CN105884999A - Preparation method of modified cation waterborne polyurethane emulsion containing hydrophilic and hydrophobic side long chains and product thereof - Google Patents

Abstract

The invention relates to a preparation method and a product thereof of a modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains. The method comprises the following steps: raw material preparation; polyester diol dehydration pretreatment; polyester diol after dehydration pretreatment and terminal polysiloxane linear body, nonionic chain extender, functional chain extender, diisocyanate in Under the catalysis of the polymerization catalyst, the prepolymerization reaction is carried out to obtain the prepolymer; the prepolymer is reacted with the cationic chain extender and part of the diluent to obtain the intermediate; the intermediate is reacted with the silane coupling agent and emulsified to obtain the . The product is a main chain block polysiloxane, a polyester-type cationic water-based polyurethane containing both hydrophilic and hydrophobic long chains, which is branched with long-chain polyether and long-chain alkyl groups in side chains and connected to silane coupling agents at the end. Polymer material with strong film-forming ability. It has obvious water-repellent, anti-fouling and easy-to-decontamination capabilities when used as a coating film. It has excellent compatibility with cationic softeners and has excellent low-temperature softness. The product is safe, environmentally friendly, and easy to use.

Description

Preparation method and product of modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains

technical field

The invention relates to a functional polyurethane emulsion for finishing various types of textile substrates, fiber modification and functional finishing of textiles, in particular to a method for preparing a modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains and its products .

Background technique

Waterborne polyurethane polymer materials are often used in the finishing process of various substrates. In the textile field, water-based polyurethane is often used for finishing textile substrates, color fixation of dyed textiles, anti-pilling of knitted textiles, fiber surface modification and special functional finishing of various textiles. In order to solve the problems of traditional water-based polyurethane materials such as low-temperature hardness, fatigue, low elongation and poor functionality, water-based polyurethane materials modified with various functional monomers are becoming mainstream products in the industrial field. Functional water-based polyurethane polymers generally introduce various functional polymerized monomers, reactive functional molecules or functional groups into the polyurethane skeleton, terminal or side chain through chemical reactions such as block, grafting and end-capping, and then carry out self-polymerization. It is produced by emulsification and dispersion process.

The above raw materials can be attributed to polymerized monomers, modifiers, auxiliary agents and water, wherein: polymerized monomers include polyether polyols, polyester polyols, diisocyanates, anionic chain extenders, nonionic chain extenders; modified Agents include polysiloxane, polybutadiene, functional chain extenders, functional polyether polyols, silane coupling agents; auxiliary agents include polymerization catalysts, neutralizers, and diluents.

At present, the preparation method of functional polyurethane finishing agent comprises the following several kinds:

1. The preparation method of solvent-based polyurethane containing fluorine in the side chain. Its raw materials include polymerized monomers, modifiers, and auxiliary agents, wherein: polymerized monomers include polyether polyols and diisocyanates; modifiers are functional expansion agents. Chain agent; auxiliary agent is diluent.

Such as Kong Fanjia, Yang Xiaohui, Yao Hongxi, etc. "Synthesis and Characterization of Polyurethane Elastomers with Fluorinated Diamines as Chain Extenders" ("Polyurethane Industry" 2008 Volume 23 No. 1) published fluorine-containing binary A method for preparing an amine chain extender and a fluorine-containing polyurethane. Among its raw materials: the polymerization monomer is toluene diisocyanate and polytetrahydrofuran diol with a molecular weight of 1000; the modifier is self-made 2, 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane; auxiliary agent is diluent N,N-dimethylformamide.

The fluorine-containing diamine chain extender prepared by this method can effectively introduce fluorine-containing side chains into the polyurethane polymer, and the fluorine-containing polyurethane prepared by using it as the chain extender is due to the strong hydrogen bond between the hard segments and the dipole effect. , so that some segments in the micro-domain are arranged in an orderly manner to form a microcrystalline structure, so it has better heat resistance and oxidation resistance, and the tensile strength and fracture elongation of the material are also better. However, the preparation process of the fluorine-containing diamine chain extender is very complicated, the yield is low, and the cost is high. The cold resistance and low-temperature flexibility of the fluorine-containing polyurethane prepared by using it as a chain extender are also poor.

2. The preparation method of silicone-modified anionic waterborne polyurethane. Its raw materials include polymerized monomers, modifiers, auxiliary agents and water, wherein: polymerized monomers include polyester polyols, diisocyanates, and anionic chain extenders; The neutralizing agent is polysiloxane; the auxiliary agent includes polymerization catalyst, neutralizing agent and diluent.

Such as the preparation method of organosilicon-modified anionic water-based polyurethane disclosed by Wei Fangni, Xu Chengshu, Xing Jianwei and others in "Preparation of Modified Anionic Water-based Polyurethane" ("Journal of Xi'an Polytechnic University" 2012 Volume 26 No. 2), it Among the raw materials: the polymerization monomer is polypropylene carbonate diol, isophorone diisocyanate and dimethylol propionic acid; the modifier is amino polysiloxane; the auxiliary agent includes the polymerization catalyst dibutyl di Tin laurate, neutralizer triethylamine, diluent acetone; emulsification medium is deionized water.

The silicone-modified anionic waterborne polyurethane prepared by the method has good dispersion stability, and compared with the traditional anionic waterborne polyurethane, its application performance has been improved to a certain extent. However, the experiment used aminopolysiloxane macromolecule containing more side chain amino groups to modify anionic polyurethane prepolymer, which will inevitably lead to high viscosity and high viscosity of the reaction system due to the introduction of high crosslinking density into the polyurethane macromolecule. The reaction is difficult to control and requires strict control of reaction conditions (especially reaction temperature). At the same time, since the functional structure is a polyurethane skeleton structure rather than a side position of the polyurethane skeleton, the functionality of the material is not obvious. In addition, due to the high cross-linking of aminopolysiloxane, the silicone chains cannot be effectively enriched on the surface of the film during the thermosetting process of the polyurethane polymer material, resulting in a high 24-hour water absorption of the material film ( Reaching 20%), not only does not have the functional characteristics of water repellency and antifouling, but also leads to a significant reduction in the elasticity of the material under wet and cold conditions.

3. The preparation method of reactive silicone-modified cationic waterborne polyurethane. Its raw materials include polymerized monomers, modified monomers, auxiliary agents and water, wherein: polymerized monomers include diisocyanates, ionic chain extenders, nonionic Chain extender; modified monomers are polysiloxane, silane coupling agent, polybutadiene; auxiliary agents include neutralizing agent and diluent.

Such as Yang Wentang, Yan Qiao, Tang Li, etc. "Cationic Waterborne Polyurethane FS20566M" ("Polyurethane Industry" 2009, Volume 24, No. 5) discloses the preparation method of reactive silicone modified cationic waterborne polyurethane. Among its raw materials: Polymerization monomer is isophorone diisocyanate, ionic chain extender N-methyldiethanolamine, non-ionic chain extender trimethylolpropane; modified monomer is modified polysiloxane with terminal hydroxyalkyl , aminopropyltrimethoxysilane coupling agent, polybutadiene; auxiliary agent is neutralizing agent acetic acid, diluent N-methylpyrrolidone; emulsifying medium is deionized water.

This method uses completely non-hydrophilic polybutadiene as polyurethane soft monomer and uses non-ionic trifunctional small molecular monomer trimethylol propane as chain extender, resulting in difficult emulsification of the product and large emulsion particle size , The particle size distribution is wide and the stability is not high; due to the limitation of the hydrophilicity of monomers used in the product, and the high density of intramolecular crosslinking of macromolecules, it must have strong cationic properties, making the modified polyurethane large Molecules cannot effectively diffuse and adsorb to the fibers.

4. The preparation method of fluorine-containing anionic water-based polyurethane. Its raw materials include polymerized monomers, modifiers, auxiliary agents and water, wherein: polymerized monomers include polyether polyols, diisocyanates, anionic chain extenders, non-ionic chain extenders chain agent; modifying agent is polysiloxane, fluorine-containing polyether polyol; auxiliary agent includes polymerization catalyst, neutralizing agent and diluent.

Such as Zhang Yingqiang, Zhang Yuanyuan, Pan Yuepei et al. "Preparation and performance analysis of water-based fluorine-containing silicon polyurethane water dispersion" ("New Building Materials" 2012 No. 3) discloses the preparation method of fluorine-containing anionic water-based polyurethane, its Among the raw materials: polymerized monomers are polyether diol N210, 4,4-dicyclohexylmethane diisocyanate, dimethylolpropionic acid, trimethylolpropane, ethylenediamine; modifiers are fluorine-containing side chains Polyether polyol, hydroxypolysiloxane; auxiliary agent includes polymerization catalyst di-n-butyltin dilaurate, neutralizer triethylamine, diluent acetone; emulsification medium is deionized water.

The fluorine-containing anion waterborne polyurethane prepared by the method has significantly better acid resistance, alkali resistance and water resistance than common waterborne polyurethane. However, this preparation method uses a small molecule trifunctional chain extender to introduce cross-links into the polyurethane polymer, resulting in the reaction process being difficult to control due to the rapid increase in the viscosity of the system and high viscosity. The short-chain cross-linking is also not conducive to the enrichment of fluorine-containing water-repellent chain segments to the surface of the film. In addition, the hydroxyl silicone oil used in the formula is difficult to react with isocyanate groups to form effective chemical bonds with polyurethane polymers, resulting in severe polyurethane microphase separation and poor water resistance. At the same time, the molecular weight of fluorine-containing polyether polyols is large and the price is high, resulting in limited access to fluorine-containing functional side chains. All of these lead to the insignificant functionality of the material, and the water resistance, especially the alkali resistance, is not ideal.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for preparing a modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains and its products. The modified cationic water-based polyurethane emulsion product containing hydrophilic polyether side long chains and hydrophobic alkyl side long chains provided by the present invention has obvious functionality and is suitable for finishing processing or fiber modification of various textile substrates. It can also be used for functional finishing of textiles. By introducing a certain density of side long-chain polyether and side long-chain alkyl into the molecule of the material, and introducing a silane coupling agent at its end, the coating film has obvious water-repellent, antifouling and easy decontamination capabilities. It has excellent compatibility with cationic softeners, and has excellent low-temperature softening properties; the product is safe and environmentally friendly, and easy to use.

The technical solution adopted by the present invention to solve the problems of the technologies described above is:

The preparation method of the modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains is characterized in that it comprises the following steps:

(1) Preparation of raw materials: polymerized monomers, modifiers, auxiliary agents and water; wherein: polymerized monomers include diisocyanates, polyester diols, and chain extenders; modifiers are hydrocarbyl-terminated polysiloxane linear bodies, Silane coupling agent, functional chain extender; auxiliary agents include polymerization catalysts, molecular weight regulators, neutralizers, diluents; water;

Polyester diol is based on adipic acid-diethylene glycol-1,4-butanediol or adipic acid-neopentyl glycol or adipic acid-diethylene glycol or adipic acid with a molecular weight of 2000-3000 - one or two polyester diols of neopentyl glycol-1,4-butanediol;

The chain extender is a kind of nonionic chain extender 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol and cationic chain extender N-methyldiethanolamine, N - a mixture of butyldiethanolamine;

Hydrocarbyl-terminated polysiloxane linear body is a kind of hydroxyl-terminated polydimethylsiloxane with a molecular weight of 2000-2500 or α, ω-diaminopropyl-terminated polydimethylsiloxane with a molecular weight of 2000-2500 A type of oxane;

The silane coupling agent is γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, γ- A kind of aminopropylmethyldiethoxysilane;

The functional chain extender is a mixture of monoglyceride stearate and linear polyethylene glycol methyl ether with a molecular weight of 1000-1500;

The mole fractions of each component are: diisocyanate 26, polyester diol 4-6, non-ionic chain extender 5-7, cationic chain extender 6-9, hydrocarbon-terminated polysiloxane linear body 0-1, Silane coupling agent 6~8, stearic acid monoglyceride 0.5~1, linear polyethylene glycol methyl ether 0.5~1, wherein the mole fraction of polyester diol and the mole fraction of polysiloxane linear body with terminal hydrocarbon The sum is 4-6, the sum of the mole fractions of non-ionic chain extender, cationic chain extender, monoglyceride stearate, and linear polyethylene glycol methyl ether is 14-16, the mole fraction of molecular weight regulator The number is [26- mole fraction of silane coupling agent × 0.5- (mole fraction of polyester diol + mole fraction of polysiloxane linear body with terminal hydrocarbon group) - (mole fraction of non-ionic chain extender + cationic chain extension Mole fraction of agent + mole fraction of monoglyceride stearate + mole fraction of linear polyethylene glycol methyl ether)]×(0.5～0.9);

(2) the step of polyester diol dehydration pretreatment, this step carries out dehydration pretreatment polyester diol under vacuum, heating condition;

(3) The step of prepolymerization, this step will dehydration pretreated polyester diol and hydrocarbon-terminated polysiloxane linear body, nonionic chain extender, functional chain extender, diisocyanate under the catalysis of polymerization catalyst Carry out prepolymerization reaction to prepare modified polyurethane prepolymer containing hydrophilic and hydrophobic side long chains;

(4) The step of chain extension, which reacts the modified polyurethane prepolymer containing hydrophilic and hydrophobic side long chains with cationic chain extenders and partial diluents to obtain modified polyurethane prepolymers containing hydrophilic and hydrophobic side long chains. Cationic waterborne polyurethane intermediate;

(5) The step of end-capping, in this step, the modified cationic water-based polyurethane intermediate containing hydrophilic and hydrophobic side long chains is reacted with a silane coupling agent to prepare a modified cationic water-based polyurethane containing hydrophilic and hydrophobic side long chains. molecular;

(6) The step of emulsification, in which the modified cationic water-based polyurethane polymer containing hydrophilic and hydrophobic side long chains, neutralizing agent, remaining diluent, molecular weight modifier, and water are mixed and emulsified to obtain a mixture containing hydrophilic and hydrophobic side long chains. Modified cationic water-based polyurethane emulsion products with long chains on the hydrophobic side.

According to the above scheme, the diisocyanate is toluene diisocyanate or isophorone diisocyanate;

The polymerization catalyst is stannous octoate or dibutyltin dilaurate; the dosage of the polymerization catalyst is 0.03-0.06% of the total weight of the polymerization monomer;

The neutralizing agent is acetic acid, and the neutralizing agent is 1 to 1.2 times the weight of the cationic chain extender;

The diluent is one of acetone, methyl ethyl ketone, and methylpyrrolidone. The amount of the diluent in the chain extension step is such that the polymerization reaction can be carried out normally, and the amount of the diluent during the emulsification process is such that the emulsification process can be carried out normally;

The water is soft water with a total hardness of less than 50ppmCaO (ie 5 degrees), and the total amount of water and diluent can be adjusted so that the solid content of the product is 30±5%;

According to the above scheme; the molecular weight regulator is ethylenediamine or methylpentamethylenediamine.

In the above scheme, the temperature of vacuum dehydration in step (2) is 110-115° C., the degree of vacuum is -0.100-0.098 MPa, and the dehydration time is 80-90 minutes.

In the above scheme, the prepolymerization reaction temperature in step (3) is 85-95° C., and the reaction time is 150-200 min.

In the above scheme, the temperature of the chain extension reaction in step (4) is 50-60° C., and the reaction time is 20-30 minutes.

In the above scheme, the capping reaction temperature in step (5) is 50-60° C., and the reaction time is 40-60 minutes.

In the above scheme, the emulsification in step (6) is to add the remaining diluent at a system temperature of 40-50°C, stir and cool down to below 40°C; add a neutralizer, stir, and then add it to water and molecular weight Stir and emulsify in the mixed system of conditioner.

In the above scheme, the preparation method of the low-temperature high-elastic water-repellent and anti-pollution polyurethane finishing agent emulsion specifically includes the following steps:

(1) Prepare raw materials;

(2) Put the polyester diol into the reactor, heat it to 110-115°C, and treat it at a vacuum of -0.100-0.098MPa for 80-90min;

(3) Cool down the polyester diol reaction system after dehydration in step (2) to 70±5°C; put in polysiloxane linear body, non-ionic chain extender, functional chain extender, diisocyanate and Maintain stirring, control the temperature of the reaction system at 75-85°C, and put in the polymerization catalyst at a constant speed within 20-30 minutes;

Maintain the temperature of the reaction system at 75-85°C and maintain the stirring reaction, then heat the reaction system to raise the temperature and maintain stirring at 85-95°C, keep the temperature for 150-200 minutes, and prepare the modified polyurethane with long chains on the hydrophilic and hydrophobic sides Prepolymer;

(4)

Cool down the reaction system in step (3) to 40-50°C; uniformly add cationic chain extender within 30-40min, and maintain the reaction temperature at 40-50°C;

The heating reaction temperature is 50-60°C, and the stirring reaction is continued for 20-30 minutes. During this period, diluents not exceeding 70% of the total amount are added several times in a timely manner to control the viscosity of the reaction system and obtain long chains containing hydrophilic and hydrophobic sides. Modified cationic waterborne polyurethane intermediate;

(5) Maintain the temperature of the reaction system in step (4) at 50-60°C; uniformly add the silane coupling agent within 15-20 minutes, then maintain the temperature at 50-60°C, stir and react for 40-60 minutes to obtain a hydrophilic And modified cationic waterborne polyurethane polymer with long chain on the hydrophobic side;

(6)

(6.1) cooling the reaction system in step (5) to 40-50°C;

Add the remaining diluent, stir and cool down to below 40°C;

Add neutralizer, keep the system temperature at 40-45°C, stir for 15-20 minutes, and set aside;

(6.2) Add 20-35°C water and a molecular weight regulator into the emulsifier, stir to dissolve, and set aside;

(6.3) Increase the stirring speed of the emulsifier, add the reactants in the (6.1) reactor to the water in the emulsifier (6.2) within 10 to 30 minutes, and then keep stirring for 40 to 60 minutes; A modified cationic water-based polyurethane emulsion product containing hydrophilic and hydrophobic side long chains is obtained.

Provided is a modified cationic water-based polyurethane emulsion product containing hydrophilic and hydrophobic side long chains prepared according to the preparation method of the above-mentioned modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains.

Compared with the prior art, the inventive method has the following advantages and characteristics:

1. The present invention uses a functional chain extender with a small molecular weight and a functional side chain to introduce a functional side long chain into the polyurethane skeleton, and the prepared product is a main chain block polysiloxane, and the side chain branch is long Polyester-type cationic water-based polyurethane polymer materials containing both hydrophilic and hydrophobic long chains of polyether chains and long-chain alkyl groups connected to silane coupling agents at the end have strong film-forming ability. The hydrophilic and hydrophobic side long chains are simultaneously introduced into the side positions of the polymer skeleton of the polyurethane material of the present invention, which can better unify the contradictory functions of "anti-fouling" and "easy decontamination" on the same polymer material, The coating film of the polyurethane material has the dual functions of antifouling and easy decontamination. Water-repellent, anti-fouling, waterproof, and easy to decontaminate, and has excellent flexibility, low temperature resistance, water resistance, acid and alkali resistance, and solvent resistance. At the same time, the product can be conveniently used in the same bath with various cationic softeners.

2. The distribution of polysiloxane chain segments and polyurethane chain segments in the molecular main chain structure of the product prepared by the method of the present invention is uniform. Due to the pulling effect of chemical bonds, polysiloxane chains and polyurethane chains have good miscibility, which improves the water resistance and alkali resistance of the material film and significantly improves the soft feel of the film.

3. In the present invention, cross-linking is introduced into the modified polyurethane polymer by using polyalkoxysilane coupling agent to block the modified polyurethane polymer, so that the modified polyurethane polymer has excellent extensibility, elasticity and film-forming property. At the same time, the cross-linked structure can effectively inhibit the polysiloxane chains from aggregating during the heat-setting and cooling process and undergoing significant microphase separation with polyurethane, thereby ensuring the excellent water resistance of the material.

3. The step-by-step reaction process and the design of the feeding sequence in the method of the present invention can conveniently and effectively control the grafting amount and distribution of the functional side long chains of polyurethane polymers, ensure that the product has significant functionality, and is easy to implement and Manipulation, strong controllability to product structure; product does not contain emulsifier, good emulsion stability, low solvent content, safety and environmental protection, easy to use; product has good application performance and wide range of uses.

detailed description

Embodiment 1 The preparation method of the modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains of the present invention

The raw material of this preparation method comprises:

1. Polymerized monomer

Diisocyanate: 26.0mol (5779.5g) of isophorone diisocyanate

Polyester diol: Polyadipate-diethylene glycol-1,4-butanediol ester diol with a molecular weight of 2500 5.0mol (12500.0g)

Chain extender: non-ionic chain extender 1,4-butanediol 6.0mol (540.7g), cationic chain extender N-methyldiethanolamine 7.5mol (893.7g)

2. Modifier

Hydrocarbyl-terminated polysiloxane linear body: 0.5mol (1150.0g) of hydroxyl-terminated polydimethylsiloxane with a molecular weight of 2300

Silane coupling agent: γ-aminopropyltriethoxysilane 7.0mol (1549.6g)

Functional chain extender: 0.7 mol (251.0 g) of monoglyceride stearate, 0.7 mol (700.0 g) of linear polyethylene glycol methyl ether with a molecular weight of 1000

3. Adjuvant

Polymerization catalyst: stannous octoate (7.9g)

Neutralizer: acetic acid (983.1g)

Diluent: Acetone (7500.0g)

Molecular weight regulator: Ethylenediamine 1.26mol (75.7g)

4. Water: soft water with total hardness less than 50ppmCaO (46229.0g)

The concrete steps of this preparation method:

(1) the step of polyester diol dehydration pretreatment, this step carries out dehydration pretreatment polyester diol under vacuum, heating condition; Be specifically:

(1.1) polyester diol is dropped into reactor;

(1.2) Heat to 110°C and treat for 80min at a vacuum of -0.099MPa.

(2) The step of prepolymerization, which prepolymerizes the polyester diol after dehydration pretreatment with polysiloxane linear body, nonionic chain extender, functional chain extender, diisocyanate, and polymerization catalyst reaction to obtain a modified polyurethane prepolymer containing hydrophilic and hydrophobic side long chains; specifically:

(2.1) cooling the reaction system in step (1.2) to 70-75°C;

(2.2) Put in terminal hydrocarbon-based polysiloxane linear body, non-ionic chain extender, functional chain extender, diisocyanate and keep stirring, control the temperature of the reaction system at 80-85°C, and put in the polymerization catalyst at a constant speed within 20-25min ;

(2.3) Maintain the temperature of the reaction system at 80-85°C and maintain the stirring reaction for 20 minutes, then heat the reaction system and maintain stirring at 90-95°C, and keep the temperature for 160 minutes to prepare the modified compound containing long chains on the hydrophilic and hydrophobic sides. permanent polyurethane prepolymer.

(3) The step of chain extension, which reacts the modified polyurethane prepolymer containing hydrophilic and hydrophobic side long chains with cationic chain extender and part of the diluent to prepare the modified polyurethane prepolymer containing hydrophilic and hydrophobic side long chains. Cationic waterborne polyurethane intermediate; specifically:

(3.1) cooling the reaction system in step (2.3) to 40-45°C;

(3.2) Evenly add cationic chain extender within 35 to 40 minutes, and maintain the reaction temperature at 40 to 45°C;

(3.3) The heating reaction temperature is 50-55°C, and the stirring reaction is continued for 20 minutes. During this period, diluents not exceeding 70% of the total amount are added several times in a timely manner to control the viscosity of the reaction system. Chain modified cationic waterborne polyurethane intermediate.

(4) The end-capping step, which reacts the modified cationic water-based polyurethane intermediate containing hydrophilic and hydrophobic side long chains with a silane coupling agent to prepare a modified cationic water-based polyurethane containing hydrophilic and hydrophobic side long chains. molecule; specifically:

(4.1) maintaining the temperature of the reaction system in step (3.3) at 50 to 55°C;

(4.2) Add the silane coupling agent evenly within 20 minutes, then maintain the temperature at 50-55°C, and stir for 50 minutes to prepare a modified cationic waterborne polyurethane polymer containing long chains on the hydrophilic and hydrophobic sides.

(5) The step of emulsification, which is to mix and emulsify the modified cationic water-based polyurethane polymer containing hydrophilic and hydrophobic side long chains, neutralizing agent, remaining diluent, molecular weight modifier, and water to obtain Modified cationic water-based polyurethane emulsion products with long chains on the hydrophobic side. Specifically:

(5.1) cooling the reaction system in step (4.2) to 45-50°C;

(5.2) Add the remaining diluent, stir and cool down to below 40°C;

(5.3) Add neutralizer, keep the system temperature at 40-45°C, stir for 15-20min, and set aside;

(5.4) Add 20-35°C water and a molecular weight regulator into the emulsifier, stir to dissolve, and set aside;

(5.5) Increase the stirring speed of the emulsifier, add the reactants in the (5.3) reactor to the water in the emulsifier (5.4) within 20 minutes, and then keep stirring for 50-55 minutes;

(5.6) Stand still and defoam to prepare a modified cationic water-based polyurethane emulsion product containing hydrophilic and hydrophobic side long chains.

The application and usage of the product prepared by the method of the invention: it can be used for finishing processing or fiber modification of various textile substrates, and can also be used for functional finishing of textiles. In the air, the instantaneous contact angle between the product coating film and water can reach 130°, and the contact angle after equilibrium is not less than 115°; in water, water can spread on the product film, so the product has obvious water repellency, antifouling and easy Decontamination ability; the product has excellent compatibility with cationic softeners, and has excellent low-temperature softening properties; the product is safe and environmentally friendly, and easy to use.

Storage of the product prepared by the method of the present invention: the finished product must be sealed and preserved in a cool, dry place.

Embodiment 2 The preparation method of the modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains of the present invention

The raw material of this preparation method comprises:

1. Polymerized monomer

Diisocyanate: toluene diisocyanate 26.0mol (4527.9g)

Polyester diol: polyadipate-neopentyl glycol ester diol with a molecular weight of 2200 4.0mol (8800.0g)

Chain extender: non-ionic chain extender 1,6-hexanediol 6.5mol (767.0g), cationic chain extender N-methyldiethanolamine 6.0mol (715.0g)

2. Modifier

Hydrocarbyl-terminated polysiloxane linear body: 0mol (0g)

Silane coupling agent: γ-aminopropylmethyldiethoxysilane 6.0mol (1148.0g)

Functional chain extender: 0.5mol (179.3g) of monoglyceride stearate, 1.0mol (1200.0g) of linear polyethylene glycol methyl ether with a molecular weight of 1200

3. Adjuvant

Polymerization catalyst: stannous octoate (7.4g)

Neutralizer: acetic acid (715.0g)

Diluent: methyl ethyl ketone (5000g)

Molecular weight modifier: Ethylenediamine 2.50mol (150.3g)

4. Water: soft water with total hardness less than 50ppmCaO (29805.0g)

The concrete steps of this preparation method:

(1) the step of polyester diol dehydration pretreatment, this step carries out dehydration pretreatment polyester diol under vacuum, heating condition; Be specifically:

(1.1) polyester diol is dropped into reactor;

(1.2) Heat to 110°C and treat for 80min at a vacuum of -0.098MPa.

(2) The step of prepolymerization, which prepolymerizes the polyester diol after dehydration pretreatment with polysiloxane linear body, nonionic chain extender, functional chain extender, diisocyanate, and polymerization catalyst reaction to obtain a modified polyurethane prepolymer containing hydrophilic and hydrophobic side long chains; specifically:

(2.1) cooling the reaction system in step (1.2) to 67-72°C;

(2.2) Put in terminal hydrocarbon-based polysiloxane linear body, non-ionic chain extender, functional chain extender, diisocyanate and keep stirring, control the temperature of the reaction system at 75-80°C, and put in the polymerization catalyst at a constant speed within 30 minutes;

(2.3) Maintain the temperature of the reaction system at 75-80°C and maintain the stirring reaction for 20 minutes, then heat the reaction system and maintain stirring at 85-90°C, keep the reaction for 180 minutes, and prepare the modified compound containing long chains on the hydrophilic and hydrophobic sides. permanent polyurethane prepolymer.

(3) The step of chain extension, which reacts the modified polyurethane prepolymer containing hydrophilic and hydrophobic side long chains with cationic chain extender and part of the diluent to prepare the modified polyurethane prepolymer containing hydrophilic and hydrophobic side long chains. Cationic waterborne polyurethane intermediate; specifically:

(3.1) cooling the reaction system in step (2.3) to 45-50°C;

(3.2) Evenly add cationic chain extender within 40 minutes, and maintain the reaction temperature at 45-50°C;

(3.3) The heating reaction temperature is 53-58°C, and the stirring reaction is continued for 30 minutes. During this period, diluents not exceeding 70% of the total amount are added several times in a timely manner to control the viscosity of the reaction system. Chain modified cationic waterborne polyurethane intermediate.

(4) The end-capping step, which reacts the modified cationic water-based polyurethane intermediate containing hydrophilic and hydrophobic side long chains with a silane coupling agent to prepare a modified cationic water-based polyurethane containing hydrophilic and hydrophobic side long chains. molecule; specifically:

(4.1) maintaining the temperature of the reaction system in step (3.3) at 53 to 58°C;

(4.2) Add the silane coupling agent evenly within 15 minutes, then maintain the temperature at 53-58°C, and stir for 60 minutes to prepare a modified cationic waterborne polyurethane polymer containing long chains on the hydrophilic and hydrophobic sides.

(5) The step of emulsification, which is to mix and emulsify the modified cationic water-based polyurethane polymer containing hydrophilic and hydrophobic side long chains, neutralizing agent, remaining diluent, molecular weight modifier, and water to obtain Modified cationic water-based polyurethane emulsion products with long chains on the hydrophobic side. Specifically:

(5.1) cooling the reaction system in step (4.2) to 40-45°C;

(5.2) Add the remaining diluent, stir and cool down to below 40°C;

(5.3) Add a neutralizing agent, and maintain the system temperature at 40-45°C, stir for 15 minutes, and set aside;

(5.4) Add 20-35°C water and a molecular weight regulator into the emulsifier, stir to dissolve, and set aside;

(5.5) Increase the stirring speed of the emulsifier, add the reactant in the reactor (5.3) to the water in the emulsifier (5.4) within 10 minutes, and then keep stirring for 60 minutes;

(5.6) Stand still and defoam to prepare a modified cationic water-based polyurethane emulsion product containing hydrophilic and hydrophobic side long chains.

The application and usage of the product prepared by the method of the invention: it can be used for finishing processing or fiber modification of various textile substrates, and can also be used for functional finishing of textiles. In the air, the instantaneous contact angle between the product film and water can reach 120°, and the contact angle after equilibrium is not less than 105°; in water, water can spread on the product film, so the product has obvious water-repellent, anti-fouling and easy Decontamination ability; the product has excellent compatibility with cationic softeners, and has excellent low-temperature softening properties; the product is safe and environmentally friendly, and easy to use.

Storage of the product prepared by the method of the present invention: the finished product must be sealed and preserved in a cool, dry place.

Embodiment 3 The preparation method of the modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains of the present invention

The raw material of this preparation method comprises:

1. Polymerized monomer

Diisocyanate: 26.0mol (5779.5g) of isophorone diisocyanate

Polyester diol: Polyadipate-diethylene glycol ester diol with a molecular weight of 2700 5.1mol (13770.0g)

Chain extender: non-ionic chain extender neopentyl glycol 5.5mol (572.8g), cationic chain extender N-butyldiethanolamine 9.0mol (1451.2g)

2. Modifier

Hydrocarbyl-terminated polysiloxane linear body: 0.9mol (2250.0g) of α,ω-diaminopropyl-terminated polydimethylsiloxane with a molecular weight of 2500

Silane coupling agent: γ-aminopropyltriethoxysilane 8.0mol (1771.0g)

Functional chain extender: 1.0mol (358.6g) of monoglyceride stearate, 0.5mol (750.0g) of linear polyethylene glycol methyl ether with a molecular weight of 1500

3. Adjuvant

Polymerization catalyst: dibutyltin dilaurate (10.9g)

Neutralizer: acetic acid (1500.0g)

Diluent: Methylpyrrolidone (10000.0g)

Molecular weight regulator: 0mol (0g)

4. Water: soft water with total hardness less than 50ppmCaO (60727.0g)

The concrete steps of this preparation method:

(1) the step of polyester diol dehydration pretreatment, this step carries out dehydration pretreatment polyester diol under vacuum, heating condition; Be specifically:

(1.1) polyester diol is dropped into reactor;

(1.2) Heat to 115°C and treat for 90min at a vacuum of -0.098MPa.

(2) The step of prepolymerization, which prepolymerizes the polyester diol after dehydration pretreatment with polysiloxane linear body, nonionic chain extender, functional chain extender, diisocyanate, and polymerization catalyst reaction to obtain a modified polyurethane prepolymer containing hydrophilic and hydrophobic side long chains; specifically:

(2.1) cooling the reaction system in step (1.2) to 70-75°C;

(2.2) Put in terminal hydrocarbon-based polysiloxane linear body, non-ionic chain extender, functional chain extender, diisocyanate and keep stirring, control the temperature of the reaction system at 80-85°C, and put in the polymerization catalyst at a constant speed within 30 minutes;

(2.3) Maintain the temperature of the reaction system at 80-85°C and maintain the stirring reaction for 20 minutes, then heat the reaction system and maintain stirring at 87-92°C, and keep the temperature for 200 minutes to prepare the modified compound containing long chains on the hydrophilic and hydrophobic sides. permanent polyurethane prepolymer.

(3) The step of chain extension, which reacts the modified polyurethane prepolymer containing hydrophilic and hydrophobic side long chains with cationic chain extender and part of the diluent to prepare the modified polyurethane prepolymer containing hydrophilic and hydrophobic side long chains. Cationic waterborne polyurethane intermediate; specifically:

(3.1) cooling the reaction system in step (2.3) to 45-50°C;

(3.2) Evenly add cationic chain extender within 30 minutes, and maintain the reaction temperature at 45-50°C;

(3.3) The heating reaction temperature is 55-60°C, and the stirring reaction is continued for 30 minutes. During this period, diluents not exceeding 70% of the total amount are added several times in a timely manner to control the viscosity of the reaction system and obtain a long Chain modified cationic waterborne polyurethane intermediate.

(4) The end-capping step, which reacts the modified cationic water-based polyurethane intermediate containing hydrophilic and hydrophobic side long chains with a silane coupling agent to prepare a modified cationic water-based polyurethane containing hydrophilic and hydrophobic side long chains. molecule; specifically:

(4.1) maintaining the temperature of the reaction system in step (3.3) at 55 to 60°C;

(4.2) Evenly add the silane coupling agent within 15-20 minutes, then maintain the temperature at 55-60°C, and stir for 40 minutes to prepare a modified cationic water-based polyurethane polymer containing hydrophilic and hydrophobic side long chains.

(5) The step of emulsification, which is to mix and emulsify the modified cationic water-based polyurethane polymer containing hydrophilic and hydrophobic side long chains, neutralizing agent, remaining diluent, molecular weight modifier, and water to obtain Modified cationic water-based polyurethane emulsion products with long chains on the hydrophobic side. Specifically:

(5.1) cooling the reaction system in step (4.2) to 45-50°C;

(5.2) Add the remaining diluent, stir and cool down to below 40°C;

(5.3) Add neutralizer, and maintain the system temperature at 40-45°C, stir for 20 minutes, and set aside;

(5.4) Add 20-35°C water and a molecular weight regulator into the emulsifier, stir to dissolve, and set aside;

(5.5) Increase the stirring speed of the emulsifier, add the reactant in the (5.3) reactor to the water in the (5.4) emulsifier within 15 minutes, and then keep stirring for 40 minutes;

(5.6) Stand still and defoam to prepare a modified cationic water-based polyurethane emulsion product containing hydrophilic and hydrophobic side long chains.

The application and usage of the product prepared by the method of the invention: it can be used for finishing processing or fiber modification of various textile substrates, and can also be used for functional finishing of textiles. In the air, the instantaneous contact angle between the product coating film and water can reach 135°~140°, and the contact angle after equilibrium is not less than 125°; in water, water can spread on the product film, so the product has obvious water repellency and water resistance. Stain and easy decontamination capabilities; the product has excellent compatibility with cationic softeners, and has excellent low-temperature softening properties; the product is safe and environmentally friendly, and easy to use.

Storage of the product prepared by the method of the present invention: the finished product must be sealed and preserved in a cool, dry place.

The above is only a preferred example of the present invention. In fact, each specific raw material listed in the present invention, as well as the upper and lower limits and interval values of each raw material, and the upper and lower limits and interval values of process parameters (such as temperature, time, etc.) Value can realize the present invention, does not enumerate embodiment one by one here.

Therefore, the above embodiments are not intended to limit the present invention, and ordinary changes and substitutions made by those skilled in the art within the scope of the technical solution of the present invention shall be included in the protection scope of the present invention.

Claims (10)

1. the preparation method of the modified cationic water-based polyurethane emulsion that contains hydrophilic and hydrophobic side long chains, it is characterized in that: comprise the following steps: (1) Preparation of raw materials: polymerized monomers, modifiers, auxiliary agents and water; wherein: polymerized monomers include diisocyanates, polyester diols, and chain extenders; modifiers are hydrocarbyl-terminated polysiloxane linear bodies, Silane coupling agent, functional chain extender; auxiliary agents include polymerization catalysts, molecular weight regulators, neutralizers, diluents; water; Polyester diol is based on adipic acid-diethylene glycol-1,4-butanediol or adipic acid-neopentyl glycol or adipic acid-diethylene glycol or adipic acid with a molecular weight of 2000-3000 - one or two polyester diols of neopentyl glycol-1,4-butanediol; The chain extender is a kind of nonionic chain extender 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol and cationic chain extender N-methyldiethanolamine, N - a mixture of butyldiethanolamine; Hydrocarbyl-terminated polysiloxane linear body is a kind of hydroxyl-terminated polydimethylsiloxane with a molecular weight of 2000-2500 or α, ω-diaminopropyl-terminated polydimethylsiloxane with a molecular weight of 2000-2500 A type of oxane; The silane coupling agent is γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, γ- A kind of aminopropylmethyldiethoxysilane; The functional chain extender is a mixture of monoglyceride stearate and linear polyethylene glycol methyl ether with a molecular weight of 1000-1500; The mole fractions of each component are: diisocyanate 26, polyester diol 4-6, non-ionic chain extender 5-7, cationic chain extender 6-9, hydrocarbon-terminated polysiloxane linear body 0-1, Silane coupling agent 6~8, stearic acid monoglyceride 0.5~1, linear polyethylene glycol methyl ether 0.5~1, wherein the mole fraction of polyester diol and the mole fraction of polysiloxane linear body with terminal hydrocarbon The sum is 4-6, the sum of the mole fractions of non-ionic chain extender, cationic chain extender, monoglyceride stearate, and linear polyethylene glycol methyl ether is 14-16, the mole fraction of molecular weight regulator The number is [26- mole fraction of silane coupling agent × 0.5- (mole fraction of polyester diol + mole fraction of polysiloxane linear body with terminal hydrocarbon group) - (mole fraction of non-ionic chain extender + cationic chain extension Mole fraction of agent + mole fraction of monoglyceride stearate + mole fraction of linear polyethylene glycol methyl ether)]×(0.5～0.9); (2) the step of polyester diol dehydration pretreatment, this step carries out dehydration pretreatment polyester diol under vacuum, heating condition; (3) The step of prepolymerization, this step will dehydration pretreated polyester diol and hydrocarbon-terminated polysiloxane linear body, nonionic chain extender, functional chain extender, diisocyanate under the catalysis of polymerization catalyst Carry out prepolymerization reaction to prepare modified polyurethane prepolymer containing hydrophilic and hydrophobic side long chains; (4) The step of chain extension, which reacts the modified polyurethane prepolymer containing hydrophilic and hydrophobic side long chains with cationic chain extenders and partial diluents to obtain modified polyurethane prepolymers containing hydrophilic and hydrophobic side long chains. Cationic waterborne polyurethane intermediate; (5) The step of end-capping, in this step, the modified cationic water-based polyurethane intermediate containing hydrophilic and hydrophobic side long chains is reacted with a silane coupling agent to prepare a modified cationic water-based polyurethane containing hydrophilic and hydrophobic side long chains. molecular; (6) The step of emulsification, in which the modified cationic water-based polyurethane polymer containing hydrophilic and hydrophobic side long chains, neutralizing agent, remaining diluent, molecular weight modifier, and water are mixed and emulsified to obtain a mixture containing hydrophilic and hydrophobic side long chains. Modified cationic water-based polyurethane emulsion products with long chains on the hydrophobic side. 2. the preparation method of the modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chain according to claim 1, is characterized in that: described diisocyanate is toluene diisocyanate or isophorone diisocyanate; The polymerization catalyst is stannous octoate or dibutyltin dilaurate; the dosage of the polymerization catalyst is 0.03-0.06% of the total weight of the polymerization monomer; The neutralizing agent is acetic acid, and the neutralizing agent is 1 to 1.2 times the weight of the cationic chain extender; The diluent is one of acetone, methyl ethyl ketone, and methylpyrrolidone. The amount of the diluent in the chain extension step is such that the polymerization reaction can be carried out normally, and the amount of the diluent during the emulsification process is such that the emulsification process can be carried out normally; The water is soft water whose total hardness is less than 50ppmCaO, and the total amount of water and diluent can be used to adjust the solid content of the product to 30±5%. 3. the preparation method of the modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains according to claim 1, characterized in that: the molecular weight regulator is ethylenediamine or methylpentamethylenediamine. 4. The preparation method of the modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains according to claim 1, characterized in that: the temperature of step (2) vacuum dehydration is 110 ~ 115 ° C, and the degree of vacuum is - 0.100～-0.098MPa, dehydration time is 80～90min. 5. the preparation method of the modified cationic water-based polyurethane emulsion that contains hydrophilic and hydrophobic side long chains according to claim 1, is characterized in that: the prepolymerization reaction temperature of step (3) is 85～95 ℃, and the reaction time is 150～200min. 6. the preparation method of the modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains according to claim 1, is characterized in that: the chain extension reaction temperature of step (4) is 50～60 ℃, and the reaction time is 20-30min. 7. the preparation method of the modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains according to claim 1, is characterized in that: the end-capping reaction temperature of step (5) is 50～60 ℃, and the reaction time is 40～60min. 8. The preparation method of the modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains according to claim 1, characterized in that: the emulsification in step (6) is added at a system temperature of 40 to 50°C For the remaining diluent, stir and lower the temperature to below 40°C; add neutralizer, stir, then add it to the mixed system of water and molecular weight regulator, stir and emulsify. 9. the preparation method of the modified cationic water-based polyurethane emulsion that contains hydrophilic and hydrophobic side long chains according to claim 1, is characterized in that: specifically comprise the following steps: (1) Prepare raw materials; (2) Put the polyester diol into the reactor, heat it to 110-115°C, and treat it at a vacuum of -0.100-0.098MPa for 80-90min; (3) Cool down the polyester diol reaction system after dehydration in step (2) to 70±5°C; put in polysiloxane linear body, non-ionic chain extender, functional chain extender, diisocyanate and Maintain stirring, control the temperature of the reaction system at 75-85°C, and put in the polymerization catalyst at a constant speed within 20-30 minutes; Maintain the temperature of the reaction system at 75-85°C and maintain the stirring reaction, then heat the reaction system to raise the temperature and maintain stirring at 85-95°C, keep the temperature for 150-200 minutes, and prepare the modified polyurethane with long chains on the hydrophilic and hydrophobic sides Prepolymer; (4) Cool down the reaction system in step (3) to 40-50°C; uniformly add cationic chain extender within 30-40min, and maintain the reaction temperature at 40-50°C; The heating reaction temperature is 50-60°C, and the stirring reaction is continued for 20-30 minutes. During this period, diluents not exceeding 70% of the total amount are added several times in a timely manner to control the viscosity of the reaction system and obtain long chains containing hydrophilic and hydrophobic sides. Modified cationic waterborne polyurethane intermediate; (5) Maintain the temperature of the reaction system in step (4) at 50-60°C; uniformly add the silane coupling agent within 15-20 minutes, then maintain the temperature at 50-60°C, stir and react for 40-60 minutes to obtain a hydrophilic And modified cationic waterborne polyurethane polymer with long chain on the hydrophobic side; (6) (6.1) cooling the reaction system in step (5) to 40-50°C; Add the remaining diluent, stir and cool down to below 40°C; Add neutralizer, keep the system temperature at 40-45°C, stir for 15-20 minutes, and set aside; (6.2) Add 20-35°C water and a molecular weight regulator into the emulsifier, stir to dissolve, and set aside; (6.3) Increase the stirring speed of the emulsifier, add the reactants in the (6.1) reactor to the water in the emulsifier (6.2) within 10 to 30 minutes, and then keep stirring for 40 to 60 minutes; A modified cationic water-based polyurethane emulsion product containing hydrophilic and hydrophobic side long chains is obtained. 10. the modified cationic water-based polyurethane containing hydrophilic and hydrophobic side long chains obtained by the preparation method of the modified cationic water-based polyurethane emulsion containing hydrophilic and hydrophobic side long chains according to any one of claims 1-9 Lotion products.