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Effect on the Properties of Grafted Fibers MD. HABIBUDDOWLA BCSIR Laboratories, Research Division, Dacca-5 Bangladesh
Graft copolymerisation reactions were carried out with KPM rayon and jute fiber in presence of a i r using ceric ammonium sulphate as the i n i t i a t o r . The tenacity and stiffness of methyl methacrylate graft ed KPM rayon, defatted and bleached jute fiber were studied and compared with those of ungrafted fibers. Grafting resulted i n the decrease i n tenacity sub stantially. The effect of grafting on the tensile properties of fiber was found to be rather obscure to propose any definite mechanism. Of the grafted fibers, KPM rayon grafted at 40°C showed a maximum of about 19% decrease i n tenacity. In general, lower temperature seemed to favor lesser decrease in tenacity for MMA grafted fibers. Grafting appreciably increased the stiffness for both KPM rayon and defatted jute fiber, but for bleached jute, the stiffness was found to decrease. A maximum of about 17% increase i n stiffness was observed for grafted KPM rayon and a maximum of about 5% decrease i n stiffness was observed for grafted bleached jute. Recently, e f f o r t s are beinp made i n Bangladesh f o r the com m e r c i a l u t i l i z a t i o n of j u t e f i b e r ÇL-2) and KPM ( K a r n a f u l i Paper M i l l ) rayon i n the t e x t i l e f i e l d to p a r t i a l l y meet the t o t a l f a b r i c requirements of the country as w e l l as to minimise import of s y n t h e t i c f i b e r . Due to low t e n s i l e s t r e n g t h , high water absorbancy and d i f f i c u l t y i n dyeing, the use of KPM rayon i n f a c t has remained r e s t r i c t e d i n t h i s f i e l d and the consequential e f f e c t i s that few t e x t i l e m i l l s of Bangladesh a r e i n a p o s i t i o n to manufacture blended yarn f o r f a b r i c p r o d u c t i o n . On the other hand, although j u t e f i b e r possesses high dimensional s t a b i l i t y (3) c e r t a i n unfavorable t e x t i l e p r o p e r t i e s , e.g., high s t i f f n e s s , very low e l a s t i c i t y , s u s c e p t i b i l i t y towards s u n l i g h t e t c . , have tremendously l i m i t e d i t s use (4). With a view to minimising t h e i r
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0097-6156/82/0187-0073$6.00/0 1982 American Chemical Society
Hon; Graft Copolymerization of Lignocellulosic Fibers ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
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undesirableness and enhancing t h e i r e f f e c t i v e n e s s f o r i n t e n s i f i e d t e x t i l e uses, g r a f t copolymerisation r e a c t i o n s were c a r r i e d out onto KPM rayon and j u t e f i b e r i n presence of a i r using e e r i e ammonium sulphate (CAS) as the i n i t i a t o r . Although, l a b o r a t o r y research on chemical m o d i f i c a t i o n of rayon and j u t e by g r a f t i n g has r e c e i v e d considerable a t t e n t i o n i n v a r i o u s c o u n t r i e s (5-12) l i t t l e i s known about the p r o p e r t i e s of g r a f t e d KPM rayon and j u t e f o r t h e i r use as t e x t i l e f i b e r s . Since encouraging r e s u l t s have been reported by only a few authors (13-14), regarding the e x t e n s i b i l i t y , d y e a b i l i t y and t e n a c i t y of the g r a f t e d j u t e , the object of t h i s work has t h e r e f o r e been towards i n v e s t i g a t i n g i n t o some of the t e n s i l e p r o p e r t i e s of the g r a f t e d j u t e and KPM rayon. Experimental Chemicals. Reagent grade chemicals were used i n the study of g r a f t i n g . Acetone, e t h y l a l c o h o l and benzene were r e d i s t i l l e d before use. Monomer, methyl methacrylate (MMA), was used f r e s h a f t e r p u r i f i c a t i o n and d i s t i l l a t i o n . I t was p u r i f i e d f o l l o w i n g the method adopted by Gupta and Nandy (15)• CAS was used a f t e r s t a n d a r d i z a t i o n by an usual method (16). A l l CAS s o l u t i o n s used f o r the study was a c i d i f i e d w i t h 1% H2SO4. Substrate and i t s P r e p a r a t i o n , The substrate used f o r g r a f t i n g purpose were j u t e f i b e r (defatted and bleached) and KPM rayon yarn. Jute f i b e r under i n v e s t i g a t i o n was of Corchorus C a p s u l a r i s v a r i e t y . I t was a r b i t r a r i l y d i v i d e d i n t o three p o r t i o n s . The middle p o r t i o n was chosen f o r the purpose of study. Defatted j u t e was prepared by t r e a t i n g i t w i t h a l c o h o l benzene (1: 2v/v) mixture i n a Soxhlet apparatus, washed w e l l w i t h a l c o h o l and a i r d r i e d . Bleaching of j u t e f i b e r was c a r r i e d out w i t h O.7% sodium c h l o r i t e f o l l o w i n g a s p e c i a l method (17). KPM rayon sample was prepared by t r e a t i n g i t w i t h d i l u t e soap s o l u t i o n , washed w e l l and d r i e d . G r a f t i n g Procedure and C a l c u l a t i o n of Percent G r a f t i n g . G r a f t copolymerisation treatment of KPM rayon yarn and j u t e f i b e r were c a r r i e d out i n a w e l l stoppered, Erlenmeyar f l a s k . F i f t y m i l l i meter CAS s o l u t i o n of known c o n c e n t r a t i o n was kept at a d e s i r e d temperature. One m i l l i m e t e r MMA was added f o l l o w i n g immediately by 1.0 gm of KPM rayon y a r n , a f t e r which the contents were s t i r r e d i n t e r m i t t e n t l y . A f t e r the end of the r e a c t i o n , the f l a s k were removed from the thermostat and methanol was immediately added. The mixture was then poured i n t o a Buchner funnel and s u c t i o n a p p l i e d . The homopolymer i n the f i l t r a t e was separated from the s o l u t i o n by f i l t e r i n g through p r e v i o u s l y weighed s i n t e r e d c r u c i b l e (G-3). I t was washed repeatedly w i t h hot water and d r i e d at 60°C. The g r a f t e d f i b e r on the funnel was e x t r a c t e d w i t h acetone f o r 10-12 hours i n a soxhlet apparatus. S i m i l a r procedure was a l s o adopted f o r j u t e f i b e r .
Hon; Graft Copolymerization of Lignocellulosic Fibers ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
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Percent g r a f t i n g has been c a l c u l a t e d u s i n g the standard f o r mula (18). Gain i n weight of the g r a f t e d f i b e r / w e i g h t of the monomer X 100. Determination of T e n a c i t y and S t i f f n e s s . T e n a c i t y has been expressed as grams/denier. The d e n i e r of both g r a f t e d and ung r a f t e d KPM rayon was d e r i v e d from the standard formula at standard c o n d i t i o n s (14). A f t e r c o n d i t i o n i n g the j u t e sample, i t was combed and the f i b e r aggregates of uniform l e n g t h was taken, weight and l e n g t h determined. The t e n a c i t y of KPM rayon yarn was determined by means of a Frank T e n s i l e Strength T e s t e r , w h i l e f o r j u t e yarn a Zweigles Strength Tester was used. S t i f f n e s s or t e n s i l e modulus at break was determined from the value of t e n a c i t y and e l o n g a t i o n at break u s i n g the f o l l o w i n g relation: ^. . . T e n a c i t y at break S t i f f n e s s at break = — -~. — τ — E l o n g a t i o n at break Λ
Λ
R e s u l t s and D i s c u s s i o n In order to study the e f f e c t s of g r a f t i n g on the t e n a c i t y and s t i f f n e s s of the f i b e r , v a r i o u s samples of KPM rayon, d e f a t t e d j u t e and bleached j u t e were g r a f t e d i n presence of 1% ï^SO^ f o l lowing the procedure as d e s c r i b e d e a r l i e r . The r e s u l t s have been presented i n Tables 1 and 2 and a l s o g r a p h i c a l l y shown i n F i g u r e s 1, 2 and 3 which show that g r a f t c o p o l y m e r i s a t i o n r e a c t i o n cons i d e r a b l y i n f l u e n c e s the t e n a c i t y and s t i f f n e s s of KPM rayon and j u t e f i b e r . From F i g u r e 1 i t i s q u i t e c l e a r that no r e g u l a r i t y i n the r e l a t i o n s h i p e x i s t between % g r a f t i n g and % decrease of t e n a c i t y f o r KPM rayon and d e f a t t e d j u t e . However f o r bleached j u t e l i n e a r p a t t e r n do e x i s t when the g r a f t load has been augmented from 19% to 40.5%. So f a r as the e f f e c t of g r a f t i n g on the t e n a c i t y of the f i b e r i s concerned, three d i f f e r e n t r e l a t i o n p a t t e r n e x i s t f o r three d i f f e r e n t tyges of f i b e r g r a f t e d between the temperature range of 30 C and 50 C (Figure 2 ) . For g r a f t e d KPM rayon and g r a f t e d bleached j u t e , % decrease of t e n a c i t y f o l l o w s l i n e a r p a t t e r n . For d e f a t t e d j u t e % decrease of t e n a c i t y i s much l e s s pronounced at 30 C., a f t e r which i n c r e a s e s s h a r p l y to about 15% as the temperature has been increased to 50 C. In the case of KPM rayon, r i s e of temperature from 30 C to 40 C enhance % decrease of t e n a c i t y l i n e a r l y from about 13% to 19% and f a l l s s h a r p l y to about 12% as the temperature has been increased to 50 C. In g e n e r a l lower temperature seems to favor l e s s e r decrease i n t e n a c i t y f o r MMA g r a f t e d f i b e r . A maximum of about 19% decrease of t e n a c i t y has been observed f o r g r a f t e d KPM rayon at 40 C and a minimum of about 1.5% decrease of t e n a c i t y has been found f o r MMA g r a f t e d d e f a t t e d j u t e at 30 C. In g e n e r a l , t h i s decrease of t e n a c i t y i s q u i t e understandable from the mechanistic viewpoint of g r a f t c o p o l y m e r i s a t i o n r e a c t i o n s of
Hon; Graft Copolymerization of Lignocellulosic Fibers ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
Hon; Graft Copolymerization of Lignocellulosic Fibers ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
o
(30°C)
g r a f t e d bleached
(30°C)
grafted
o
1% H S0, t r e a t e d 2 4 d e f a t t e d j u t e (40°C)
1% H S0. t r e a t e d 2 4 rayon (40°C)
jute
MMA
jute
MMA
defatted
g r a f t e d rayon
(30°C)
MMA
1% H.SO, t r e a t e d 2 4 bleached j u t e (30°C)
1% H.SO, t r e a t e d 2 4 d e f a t t e d j u t e (30°C)
1% H-SO. t r e a t e d 2 4 rayon (30°C)
Sample
grafted
30.50
12.85
1.49
13.50
2.12
1.35
10.30
1.95
O.83
1.80
1.98
O.75
1.85
2.15
-
50.70
2.01
1.52
O.86
Tenacity (gms/denier)
13.80
Elongation at break (B.L.) (%)
-
Grafting 7o
130.10
6.15
84.90
146.60
7.28
86.04
132.20
6.23
T e n s i l e modulas a t break (Stiffness)
D e s s i c a t o r atmosphere c o n d i t i o n e d a t R.H. o f 75% and a temperature o f 26°C. Twist/cm ( j u t e f i b e r ) = 1. L i g n i n content of bleached j u t e = 10%.
T a b l e - I. E f f e c t o f g r a f t i n g on the t e n s i l e p r o p e r t i e s o f MMA KPM rayon and j u t e f i b e r . Continued on next page.
Hon; Graft Copolymerization of Lignocellulosic Fibers ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
jute
MMA
jute
MMA
(50°C)
g r a f t e d bleached
(50°C)
grafted
defatted
g r a f t e d rayon
(50°C)
MMA
o
1% H S0. t r e a t e d 2 4 bleached j u t e (50°C)
(50°C)
19.08
5.66
37.0
-
-
defatted jute
2
1% H S0^ t r e a t e d
21.19
13.66
-
(40°C)
g r a f t e d bleached
(40°C)
grafted
39.80
-
Grafting
1% H SO, t r e a t e d 2 4 rayon (50 C)
jute
MMA
jute
MMA
defatted
g r a f t e d rayon
(40°C)
MMA
1% H.SO. t r e a t e d 2 4 bleached j u t e (40°C)
Sample
2.08
1.72
1.63
O.69
10.80
1.22
1.75
82.69
133.60
6.38
85.36
130.61
1.92
1.47
2.05
6.04
81.27
O.81
1.78
137.41
13.40
2.19
1.91
6.20
O.67
10.80
1.39
85.44
T e n s i l e modulas a t break (Stiffness)
1.82
Tenacity (gms/denier)
2.13
(%)
Elongation at break (B.L.)
T a b l e - I. Continued. E f f e c t of g r a f t i n g on the t e n s i l e p r o p e r t i e s o f MMA g r a f t e d KPM rayon and j u t e f i b e r .
Hon; Graft Copolymerization of Lignocellulosic Fibers ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
12.85
Defatted
(40°C)
(50°C)
(30°C)
(40°C)
(50°C)
19.08
21.19
30.50
5.66
-
-
1.39
17.0
6.71
11.18
19.40
20.00
25.36
%decrease breaking elongation
1.46
2.81
-
-
1.71
2.19
2.70
15.10
2.05
1.49
-
-
14.81
19.27
-
12.79
%decrease o f tenacity
-
%increase of b r e a k i n g elongation
C h l o r i t e bleached j u t e prepared under minimum c e l l u l o s i c d e g r a d a t i o n
jute
Bleached
jute
*Bleached
jute
Bleached
jute
Defatted
jute
Defatted
13.66
37.0
Rayon (50°C)
(30°C)
39.8
Rayon (40°C)
jute
50.7
%
Grafting
Rayon (30°C)
Sample
-
-
-
2.29
5.62
10.8
5.63
O.81
16.85
%increase of s t i f f ness
fiber.
3.13
4.88
1.32
-
-
-
-
-
-
%decrease of s t i f f ness
( L i g n i n content = 10%).
g r a f t e d KPM rayon and j u t e
Table - I I
T e n s i l e p r o p e r t i e s of MMA
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79
20 30 GRAFTING (%) Figure 1. Plot of percent decrease of tenacity vs. percent grafting. Key: ., rayon yarn; O, defatted jute; O, bleached jute.
30
40 50 TEMPERA TURE(°C)
Figure 2.Changes of tenacity of MMA grafted fiber. Key: ., rayon yarn; O, defatted jute; O, bleached jute.
Hon; Graft Copolymerization of Lignocellulosic Fibers ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
Figure 3. Changes of stiffness of MMA grafted fiber. Key: ., rayon yarn; Q , defatted jute; O , bleached jute.
Hon; Graft Copolymerization of Lignocellulosic Fibers ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
6.
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Methyl Methacrylate Grafting Onto Rayon and Jute 81
c e l l u l o s i c f i b e r w i t h v i n y l monomer (14). C e r t a i n l y , the presence of a i r has a d i r e c t e f f e c t on the c e l l u l o s i c c h a i n of the f i b e r f a v o r i n g o x i d a t i o n r e a c t i o n s and r e s u l t i n g i n profound decrease of t e n a c i t y . As f a r as the s t i f f n e s s i s concerned, g r a f t i n g has an appreci a b l e i n f l u e n c e on the s t i f f n e s s of both KPM rayon and d e f a t t e d j u t e f i b e r . However f o r bleached j u t e , the s t i f f n e s s has been found to decrease. The r e s u l t s have been shown i n Tables 1 and 2 and g r a p h i c a l l y represented i n F i g u r e 3 which r e p r e s e n t s three d i f f e r e n t r e l a t i o n p a t t e r n s f o r three d i f f e r e n t k i n d s of samples. In the case of d e f a t t e d j u t e , r i s e of temperature from 30 C t o 50 C reduces % increase of s t i f f n e s s l i n e a r l y from about 11% t o 2%. I n other words, higher temperature has been found to favor l e s s e r i n c r e a s e s i n s t i f f n e s s . For KPM rayon i n c r e a s e of temperature from 30 C to 40 C decreases % i n c r e a s e of s t i f f n e s s s u b s t a n t i a l l y from about 17% to 1% but as the temperature i s r a i s e d from 40 C to 50 C i n c r e a s e of s t i f f n e s s i s not so prominent. Opposite r e s u l t s have been obtained f o r bleached j u t e where a decrease of s t i f f n e s s was observed when g r a f t i n g was c a r r i e d out at a temperature of 30, 40 & 50 C. A maximum of about 5% decrease i n s t i f f n e s s has been observed f o r g r a f t e d bleached j u t e . The o v e r a l l e f f e c t of g r a f t i n g on the t e n s i l e p r o p e r t i e s of f i b e r was found to be r a t h e r obscure to propose any d e f i n i t e mechanism. Acknowledgements The author wishes t o express s i n c e r e thanks t o the authori t i e s of the B.C.S.I.R. L a b o r a t o r i e s , Dacca f o r the arrangements made f o r determining the p r o p e r t i e s of the f i b e r . Mr. Monsur Ahmed, T. O., A r t s & C r a f t s s e c t i o n of B.C.S.I.R Labs., a l s o deserve thanks f o r p r e p a r i n g the graphs and f i g u r e s . Literature Cited 1. 2. 3. 4. 5. 6.
7.
8.
Jute and Fabrics, Bangladesh; 1980, July, 6, No. 7. Jute and Fabrics, Bangladesh; 1980, June. Science News, series 54, 1-55. L i t t l e , Arthur D. "The Engineering Properties of Fibers" Incorporated Cambridge, Massachusetts, 1966. Richards, G. N.; J. Soc. Dyers, Colourists, 1964, 80 (12), 640-2 (1964) Yoshitake, I; Obuchi, S; Tsuneda, T; Maeda, H; (Nippan Rayon Co., Ltd, Kyoto, Japan) Sen-i-Gakkashi, 1965, 19 (7), 540-6. Morin, B. P.; Stanchenko, G-I; Rovenkova, T. A; Gracheva, Y. L.; Bershova, N. W (Mosk, Tekst, Inst, Moscow, USSR) Khim Volknan, 1975, 2, 22-4 Nakamura, Y; Negeshi, M.; Kakimuma, T.; (Gumma Univ, Kiryn, Japan) J. Poly. Sci. Part C, 1966, Pub 69, No 23 (Pt 2), 623-45.
Hon; Graft Copolymerization of Lignocellulosic Fibers ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
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GRAFT COPOLYMERIZATION OF LIGNOCELLULOSIC FIBERS
9.
Livshits, R. M. ; Stanchenko, G-I; USSR, Naush Issled, Tr. Mosk, Tekst, Inst, 1969, 22, 317-23. 10. Rogovin, Ζ. Α.; (Text Inst. Moscow, USSR), Tappi, 1974, 57 (7), 65-8. 11. Siddique F.R.Al; Zaman, Μ. Α.; Nuclear Science and Application, Series B, 1976, 9, 80-82. 12. Huque, M. M.; Habibuddowla, Md.; Mahmood, A. J.; Mian, A. J.; J. Polym. Sci., Polymer Chemistry Ed., 1980, 18, 1447-1458. 13. Trivedi, I. M.; Mehta, P. C.; Cellulose Chem. Technol, 1973, 7, 401-416. 14. Haque, M. M. and Habibuddowla, Md; Bangladesh J. S c i . Ind. Res, 1980, 15, No. 1-4, 64-70. 15. Gupta, S. N.; Nandi, U. S.; J. Polym. Sci., Α-1; 1970, 8, 3019-3031. 16. Vogel, A-I; "Quantitative Inorganic Analysis," ELBS & Lognman, 3rd Ed, 1961, p. 319. 17. Rahman, M. H. and Haque, M. M.; Pak, J . Sci. Ind. Res 1970, No. 13, 303. 18. Kojima K; Iwabuchi, S; Kojima, J . Polym. Sci.; Polym. Letter Ed, 1971, 9, 25-29. RECEIVED December 23,
1981.
Hon; Graft Copolymerization of Lignocellulosic Fibers ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
