CN109232824B - Cationic polyurethane modified polyacrylate emulsion with crosslinked core-shell structure and preparation method thereof - Google Patents
Cationic polyurethane modified polyacrylate emulsion with crosslinked core-shell structure and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
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- C—CHEMISTRY; METALLURGY
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- 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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Abstract
The invention relates to the field of high-molecular adhesives, in particular to a cationic polyurethane modified polyacrylate emulsion with a cross-linked core-shell structure and a preparation method thereof. The preparation method comprises the following steps: in the presence of a polyurethane catalyst, reacting a PU active prepolymer monomer to obtain a PU active prepolymer; mixing the PU active prepolymer, part of polyacrylate monomer raw materials, part of emulsifier, acetic acid and water to obtain PUm active prepolymer emulsion; mixing the rest of polyacrylate monomer raw material, the rest of emulsifier and water, stirring and emulsifying to obtain PA pre-emulsion; in the presence of an initiator, carrying out prepolymerization reaction on the PA pre-emulsion, and then adding the PUm active prepolymer emulsion to carry out polymerization reaction. The adhesive film formed by the polyurethane modified polyacrylate emulsion prepared by the invention has good water resistance, alkali resistance, compatibility with a softening agent and moderate film forming speed.
Description
Technical Field
The invention relates to the field of high-molecular adhesives, in particular to a cationic polyurethane modified polyacrylate emulsion with a cross-linked core-shell structure and a preparation method thereof.
Background
Compared with the anionic polyurethane modified polyacrylate (anionic PUA), the cationic polyurethane modified polyacrylate (cationic PUA) has the advantages of obviously better film forming fullness and flexibility, strong alkali corrosion resistance, good washing fastness and excellent compatibility with a softening agent in textile printing and dyeing processing. In addition, the cationic polyurethane modified polyacrylate emulsion has excellent adhesion, weather resistance and low temperature resistance, and can be widely used in the fields of textile adhesion and paint dyeing and the surface anti-fuzzing and anti-pilling finishing of textiles.
At present, most of textile adhesives are anionic polyacrylate or polyvinyl acetate types, and have the problems of high hardness, poor elasticity, poor extensibility and the like, particularly the problems of easy demulsification, equipment contamination, difficult cleaning and the like due to strong hydrophobicity and quick film forming. In addition, the adhesives are not suitable for pigment dyeing of textiles due to high requirements on fastness and soft hand feeling. Although the polyacrylate modified by organosilicon and polyurethane can improve the performances of polyacrylate to some extent, the products prepared by the prior art have poor compatibility of polyurethane and polyacrylate structure, too low grafting amount of polyurethane, lack of structural hierarchy and few cationic products. Meanwhile, the product mostly has a linear structure, and the cohesiveness, the film forming capability, the solvent resistance and the flexibility of the adhesive film of the product are not satisfactory, so that the practical application of the product is limited.
Disclosure of Invention
The invention aims to provide a cationic polyurethane modified polyacrylate emulsion with a cross-linked core-shell structure and a preparation method thereof. The cationic polyurethane modified polyacrylate has higher crosslinking degree, obviously improves the compatibility of a polyurethane structure and a polyacrylate structure, has high grafting amount of polyurethane and an obvious hierarchical structure, has excellent water resistance and alkali resistance of an adhesive film, has excellent compatibility with a common softener, and is soft in hand feeling and good in elasticity of an adhesive fabric.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a cationic polyurethane-modified polyacrylate emulsion having a crosslinked core-shell structure, the method comprising the steps of:
(1) in the presence of a polyurethane catalyst, reacting PU reactive prepolymer monomers, namely, hydroxyalkyl polysiloxane, polytetrahydrofuran, isophorone diisocyanate, trimethylolpropane monoallyl ether, 1, 4-butanediol, polyethylene glycol monomethyl ether, N-methyldiethanolamine and hydroxyethyl methacrylate in the ratio of (0.08-0.3): (0.2-0.4): 3.33: (0.9-1.1): (0.4-0.6): (0.1-0.3): (0.6-1): (0.6-1.1), wherein the molar ratio of the sum of the hydroxyalkyl polysiloxane, the polytetrahydrofuran, the 1, 4-butanediol, the polyethylene glycol methyl ether and the N-methyldiethanolamine to the isophorone diisocyanate is (1.9-2.1): 3.33, the molar ratio of the sum of hydroxyalkylpolysiloxane, polytetrahydrofuran, trimethylolpropane monoallyl ether, 1, 4-butanediol, polyethylene glycol monomethyl ether and N-methyldiethanolamine to isophorone diisocyanate does not exceed 3: 3.33, obtaining a PU active prepolymer;
(2) mixing the PU active prepolymer, part of polyacrylate monomer raw materials, part of emulsifier, acetic acid and water to obtain PUm active prepolymer emulsion;
(3) mixing the rest of polyacrylate monomer raw material, the rest of emulsifier and water, stirring and emulsifying to obtain PA pre-emulsion; in the presence of an initiator, carrying out prepolymerization reaction on the PA pre-emulsion, and then adding the PUm active prepolymer emulsion to carry out polymerization reaction.
The invention also provides the cationic polyurethane modified polyacrylate emulsion with the cross-linked core-shell structure, which is prepared by the method.
Compared with the prior art, the adhesive film formed by the cationic polyurethane modified polyacrylate emulsion with the cross-linked core-shell structure has better water resistance and alkali resistance. Specifically, the 24-hour water-resistant weight gain rate of the adhesive film is less than 15% (room temperature pure water), the 24-hour acid-resistant weight gain rate is less than 16% (room temperature 10g/L hydrochloric acid), the 24-hour alkali-resistant weight gain rate is less than 5% (room temperature 10g/L sodium hydroxide), the weight gains are respectively reduced by 55%, 20% and 90% compared with that of an unmodified polyacrylate adhesive, and the emulsion stability is excellent. In addition, the cationic polyurethane modified polyacrylate emulsion is used as an adhesive, so that the soft hand feeling and the elasticity of the fabric can be obviously improved. The reason is that:
(1) in the method, a PU (polyurethane) molecular chain skeleton contains hydrophilic cationic groups, when the PU molecular chain skeleton is copolymerized with acrylate, the PU molecular chain with strong hydrophilicity tends to the surface of particles and gradually migrates from inside to outside, meanwhile, an acrylate monomer with strong hydrophobicity swells from outside to inside and enters the PU particles, and the acrylate monomer and carbon-carbon double bonds positioned at the side chain and the tail end of the polyurethane macromolecular skeleton undergo polymerization reaction, so that a complex phase structure with PU as a shell and PA (polyacrylate) as a core is formed, and the PU and the PA are crosslinked to a certain degree, so that the cationic polyurethane modified polyacrylate emulsion prepared by the method has a crosslinked core-shell structure.
(2) In the method, double bonds can be introduced into side chains of the active polyurethane Prepolymer (PU) by introducing monomer trimethylolpropane monoallyl ether with double bonds, and double bonds are formed at two ends of the PU active prepolymer after the end capping of hydroxyethyl methacrylate, and the double bonds are beneficial to the polymerization and crosslinking between PU and PA; by introducing polyethylene glycol methyl ether, polyether can be introduced into the side chain of the PU active prepolymer, which is beneficial to improving the emulsion stability, film forming speed and salt tolerance of the prepared cationic polyurethane modified polyacrylate emulsion.
(3) In the method, a crosslinking cationic polyurethane structure with a larger proportion is grafted into a polyacrylate framework, so that the flexibility, the flexibility and the cohesiveness of the polyacrylate macromolecule are obviously improved.
(4) The cationic polyurethane modified polyacrylate emulsion with the cross-linked core-shell structure has narrow particle size distribution, the average particle size is 90-110nm, and the surface tension is about 30 mN/m.
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 cationic polyurethane modified polyacrylate emulsion with the cross-linked core-shell structure comprises the following steps:
(1) in the presence of a polyurethane catalyst, reacting PU active prepolymer monomers (namely hydroxyalkyl polysiloxane, polytetrahydrofuran, isophorone diisocyanate, trimethylolpropane monoallyl ether, 1, 4-butanediol, polyethylene glycol monomethyl ether, N-methyldiethanolamine and hydroxyethyl methacrylate) to obtain a PU active prepolymer;
(2) mixing the PU active prepolymer, part of polyacrylate monomer raw materials, part of emulsifier, acetic acid and water to obtain PUm active prepolymer emulsion;
(3) mixing the rest of polyacrylate monomer raw material, the rest of emulsifier and water, stirring and emulsifying to obtain PA pre-emulsion; in the presence of an initiator, carrying out prepolymerization reaction on the PA pre-emulsion, and then adding the PUm active prepolymer emulsion to carry out polymerization reaction.
In the step (1), the molar ratio of the hydroxyalkyl polysiloxane, the polytetrahydrofuran, the isophorone diisocyanate, the trimethylolpropane monoallyl ether, the 1, 4-butanediol, the polyethylene glycol monomethyl ether, the N-methyldiethanolamine and the hydroxyethyl methacrylate is (0.08-0.3): (0.2-0.4): 3.33: (0.9-1.1): (0.4-0.6): (0.1-0.3): (0.6-1): (0.6-1.1). Only when the monomer raw materials in the step (1) react strictly according to the molar ratio, the adhesive film formed by the prepared polyurethane modified polyacrylate emulsion can show better water resistance, alkali resistance and compatibility with a softening agent.
In a preferable case, in order to further improve the water resistance and alkali resistance of the prepared polyurethane modified polyacrylate emulsion, the molar ratio of the hydroxyalkyl polysiloxane, the polytetrahydrofuran, the isophorone diisocyanate, the trimethylolpropane monoallyl ether, the 1, 4-butanediol, the polyethylene glycol methyl ether, the N-methyldiethanolamine and the hydroxyethyl methacrylate is (0.15-0.25): (0.25-0.35): 3.33: (0.95-1.05): (0.42-0.5): (0.15-0.25): (0.7-0.9): (0.65-1), most preferably 0.2: 0.3: 3.33: 1.02: 0.46: 0.2: 0.8: 0.7.
in step (1), the molar ratio of the sum of the hydroxyalkyl polysiloxane, the polytetrahydrofuran, the 1, 4-butanediol, the polyethylene glycol monomethyl ether and the N-methyldiethanolamine to the isophorone diisocyanate is 1.9-2.1: 3.33, preferably 1.9-2: 3.33, more preferably 1.92 to 1.98: 3.33.
in step (1), the molar ratio of the sum of hydroxyalkylpolysiloxane, polytetrahydrofuran, trimethylolpropane monoallyl ether, 1, 4-butanediol, polyethylene glycol monomethyl ether and N-methyldiethanolamine to isophorone diisocyanate is not more than 3: 3.33, preferably 2.8 to 3: 3.33, more preferably 2.9 to 3: 3.33.
in a preferred embodiment, the reaction process of step (1) comprises: the preparation method comprises the following steps of dehydrating hydroxyalkyl polysiloxane and polytetrahydrofuran, adding isophorone diisocyanate and part of a polyurethane catalyst for prepolymerization, adding polyethylene glycol monomethyl ether, trimethylolpropane monoallyl ether, 1, 4-butanediol and the rest of the polyurethane catalyst for chain extension reaction, adding N-methyldiethanolamine for secondary chain extension reaction, adding hydroxyethyl methacrylate for end-capping reaction, and adding a terminator for terminating reaction. The weight ratio of the portion of polyurethane catalyst to the remaining portion of polyurethane catalyst may be 60-70: 40-30, most preferably 67: 33. according to the above preferred embodiment, by subjecting the polyester diol and the poly (butadiene) diol to dehydration treatment, it is possible to prevent the introduction of water, so that the viscosity of the reaction system increases, thereby making it difficult to smoothly perform the reaction; and the PU active prepolymer with proper molecular weight and reasonable structure distribution can be prepared by performing prepolymerization reaction, chain extension reaction and end capping reaction in sequence according to the charging sequence.
Further preferably, the reaction process in step (1) is as follows: putting hydroxyl alkyl polysiloxane and polytetrahydrofuran, and dehydrating at the temperature of 100-120 ℃ for 80-100 min; cooling to below 75 ℃, adding isophorone diisocyanate and 60-70 wt% of polyurethane catalyst, heating to 85-90 ℃, and keeping the temperature for 1.5-2.5 h; then cooling to 55-65 ℃, dropwise adding a mixed solution of polyethylene glycol methyl ether, trimethylolpropane monoallyl ether and 1, 4-butanediol, and reacting for 20-45min under the condition of heat preservation; then adding the rest polyurethane catalyst, heating to 70-75 ℃, carrying out heat preservation reaction for 90-150min, and optionally adding ethyl pyrrolidone for viscosity reduction; then cooling to 35-45 ℃, dropwise adding N-methyldiethanolamine, keeping the temperature and reacting for 40-60min, then adding hydroxyethyl methacrylate, reacting for 60-90min at 70-75 ℃, and then adding a terminator to terminate the reaction.
In step (1), the molecular weight of the hydroxyalkyl polysiloxane may be 1800-. In a specific embodiment, the hydroxyalkyl polysiloxane may be PS3667, which is a commercially available product and has a molecular weight of 2300.
In the step (1), the molecular weight of the polytetrahydrofuran can be 1000-5000; preferably 1500-. In a specific embodiment, the polytetrahydrofuran may use a commercial product PTMG2000 having a molecular weight of 2000.
In the step (1), the molecular weight of the polyethylene glycol methyl ether may be 800-1500, preferably 1000-1200. In a specific embodiment, the polyethylene glycol methyl ether may be a commercially available product N120 having a molecular weight of 1000.
In the invention, the polyurethane catalyst can accelerate the polymerization reaction and improve the synthesis rate and the synthesis efficiency of polyurethane. In the present invention, the polyurethane catalyst is preferably dibutyltin dilaurate or stannous octoate.
In step (1), the amount of the polyurethane catalyst used is not particularly limited, and may be an amount conventionally used in the art. Preferably, the total amount of the polyurethane catalyst used is from 0.02 to 0.05% by weight, more preferably from 0.025 to 0.035% by weight, most preferably 0.03% by weight, based on the total amount of the PU reactive prepolymer monomers.
In the present invention, the terminator may be conventionally selected in the art, and for example, may be a terminator conventionally used in the art, such as ethanol.
In the method of the present invention, the viscosity of the PU active prepolymer prepared in step (1) is relatively high, which is not favorable for the subsequent reaction, so that the viscosity is reduced by adding the raw material of polyacrylate monomer in step (2) and becomes a part of the shell monomer. In a preferred embodiment, the mixing process of step (2) comprises: adding part of polyacrylate monomer raw materials into the PU active prepolymer, cooling to below 50 ℃, adding acetic acid for neutralization for 10-15min, and then adding part of water and part of emulsifier for emulsification.
In step (2), the PU reactive prepolymer can be neutralized by adding acetic acid. Preferably, the weight ratio of the acetic acid to the N-methyldiethanolamine is (1-1.5): 1, most preferably 1.2: 1.
in a more preferred embodiment, the operation process of step (3) is as follows:
mixing the rest of polyacrylic acid monomer raw material with the rest of emulsifier and part of water, and stirring and emulsifying in water to obtain PA pre-emulsion; dissolving an initiator in part of water to prepare an initiator aqueous solution;
mixing 15-18 wt% of the PA pre-emulsion with the rest water, heating to 75-80 ℃, dropwise adding 20-30 wt% of the initiator aqueous solution, and reacting for 30-60min under heat preservation; controlling the temperature to be 78-82 ℃, dropwise adding the rest of PA pre-emulsion and 35-40 wt% of initiator aqueous solution, dropwise adding the PUm active prepolymer emulsion and 20-30 wt% of initiator aqueous solution, and then carrying out heat preservation reaction for 10-60 min; then heating to 80-85 ℃, adding the rest initiator aqueous solution, and reacting for 20-30min under the condition of heat preservation; then the temperature is reduced to below 50 ℃.
Further preferably, the operation process of step (3) is: mixing the PA pre-emulsion of 1/6 with the rest water, heating to 75-80 ℃, dropwise adding 2/8 of the initiator aqueous solution, and reacting for 30-60min under heat preservation; controlling the temperature to be 78-82 ℃, dripping 5/6 PA pre-emulsion and 3/8 initiator aqueous solution, dripping PUm active prepolymer emulsion and 2/8 initiator aqueous solution, and then carrying out heat preservation reaction for 10-60 min; then heating to 80-85 ℃, adding 1/8 of the initiator aqueous solution, and keeping the temperature for reaction for 20-30 min; then the temperature is reduced to below 50 ℃.
According to the operation step (3) of the preferred embodiment, the comprehensive performance of the prepared polyurethane modified polyacrylate emulsion can be further improved, and particularly, a glue film formed by the polyurethane modified polyacrylate emulsion has good water resistance, alkali resistance and compatibility with a softening agent, and the film forming speed is moderate.
In the present invention, the polyacrylate monomer raw material may be a conventional choice in the art. Preferably, in the step (3), the polyacrylate monomer raw materials comprise 43 to 58 wt% of butyl acrylate, 12 to 18 wt% of isooctyl acrylate, 27 to 35 wt% of ethyl acrylate, 2.5 to 3.5 wt% of hydroxyethyl methacrylate and 0.5 to 0.8 wt% of methylene methyl bisacrylamide, and the total of the polyacrylate monomer raw materials is 100%. Further preferably, the polyacrylate monomer raw material comprises 48 to 52 weight percent of butyl acrylate, 13 to 15 weight percent of isooctyl acrylate, 28 to 30 weight percent of ethyl acrylate, 2.5 to 3 weight percent of hydroxyethyl methacrylate and 0.5 to 0.6 weight percent of methylene methyl bisacrylamide, and the sum of the polyacrylate monomer raw materials is 100%.
In the present invention, the initiator is preferably azobisisobutylamidine hydrochloride. In one embodiment, the azobisisobutylamidine hydrochloride may be the commercially available product V50.
In the method of the present invention, the total amount of the polyacrylate monomer raw materials is preferably 80 to 125 parts by weight, more preferably 90 to 110 parts by weight, and most preferably 100 parts by weight, based on 100 parts by weight of the PU reactive prepolymer.
In the method of the present invention, the weight ratio of the portion of the polyacrylate monomer raw material in the step (2) to the remaining portion of the polyacrylate monomer raw material in the step (3) is 1: 2.5-3.5, preferably 1: 2.8-3.2, most preferably 1: 3.
in the method of the present invention, preferably, the total amount of the emulsifier is 3 to 5 wt%, most preferably 4 wt% of the total amount of the raw materials of the PU reactive prepolymer monomer and the polyacrylate monomer.
In the method of the present invention, preferably, the emulsifier comprises 1-2 wt% of octadecyl trimethyl ammonium chloride and 2-3 wt% of fatty alcohol-polyoxyethylene ether based on the total amount of the PU reactive pre-polymerization monomer and the polyacrylate monomer raw material. The octadecyl trimethyl ammonium chloride may be commercially available as product S1831. The fatty alcohol polyoxyethylene ether may be used as a commercially available product AEO 9.
In the method of the present invention, preferably, the weight ratio of the part of the emulsifier added in step (2) to the rest of the emulsifier added in step (3) is 1: 3.5-4.5, more preferably 1: 3.8-4.2, most preferably 1: 4. the emulsifiers added in the step (2) and the step (3) are mixed emulsifiers, namely the mixed emulsifiers containing octadecyl trimethyl ammonium chloride and fatty alcohol-polyoxyethylene ether accounting for 1-2 wt% of the total amount of the PU reactive pre-polymerization monomer and the polyacrylate monomer raw materials and accounting for 2-3 wt% of the total amount of the PU reactive pre-polymerization monomer and the polyacrylate monomer raw materials.
The invention also provides the cationic polyurethane modified polyacrylate emulsion with the cross-linked core-shell structure, which is prepared by the method.
The present invention will be described in detail below by way of examples. It is to be understood that these examples are for the purpose of illustration and explanation only and are not intended to limit the present invention.
Example 1
(1) Preparation of PU active prepolymer
Dehydrating 23g of hydroxyalkyl polysiloxane (PS3667, molecular weight 2300) and 30g of polytetrahydrofuran (PTMG, molecular weight 2000) at 110 deg.C for 90 min; cooling to 75 ℃, adding 37.011g of isophorone diisocyanate (IPDI) and 0.024g of dibutyltin dilaurate (DBTDL), gradually heating to 85 ℃, and keeping the temperature for 2 h; then cooling to 60 ℃, slowly dripping a mixed solution of 10g of polyethylene glycol monomethyl ether (N120, molecular weight 1000), 8.886g of trimethylolpropane monoallyl ether (TMPME) and 2.073g of 1, 4-Butanediol (BDO) within 20min, and keeping the temperature for 30 min; then adding 0.012g of dibutyltin dilaurate (DBTDL), heating to 75 ℃, keeping the temperature for 120min, and adding 40g of ethyl pyrrolidone (NEP) for viscosity reduction; then cooling to 40 ℃, uniformly dripping 4.766g N-Methyldiethanolamine (MDEA) dropwise within 15min, carrying out heat preservation reaction for 50min, then adding 4.555g of hydroxyethyl methacrylate (HEMA), carrying out reaction for 75min at 75 ℃, and then adding ethanol to terminate the reaction, thereby obtaining a PU active prepolymer;
(2) preparation of PUm active prepolymer emulsion
Adding 14.947g of Butyl Acrylate (BA), 4.484g of isooctyl acrylate (EHA), 9.566g of Ethyl Acrylate (EA), 0.897g of hydroxyethyl methacrylate (HEMA) and 0.18g of methylene methyl bisacrylamide (NAPP) into the PU active prepolymer, cooling to below 50 ℃, adding 5.72g of acetic acid (HAc) for neutralization for 15min, then adding 315.155g of water, 1.275g of fatty alcohol polyoxyethylene ether (AEO9) and 0.65g of octadecyl trimethyl ammonium chloride (S1831) for emulsification to obtain PUm active prepolymer emulsion;
(3) preparation of PUA emulsion
0.722g of azobisisobutylamidine hydrochloride is uniformly mixed in 78.382g of water to obtain 79.104g of initiator aqueous solution with the mass concentration of 0.91 wt%;
44.84g of Butyl Acrylate (BA), 13.452g of isooctyl acrylate (EHA), 28.698g of Ethyl Acrylate (EA), 2.69g of hydroxyethyl methacrylate (HEMA), 0.539g of methylene methyl bisacrylamide (NAPP), 5.1g of fatty alcohol polyoxyethylene ether (AEO9), 2.598g of octadecyl trimethyl ammonium chloride (S1831) and 156g of deionized water are mixed, stirred and emulsified to prepare 253.917g of PA pre-emulsion;
mixing 42g of PA pre-emulsion with 157.258g of water, heating to 78 ℃, uniformly dripping 2/8 of the initiator aqueous solution within 20min, and carrying out heat preservation reaction for 40 min; controlling the temperature to be 80 ℃, uniformly dripping 211.917g of PA pre-emulsion and 3/8 of the initiator aqueous solution within 60min, then uniformly dripping PUm active prepolymer emulsion and 2/8 of the initiator aqueous solution within 40min, and then carrying out heat preservation reaction for 40 min; then heating to 82 ℃, adding 1/8 of the initiator aqueous solution, and keeping the temperature for reaction for 30 min; and then cooling to below 50 ℃ to obtain the cationic polyurethane modified polyacrylate emulsion A1 with the cross-linked core-shell structure.
Example 2
(1) Preparation of PU active prepolymer
17.25g of a hydroxyalkyl polysiloxane (PS3667, MW 2300) and 35g of polytetrahydrofuran (PTMG, MW 2000) are dehydrated at 100 ℃ for 100 min; cooling to 75 ℃, adding 37.011g of isophorone diisocyanate (IPDI) and 0.018g of dibutyltin dilaurate (DBTDL), gradually heating to 85 ℃, and keeping the temperature for 2.5 h; then cooling to 55 ℃, slowly dripping a mixed solution of 7.5g of polyethylene glycol methyl ether (N120, molecular weight 1000), 9.15g of trimethylolpropane monoallyl ether (TMPME) and 1.89g of 1, 4-Butanediol (BDO) within 20min, and keeping the temperature for 45 min; then adding 0.012g of dibutyltin dilaurate (DBTDL), heating to 70 ℃, carrying out heat preservation reaction for 150min, and adding 40g of ethyl pyrrolidone (NEP) for viscosity reduction; then cooling to 35 ℃, dropwise adding 4.17g N-Methyldiethanolamine (MDEA) for heat preservation reaction for 60min, then adding 6.51g of hydroxyethyl methacrylate (HEMA), reacting for 60min at 75 ℃, and then adding ethanol to terminate the reaction to obtain a PU active prepolymer;
(2) preparation of PUm active prepolymer emulsion
Adding 12.99g of Butyl Acrylate (BA), 5.4g of isooctyl acrylate (EHA), 10.38g of Ethyl Acrylate (EA), 0.99g of hydroxyethyl methacrylate (HEMA) and 0.24g of methylene methyl bisacrylamide (NAPP) into the PU active prepolymer, cooling to below 50 ℃, adding 5.4g of acetic acid (HAc) for neutralization for 10min, then adding 315.155g of water, 0.96g of fatty alcohol polyoxyethylene ether (AEO9) and 0.64g of octadecyl trimethyl ammonium chloride (S1831) for emulsification to obtain PUm active prepolymer emulsion;
(3) preparation of PUA emulsion
0.722g of azobisisobutylamidine hydrochloride is uniformly mixed in 78.382g of water to obtain 79.104g of initiator aqueous solution with the mass concentration of 0.91 wt%;
38.97g of Butyl Acrylate (BA), 16.2g of isooctyl acrylate (EHA), 31.14g of Ethyl Acrylate (EA), 2.97g of hydroxyethyl methacrylate (HEMA), 0.72g of methylene methyl bisacrylamide (NAPP), 3.36g of fatty alcohol polyoxyethylene ether (AEO9), 2.24g of octadecyl trimethyl ammonium chloride (S1831) and 156g of deionized water are mixed, stirred and emulsified to prepare 248.8g of PA pre-emulsion;
mixing 42gPA pre-emulsion with 157.258g of water, heating to 75 ℃, uniformly dripping 2/8 of the initiator aqueous solution in 20min, and carrying out heat preservation reaction for 60 min; controlling the temperature to be 78 ℃, uniformly dripping 206.8g of PA pre-emulsion and 3/8 of the initiator aqueous solution within 60min, then uniformly dripping PUm active prepolymer emulsion and 2/8 of the initiator aqueous solution within 40min, and then carrying out heat preservation reaction for 10 min; then heating to 85 ℃, adding 1/8 of the initiator aqueous solution, and keeping the temperature for reaction for 30 min; then the temperature is reduced to below 50 ℃.
To obtain the cationic polyurethane modified polyacrylate emulsion A2 with a cross-linked core-shell structure.
Example 3
(1) Preparation of PU active prepolymer
28.75g of a hydroxyalkyl polysiloxane (PS3667, MW 2300) and 25g of polytetrahydrofuran (PTMG, MW 2000) were dehydrated at 120 ℃ for 80 min; cooling to 75 ℃, adding 37.011g of isophorone diisocyanate (IPDI) and 0.029g of dibutyltin dilaurate (DBTDL), gradually heating to 90 ℃, and keeping the temperature for 1.5 h; then cooling to 65 ℃, slowly dripping a mixed solution of 12.5g of polyethylene glycol methyl ether (N120, molecular weight 1000), 8.28g of trimethylolpropane monoallyl ether (TMPME) and 2.25g of 1, 4-Butanediol (BDO) within 20min, and keeping the temperature for 20 min; then adding 0.013g of dibutyltin dilaurate (DBTDL), heating to 75 ℃, preserving heat for 90min, and adding 40g of ethyl pyrrolidone (NEP) for viscosity reduction; then cooling to 45 ℃, dropwise adding 5.36g N-Methyldiethanolamine (MDEA) for heat preservation reaction for 40min, then adding 4.22g of hydroxyethyl methacrylate (HEMA), reacting for 90min at 70 ℃, and then adding ethanol to terminate the reaction to obtain a PU active prepolymer;
(2) preparation of PUm active prepolymer emulsion
Adding 17.4g of Butyl Acrylate (BA), 3.6g of isooctyl acrylate (EHA), 8.1g of Ethyl Acrylate (EA), 0.75g of hydroxyethyl methacrylate (HEMA) and 0.15g of methylene methyl bisacrylamide (NAPP) into the PU active prepolymer, cooling to below 50 ℃, adding 5.6g of acetic acid (HAc) for neutralization for 15min, then adding 315.155g of water, 1.54g of fatty alcohol polyoxyethylene ether (AEO9) and 0.66g of octadecyl trimethyl ammonium chloride (S1831) for emulsification to obtain PUm active prepolymer emulsion;
(3) preparation of PUA emulsion
0.722g of azobisisobutylamidine hydrochloride is uniformly mixed in 78.382g of water to obtain 79.104g of initiator aqueous solution with the mass concentration of 0.91 wt%;
52.2g of Butyl Acrylate (BA), 10.8g of isooctyl acrylate (EHA), 24.3g of Ethyl Acrylate (EA), 2.25g of hydroxyethyl methacrylate (HEMA), 0.45g of methylene methyl bisacrylamide (NAPP), 6.86g of fatty alcohol polyoxyethylene ether (AEO9) and 2.94g of octadecyl trimethyl ammonium chloride (S1831) are mixed with 156g of deionized water, stirred and emulsified to prepare 255.8g of PA pre-emulsion;
mixing 42.6g of PA pre-emulsion with 157.258g of water, heating to 80 ℃, uniformly dripping 2/8 of the initiator aqueous solution within 20min, and carrying out heat preservation reaction for 30 min; controlling the temperature to be 82 ℃, uniformly dripping 213.2g of PA pre-emulsion and 3/8 of the initiator aqueous solution within 60min, then uniformly dripping PUm active prepolymer emulsion and 2/8 of the initiator aqueous solution within 40min, and then carrying out heat preservation reaction for 60 min; then heating to 80 ℃, adding 1/8 of the initiator aqueous solution, and keeping the temperature for reaction for 20 min; then the temperature is reduced to below 50 ℃.
To obtain the cationic polyurethane modified polyacrylate emulsion A3 with a cross-linked core-shell structure.
Example 4
The process of example 1 was followed except that: the ratio of the partial polyacrylate monomer raw material in the step (2) to the rest polyacrylate monomer raw material in the step (3) is 1: 2.5; the method comprises the following specific steps:
the components of the raw materials of the partial polyacrylate monomer in the step (2) are as follows: 17.082g of butyl acrylate, 5.125g of isooctyl acrylate, 10.933g of ethyl methacrylate, 1.025g of hydroxyethyl methacrylate, 0.205g of methylenemethyldiacrylamide,
the rest of the polyacrylate monomer raw material in the step (3) comprises the following components: 42.705g of butyl acrylate, 12.811g of isooctyl acrylate, 27.331g of ethyl methacrylate, 2.562g of hydroxyethyl methacrylate and 0.514g of methylenebisacrylamide.
To obtain the cationic polyurethane modified polyacrylate emulsion A4 with a cross-linked core-shell structure.
Example 5
The process of example 1 was followed except that: the ratio of the partial polyacrylate monomer raw material in the step (2) to the rest polyacrylate monomer raw material in the step (3) is 1: 3.5; the method comprises the following specific steps:
the components of the raw materials of the partial polyacrylate monomer in the step (2) are as follows: 13.286g of butyl acrylate, 3.986g of isooctyl acrylate, 8.503g of ethyl methacrylate, 0.797g of hydroxyethyl methacrylate, 0.16g of methylenemethyldiacrylamide,
the rest of the polyacrylate monomer raw material in the step (3) comprises the following components: 46.501g of butyl acrylate, 13.95g of isooctyl acrylate, 29.761g of ethyl methacrylate, 2.79g of hydroxyethyl methacrylate and 0.559g of methylenemethyldiacrylamide.
To obtain the cationic polyurethane modified polyacrylate emulsion A5 with a cross-linked core-shell structure.
Example 6
The process of example 1 was followed except that: the ratio of the total weight of the polyurethane monomer raw materials (hydroxyalkyl polysiloxane, polytetrahydrofuran, isophorone diisocyanate, trimethylolpropane monoallyl ether, 1, 4-butanediol, polyethylene glycol monomethyl ether, N-methyldiethanolamine and hydroxyethyl methacrylate) in the step (1) to the total weight of the polyacrylate monomer raw materials is 1: 1.25, specifically, the preparation method of the PU active prepolymer in the step (1) comprises the following steps:
dehydrating 18.4g of a hydroxyalkyl polysiloxane (PS3667, MW 2300) and 24g of polytetrahydrofuran (PTMG, MW 2000) at 110 ℃ for 90 min; cooling to below 75 ℃, adding 29.609g of isophorone diisocyanate (IPDI) and 0.024g of dibutyltin dilaurate (DBTDL), gradually heating to 85 ℃, and keeping the temperature for 2 hours; then cooling to 60 ℃, slowly dripping a mixed solution of 8g of polyethylene glycol monomethyl ether (N120, molecular weight 1000), 7.109g of trimethylolpropane monoallyl ether (TMPME) and 1.658g of 1, 4-Butanediol (BDO) within 20min, and keeping the temperature for 30 min; then adding 0.012g of dibutyltin dilaurate (DBTDL), heating to 75 ℃, keeping the temperature for 120min, and adding 40g of ethyl pyrrolidone (NEP) for viscosity reduction; then, the temperature is reduced to 40 ℃, 3.813g N-Methyldiethanolamine (MDEA) is uniformly dripped in 15min for heat preservation reaction for 50min, 3.644g of hydroxyethyl methacrylate (HEMA) is added, the reaction is carried out for 75min at 75 ℃, and then ethanol is added to stop the reaction, so as to obtain the PU active prepolymer.
To obtain the cationic polyurethane modified polyacrylate emulsion A6 with a cross-linked core-shell structure.
Example 7
The process of example 1 was followed except that: in the step (1), the ratio of the total weight of the PU monomer raw materials (the total weight of hydroxyalkyl polysiloxane, polytetrahydrofuran, isophorone diisocyanate, trimethylolpropane monoallyl ether, 1, 4-butanediol, polyethylene glycol monomethyl ether, N-methyldiethanolamine and hydroxyethyl methacrylate) to the total weight of the polyacrylate monomer raw materials is 1: 0.8, specifically, the preparation method of the PU active prepolymer in the step (1) comprises the following steps:
27.6g of hydroxyalkyl polysiloxane (PS3667, MW 2300) and 36g of polytetrahydrofuran (PTMG, MW 2000) were dehydrated at 110 ℃ for 90 min; cooling to below 75 ℃, adding 44.413g of isophorone diisocyanate (IPDI) and 0.024g of dibutyltin dilaurate (DBTDL), gradually heating to 85 ℃, and keeping the temperature for 2 hours; then cooling to 60 ℃, slowly dripping a mixed solution of 12g of polyethylene glycol monomethyl ether (N120, molecular weight 1000), 10.663g of trimethylolpropane monoallyl ether (TMPME) and 2.488g of 1, 4-Butanediol (BDO) within 20min, and keeping the temperature for 30 min; then adding 0.012g of dibutyltin dilaurate (DBTDL), heating to 75 ℃, keeping the temperature for 120min, and adding 40g of ethyl pyrrolidone (NEP) for viscosity reduction; then, the temperature is reduced to 40 ℃, 5.719g N-Methyldiethanolamine (MDEA) is uniformly dripped in 15min for heat preservation reaction for 50min, 5.466g of hydroxyethyl methacrylate (HEMA) is added, the reaction is carried out for 75min at 75 ℃, and then ethanol is added to stop the reaction, so as to obtain the PU active prepolymer.
To obtain the cationic polyurethane modified polyacrylate emulsion A7 with a cross-linked core-shell structure.
Comparative example 1
The process of example 1 was followed except that: in step (1), trimethylolpropane monoallyl ether was not added. To obtain the cationic polyurethane modified polyacrylate emulsion B1 with a cross-linked core-shell structure.
Comparative example 2
The process of example 1 was followed except that: in step (1), no polyethylene glycol methyl ether was added. To obtain the cationic polyurethane modified polyacrylate emulsion B2 with a cross-linked core-shell structure.
Comparative example 3
The process of example 1 was followed except that, in step (1), the molar ratio of the hydroxyalkyl polysiloxane, polytetrahydrofuran, isophorone diisocyanate, trimethylolpropane monoallyl ether, 1, 4-butanediol, polyethylene glycol monomethyl ether, N-methyldiethanolamine, hydroxyethyl methacrylate was 0.2: 0.3: 3.33: 0.88: 0.46: 0.32: 0.8: 0.7. specifically, the preparation method of the PU active prepolymer in the step (1) comprises the following steps:
dehydrating 23g of hydroxyalkyl polysiloxane (PS3667, molecular weight 2300) and 30g of polytetrahydrofuran (PTMG, molecular weight 2000) at 110 deg.C for 90 min; cooling to 75 ℃, adding 37.011g of isophorone diisocyanate (IPDI) and 0.024g of dibutyltin dilaurate (DBTDL), gradually heating to 85 ℃, and keeping the temperature for 2 h; then cooling to 60 ℃, slowly dripping a mixed solution of 16g of polyethylene glycol monomethyl ether (N120, molecular weight 1000), 7.667g of trimethylolpropane monoallyl ether (TMPME) and 2.073g of 1, 4-Butanediol (BDO) within 20min, and keeping the temperature for 30 min; then adding 0.012g of dibutyltin dilaurate (DBTDL), heating to 75 ℃, keeping the temperature for 120min, and adding 40g of ethyl pyrrolidone (NEP) for viscosity reduction; then, the temperature is reduced to 40 ℃, 4.766g N-Methyldiethanolamine (MDEA) is uniformly dripped in 15min for heat preservation reaction for 50min, 4.555g of hydroxyethyl methacrylate (HEMA) is added, the reaction is carried out for 75min at 75 ℃, and then ethanol is added to stop the reaction, so as to obtain the PU active prepolymer.
To obtain the cationic polyurethane modified polyacrylate emulsion B3 with a cross-linked core-shell structure.
Test example:
(1) the average particle diameters of the cationic polyurethane modified polyacrylate emulsions A1-A7 and B1-B3 having the crosslinked core-shell structure were measured by a laser particle size analyzer, and the experimental results are shown in Table 1.
(2) The surface tension of the cationic polyurethane modified polyacrylate emulsion A1-A7 and B1-B3 with a crosslinked core-shell structure was tested by a ring pulling method (25 ℃), and the experimental results are shown in Table 1.
(3) Solvent resistance test
Preparing the cationic polyurethane modified polyacrylate emulsion A1-A7 and B1-B3 with a cross-linked core-shell structure into adhesive films, and obtaining adhesive films C1-C7 and adhesive films D1-D3.
The glue films C1-C7 and the glue films D1-D3 are respectively placed in water, 10g/L hydrochloric acid and 10g/L sodium hydroxide which are 20 times of the weight of the glue films at room temperature, after the glue films are placed for 24 hours, the water on the surfaces of the dry glue films is wiped, the weight gain rate of the glue films is calculated, and the experimental results are shown in Table 2.
The weight gain rate is 100 × (m)2-m1)/m1；
Wherein m is1Is the initial weight of the adhesive film, m2The weight of the adhesive film after being placed in the solvent for 24 hours.
TABLE 1
As can be seen from Table 1, the cationic polyurethane-modified polyacrylate emulsion having a crosslinked core-shell structure had an average particle diameter in the range of 90 to 110nm and a narrow particle diameter distribution, and the surface tension of the emulsion was about 30 mN/m.
TABLE 2
As can be seen from Table 2, the adhesive film prepared from the cationic polyurethane modified polyacrylate emulsion with the crosslinked core-shell structure has excellent water resistance and alkali resistance, and good acid resistance, specifically, the 24-hour water-resistant weight gain rate of the adhesive film is less than 15% (pure water at room temperature), the 24-hour acid-resistant weight gain rate is less than 16% (hydrochloric acid at room temperature of 10 g/L), and the 24-hour alkali-resistant weight gain rate is less than 5% (sodium hydroxide at room temperature of 10 g/L).
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. A preparation method of cationic polyurethane modified polyacrylate emulsion with a cross-linked core-shell structure is characterized by comprising the following steps:
(1) in the presence of a polyurethane catalyst, reacting PU reactive prepolymer monomers, namely, hydroxyalkyl polysiloxane, polytetrahydrofuran, isophorone diisocyanate, trimethylolpropane monoallyl ether, 1, 4-butanediol, polyethylene glycol monomethyl ether, N-methyldiethanolamine and hydroxyethyl methacrylate in the ratio of (0.08-0.3): (0.2-0.4): 3.33: (0.9-1.1): (0.4-0.6): (0.1-0.3): (0.6-1): (0.6-1.1), wherein the molar ratio of the sum of the hydroxyalkyl polysiloxane, the polytetrahydrofuran, the 1, 4-butanediol, the polyethylene glycol methyl ether and the N-methyldiethanolamine to the isophorone diisocyanate is (1.9-2.1): 3.33, the molar ratio of the sum of hydroxyalkylpolysiloxane, polytetrahydrofuran, trimethylolpropane monoallyl ether, 1, 4-butanediol, polyethylene glycol monomethyl ether and N-methyldiethanolamine to isophorone diisocyanate does not exceed 3: 3.33, obtaining a PU active prepolymer;
(2) mixing the PU active prepolymer, part of polyacrylate monomer raw materials, part of emulsifier, acetic acid and water to obtain PUmAn active prepolymer emulsion;
(3) mixing the rest of polyacrylate monomer raw material, the rest of emulsifier and water, stirring and emulsifying to obtain PA pre-emulsion; in the presence of an initiator, the PA pre-emulsion is subjected to a pre-polymerization reaction, and then the PU is addedmCarrying out polymerization reaction on the active prepolymer emulsion, wherein the polyacrylate monomer raw materials comprise 43-58 wt% of butyl acrylate, 12-18 wt% of isooctyl acrylate, 27-35 wt% of ethyl acrylate, 2.5-3.5 wt% of hydroxyethyl methacrylate and 0.5-0.8 wt% of methylene bisacrylamide, and the sum of the polyacrylate monomer raw materials is 100%.
2. The production method according to claim 1, wherein in the step (1), the reaction comprises: the preparation method comprises the following steps of dehydrating hydroxyalkyl polysiloxane and polytetrahydrofuran, adding isophorone diisocyanate and part of a polyurethane catalyst for prepolymerization, adding polyethylene glycol monomethyl ether, trimethylolpropane monoallyl ether, 1, 4-butanediol and the rest of the polyurethane catalyst for chain extension reaction, adding N-methyldiethanolamine for secondary chain extension reaction, adding hydroxyethyl methacrylate for end-capping reaction, and adding a terminator for terminating reaction.
3. The method according to claim 2, wherein in the step (1), the reaction process is: putting hydroxyl alkyl polysiloxane and polytetrahydrofuran, and dehydrating at the temperature of 100-120 ℃ for 80-100 min; cooling to below 75 ℃, adding isophorone diisocyanate and 60-70 wt% of polyurethane catalyst, heating to 85-90 ℃, and keeping the temperature for 1.5-2.5 h; then cooling to 55-65 ℃, dropwise adding a mixed solution of polyethylene glycol methyl ether, trimethylolpropane monoallyl ether and 1, 4-butanediol, and reacting for 20-45min under the condition of heat preservation; then adding the rest polyurethane catalyst, heating to 70-75 ℃, carrying out heat preservation reaction for 90-150min, and adding ethyl pyrrolidone for viscosity reduction; then cooling to 35-45 ℃, dropwise adding N-methyldiethanolamine, keeping the temperature and reacting for 40-60min, then adding hydroxyethyl methacrylate, reacting for 60-90min at 70-75 ℃, and then adding a terminator to terminate the reaction.
4. The production method as claimed in any one of claims 1 to 3, wherein in the step (1), the hydroxyalkyl polysiloxane has a molecular weight of 1800-4000;
the molecular weight of the polytetrahydrofuran is 1000-5000;
the molecular weight of the polyethylene glycol monomethyl ether is 800-1500;
the polyurethane catalyst is dibutyltin dilaurate or stannous octoate.
5. The method according to claim 1, wherein in the step (2), the mixing comprises: adding part of polyacrylate monomer raw materials into the PU active prepolymer, cooling to below 50 ℃, adding acetic acid for neutralization for 10-15min, and then adding part of water and part of emulsifier for emulsification.
6. The method according to claim 1, wherein the step (3) is carried out by: mixing the rest of polyacrylic acid monomer raw material with the rest of emulsifier and part of water, and stirring and emulsifying in water to obtain PA pre-emulsion; dissolving an initiator in part of water to prepare an initiator aqueous solution;
mixing 15-18 wt% of the PA pre-emulsion with the rest water, heating to 75-80 ℃, dropwise adding 20-30 wt% of the initiator aqueous solution, and reacting for 30-60min under heat preservation; controlling the temperature to be 78-82 ℃, dropwise adding the rest of the PA pre-emulsion and 35-40 wt% of the initiator aqueous solution, and then dropwise adding the PUmReacting the active prepolymer emulsion and 20-30 wt% of the initiator aqueous solution for 10-60min in a heat preservation way; then heating to 80-85 ℃, adding the rest initiator aqueous solution, and reacting for 20-30min under the condition of heat preservation; then the temperature is reduced to below 50 ℃.
7. The method according to claim 6, wherein the step (3) is carried out by: mixing the PA pre-emulsion of 1/6 with the rest water, heating to 75-80 ℃, dropwise adding 2/8 of the initiator aqueous solution, and reacting for 30-60min under heat preservation; controlling the temperature to be 78-82 ℃, dripping 5/6 of the PA pre-emulsion and 3/8 of the aqueous initiator solution, and then dripping the PUmReacting the active prepolymer emulsion and 2/8 aqueous solution of the initiator for 10-60min in a heat preservation way; then heating to 80-85 ℃, adding 1/8 of the initiator aqueous solution, and keeping the temperature for reaction for 20-30 min; then the temperature is reduced to below 50 ℃.
8. The method of claim 1, wherein in step (3), the emulsifier comprises octadecyl trimethyl ammonium chloride in an amount of 1-2 wt% and fatty alcohol-polyoxyethylene ether in an amount of 2-3 wt% based on the total amount of the PU reactive pre-polymerization monomer and the polyacrylate monomer raw material.
9. The method according to claim 1, wherein in step (3), the initiator is azobisisobutylamidine hydrochloride.
10. The method according to any one of claims 1 to 3 and 5 to 9, wherein the total amount of the polyacrylate monomer raw materials is 80 to 125 parts by weight based on 100 parts by weight of the PU reactive prepolymer.
11. The method according to any one of claims 1 to 3 and 5 to 9, wherein the weight ratio of the portion of the polyacrylate monomer raw material in the step (2) to the remaining portion of the polyacrylate monomer raw material in the step (3) is 1: 2.5-3.5.
12. The method according to any one of claims 1 to 3 and 5 to 9, wherein the weight ratio of the partial emulsifier in step (2) to the remaining partial emulsifier in step (3) is 1: 3.5-4.5.
13. The method according to any one of claims 1 to 3 and 5 to 9, wherein in the steps (2) and (3), the total amount of the emulsifier is 3 to 5% by weight based on the total amount of the PU reactive prepolymer monomer and the polyacrylate monomer raw material.
14. The cationic polyurethane-modified polyacrylate emulsion having a crosslinked core-shell structure prepared by the preparation method of any one of claims 1 to 13.
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