wl-hydrophilic-polymer/task2/task2-paper-info/bayer2655-US6767958.json

{
    "protocol": "The article provides a detailed experimental procedure for the synthesis of hydrophilic polymers with functional groups using modified polyisocyanates. First, the polyisocyanate is reacted with a suitable polyol or amine compound under controlled temperature conditions to achieve the desired functionalization. The reaction is carried out in a solvent that enhances solubility and ensures thorough mixing. The modified product is then precipitated out, washed, and dried to obtain the final hydrophilic polymer. Specific ratios of reactants and the reaction time are crucial for optimizing the functional groups on the polymer backbone.The synthesis of hydrophilic polymers with functional groups, specifically water-dispersible polyisocyanates, involves the modification of polyisocyanates with polyethers to increase hydrophilicity. Additionally, the incorporation of ionic groups, such as chemically bonded carboxyl groups, is explored to enhance dispersibility in aqueous systems. The process includes neutralization of carboxyl groups to allow for easier stirring into aqueous systems without requiring high shear forces. Emulsifiers are formed from the reaction of polyisocyanates with hydroxy-, mercapto-, or amino-functional compounds that possess at least one sulfuric acid group or its anion. Preferred emulsifiers include hydroxysulfonic acids or their sodium salts, which are prepared in forms suitable for industrial scaling. The final products aim for compatibility with conventional paint binders while avoiding undesirable characteristics such as excessive yellowing or permanent hydrophilicity from sodium ions.2-(cyclohexylamino)-ethanesulfonic acid or 3-(cyclohexylamino)-propanesulfonic acid is reacted with polyisocyanates under mild reaction conditions in the presence of a suitable neutralization amine to obtain storage-stable, light-coloured products that can be emulsified in water.A) A polyisocyanate component with an average functionality of 2.0 to 5.0 and a content of aliphatically, cycloaliphatically, araliphatically and/or aromatically bonded isocyanate groups of 8.0 to 27.0 wt. %. B) 0.3 to 25.0 wt. %, based on the total weight of components A) and B), of 2-(cyclohexylamino)-ethanesulfonic acid and/or 3-(cyclohexylamino)-propanesulfonic acid. C) Up to 25 wt. %, based on the total weight of components A), B) and C), of a monohydric polyalkylene oxide polyether alcohol containing a statistical average of 5 to 35 ethylene oxide units. D) 0.2 to 2.0 equivalents, based on the sulfonic acid groups of component B), of a tertiary amine. These components are reacted while observing an equivalent ratio of isocyanate (NCO) groups to groups which are reactive towards NCO groups of 2:1 to 400:1.To synthesize hydrophilic polymers with functional groups, follow these steps: 1. Use polyisocyanates (Component A) that have exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups, preferably those with an isocyanurate structure based on HDI, IPDI, or 4,4'-diisocyanatodicyclohexylmethane. 2. Optionally, include polyisocyanates modified hydrophilically with ethylene oxide polyethers. 3. Choose aminosulfonic acids (Component B), such as 2-(cyclohexylamino)-ethanesulfonic acid (CHES) or 3-(cyclohexylamino)-propanesulfonic acid (CAPS), in amounts ranging from 0.3 to 25 wt.%, preferably 0.5 to 25 wt.%, based on the total weight of components A and B. 4. Optionally, incorporate monohydric polyalkylene oxide polyether alcohols (Component C), containing a statistical average of 5 to 35 ethylene oxide units, in amounts of up to 25 wt.%, preferably up to 20 wt.%, based on the total weight of components A, B, and C. 5. Introduce tertiary amines (Component D) for neutralizing the sulfonic acid groups, in amounts that maintain an equivalent ratio of tertiary amino groups to sulfonic acid groups of 0.2 to 2.0, preferably 0.5 to 1.5. 6. React components A, B, and optionally C, in the presence of amine D at temperatures between 40 to 150 °C, observing an equivalent ratio of NCO groups to reactive groups of 2:1 to 400:1, preferably 4:1 to 250:1, until the theoretically calculated NCO content is reached. 7. Additional catalysts may be used to accelerate the reaction.The synthesis of hydrophilic polymers with functional groups involves the use of polyisocyanates characterized by an average NCO functionality preferably between 2.0 to 4.8, an NCO content of 7.0 to 23.0 wt. %, a sulfonate group content (calculated as SO3-) preferably within 0.2 to 6.3 wt. %, and a content of ethylene oxide units in the polyether chains preferably up to 17 wt. %. The process is carried out in a suitable solvent that is inert to isocyanate groups, such as ethyl acetate, butyl acetate, acetone, and N-methylpyrrolidone among others. The resulting polyisocyanates should be converted into sedimentation-stable dispersions by stirring into water. The polyisocyanates can then be used to prepare polyisocyanate plastics through the isocyanate polyaddition process, preferably in the form of aqueous emulsions reacted with polyhydroxy compounds that contain groups reactive with isocyanate, such as alcoholic hydroxyl groups.900 g (4.97 eq) of a polyisocyanate which contains isocyanurate groups and is based on HDI, with an NCO content of 23.2%, an average NCO functionality of 3.2, a content of monomeric HDI of 0.1%, and a viscosity of 1,200 mPas (23°C) are stirred together with 100 g (0.45 eq) CAPS and 57 g (0.45 mol) dimethylcyclohexylamine under dry nitrogen for 10 hours at 80°C. After cooling to room temperature, a practically colourless clear polyisocyanate mixture according to the invention with the following characteristic data is present.$950\\\\mathrm{~g~}$ (4.90 eq) of a polyisocyanate which contains isocyanurate groups and is based on 1,6-diisocyanatohexane (HDI), with an NCO content of $21.7\\\\%$, an average NCO functionality of 3.5 (according to GPC), a content of monomeric HDI of $0.1\\\\%$ and a viscosity of $3,000\\\\mathrm{mPas}$ $(23^{\\\\circ}\\\\mathrm{C})$, are stirred together with $50\\\\mathrm{g}(0.23\\\\mathrm{eq})$ 3-(cyclohexylamino)- propanesulfonic acid (CAPS), $29\\\\mathrm{g}\\\\left(0.23\\\\mathrm{mol}\\\\right)$ dimethylcyclohexylamine and $257\\\\mathrm{g}1$ -methoxyprop-2-yl acetate under dry nitrogen for 5 hours at $80^{\\\\circ}\\\\mathrm{~C~}$. After cooling to room temperature, a practically colourless clear solution of a polyisocyanate mixture according to the invention with the following characteristic data is present:$950\\ \\mathrm{~g~}$ (4.90 eq) of the polyisocyanate containing isocyanurate groups based on HDI is stirred with $50\\ \\mathrm{~g~}$ (0.36 eq) 2-methylaminoethanesulfonic acid, $\\boldsymbol{46}_{\\mathrm{~\\scriptsize~g~}}$ (0.36~\\mathrm{~mol}) dimethylcyclohexylamine, and $262\\ \\mathrm{~g~}$ 1-methoxyprop-2-yl acetate under dry nitrogen at $80^{\\circ}\\mathrm{~C~}$. The reaction is carried out for a total of 12 hours, with the temperature increased to $120^{\\circ}\\mathrm{~C~}$ after 8 hours. The reaction mixture remains cloudy and inhomogeneous, and methyltaurine settles as a crystalline sediment.100 g deionized water were added to a conical flask with 35 g of polyisocyanate mixtures, including 15 g of an 80% solution from examples 1, 2, and 4, 40 g of a 70% solution from example 5, and 25 g of the polyisocyanate mixture from example 3, resulting in a solids content of approximately 20 wt%. The mixtures were stirred for 1 min with a magnetic stirrer at 900 rpm. The emulsions obtained were stable for 5 hours without visible CO2 evolution, precipitates, or sediment.Combine 950 g (4.90 eq) of polyisocyanate containing isocyanurate groups based on HDI with 50 g (0.40 eq) of 2-aminoethanesulfonic acid (taurine), 51 g (0.40 mol) of dimethylcyclohexylamine, and 263 g of 1-methoxyprop-2-yl acetate. Stir the mixture under dry nitrogen at 80°C for 8 hours. If the reaction mixture remains cloudy, increase the temperature to 120°C and continue stirring for an additional 6 hours. Observe that methyltaurine may settle as a crystalline sediment in the reaction mixture.Initially introduce 350 g of the polyisocyanate mixture into the reaction vessel at 70°C. Add 126 g of 3,5-dimethylpyrazole in portions over 30 min while maintaining the temperature of the reaction mixture below 80°C. Stir the mixture for approximately 2 hours at 70°C until free isocyanate groups are no longer detectable by IR spectroscopy. Cool the mixture to 40°C, then allow 539 g of deionized water to run in with vigorous stirring over 30 min.Combine up to 20 wt. % of a monohydric polyalkylene oxide polyether alcohol, containing an average of 5 to 35 ethylene oxide units, with 0.5 to 1.5 equivalents of a tertiary amine based on the sulfonic acid groups of the other components. Use a polyisocyanate prepared from at least two molecules of specified isocyanates such as 1,6-diisocyanatohexane or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane."
}
	`{`
	"protocol": "The article provides a detailed experimental procedure for the synthesis of hydrophilic polymers with functional groups using modified polyisocyanates. First, the polyisocyanate is reacted with a suitable polyol or amine compound under controlled temperature conditions to achieve the desired functionalization. The reaction is carried out in a solvent that enhances solubility and ensures thorough mixing. The modified product is then precipitated out, washed, and dried to obtain the final hydrophilic polymer. Specific ratios of reactants and the reaction time are crucial for optimizing the functional groups on the polymer backbone.The synthesis of hydrophilic polymers with functional groups, specifically water-dispersible polyisocyanates, involves the modification of polyisocyanates with polyethers to increase hydrophilicity. Additionally, the incorporation of ionic groups, such as chemically bonded carboxyl groups, is explored to enhance dispersibility in aqueous systems. The process includes neutralization of carboxyl groups to allow for easier stirring into aqueous systems without requiring high shear forces. Emulsifiers are formed from the reaction of polyisocyanates with hydroxy-, mercapto-, or amino-functional compounds that possess at least one sulfuric acid group or its anion. Preferred emulsifiers include hydroxysulfonic acids or their sodium salts, which are prepared in forms suitable for industrial scaling. The final products aim for compatibility with conventional paint binders while avoiding undesirable characteristics such as excessive yellowing or permanent hydrophilicity from sodium ions.2-(cyclohexylamino)-ethanesulfonic acid or 3-(cyclohexylamino)-propanesulfonic acid is reacted with polyisocyanates under mild reaction conditions in the presence of a suitable neutralization amine to obtain storage-stable, light-coloured products that can be emulsified in water.A) A polyisocyanate component with an average functionality of 2.0 to 5.0 and a content of aliphatically, cycloaliphatically, araliphatically and/or aromatically bonded isocyanate groups of 8.0 to 27.0 wt. %. B) 0.3 to 25.0 wt. %, based on the total weight of components A) and B), of 2-(cyclohexylamino)-ethanesulfonic acid and/or 3-(cyclohexylamino)-propanesulfonic acid. C) Up to 25 wt. %, based on the total weight of components A), B) and C), of a monohydric polyalkylene oxide polyether alcohol containing a statistical average of 5 to 35 ethylene oxide units. D) 0.2 to 2.0 equivalents, based on the sulfonic acid groups of component B), of a tertiary amine. These components are reacted while observing an equivalent ratio of isocyanate (NCO) groups to groups which are reactive towards NCO groups of 2:1 to 400:1.To synthesize hydrophilic polymers with functional groups, follow these steps: 1. Use polyisocyanates (Component A) that have exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups, preferably those with an isocyanurate structure based on HDI, IPDI, or 4,4'-diisocyanatodicyclohexylmethane. 2. Optionally, include polyisocyanates modified hydrophilically with ethylene oxide polyethers. 3. Choose aminosulfonic acids (Component B), such as 2-(cyclohexylamino)-ethanesulfonic acid (CHES) or 3-(cyclohexylamino)-propanesulfonic acid (CAPS), in amounts ranging from 0.3 to 25 wt.%, preferably 0.5 to 25 wt.%, based on the total weight of components A and B. 4. Optionally, incorporate monohydric polyalkylene oxide polyether alcohols (Component C), containing a statistical average of 5 to 35 ethylene oxide units, in amounts of up to 25 wt.%, preferably up to 20 wt.%, based on the total weight of components A, B, and C. 5. Introduce tertiary amines (Component D) for neutralizing the sulfonic acid groups, in amounts that maintain an equivalent ratio of tertiary amino groups to sulfonic acid groups of 0.2 to 2.0, preferably 0.5 to 1.5. 6. React components A, B, and optionally C, in the presence of amine D at temperatures between 40 to 150 °C, observing an equivalent ratio of NCO groups to reactive groups of 2:1 to 400:1, preferably 4:1 to 250:1, until the theoretically calculated NCO content is reached. 7. Additional catalysts may be used to accelerate the reaction.The synthesis of hydrophilic polymers with functional groups involves the use of polyisocyanates characterized by an average NCO functionality preferably between 2.0 to 4.8, an NCO content of 7.0 to 23.0 wt. %, a sulfonate group content (calculated as SO3-) preferably within 0.2 to 6.3 wt. %, and a content of ethylene oxide units in the polyether chains preferably up to 17 wt. %. The process is carried out in a suitable solvent that is inert to isocyanate groups, such as ethyl acetate, butyl acetate, acetone, and N-methylpyrrolidone among others. The resulting polyisocyanates should be converted into sedimentation-stable dispersions by stirring into water. The polyisocyanates can then be used to prepare polyisocyanate plastics through the isocyanate polyaddition process, preferably in the form of aqueous emulsions reacted with polyhydroxy compounds that contain groups reactive with isocyanate, such as alcoholic hydroxyl groups.900 g (4.97 eq) of a polyisocyanate which contains isocyanurate groups and is based on HDI, with an NCO content of 23.2%, an average NCO functionality of 3.2, a content of monomeric HDI of 0.1%, and a viscosity of 1,200 mPas (23°C) are stirred together with 100 g (0.45 eq) CAPS and 57 g (0.45 mol) dimethylcyclohexylamine under dry nitrogen for 10 hours at 80°C. After cooling to room temperature, a practically colourless clear polyisocyanate mixture according to the invention with the following characteristic data is present.$950\\\\mathrm{~g~}$ (4.90 eq) of a polyisocyanate which contains isocyanurate groups and is based on 1,6-diisocyanatohexane (HDI), with an NCO content of $21.7\\\\%$, an average NCO functionality of 3.5 (according to GPC), a content of monomeric HDI of $0.1\\\\%$ and a viscosity of $3,000\\\\mathrm{mPas}$ $(23^{\\\\circ}\\\\mathrm{C})$, are stirred together with $50\\\\mathrm{g}(0.23\\\\mathrm{eq})$ 3-(cyclohexylamino)- propanesulfonic acid (CAPS), $29\\\\mathrm{g}\\\\left(0.23\\\\mathrm{mol}\\\\right)$ dimethylcyclohexylamine and $257\\\\mathrm{g}1$ -methoxyprop-2-yl acetate under dry nitrogen for 5 hours at $80^{\\\\circ}\\\\mathrm{~C~}$. After cooling to room temperature, a practically colourless clear solution of a polyisocyanate mixture according to the invention with the following characteristic data is present:$950\\ \\mathrm{~g~}$ (4.90 eq) of the polyisocyanate containing isocyanurate groups based on HDI is stirred with $50\\ \\mathrm{~g~}$ (0.36 eq) 2-methylaminoethanesulfonic acid, $\\boldsymbol{46}_{\\mathrm{~\\scriptsize~g~}}$ (0.36~\\mathrm{~mol}) dimethylcyclohexylamine, and $262\\ \\mathrm{~g~}$ 1-methoxyprop-2-yl acetate under dry nitrogen at $80^{\\circ}\\mathrm{~C~}$. The reaction is carried out for a total of 12 hours, with the temperature increased to $120^{\\circ}\\mathrm{~C~}$ after 8 hours. The reaction mixture remains cloudy and inhomogeneous, and methyltaurine settles as a crystalline sediment.100 g deionized water were added to a conical flask with 35 g of polyisocyanate mixtures, including 15 g of an 80% solution from examples 1, 2, and 4, 40 g of a 70% solution from example 5, and 25 g of the polyisocyanate mixture from example 3, resulting in a solids content of approximately 20 wt%. The mixtures were stirred for 1 min with a magnetic stirrer at 900 rpm. The emulsions obtained were stable for 5 hours without visible CO2 evolution, precipitates, or sediment.Combine 950 g (4.90 eq) of polyisocyanate containing isocyanurate groups based on HDI with 50 g (0.40 eq) of 2-aminoethanesulfonic acid (taurine), 51 g (0.40 mol) of dimethylcyclohexylamine, and 263 g of 1-methoxyprop-2-yl acetate. Stir the mixture under dry nitrogen at 80°C for 8 hours. If the reaction mixture remains cloudy, increase the temperature to 120°C and continue stirring for an additional 6 hours. Observe that methyltaurine may settle as a crystalline sediment in the reaction mixture.Initially introduce 350 g of the polyisocyanate mixture into the reaction vessel at 70°C. Add 126 g of 3,5-dimethylpyrazole in portions over 30 min while maintaining the temperature of the reaction mixture below 80°C. Stir the mixture for approximately 2 hours at 70°C until free isocyanate groups are no longer detectable by IR spectroscopy. Cool the mixture to 40°C, then allow 539 g of deionized water to run in with vigorous stirring over 30 min.Combine up to 20 wt. % of a monohydric polyalkylene oxide polyether alcohol, containing an average of 5 to 35 ethylene oxide units, with 0.5 to 1.5 equivalents of a tertiary amine based on the sulfonic acid groups of the other components. Use a polyisocyanate prepared from at least two molecules of specified isocyanates such as 1,6-diisocyanatohexane or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane."
	`}`