Patent Application: US-33111508-A

Abstract:
the present invention is directed to a fatty amide acrylate monomer , methods of making the monomer , and latex polymers comprising the fatty amide acrylate monomer . the monomers are derived by reacting unsaturated vegetable oils with ethanolamine or substituted ethanolamine . the vegetable oil derivative is then reacted with either acryloyl chloride or acrylic acid to form a fatty amide acrylate monomer or the product of the reaction of hydroxyethyl acrylate reacted with isophorone diisocyanate to form a urethane fatty amide acrylate monomer . the increased hydrophilicity of the fatty amide acrylate monomer facilitates the diffusion through the aqueous phase . the monomer synthesis is designed to be glycerol ester - free to increase long term stability for monomers and polymers .

Description:
the present invention is directed to a series of vegetable oil macromonomers and their use in latexes and coatings . the invention is also directed to the method of producing these macromonomers . the monomers are derived by reacting unsaturated vegetable oils with ethanolamine or substituted ethanolamine . the vegetable oil derivative is then reacted with either ( meth ) acryloyl chloride or ( meth ) acrylic acid to form a fatty amide ( meth ) acrylate monomer or the product of the reaction of hydroxyethyl ( meth ) acrylate reacted with isophorone diisocyanate to form a urethane fatty amide ( meth ) acrylate monomer . in a preferred embodiment , a vegetable oil such as soybean oil , coconut oil , or linseed oil is reacted with ethanolamine ( or substituted ethanolamine ) followed by reaction with ( meth ) acryloyl chloride or ( meth ) acrylic acid to form the fatty amide ( meth ) acrylate monomer . examples of substituted ethanolamines include n - methyl ethanolamine , n - oleoylethanolamine , n - ethylethanolamime , n - propylethanolamine , n - butylethanolamine , n - tert - butylethanolamine , n -( tert - butoxycarbonyl ) ethanolamine , n -( allyloxycarbonyl ) ethanolamine , benzyl n -( 2 - hydroxyethyl ) carbamate , ethyl - n -( 2 - hydroxyethyl )- carbamate , and diethanolamine . the reaction mechanism is schematically shown in reaction 1 . any vegetable oil can be used in the present invention . however , linseed oil , soybean oil and coconut oil are preferred . various compounds can be used to modify the fatty amide . examples include but are not limited to ( meth ) acryloyl chloride and ( meth ) acrylic acid . in another preferred embodiment , urethane fatty amide monomers are synthesized . first , hydroxyethyl ( meth ) acrylate is reacted with isophorone diisocyanate . in a preferred embodiment , the hydroxyl ( meth ) acrylate is reacted in equimolar proportion with isophorone diisocyanate . in a separate reaction , a vegetable oil , for example , soybean oil , coconut oil , or linseed oil is reacted with ethanolamine ( or substituted ethanolamine ) to form the hydroxyl functional fatty amide . the products of the two reactions were reacted to form the urethane fatty amide ( meth ) acrylate monomer schematically shown in reaction 2 . the macromonomers of the present invention can be used to make latexes and coatings compositions . the monomers described in this patent application can be polymerized in a single or multi - stage emulsion polymerization process to include macroemulsion , miniemulsion , microemulsion and processing can be batch , semi - batch or continuous . although it is possible to use this monomer in a staged emulsion polymerization , as disclosed in published u . s . application 2003 / 0045609 , the teachings of which are hereby incorporated by reference , it is not a requirement for efficient polymerization . a latex polymer can be formed from the polymerization product of the fatty amide ( meth ) acrylate monomer and an ethylenically unsaturated monomer suitable for forming a latex composition . suitable ethylenically unsaturated monomers include vinyl acetate , vinyl chloride , vinyl ester of a saturated tertiary branched carboxylic acid , acrylonitrile , acrylamide , 2 - ethylhexyl acrylate , 2 - ethylhexyl methacrylate , 2 - hydroxyethyl acrylate , 2 - hydroxyethyl methacrylate , glycidyl acrylate , glycidyl methacrylate , acrylic acid , methacrylic acid , butyl acrylate , butyl methacrylate , methyl methacrylate , methyl acrylate , p - acetoxystyrene , and styrene . the invention is further understood by reference to the following examples which describe the formation of various macromonomers as well as the formulation of latexes and coatings . a three - neck , 1000 ml round bottom flask was purged with nitrogen once equipped with mechanical stirrer , thermometer , condenser and was charged with 500 g soybean oil . nitrogen was bubbled through the oil overnight to deoxygenate the oil . the flask was placed in an oil bath at 80 ° c ., and 50 g of a sodium methoxide methanol solution ( 25 % in methanol ) was added to the flask . the reaction mixture was equilibrated to 80 ° c ., and 125 . 46 g of n - methyl ethanolamine was added to the flask . an exotherm of approximately 10 ° c . was noted . the reaction was maintained and the reaction progress was monitored by fourier transform infrared spectroscopy ( ftir ). complete conversion via ftir was observed after 4 hours . the reactor was cooled to ambient conditions and diluted with 100 g of methylene chloride . the contents were washed three times with 500 ml of brine ( 5 % sodium chloride ). the aqueous phase was discarded and the organic phase was dried with magnesium sulfate . methylene chloride was removed under reduced pressure , and the product ( soya - 1 ) was characterized by gel permeation chromatography ( gpc ), high pressure liquid chromatography ( hplc ), and nuclear magnetic resonance ( nmr ) spectroscopy . a three - neck , 1000 ml round bottom flask was purged with nitrogen once equipped with mechanical stirrer , thermometer , condenser and was charged with 500 g soybean oil . nitrogen was bubbled into the mixture overnight to deoxygenate the oil . the flask was placed in an oil bath at 80 ° c ., and 50 g of a sodium methoxide methanol solution ( 25 % in methanol ) was added to the flask . the reaction mixture was equilibrated to 80 ° c ., and 186 . 05 g of ethanolamine was added to the flask . an exotherm of approximately 10 ° c . was noted . the reaction was maintained and the reaction progress was monitored by fourier transform infrared spectroscopy ( ftir ). complete conversion via ftir was observed after 4 hours . the reactor was cooled to ambient conditions and diluted with 100 g of methylene chloride . the contents were washed three times with 500 ml of brine ( 5 % sodium chloride ). the aqueous phase was discarded and the organic phase was dried with magnesium sulfate . methylene chloride was removed under reduced pressure , and the product ( soya - 2 ) was characterized by gpc , hplc , and nmr spectroscopy . a three - neck , 1000 ml round bottom flask equipped with thermometer , mechanical stirrer , and addition funnel was charged with 250 . 00 g of soya - 1 , 100 . 00 ml of methylene chloride , and 74 . 94 g of triethylamine . the flask was placed in an ice bath and equilibrated to 0 ° c . 70 . 00 g of acryloyl chloride was charged to the addition funnel , and added dropwise into the flask over 4 hours . the flask was allowed to equilibrate to ambient conditions overnight . the contents were washed 5 times with 500 ml of brine ( 5 % sodium chloride ) to remove unreacted acryloyl chloride , triethylamine , and hydrochloric acid . the aqueous phase was discarded and the organic phase was dried with magnesium sulfate . methylene chloride was removed under reduced pressure , and the product ( soyaa - 1 ) was characterized by gpc , hplc , and nmr spectroscopy . a three - neck , 1000 ml round bottom flask equipped with thermometer , mechanical stirrer , and addition funnel was charged with 250 . 00 g of soya - 2 , 100 . 00 ml of methylene chloride , and 78 . 19 g triethylamine . the flask was placed in an ice bath and equilibrated to 0 ° c . 70 . 00 g of acryloyl chloride was charged to the addition funnel , and added dropwise into the flask over 4 hours . the flask was allowed to equilibrate to ambient conditions overnight . the reactor contents were washed 5 times with 500 ml of brine ( 5 % sodium chloride ) to remove unreacted acryloyl chloride , triethylamine , and hydrochloric acid . the aqueous phase was discarded and the organic phase was dried with magnesium sulfate . methylene chloride was removed under reduced pressure , and the product ( soyaa - 2 ) was characterized by gpc , hplc , and nmr spectroscopy . a three - neck , 1000 ml round bottom flask was purged with nitrogen after being equipped with a mechanical stirrer , thermometer , condenser and was charged with 500 g coconut oil . nitrogen was bubbled through the oil overnight to deoxygenate the oil . the flask was placed in an oil bath at 80 ° c ., and 50 g of a sodium methoxide methanol solution ( 25 % in methanol ) was added to the flask . the reaction mixture was equilibrated to 80 ° c ., and 125 . 46 g of n - methyl ethanolamine was added to the flask . an exotherm was noted . the reaction was maintained at 80 ° c . and the reaction progress was monitored by ftir . complete conversion was observed after 4 hours . the reactor was then cooled to ambient conditions and 100 g of methylene chloride was added to the flask . the contents were washed three times with 500 ml of brine ( 5 % sodium chloride ). the aqueous phase was discarded and the organic phase was dried with magnesium sulfate . methylene chloride was removed under reduced pressure , and the product ( cocoa - 1 ) was characterized by gpc , hplc , and nmr spectroscopy . a three - neck , 1000 ml round bottom flask equipped with thermometer , mechanical stirrer , and addition funnel was charged with 401 . 62 g of cocoa - 1 , 100 . 00 ml of methylene chloride , and 120 . 40 g of triethylamine . the flask was placed in an ice bath and equilibrated to 0 ° c . 107 . 69 g of acryloyl chloride was charged to the addition funnel , and added dropwise into the flask over 4 hours . the flask was allowed to equilibrate to ambient conditions overnight . the contents were washed 5 times with 500 ml of brine ( 5 % sodium chloride ) to remove unreacted acryloyl chloride , triethylamine , and hydrochloric acid . the aqueous phase was discarded and the organic phase was dried with magnesium sulfate . methylene chloride was removed under reduced pressure , and the product ( cocoaa - 1 ) was characterized by gpc , hplc , and nmr spectroscopy . a three - neck , 500 ml round bottom flask equipped with thermometer , mechanical stirrer , and addition funnel was charged with 64 . 44 g isophorone diisocyanate and 0 . 02 g dibutyl tin dilaurate . 33 . 64 g hydroxylethyl acrylate was charged to the addition funnel and added dropwise to the flask over 4 hours . next , the addition funnel was charged with 100 . 00 g soya - 1 , and added to the flask over 1 hour . the reaction progress was monitored by ftir , and deemed complete when residual isocyanate could not be identified in the ftir spectra . the product ( soyua - 1 ) was characterized by gpc , hplc , and nmr spectroscopy . a three - neck , 1000 ml round bottom flask purged with nitrogen was equipped with mechanical stirrer , thermometer , condenser and was charged with 250 g coconut oil . nitrogen was bubbled through the oil overnight to deoxygenate the oil . the flask was placed in an oil bath at 80 ° c ., and 25 g of a sodium methoxide methanol solution ( 25 % in methanol ) was added to the flask . the reaction mixture was equilibrated to 80 ° c ., and 63 . 78 g of n - methyl ethanolamine was added to the flask . an exotherm was noted . the reaction was maintained at 80 ° c . and the reaction progress was monitored by ftir . complete conversion was observed after 4 hours . the reactor was cooled to ambient conditions and 100 g of methylene chloride was added to the flask . the contents were washed three times with 500 ml of brine ( 5 % sodium chloride ). the aqueous phase was discarded and the organic phase was dried with magnesium sulfate . methylene chloride was removed under reduced pressure , and the product ( lina - 1 ) was characterized by gpc , hplc , and nmr spectroscopy . a three - neck , 500 ml round bottom flask equipped with thermometer , mechanical stirrer , and addition funnel was charged with 200 . 00 g of lina - 1 , 100 . 00 ml of methylene chloride , and 60 . 00 g of triethylamine . the flask was placed in an ice bath and equilibrated to 0 ° c . 60 . 00 g of acryloyl chloride was charged to the addition funnel , and added dropwise into the flask over 2 hours . the flask was allowed to equilibrate to ambient conditions overnight . the contents were washed 5 times with 500 ml of brine ( 5 % sodium chloride ) to remove unreacted acryloyl chloride , triethylamine , and hydrochloric acid . the aqueous phase was discarded and the organic phase was dried with magnesium sulfate . methylene chloride was removed under reduced pressure , and the product ( linaa - 1 ) was characterized by gpc , hplc , and nmr spectroscopy . a three - neck , 1000 ml round bottom flask equipped with thermometer , mechanical stirrer , and addition funnel was charged with 200 . 00 g of soya - 1 , 100 . 00 ml of methylene chloride , and 55 . 06 g of triethylamine . the flask was placed in an ice bath and equilibrated to 0 ° c . 49 . 25 g of methacryloyl chloride was charged to the addition funnel , and added dropwise into the flask over 2 hours . the flask was allowed to equilibrate to ambient conditions overnight . the reactor contents were washed 5 times with 500 ml of brine ( 5 % sodium chloride ) to remove unreacted acryloyl chloride , triethylamine , and hydrochloric acid . the aqueous phase was discarded and the organic phase was dried with magnesium sulfate . methylene chloride was removed under reduced pressure , and the product ( soyma - 1 ) was characterized by gpc , hplc , and nmr spectroscopy . a 500 ml round bottom flask was charged with 100 . 0 g soya - 1 , 21 . 5 g acrylic acid , and 100 . 0 g toluene . the mixture was heated to 100 ° c . and 2 . 5 g methane sulfonic acid was added . the reaction was continued until no further water was released . the toluene was removed under reduced pressure to yield soyaa - 1 and characterized by gpc , hplc , and nmr spectroscopy . a three - neck , 1000 ml round bottom flask equipped with thermometer , mechanical stirrer , and addition funnel was charged with 111 . 11 g isophorone diisocyanate , 60 . 0 g hexane , 0 . 17 g phenothiazine ( ptz ), 0 . 17 g methyl hydroquinone ( mehq ) and 0 . 02 g dibutyl tin dilaurate . 58 . 00 g hydroxylethyl acrylate was charged to the addition fiumnel and added dropwise to the flask over 2 hours . the temperature was raised to 65 ° c . and 168 . 78 g of lina - 1 was added to the flask through the addition funnel over 1 hour . the reaction progress was monitored by ftir , and deemed complete when residual isocyanate could not be identified in the ftir spectra . the hexane was removed under reduced pressure , and the product ( linua - 1 ) was characterized by gpc , hplc , and nmr spectroscopy . a three - neck , 1000 ml round bottom flask was purged with nitrogen while equipped with mechanical stirrer , thermometer , condenser and was charged with 150 . 00 g of soybean oil and 150 . 00 g of tung oil . nitrogen was bubbled through the oil overnight to deoxygenate the oil . the flask was placed in an oil bath at 80 ° c ., and 24 g of a sodium methoxide methanol solution ( 25 % in methanol ) was added to the flask . the reaction mixture was equilibrated to 80 ° c ., and 125 . 46 g of n - methyl ethanolamine was added to the flask . an exotherm of approximately 10 ° c . was noted . the reaction was maintained at 80 ° c . and the progress was monitored by ftir . complete conversion was observed after 4 hours . the reactor was then cooled to ambient conditions and 100 g of methylene chloride was added to the flask . the contents were washed three times with 500 ml of brine ( 5 % sodium chloride ). the aqueous phase was discarded and the organic phase was dried with magnesium sulfate . methylene chloride was removed under reduced pressure , and the product ( soy - tunga - 1 ) was characterized by gpc , hplc , and nmr spectroscopy . a three - neck , 500 ml round bottom flask equipped with thermometer , mechanical stirrer , and addition funnel was charged with 250 . 00 g of soy - tunga - 1 , 100 . 00 ml of methylene chloride , and 74 . 94 g of triethylamine . the flask was placed in an ice bath and equilibrated to 0 ° c . 67 . 03 g of acryloyl chloride was charged to the addition funnel , and added dropwise into the flask over 2 hours . the flask was allowed to equilibrate to ambient conditions overnight . the reactor contents were washed 5 times with 500 ml of brine ( 5 % sodium chloride ) to remove unreacted acryloyl chloride , triethylamine , and hydrochloric acid . the aqueous phase was discarded and the organic phase was dried with magnesium sulfate . methylene chloride was removed under reduced pressure , and the product ( soytung aa - 1 ) was characterized by gpc , hplc , and nmr spectroscopy . a 1 l kettle was charged with 130 . 00 g of deionized ( di ) water and 1 . 21 g of rhodapex ® co - 436 , purged with nitrogen for 15 minutes , and stirred while heating to 70 ° c . the seed was prepared by preemulsifying a mixture of di water ( 8 . 80 g ), rhodapex co - 436 ( 0 . 55 g ), igepal ® co - 887 ( 0 . 20 g ), butyl acrylate ( 8 . 20 g ), methyl methacrylate ( 6 . 30 g ), and methacrylic acid ( 0 . 10 g ) at 1 , 800 rpm for 20 minutes , and was transferred to the kettle . ammonium persulfate ( 2 . 80 g ) was dissolved in 30 . 00 g of di water and 3 . 3 ml of this solution was added to the kettle . meanwhile , a monomer feed was prepared by preemulsifying a mixture of di water ( 160 . 00 g ), sodium bicarbonate ( 1 . 65 g ), rhodapex co - 436 ( 6 . 00 g ), igepal co - 887 ( 5 . 00 g ), butyl acrylate ( 150 . 00 g ), methyl methacrylate ( 170 . 00 g ), and methacrylic acid ( 6 . 00 g ) at 1 , 800 rpm for 20 minutes . the monomer feed was added to the kettle over 2 hours while the remaining initiator solution was added over a period of 2 . 25 hours . after complete addition , the reaction was allowed to continue at 70 ° c . for 4 hours . two chaser solutions were prepared — one by dissolving t - butyl hydroperoxide ( 0 . 36 g ) in 10 . 00 g of di water and the other by dissolving sodium bisulfite ( 0 . 35 g ) in 10 . 00 g of di water . both chaser solutions were fed to the kettle over a period of 1 hour , and the emulsion was allowed to cool to ambient temperature and discharged . a 1 l kettle was charged with 130 . 00 g of di water and 1 . 21 g of rhodapex co - 436 , purged with nitrogen for 15 minutes , and stirred while heating to 70 ° c . the seed was prepared by preemulsifying a mixture of di water ( 8 . 80 g ), rhodapex co - 436 ( 0 . 55 g ), igepal co - 887 ( 0 . 20 g ), butyl acrylate ( 8 . 20 g ), methyl methacrylate ( 6 . 30 g ), and methacrylic acid ( 0 . 10 g ) at 1 , 800 rpm for 20 minutes , and was transferred to the kettle . ammonium persulfate ( 2 . 80 g ) was dissolved in 30 . 00 g of di water and 3 . 3 ml of this solution was added to the kettle . meanwhile , a monomer feed was prepared by preemulsifying a mixture of di water ( 160 . 00 g ), sodium bicarbonate ( 1 . 65 g ), rhodapex co - 436 ( 6 . 00 g ), igepal co - 887 ( 5 . 00 g ), butyl acrylate ( 85 . 00 g ), methyl methacrylate ( 170 . 00 g ), soyaa - 1 ( 65 . 00 g ), and methacrylic acid ( 6 . 00 g ) at 1 , 800 rpm for 20 minutes . the monomer feed was added to the kettle over 2 hours while the remaining initiator solution was added over a period of 2 . 25 hours . after complete addition , the reaction was allowed to continue at 70 ° c . for 4 hours . two chaser solutions were prepared — one by dissolving t - butyl hydroperoxide ( 0 . 36 g ) in 10 . 00 g of di water and the other by dissolving sodium bisulfite ( 0 . 35 g ) in 10 . 00 g of di water . both chaser solutions were fed to the kettle over a period of 1 hour , and the emulsion was allowed to cool to ambient temperature and discharged . the latexes described in examples 15 and 16 were formulated into semi - gloss coatings as per the formulation shown in table 2 . a 500 ml kettle was charged with 110 . 00 g of di water and 0 . 80 g of rhodapex co - 436 , purged with nitrogen for 15 minutes , and stirred while heating to 70 ° c . the seed was prepared by preemulsifying a mixture of di water ( 6 . 00 g ), rhodapex co - 436 ( 0 . 37 g ), igepal co - 887 ( 0 . 13 g ), butyl acrylate ( 5 . 50 g ), methyl methacrylate ( 4 . 20 g ), and methacrylic acid ( 0 . 07 g ) at 1 , 800 rpm for 20 minutes , and was transferred to the kettle . ammonium persulfate ( 2 . 80 g ) was dissolved in 30 . 00 g of di water and 3 . 3 ml of this solution was added to the kettle . meanwhile , the monomer feed was prepared by preemulsifying a mixture of di water ( 107 . 00 g ), sodium bicarbonate ( 1 . 10 g ), rhodapex co - 436 ( 4 . 00 g ), igepal co - 887 ( 3 . 33 g ), butyl acrylate ( 74 . 70 g ), methyl methacrylate ( 82 . 70 g ), styrene ( 20 . 00 g ), methacrylic acid ( 4 . 00 g ), diacetone acrylamide ( 3 . 08 g ), and soyaa - 1 ( 36 . 00 g ) at 1 , 800 rpm for 20 minutes . the monomer feed was added to the kettle over 2 hours while the remaining initiator solution was added over a period of 2 . 25 hours . after complete addition , the reaction was allowed to continue at 70 ° c . for 4 hours . two chaser solutions were prepared — one by dissolving t - butyl hydroperoxide ( 0 . 36 g ) in 10 . 00 g of di water and the other by dissolving sodium bisulfite ( 0 . 35 g ) in 10 . 00 g of di water . both chaser solutions were fed to the kettle over a period of 1 hour . the emulsion was allowed to cool to ambient temperature and the ph was adjusted to 9 by adding ammonia followed by adipic dihydrazide solution ( 4 . 6 g in 11 . 00 g of di water ). a 500 ml kettle was charged with 110 . 00 g of di water and 0 . 80 g of rhodapex co - 436 , purged with nitrogen for 15 minutes , and stirred while heating to 70 ° c . the seed was prepared by preemulsifying a mixture of di water ( 6 . 00 g ), rhodapex co - 436 ( 0 . 37 g ), igepal co - 887 ( 0 . 13 g ), butyl acrylate ( 5 . 50 g ), methyl methacrylate ( 4 . 20 g ), and methacrylic acid ( 0 . 07 g ) at 1 , 800 rpm for 20 minutes , and was transferred to the kettle . ammonium persulfate ( 2 . 80 g ) was dissolved in 30 . 00 g of di water and 3 . 3 ml of this solution was added to the kettle . meanwhile , the monomer feed was prepared by preemulsifying a mixture of di water ( 107 . 00 g ), sodium bicarbonate ( 1 . 10 g ), rhodapex co - 436 ( 4 . 00 g ), igepal co - 887 ( 3 . 33 g ), butyl acrylate ( 74 . 70 g ), methyl methacrylate ( 82 . 70 g ), styrene ( 20 . 00 g ), methacrylic acid ( 4 . 00 g ), diacetone acrylamide ( 3 . 08 g ), and linaa - 1 ( 36 . 00 g ) at 1 , 800 rpm for 20 minutes . the monomer feed was added to the kettle over 2 hours while the remaining initiator solution was added over a period of 2 . 25 hours . after complete addition , the reaction was allowed to continue at 70 ° c . for 4 hours . two chaser solutions were prepared — one by dissolving t - butyl hydroperoxide ( 0 . 36 g ) in 10 . 00 g of di water and the other by dissolving sodium bisulfite ( 0 . 35 g ) in 10 . 00 g of di water . both chaser solutions were fed to the kettle over a period of 1 hour . the emulsion was allowed to cool to ambient temperature and the ph was adjusted to 9 by adding ammonia followed by adipic dihydrazide solution ( 4 . 6 g in 11 . 00 g of di water ). thames , shelby f . ; smith , oliver w . ; evans , james m . ; dutta , sandipan ; chen , lianzhou . 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