Modification of Cotton with Tin Reactants - American Chemical Society

25 Modification of Cotton with Tin Reactants

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CHARLES E. CARRAHER, JR., JACK A. SCHROEDER, CHRISTY McNEELY, and JEFFREY H . WORKMAN Department of Chemistry, Wright State University, Dayton, O H 45435 DAVID J. GIRON Microbiology and Immunology, Wright State University, Dayton, O H 45435

Cellulose is a naturally occurring polymeric carbohydrate, hydrolyzable to glucose, consisting of anhydroglucose units linked through a beta-glucosidic bonding. Natural cellulose exhibits usual chain lengths of 1000 to 3000 units long. It is a very common material making up about one-third of all vegetable matter. In actuality cellulose is quite complex and varying in exact composition. Cotton is a relatively pure natural cellulose, containing only 3-15% of noncellulosic material. The modification of cotton has occurred for years being one of the earliest executed chemical processes in man's history. Even so, much s t i l l remains with many of the more recent studies catalyzed by the increasing need to utilize regenerable materials as feedstock in a widening variety of uses. Most of these modifications are topochemical in nature, occurring with cellulosic reactive groups which are available in the amorphorus regions and on the surfaces of crystalline areas. We chose to attempt more intimate, complete modification of cotton. There are few, i f any techniques for completely solubilizing cellulose. Generally "solution" is effected through chain degradation where the cellulosic material actually forms a gell-like solution. The use of bisethylenediamine copper (II) hydroxide solutions to effect solution of cotton has been practiced for many years and is s t i l l industrially practiced on a small scale as a method of regeneration of cotton. Copper-amine solutions were utilized for this study for a number of reasons including a. as noted above, an abundance of prior knowledge exists concerning the technique; b. i t allows fairly good solution of the cotton; c. i t was found, early in our work, to allow the execution of the types of modification desired; and d. i t is easily handled and can be utilized on the gram as well as ton scale. Further purity of modified material, i.e. effectiveness of removal of unreacted, etc. material is easily followed through analysis of the copper present in the modified material. 0-8412-0540-X/80/47-121-381$05.00/0 © 1980 American Chemical Society Carraher and Tsuda; Modification of Polymers ACS Symposium Series; American Chemical Society: Washington, DC, 1980.

MODIFICATION OF POLYMERS

382

Here we w i l l concentrate on the m o d i f i c a t i o n o f cotton through r e a c t i o n with t i n - c o n t a i n i n g r e a c t a n t s and thermal charact e r i z a t i o n o f the products.


EXPERIMENTAL Reaction apparatus was d e s c r i b e d elsewhere (1_). B r i e f l y i t i s a one p i n t Kimex e m u l s i f y i n g j a r placed on a Waring Blendor (Model 1120). D i p r o p y l t i n d i c h l o r i d e , d i b u t y l t i n d i c h l o r i d e , diphenyltin dichloride, triphenyltin chloride, dimethyltin d i c h l o r i d e and d i o c t y l t i n d i c h l o r i d e ( A l f a I n o r g a n i c s , Inc., B e v e r l y , Mass.) were used as r e c e i v e d . A predetermined volume o f bisethylenediaminecopper ( I I ) h y d r o x i d e - c e l l u l o s e s o l u t i o n formed by d i s s o l v i n g cotton (Padco N o n - s t e r i l e Cotton manufact u r e d by The Absorbant Cotton Co., V a l l e y Park, Mo.) i n b i s e t h y lenediaminecopper ( I I ) hydroxide (Ecusta Paper Corp., Pisgah F o r e s t , North C a r o l i n a ; e f f e c t e d with two hours o f mechanical s t i r r i n g (2,3.4) was added to a s t i r r e d (ça 20,500 rpm, no load) s o l u t i o n s o f organic s o l v e n t c o n t a i n i n g the organotin h a l i d e . The products were c o l l e c t e d , a f t e r s u c t i o n f i l t r a t i o n , i n a s i n t e r e d g l a s s f u n n e l . Repeated washings with water were c a r r i e d out u n t i l a f t e r the blue c o l o r a t i o n ceased. D i l u t e s u l f u r i c a c i d was added to some r e a c t i o n s o l u t i o n s to e f f e c t n e u t r a l i z a t i o n and consequently p r e c i p i t a t i o n o f unreacted (usual) and a d d i t i o n a l modified product. The p r e c i p i t a t e d m a t e r i a l was t e s t e d f o r t i n and where t i n i n c l u s i o n o c c u r r e d , the samples were kept separate from the o r i g i n a l l y p r e c i p i t a t e d material. I n f r a r e d s p e c t r a were obtained using a Perkin-Elmer 457 G r a t i n g I n f r a r e d Spectrometer u t i l i z i n g KBr p e l l e t s . Thermal a n a l y s i s was e f f e c t e d u t i l i z i n g a duPont 951 Thermogravimetric A n a l y z e r , duPont 990 Thermoanalyzer, duPont D i f f e r e n t i a l Scanning C a l o r i m e t e r and Fisher-Johns M e l t i n g Point Apparatus. Elemental a n a l y s i s was e f f e c t e d f o r copper and t i n u t i l i z i n g a Varian Techtron AA6 Atomic Absorption Spectrophotometer u t i l i z i n g P r i c e s technique f o r sample p r e p a r a t i o n (4). f

RESULTS Synthesis Reaction appears to be general with wide v a r i a t i o n o f product y i e l d and t i n - m o i e t y i n c l u s i o n ranging from low to high depending on the s p e c i f i c r e a c t i o n c o n d i t i o n s ( f o r i n s t a n c e Table 1 ) . Thus both amount ( p r o p o r t i o n ) and frequency (extent) o f cotton m o d i f i c a t i o n can be e a s i l y c o n t r o l l e d lending i t s e l f to useful i n d u s t r i a l u t i l i z a t i o n .

Carraher and Tsuda; Modification of Polymers ACS Symposium Series; American Chemical Society: Washington, DC, 1980.

25.

C A R R A H E R E T AL.

Modification

of Cotton with Tin Reactants

383

Previous work by us has l e d to the s y n t h e s i s o f s i l i c o n , germanium and t i n p o l y e t h e r s u t i l i z i n g i n t e r f a c i a l systems ( f o r i n s t a n c e 5-9). The t i n - c o t t o n products should possess an analogous s t r u c t u r e from p r e v i o u s l y r e p o r t e d s i m i l a r i t i e s i n r e a c t i v i t y o f s o l u b l e c e l l u l o s i c hydroxyls with o r g a n i c a c i d c h l o r i d e s .


R

2

MX + HO-R-OH 2

R >{H-0-R-0) R I.

The s t r u c t u r e o f the m o d i f i e d products i s probably a mixture of mono-, d i - and t r i s u b s t i t u t e d m a t e r i a l s with the amounts o f d i and t r i s u b s t i t u t i o n i n c r e a s i n g as the p r o p o r t i o n o f t i n - m o i e t y i n c r e a s e s even though f o r the products with d i b u t y l t i n d i c h l o r i d e t i n moiety i n c l u s i o n remained high throughout the t i n r c o t t o n range o f 0.30:1 to 5:1 being about the value expected f o r t r i substitution. R e p r e s e n t a t i v e i n f r a r e d s p e c t r a o f m o d i f i e d c o t t o n products appear i n F i g u r e s 1A and I B . A n a l y s i s o f the i n f r a r e d spectrum o f the products were c o n s i s t e n t with the t i n - m o d i f i e d product being formed. For i n s t a n c e f o r the d i - n - p r o p y l t i n d i c h l o r i d e - c e l l u l o s e product a l a r g e , broad band appeared from 3200-3500 cm-1 charact e r i s t i c o f Sn-OH and R-0H groupings. The a l i p h a t i c CH s t r e t c h i n g v i b r a t i o n s f o r both the d i p r o p y l t i n and c e l l u l o s e are present between 2850 and 2860 cm-1. Bands c h a r a c t e r i s t i c o f a l i p h a t i c C-H out o f p l a c e deformations c h a r a c t e r i s t i c o f d i p r o p y l t i n appear a t 1425, 1415, 1380 and 1130 cm-1. The Sn-0 asymmet r i c s t r e t c h from Sn-0-R occurs a t 670 cm"! d the Sn-0-R symmetric s t r e t c h f o r t i n e t h e r s occurs a t 610 cm"! _ both bands are present i n the m o d i f i e d products ( T J U J ) . The Sn-Cl s t r e t c h i n g band occurs between 320 t o 350 cm" depending on t i n s u b s t i t u t i o n (12). Some products e x h i b i t small bands i n t h i s r e g i o n charact e r i s t i c o f unreacted Sn-Cl groups but s p e c t r a o f most o f the products are c l e a r i n t h i s r e g i o n . F u r t h e r , n e g a t i v e AgN03sodium f u s s i o n r e s u l t s were found f o r the products which were c l e a r i n the 320 to 350 cm" r e g i o n . A broad band c e n t e r i n g about 3300 to 3400 cm" i s c h a r a c t e r i s t i c o f c e l l u l o s i c -OH groups. Bands c h a r a c t e r i s t i c o f the Sn-OH moiety vary between 3400 to 3500 cm" , making i d e n t i f i c a t i o n o f Sn-OH e x h i b i t i n g bands i n the lower (ca 3400 cm-1) r e g i o n d i f f i c u l t . Bands c h a r a c t e r i s t i c o f the presence o f Sn-OH are present and i d e n t i f i a b l e where the Sn-OH band occurs w i t h i n the upper r e g i o n (ça 3470 to 3500 cm" ). Thus products from d i b u t y l t i n d i c h l o r i d e (even when employing a f i v e f o l d excess o f the t i n monomer) e x h i b i t a band c e n t e r i n g about 3490 cm" c h a r a c t e r i s t i c o f the Sn-OH grouping and no band i n the 320 to 350 cm- r e g i o n . a n

1

1

1

1

1

1

1




384

Figure 1. IR spectra of condensation product of cotton with (A) diphenyltin dichloride and (B) dibutyltin dichloride


25. CARRAHER ET AL.

Modification of Cotton with Tin Reactants

385


Because o f the shown presence o f Sn-OH groups f o r products employing d i h a l o reactants and r e l a t i v e l y high i n c l u s i o n o f t i n moiety c a l c u l a t i o n s contained i n Table 1 were based on Forms I I and I I I .

M

H

2 " C

0 V

SnR 0 2

Product p u r i f i c a t i o n i s e a s i l y followed by monitoring the decrease i n blue-green c o l o r a t i o n p o s s i b l e because o f t h e high c o l o r a t i o n o f copper II complexes. The presence o f copper i n t h e modified product was followed using AA. Copper l e v e l s were t y p i c a l l y l e s s than 1 0 - % f o r compounds reported i n t h i s paper. Thus simple, repeated water washings a r e s u f f i c i e n t t o remove copper and presumably unreacted t i n monomer. The l a t t e r may n o t always be t r u e i f q u i t e excessive amounts o f the t i n r e a c t a n t a r e employed such as i n Table 1 where a 5:1 t i n : c o t t o n r a t i o was employed g i v i n g a yieîd i n s l i g h t excess o f 100%, presumably due to the i n c l u s i o n o f some unreacted t i n monomer. While i t may be d e s i r e d that complete removal o f t h e t i n monomer be e f f e c t e d , i t i s probably not c r i t i c a l f o r a number o f p o t e n t i a l a p p l i c a t i o n s where t h e b i o l o g i c a l p r o p e r t i e s a r e experienced through c o n t r o l r e l e a s e s i n c e small amounts o f unreacted t i n monomer w i l l probably only a f f e c t the i n i t i a l r a t e o f " c o n t r o l l e d r e l e a s e " o f the t i n . 2

Physical

Properties

A l l o f t h e products a r e i n s o l u b l e i n a l l attempted solvents i n c l u d i n g DMSO, HMPA and DMF t y p i c a l o f c r o s s l i n k e d products. They a r e hydrophobic and r e s i s t a n t t o h y d r o l y s i s because o f t h e i r hydrophobic nature. This change t o a hydrophobic nature i s p o s i t i v e f o r a p p l i c a t i o n s r e q u i r i n g water s t a b i l i t y , r e s i s t a n c e and r e p e l l e n c y and i s t y p i c a l o f most water s o l u b l e polymers (such as p o l y ( a c r y l i c a c i d ) , polyethyleneimine and p o l y v i n y l a l c o h o l )



386


Table I R e s u l t s as a f u n c t i o n o f t i n monomer Organ- Amount Molar Y i e l d Yield Tin T i n Initial otin T i n Re- Ratio (grams) Assum- Found Calcu- Degradation Halide actant T i n : ing (%) l a t e d Assum- Temp. (mmole) Cotton Complete Air „ ing Inclusion Reactive (°C) ComGroups (%) plete Inclusion 21 27 D i p r o p y l - 0.93 1:1 0.19 280 38 tin Dichloride D i b u t y l - 0.28 0:30:1 0.0085 41 40 270 tin Dichloride D i b u t y l - 0.47 44 40 0:50:1 0.047 15 tin Dichloride D i b u t y l - 0.69 0.75:1 0.087 21 tin Dichloride D i b u t y l - 0.93 1:1 14 0.077 tin Dichloride 52 D i b u t y l - 1.86 2:1 0.29 tin Dichloride D i b u t y l - 2.33 2.5:1 0.43 77 41 40 tin Dichloride a



25.

C A R R A H E R E T AL.

Dibutyl4.65 t i n Dichloride T r i p h e n y l - 0.93 t i n Chloride T r i p h e n y l - 1.86 t i n Chloride Dimethyl- 0.93 t i n Dichloride Dimethyl- 2.79 tin Dichloride Dioctyl0.93 tin Dichloride Dioctyl2.79 tin Dichloride Diphenyl- 0.93 tin Dichloride

Modification

5:1

of Cotton with Tin

0.58

103

0.5:1 0.39

100 65

37

Reactants

387

40

240

1:1

0.50

19

29

1:1

0.11

32

3:1

0.14

41

1:1

0.31

40

3:1

0.66

86

210

1:1

0.024

4

280

Reaction c o n d i t i o n s : Aqueous s o l u t i o n s o f cotton (0.100 g; 0.62 moles) with bisethylenediamine copper ( I I ) hydroxide to give 25 ml s o l u t i o n are added to r a p i d l y s t i r r e d (about 20,500 rpm no load) carbon t e t r a c h l o r i d e (25 ml) s o l u t i o n s c o n t a i n i n g the organotin h a l i d e a t about 25°C, 30 sees s t i r r i n g time. a.

For cotton = 310°C



Figure 2. TGA thermograms of products from dipropyltin dichloride ( ), tripropyltin dichloride (- · '), dioctyltin dichloride ( A / ' V ) , dibutyltin dichloride ( ), diphenyltin dichloride ( ), and cotton itself (- · -)ata heating rate of 20°C/min in air


Modification

of Cotton with Tin

Reactants


CARRAHER ET AL.



390


modified through condensation with organometallic halides. resulting from a replacement of the "hydrogen bonding proton" by a dipolar aprotic moiety (such as lj^-CSee Figures 2 and 3.) The products are solid, generally exhibiting flexibility. They appear to degrade without softening with initial degradation near that of cotton itself (for instance Table I). The tin moiety typically remains as part of the residue to greater than 900°C in air and nitrogen. This is important for applications such as use in commercial and residential insulation where "safe" burning is necessary to meet building codes since many volatile organotin moieties appear to have some toxicity and are known to cause headaches. Biological Activity Insoluble cellulose and modified cellulose products were added to paper disks contained on plates seeded with approximately 1000 spores of tested organisms. Amount added was several granules (about 0,1 mg and less) per spot. The plates were then incubated at 25°C for 24 hours and the inhibition of confluent growth recorded. All but the products form dioctyltin dichloride showed good fungi inhibition. The fungi tested are typical and widespread and represent a good cross sectional test for the applicability of such modified cellulosic products as retarders of fungi related to rot and mildew. Literature Cited 1. 2. 3. 4. 5. 6.

Carraher, C., J. Chemical Education (1969), 46, 314. Whistler, R., "Methods in Carbohydrate Chemistry", Vol. III, (1963), 78-79. McCaffery, E., "Laboratory Preparation for Macromolecular Chemistry", McGraw-Hill, New York, 1970, 140-144. Price, W.J., "Analytical Atomic Absorption Spectroscopy", 1974, 151-153. Carraher, C., J. Polymer Sci., A-1 (1969), 7., 2351 and 2357. Carraher, C., and Klimiuk, G., J. Polymer Sci., A-1 (1970), 8, 973. 7. Carraher, C. and Scherubel, G., J. Polymer Sci., A-1 (1971), 9, 983. 8. Carraher, C. and Klimiuk, G., Makromolekulare Chemie (1970), 133, 211. 9. Carraher C. and Scherubel, G., Makromolekulare Chemie (1972), 152, 61. 10. Butcher, F., Gerrard, W., Mooney, E. and Rees, R. and Witlis, H., Spectrochim Acta, (1964), 20, 51. 11. Hester, R., J. Organometallic Chem., (1970), 23(1), 123. 12. Carraher, C., Angew. Makromolekulare Chemie, (1973), 31, 115. 13. Carraher, C., "Interfacial Synthesis", Vol. II, Edited by Millich, F. and Carraher, C., Chpt. 19, Dekker, New York, 1978. RECEIVED September 28, 1979. Carraher and Tsuda; Modification of Polymers ACS Symposium Series; American Chemical Society: Washington, DC, 1980.

Modification of Cotton with Tin Reactants - American Chemical Society

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