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Synthesis of 2-hydroxy-3-chloropropyl cellulose ester and its polymer analogue conversions
SYNTHESIS OF 2-HYDROXY-3-CHLOROPROPYL CELLULOSE ESTER AND ITS POLYMER ANALOGUE CONVERSIONS Yr.. F. SH~KOVA, A. D. VIR~IK and Z. A. ROGOVIN Moscow Textile I n s t i t u t e
(Received 9 July 1965)
I~; [1] we demonstrated the possibility of synthesizing a number of cellulose derivatives with ion-exchange properties by polymer analogue conversions of the graft copolymer of cellulose and glycidyl methacrylate [1]. Considerable interest attaches to the addition of epoxy groups to the cellulose macromoleeule by the alkylation of the cellulose hydroxyl groups rather than by synthesizing the graft cellulose copolymer. In view of the high reactivity of epoxy groups, we think they are best added to the cellulose macromoleeule in the "latent f o r m " i.e. as chlorohydrin groups. A chlorohydrin group was added to a cellulose maeromoleeule by treating viscose staple fibre in epichlorohydrin in the presence of an acid catalyst. The staple fibre was treated for 10 rain at 20° in a 1-8 % solution of Zn (BFd)~, squeezed out to the amount of twice the weight increment and treated in epichlorohydrin or its solution in organic solvents under various conditions, after which it was washed in acetone followed by water, extracted in acetone and dried. To characterize the composition of the product, the chlorine content [2] and epoxy-group content [3] were determined. The experiments showed that with these reaction conditions the cellulose preparations obtained had a chlorine content of 1--12% with an epoxy-group content of not more than 0.52%. This shows that the main feature of the reaction of epichlorohydrin with cellulose hydroxyl groups is the opening up , f the a-oxide ring according to: [CeH,O~(OH)s]. + CH2--CH--CH,C1 ->
\o/ -> [C6HT02(OH)3-= (OCH~--CH--CH~C1)~].
I
OH The figures in Table I illustrate the influence of alkylation conditions on the ~omposition of the products. The results show that up to a catalyst concentration of 5% the alkylation of the hydroxyl groups increases; subsequent increase in catalyst concentration does not cause any particular increase in the degree of alkylation. If a 3% solution of * Vysokomol. soyed. 8: No. 8, 1450--1454, 1966. 1596
Synthesis of 2-hydroxy-3-chloropropyl cellulose
1597
Zn (BF4)~ is used as catalyst and the reaction performed at 100 °, it is practically complete in three hours. The degree of hydroxyl-group alkylation falls sharply if the reaction temperature is lowered. The presence of hydroxyl groups in the synthesized cellulose ether was proved by the fact that epoxy groups formed after the product had been treated in a solution of caustic soda. TABLE 1. EFFECT
Zn(BF4)~ concentration,
%
OF REACTION
CONDITIONS
Reaction temperature, °C
ON THE COMPOSITIOlq OF THE PRODUCTS
Reaction time, hr
Chlorine content,
Degree of alkylation
%
(r)
0"66 6'27 10"19 11"34 12"58 1"87 5"58 5'88 6"71
3"1 34"2 63'2 73'5 85"7 9'0 29"9 31"7 36"8
100 100 10O 100 100 100 100 100 100 20 40 60 80
0"2 0"5 1"3
0"9 2"3 6"2
Note: Epichlorohydrinconcentration100%, bath ratio 20~
To verify this proposition the cellulose ether with ~ = 5 5 was treated in a solution of caustic soda containing 1.5 mole N a O H per 1 chlorohydrin group for 1 hr. The chlorine content of the reaction product had fallen to 1.2%, while the epoxygroup content was 7-35%. The cellulose ether produced b y us can therefore be used, with some fairly simple processes, to synthesize cellulose derivatives containing free epoxy groups. When the synthesized cellulose ether is treated in alkali, not all the chlorine atoms are detached with formation of a-oxide rings. The reason for this seems to be that the epichlorohydrin not only reacts with the hydroxyl groups of cellulose macromolecules on synthesis of the cellulose ether, b u t also with those of the alkyt radicals. Besides this, the reaction of epichlorohydrin with cellulose hydroxyl groups frequently follows the scheme: [CeH,O~(OH)8]~ + CH2 ~CH--CH,C1
-~
\o/ CH2OH
I
[C,H,O,(0H),-~ (OCH--CH,CI)x]n In the 2-hydroxy-3-chloropropyl
cellulose ester produced, we determined
the
d i s t r i b u t i o n o f a l k y l g r o u p s i n t h e e l e m e n t a r y u n i t o f t h e cellulose m a c r o m o l e c u l e .
1598
YE. F. SHARKOVA e$ a~.
D e t e r m i n a t i o n of t h e p r i m a r y h y d r o x y l c o n t e n t o f t h e cellulose e t h e r b y t i t r a t i o n s h o w e d t h a t u n d e r our conditions of synthesis t h e e p i c h l o r o h y d r i n does n o t r e a c t w i t h t h e m . D e t e r m i n a t i o n of t h e glycol g r o u p s in t h e m a c r o m o l e c u l e of t h e s y n t h e sized cellulose ester b y o x i d a t i o n w i t h iodie acid [4] showed t h a t t h e epichloroh y d r i n r e a c t s w i t h t h e s e c o n d a r y h y d r o x y l g r o u p s of cellulose. F o r cellulose e t h e r p r e p a r a t i o n s w i t h 7 ~ 4 8 t h e a m o u n t of free glycol g r o u p s p e r 100 units was 70. TABLe. 2. E~FECT O~ CONDITIONSOF TREATMENTIN ~ONO~.THASOLA~E ON ~H~. COMPOSXTmN OF THE PRODUCTS Monoethanolamine concentration. ~o 5 1O 20 50 50 50 50 50 50 50 50 50 50
Treatment temperature, °C
100 100 100 100 100 100 1O0 100 80 60 40 20 20
Treatment time, hr 5 5 5 5 0"25 0"5 1 3 5 5 5 5 24
Nitrogen content
%
Conversion of chlorohydrin groups*, %
1"23 1"45 1"60 2'20 1"56 1"85 2"01 2"12 1"92 1"56 1"44 1"32
55 65 71 98 70 82 90 95 85 70 64 59 69
1-54
* In calculatingthe degreeof conversionof chlorohydringroupsin the reactions of polymeranalogueconversionsit must be assumed that all the chlorine atoms are contained in the composition of the chlorohydrlngroups. T h e presence of c h l o r o h y d r i n g r o u p s in t h e cellulose e t h e r s y n t h e s i z e d m e a n s t h a t p o l y m e r a n a l o g u e conversions c a n o c c u r w i t h v a r i o u s different r e a c t a n t s . I f t h e cellulose e t h e r is t r e a t e d w i t h m o n o e t h a n o l a m i n e , d i e t h y l a m i n e , s o d i u m sulphite, 1 - a m i n o - 3 , 6 , 8 - n a p h t h a l e n e t r i s u l p h o n i c acid a n d a n t h r a n i l i c acid, cellulose d e r i v a t i v e s are synthesized, which c o n t a i n imino groups, t e r t i a r y n i t r o g e n a t o m s , sulpho g r o u p s a n d a n t h r a n i l i c acid radicals. 2 - H y d r o x y - 3 - c h l o r o p r o p y l cellulose e t h e r c o n t a i n i n g 6 ~ chlorine (~-=32.5) was t r e a t e d in a n a q u e o u s solution of m o n o e t h a n o l a m i n e (ratio 15 : 1). T h e r e a c t i o n followed t h e scheme: :C,H,O~(OCH)s-~(0CH,--CH--CHzCI)x]n-b
H2NCH2CH~OH
->
-> [C,H.O,(0H).-~ (OCH,--CH--CH,NHCH,CH.OH)x]n
T h e figures i n T a b l e 2 show t h e influence of t r e a t m e n t conditions on t h e c o m position of t h e p r o d u c t s . I t can b e seen t h a t w h e n t h e cellulose e t h e r is t r e a t e d in
Synthesis of 2-hydroxy-3-chloropropyl cellulose
1599
a 50% aqueous solution of monoethanolamine for 5 hr at 100 ° the chlorine in the molecule is almost completely replaced by monoethanolamine radicals. The anionexchange capacity of the product containing 2.2% nitrogen is 1.5 mg-equ/g. Under analogous conditions we obtained the product of the reaction of 2-hydroxy-3-chtoropropyl cellulose ether with diethylamine having the following structure: [C,H,O~(OH)3-~ (OCH~--CH--CH~)~]n 1 l OH N(C~H,), The experiments show that the reactivity of diethylamine with the cellulose ether is considerably less than that of monoethanolamine. For instance, under conditions in which the reaction of the cellulose ether with monoethanolamine is complete, not more t h a n 75% conversion of chlorohydrin groupings is achieved in reaction with diethylamine. The anion-exchange capacity of the product obtained b y treating the cellulose ether (7=54) in 50% aqueous solution of diethylamine containing 2.2% nitrogen at 60 ° for 5 hr is 1-7 mg-equ/g. Cellulose ethers with cation exchange properties were produced by polymer analogue conversions of 2-hydroxy-3-chloropropyl cellulose ether. The interaction with sodium sulphite follows the scheme: [CeHTO2(OH),-x (OCH~--CH--CH2C1)x],q- Na~SO~ -->
I
OH -> [CeHvO~(OH)s-x (OCH~--CH--CH2)z]n
I
OH
B
SOsNa
Specimens of 2-hydroxy-3-chloropropyl cellulose ether containing 6% chlorine were t r e a t e d in a saturated solution of sodium sulphite (pH----9.6). T he sulphur content and exchange capacity were determined. Table 3 sets out the dat a on t he influence of reaction conditions on t he composition of the product. Th e results show t h a t when the cellulose ether is t reat ed in a saturated solution of sodium sulphite for 1 hr at 100 °, 83% of the chlorine atoms is substituted b y sulpho groups, and complete substitution of all the chlorine atoms TABLE 3. EFFECT OF CONDITIONSOF TREATMENTWITHA SOLUTIONOF SODIUMSULPHITEON THE
COMPOSITION
I
Treatment Treatment tempertime, hr ature, °C
Sulphur content,
%
OF THE
PRODUCTS
Conversion ConversioE of chloro- Treatment Treat- Sulphur of chloroment, content, hydrin hydrin temper% groups, % groups, ~o ature, °C time, hr I
100 100 100 100
3
5 10
4-0 4.10 4.47 4.80
83 85 92 99
50 20 20
5 10 48
2"13 0"37 1'08
44 7"7 22
Y~.. F . SHARKOVA ~-~ ~ .
1600
occurs of a saturated solution of sodium nitrate ( p H : 9 . 6 ) is used for 10 hr at 100°. The cation-exchange capacity of the product containing 4-47% sulphur is 1.52 mg-equ/g. The interaction of the cellulose ether with sodium nitrate, as also the other reactions of polymer analogue conversions in an alkaline medium, may well involve the formation of an intermediate product containing epoxy groups. If the reaction is carried out in sodium nitrate at a low temperature the epoxy groups remain for a long time. For instance, the product resulting from the treatment of the cellulose ether in a saturated solution of sodium sulphite for 48 hr a t 20 °, contains 1.5% Spoxy groups. A cellulose ether containing sulpho groups combined with an aromatic ring was produced by the reaction of 2-hydroxy-3-chloropropyl cellulose ether with 1-amino-3,6,8-naphthalene trisulphonic acid. The reaction followed the scheme: SOsNa
HiN
+
L
I
OH A. i-C6H,0, (0H),-~ (0CH,--CH--OII,--NH
OH
L
-i I [
80,Na ~ P I
Na0,S_ ~l~i~J __S 0 ,Na_i~
When 2-hydroxy-3-chloropropyl ether of cellulose containing 5-7% chlorine was treated in a 25% aqueous solution of the sodium salt of 1-amino-3,6,8-naphthalene trisulphonic acid in the presence of soda (the amount being equivalent to the chlorohydrin-group content) the product contained 3.98% sulphur and 1.92% chlorine and had a cation-exchange capacity of 1.4 mg-equ/g. This means that the chlorine-atom substitution under these conditions is 43.5%. Cellulose derivatives containing complexing groups were also formed by polymer analogue conversions. For instance, using the cellulose ether.containing 8.7% chlorine, and a 25% aqueous solution of anthranilic acid at p H = 9 , cellulose derivatives were synthesized with 8.9 % carboxy groups, 2.3 % nitrogen and 1.2 % chlorine. Under these conditions the chlorohydrin group conversion was 74.5%. The scheme of the reaction is as follows: COOH [
+
OH
i-
-+i
.+
J.
• '7°°'G
i:
Deformation of crystalline polybutylene
1601
CONCLUSIONS
(1) 2-Hydroxy-3-chloropropyl ether of cellulose has been synthesized by the reaction of cellulose with epichlorohydrin in the presence of an acid catalyst. The maximum substitution of the ethers produced is 7----85.7. The reaction conditions have been studied as affecting the composition of the products. (2) Treatment of 2-hydroxy-3-chloropropyl ether of cellulose in monoethanolamine and diethylamine produced nitrogen-containing cellulose derivatives with anion-exchange properties. (3) Cellulose derivatives containing sulpho groups and having cation-exchange properties were synthesized by the reaction of 2-hydroxy-3-chloropropyl ether of cellulose with sodium sulphite and 1-amino-3,6,8-naphthalene trisulphonic acid. Translated by V. AIFORD REFERENCES 1. Ye. F. SHARKOVA, A. D. VIRNIK and Z. A. ROGOVIN, Vysokomol. soyed., 6, 951, 1964 (Translated in Polymer Sei. U.S.S.R. 6, 1050, 1965) 2. K. F. NIKOLAYEVA, N. I. BASAl{GIN and M. F. TSYGANKOVA, Zh. Analyt. Khim., 16: 3, 348, 1961 $. A.M. PAKEN, Epoksida. soyed, i smoly. (Epoxy Compounds and Resins.) Goshkimizdat, 918, 1962 4. J. MAHONEY and C. PURVES, J. Amer. Chem. Soc. 64: 15, 1942
DEFORMATION OF CRYSTALLINE POLYBUTYLENE* V. A. KARG~Xand I. Yu. TSAREVSKAYA I n s t i t u t e of Petrochemical Synthesis, U.S.S.R. Academy of Sciences
(Received 10 July 1965)
U~TIL recently it has been assumed that only rubber-like polymers have the capacity for reversible deformation. Recently it was shown [1, 2] that crystalline polymers may also be reversibly deformed up to a certain degree. But to do this certain artificial conditions were created. The specimen was contracted close to the melting point of the crystalline structures (Tin), where there is a big increase in the kinetic mobility of the structural elements; or the polymer used contained branches in the molecular chain so that the crystalline formations were highly imperfect. The present work dealt with the study of the tensile deformation and spontaneous contraction of well-crystallized polybutylene (PB) in a wide temperature range as dependent on the conditions of structurization. * Vysokomol. soyed. 8: No. 8, 1455-1458, 1966.
(Received 9 July 1965)
I~; [1] we demonstrated the possibility of synthesizing a number of cellulose derivatives with ion-exchange properties by polymer analogue conversions of the graft copolymer of cellulose and glycidyl methacrylate [1]. Considerable interest attaches to the addition of epoxy groups to the cellulose macromoleeule by the alkylation of the cellulose hydroxyl groups rather than by synthesizing the graft cellulose copolymer. In view of the high reactivity of epoxy groups, we think they are best added to the cellulose macromoleeule in the "latent f o r m " i.e. as chlorohydrin groups. A chlorohydrin group was added to a cellulose maeromoleeule by treating viscose staple fibre in epichlorohydrin in the presence of an acid catalyst. The staple fibre was treated for 10 rain at 20° in a 1-8 % solution of Zn (BFd)~, squeezed out to the amount of twice the weight increment and treated in epichlorohydrin or its solution in organic solvents under various conditions, after which it was washed in acetone followed by water, extracted in acetone and dried. To characterize the composition of the product, the chlorine content [2] and epoxy-group content [3] were determined. The experiments showed that with these reaction conditions the cellulose preparations obtained had a chlorine content of 1--12% with an epoxy-group content of not more than 0.52%. This shows that the main feature of the reaction of epichlorohydrin with cellulose hydroxyl groups is the opening up , f the a-oxide ring according to: [CeH,O~(OH)s]. + CH2--CH--CH,C1 ->
\o/ -> [C6HT02(OH)3-= (OCH~--CH--CH~C1)~].
I
OH The figures in Table I illustrate the influence of alkylation conditions on the ~omposition of the products. The results show that up to a catalyst concentration of 5% the alkylation of the hydroxyl groups increases; subsequent increase in catalyst concentration does not cause any particular increase in the degree of alkylation. If a 3% solution of * Vysokomol. soyed. 8: No. 8, 1450--1454, 1966. 1596
Synthesis of 2-hydroxy-3-chloropropyl cellulose
1597
Zn (BF4)~ is used as catalyst and the reaction performed at 100 °, it is practically complete in three hours. The degree of hydroxyl-group alkylation falls sharply if the reaction temperature is lowered. The presence of hydroxyl groups in the synthesized cellulose ether was proved by the fact that epoxy groups formed after the product had been treated in a solution of caustic soda. TABLE 1. EFFECT
Zn(BF4)~ concentration,
%
OF REACTION
CONDITIONS
Reaction temperature, °C
ON THE COMPOSITIOlq OF THE PRODUCTS
Reaction time, hr
Chlorine content,
Degree of alkylation
%
(r)
0"66 6'27 10"19 11"34 12"58 1"87 5"58 5'88 6"71
3"1 34"2 63'2 73'5 85"7 9'0 29"9 31"7 36"8
100 100 10O 100 100 100 100 100 100 20 40 60 80
0"2 0"5 1"3
0"9 2"3 6"2
Note: Epichlorohydrinconcentration100%, bath ratio 20~
To verify this proposition the cellulose ether with ~ = 5 5 was treated in a solution of caustic soda containing 1.5 mole N a O H per 1 chlorohydrin group for 1 hr. The chlorine content of the reaction product had fallen to 1.2%, while the epoxygroup content was 7-35%. The cellulose ether produced b y us can therefore be used, with some fairly simple processes, to synthesize cellulose derivatives containing free epoxy groups. When the synthesized cellulose ether is treated in alkali, not all the chlorine atoms are detached with formation of a-oxide rings. The reason for this seems to be that the epichlorohydrin not only reacts with the hydroxyl groups of cellulose macromolecules on synthesis of the cellulose ether, b u t also with those of the alkyt radicals. Besides this, the reaction of epichlorohydrin with cellulose hydroxyl groups frequently follows the scheme: [CeH,O~(OH)8]~ + CH2 ~CH--CH,C1
-~
\o/ CH2OH
I
[C,H,O,(0H),-~ (OCH--CH,CI)x]n In the 2-hydroxy-3-chloropropyl
cellulose ester produced, we determined
the
d i s t r i b u t i o n o f a l k y l g r o u p s i n t h e e l e m e n t a r y u n i t o f t h e cellulose m a c r o m o l e c u l e .
1598
YE. F. SHARKOVA e$ a~.
D e t e r m i n a t i o n of t h e p r i m a r y h y d r o x y l c o n t e n t o f t h e cellulose e t h e r b y t i t r a t i o n s h o w e d t h a t u n d e r our conditions of synthesis t h e e p i c h l o r o h y d r i n does n o t r e a c t w i t h t h e m . D e t e r m i n a t i o n of t h e glycol g r o u p s in t h e m a c r o m o l e c u l e of t h e s y n t h e sized cellulose ester b y o x i d a t i o n w i t h iodie acid [4] showed t h a t t h e epichloroh y d r i n r e a c t s w i t h t h e s e c o n d a r y h y d r o x y l g r o u p s of cellulose. F o r cellulose e t h e r p r e p a r a t i o n s w i t h 7 ~ 4 8 t h e a m o u n t of free glycol g r o u p s p e r 100 units was 70. TABLe. 2. E~FECT O~ CONDITIONSOF TREATMENTIN ~ONO~.THASOLA~E ON ~H~. COMPOSXTmN OF THE PRODUCTS Monoethanolamine concentration. ~o 5 1O 20 50 50 50 50 50 50 50 50 50 50
Treatment temperature, °C
100 100 100 100 100 100 1O0 100 80 60 40 20 20
Treatment time, hr 5 5 5 5 0"25 0"5 1 3 5 5 5 5 24
Nitrogen content
%
Conversion of chlorohydrin groups*, %
1"23 1"45 1"60 2'20 1"56 1"85 2"01 2"12 1"92 1"56 1"44 1"32
55 65 71 98 70 82 90 95 85 70 64 59 69
1-54
* In calculatingthe degreeof conversionof chlorohydringroupsin the reactions of polymeranalogueconversionsit must be assumed that all the chlorine atoms are contained in the composition of the chlorohydrlngroups. T h e presence of c h l o r o h y d r i n g r o u p s in t h e cellulose e t h e r s y n t h e s i z e d m e a n s t h a t p o l y m e r a n a l o g u e conversions c a n o c c u r w i t h v a r i o u s different r e a c t a n t s . I f t h e cellulose e t h e r is t r e a t e d w i t h m o n o e t h a n o l a m i n e , d i e t h y l a m i n e , s o d i u m sulphite, 1 - a m i n o - 3 , 6 , 8 - n a p h t h a l e n e t r i s u l p h o n i c acid a n d a n t h r a n i l i c acid, cellulose d e r i v a t i v e s are synthesized, which c o n t a i n imino groups, t e r t i a r y n i t r o g e n a t o m s , sulpho g r o u p s a n d a n t h r a n i l i c acid radicals. 2 - H y d r o x y - 3 - c h l o r o p r o p y l cellulose e t h e r c o n t a i n i n g 6 ~ chlorine (~-=32.5) was t r e a t e d in a n a q u e o u s solution of m o n o e t h a n o l a m i n e (ratio 15 : 1). T h e r e a c t i o n followed t h e scheme: :C,H,O~(OCH)s-~(0CH,--CH--CHzCI)x]n-b
H2NCH2CH~OH
->
-> [C,H.O,(0H).-~ (OCH,--CH--CH,NHCH,CH.OH)x]n
T h e figures i n T a b l e 2 show t h e influence of t r e a t m e n t conditions on t h e c o m position of t h e p r o d u c t s . I t can b e seen t h a t w h e n t h e cellulose e t h e r is t r e a t e d in
Synthesis of 2-hydroxy-3-chloropropyl cellulose
1599
a 50% aqueous solution of monoethanolamine for 5 hr at 100 ° the chlorine in the molecule is almost completely replaced by monoethanolamine radicals. The anionexchange capacity of the product containing 2.2% nitrogen is 1.5 mg-equ/g. Under analogous conditions we obtained the product of the reaction of 2-hydroxy-3-chtoropropyl cellulose ether with diethylamine having the following structure: [C,H,O~(OH)3-~ (OCH~--CH--CH~)~]n 1 l OH N(C~H,), The experiments show that the reactivity of diethylamine with the cellulose ether is considerably less than that of monoethanolamine. For instance, under conditions in which the reaction of the cellulose ether with monoethanolamine is complete, not more t h a n 75% conversion of chlorohydrin groupings is achieved in reaction with diethylamine. The anion-exchange capacity of the product obtained b y treating the cellulose ether (7=54) in 50% aqueous solution of diethylamine containing 2.2% nitrogen at 60 ° for 5 hr is 1-7 mg-equ/g. Cellulose ethers with cation exchange properties were produced by polymer analogue conversions of 2-hydroxy-3-chloropropyl cellulose ether. The interaction with sodium sulphite follows the scheme: [CeHTO2(OH),-x (OCH~--CH--CH2C1)x],q- Na~SO~ -->
I
OH -> [CeHvO~(OH)s-x (OCH~--CH--CH2)z]n
I
OH
B
SOsNa
Specimens of 2-hydroxy-3-chloropropyl cellulose ether containing 6% chlorine were t r e a t e d in a saturated solution of sodium sulphite (pH----9.6). T he sulphur content and exchange capacity were determined. Table 3 sets out the dat a on t he influence of reaction conditions on t he composition of the product. Th e results show t h a t when the cellulose ether is t reat ed in a saturated solution of sodium sulphite for 1 hr at 100 °, 83% of the chlorine atoms is substituted b y sulpho groups, and complete substitution of all the chlorine atoms TABLE 3. EFFECT OF CONDITIONSOF TREATMENTWITHA SOLUTIONOF SODIUMSULPHITEON THE
COMPOSITION
I
Treatment Treatment tempertime, hr ature, °C
Sulphur content,
%
OF THE
PRODUCTS
Conversion ConversioE of chloro- Treatment Treat- Sulphur of chloroment, content, hydrin hydrin temper% groups, % groups, ~o ature, °C time, hr I
100 100 100 100
3
5 10
4-0 4.10 4.47 4.80
83 85 92 99
50 20 20
5 10 48
2"13 0"37 1'08
44 7"7 22
Y~.. F . SHARKOVA ~-~ ~ .
1600
occurs of a saturated solution of sodium nitrate ( p H : 9 . 6 ) is used for 10 hr at 100°. The cation-exchange capacity of the product containing 4-47% sulphur is 1.52 mg-equ/g. The interaction of the cellulose ether with sodium nitrate, as also the other reactions of polymer analogue conversions in an alkaline medium, may well involve the formation of an intermediate product containing epoxy groups. If the reaction is carried out in sodium nitrate at a low temperature the epoxy groups remain for a long time. For instance, the product resulting from the treatment of the cellulose ether in a saturated solution of sodium sulphite for 48 hr a t 20 °, contains 1.5% Spoxy groups. A cellulose ether containing sulpho groups combined with an aromatic ring was produced by the reaction of 2-hydroxy-3-chloropropyl cellulose ether with 1-amino-3,6,8-naphthalene trisulphonic acid. The reaction followed the scheme: SOsNa
HiN
+
L
I
OH A. i-C6H,0, (0H),-~ (0CH,--CH--OII,--NH
OH
L
-i I [
80,Na ~ P I
Na0,S_ ~l~i~J __S 0 ,Na_i~
When 2-hydroxy-3-chloropropyl ether of cellulose containing 5-7% chlorine was treated in a 25% aqueous solution of the sodium salt of 1-amino-3,6,8-naphthalene trisulphonic acid in the presence of soda (the amount being equivalent to the chlorohydrin-group content) the product contained 3.98% sulphur and 1.92% chlorine and had a cation-exchange capacity of 1.4 mg-equ/g. This means that the chlorine-atom substitution under these conditions is 43.5%. Cellulose derivatives containing complexing groups were also formed by polymer analogue conversions. For instance, using the cellulose ether.containing 8.7% chlorine, and a 25% aqueous solution of anthranilic acid at p H = 9 , cellulose derivatives were synthesized with 8.9 % carboxy groups, 2.3 % nitrogen and 1.2 % chlorine. Under these conditions the chlorohydrin group conversion was 74.5%. The scheme of the reaction is as follows: COOH [
+
OH
i-
-+i
.+
J.
• '7°°'G
i:
Deformation of crystalline polybutylene
1601
CONCLUSIONS
(1) 2-Hydroxy-3-chloropropyl ether of cellulose has been synthesized by the reaction of cellulose with epichlorohydrin in the presence of an acid catalyst. The maximum substitution of the ethers produced is 7----85.7. The reaction conditions have been studied as affecting the composition of the products. (2) Treatment of 2-hydroxy-3-chloropropyl ether of cellulose in monoethanolamine and diethylamine produced nitrogen-containing cellulose derivatives with anion-exchange properties. (3) Cellulose derivatives containing sulpho groups and having cation-exchange properties were synthesized by the reaction of 2-hydroxy-3-chloropropyl ether of cellulose with sodium sulphite and 1-amino-3,6,8-naphthalene trisulphonic acid. Translated by V. AIFORD REFERENCES 1. Ye. F. SHARKOVA, A. D. VIRNIK and Z. A. ROGOVIN, Vysokomol. soyed., 6, 951, 1964 (Translated in Polymer Sei. U.S.S.R. 6, 1050, 1965) 2. K. F. NIKOLAYEVA, N. I. BASAl{GIN and M. F. TSYGANKOVA, Zh. Analyt. Khim., 16: 3, 348, 1961 $. A.M. PAKEN, Epoksida. soyed, i smoly. (Epoxy Compounds and Resins.) Goshkimizdat, 918, 1962 4. J. MAHONEY and C. PURVES, J. Amer. Chem. Soc. 64: 15, 1942
DEFORMATION OF CRYSTALLINE POLYBUTYLENE* V. A. KARG~Xand I. Yu. TSAREVSKAYA I n s t i t u t e of Petrochemical Synthesis, U.S.S.R. Academy of Sciences
(Received 10 July 1965)
U~TIL recently it has been assumed that only rubber-like polymers have the capacity for reversible deformation. Recently it was shown [1, 2] that crystalline polymers may also be reversibly deformed up to a certain degree. But to do this certain artificial conditions were created. The specimen was contracted close to the melting point of the crystalline structures (Tin), where there is a big increase in the kinetic mobility of the structural elements; or the polymer used contained branches in the molecular chain so that the crystalline formations were highly imperfect. The present work dealt with the study of the tensile deformation and spontaneous contraction of well-crystallized polybutylene (PB) in a wide temperature range as dependent on the conditions of structurization. * Vysokomol. soyed. 8: No. 8, 1455-1458, 1966.