SILANE MODIFIED POLYMERS

Abstract: Novel product having formula (I), where ''polymer'' is an amine functional polymer, such as amine terminated polyethylene imine, amine terminated polyalkylene glycols, amine terminated anilineformaldehyde, amine terminated nylons, amine functional silicones; R<1>, R<2>, and R<3> are C1-C8 monovalent hydrocarbyl radicals, m is 1 to 3 and n is 1 to 10.

Description: SILANE MODIFIED POLYMERS This invention relates to certain silane modified polymers, and more particularly to the modi¬ fication of amine terminated polymers with a carboxyalkylalkoxysilane. BACKGROUND OF THE INVENTION AND PRIOR ART Heretofore, various olefin-, amino-, or hydroxyl-functional polymers have been modified with silicon containing reagents, such as hydrido-silane, silane isocyanate; silane alkyl chlorides, etc. Silane isocyanate, for example, is expensive. Silane alkyl chlorides leave residual chloride in the product and hydrido silanes require a catalyst which intro¬ duces processing difficulties. It has been found that silicon may be easily introduced into amine terminated polymers using a carboxyalkylalkoxysilane as the reagent. We believe that the reaction is novel and the products are novel. DETAILED DESCRIPTION OF THE INVENTION As indicated above, this invention contem¬ plates the novel reaction between an amine terminated polymer and a carboxyalkyl alkoxysilane which is represented as follows: R, , , 0 | ( 3-m) it Polymer [NH, —_] iX + n (R' 0) m III - Si - R 4 - C - OR 3 Polymer The "polymer" group is selected from polyethyleneimine, [CH 2 CH 2 -NH] 1 _ 100 polypropylene glycol, (CH 2 CH(CH 3 )- 0] l -ioo'" P° Y eth Y lene glycol, [ CH 2 CH 2 -O] 1 _ 100 ; copolymers of polyethylene glycol and polypropylene glycol; anilineformaldehyde resin, [NH -ø-CH-]- I _ 1Q O ; nylons, e.g., [NH-(CH 2 ) 5 ~CO-NH-(CH 2 ) 5 ~CO]^-L QQ ; 0 II [NH- (CH 2 ) 10 -C-NH- (CH 2 ) 10 "CO] l . 1Q Q l [NH- (.CH 2 ) 6 ~NH-CO- (CH 2 ) 4 -CO] 1-100 and [Si-O-Si] 1„10Q - R 1 , R 2 and R 3 are independently selected from C,-=C S hydrocarbyl including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, 3-methylbutyl, hexyl groups, cyclohexyl, heptyl groups, octyl groups, phenyl, 4-methylphenyl, etc. R. is an alkylene radical con- taining from 1 to 3 carbon atoms. The number of alkoxy groups, m, ranges from 1 to 3. The number of -NH_ groups, n, ranges from 1 to 10. 0 as used herein represents phenyl. The process of this invention contemplates reacting in a dry environment, e.g., a nonaqueous medium, preferably with an inert gas blanket, an amine terminated polymer as above defined, with a carboxyalkyl alkoxy silanes. at a relatively low temperature in the range of from 25°C. to 200°C, preferably in the range of 90° to 150°C. Desirably, the reaction is carried out in a solvent such as, methanol, ethanol, propanol, dimethyl sulfoxide, etc. A catalyst, especially an alkali metal alkoxide such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, etc., apparently catalyzes an exchange reaction between a methanol solvent and the ethoxy groups of the silane and ester to yield the methoxy homologue. The latter reacts more rapidly with the amine groups. Alternatively, the methyl analog of the carboxyethyltriethoxysilane may be used with¬ out the alkoxide catalyst. Among the advantages of this novel method of silanating functional polymers are the relatively low cost and availability of the silane esters, and the ease of processing. The silanated functional polymers are useful as paper and textile sizing agents, stabilizers for silicate solutions, floatation aids, treating agents for fillers for paper and plastics, hydrophilic coatings for glass, plastics, and minerals, aids for pigment dispersion, anticorrosion agents for metal surfaces, and adhesion promotors for metal primers and paints. The products are soluble in methanol and conveniently are applied using a 0.1% to 15% solids solution in the alkanol. To coat metal surfaces, e.g., iron . or steel, a 10% solids solution in methanol is applied to the metal and the solvent evaporated spontaneously or with heat. The coated metal surface resists salt corrosion and improves adhesion of primers and paints to the surface. It is convenient to illustrate the process and the following examples and representative an illustrative only and are not to be construed as limit- ing the invention to the scope thereof. EXAMPLE I Preparation of a Silane Modified Polyethylene Imine According to the best mode of carrying out our invention to a solution of 58.1 g. (0.22 mole) of 2-carboethoxyethyltriethoxysilane in 100 ml of dry methanol were added 5.0 ml. of-25% sodium methoxide in methanol. About 80 ml. of alcohol distillate was collected under nitrogen before adding 75 ml. of methanol and collecting another 75 ml. of alcohol distillate. A solution of 60 g. (0.10 mole) of amine terminated polyethylene imine (mw 600) in 30 ml. of methanol was added and the reaction mass heated slowly to 90°C. with continuous, removal of distillate. Infrared analysis at this point revealed strong amide peaks at 1660 and 1530 cm , and an absence of the ester peaks at 1730 cm The product weighed 119 g. (125%) due to retained methanol; was a slightly cloudy pale yellow oil. An IR scan of the neat film on NaCl showed peaks at 3350, 1655, 1550, 1090 and 810 cm "1' . The product was dissolved in ethanol because the neat product gels quickly in moist air. A portion of the ethanol solution was diluted with water, and a glass slide dipped into the aqueous/alcohol solution. Drying and curing the coating at 100°C. for 30 minutes produced a hard, hydrophilic, water insoluble film. EXAMPLE II Preparation of Silane Modified Amine Terminate • Propylene Oxide Capped Polyethylene Glycol To a solution of 58.1 g. (0.22 mole) of 2-carboethoxyethyltriethoxysilane in 100 ml. of dry methanol under nitrogen were added 5.0 ml. of 25% sodium methoxide in methanol. The reaction mass was heated to distill out about 90 ml. of alcohol. A solution of 60 g. i'n 60 ml. dry methanol of Jeffamine ED 600 (amine terminated, propylene oxide capped polyethylene glycol (MW 600) from Texaco Chemicals) was added, and the reaction mass heated to 150°C. over a period of 3 hours and held there for 1 hour. 80 ml. Of distillate were recovered. IR analysis showed that only a trace of unreacted ester remained. The reaction mass was cooled to 90°C. Ethanol was added to a weight of 200 gms. (50% solids) of clear, yellow solution. An IR scan of the neat film showed peaks at 3300, 1735 (small), 1650, 1535, 1100, 955 and 810 cm . NMR (CDC1 3 ) 0.8-1.5 (m; rel area 4), 2.1-2.4 (m; rel. area 1); 3.1-4.2 (m; rel. area 12) with peaks at 3.55 (Si-OCH^) and 3.63 ppm (polyethylene glycol) . A glass slide was treated as in Example I and gave a hard, clear, water insoluble hydrophilic film. EXAMPLE III Preparation of Silane Modified Polyethylene Imine To a solution of 82.5 g. (0.33 mole) of 2-carboethoxyethyltriethoxysilane in 100 ml dry methanol under nitrogen were added 5.0 ml of 25% sodium methoxide in methanol. The mass was heated to 100°C. to give 105 ml. of alcohol distillate. A solution of 37.5 g. (0.15 mole) of polyethylene imine (M. W. 250) in 50 ml dry methanol was added, and the reaction mass heated to 100°C. giving 70 ml. of distillate and a slightly cloudy, pale yellow, thick solution. The hot solution was diluted with enough n-butanol to give 200 g. of product (50% solids). The analysis was the same as for Example I. EXAMPLE IV Preparation of a Silane Modified Polypropylene Glycol A solution of 45.8 g. (0.22 mole) of 2- carbomethoxyethyltri ethoxysilane, 5.0 ml of 25% sodium methoxide in methanol, and 200 g (0.10 mole) of Jeffamine D-2000 (amine terminated polypropylene oxide, M. W. 2000, from Texaco Chemicals) is gradually heated to 160°C. under nitrogen. After 2 hours at 160°C, 14 ml of alcohol distillate are collected. IR analysis shows that only a trace of unreacted ester remains. The reaction is cooled to 90°C. and ethanol added to give a product weight of 460 g (50% solids) of clear yellow solution. A glass slide is treated as in Example I with similar results. EXAMPLE V Preparation of a Silane Modified Polyethylene Imine To 78.0 g (0.33 mole) of 2- carboethoxyethyldiethoxymethylsilane in 100 ml dry methanol under nitrogen are added 5.0 ml of 25% sodium methoxide in methanol. The mass is heated to 1 0°C. to give 107 ml of alcohol distillate. A solution of 180 g (0.15 mole) of polyethylene imine (M. W. 1200) in 200 ml dry methanol is added, and the ' reaction mass heated to 100°C. giving 210 ml of distillate and a slightly cloudy, pale yellow, viscous solution. The hot solution is diluted with enough dry ethanol to give 500 g of product (50% solids). A glass slide is coated as in Example I with similar results. EXAMPLE VI Preparation of Silane Modified Nylon 6/6 In a 250 ml round bottom flask equipped with a thermometer, mechanical stirrer, and distilling head are placed 58.0 g. (0.50 mole) hexamethylene diamine, 69.6 g (0.40 mole) dimethyl adipate, and 5.0 ml of 25% sodium methoxide in methanol. The mixture is gradually heated to 160°C. under nitrogen with removal of the evolved methanol. After 16 hours at 160°C, IR analysis of the viscous, yellow oil reveals amide bands at 1645 and 1540 cm and the absence of ester bands at 1750 cm " . To the hot reaction mixture is added 41.6 g (0.20 mole) of 2-carbomethoxyethyltrimethoxysilane, and the reaction was held at 160°C. with removal of the evolved methanol for 2 hours. IR analysis of the viscous, yellow oil shows the absence of an ester band at 1740 cm "1 . IIRR (melt) 3350, 2980, 1645, 1540, 1100, After cooling to 100°C. , the reaction mixture is diluted with 90 g of 1,4-dioxane to give a viscous yellow solution that is 65% solids. A glass slide dipped into this solution and cured at 100°C. for 1 hour produced a strongly bound, hard, yellow film that does not dissolve in boiling water or boiling ethanol. EXAMPLE VII Preparation of a Silane Modified Silicone A solution of 20.8 g (0.10 mole) of carbomethoxyethyltrimethoxysilane, 1.0 ml of 25% sodium methoxide in methanol, and 100 g of 3- aminoprop l functional polydimethyl siloxane con¬ taining 1.0 meq. - NH 2 /g polymer (viscosity = 1000 cps) is gradually heated to 160°C. under nitrogen. After 2 hours at 160°C, 4 ml of alcohol distillate is collected, and IR analysis of the viscous yellow oil shows the absence of ester bands at 1740 cm IR (neat film) 3350, 2860, 1650, 1540, 1260, 1100, 960, 805 cm . A glass slide dipped into a 10% solution of this product in ethanol is cured at 100°C. for one hour. The resulting hard, clear film is not affected by boiling water, and it is reversibly softened by boiling ethanol.

Claims: C L A I M S 1. The reaction product of (a) an aminofunctional polymer having the structure: Polymer-(NH 2 ) n wherein "polymer" is selected from (CH 2 CH 2 H),_ 100 ' (CH 2 -CH 2 -O) 1-100 ; (CH 2 CH(CH 3 )-O-) 1 _ 100 ; copolymers of propylene glycol and ethylene glycol; [NH 2 -0-CH 2 -] ι _ 100 [NH-(CH 2 ) 5 -CO-NH-(CH 2 ) 5 C0] 1 _ 10Q ; [NH-(CH 2 ) 1Q CO-NH-(CH 2 ) 1Q - CO] 1-100 7 [NH-(CH 2 ) 6 -NH-CO-(CH 2 ) 4 CO] 1 _ 100 ; and [Si-O-Si] 1-1Q(J and n is a whole number from 1 to 10, and (b) an alkoxysilane having the general formula: (R 10) SIi (3" - m R 4 - CH - OR3 wherein R 1, R2 and R3 are independently selected from C,- C_ monovalent hydrocarbyl radicals, R 4 is alkylene con¬ taining from 1 to 3 carbon atoms and m is a whole number from 1 ' to 3; the number -of moles of (b) being no greater than n; and said reaction being carried out in a dry environment at a temperature of from 90°C. to 150°C, and the molar ratio of (b) to (a) being from 1:2 to 10:1. 2. A product having the general formula: 0 R If (3-m) Polymer[NHC - R - Si - ( .O„.R-.! ,) ] wherein "polymer" is selected from (CH 2 -CH 2 -NH) , .. QQ ; (CI^-CH^OJ-^ QQ ; (CH 2 CH(CH 3 )-O-) 1 _ 100 ; copolymers of propylene glycol and ethylene glycol; [NH 2 -0-CH 2 -] •,_-. Q0 ; [NH-(CH 2 ) 5 -C0-NH-(CH 2 ) 5 -CO] 1 _ 10Q ; [NH-(CH 2 ) 1Q -C0-NH- ^lO-∞ 1 1-100'- I NH -< CH 2 ) 6- NH - CO - (CH 2 ) 4- CO] 1-100; and [Si-O-Si] , , QQ ; R 1, R2 and R3 are independently selected from C,-C_ monovalent hydrocarbyl radicals; R is an alkylene radical containing from 1 to 3 carbon atoms; n is a whole number from 1 to 10; and m is a whole number from 1 to 3. 3. A product as defined in claim 1 or 2, wherein R is ethyl. 4. A product as defined in any one of claims 1, 2 and 3, wherein m is 3. 5. A product as defined in any one of the preceding 3 claims, wherein R is ethyl. 6. A product as defined in claim 1, wherein component (b) is 2-carboethoxyethyltrialkoxysilane. 7. A product as defined in claim 2, wherein R , 2 3 R and R a re each ethyl and m is 3. 8. A product as defined in claim 1, wherein component (a) is a polyethyleneimine, preferably a polyethyleneimine has a molecular weight of about 600. 9. A process for making a product as claimed in any one of the preceding claims, which comprises reacting in a dry environment at a temperature of from 90°C. to 150°C. (a) an aminofunctional polymer having the structure: Polymer- [NH 2 _ wherein "polymer" is as defined above, with an amount no more than stoichiometrically equivalent to n of (b) an alkoxysilane having the general formula: (R 0) - Sli (3 -- m R , 4 - 1C - O 3 ,m R wherein R 1, R2, R3 and-R4 and m are as defined in any one of the preceding claims, ratio of (b) to (a) being from 1:2 to 10:1. 10. A process as defined in claim 9, wherein the reaction is carried out in the presence of a dry alkanol containing from 1 to 3 carbon atoms. 11. A process as defined in claim 10, wherein the reaction mass is further characterized by the presence therein of an alkali metal alkoxide, preferably sodium methoxide. 12. A process according to any one of claims 9-11, 4 for the production of a product therein R is ethylene wherein the Polymer [NH 2- component is dissolved in anhydrous methanol, the reaction mass is characterized by the presence therein of sodium methoxide and the reaction mass is heated to distill off alcohol prior to the addition of component (b) .

Inventors: DEPASQUALE RALPH J, WILSON MICHAEL E, DEPASQUALE, RALPH, J., WILSON, MICHAEL, E.
Applicants: SCM CORP, SCM CORPORATION
Application year: 1986
Main classification: C08G77
IPC codes: C08G65, C08G77, C08G85