CN109970945B - Organosilicon-modified weak zwitterionic polyurethane emulsion and preparation method thereof - Google Patents
Organosilicon-modified weak zwitterionic polyurethane emulsion and preparation method thereof Download PDFInfo
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- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
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- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/35—Abrasion, pilling or fibrillation resistance
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Abstract
The invention relates to the field of textiles and discloses an organosilicon modified weak zwitterionic polyurethane emulsion and a preparation method thereof. The preparation method comprises the following steps: preparing raw materials: polymerized monomers, modified monomers, auxiliary agents and water; pre-polymerization; chain extension; end capping; emulsifying to obtain the organosilicon modified weak zwitter-ion type polyurethane emulsion product. The preparation method has strong controllability and smooth process. The organosilicon modified weak zwitterionic polyurethane emulsion product prepared by the method can be widely used for functional finishing processing of various textile products, such as style and hand feeling, surface coating, fuzzing and pilling resistance, and the like. The polyurethane polymer is introduced with a proper amount of polyether side chains and a small amount of anion and cation groups, has excellent compatibility with various common textile chemicals, and is convenient and safe to use. Meanwhile, a proper amount of cross-linking type active end capping is introduced into the polyurethane polymer tail group, so that the adhesive film has enough elasticity, fine and smooth hand feeling and the style of silica gel.
Description
Technical Field
The invention relates to weak zwitterionic polyurethane emulsion for functional finishing processing of style, hand feeling, surface coating, fuzzing and pilling resistance and the like of various textiles, in particular to organosilicon modified weak zwitterionic polyurethane emulsion and a preparation method thereof.
Background
Aqueous polyurethane polymers are increasingly used for finishing of surface effects such as style, hand feeling, surface coating and pilling resistance of various textile products, and are one of the most important development directions of textile auxiliaries in recent years. Because the organosilicon modified polyurethane polymer has the characteristics of smoothness and softness of the organosilicon polymer and high elasticity and high elongation of the polyurethane polymer, the organosilicon modified polyurethane polymer becomes one of the most widely applied water-based polymer materials in the field of textile processing. However, the related products based on the prior art all have strong ionic property, and are all single anionic property or single cationic property, and the compatibility with common textile auxiliaries is poor, so that the applied technical process is complex, the effect is unstable, and the control is not easy. Meanwhile, organosilicon modified cationic waterborne polyurethane is generally poor in film-forming property and limited in application. These organosilicon modified polyurethane aqueous polymers are generally realized by copolymerization, block polymerization or modification methods such as grafting, end capping, interpenetrating networks, blending and the like of various monomers.
At present, the preparation method of the organosilicon modified polyurethane polymer emulsion comprises the following steps:
(1) the raw materials of the organosilicon modified anionic waterborne polyurethane comprise a polymeric monomer, a modifier, an auxiliary agent and water, wherein the polymeric monomer comprises polyester polyol, diisocyanate and an anionic chain extender; the modifier is polysiloxane; the adjuvants include a polymerization catalyst, a neutralizing agent, and a diluent.
For example, the preparation method of organosilicon modified anionic waterborne polyurethane disclosed in "preparation of modified anionic waterborne polyurethane" by weifanny, xucheng book, chenjianwa, etc. (proceedings of the university of siegan engineering, 26 vol. 2, 2012) comprises the following steps: the polymerization monomers are polypropylene carbonate dihydric alcohol, isophorone diisocyanate and dimethylolpropionic acid; the modifier is amino polysiloxane; the auxiliary agents comprise a polymerization catalyst of dibutyl tin dilaurate, a neutralizing agent of triethylamine and a diluting agent of acetone; the emulsifying medium is deionized water.
The organosilicon modified anionic waterborne polyurethane prepared by the method has good dispersion stability, and the application performance of the organosilicon modified anionic waterborne polyurethane is improved to a certain extent compared with unmodified anionic waterborne polyurethane. However, in the experiment, the amino polysiloxane polymer containing more side chain amino groups is adopted to modify the anionic polyurethane prepolymer, and the problems of high viscosity of a reaction system, high acetone dosage, difficult reaction control and the like are caused by introducing higher crosslinking density into the polyurethane polymer. Meanwhile, the product has strong anionic property, so that the compatibility and compatibility of the product with common textile auxiliaries are poor, and the application of the product is limited.
(2) The raw materials of the organosilicon modified nonionic polyurethane comprise a polymerization monomer, a modified monomer and an auxiliary agent, wherein the basic monomer comprises polyether glycol, diisocyanate and a non-son chain extender; the modified monomer is hydroxyl alkyl polysiloxane; the adjuvants include a basic monomer catalyst and an organic solvent.
For example, the preparation method of the organosilicon modified polyurethane disclosed in "synthesis of organosilicon modified polyurethane and its properties" by guoguifei, halihong, liu zheng et al (section 10 of 30 vol. 2009, the academy of textile sciences), comprises the following raw materials: the polymerization monomer is polypropylene glycol with molecular weight of 1000, isophorone diisocyanate, non-ionic chain extender 1, 4-butanediol and trimethylolpropane; the modified monomer is hydroxyl-terminated polydimethylsiloxane with molecular weight of 2000; the auxiliary agent is organic solvent butanone, butyl acetate and catalyst dibutyltin dilaurate.
Although the nonionic organosilicon modified polyurethane has good water resistance and compatibility, the nonionic organosilicon modified polyurethane is not easy to disperse and emulsify in a water phase due to extremely poor hydrophilicity, so that the use is inconvenient or the effect is poor. In addition, the organosilicon modified polyurethane prepared by the method has weak hydrophilicity and larger molecular weight, adopts micromolecule crosslinking with higher density, and has poor emulsion stability even if being forcedly emulsified, so the organosilicon modified polyurethane is not suitable for the production and processing of textile printing and dyeing products.
(3) The raw materials of the reactive organosilicon modified cationic waterborne polyurethane comprise a polymerization monomer, a modifier, an auxiliary agent and distilled water, wherein the polymerization monomer comprises hydroxyl-terminated polysiloxane and an aminosilane coupling agent; the modifier comprises polyolefin polyol, diisocyanate, a cationic chain extender and a nonionic chain extender; the auxiliary agents include quaternizing agents, neutralizing agents and diluents.
For example, a method for preparing a reactive organosilicon-modified cationic waterborne polyurethane disclosed in "cationic waterborne polyurethane FS 20566M" (product 5 of 24 vol. 2009, polyurethane industry) "issued by yan wentang, yan qiao, tang li, etc., comprises the following steps: the polymerization monomer comprises hydroxyl-terminated polysiloxane, aminopropyl trimethoxy silane coupling agent, isophorone diisocyanate, cationic chain extender N-methyldiethanolamine and nonionic chain extender trimethylolpropane; the modifier is polybutadiene diol; the auxiliary agents are a quaternization agent methyl iodide, a neutralizing agent acetic acid and a diluting agent N-methyl pyrrolidone.
In the method, completely non-hydrophilic polybutadiene diol is used as a soft polyurethane monomer, and a non-ionic trifunctional micromolecular monomer trimethylolpropane is used as a chain extender, so that the product is not easy to emulsify, and the emulsion has large particle size, wide particle size distribution and low stability; due to the poor hydrophilicity of the monomers used and the high molecular weight with high density of intramolecular cross-linking, it is necessary to have strong cationic properties, so that the high molecular weight cannot diffuse and adsorb to the fibers in large quantities. Meanwhile, the product is of a strong cationic quaternary ammonium salt type, and has poor compatibility and compatibility with common textile auxiliaries, so that the application of the product is limited.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: an organosilicon modified weak zwitter-ion type polyurethane emulsion and a preparation method thereof are provided. The preparation method has strong controllability and is easy to operate. The organosilicon modified weak zwitterionic polyurethane emulsion product prepared by the method can be widely used for functional finishing processing of various textile products, such as style and hand feeling, surface coating, fuzzing and pilling resistance, and the like. The modified polyurethane polymer is introduced with a proper amount of polyether side chains and a small amount of anion and cation groups, has good emulsion stability, has excellent compatibility with various common textile chemicals, and is convenient to use. Meanwhile, a small amount of cross-linking type active end-capping and micro-cross-linking are introduced into the polyurethane polymer tail group, and (or) the polyurethane polymer tail group has a long-chain cross-linking structure, so that the adhesive film has good elasticity, fine and smooth hand feeling and the style of silica gel.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of organosilicon modified weak zwitterionic polyurethane emulsion, which comprises the following steps:
(1) pre-polymerization: carrying out prepolymerization reaction on diisocyanate, polyester polyol and/or polyether polyol, a polymerization catalyst and optional hydroxyl-terminated polysiloxane to obtain a weak zwitter-ion type polyurethane prepolymer;
(2) chain extension: reacting the weak zwitter-ion type polyurethane prepolymer with a nonionic chain extender, an anionic chain extender and a part of diluent to prepare a weak zwitter-ion type polyurethane intermediate;
(3) end capping: reacting the weak zwitterionic polyurethane intermediate with a silane coupling agent to prepare an organic silicon modified weak zwitterionic polyurethane polymer;
(4) emulsification: mixing and emulsifying the organosilicon-modified weak zwitterionic polyurethane polymer, a neutralizing agent, the rest of diluent, a cationic chain extender and water to prepare organosilicon-modified weak zwitterionic polyurethane emulsion;
wherein the molar parts of the components are as follows: 2.5 parts of diisocyanate, 0-1 part of polyester polyol, 0-0.8 part of polyether polyol, 0.2-0.8 part of nonionic chain extender, 0.1-0.5 part of anionic chain extender, 0-0.15 part of hydroxyl-terminated polysiloxane, 0.4-0.8 part of silane coupling agent, wherein the molar fraction of the polyester polyol plus (the molar fraction of the polyether polyol is multiplied by 1.5) is 0.7-1.1 part;
the sum of the mole parts of polyester polyol, (the mole parts of polyether polyol multiplied by 1.5), the mole parts of nonionic chain extender, the mole parts of anionic chain extender and the mole parts of hydroxyl-terminated polysiloxane is 1.6-1.9;
the sum of the mole fraction of polyester polyol, (the mole fraction of polyether polyol multiplied by 1.5), the mole fraction of nonionic chain extender, the mole fraction of anionic chain extender, the mole fraction of hydroxyl-terminated polysiloxane and (the mole fraction of silane coupling agent multiplied by 0.5) is 1.9-2.2;
the mole fraction of the cationic chain extender is (2.5-polyester polyol mole fraction-polyether polyol mole fraction multiplied by 1.5-nonionic chain extender mole fraction-anionic chain extender mole fraction-hydroxyl terminated polysiloxane mole fraction-silane coupling agent mole fraction multiplied by 0.5) multiplied by (0.5-1.0);
the total using amount of diisocyanate, polyester polyol, polyether polyol, a nonionic chain extender, an anionic chain extender and a cationic chain extender is 100 parts by weight, and the using amount of the polymerization catalyst is 0.04-0.06 part by weight;
the dosage of the neutralizing agent is 0.6-0.9 time of the weight of the anionic chain extender;
the polyester polyol is adipic acid/diethylene glycol copolymer glycol with the water content not higher than 2 per mill and the molecular weight of 1500-3000 and/or adipic acid/1, 4-butanediol/diethylene glycol copolymer glycol with the molecular weight of 1500-3000;
the polyether polyol is ethylene oxide/propylene oxide copolymer triol with the water content not higher than 2 per mill and the molecular weight of 2000-4000;
the hydroxyl-terminated polysiloxane is hydroxyl-terminated polydimethylsiloxane with the molecular weight of 1500-3000;
the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane and gamma-aminopropylmethyldimethoxysilane;
the non-ionic chain extender is linear polyethylene glycol monomethyl ether with the molecular weight of 800-1200, or a mixture of the linear polyethylene glycol monomethyl ether with the molecular weight of 800-1200 and 1, 4-butanediol and/or neopentyl glycol;
the cationic chain extender is N-methyldiethanolamine and/or N-butyldiethanolamine.
Preferably, the operation process of step (1) is as follows:
(1.1) putting polyester polyol and/or polyether polyol and optional hydroxyl-terminated polysiloxane into a reactor, and heating to 70-80 ℃;
(1.2) adding diisocyanate and maintaining stirring, controlling the temperature of a reaction system to be 75-85 ℃, and reacting for 15-30 min;
(1.3) maintaining the temperature of the reaction system at 75-85 ℃, and feeding a polymerization catalyst at a constant speed within 10-20 min;
and (1.4) heating, controlling the temperature of a reaction system to be 85-95 ℃, and carrying out heat preservation reaction for 80-120 min to obtain the weak zwitterionic polyurethane prepolymer.
Preferably, the operation process of step (2) is as follows:
(2.1) cooling the system of the weak zwitterionic polyurethane prepolymer prepared in the step (1) to 75-85 ℃;
(2.2) uniformly adding a nonionic chain extender and an anionic chain extender within 20-30 min, and maintaining the temperature at 75-85 ℃;
and (2.3) controlling the reaction temperature to be 75-85 ℃, continuously stirring and reacting for 150-180 min, and adding a diluent with the weight not more than 80% of the total amount in multiple times in the stirring reaction process to control the viscosity of the reaction system so as to prepare the weak zwitterionic polyurethane intermediate.
Preferably, the operation process of step (3) is as follows:
(3.1) cooling the system of the weak zwitterionic polyurethane intermediate prepared in the step (2) to 55-65 ℃;
and (3.2) uniformly adding a silane coupling agent within 10-20 min, then maintaining the temperature at 55-65 ℃, and stirring for reacting for 50-70 min to prepare the organosilicon-modified weak zwitterionic polyurethane polymer.
Preferably, the operation process of step (4) is as follows:
(4.1) adding the rest of diluent into the organosilicon modified weak zwitterionic polyurethane polymer system prepared in the step (3), stirring and cooling to below 50 ℃;
(4.2) adding a neutralizing agent, keeping the temperature of the system at 40-50 ℃, and stirring for 15-20 min;
(4.3) adding water with the temperature of 20-35 ℃ and a cationic chain extender into an emulsifying machine, and stirring for dissolving;
(4.4) increasing the stirring speed of the emulsifying machine, adding the reactant in the reactor in the step (4.2) into the emulsifying machine in the step (4.3), and then maintaining stirring for 40-60 min;
and (4.5) standing and defoaming to prepare the organosilicon modified weak zwitterionic polyurethane emulsion product.
Preferably, the diisocyanate is isophorone diisocyanate.
Preferably, the polymerization catalyst is stannous octoate and/or dibutyltin dilaurate.
Preferably, the anionic chain extender is dimethylolpropionic acid and/or dimethylolbutyric acid.
Preferably, the diluent is at least one of acetone, methyl ethyl ketone and ethyl pyrrolidone.
Preferably, the neutralizing agent is triethylamine.
Preferably, the water used in step (4) is soft water having a total hardness of 50ppm caO or less.
Preferably, the amount of the water and the diluent is such that the solid content of the prepared organosilicon-modified weak zwitterionic polyurethane emulsion is 30-35%.
The invention also provides the organosilicon modified weak zwitterionic polyurethane emulsion prepared by the method.
Preferably, the solid content of the organosilicon-modified weak zwitterionic polyurethane emulsion is 30-35%.
Through the technical scheme, the method provided by the invention has the following advantages and characteristics:
(1) the macromolecule prepared by the preparation method of the organosilicon modified weak zwitterionic polyurethane emulsion is weak anion-cation zwitterionic, has excellent compatibility and compatibility with various textile chemicals, and has simple application process, wide application and strong adaptability.
(2) The preparation method of the organosilicon modified weak zwitter-ion type polyurethane emulsion introduces a proper amount of polyether side chains into a product high molecular structure, is easy to disperse and emulsify, and has good emulsion stability.
(3) The preparation method of the organosilicon modified weak zwitter-ion type polyurethane emulsion introduces a small amount of micro-crosslinking structures into the tail groups of the high polymers of the product, and (or) the organosilicon modified weak zwitter-ion type polyurethane emulsion has a long-chain crosslinking structure, solves the problem of poor film forming property of the weak ion type high polymers, and has good elasticity of the adhesive film, fine and smooth hand feeling and the style of silica gel.
(4) According to the preparation method of the organosilicon modified weak zwitter-ion type polyurethane emulsion, tertiary amine chain extenders with high activity are adopted to carry out in-bath chain extension on a small amount of reserved polyurethane isocyanate end groups in water, and the high viscosity phenomenon in the reaction process is avoided while cationic groups are introduced.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The preparation method of the organosilicon modified weak zwitterionic polyurethane emulsion comprises the following steps:
(1) pre-polymerization: carrying out prepolymerization reaction on diisocyanate, polyester polyol and/or polyether polyol, a polymerization catalyst and optional hydroxyl-terminated polysiloxane to obtain a weak zwitter-ion type polyurethane prepolymer;
(2) chain extension: reacting the weak zwitter-ion type polyurethane prepolymer with a nonionic chain extender, an anionic chain extender and a part of diluent to prepare a weak zwitter-ion type polyurethane intermediate;
(3) end capping: reacting the weak zwitterionic polyurethane intermediate with a silane coupling agent to prepare an organic silicon modified weak zwitterionic polyurethane polymer;
(4) emulsification: and mixing and emulsifying the organosilicon-modified weak zwitterionic polyurethane polymer, a neutralizing agent, the rest of diluent, a cationic chain extender and water to obtain the organosilicon-modified weak zwitterionic polyurethane emulsion.
In a more preferred embodiment, the operation process of step (1) is as follows:
(1.1) putting polyester polyol and/or polyether polyol and optional hydroxyl-terminated polysiloxane into a reactor, and heating to 70-80 ℃;
(1.2) adding diisocyanate and maintaining stirring, controlling the temperature of a reaction system to be 75-85 ℃, and reacting for 15-30 min;
(1.3) maintaining the temperature of the reaction system at 75-85 ℃, and feeding a polymerization catalyst at a constant speed within 10-20 min;
and (1.4) heating, controlling the temperature of a reaction system to be 85-95 ℃, and carrying out heat preservation reaction for 80-120 min to obtain the weak zwitterionic polyurethane prepolymer.
In a more preferred embodiment, the operation process of step (2) is as follows:
(2.1) cooling the system of the weak zwitterionic polyurethane prepolymer prepared in the step (1) to 75-85 ℃;
(2.2) uniformly adding a nonionic chain extender and an anionic chain extender within 20-30 min, and maintaining the temperature at 75-85 ℃;
and (2.3) controlling the reaction temperature to be 75-85 ℃, continuously stirring and reacting for 150-180 min, and adding a diluent with the weight not more than 80% of the total amount in multiple times in the stirring reaction process to control the viscosity of the reaction system so as to prepare the weak zwitterionic polyurethane intermediate.
In a preferred embodiment, the operation process of step (3) is as follows:
(3.1) cooling the system of the weak zwitterionic polyurethane intermediate prepared in the step (2) to 55-65 ℃;
and (3.2) uniformly adding a silane coupling agent within 10-20 min, then maintaining the temperature at 55-65 ℃, and stirring for reacting for 50-70 min to prepare the organosilicon-modified weak zwitterionic polyurethane polymer.
In a more preferred embodiment, the operation process of step (4) is as follows:
(4.1) adding the rest of diluent into the organosilicon modified weak zwitterionic polyurethane polymer system prepared in the step (3), stirring and cooling to below 50 ℃;
(4.2) adding a neutralizing agent, keeping the temperature of the system at 40-50 ℃, and stirring for 15-20 min;
(4.3) adding water with the temperature of 20-35 ℃ and a cationic chain extender into an emulsifying machine, and stirring for dissolving;
(4.4) increasing the stirring speed of the emulsifying machine, adding the reactant in the reactor in the step (4.2) into the emulsifying machine in the step (4.3), and then maintaining stirring for 40-60 min;
and (4.5) standing and defoaming to prepare the organosilicon modified weak zwitterionic polyurethane emulsion product.
In the method of the present invention, among the raw materials used, the polymeric monomers include diisocyanate, polyester polyol, polyether polyol, and chain extenders (i.e., nonionic chain extenders, anionic chain extenders, and cationic chain extenders); the modified monomer is a mixture of hydroxyl-terminated polysiloxane and a silane coupling agent or the silane coupling agent; the adjuvants include a polymerization catalyst, a neutralizing agent, and a diluent.
In a specific embodiment, the diisocyanate is isophorone diisocyanate.
In the process of the present invention, a polyester polyol, a polyether polyol or a mixture of both may be added in step (1). In a particular embodiment, only the polyester polyol or polyether polyol is added in step (1).
In the invention, the polyester polyol is adipic acid/diethylene glycol copolymer glycol with the water content not higher than 2 per mill and the molecular weight of 1500-3000 and/or adipic acid/1, 4-butanediol/diethylene glycol copolymer glycol with the molecular weight of 1500-3000. As specific examples, the polyester polyol is adipic acid/1, 4-butanediol/diethylene glycol copolymer glycol with water content of not more than 2% and molecular weight of 2500 or adipic acid/diethylene glycol copolymer glycol with water content of not more than 2% and molecular weight of 2000.
In the invention, the polyether polyol is ethylene oxide/propylene oxide copolymer triol with the water content not higher than 2 per mill and the molecular weight of 2000-4000. As a specific example, the polyether polyol is ethylene oxide/propylene oxide copolymer triol with the water content not higher than 2 per mill and the molecular weight of 3000.
In the method of the present invention, the chain extender includes a nonionic chain extender, an anionic chain extender, and a cationic chain extender. The non-ionic chain extender is linear polyethylene glycol monomethyl ether with the molecular weight of 800-1200, or a mixture of the linear polyethylene glycol monomethyl ether with the molecular weight of 800-1200 and 1, 4-butanediol and/or neopentyl glycol. In specific examples, the nonionic chain extender is linear polyethylene glycol methyl ether having a molecular weight of 1000, or a mixture of linear polyethylene glycol methyl ether having a molecular weight of 1000 and 1, 4-butanediol. In the invention, by adding the nonionic chain extender, a proper amount of polyether side chain can be introduced into a high molecular structure of a product, so that the prepared weak zwitterion type polyurethane emulsion product is easy to disperse and emulsify and has good emulsion stability.
The anionic chain extender may be dimethylolpropionic acid and/or dimethylolbutyric acid. In a specific example, the anionic chain extender is dimethylolpropionic acid or dimethylolbutyric acid.
The cationic chain extender is N-methyldiethanolamine and/or N-butyldiethanolamine. In the invention, the tertiary amine with higher activity is added as the chain extender in the bath, so that the chain extension in the bath can be effectively and controllably carried out on a small amount of reserved polyurethane isocyanate end groups, and the high viscosity phenomenon in the reaction process can be avoided while introducing the cationic group. In specific examples, the cationic chain extender is N-methyldiethanolamine or N-butyldiethanolamine.
In the method, the modifying monomer is a mixture of hydroxyl-terminated polysiloxane and a silane coupling agent or the silane coupling agent, wherein the hydroxyl-terminated polysiloxane is an optional added component. In the invention, a small amount of micro-crosslinking structures can be introduced into the tail group of the product macromolecule by adding the modified monomer silane coupling agent, and a long-chain crosslinking structure can be optionally introduced, so that the problem of poor film-forming property of the weak ionic macromolecule can be solved, and the adhesive film has good elasticity, fine and smooth hand feeling and has the style of silica gel.
In the method, the hydroxyl-terminated alkyl polysiloxane is hydroxyl-terminated alkyl polydimethylsiloxane with the molecular weight of 1500-3000. In specific examples, the terminal hydroxyalkyl polysiloxane is a terminal hydroxyalkyl polydimethylsiloxane having a molecular weight of 2000 or a terminal hydroxyalkyl polydimethylsiloxane having a molecular weight of 2500.
In the method, the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane and gamma-aminopropylmethyldimethoxysilane. In specific examples, the silane coupling agent is gamma-aminopropylmethyldiethoxysilane, or gamma-aminopropyltriethoxysilane.
In the method of the present invention, the auxiliary agents include a polymerization catalyst, a neutralizing agent, and a diluent. In the present invention, the polymerization catalyst may be conventionally selected in the art. In a specific embodiment, the polymerization catalyst is stannous octoate and/or dibutyltin dilaurate.
In a specific embodiment, the neutralizing agent is triethylamine.
In a specific embodiment, the diluent is at least one of acetone, methyl ethyl ketone, and ethyl pyrrolidone. In the present invention, the diluent is added in two steps, one part being added during the chain extension in step (2), and the remaining part being added during the emulsification in step (4). In the step (2) and the step (4), the diluent is used in an amount such that the polymerization reaction and the emulsification process can be normally performed. In a more preferred embodiment, the amount of diluent added in step (2) does not exceed 80% by weight, preferably from 60 to 80% by weight, of the total amount of diluent used, and the amount of diluent added in step (4) is from 20 to 40% by weight of the total amount of diluent used.
In a specific embodiment, the water used in step (4) is soft water having a total hardness of 50ppm cao or less, and specifically, may be, for example, 30 to 50ppm cao soft water.
In the method, the molar parts of the components used in the steps (1) to (4) are as follows: 2.5 parts of diisocyanate, 0-1 part of polyester polyol, 0-0.8 part of polyether polyol, 0.2-0.8 part of nonionic chain extender, 0.1-0.5 part of anionic chain extender, 0-0.15 part of hydroxyl-terminated polysiloxane, 0.4-0.8 part of silane coupling agent, and the molar fraction of polyester polyol plus (the molar fraction of polyether polyol is multiplied by 1.5) is 0.7-1.1.
Preferably, the sum of the mole parts of the polyester polyol, the mole parts of the polyether polyol multiplied by 1.5, the mole parts of the nonionic chain extender, the mole parts of the anionic chain extender and the mole parts of the hydroxyl-terminated polysiloxane is 1.6 to 1.9.
Preferably, the sum of the molar fraction of the polyester polyol, (the molar fraction of the polyether polyol × 1.5), the molar fraction of the nonionic chain extender, the molar fraction of the anionic chain extender, the molar fraction of the hydroxyl-terminated polysiloxane, and (the molar fraction of the silane coupling agent × 0.5) is 1.9 to 2.2.
Preferably, the mole fraction of the cationic chain extender is (2.5-polyester polyol mole fraction-polyether polyol mole fraction × 1.5-nonionic chain extender mole fraction-anionic chain extender mole fraction-hydroxyl terminated polysiloxane mole fraction-silane coupling agent mole fraction × 0.5) × (0.5-1.0).
In the method, the amount of the polymerization catalyst is 0.04-0.06 parts by weight based on 100 parts by weight of the total amount of diisocyanate, polyester polyol, polyether polyol, a nonionic chain extender, an anionic chain extender and a cationic chain extender.
In the method, the dosage of the neutralizing agent can be 0.6-0.9 time of the weight of the anionic chain extender.
In the method, the water and the diluent are preferably used in amounts such that the solid content of the prepared organosilicon-modified weak zwitterionic polyurethane emulsion is 30-35%.
The invention also provides the organosilicon modified weak zwitterionic polyurethane emulsion, wherein the organosilicon modified weak zwitterionic polyurethane emulsion is prepared by the method. The solid content of the organosilicon-modified weak zwitterionic polyurethane emulsion can be 30-35%.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The various starting materials and the amounts thereof used in the following examples 1-3 are shown in Table 1 below.
TABLE 1
Example 1
(1) Prepolymerization
(1.1) putting polyester polyol and hydroxyl-terminated polysiloxane into a reactor, and heating to 75 ℃;
(1.2) adding diisocyanate and maintaining stirring, controlling the temperature of a reaction system to be 80 ℃, and reacting for 20 min;
(1.3) maintaining the temperature of the reaction system at 80 ℃, and feeding a polymerization catalyst at a constant speed within 15 min;
and (1.4) heating and controlling the temperature of a reaction system to be 92 ℃, and carrying out heat preservation reaction for 90min to obtain the organic silicon modified weak zwitterionic polyurethane prepolymer.
(2) Chain extension
(2.1) cooling the reaction system in the step (1.4) to 85 ℃;
(2.2) uniformly adding a nonionic chain extender and an anionic chain extender within 20min, and maintaining the temperature at 85 ℃;
and (2.3) controlling the reaction temperature to be 85 ℃, continuously stirring and reacting for 170min, and adding a diluent which is not more than 80 percent of the total amount in time for multiple times to control the viscosity so as to prepare the organosilicon modified weak zwitterionic polyurethane intermediate.
(3) End capping
(3.1) reducing the temperature of the reaction system in the step (2.3) to 60 ℃;
and (3.2) uniformly adding a silane coupling agent within 15min, then maintaining the temperature at 60 ℃, and stirring for reacting for 60min to prepare the organosilicon-modified weak zwitterionic polyurethane polymer.
(4) Emulsification
(4.1) adding the rest part of the diluent into the reaction system in the step (3.2), stirring and cooling to 48 ℃;
(4.2) adding a neutralizing agent, maintaining the temperature of the system at 48 ℃, and stirring for 20 min;
(4.3) adding water with the temperature of 30 ℃ and a cationic chain extender into an emulsifying machine, and stirring for dissolving;
(4.4) increasing the stirring speed of the emulsifier, adding the reactant in the reactor in the step (4.2) into the emulsifier in the step (4.3), and then maintaining stirring for 50 min;
and (4.5) standing and defoaming to obtain an organosilicon modified weak zwitterionic polyurethane emulsion product A1.
The product application and use method of the organosilicon modified weak zwitterionic polyurethane emulsion product A1 is as follows: the product emulsion has good stability, excellent compatibility and compatibility with various common textile chemicals, and convenient use. The coating can be widely used for functional finishing processing of various textile products, such as style and hand feeling, surface coating, fuzzing and pilling resistance, and the like, and the coating has good elasticity, fine and smooth hand feeling and the style of silica gel.
The product storage of the organosilicon-modified weakly zwitterionic polyurethane emulsion product A1: the finished product should be stored in a shady, cool and dry place in a sealed way.
Example 2
(1) Prepolymerization
(1.1) putting polyether polyol into a reactor, and heating to 80 ℃;
(1.2) adding diisocyanate and maintaining stirring, controlling the temperature of a reaction system to be 85 ℃, and reacting for 20 min;
(1.3) maintaining the temperature of the reaction system at 85 ℃, and feeding a polymerization catalyst at a constant speed within 20 min;
and (1.4) heating and controlling the temperature of the reaction system to be 89 ℃, and carrying out heat preservation reaction for 100min to obtain the weak zwitterion type polyurethane prepolymer.
(2) Chain extension
(2.1) cooling the reaction system in the step (1.4) to 80 ℃;
(2.2) uniformly adding a nonionic chain extender and an anionic chain extender within 30min, and maintaining the temperature at 80 ℃;
and (2.3) controlling the reaction temperature to be 80 ℃, continuously stirring and reacting for 150min, and adding a diluent which is not more than 80 percent of the total amount in time for multiple times to control the viscosity so as to prepare the weak zwitterionic polyurethane intermediate.
(3) End capping
(3.1) reducing the temperature of the reaction system in the step (2.3) to 55 ℃;
and (3.2) uniformly adding a silane coupling agent within 15min, then maintaining the temperature at 55 ℃, and stirring for reacting for 60min to prepare the organosilicon-modified weak zwitterionic polyurethane polymer.
(4) Emulsification
(4.1) adding the rest part of the diluent into the reaction system in the step (3.2), stirring and cooling to 40 ℃;
(4.2) adding a neutralizing agent, maintaining the temperature of the system at 40 ℃, and stirring for 15 min;
(4.3) adding water with the temperature of 35 ℃ and a cationic chain extender into an emulsifying machine, and stirring for dissolving;
(4.4) increasing the stirring speed of the emulsifier, adding the reactant in the reactor in the step (4.2) into the emulsifier in the step (4.3), and then maintaining stirring for 60 min;
and (4.5) standing and defoaming to obtain an organosilicon modified weak zwitterionic polyurethane emulsion product A2.
The product application and use method of the organosilicon modified weak zwitterionic polyurethane emulsion product A2 is as follows: the product emulsion has good stability, excellent compatibility and compatibility with various common textile chemicals, and convenient use. The coating can be widely used for functional finishing processing of various textile products, such as style and hand feeling, surface coating, fuzzing and pilling resistance, and the like, and the coating has good elasticity, fine and smooth hand feeling and the style of silica gel.
The product storage of the organosilicon-modified weakly zwitterionic polyurethane emulsion product A2: the finished product should be stored in a shady, cool and dry place in a sealed way.
Example 3
(1) Prepolymerization
(1.1) putting polyester polyol and hydroxyl-terminated polysiloxane into a reactor, and heating to 70 ℃;
(1.2) adding diisocyanate and maintaining stirring, controlling the temperature of a reaction system to be 75 ℃, and reacting for 25 min;
(1.3) maintaining the temperature of the reaction system at 75 ℃, and feeding a polymerization catalyst at a constant speed within 20 min;
and (1.4) heating and controlling the temperature of the reaction system to be 87 ℃, and carrying out heat preservation reaction for 80min to obtain the organic silicon modified weak zwitterionic polyurethane prepolymer.
(2) Chain extension
(2.1) cooling the reaction system in the step (1.4) to 77 ℃;
(2.2) uniformly adding a nonionic chain extender and an anionic chain extender within 25min, and maintaining the temperature at 77 ℃;
and (2.3) controlling the reaction temperature to be 77 ℃, continuously stirring and reacting for 170min, and adding a diluent which is not more than 80 percent of the total amount in time for multiple times to control the viscosity so as to prepare the organosilicon modified weak zwitterionic polyurethane intermediate.
(3) End capping
(3.1) reducing the temperature of the reaction system in the step (2.3) to 58 ℃;
and (3.2) uniformly adding a silane coupling agent within 15min, then maintaining the temperature at 58 ℃, and stirring for reacting for 60min to prepare the organosilicon-modified weak zwitterionic polyurethane polymer.
(4) Emulsification
(4.1) adding the rest diluent into the reaction system in the step (3.2), stirring and cooling to 45 ℃;
(4.2) adding a neutralizing agent, maintaining the temperature of the system at 45 ℃, and stirring for 15 min;
(4.3) adding water with the temperature of 30 ℃ and a cationic chain extender into an emulsifying machine, and stirring for dissolving;
(4.4) increasing the stirring speed of the emulsifier, adding the reactant in the reactor in the step (4.2) into the emulsifier in the step (4.3), and then maintaining stirring for 40 min;
and (4.5) standing and defoaming to obtain an organosilicon modified weak zwitterionic polyurethane emulsion product A3.
The product application and use method of the organosilicon modified weak zwitterionic polyurethane emulsion product A3 is as follows: the product emulsion has good stability, excellent compatibility and compatibility with various common textile chemicals, and convenient use. The coating can be widely used for functional finishing processing of various textile products, such as style and hand feeling, surface coating, fuzzing and pilling resistance, and the like, and the coating has good elasticity, fine and smooth hand feeling and the style of silica gel.
The product storage of the organosilicon-modified weakly zwitterionic polyurethane emulsion product A3: the finished product should be stored in a shady, cool and dry place in a sealed way.
Comparative example 1
A weakly zwitterionic polyurethane emulsion was prepared according to the method of example 2, except that no silane coupling agent was added during the end-capping in step (3), thereby obtaining weakly zwitterionic polyurethane emulsion product D1.
The product application and use method of the weak zwitterionic polyurethane emulsion product D1 is as follows: the product emulsion has high viscosity and good stability; the adhesive film has general flexibility, good elasticity, good compatibility and compatibility with various common textile chemicals, and convenient use. Can be widely used for the style, hand feeling and surface coating processing of various textile products.
Comparative example 2
A polyurethane emulsion was prepared by following the procedure of example 2, except that no cationic chain extender was added during the emulsification of step (4), thereby obtaining a polyurethane emulsion product D2.
The product application and usage of the polyurethane emulsion product D2 are as follows: the product emulsion has high viscosity and good stability; the adhesive film has general flexibility, good elasticity, and good compatibility and compatibility with various common anionic textile chemicals. Can be widely used for the surface finishing, the anti-pilling and other functional finishing processing of various textile products.
Test example
(1) Detecting the solid contents of the polyurethane emulsion products A1-A3 and D1-D2 according to the method of GB/T2793-1995;
(2) polyurethane emulsion products A1-A3 and D1-D2 have emulsion stability measured in terms of emulsion average particle size.
The results of the measurements are shown in Table 2 below.
TABLE 2
| Example numbering | Polyurethane emulsion products | Solid content of emulsion | Average particle diameter of emulsion |
| Example 1 | A1 | 33％ | 71nm |
| Example 2 | A2 | 33％ | 87nm |
| Example 3 | A3 | 34％ | 63nm |
| Comparative example 1 | D1 | 30％ | 113nm |
| Comparative example 2 | D2 | 30％ | 127nm |
As can be seen from the results in Table 2, the organosilicon modified weak zwitterionic polyurethane emulsion product prepared by the method of the invention has better emulsion stability.
The above description is only a preferred example of the present invention, and actually, the specific raw materials listed in the present invention, the upper and lower limits and interval values of each raw material, and the upper and lower limits and interval values of the process parameters (such as temperature, time, etc.) can all implement the present invention, and the examples are not listed here.
Therefore, the above embodiments are not intended to limit the present invention, and general changes and substitutions by those skilled in the art within the technical scope of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. A preparation method of organosilicon modified weak zwitterionic polyurethane emulsion is characterized by comprising the following steps:
(1) pre-polymerization: carrying out prepolymerization reaction on diisocyanate, polyester polyol and/or polyether polyol, a polymerization catalyst and optional hydroxyl-terminated polysiloxane to obtain a polyurethane prepolymer;
(2) chain extension: reacting the polyurethane prepolymer with a nonionic chain extender, an anionic chain extender and a part of diluent to prepare a polyurethane intermediate;
(3) end capping: reacting the polyurethane intermediate with a silane coupling agent to prepare an organic silicon modified polyurethane polymer;
(4) emulsification: mixing and emulsifying the organosilicon-modified polyurethane polymer, a neutralizing agent, the rest of diluent, a cationic chain extender and water to prepare organosilicon-modified weak zwitterionic polyurethane emulsion;
wherein the molar parts of the components are as follows: 2.5 parts of diisocyanate, 0-1 part of polyester polyol, 0-0.8 part of polyether polyol, 0.2-0.8 part of nonionic chain extender, 0.1-0.5 part of anionic chain extender, 0-0.15 part of hydroxyl-terminated polysiloxane, 0.4-0.8 part of silane coupling agent, wherein the molar fraction of the polyester polyol plus (the molar fraction of the polyether polyol is multiplied by 1.5) is 0.7-1.1 part;
the sum of the mole parts of polyester polyol, (the mole parts of polyether polyol multiplied by 1.5), the mole parts of nonionic chain extender, the mole parts of anionic chain extender and the mole parts of hydroxyl-terminated polysiloxane is 1.6-1.9;
the sum of the mole fraction of polyester polyol, (the mole fraction of polyether polyol multiplied by 1.5), the mole fraction of nonionic chain extender, the mole fraction of anionic chain extender, the mole fraction of hydroxyl-terminated polysiloxane and (the mole fraction of silane coupling agent multiplied by 0.5) is 1.9-2.2;
the mole fraction of the cationic chain extender is (2.5-polyester polyol mole fraction-polyether polyol mole fraction multiplied by 1.5-nonionic chain extender mole fraction-anionic chain extender mole fraction-hydroxyl terminated polysiloxane mole fraction-silane coupling agent mole fraction multiplied by 0.5) multiplied by (0.5-1.0);
the total using amount of diisocyanate, polyester polyol, polyether polyol, a nonionic chain extender, an anionic chain extender and a cationic chain extender is 100 parts by weight, and the using amount of the polymerization catalyst is 0.04-0.06 part by weight;
the dosage of the neutralizing agent is 0.6-0.9 time of the weight of the anionic chain extender;
the polyester polyol is adipic acid/diethylene glycol copolymer glycol with the water content not higher than 2 per mill and the molecular weight of 1500-3000 and/or adipic acid/1, 4-butanediol/diethylene glycol copolymer glycol with the molecular weight of 1500-3000;
the polyether polyol is ethylene oxide/propylene oxide copolymer triol with the water content not higher than 2 per mill and the molecular weight of 2000-4000;
the hydroxyl-terminated polysiloxane is hydroxyl-terminated polydimethylsiloxane with the molecular weight of 1500-3000;
the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane and gamma-aminopropylmethyldimethoxysilane;
the non-ionic chain extender is linear polyethylene glycol monomethyl ether with the molecular weight of 800-1200, or a mixture of the linear polyethylene glycol monomethyl ether with the molecular weight of 800-1200 and 1, 4-butanediol and/or neopentyl glycol;
the cationic chain extender is N-methyldiethanolamine and/or N-butyldiethanolamine.
2. The method of claim 1, wherein the operation procedure of step (1) is as follows:
(1.1) putting polyester polyol and/or polyether polyol and optional hydroxyl-terminated polysiloxane into a reactor, and heating to 70-80 ℃;
(1.2) adding diisocyanate and maintaining stirring, controlling the temperature of a reaction system to be 75-85 ℃, and reacting for 15-30 min;
(1.3) maintaining the temperature of the reaction system at 75-85 ℃, and feeding a polymerization catalyst at a constant speed within 10-20 min;
and (1.4) heating, controlling the temperature of a reaction system to be 85-95 ℃, and carrying out heat preservation reaction for 80-120 min to obtain the polyurethane prepolymer.
3. The method of claim 1, wherein the operation procedure of step (2) is as follows:
(2.1) cooling the system of the polyurethane prepolymer prepared in the step (1) to 75-85 ℃;
(2.2) uniformly adding a nonionic chain extender and an anionic chain extender within 20-30 min, and maintaining the temperature at 75-85 ℃;
and (2.3) controlling the reaction temperature to be 75-85 ℃, continuously stirring and reacting for 150-180 min, and adding a diluent which is not more than 80 wt% of the total amount in multiple times in the stirring reaction process to control the viscosity of the reaction system so as to prepare the polyurethane intermediate.
4. The method of claim 1, wherein the operation procedure of step (3) is as follows:
(3.1) cooling the system of the polyurethane intermediate prepared in the step (2) to 55-65 ℃;
and (3.2) uniformly adding a silane coupling agent within 10-20 min, then maintaining the temperature at 55-65 ℃, and stirring for reacting for 50-70 min to prepare the organic silicon modified polyurethane polymer.
5. The method of claim 1, wherein the operation procedure of step (4) is as follows:
(4.1) adding the rest of diluent into the organosilicon modified polyurethane polymer system prepared in the step (3), stirring and cooling to below 50 ℃;
(4.2) adding a neutralizing agent, keeping the temperature of the system at 40-50 ℃, and stirring for 15-20 min;
(4.3) adding water with the temperature of 20-35 ℃ and a cationic chain extender into an emulsifying machine, and stirring for dissolving;
(4.4) increasing the stirring speed of the emulsifying machine, adding the reactant in the reactor in the step (4.2) into the emulsifying machine in the step (4.3), and then maintaining stirring for 40-60 min;
and (4.5) standing and defoaming to prepare the organosilicon modified weak zwitterionic polyurethane emulsion product.
6. A process according to any one of claims 1 to 5, characterised in that the diisocyanate is isophorone diisocyanate.
7. A process according to any one of claims 1 to 5, characterised in that the polymerisation catalyst is stannous octoate and/or dibutyltin dilaurate.
8. A method according to any one of claims 1 to 5, characterised in that the anionic chain extender is dimethylolpropionic acid and/or dimethylolbutyric acid.
9. The method according to any one of claims 1 to 5, wherein the diluent is at least one of acetone, methyl ethyl ketone and ethyl pyrrolidone.
10. The method of any one of claims 1 to 5, wherein the neutralizing agent is triethylamine.
11. The process according to any one of claims 1 to 5, wherein the water used in step (4) is soft water having a total hardness of 50ppm or less.
12. The method according to any one of claims 1 to 5, wherein the water and the diluent are used in such an amount that the prepared organosilicon-modified weakly zwitterionic polyurethane emulsion has a solid content of 30 to 35%.
13. An organosilicon-modified weakly zwitterionic polyurethane emulsion, characterized in that it is obtainable by a process according to any one of claims 1 to 12.
14. The silicone-modified weakly zwitterionic polyurethane emulsion of claim 13, wherein the silicone-modified weakly zwitterionic polyurethane emulsion has a solid content of 30-35%.
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