth by a number of adhesives. 39 In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

40

CELLULOSE

FAC

PULP ^

Q_ _l

A

LL

Ζ


x3000-

% PPE

Figure 15. Strength variation of dry papers obtained from (a) unbeaten and (b) beaten bleached softwood sulfate pulps, with an addition of PPE resin

2500 r 22502000•1750 r H1500E

§ i o o o -

* 750-

(/>

t

h 500fi

OLu-

Q5

1.0

2.0

%.PPE

3.0

Figure 16. Strength variation of wet papers obtained from (a) unbeaten and (b) beaten ground bleached softwood sulfate pulps with an addition of PPE resin

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

2.

siMiONESCu

Fibrous Materials and Paper Products

55

1.0-

I 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 PPE,%

ο J

*0

Figure 17. Dimensional variation of two types of paper with the amount of added PPE resin. (1) Di­ mensional variation of type 1 under the influence of a 2% melamine addition; (2) dimensional varia­ tion of type 1 with the addition of PPE resin; (3) dimensional variation of type 2 under the influence of a 5% melamine addition; (4) size variation of type 2 with the addition of PPE resin.

2

\.,PPE

a

°

Figure 18. Suspension breaking length variation vs. the addition of PPE resin and consistence in bleached sulfate pulps from unbeaten softwood materials

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

CELLULOSE AND FIBER SCIENCE

56

A s i m i l a r v a r i a t i o n takes place i n dry and wet r e s i s t a n c e s and dimensional s t a b i l i t y as can be seen i n f i g u r e 19. The changes c i t e d above may be accounted f o f by the p e c u l i a r T h e o l o g i c a l behaviour of the f i b r o u s suspension i n the r e g i o n of the i s o e l e c t r i c point, which ensures optimum conditions f o r the paper f o r ­ mation* Operations such as s i z i n g , short f i b r o u s materials r e t e n t i o n , f i l l i n g materials r e t e n t i o n and even dewatering on the paper-machine are also l a r g e l y i n ­ fluenced by introducing PPE adhesive i n t o the paste(1S)« A maximum degree of s i z i n g i s achieved with an a d d i t i o n of only 1 percent aluminium sulphate i n case of the output i n usual processing. The papers thus obtained have a pH tending to the n e u t r a l value (6,5) and physical-mechanical p r o p e r t i e s s i m i l a r to those r e s u l t i n g from the c l a s s i c a l r e c e p t i o n (14* 2021). Figure 20 shows the described v a r i a t i o n s . As regards the recorded e f f e c t s upon f i l l i n g materials r e t e n t i o n and short f i b r e s r e t e n t i o n , they are to be found i n f i g u r e s 21 and 22. The study of vallum papers, processed i n the presence of the PPE adhesive, r e s u l t e d i n the f o l l o w ­ ing c o r r e l a t i n g equations: F(%) = 0.5

3(mV) = 0.12

0.5 χ

+ 0.73 x

χ

0.03 χ 0.105

2 χ

- 0.442 x x 2

2

+ 1·383 χ

- 0.725 x

+ 0.116 x ^

2

- 1.25 x| - l . l x

+ 0.934 x

χ

χ

5

2 2

?

-

- 0.011 x

+ 0.262 x ^

(1)

5

2 ?

+

-

5

(2)

where the dependent v a r i a b l e s are: F - fibrous material retention y i e l d J - zetha e l e c t r o k i n e t i c p o t e n t i a l of the suspension The independent

v a r i a b l e s are the f o l l o w i n g :

x ^ colophony glue a d d i t i o n x - aluminium sulphate a d d i t i o n x*- PPE r e s i n a d d i t i o n 2

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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siMiONEScu

Fibrous Materials and Paper Products

57

ε

CL

3θηΙ—«-J ^ 0

1.0

J U

2.0

3.0 Ρ Ρ Ε , %

Figure 19. Suspension breaking length variation vs. the addition of PPE resin and consistence in bleached sulfate pulps from beaten softwood materials

100-

Figure 20. pH of the environment and the sizing degree of the papers obtained with 3% colophony glue with and/or with­ out an addition of 1% PPE resin and rising quantities of aluminum sulfate or natrium aluminate + aluminum sulfate. Degree of sizing: (O) 5% aluminum sulfate; (Φ) 1% PPE + 1% Al (SO ) ; ((D) 1% PPE + 1% aluminum sulfate + natrium aluminate. pH: (X) 5% aluminum sulfate; (-{-) 1% PPE + I % aluminum sulfate. 2

%Al2(SO^) .18H 0 3

2

k s

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

58

CELLULOSE AND FIBER SCIENCE

Figure 21. Retention yield variation of the calcium carbonate with bleached sulfate pulp which has been beaten for 35 min with an initial addition of 1-10% fillings; 2-20% fill­ ings; 3-5% fillings

6Θ-

%,PPE

Figure 22. Variation of the titanium dioxide with PPE resin addition retention yield, in the case of bleached sulfate softwood pulp which has been beaten for 35 min in a Jokro mill, with an initial addition of 1-20%fillings;2-10%fillings;3-5% fillings

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

2.

siMiONESCu

Fibrous Materials and Paper Products

59

The l a s t values have the f o l l o w i n g l i m i t s : s

x^ = 0-3 percent; x 0 - 8 percent; x^=0-1.2 percent 2

In the s p e c i f i c case when i n equation (1) we use 3 percent colophony glue ( x = +1.682) and 4 percent of aluminium sulphate (x - 0 ) , we obtain equation (3): 1

0

d

F » 95.84 + 0.73 x

- 1.1 x

?

2

(3)

The r e l a t i o n describes a curve having a maximum when F = 95.97 percent, corresponding to a quantity of 0.718 percent PPE r e s i n (x^ = +0.332). The y i e l d increas r e t e n t i o n i s F = 9.1 percent. Under s i m i l a r c o n d i t i o n s , we get equation

3

(4)

2

-0.23 + 1.82 x - 0.011 x (4) where from we f i n d the f o l l o w i n g value J = +0.37 mV, f o r which the y i e l d i s at i t s highest (region o f the isoelectric point). S i m i l a r l y i n f l u e n c i n g f a c t o r s of the PPE a d d i t i o n i n the stock dewatering process on the newspapermachine have been determined. The f o l l o w i n g c o r r e l a t ­ ing equations have been used: s

3

?

1

Κ (cm s*" ) = 9.1 - 1.18 χ - 0.42 χ

2

- 0.32 x

χ

1

(Hcrn^ )

2

+ 0.322 x

χ

- 0.294 x ^

2

= 2.87 + 0.273 χ

χ

- 0.1 x + 0.04 x-j + 0.05 x + 0.0146 XjXg 5

- 0.203 χ - 0.43 x

2 χ

2 3

- 0.763 x

2 2

- 0.092 x ^

2 3

+ 2.28

2

(5)

+ 0.0167 x

2

J (mV) = 1.18 + 0.885 x

-

?

-

2

+ (6) -

- 0.763 x

2

-

2

- 0.705 χ χ 2

?

(7)

As dependent v a r i a b l e s the f o l l o w i n g have been assumed: Κ - f i l t e r i n g rate / (> 'c ΟC Ε %

73

determining influences

PAPER

determining influences

Figure 23. Diagram tives-paper product interrelations

Figure 24

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

SCIENCE

2.

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Fibrous Materials and Paper Products

69

The diagram provides the p o s s i b i l i t y of systematica l l y exploring the interferences of the three i n fluencing factors. The concern with using mixtures of chemical and pulp f i b r e s o r i g i n a t e d f i r s t l y i n the l i m i t e d performances of t r a d i t i o n a l paper i n some of i t s uses and secondly i n the high cost of synthetic paper obtained from chemical f i b r e s 100 percent* A compet i t i v e evolution of the two types may be foreseen. Economical reasons and improvement of e x i s t i n g technologies w i l l exert a great influence on t h i s evolution. Conclusions The i n t e r r e l a t i o n product have been c o n s i s t e n t l y c h a r a c t e r i z e d . The leading general concept asserts the i n t e r ference of moderate influences or of determining actions r e s u l t i n g from the fundamental operations and the a d d i t i o n of a d d i t i v e s , between the properties of the i n i t i a l f i b r o u s material and those of the f i n a l paper product. The i n v e s t i g a t i o n has been d i r e c t e d towards the f i b r o u s material-additives-fundamental operations-paper c h a r a c t e r i s t i c s system i n the case of short f i b r e s from annual plants pulp (reed, straw) and hardwoods. Q u a l i t a t i v e c o r r e l a t i o n s has been determined i n the f i r s t place and afterwards quantit a t i v e i n t e r p r e t a t i o n has been given to them. Some r e l a t i o n s proved apt f o r being introduced into a mathematic model, the i n f l u e n c i n g f a c t o r s enabling the optimization of paper c h a r a c t e r i s t i c s or of the fundamental operations. The determining influence of a d d i t i v e s has been i l l u s t r a t e d by use of the c a t i o n - a c t i v e PPE r e s i n . The r e s i n modifies e s s e n t i a l l y some fundamental operations and has a d i r e c t e f f e c t on improving paper properties. S i m i l a r i n t e r r e l a t i o n s have been determined i n the case of a r t i f i c i a l and synthetic polymers introduce ced i n the composition of the pulp f i b r o u s m a t e r i a l . The e f f e c t s are due to the symbiosis between the properties of the paper properties of the synthetic polymers and of the n a t u r a l pulp.

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

70

CELLULOSE AND FIBER SCIENCE Literature

1 Cr. Simionescu, Gh. Rozmarin, Chimia stufului, Ed. Tehnică, Bucureşti, 1966. 2 Cr. Simionescu et all, Zellstoff und Papier, 1963, 12, 327. 3 E. Poppel, S. Petrovan, Cr. Simionescu, Buletinul Inst. politehnic Iaşi, 10 (14), 1-2, 155 (1964). 4 Cr. Simionescu, Gh. Rozmarin, Chimia lemnului şi a celulozei, v o l . I , Litografia I . P . I a ş i , 1972. 5 V. Diaconescu, E. I.P. I a ş i , 9(13), 3-4, 155 (1963). 6 V. Diaconescu, E . Poppel, P. Obrocea, Celluloză

şi Hîrtie, 12, 5-6, 184(1963). 7 Cr. Simionescu, M. G r i g o r a ş , A. Cernătescu-Asandei Chimia lemnului din RPR, Ed. Academiei R.P.R., Bucureşti, 1964. 8 E . Poppel, S. Petrovan, Contract de cercetare ştiinţifică (Combinatul de C e l u l o z ă şi Hîrtie Drobeta Turnu-Severin), 1974. 9 Ε. Poppel, S. Petrovan, Das Papier, under press. 10 E. Poppel, S. Petrovan, Contract de cercetare ştiinţifică (Combinatul de C e l u l o z ă şi Hîrtie Drobeta Turnu-Severin), 1975. 11 Cr. Simionescu, E . Poppel, S. Petrovan, Paper presented at the International Meeting of the International Academy of Wood Science, Banska Bystrica, 1975. 12 13 14

E . Poppel, S. Petrovan, Cr. Simionescu, Chem. and Technol. 2, 4, 444 (1968).

Cellulose

E. Poppel, I . Bicu, Das Papier, 2 2 , 12, 882(1968). E . Poppel, I . Bicu, Das Papier, 23, 10 A, 672(1969)

15

E . Poppel, I . Bicu, Das Papier, 26, 4, 162 (1972).

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

2.SIMIONESCUFibrous Materials ajid Paper Products

71

16 I . Bicu, V. Popa, E. Poppel, Cr. Simionescu, Z e l l stoff und Papier, 2 1 , 1,8 (1972). 17 18

E. Poppel, I. Bicu, V. Dobronăuţeanu, Das Papier, 29, 3,93 (1975). E. Poppel, I . Bicu, Z. Ládo, Cellulose Chem. and Technol., 9, 4, 413 (1975).

19 20 21 22

I. Bicu, V. Popa, E . Poppel, C e l u l o z ă şi H î r t i e , 18, 10, 498 (1969). Ε. Poppel, Cr. Simionescu, Buletinul I.P. Iaşi, 8 (12), 1-2, 1977 (1962) I. Bicu, Doctora

ş

E. Poppel, D. Ciobanu, Zellstoff u. Papier, 1975, 3, 68. 23 24 25 26

E. Poppel, D. Ciobanu, Zellstoff u. Papier, 1975, 5, 135. E. Poppel, D. Ciobanu, F. Andruchovici, Zellstoff u. Papier, 1975, 11, 323. E. Poppel, D. Ciobanu, Zellstoff u. Papier, under press. Cr. Simionescu, A. Liga, Patent R.S.R. 73064(1972)

27 28

N. Asandei, A. Liga, C. Stan, C. Moisă, Patent R.S.R. 59353 (1976). Cr. Simionescu, V. Rusan, A. Liga, V. Nuţă, D. Buhman, unpublished data.

29

D. Feldman, M. Ciubotaru, M. Ciugureanu, Rev. Roum. de Chimie, 1976 (under print) 30

A. Stoleriu, paper communicated at the first Microsymposium of macromolecular chemistry, I a ş i ,

November 14-15, 1975. 31

D. Buhman, Z. Ládo, V. Ungureanu, paper communicat­ ed at the 1st Microsymp.macromo.chem.Iaşi,14-15.XI. 1975.

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

3 History and Future Trend of Synthetic Paper Technology in Japan SHOZO IMOTO Toppan Printing Co., Ltd., 5,1-Chome Taito, Taito-ku, Tokyo, Japan

The brief history of Synthetic Paper or Plastic Paper in Japan i s summarized as f o l l o w s : (1) U n t i l the year o f 1967 when Foamed P o l y s t y r e n e or Polyethylene Sheet was developed, (2) U n t i l the year o f 1970 when the idea o f Raw M a t e r i a l Revolution, so to speak, c e n t r a l i z i n g the u t i l i z a t i o n o f P l a s t i c Paper or S y n t h e t i c Paper with P l a s t i c F i l m Base, was embodied i n the form of i n d u s t r i a l i z a t i o n . (3) U n t i l .the year o f 1975 when White P l a s t i c Sheet f o r Vacuum Molding, i n p a r t i c u l a r , r e s u l t i n g from a mixture o f M i n e r a l F i l l e r i n l a r g e q u a n t i t i e s and S y n t h e t i c Pulp, as w e l l , was i n d u s t r i a l i z e d . With the above d i v i s i o n a l periods i n mind, f i r s t o f a l l , I would l i k e to describe the trend mainly from the t e c h n o l o g i c a l point o f view: L a s t l y , I would l i k e to introduce the newest type o f S y n t h e t i c Paper on which we are a t present doing research, attempting to sound the t e c h n o l o g i c a l trend i n the f u t u r e . (1) Foamed Sheet Age (Up to 1967) In the wake o f Wood Pulp Paper d i d the second paper, v i z . , Non-Woven F a b r i c s come out. The t h i r d paper was none other than Foamed P o l y s t y r e n e Sheet that made i t s debut i n i 9 6 0 . None-Woven F a b r i c s are mostly used i n s t e a d o f c l o t h , while Foamed P o l y s t y r e n e Sheet could be used i n the main f o r lunch boxes and other sundry items a f t e r vacuum molding, being seldom made use o f as a s u b s t i t u t e f o r paper. As regards Foamed P o l y s t y r e n e Sheet, s e v e r a l Japanese manuf a c t u r e r s such as SEKISUI KAGAKU CO. and K0KUSAI PULP CO. became capable o f producing 500 t . - 1,000 t . per year r e s p e c t i v e l y i n or about the year o f i 9 6 0 . T h i s Sheet was aimed a t being developed enough to r e p l a c e paper i n uses due p a r t i a l l y to i t s p e a r l - l i k e b e a u t i f u l g l o s s y

72

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Synthetic Paper Technology in Japan

surface and p a r t i a l l y to i t s p a p e r - l i k e r i g i d i t y and opaqueness characteristically. Above a l l , SEKISUI had e s t a b l i s h e d i t s plant i n the u n i t e d States,too, r e i n f o r c i n g i t s o p e r a t i o n t h e r e . Nevertheless, i t proved to be i n s u f f i c i e n t as paper i n p o i n t o f s t r e n g t h , p r i n t a b i l i t y , e t c . , with the r e s u l t that i t s s a l e s amount was not as s a t i s f a c t o r y as had been a n t i c i p a t e d . I t was not u n t i l the year o f i960 that NIPPON ART PAPER CO.R. & D. D i v i s i o n , present JAPAN SYNTHETIC PAPER CO., improved the stength and p r i n t a b i l i t y o f t h i s Foamed Polystyrene Sheet under the brand o f "Q-Foam" o f Foamed Polyethylene Sheet. Subsequently, from 1965 through 1971 t h i s improved type o f Foamed Polyethylene Sheet had been produced and o f f e r e d f o r s a l e by JAPAN SYNTHETIC PAPER CO. Then, MITSUI POLYCHEMICAL CO.'s wholly-owned s u b s i d i a r y HI-SHEET KOGYO CO took th produc t i o n , producing 3*000 t connection, i t s p h y s i c a p r o p e r t i e represente y TABLE ( 1 ) . (2) F i l m Base Type S y n t h e t i c Paper Age(from 1967 t o 1970) I t was i n 1966 that JAPAN SYNTHTIC PAPER CO. announced another brand, "Q-Per", a type o f S y n t h e t i c Paper with o n l y i t s s u r f a c e paperized by c h e m i c a l l y t r e a t i n g by means o f the same f i l m as the S y n t h e t i c Paper with the brand o f " Q - K o t e " , f i n a l l y became the cynosure o f a l l eyes not o n l y i n Japan but a l s o a l l over the world what with i t s p r i n t a b i l i t y and p r i n t i n g e f f e c t estimated a t the highest q u a l i t y as p r i n t i n g paper. I f the cost o f the b i a x i a l l y o r i e n t e d -film could reach a t 60 cents per kg. through the mass-production o f 1,000 ton per month and the new t e n t e r i n g technology being under developing by Dr. Shoei Yazawa o r Mitsubishi-Monsanto Chemical Co., the S y n t h e t i c Paper Q-Kote s p r i c e would be estimated approximately 1.5 times as much as the high q u a l i t y coated paper. On the occasion o f t h i s t e c h n o l o g i c a l development, the Japanese Science and Technology Agency i n the Japanese Government was s t r o n g l y convinced that S y n t h e t i c Paper would f i l l i n the shortage o f pulp f o r paper i n Japan and c o n t r i b u t e to development of Japan's Petrochemical Industry, too. As a Government p o l i c y , they t h e r e f o r e decided to promote t h i s i n d u s t r y . Encouraged by t h i s Government p o l i c y , on the other hand, JAPAN SYNTHETIC PAPER CO. completed i t s production f a c i l i t i e s f o r Q-KoteQ and "Q-Per" capable o f producing 3*000 t . per year i n 1969 as i t s 1st term program. Afterward, OJI-YUKA SYNTHETIC PAPER CO. with the brand o f "UPO-EF" and SEKISUI KAGAKU CO. with the brand o f " P r i n t e l " r e s p e c t i v e l y set up t h e i r production f a c i l i t i e s f o r t h e i r products i n I 9 7 L In t h i s regard, "Q-Kote", "Q-Per", "UPO-EF", and " P r i n t e l a r e as represented i n performance by TABLE(1). Furthermore, p r a c t i c a l i t y o f t h i s type o f S y n t h e t i c Paper was promoted. To c i t e a few examples, books made o n l y from f,

flt

ff

1 1

11

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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"Q-Kote" and "Q-Per" were published, and some pages o f a c e r t a i n l e a d i n g weekly with i t s weekly c i r c u l a t i o n o f 1,000,000 copies were composed o f t h i s type o f S y n t h e t i c Paper t o say nothing o f Posters, Pamphlets and W r i t i n g Paper. In a d d i t i o n t o the above three(3) manufacturers n e a r l y ten (10) others announced F i l m Base Type S y n t h e t i c Paper along with t h e i r samples. Meanwhile, UCC, MEAD CORP.(U.S.A.) and XYLONITE CO.(U.K.) had been developing Pigmented F i l m Type S y n t h e t i c Paper. F o r example, the performace o f MEAD CORP. s "Aero-Art" i s as represented by TABLE ( 1 ) . Simultaneously i n Japan such manufacturers as CHISSO CO. and NITTO-BOSEKI CO. had been making researches on S y n t h e t i c F i b e r o r Pulp f o r paper, though they could not i n d u s t r i a l i z e this material. (3) S y n t h e t i c Pul Age (1971 - 1975) 1. Slump i n F i l m Base Type Demand Development o f demand f o r S y n t h e t i c Paper as replacement o f conventional paper has turned out to be extremely d i f f i c u l t owing to Japan's economic r e c e s s i o n on the whole, deep business depression adversely a f f e c t i n g the high c l a s s paper i n d u s t r y i n p a r t i c u l a r , the " D o l l a r Shock", r a i s e s i n petrochemical m a t e r i a l s caused by boosts i n o i l , e t c . The a f o r e s a i d preceding three(3) manufacturers have e x t e r t e d every e f f o r t to commercialize t h e i r products, i n the hope that the products could be a p p l i e d to users even a t high p r i c e s , suf£ f e r i n g from t h e i r r e s p e c t i v e low o p e r a t i o n . However, i n my personal estimation, t h e i r r e s p e c t i v e product i o n i n the year o f 197^ i s as represented by TABLE (2) 2. Debut o f S y n t h e t i c Pulp MITSUI-ZELLERBACH CO.(JAPAN), a J o i n t Venture f i r m e s t a b l i s h e d by CROWN-ZELLERBACH CO.(U.S.A.) and MITSUI PETROCHEMICAL CO. b u i l t a plant capable o f producing 500 t . per month o f S y n t h e t i c Pulp under the brand o f "SWP"(Synthetic Wood Pulp) i n 1973, throwing l i g h t on the S y n t h e t i c Pulp Age. According t o the manufacturing method o f S y n t h e t i c Pulp that had been p r a c t i c e d u n t i l then, i n the f i r s t place, p l a s t i c P o l y mer was produced, and i t was converted i n t o f i b e r or pulp, though. "SWP" was prepared by a new process, s u b j e c t i n g Monomer t o Polymerization and converting i t i n t o f i b e r simultaneously. T h i s S y n t h e t i c Pulp was the f r u i t o f exceedingly epochal t e c h n o l o g i c a l development, resembling Wood Pulp a great deal i n both shape and q u a l i t y . For some uses i t cou;d blend with Wood Pulp and be formed p r o p e r l y by the conventional paper machine. "SWP" only could be subject t o paper-forming, however. As compared with conventional paper made from Woof Pulp only, t h i s mixture could be c h a r a c t e r i s t i c i n performance o f High Opaci t y and Brightness, L i g h t e r Weight, Higher Clearness, Dimension 1

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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S t a b i l i t y against Humidity, Heat S e a l a b i l i t y and Emobossability. On top of these p r o p e r t i e s , i t i s e x c e l l e n t i n dehydration and evaporation. In c o n c l u s i o n , a d d i t i o n of S y n t h e t i c Pulp i s s a i d to enlarge the Machine Speed. Subsequent to MITSUI-ZELLERBACH CO.'s development, HITACHI KASEI CO., TORAY CO., e t c . s t a r t e d developing S y n t h e t i c Pulp. In consequence, the e n t i r e production of S y n t h e t i c Pulp i s estimated to exceed that of F i l m Type S y n t h e t i c Paper, as represented by TABLE (2)during the p e r i o d of 1975 and 1976. 3· H i g h l y Pigmented F i l m Type In view of the f a c t that the cost of Petrochemical Resin skyrocketed, causing a boost i n the p r i c e of the product, and that the combustion furnace i s apt to be damaged due to high c a l o r i e when i t be burned, s e v e r a l manufacturers have promptly s t a r t e d to develop H i g h l Pigmented F i l Shee c o n t a i n i n more than 60% of low-price lower combustion c a l o r i e , 1971· larges , LION YUSHI CO. has begun to turn out the above i n i t s production c a p a c i t y of 10,000 t . per year. I t s product under the brand of "Kalp" i s as represented i n performance by TABLE ( 1 ) . Sulphur emanates from Crude Petroleum when i t burns. T h i s sulphur could be converted i n t o Gypsum, which could be made i n sheetings by means of P o l y o l e f i n Resin as Binder i n a s k i l l f u l , but simple way. Crude Petroleum imported i n t o Japan contains l o t s of S u l f u r , and t h e r e f o r e i t would be f o r c i b l y changed to CaS04 i n order to prevent a i r p o l l u t i o n , just a f t e r combustion. A n d , P in l a r g e q u a n t i t i e s could be s u p p l i e d to us at a low cost, as i3ie good f i l l e r . Probably because of imcomplete engineering i n the field of P a p e r i z a t i o n only t h i c k sheet f o r Vacuum Molding has so f a r been put on the market here i n Japan, though, I t i s expected that P a p e r - l i k e F i l m would be produced i n the near future. Aside from the above, P o l y o l e f i m Sheet f o r Vacuum Molding c o n t a i n i n g over 60% of such Iorganic F i l l e r as Ca C03 and CaS04 i s at present manufactured by four(4) Japanese makers. I t s d e n s i t y i s 1.4 - 1.6, i t s combustion c a l o r i e , 3»000 - 4,000 Kcal/kg«i i t s thickness, 0.5 - 1mm. and i t i s noteworthy that i t could he deeply molded i n almost the same as C l e a r Resin. Such improvement of High F i l l e r P l a s t i c Sheet, to the best of my knowledge, could be a s c r i b e d not merely to progress i n Technology on Treatment of Inorganic M a t e r i a l but to betterment of Engineering i n Mixing and Sheeting, yoo. 4. Prospects. 1. I t i s expected that S y n t h e t i c Pulp w i l l be popular with users at l a r g e . / d ^ In case of recovery of Scrapped Paper, or Spoilage, on the con^ion that some per cent of S y n t h e t i c Pulp i n v o l v e d i n i t , should prove not to i n t e r f e r e , u t i l i z a t i o n of S y n t h e t i c Paper G v

s u m

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Tabled)Properties and Printability of each Synthetic Paper Type Type Physical properties Item Thickness, μ Density, tin? Whiteness, 7.

Opicity. % Gloss.

front. %

Test method JI5P-8124 JISf*81l8 JISP-8I18 JISP-8123 JISP-8138 JISP-8142

(«fr~-6Vo back. %

•

Smoothness, front, m m t y back, m m r * Tensile strength MP, Ιφ6τί JISP-8113 Elongation MD. % JISP-8132 CD,% * Tming strength MD, ^ JIS P-8M6 CD.* • Ink lusterdndifo), ·/. JIS P-8K2 Ink depositing — Ink absorption — Ink Transfer Ink setting time. m i n . —

-

wfocepdperiaq Co* paperizjnj PR IN TEL Q-FOAM

(bmjwRUive tests HiSoftwood First productio world Production of x y l o s e a s dissolving kraft pulp by-products Table 7 Consumed pulpwood statistics (1,000 m ) 3

Year 1960 62 64 66 68 70 72 73 74 75

Softwood 7.861 7.674 7.894 8.132 9.348 12.018 13,550 15.131 15.912 14,096

Hardwood 4,481 6,516 8.538 10,352 12.698 16.325 17.258 17.783 17.163 14.553

Total 12.342 14.190 16.432 18.482 22.046 28.343 30.808 32.914 33.075 28,649

Table 8 Supplied p u l p w o o d statistics(1,000m ) 3

Year 1960 65 67 68 70 72 73 74 75

Domestic Roundwood Chip 7,983 7,673 9.975 7,401 6,566 4,419 3,712 3,799 2,672

3.040 8.479 10,005 11.950 16.050 17.966 17,446 17,716 14,324

Imports Roundwood 193 207 163 299 559 370 667 1,232 578

Chip

—

254 1,401 2.927 4.726 7.159 10.556 12.820 11,213

Total 11.216 16.613 21,544 22.577 27,901 29.914 32.381 35,627 28,787

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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Table 9 Imported p u l p w o o d statistics(1,000m ) 3

Year

North America

—

1960 65 67 68 70 72 73 74 75

253 U02 2,909 4,091 5.435 7,501 8.729 7,533

Soviet Union 193 167 97 55 257 128 417 579 723

O c e a n i a Others

— — —

— 41

65 3 259 779 158 854 1,112 2,349 956 4.744 3,535

Total 193 461 1.564 3,226 5.285 7,529 11,223 14.052 11,791

TablelO W o o d s p e c i e s a s p u l p w o o d Wood s p e c i e s Softwood

Domestic w o o d

Hardwood

8.

Foreign wood Soviet U S.A. Southern a r e a Domestic w o o d

pine. fir. s p r u c e , hemlock. sugi(Cryptomeria), cypress, l a r c h , hiba(Thujopsis) spruce, fir, Scotch pine, larch Douglas f i r, hemlock. white fir, spruce, cedar merkusii p i n e , r a d i a t a pine b e e c h , birch, alder, oak,tabu(Machilus), shii(Shiia)

Foreign w o o d Soviet Southern area

white birch, e l m , a s p e n , a s h mangrove, eucalyptus, lauan, gum(waste wood)

Table 11 Outlook of supply a n d d e m a n d of pulp a n d p a p e r ( U n i t : 1,0001) Items Pulp Demand Production Capacity Rate of operation,% Paper Demand Production Capacity Rate of operation^

1973

1974

11.475 10,781 1Q200 9.558 11.461 11.868 89.0

80.5

16.954 14.246 ]6J§2& 14.433 16,498 17,935 100.8

80.5

1975

1976

1977

1978

10,445 9.395 12,472

10.661 9.311 12.460

11.131 9.581 12,779

13,448 10.848

75.2

74.7

14,564 14.100 19.967

15.523 15,337 20.058

70.6

76.5

75.0

— —

16,227 20.752 16 7QQ 20.468 20.740 f

80.5

— —

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

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a l o n g range view o f p u l p raw

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materials.

Resource developments i n o t h e r c o u n t r i e s Table 12 summarizes the r e s o u r c e development i n o t h e r c o u n t r i e s . At p r e s e n t , Japan i s p u r s u i n g a p a t t e r n which w i l l c o n t r i b u t e more t o the p r o s p e r i t y o f the h o s t c o u n t r i e s , i n o t h e r words, the i n d u s t r y i s t r y i n g t o go i n t o t i e - u p s w i t h the h o s t c o u n t r i e s t o undertake p l a n t a t i o n and even p u l p and paper p r o d u c t i o n i n t h e s e c o u n t r i e s . One o f the s u c c e s s f u l c a s e s o f the economic c o o p e r a t i o n i n the manner mentioned above i s the p r o j e c t i n B r a z i l . Waste paper T a b l e 13 shows the o r i g i n o f waste paper i n Japan. The share o f waste paper was i n 37~ 4 1 % o f paper and paperboard p r o d u c t i o fro 1969 t 1974. The i n d u s t r waste paper as p u l p raw m a t e r i a l . F o r t h i s purpose, The C e n t e r f o r the P r o m o t i o n o f the Use o f Waste Paper has been e s t a b l i s h e d t o f a c i l i t a t e the c o n s t a n t s u p p l y of waste paper and t o i n c r e a s e the share o f waste paper. The c h r o n i c i n s u f f i c i e n c y o f the waste paper r e c o v e r y system i n Japan has l o n g p r e v e n t e d the i n c r e a se of r e c o v e r y r a t e . At p r e s e n t , the i n d u s t r y w i s h e s to i n c r e a s e the share of waste paper used as raw mater i a l t o 45% by 1 9 8 5 . Non-woody p l a n t f i b e r The use of r i c e straw as raw m a t e r i a l was e a r l i e r t h a n t h a t of wood, t h a t i s i n 1878. The i n c l i n a t i o n o f c o l l e c t i o n season, the i n convenience o f c o l l e c t i o n , t r a n s p o r t a t i o n and s t o r a g e , low p u l p y i e l d and so on have p r e v e n t e d the i n c r e a s e o f straw p u l p p r o d u c t i o n . R e c e n t l y , a l l straw p u l p m i l l s stopped the p r o d u c t i o n o f i t i n Japan, because the e f f u i e n t problems was f u r t h e r t a k e n p a r t . However, from a p o i n t of f u t u r e s h o r t a g e o f p u l p raw m a t e r i a l , r i c e s t r a w s h o u l d be used a g a i n . I n the case o f r i c e s t r a w p u l p p r o d u c t i o n , a new p u l p i n g way must be found out, because the ash c o n t e n t o f r i c e s t r a w (about 17%) i s more t h a n t h a t o f wheat s t r a w (about 8%). Also, new s t r a w p u l p m i l l would be b e t t e r t o o p e r a t e i n s m a l l p r o d u c t i o n c a p a c i t y from a p o i n t o f the p o s s i b i l i t y o f easy c o l l e c t i o n . I n Japan, we can e s t i m a t e 1 2 , 0 0 0 , 0 0 0 t / y e a r of r i c e straw. Supposing t h a t the i n d u s t r y w i l l use 3 , 0 0 0 , 0 0 0 t / y e a r of r i c e straw and p u l p y i e l d i s 40%, about 1 , 2 0 0 , 0 0 0 t / y e a r o f s t r a w p u l p a r e t o be produced. C o n c e r n i n g p u l p p r o d u c t i o n from non-woody p l a n t , one company i s now making the p l a n t a t i o n o f some h e r b s , s o - c a l l e d pulp grass.

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P o l l u t i o n problems The p u l p and paper i n d u s t r y must meet t h e r e g u l a t i o n o f a n t i - p o l l u t i o n s e t by t h e government and t h e l o c a l a u t h o r i t i e s , a l t h o u g h t h e government has p e r m i t ted a t r a n s i t i t i o n a l p e r i o d d u r i n g which the i n d u s t r y can improve t h e p r o d u c t i o n system t o meet t h e e n v i r o n mental standards. The i n d u s t r y was r e q u e s t e d t o a c h i e v e BOD and COD 1 20 ppm and SS 150 ppm by June i n 1976. The s t a n d a r d s s e t by t h e l o c a l a u t h o r i t i e s a r e even more s t r i c t . A new paper m i l l e s t a b l i s h e d i n 1974 has agreed upon 12 ppm o f BOD w i t h t h e l o c a l a u t h orities. T h i s m i l l has been a d o p t i n g t h e c o a g u l a t i o n and a c t i v e carbon t r e a t m e n t s o f e f f l u e n t s . P o l l u t i o n abatement i n e x i s t i n g p u l p and paper m i l l s The e x i s t i n the closed' system o as a commonsence, p o l l u t a n t s s h o u l d be t a k e n i n t h e production processes. I t i s a l s o c o n s i d e r e d i n what p r o c e s s t h e s u r p l u s m a t e r i a l s s h o u l d be d i s c h a r g e d . Decrease o f w a t e r consumption I t i s well-known t h a t p u l p and paper m i l l s a r e s t r u g g l i n g t o save t h e w a t e r consumption. T h i s i s a c h i e v e d by i n c r e a s i n g the use o f r e c o v e r e d water and r e c y c l i n g w a t e r . There i s a n o n - e f f l u e n t paper board m i l l w h i c h i s u s i n g waste paper, a l t h o u g h t h e w a t e r consumption i s a c t u a l l y 2 - 3 ^/t paperboard. T h i s m i l l announced t h a t t h e i n c r e a s e o f o p e r a t i o n temperature cused by none f f l u e n t s o p e r a t i o n has p r e v e n t e d t h e s l i m e t r o u b l e . The m a t e r i a l y i e l d was about 90% s e v e r a l y e a r s ago, but a t p r e s e n t i n c r e a s e d t o 9 6 ~ 9 7 % * a f t e r t h e improvement o f the p r o c e s s e s . That i s , t h e p r e v i o u s p o l l u t a n t s was t o be t a k e n i n t h e p r o d u c t s , and t h e r e i s no d i f f e r e n c e from t h e former q u a l i t i e s o f paperboard. Although people says t h a t t h i s i s p o s s i b l e o n l y i n a paperboard m i l l , t h e r e may be a few p r o c e s s e s w h i c h c o u l d be a p p l i e d i n t h e p r o d u c t i o n o f c o n v e n t i o n paper. Development o f p o l l u t i o n f r e e p u l p i n g There a r e two p r o c e s s e s w h i c h have been p r o g r e s s e d by t h e use o f p i l o t p l a n t ; PFP p r o c e s s by Japan P u l p and Paper I n s t i t u t e and HOPES p r o c e s s by Toyo P u l p Company. Both p r o c e s s e s have been f i n a n c e d by s u b s i d y o f t h e Government. Another p u l p i n g p r o c e s s , s o - c a l l e d a l k a l i methanol p u l p i n g has been s t u d y i n g by us s i n c e 1 9 7 4 . As shown i n F i g u r e 1, t h i s p r o c e s s i s from sodium h y d r o x i d e c o o k i n g o f c h i p s and d e f i b r a t i o n o f cooked c h i p s f o l l o w e d by t h e r e p e a t e d t r e a t m e n t s w i t h chemi*c a l s such as c h l o r i n e , c h l o r i n e d i o x i d e and sodium

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

180

CELLULOSE AND FD3ER SCIENCE

hydroxide for a s e l e c t i v e d e l i g n i f i c a t i o n . For an example, t h e r e i s C - E - H - E - D - E - D sequence a f t e r p r e cooking. P u l p y i e l d i s 6 0 - 7 0 % depending on the p u l p ­ i n g c o n d i t i o n s , and the spent l i q u o r i s w h o l l y r e c o v e r ­ ed, c o n c e n t r a t e d and b u r n t t o o b t a i n s m e l t of sodium c h l o r i d e and sodium c a r b o n a t e . Sodium c h l o r i d e i s s u b j e c t e d t o e l e c t r o l y s i s t o produce c h l o r i n e and sodium h y d r o x i d e . C h l o r i n e i s used t o produce c h l o ­ rine dioxide. The advantages o f t h i s p r o c e s s a r e i n low t e m p e r a ­ t u r e p u l p i n g under normal p r e s s u r e , no o f f e n s i v e odor l i k e k r a f t p r o c e s s and f r e e c o n t r o l l i n g o f p u l p y i e l d depending on the p u l p q u a l i t i e s r e q u i r e d . And the p o l l u t i o n load i s also quite small. However, h i g h power consumption and c o r r o s i o n o f the r e c o v e r y e q u i p ­ ment s h o u l d be p o i n t e t h i s process. Paper t e n d s t o be low i n o p a c i t y and t e a r i n g s t r e n g t h , because p u l p c o n t a i n s much h e m i cellulose. Flow c h a r t o f the HOPES p r o c e s s w i l l be shown i n Figure,2. T h i s p r o c e s s i s from two s t a g e p u l p i n g w h i c h i s from sodium h y d r o x i d e t r e a t m e n t a t Ί 6 0 - 1 7 0 ° C and sodium h y d r o x i d e - o x y g e n t r e a t m e n t a t 1 2 0 - 1 3 0 ° C under oxygen p r e s s u r e l e s s t h a n 1 Okg/cm . A modified Kamyr d i g e s t e r i s t o be a d o p t e d . Spent l i q u o r i s s u b j e c t e d t o a wet combustion p r o c e s s t o decompose o r g a n i c m a t t e r s and t o r e c o v e r sodium c a r b o n a t e . Pulp y i e l d i s s a i d t o be 2 - 3 % h i g h e r t h a n k r a f t p u l p and pulp strength equivalent to k r a f t pulp i n breaking l e n g t h and b u r s t s t r e n g t h and t o s u l f i t e p u l p i n t e a r strength. Toyo P u l p Company announce t h a t t h e y have a f a i r p r o s p e c t o f i n d u s t r i a l i z a t i o n and a 50 t/D p l a n t i s now undr c o n s t r u c t i o n . Flow c h a r t o f a l k a l i - m e t h a n o l p u l p i n g p r o c e s s i s shown i n F i g u r e 3 . Wood c h i p s a r e cooked w i t h 4 0 % methanol i n aqueous sodium h y d r o x i d e or sodium c a r b o ­ nate a t the maximum t e m p e r a t u r e o f 1 6 0 - 1 8 0 ° C . The advantages a r e i n about 3~5% h i g h e r p u l p y i e l d t h a n k r a f t p u l p and i n e q u i v a l e n t p u l p s t r e n g t h t o k r a f t pulp. The development o f t h i s p r o c e s s depends on methanol p r i c e . I t i s worth n o t i n g that a part of methanol comes from wood c o n s t i t u e n t s . E n v i r o n m e n t a l p r o t e c t i o n s i t u a t i o n The p u l p and paper i n d u s t r y has t o meet a n t i - p o l l u t i o n s t a n d a r d s s e t by the government. I t i s assumed t h a t the g o v e r n ­ ment w i l l s h i f t i t s c o n t r o l system from BOD and COD t o TOD and TOC, and a l s o from ppm base t o t o t a l l o a d base of p o l l u t a n t s . F u r t h e r m o r e , the l o c a l a u t h o r i t i e s s e t the r e g u l a t i o n f o r the o f f e n s i v e odor o f k r a f t m i l l .

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Japanese Pulp and Paper Industry

NAKANO

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