CN117567714B - Organosilicon hydrophilic flame-retardant finishing agent and preparation method thereof - Google Patents
Organosilicon hydrophilic flame-retardant finishing agent and preparation method thereof Download PDFInfo
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Abstract
本发明涉及织物整理技术领域，且公开了一种有机硅亲水阻燃整理剂及其制备方法，有机硅亲水阻燃整理剂分子主链中含有亲水性的醚键、羧基、脲基基团，改善了有机硅整理剂在水中的分散性，溶液均一稳定，离心稳定性优异。对棉织物整理后，可以有效提高棉织物的亲水性，有利于改善棉织物的吸水吸湿性能。并且主链的有机硅链段，可以使棉织物在保持亲水性的同时，具有很好的柔顺性和抗皱性。有机硅亲水阻燃整理剂分子主链中的磷酸酯结构、含氮杂环和有机硅氧烷形成氮磷硅协效阻燃效果，使棉织物表现出优异的阻燃性能。The invention relates to the technical field of fabric finishing, and discloses a silicone hydrophilic flame retardant finishing agent and a preparation method thereof. The main chain of the molecule of the organic silicon hydrophilic flame retardant finishing agent contains hydrophilic ether bonds, carboxyl groups, and urea groups. The group improves the dispersion of silicone finishing agents in water, making the solution uniform and stable, and has excellent centrifugal stability. After finishing the cotton fabric, the hydrophilicity of the cotton fabric can be effectively improved, which is beneficial to improving the water absorption and hygroscopicity of the cotton fabric. And the silicone segment of the main chain can make cotton fabrics have good flexibility and wrinkle resistance while maintaining hydrophilicity. The phosphate ester structure, nitrogen-containing heterocycle and organosiloxane in the main chain of the organic silicone hydrophilic flame retardant finishing agent form a synergistic flame retardant effect of nitrogen, phosphorus and silicon, making cotton fabrics exhibit excellent flame retardant properties.
Description
Technical Field
The invention relates to the technical field of fabric finishing, in particular to an organosilicon hydrophilic flame retardant finishing agent and a preparation method thereof.
Background
With the continuous improvement of living standard, people have pursued higher quality of life, and more importance is attached to clothing wear, and cotton fabrics have the advantages of light warmth retention, strong hygroscopicity, good air permeability and the like, and have wide application in the aspects of high-grade fabric clothing, special clothing protection and the like. In order to endow the cotton fabric with the characteristics of flexibility, flame retardance and the like, the cotton fabric needs to be finished; the current finishing agent mainly comprises polyether finishing agent, organic silicon finishing agent and the like.
The organosilicon finishing agent can well improve the flexibility, crease resistance and hand feeling of the fabric, but the traditional organosilicon finishing agent has hydrophobicity, and the hydrophilicity and hygroscopicity of the finished fabric can be reduced. Patent CN111607969B discloses that a highly hydrophilic silicone finish is prepared from chlorine-containing monomers, epoxy-terminated silicone oils, polyetheramines, and the like as raw materials. But the silicone finish does not impart flame retardant properties to cotton fabrics. The invention aims to prepare the organosilicon hydrophilic flame-retardant finishing agent, which is applied to finishing of fabrics such as cotton fabrics and the like, and improves the properties of hydrophilicity, softness, flame retardance and the like of the fabrics.
Disclosure of Invention
The invention solves the technical problems that: the organic silicon hydrophilic flame-retardant finishing agent is applied to finishing of fabrics such as cotton fabrics and the like, and improves the properties of hydrophilicity, softness, flame retardance and the like of the fabrics.
The technical scheme provided by the invention is as follows:
an organosilicon hydrophilic flame-retardant finishing agent comprises the following raw materials in proportion of (0.4-0.75) mol (0.25-0.6) mol (0.001-0.0015) mol of amino-terminated polysiloxane, phenyl phosphate di (ether tryptophan) compound, diisocyanate compound and dibutyl tin dilaurate.
The structural formula of phenyl phosphate di (ether tryptophan) is as follows:
。
the diisocyanate compound includes toluene-2, 4-diisocyanate and diphenylmethane-4, 4' -diisocyanate.
Further, the preparation method of the organosilicon hydrophilic flame retardant finishing agent comprises the following steps: adding N, N-dimethylformamide, amino-terminated polysiloxane, phenyl phosphate di (ether tryptophan) compound and diisocyanate compound into a flask, stirring and dissolving, introducing nitrogen, adding dibutyltin dilaurate, reacting at 60-80 ℃ for 2-4h, cooling, pouring the solution into ethanol for precipitation, filtering, washing with ethanol, and drying to obtain the organosilicon hydrophilic flame-retardant finishing agent.
Further, the preparation method of the phenyl phosphate di (ether tryptophan) compound comprises the following steps:
(1) Adding a reaction solvent, 2- [2- (2-chloroethoxy) ethoxy ] ethanol and triethylamine into a flask, adding phenylphosphonic dichloride at the temperature of between-5 and 0 ℃, stirring for 10 to 30 minutes, heating to 25 to 35 ℃, reacting for 3 to 6 hours, removing the solvent by rotary evaporation, washing with petroleum ether, and drying to obtain the intermediate 1. The reaction route is as follows:
。
(2) Adding 1, 4-dioxane, an intermediate 1, N- (tert-butoxycarbonyl) -L-tryptophan, a catalyst and cosolvent water into a flask, heating to 75-90 ℃, reacting for 8-24h, removing the 1, 4-dioxane by rotary evaporation, adding ethyl acetate and water for extraction, drying an organic phase, removing the ethyl acetate by rotary evaporation, washing petroleum ether, adding an intermediate product into dichloromethane, adding trifluoroacetic acid (TFA), reacting for 3-5h at 20-35 ℃, removing the solvent by rotary evaporation, and recrystallizing the product by ethyl acetate to obtain the phenyl phosphate di (ether tryptophan) compound. The reaction route is as follows:
。
further, the ratio of the reaction solvent, 2- [2- (2-chloroethoxy) ethoxy ] ethanol, triethylamine and phenylphosphonic acid dichloride in the step (1) is (3-5) L (1.9-2.4) mol (2-2.4) mol to 1mol.
Further, the reaction solvent comprises dichloromethane, chloroform and toluene.
Further, in the step (2), the ratio of 1, 4-dioxane, intermediate 1, N- (tert-butoxycarbonyl) -L-tryptophan, catalyst and water is (3-4) L, 1mol (2-2.5) mol (2.4-2.8) mol (0.8-1.5) L. Further, the catalyst comprises sodium hydride, sodium hydroxide and potassium hydroxide.
The invention has the technical effects that: the invention takes cheap and easily available 2- [2- (2-chloroethoxy) ethoxy ] ethanol, phenylphosphonic dichloride, N- (tert-butoxycarbonyl) -L-tryptophan and the like as raw materials to prepare phenyl phosphate di (ether tryptophan) compound which contains two amino groups and is subjected to polymerization reaction with amino-terminated polysiloxane and diisocyanate compound to obtain the novel organosilicon hydrophilic flame retardant finishing agent; the main chain of the finishing agent contains hydrophilic ether bond, carboxyl and ureido groups, so that the dispersibility of the organic silicon finishing agent in water is improved, the solution is uniform and stable, and the centrifugal stability is excellent.
After the organosilicon hydrophilic flame retardant finishing agent is used for finishing cotton fabrics, the hydrophilicity of the cotton fabrics can be effectively improved, and the water absorption and moisture absorption properties of the cotton fabrics are improved. And the organic silicon chain segment of the main chain can ensure that the cotton fabric has good flexibility and wrinkle resistance while keeping the hydrophilicity. And the main chain of the finishing agent molecule contains a nontoxic and environment-friendly tryptophan structural unit, and the introduction of an amino acid structure is beneficial to improving the biocompatibility of the finishing agent.
The organic silicon hydrophilic flame retardant finishing agent has the advantages that the phosphate structure, the nitrogen-containing heterocycle and the organic siloxane in the molecular main chain of the organic silicon hydrophilic flame retardant finishing agent form a nitrogen-phosphorus-silicon synergistic flame retardant effect, nitrogen-phosphorus elements can promote cotton fabrics to form carbon during combustion, organic silicon is combusted and pyrolyzed to generate inorganic silicon oxide, and a continuous and stable barrier layer is formed with the carbon layer, so that oxygen is isolated, and the combustion process is inhibited. The continuous burning time and smoldering time during burning are obviously reduced, the damage length is reduced, and the cotton fabric shows excellent flame retardant property.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Amino-terminated polysiloxanes: CAS number 106214-84-0. The structural formula is as follows:
。
2- [2- (2-chloroethoxy) ethoxy ] ethanol: CAS number 5197-62-6.
Phenylphosphonic acid dichloride: CAS number 824-72-6.
N- (tert-butoxycarbonyl) -L-tryptophan: CAS number 13139-14-5.
Toluene-2, 4-diisocyanate: CAS number 584-84-9.
Diphenylmethane-4, 4' -diisocyanate: CAS number 101-68-8.
Example 1
(1) 250mL of toluene solvent, 128mmol of 2- [2- (2-chloroethoxy) ethoxy ] ethanol and 130mmol of triethylamine are added into a flask, 60mol of phenylphosphonic dichloride is added at the temperature of minus 5 ℃, stirring is carried out for 30min, the temperature is increased to 25 ℃ for reaction for 6h, the solvent is removed by rotary evaporation, and the intermediate 1 is obtained by washing with petroleum ether and drying.
(2) Into a flask were added 120mL of 1, 4-dioxane, 40mmol of intermediate 1, 100mmol of N- (tert-butoxycarbonyl) -L-tryptophan, 112mmol of catalyst sodium hydroxide and 60mL of water, the temperature was raised to 90 ℃, the reaction was conducted for 12 hours, the 1, 4-dioxane was removed by rotary evaporation, ethyl acetate and water were added for extraction, the organic phase was dried, ethyl acetate was removed by rotary evaporation, after washing with petroleum ether, the intermediate product was added to 400mL of methylene chloride, 620mmol of trifluoroacetic acid (TFA) was added, the reaction was conducted for 4 hours at 35 ℃, the solvent was removed by rotary evaporation, and the product was recrystallized with ethyl acetate to obtain phenyl phosphate bis (ether tryptophan).
(3) 400mL of N, N-dimethylformamide, 75mmol of amino-terminated polysiloxane, 25mmol of phenyl phosphate di (ether tryptophan) compound and 100mmol of diphenylmethane-4, 4' -diisocyanate are added into a flask, nitrogen is introduced after stirring and dissolving, 0.12mmol of dibutyltin dilaurate is added for reaction at 70 ℃ for 2 hours, the solution is poured into ethanol for precipitation after cooling, and the solution is filtered, washed by ethanol and dried to obtain the organosilicon hydrophilic flame retardant finishing agent.
Example 2
(1) 300mL of methylene chloride solvent, 144mmol of 2- [2- (2-chloroethoxy) ethoxy ] ethanol and 144mmol of triethylamine are added into a flask, 60mol of phenylphosphonic dichloride is added at the temperature of 0 ℃, the mixture is stirred for 30min, the temperature is increased to 25 ℃ for reaction for 6h, the solvent is removed by rotary evaporation, and the mixture is washed by petroleum ether and dried to obtain the intermediate 1.
(2) To the flask were added 160mL of 1, 4-dioxane, 40mmol of intermediate 1, 100mmol of N- (t-butoxycarbonyl) -L-tryptophan, 102mmol of potassium hydroxide as a catalyst and 55mL of water, the mixture was heated to 75℃and reacted for 24 hours, the 1, 4-dioxane was removed by rotary evaporation, ethyl acetate and water were added for extraction, the organic phase was dried, ethyl acetate was removed by rotary evaporation, after washing with petroleum ether, the intermediate product was added to 400mL of methylene chloride, 620mmol of trifluoroacetic acid (TFA) was added, the reaction was carried out for 5 hours at 20℃and the solvent was removed by rotary evaporation, and the product was recrystallized from ethyl acetate to give phenyl phosphate bis (ether tryptophan).
(3) 300mL of N, N-dimethylformamide, 60mmol of amino-terminated polysiloxane, 40mmol of phenyl phosphate di (ether tryptophan) compound and 100mmol of diphenylmethane-4, 4' -diisocyanate are added into a flask, nitrogen is introduced after stirring and dissolving, 0.1mmol of dibutyltin dilaurate is added for reaction for 4 hours at 60 ℃, the solution is poured into ethanol for precipitation after cooling, and the solution is washed by ethanol and dried to obtain the organosilicon hydrophilic flame retardant finishing agent.
Example 3
(1) 180mL of chloroform solvent, 114mmol of 2- [2- (2-chloroethoxy) ethoxy ] ethanol and 120mmol of triethylamine are added into a flask, 60mol of phenylphosphonic dichloride is added at the temperature of 0 ℃, the mixture is stirred for 10min, the temperature is increased to 35 ℃ for reaction for 3h, the solvent is removed by rotary evaporation, and the mixture is washed by petroleum ether and dried to obtain the intermediate 1.
(2) 120mL of 1, 4-dioxane, 40mmol of intermediate 1, 80mmol of N- (tert-butoxycarbonyl) -L-tryptophan, 96mmol of sodium hydride as a catalyst and 32mL of water are added into a flask, the temperature is raised to 80 ℃, the reaction is carried out for 8 hours, the 1, 4-dioxane is removed by rotary evaporation, ethyl acetate and water are added for extraction, an organic phase is dried, the ethyl acetate is removed by rotary evaporation, after petroleum ether is washed, the intermediate product is added into 500mL of dichloromethane, 750mmol of trifluoroacetic acid (TFA) is added, the reaction is carried out for 3 hours at 25 ℃, the solvent is removed by rotary evaporation, and the product is recrystallized by ethyl acetate to obtain phenyl phosphate di (ether tryptophan) compound.
(3) 300mL of N, N-dimethylformamide, 40mmol of amino-terminated polysiloxane, 60mmol of phenyl phosphate di (ether tryptophan) compound and 100mmol of toluene-2, 4-diisocyanate are added into a flask, nitrogen is introduced after stirring and dissolution, 0.15mmol of dibutyltin dilaurate is added for reaction at 80 ℃ for 2 hours, the solution is poured into ethanol for precipitation after cooling, and the solution is filtered, washed by ethanol and dried to obtain the organosilicon hydrophilic flame retardant finishing agent.
Comparative example 1
400mL of N, N-dimethylformamide, 100mmol of amino-terminated polysiloxane and 100mmol of diphenylmethane-4, 4' -diisocyanate are added into a flask, nitrogen is introduced after stirring and dissolution, 0.12mmol of dibutyltin dilaurate is added for reaction, the reaction is carried out for 2 hours at 70 ℃, the solution is poured into ethanol for precipitation after cooling, filtering, ethanol washing and drying are carried out, and the finishing agent is obtained.
Comparative example 2
400mL of N, N-dimethylformamide, 100mmol of phenyl phosphate di (ether tryptophan) compound and 100mmol of diphenylmethane-4, 4' -diisocyanate are added into a flask, nitrogen is introduced after stirring and dissolution, 0.12mmol of dibutyltin dilaurate is added for reaction at 70 ℃ for 2 hours, the solution is cooled and poured into ethanol for precipitation, filtration, ethanol washing and drying are carried out, and the finishing agent is obtained.
Adding the finishing agent into water, stirring at high speed to prepare a solution with the mass concentration of 5-50g/L, adding the finishing agent into a centrifuge tube, rotating at 3000r/min for 30min, and observing the centrifugal stability of the emulsion.
Table 1 centrifugal stability test of emulsions
Examples 1 to 3 use amino-terminated polysiloxane, phenyl phosphate di (ether tryptophan) compound and diisocyanate compound to carry out polymerization reaction to obtain the organosilicon hydrophilic flame retardant finishing agent, and the molecular main chain contains hydrophilic ether bond, carboxyl and ureido groups, so that the dispersibility of the organosilicon finishing agent in water is improved, the solution is uniform and stable, and the centrifugal stability is excellent.
In comparative example 1, polymerization reaction is carried out by using amino-terminated polysiloxane and diphenylmethane-4, 4' -diisocyanate, and phenyl phosphate di (ether tryptophan) compound is not added, so that the obtained finishing agent does not contain hydrophilic ether bond, and when the mass concentration is large, the centrifugal stability of the finishing agent solution is poor, and demulsification is carried out.
Adding the finishing agent into water, stirring and dispersing at high speed to prepare finishing liquid with the mass concentration of 20g/L, adding cotton fabric into the finishing liquid, performing twice-soaking and twice-rolling finishing by adopting a rolling machine, controlling the temperature of the finishing liquid to be 40 ℃, and then baking at 180 ℃ to obtain 60 s.
With reference to AATCC 79-2000 standard water dripping method, the hydrophilicity of the cotton fabric after finishing is tested, and the longer the time, the better the hydrophilicity.
With reference to the standard of GB/T3819-1997, the fabric crease recovery angle of cotton fabric is measured by a fabric crease elastometer, and the larger the crease recovery angle is, the better the fabric flexibility and crease resistance are.
Table 2 cotton fabric performance test
The silicone hydrophilic flame retardant finishes of examples 1 to 3 contain ether linkages, carboxyl groups, ureido groups) Hydrophilic groups can effectively improve the hydrophilicity of the cotton fabric after finishing the cotton fabric, and are beneficial to improving the water absorption and moisture absorption properties of the cotton fabric. And the organic silicon chain segment of the main chain can ensure that the cotton fabric has good flexibility and wrinkle resistance while keeping the hydrophilicity.
Adding the finishing agent into water, stirring and dispersing at high speed to prepare finishing liquid with mass concentration of 20g/L and 50g/L respectively, adding cotton fabric into the finishing liquid, performing twice-soaking and twice-rolling finishing by adopting a rolling machine, controlling the temperature of the finishing liquid to be 40 ℃, and then baking at 180 ℃ to obtain 60 s.
The flame retardant property of the finished cotton fabric is tested according to the method of GB/T5455-2014.
Table 3 flame retardancy test of cotton fabrics
Table 4 flame retardant performance test of cotton fabrics
Examples 1 to 3 utilize amino-terminated polysiloxane, phenyl phosphate di (ether tryptophan) compound and diisocyanate compound to carry out polymerization reaction to obtain organosilicon hydrophilic flame retardant finishing agent, after finishing cotton fabric, phosphate, nitrogen-containing heterocycle and organosiloxane in the molecular main chain of the finishing agent form nitrogen-phosphorus-silicon synergistic flame retardant effect, nitrogen-phosphorus element can promote cotton fabric to form charcoal during combustion, organosilicon burns and pyrolyzes to generate inorganic silicon oxide, and forms a continuous and stable barrier layer with the charcoal layer, thereby being beneficial to isolating oxygen and inhibiting combustion process. The continuous burning time and smoldering time during burning are obviously reduced, the damage length is reduced, and the cotton fabric shows excellent flame retardant property.
The finishing agent of comparative example 1 is free of phenyl phosphate di (ether tryptophan) compound, contains no nitrogen-phosphorus flame retardant structure, and has the worst flame retardant property; comparative example 2 was not added with amino-terminated polysiloxane, did not form nitrogen-phosphorus-silicon synergistic flame retardant effect, and was poor in flame retardant property.
Claims (8)
1. The organosilicon hydrophilic flame retardant finishing agent is characterized by comprising the following raw materials in proportion of (0.4-0.75) mol (0.25-0.6) 1mol (0.001-0.0015) mol of amino-terminated polysiloxane, phenyl phosphate di (ether tryptophan) compound, diisocyanate compound and dibutyl tin dilaurate;
the structural formula of the phenyl phosphate di (ether tryptophan) compound is as follows:
；
the diisocyanate compound includes toluene-2, 4-diisocyanate and diphenylmethane-4, 4' -diisocyanate.
2. A method for preparing the silicone hydrophilic flame retardant finish according to claim 1, comprising the steps of: adding N, N-dimethylformamide, amino-terminated polysiloxane, phenyl phosphate di (ether tryptophan) compound and diisocyanate compound into a flask, stirring and dissolving, introducing nitrogen, adding dibutyltin dilaurate, reacting, cooling for precipitation, filtering, washing and drying to obtain the organosilicon hydrophilic flame-retardant finishing agent.
3. The method for preparing the organosilicon hydrophilic flame retardant finishing agent according to claim 2, wherein the reaction temperature is 60-80 ℃ and the reaction time is 2-4h.
4. The method for preparing the silicone hydrophilic flame retardant finishing agent according to claim 2, wherein the method for preparing the phenyl phosphate di (ether tryptophan) compound comprises the following steps:
(1) Adding a reaction solvent, 2- [2- (2-chloroethoxy) ethoxy ] ethanol and triethylamine into a flask, adding phenylphosphonic dichloride at the temperature of between-5 and 0 ℃, stirring for 10 to 30 minutes, heating to 25 to 35 ℃, reacting for 3 to 6 hours, removing the solvent by rotary evaporation, washing and drying to obtain an intermediate 1;
(2) Adding 1, 4-dioxane, an intermediate 1, N- (tert-butoxycarbonyl) -L-tryptophan, a catalyst and cosolvent water into a flask, heating to 75-90 ℃, reacting for 8-24 hours, removing the 1, 4-dioxane by rotary evaporation, extracting, washing, adding an intermediate product into dichloromethane, adding trifluoroacetic acid, reacting for 3-5 hours at 20-35 ℃, removing the solvent by rotary evaporation, and recrystallizing the product to obtain the phenyl phosphate di (ether tryptophan) compound.
5. The method for preparing a hydrophilic flame retardant silicone finish according to claim 4, wherein the ratio of the reaction solvent, 2- [2- (2-chloroethoxy) ethoxy ] ethanol, triethylamine, and phenylphosphonic acid dichloride in step (1) is (3-5) L (1.9-2.4) mol (2-2.4) 1mol.
6. The method for preparing the hydrophilic flame retardant finishing agent according to claim 5, wherein the reaction solvent comprises methylene chloride, chloroform and toluene.
7. The method for preparing a hydrophilic flame retardant silicone finish according to claim 4, wherein the ratio of 1, 4-dioxane, intermediate 1, N- (t-butoxycarbonyl) -L-tryptophan, catalyst and cosolvent water in step (2) is (3-4) L1 mol (2-2.5) mol (2.4-2.8) mol (0.8-1.5) L.
8. The method for preparing the silicone hydrophilic flame retardant finishing agent according to claim 7, wherein the catalyst comprises sodium hydride, sodium hydroxide and potassium hydroxide.
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