CN106810646A - A kind of self-cross linking type water-proof emulsion and preparation method thereof and the waterproof basement membrane prepared using the water-proof emulsion - Google Patents

Abstract

The invention relates to the technical field of film-forming materials, in particular to a self-crosslinking waterproof emulsion and its preparation method and a waterproof base film prepared by using the waterproof emulsion. The emulsion includes the following raw materials in parts by weight: polyisocyanate, oligomer multi-component Alcohol, chain extender, end-capping agent, catalyst, comonomer, emulsifier, initiator, pH regulator, deionized water, described comonomer is hard monomer, soft monomer and functional monomer mass parts The mixing ratio is 30~50:10~20:5~20, the emulsion can realize self-crosslinking, the degree of crosslinking is high, and the weather resistance is good; the preparation method is simple, and the preparation process does not pollute the environment; the prepared Waterproof base film, the base film has a high degree of crosslinking, good water resistance, strong impact resistance, strong tear resistance, strong bonding with the base surface, strong flexibility, and good weather resistance.

Description

A self-crosslinking waterproof emulsion and its preparation method and the preparation of the waterproof emulsion Waterproof Base Membrane

technical field

The invention relates to the technical field of film-forming materials, in particular to a self-crosslinking waterproof emulsion, a preparation method thereof, and a waterproof base film prepared by using the waterproof emulsion.

Background technique

In the prior art, the base film is a wall surface treatment material with anti-alkali, moisture-proof, and mildew-proof functions, which can effectively prevent the moisture and alkaline substances from the construction base surface from seeping out, and avoid damage to the wall decoration materials: such as Wall paper, paint layer, plywood, decorative board damp, mildew and blackening and other adverse damage. However, as there are more and more problems in today's buildings, the problems of cracks and water seepage are becoming more and more serious. Ordinary base film products cannot cope with such a harsh wall environment, which greatly shortens the use of wall decoration materials. life.

There are also some base films with waterproof function on the market, some are solvent-based waterproof base films, and their environmental friendliness is poor; some replace solvent-based base films with water-based waterproof base films. Difference. At the same time, a two-component waterproof base film with excellent waterproof performance and good environmental protection performance has also appeared. However, this type of base film is relatively complicated and has high requirements for on-site operations, because the A\B of the base film must be adjusted before use. The components are mixed evenly, the curing and crosslinking process can be fully achieved, and the waterproof effect of the base film can be optimized. And because the two components of the two-component base film are separated before use, it also brings a lot of inconvenience to its production, packaging, and transportation processes.

Application No. 201110388142.6 discloses a normal temperature self-crosslinking acrylic emulsion and its preparation method. The preparation method of this method is complicated, requires multiple polymerization initiations, and takes a long time to prepare, which is not conducive to mass production.

The application number is 201110423428.3, which discloses a room temperature self-crosslinking styrene-acrylic emulsion resistant to ethanol dilution and its preparation method. Coating film.

Contents of the invention

The object of the present invention is to address the above-mentioned deficiencies in the prior art, and provide a self-crosslinking waterproof emulsion, which can realize self-crosslinking, has a high degree of crosslinking, stable performance, long storage time and good weather resistance.

Another object of the present invention is to provide a method for preparing a self-crosslinking waterproof emulsion, which has a simple preparation process, does not pollute the environment, and is environmentally friendly and non-toxic.

Another object of the present invention is to address the above-mentioned deficiencies in the prior art, to provide a waterproof base film, the base film has a high degree of crosslinking, good water resistance, strong impact resistance, strong tear resistance, and strong bonding force with the base surface Strong and has strong flexibility.

The object of the present invention is achieved through the following technical solutions:

A self-crosslinking type waterproof emulsion, comprising the following raw materials in parts by weight:

20-80 parts of polyisocyanate

10-60 parts of oligomer polyol

Chain extender 10~30 parts

Blocking agent 10~40 parts

Catalyst 0.1~5 parts

Comonomer 40~90 parts

Emulsifier 1~15 parts

Initiator 1~10 parts

pH adjuster 1~15 parts

5~60 parts of deionized water

Wherein, the comonomer is a mixture of hard monomers, soft monomers and functional monomers in a mass fraction ratio of 30-50:10-20:5-20.

The comonomers of the self-crosslinking waterproof emulsion of the present invention include three types of hard monomers, soft monomers and functional monomers. The hard monomer has a higher glass transition temperature Tg, which can increase the Tg of the copolymer, which can improve the wear resistance, hardness and strength of the coating film; the glass transition temperature Tg of the soft monomer is generally lower than the ambient temperature, which can Reducing the Tg of the copolymer can make the coating film durable and flexible; functional monomers have different functional groups to achieve different cross-linking methods, increase cross-linking density, improve heat resistance and mechanical properties, and improve impact resistance and tear resistance cracking ability, and has good water resistance and weather resistance; at the same time, the self-crosslinking waterproof emulsion of the present invention uses an alcohol chain extender and a hydrophilic chain extender in combination, so that the prepared emulsion has better particle size and dispersibility , better stability, no delamination, longer storage time, stronger impact resistance and tear resistance of the base film after coating.

Preferably, the following raw materials are included in parts by weight:

30-70 parts of polyisocyanate

15-50 parts of oligomer polyol

Chain extender 10~20 parts

Capping agent 20~30 parts

Catalyst 0.1~2 parts

Comonomer 45~90 parts

Emulsifier 1~10 parts

Initiator 1~5 parts

pH adjuster 1~10 parts

10~50 parts of deionized water.

Wherein, the oligomer polyol is 1,4-cyclohexanedimethanol, polycaprolactone diol, polyethylene adipate glycol, polycarbonate diol, polypropylene oxide diol, polyoxypropylene glycol One or more of propylene triol and polyoxypropylene tetraol. The molecular weight of the oligomer polyol is between 500 and 3000, all of which have a low functionality of 2 or 3. In the polyurethane polymerization process, the greater the functionality, the easier it is to polymerize into a network, but the reaction rate of polymerization will decrease. decline, which is not conducive to the next chain extension reaction.

Wherein, the polyisocyanate is siloxane modified water-based polyisocyanate, xylylene diisocyanate, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate, formaldehyde One or two or more of the base styrene isocyanates.

Wherein, the chain extender includes an alcohol chain extender and a hydrophilic chain extender in a ratio of 1:1.2-2:1 in parts by mass. The chain extender has a characteristic group that can chemically react with the reaction system. It has a low molecular weight and is reactive. It constitutes a strong reaction competition probability for the isocyanate and polyalcohol systems. They can effectively adjust the reaction speed of the reaction system and make the emulsion The particle size is smaller and the emulsion is more uniform; the alcohol chain extender is a low molecular weight chain extender, which can react with excess isocyanate to form a carbamate or biuret structure, and the chain segment of this structure is rigid , while the oligomer polyol is a polyurethane structure, the chain segment of this structure is flexible, and the reaction mainly generates a rigid segment, which makes the cured base film stronger in impact resistance and tear resistance, and the rigid segment and The combined use of flexible segments makes the base film have both hardness and good flexibility, without hollowing and water channeling layer. The hydrophilic chain extender introduces a hydrophilic group into the polyurethane chain segment, which promotes the emulsification of the prepolymer and promotes the stable dispersion of the emulsion particles. At the same time, the self-crosslinking type waterproof emulsion of the present invention uses an alcohol chain extender and a hydrophilic chain extender in combination, so that the prepared emulsion has better particle size and dispersibility, better stability, no delamination, and longer storage time. Longer, the impact resistance and tear resistance of the base film after coating are stronger.

Wherein, the alcohol chain extender is one or more of trimethylolpropane, glycerol, and 1,2,6-hexanetriol. The group of the alcohol chain extender can make the soft and hard chain segments produce micro-domain separation after polymerization, and at the same time crystallization and orientation arrangement make it easier to form hydrogen chains between polymer molecules, which can produce better ordered crystallization, and finally in the crystallization The anti-spin effect and polymer chain segment migration show that the polymer has excellent toughness and hardness, which makes the cured base film stronger in impact resistance and tear resistance.

Wherein, the hydrophilic chain extender is one of diaminobenzoic acid, dimethylolpropionic acid, sodium ethylenediaminoethanesulfonate, 1,4-butanediol-2-sulfonate and derivatives thereof species or two or more. Such chain extenders often contain carboxyl groups, sulfonic acid groups or secondary amino groups. When they are combined into polyurethane molecules, the polyurethane chain segments have functional groups that can be ionized. This type of chain extender not only Participate in the reaction, have the effect of chain extension and crosslinking, improve the rigidity and mechanical properties of the product, at the same time, it can also reduce the viscosity of the raw material components, improve the compatibility of each component of the raw material, and make the prepared emulsion have better particle size and dispersion performance, better stability.

Wherein, the end-capping agent is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, methyl ethyl ketoxime and caprolactam. The end-capping agent can participate in the end of the chain reaction and carry out end-capping reaction with the end without causing side reactions.

Wherein, the catalyst includes catalysts of organotin compounds and tertiary amine compounds. The catalyst can greatly reduce the reaction energy, make the reaction proceed hundreds of times, and increase the reaction rate.

Wherein, the emulsifier is a compound emulsifier mixed with ammonium perfluorooctanoate and sodium lauryl sulfate in any proportion. The emulsifier of the invention can improve the surface tension between various constituent phases in the emulsion to form a uniform and stable dispersion system and make the prepared monomer pre-emulsion more stable.

Wherein, the initiator is one of potassium persulfate, ammonium persulfate and hydrogen peroxide, and the usage amount of the initiator is 0.2%-0.8% of the total mass of the monomer. The initiator has a weak bond, which can initiate the polymerization reaction of the monomer pre-emulsion, so that the polymerization reaction can proceed smoothly.

Wherein, the pH regulator is ammonia water.

Wherein, the functional monomer is glycidyl methacrylate and the organosilicon active monomer in a mass fraction ratio of 1-10:1-20. Glycidyl methacrylate has two functional groups, active vinyl group and epoxy group with ionic reaction, which can be polymerized by functional group or by ion reaction, which can improve the hardness, gloss and adhesion of the coating film. Strength and weather resistance, especially the epoxy group can increase the connection between polyamide and polyurethane. With the volatilization of water in the film forming process, the epoxy and carboxyl group react, so that the water resistance and solvent resistance are improved. ; Silicone active monomer can improve the heat resistance, solvent resistance and hardness of the hybrid emulsion coating film, so that it has good oxidation resistance and low surface energy, good oxidation resistance provides excellent weather resistance, and low The excellent hydrophobicity generated by the surface energy greatly improves the water resistance. The active siloxane groups enriched on the surface of the emulsion are hydrolyzed to form silanols under certain conditions, and the silanols condense with the active groups inside or on the surface of the polymer to form a three-dimensional network (Si-O-Si) crosslinking structure, which can Increase the chemical crosslinking points inside the emulsion, enhance the surface density of the coating film, improve the heat resistance and mechanical properties of the coating film, and improve the water resistance and solvent resistance of the polymer coating film.

Wherein, the silicone active monomer includes one or more than two kinds of vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane. Vinyl triethoxysilane can significantly improve the weather resistance, water resistance and heat resistance of the emulsion; γ-methacryloxypropyl trimethoxysilane contains methacryloxy Silane functional group, easy to hydrolyze, condense to form polysiloxane, improve the mechanical properties of the emulsion, and increase the density; vinyl trimethoxysilane is a colorless and transparent liquid, has good cross-linking property, and improves the cross-linking structure of silanol and polymer , Enhance the density of the coating film.

A preparation method of self-crosslinking type waterproof emulsion, comprising the following steps:

a. Weigh the above-mentioned polyisocyanate in parts by mass, stir and heat up to 60~80°C, add chain extender dropwise, react for 3h~4h, then raise the temperature to 80-100°C for 1~2h, then add dropwise the low temperature after vacuum dehydration Polymer polyol, react for 1~2h, then add end-capping agent and catalyst, react for 1~2h to obtain polyurethane prepolymer;

b. Cool down the polyurethane prepolymer to 40~60℃, add 30-40% emulsifier first, then add comonomer dropwise, and stir rapidly for 0.5~1h to obtain monomer preemulsion;

c. Introduce the remaining emulsifier and 30~40% initiator into the reactor, and protect it with nitrogen, add 10~30% monomer pre-emulsion, raise the temperature to 80~100°C, stir until the emulsion is slightly blue, add dropwise Add the remaining monomer pre-emulsion and 60~70% initiator aqueous solution dropwise within 2 hours, add deionized water to disperse, control the temperature at 75~85°C, stir for 1~1.5 hours, then cool, add dropwise to adjust pH agent to adjust the pH value to 6.5-8.5, cool down and filter the material, obtained from cross-linked waterproof emulsion.

The preparation method of the self-crosslinking waterproof emulsion of the present invention has a simple preparation process, no pollution to the environment in the preparation process, environmental protection and non-toxicity, can be produced in batches, and has high operability.

A waterproof base film. The waterproof base film is made of the following raw materials in parts by weight: 5 to 20 parts of additives, 1 to 10 parts of deionized water, and the self-crosslinking waterproof emulsion 70 according to claims 1-9. ~100 parts, the additives include 1-3 parts by weight of thickener, 0.1-0.5 parts of defoamer, 2-6 parts of wetting agent, 5-9 parts of film-forming aid, 2-6 parts Leveling agent, 0.5-2.5 parts of antifungal agent, 0.1-0.5 parts of dispersant. The preparation method of the waterproof base film includes: take the above-mentioned deionized water, dispersant, wetting agent, film-forming aid and leveling agent, add an appropriate amount of defoamer, stir and disperse evenly, and the stirring speed is 200-500 rpm Add self-crosslinking waterproof emulsion, stir and disperse evenly, stirring speed 500-1000 rpm; finally add the remaining amount of defoamer, thickener, anti-fungal agent, stir and disperse evenly, stirring speed 200-500 RPM, let it stand for 1-2h, it can be obtained from the cross-linked waterproof base film.

The thickener is an associative thickener, preferably, using TEGO ViscoPlus 3030 associative water-based thickener, the defoamer is polysiloxane compound or modified polysiloxane compound, so The wetting agent is a mixture of alkylnaphthalene sulfonate and anionic wetting agent, the film-forming aid is a mixture of ethylene glycol monobutyl ether/dipropylene glycol butyl ether or alcohol ester compound, and the leveling agent is acrylic acid copolymer compound or polysiloxane compound, the dispersant is a polymer-type anionic dispersant, and the antifungal agent is Nipacide DFX/1 antifungal agent from Clariant Company.

A waterproof base film of the present invention has high cross-linking degree, good water resistance, strong impact resistance, strong tear resistance, strong bonding force with the base surface, strong flexibility, acid and alkali resistance, and corrosion resistance. There will be no hollowing and water channeling layer, and it can seal loose substrates, special-shaped parts and pre-cast joints.

Beneficial effects of the present invention:

(1) A self-crosslinking waterproof emulsion. The emulsion can realize self-crosslinking. The comonomer includes a variety of monomers, has a suitable glass transition temperature, and different functional groups increase the crosslinking method and increase the crosslinking density. , and the use of alcohol chain extenders and hydrophilic chain extenders makes the emulsion have better particle size and dispersibility, and the emulsion stability is better.

(2) A method for preparing a self-crosslinking waterproof emulsion. The preparation process is simple and can be produced in batches. The preparation process does not pollute the environment and is environmentally friendly and non-toxic.

(3) A waterproof base film of the present invention has a high degree of crosslinking, good water resistance, strong impact resistance, strong tear resistance, strong binding force with the base surface, strong flexibility, acid and alkali resistance , Anti-corrosion, no hollowing and water channeling layer, and can seal loose substrates, special-shaped parts and pre-cast joints.

detailed description

The present invention is further described in conjunction with the following examples.

Example 1

The self-crosslinking type waterproof emulsion of the present embodiment includes the following raw materials in parts by weight: 20 parts of polyisocyanate, 20 parts of oligomer polyol, 15 parts of chain extender, 20 parts of end-capping agent, 0.2 part of catalyst, comonomer 55 parts, 5 parts of emulsifier, 5 parts of initiator, 5 parts of pH regulator, 8 parts of deionized water, the comonomer is hard monomer, soft monomer and functional monomer in a mass ratio of 20:12: 8 mixes.

Wherein, the capping agent is methyl ethyl ketone oxime. Wherein, the catalyst is a catalyst of organotin compound: dibutyltin dilaurate. Wherein, the emulsifier is a composite emulsifier in which ammonium perfluorooctanoate and sodium lauryl sulfate are mixed at a ratio of 1:1 in parts by mass. Wherein, initiator is potassium persulfate. Wherein, the pH regulator is ammonia water. The oligomer polyol is 1,4-cyclohexanedimethanol, polyethylene adipate, polycarbonate diol and polyoxypropylene triol in a ratio of 1:1.5:2:2.5 in parts by mass mixture. The chain extender includes an alcohol chain extender and a hydrophilic chain extender in a ratio of 1.8:1 in parts by mass. The alcohol chain extender is trimethylolpropane. The hydrophilic chain extender is sodium ethylenediaminoethanesulfonate. The functional monomer is glycidyl methacrylate and silicone active monomer in a ratio of 8:15 by mass. The silicone reactive monomer includes vinyltriethoxysilane.

A preparation method of self-crosslinking type waterproof emulsion, comprising the following steps:

a. Weigh the above-mentioned polyisocyanate in parts by mass, stir and heat up to 60°C, add chain extender dropwise, react for 3h, then heat up to 80°C for 1h, then add oligomer polyol dropwise after vacuum dehydration, react for 1h, Then add an end-capping agent and a catalyst, and react for 1 hour to obtain a polyurethane prepolymer;

b. Cool the polyurethane prepolymer to 60°C, first add 40% of the emulsifier, then dropwise add the comonomer, stir rapidly for 1 hour, and obtain the monomer pre-emulsion;

c. Import the remaining emulsifier and 30% initiator into the reactor, and protect it with nitrogen, add 10% monomer pre-emulsion, heat up to 80°C, stir until the emulsion is slightly blue, add the remaining monomer pre-emulsion dropwise Liquid and 60% initiator aqueous solution, the dropwise addition is completed within 2 hours, and add deionized water to disperse, control the temperature at 75 ° C, stir for 1 hour, then cool, add a pH regulator dropwise to adjust the pH value to 6.5, cool down and filter the material, Derived from cross-linked water repellent emulsion.

The waterproof base film comprises the raw materials of following parts by weight: 12 parts of auxiliary agent, 8 parts of deionized water and 80 parts of self-crosslinking type waterproof emulsion described in claims 1-9, said auxiliary agent includes parts by weight It is 1 part of thickener, 0.1 part of defoamer, 3 parts of wetting agent, 6 parts of film-forming aid, 5 parts of leveling agent, 2 parts of antifungal agent, and 0.4 part of dispersant. The thickener is TEGO ViscoPlus3030 associative water-based thickener, the defoamer is polysiloxane compound, and the wetting agent is alkyl naphthalene sulfonate and anionic wetting agent in a ratio of 1:2 mixture, the film-forming aid is ethylene glycol monobutyl ether, the leveling agent is an acrylic acid copolymer, and the dispersant is a polymer-type anionic dispersant: modified polyacrylic acid ammonium salt dispersant, anti-mildew The agent is Nipacide DFX/1 antifungal agent from Clariant Company.

Example 2

The self-crosslinking type waterproof emulsion of the present embodiment includes the following raw materials in parts by weight: 40 parts of polyisocyanates, 50 parts of oligomer polyols, 25 parts of chain extenders, 35 parts of end-capping agents, 3 parts of catalysts, comonomers 65 parts, 12 parts of emulsifier, 8 parts of initiator, 10 parts of pH adjuster, 36 parts of deionized water, comonomers are hard monomers, soft monomers and functional monomers in a mass ratio of 43:18: 18 mixes.

Wherein, the end-capping agent is a mixture of hydroxyethyl acrylate and hydroxyethyl methacrylate in a ratio of 1:3.5 in parts by mass. Wherein, the catalyst is a catalyst of organotin compound: stannous octoate. Wherein, the emulsifier is a mixture of ammonium perfluorooctanoate and sodium lauryl sulfate at a ratio of 3:1.5 in parts by mass. Wherein, the initiator is ammonium persulfate. Wherein, the pH regulator is ammonia water. The oligomer polyol is 1,4-cyclohexanedimethanol, polycaprolactone diol, polyethylene adipate, polycarbonate diol according to the following mass fraction ratio 4:0.1:0.5 : a mixture of 3. The chain extender includes an alcohol chain extender and a hydrophilic chain extender in a ratio of 1:1 in parts by mass. The alcohol chain extender is one or more of trimethylolpropane, glycerol and 1,2,6-hexanetriol. The hydrophilic chain extender is a mixture of diaminobenzoic acid, dimethylolpropionic acid and sodium ethylenediaminoethanesulfonate in the following parts by weight ratio of 0.1:2:3:7:0.5. The functional monomer is glycidyl methacrylate and silicone active monomer in a ratio of 8:6 by mass. The silicone reactive monomer includes γ-methacryloxypropyltrimethoxysilane.

A preparation method of self-crosslinking type waterproof emulsion, comprising the following steps:

a. Weigh the above-mentioned polyisocyanate in parts by mass, stir and heat up to 80°C, add chain extender dropwise, react for 4h, then heat up to 100°C for 2h, then add oligomer polyol dropwise after vacuum dehydration, react for 2h, Add end-capping agent, catalyst again, react for 2h, obtain polyurethane prepolymer;

b. Cool down the polyurethane prepolymer to 50°C, first add 35% into the emulsifier, then dropwise add the comonomer, and stir rapidly for 0.8h to obtain the monomer pre-emulsion;

c. Import the remaining emulsifier and 35% initiator into the reactor, and protect it with nitrogen, add 25% monomer pre-emulsion, heat up to 90°C, stir until the emulsion is slightly blue, add the remaining monomer pre-emulsion dropwise solution and 65% initiator aqueous solution, the dropwise addition is completed within 2 hours, and then add deionized water to disperse, control the temperature at 80°C, stir for 1.2 hours, then cool, add a pH regulator dropwise to adjust the pH value to 7, cool down and filter the material , obtained from a cross-linked waterproof emulsion.

The waterproof base film comprises the raw materials of following parts by weight: 5 parts of auxiliary agent, 2 parts of deionized water and 70 parts of self-crosslinking type waterproof emulsion described in claims 1-9, said auxiliary agent includes parts by weight It is 1 part of thickener, 0.1 part of defoamer, 2 parts of wetting agent, 5 parts of film-forming aid, 2 parts of leveling agent, 0.5 part of antifungal agent, and 0.1 part of dispersant. The thickener is TEGO ViscoPlus3030 associative water-based thickener, the defoamer is a modified polysiloxane compound, and the wetting agent is alkyl naphthalene sulfonate and anionic wetting agent in parts by mass Ratio is a mixture of 2:0.5, the film-forming aid is an alcohol ester compound, the leveling agent is a polysiloxane compound, and the dispersant is a polymer-type anionic dispersant, and the model is Hesman dispersant 7040, The antifungal agent is Nipacide DFX/1 antifungal agent from Clariant Company.

Example 3

The self-crosslinking type waterproof emulsion of the present embodiment includes the following raw materials in parts by weight: 30 parts of polyisocyanate, 20 parts of oligomer polyol, 14 parts of chain extender, 26 parts of end-capping agent, 2.0 parts of catalyst, comonomer 45 parts, 8 parts of emulsifier, 9 parts of initiator, 6 parts of pH adjuster, 55 parts of deionized water, comonomer is hard monomer, soft monomer and functional monomer, the mass ratio is 35:16: 13 mixes.

Wherein, the end-capping agent is a mixture of hydroxyethyl acrylate, hydroxyethyl methacrylate and caprolactam in a ratio of 1:3:6 in parts by mass. Wherein, the catalyst is a tertiary amine compound: N,N-dimethylcyclohexylamine. Wherein, the emulsifier is a mixture of ammonium perfluorooctanoate and sodium lauryl sulfate at a ratio of 2:7 in parts by mass. Wherein, the initiator is ammonium persulfate. Wherein, the pH regulator is ammonia water. The oligomer polyol is a mixture of 1,4-cyclohexanedimethanol, polycaprolactone diol and polyethylene adipate in a ratio of 2:3.5 in parts by mass. The chain extender includes an alcohol chain extender and a hydrophilic chain extender in a ratio of 7:6 in parts by mass. The alcohol chain extender is trimethylolpropane and 1,2,6-hexanetriol in a ratio of 2:1 in parts by mass. The hydrophilic chain extender is a mixture of diaminobenzoic acid, sodium ethylenediaminoethanesulfonate and sodium 1,4-butanediol-2-sulfonate in a ratio of parts by mass of 3:2.5:4. The functional monomer is glycidyl methacrylate and silicone active monomer in a ratio of 7:15 by mass. The silicone reactive monomer includes vinyltrimethoxysilane.

A preparation method of self-crosslinking type waterproof emulsion, comprising the following steps:

a. Weigh the above-mentioned polyisocyanate in parts by mass, stir and heat up to 70°C, add a chain extender dropwise, react for 3.5h, then raise the temperature to 90°C for 1.5h, then add dropwise the oligomer polyol after vacuum dehydration, and react 1.5h, add end-capping agent, catalyst again, react 1.5h, obtain polyurethane prepolymer;

b. Cool down the polyurethane prepolymer to 40°C, first add 30% of emulsifier, then dropwise add comonomer, and stir rapidly for 0.5h to obtain monomer pre-emulsion;

c. Import the remaining emulsifier and 40% initiator into the reactor, and protect it with nitrogen, add 30% monomer pre-emulsion, raise the temperature to 100°C, stir until the emulsion is slightly blue, add the remaining monomer pre-emulsion dropwise Liquid and 70% initiator aqueous solution, the dropwise addition is completed within 2 hours, and add deionized water to disperse, control the temperature at 85°C, stir for 1.5 hours, then cool, add pH regulator dropwise to adjust the pH value to 8.5, cool down and filter the material , obtained from a cross-linked waterproof emulsion.

The waterproof base film comprises the raw materials of following parts by weight: 20 parts of auxiliary agents, 15 parts of deionized water and 100 parts of self-crosslinking type waterproof emulsion described in claims 1-9, said auxiliary agents include parts by weight It is 2.5 parts of thickener, 0.5 parts of defoamer, 5.5 parts of wetting agent, 6 parts of film-forming aid, 5 parts of leveling agent, 2.5 parts of antifungal agent, and 0.5 part of dispersant. The thickener is TEGOViscoPlus 3030 associative water-based thickener, the defoamer is a modified polysiloxane compound, and the wetting agent is alkyl naphthalene sulfonate and anionic wetting agent in parts by mass The ratio is a mixture of 1:2, the film-forming aid is a mixture of dipropylene glycol butyl ether mixture and alcohol ester compound in a ratio of 0.5:1 by mass and number, and the leveling agent is polysiloxane compound, dispersant It is a polymer-type anionic dispersant: a modified polyacrylic acid ammonium salt dispersant, and the antifungal agent is NipacideDFX/1 antifungal agent from Clariant Company.

Example 4

The self-crosslinking type waterproof emulsion of the present embodiment includes the following raw materials in parts by weight: 80 parts of polyisocyanates, 60 parts of oligomer polyols, 30 parts of chain extenders, 40 parts of end-capping agents, 4.5 parts of catalysts, comonomers 85 parts, 13 parts of emulsifier, 7 parts of initiator, 17 parts of pH regulator, 60 parts of deionized water, comonomers are hard monomers, soft monomers and functional monomers in a mass ratio of 30:19: 20's mix.

Wherein, the end-capping agent is a mixture of hydroxyethyl acrylate, hydroxyethyl methacrylate and caprolactam in a ratio of 2:5:2.5:1 in parts by weight. Wherein, the catalyst is a catalyst of organotin compound: dibutyltin diacetate. Wherein, the emulsifier is a mixture of ammonium perfluorooctanoate and sodium lauryl sulfate at a weight ratio of 2:3. Wherein, the initiator is one of hydrogen peroxide. Wherein, the pH regulator is ammonia water. The oligomer polyol is 1,4-cyclohexanedimethanol, polycaprolactone diol, polyethylene adipate polyoxypropylene triol and polyoxypropylene tetraol in a ratio of 1 in parts by mass :1:1:1 mixture. The chain extender includes an alcohol chain extender and a hydrophilic chain extender in a ratio of 1:1.2-2:1 in parts by mass. The alcohol chain extender is 1,2,6-hexanetriol. The hydrophilic chain extender is diaminobenzoic acid, dimethylolpropionic acid, sodium ethylenediaminoethanesulfonate and 1,4-butanediol-2-sodium sulfonate in parts by weight ratio of 2: 2:1.5:3 mixture. The functional monomer is glycidyl methacrylate and silicone active monomer in a ratio of 5:20 by mass. The silicone active monomer comprises a mixture of vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane in a ratio of 3:7:1.5 in parts by mass.

A preparation method of self-crosslinking type waterproof emulsion, comprising the following steps:

a. Weigh the above-mentioned polyisocyanate in parts by mass, stir and heat up to 70°C, add a chain extender dropwise, react for 3.5h, then raise the temperature to 90°C for 1.5h, then add dropwise the oligomer polyol after vacuum dehydration, and react 1.5h, add end-capping agent, catalyst again, react 1.5h, obtain polyurethane prepolymer;

b. Cool down the polyurethane prepolymer to 40°C, first add 30% of emulsifier, then dropwise add comonomer, and stir rapidly for 0.5h to obtain monomer pre-emulsion;

c. Import the remaining emulsifier and 40% initiator into the reactor, and protect it with nitrogen, add 30% monomer pre-emulsion, raise the temperature to 100°C, stir until the emulsion is slightly blue, add the remaining monomer pre-emulsion dropwise Liquid and 70% initiator aqueous solution, the dropwise addition is completed within 2 hours, and add deionized water to disperse, control the temperature at 85°C, stir for 1.5 hours, then cool, add pH regulator dropwise to adjust the pH value to 8.5, cool down and filter the material , obtained from a cross-linked waterproof emulsion.

The waterproof base film comprises the raw materials of following parts by weight: 10 parts of auxiliary agent, 10 parts of deionized water and 80 parts of self-crosslinking type waterproof emulsion described in claims 1-9, said auxiliary agent includes parts by weight It is 3 parts of thickener, 0.5 part of defoamer, 5 parts of wetting agent, 8 parts of film-forming aid, 6 parts of leveling agent, 2 parts of antifungal agent, and 0.4 part of dispersant. The thickener is TEGO ViscoPlus3030 associative water-based thickener, the defoamer is a modified polysiloxane compound, and the wetting agent is alkyl naphthalene sulfonate and anionic wetting agent in parts by mass Ratio of 0.5:3 mixture, the film-forming aid is an alcohol ester compound, the leveling agent is an acrylic acid copolymer, the dispersant is a polymer-type anionic dispersant, and the model is Hesme dispersant 7040, and the anti-fungal agent Nipacide DFX/1 antifungal agent from Clariant Company was selected.

Example 5

The self-crosslinking type waterproof emulsion of the present embodiment includes the following raw materials in parts by weight: 20 parts of polyisocyanate, 20 parts of oligomer polyol, 15 parts of chain extender, 20 parts of end-capping agent, 0.2 part of catalyst, comonomer 55 parts, 5 parts of emulsifier, 5 parts of initiator, 5 parts of pH regulator, 8 parts of deionized water, the comonomer is hard monomer, soft monomer and functional monomer in a mass ratio of 20:12: 8 mixes.

Wherein, the end-capping agent is a mixture of hydroxyethyl acrylate, hydroxyethyl methacrylate and caprolactam in a ratio of 1:3:6 in parts by mass. Wherein, the catalyst is a tertiary amine compound: N,N-dimethylcyclohexylamine. Wherein, the emulsifier is a mixture of ammonium perfluorooctanoate and sodium lauryl sulfate at a ratio of 2:7 in parts by mass. Wherein, the initiator is ammonium persulfate. Wherein, the pH regulator is ammonia water. The oligomer polyol is a mixture of 1,4-cyclohexanedimethanol, polycaprolactone diol and polyethylene adipate in a ratio of 2:3.5 in parts by mass. The chain extender includes an alcohol chain extender and a hydrophilic chain extender in a ratio of 7:6 in parts by mass. The alcohol chain extender is trimethylolpropane and 1,2,6-hexanetriol in a ratio of 2:1 in parts by mass. The hydrophilic chain extender is a mixture of diaminobenzoic acid, sodium ethylenediaminoethanesulfonate and sodium 1,4-butanediol-2-sulfonate in a ratio of parts by mass of 3:2.5:4. The functional monomer is glycidyl methacrylate and silicone active monomer in a ratio of 7:15 by mass. The silicone reactive monomer includes vinyltrimethoxysilane.

A preparation method of self-crosslinking type waterproof emulsion, comprising the following steps:

a. Weigh the above-mentioned polyisocyanate in parts by mass, stir and heat up to 80°C, add chain extender dropwise, react for 4h, then heat up to 100°C for 2h, then add oligomer polyol dropwise after vacuum dehydration, react for 2h, Add end-capping agent, catalyst again, react for 2h, obtain polyurethane prepolymer;

b. Cool down the polyurethane prepolymer to 50°C, first add 35% into the emulsifier, then dropwise add the comonomer, and stir rapidly for 0.8h to obtain the monomer pre-emulsion;

c. Import the remaining emulsifier and 35% initiator into the reactor, and protect it with nitrogen, add 25% monomer pre-emulsion, heat up to 90°C, stir until the emulsion is slightly blue, add the remaining monomer pre-emulsion dropwise solution and 65% initiator aqueous solution, the dropwise addition is completed within 2 hours, and then add deionized water to disperse, control the temperature at 80°C, stir for 1.2 hours, then cool, add a pH regulator dropwise to adjust the pH value to 7, cool down and filter the material , obtained from a cross-linked waterproof emulsion.

The waterproof base film comprises the raw materials of following parts by weight: 20 parts of auxiliary agents, 15 parts of deionized water and 100 parts of self-crosslinking type waterproof emulsion described in claims 1-9, said auxiliary agents include parts by weight It is 2.5 parts of thickener, 0.5 parts of defoamer, 5.5 parts of wetting agent, 6 parts of film-forming aid, 5 parts of leveling agent, 2.5 parts of antifungal agent, and 0.5 part of dispersant. The thickener is TEGOViscoPlus 3030 associative water-based thickener, the defoamer is a modified polysiloxane compound, and the wetting agent is alkyl naphthalene sulfonate and anionic wetting agent in parts by mass The ratio is a mixture of 1:2, the film-forming aid is a mixture of dipropylene glycol butyl ether mixture and alcohol ester compound in a ratio of 0.5:1 by mass and number, and the leveling agent is polysiloxane compound, dispersant It is a polymer-type anionic dispersant: a modified polyacrylic acid ammonium salt dispersant, and the antifungal agent is NipacideDFX/1 antifungal agent from Clariant Company.

Example 6

The self-crosslinking type waterproof emulsion of the present embodiment includes the following raw materials in parts by weight: 30 parts of polyisocyanate, 20 parts of oligomer polyol, 14 parts of chain extender, 26 parts of end-capping agent, 2.0 parts of catalyst, comonomer 45 parts, 8 parts of emulsifier, 9 parts of initiator, 6 parts of pH adjuster, 55 parts of deionized water, comonomer is hard monomer, soft monomer and functional monomer, the mass ratio is 35:16: 13 mixes.

Wherein, the end-capping agent is a mixture of hydroxyethyl acrylate and hydroxyethyl methacrylate in a ratio of 1:3.5 in parts by mass. Wherein, the catalyst is a catalyst of organotin compound: stannous octoate. Wherein, the emulsifier is a mixture of ammonium perfluorooctanoate and sodium lauryl sulfate at a ratio of 3:1.5 in parts by mass. Wherein, the initiator is ammonium persulfate. Wherein, the pH regulator is ammonia water. The oligomer polyol is 1,4-cyclohexanedimethanol, polycaprolactone diol, polyethylene adipate, polycarbonate diol according to the following mass fraction ratio 4:0.1:0.5 : a mixture of 3. The chain extender includes an alcohol chain extender and a hydrophilic chain extender in a ratio of 1:1 in parts by mass. The alcohol chain extender is a mixture of trimethylolpropane, glycerol, and 1,2,6-hexanetriol in a ratio of 2:1.5:3 in parts by mass. The hydrophilic chain extender is a mixture of diaminobenzoic acid, dimethylolpropionic acid and sodium ethylenediaminoethanesulfonate in the following parts by weight ratio of 0.1:2:3:7:0.5. The functional monomer is glycidyl methacrylate and silicone active monomer in a ratio of 8:6 by mass. The silicone reactive monomer includes γ-methacryloxypropyltrimethoxysilane.

A preparation method of self-crosslinking type waterproof emulsion, comprising the following steps:

a. Weigh the above-mentioned polyisocyanate in parts by mass, stir and heat up to 80°C, add chain extender dropwise, react for 4h, then heat up to 100°C for 2h, then add oligomer polyol dropwise after vacuum dehydration, react for 2h, Add end-capping agent, catalyst again, react for 2h, obtain polyurethane prepolymer;

b. Cool down the polyurethane prepolymer to 50°C, first add 35% into the emulsifier, then dropwise add the comonomer, and stir rapidly for 0.8h to obtain the monomer pre-emulsion;

c. Import the remaining emulsifier and 35% initiator into the reactor, and protect it with nitrogen, add 25% monomer pre-emulsion, heat up to 90°C, stir until the emulsion is slightly blue, add the remaining monomer pre-emulsion dropwise solution and 65% initiator aqueous solution, the dropwise addition is completed within 2 hours, and then add deionized water to disperse, control the temperature at 80°C, stir for 1.2 hours, then cool, add a pH regulator dropwise to adjust the pH value to 7, cool down and filter the material , obtained from a cross-linked waterproof emulsion.

The waterproof base film comprises the raw materials of following parts by weight: 10 parts of auxiliary agent, 10 parts of deionized water and 80 parts of self-crosslinking type waterproof emulsion described in claims 1-9, said auxiliary agent includes parts by weight It is 3 parts of thickener, 0.5 part of defoamer, 5 parts of wetting agent, 8 parts of film-forming aid, 6 parts of leveling agent, 2 parts of antifungal agent, and 0.4 part of dispersant. The thickener is TEGO ViscoPlus3030 associative water-based thickener, the defoamer is a modified polysiloxane compound, and the wetting agent is alkyl naphthalene sulfonate and anionic wetting agent in parts by mass Ratio of 0.5:3 mixture, the film-forming aid is an alcohol ester compound, the leveling agent is an acrylic acid copolymer, the dispersant is a polymer-type anionic dispersant, and the model is Hesme dispersant 7040, and the anti-fungal agent Nipacide DFX/1 antifungal agent from Clariant Company was selected.

Example 7

The self-crosslinking type waterproof emulsion of the present embodiment includes the following raw materials in parts by weight: 20 parts of polyisocyanate, 20 parts of oligomer polyol, 15 parts of chain extender, 20 parts of end-capping agent, 0.2 part of catalyst, comonomer 55 parts, 5 parts of emulsifier, 5 parts of initiator, 5 parts of pH regulator, 8 parts of deionized water, the comonomer is hard monomer, soft monomer and functional monomer in a mass ratio of 20:12: 8 mixes.

Wherein, the end-capping agent is a mixture of hydroxyethyl acrylate, hydroxyethyl methacrylate and caprolactam in a ratio of 2:5:2.5:1 in parts by weight. Wherein, the catalyst is a catalyst of organotin compound: dibutyltin diacetate. Wherein, the emulsifier is a mixture of ammonium perfluorooctanoate and sodium lauryl sulfate at a weight ratio of 2:3. Wherein, the initiator is one of hydrogen peroxide. Wherein, the pH regulator is ammonia water. The oligomer polyol is 1,4-cyclohexanedimethanol, polycaprolactone diol, polyethylene adipate polyoxypropylene triol and polyoxypropylene tetraol in a ratio of 1 in parts by mass :1:1:1 mixture. The chain extender includes an alcohol chain extender and a hydrophilic chain extender in a ratio of 1:1.2-2:1 in parts by mass. The alcohol chain extender is 1,2,6-hexanetriol. The hydrophilic chain extender is diaminobenzoic acid, dimethylolpropionic acid, sodium ethylenediaminoethanesulfonate and 1,4-butanediol-2-sodium sulfonate in parts by weight ratio of 2: 2:1.5:3 mixture. The functional monomer is glycidyl methacrylate and silicone active monomer in a ratio of 5:20 by mass. The silicone active monomer comprises a mixture of vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane in a ratio of 3:7:1.5 in parts by mass.

A preparation method of self-crosslinking type waterproof emulsion, comprising the following steps:

a. Weigh the above-mentioned polyisocyanate in parts by mass, stir and heat up to 60°C, add chain extender dropwise, react for 3h, then heat up to 80°C for 1h, then add oligomer polyol dropwise after vacuum dehydration, react for 1h, Then add an end-capping agent and a catalyst, and react for 1 hour to obtain a polyurethane prepolymer;

b. Cool the polyurethane prepolymer to 60°C, first add 40% of the emulsifier, then dropwise add the comonomer, stir rapidly for 1 hour, and obtain the monomer pre-emulsion;

c. Import the remaining emulsifier and 30% initiator into the reactor, and protect it with nitrogen, add 10% monomer pre-emulsion, heat up to 80°C, stir until the emulsion is slightly blue, add the remaining monomer pre-emulsion dropwise Liquid and 60% initiator aqueous solution, the dropwise addition is completed within 2 hours, and add deionized water to disperse, control the temperature at 75 ° C, stir for 1 hour, then cool, add a pH regulator dropwise to adjust the pH value to 6.5, cool down and filter the material, Derived from cross-linked water repellent emulsion.

The waterproof base film comprises the raw materials of following parts by weight: 5 parts of auxiliary agent, 2 parts of deionized water and 70 parts of self-crosslinking type waterproof emulsion described in claims 1-9, said auxiliary agent includes parts by weight It is 1 part of thickener, 0.1 part of defoamer, 2 parts of wetting agent, 5 parts of film-forming aid, 2 parts of leveling agent, 0.5 part of antifungal agent, and 0.1 part of dispersant. The thickener is TEGO ViscoPlus3030 associative water-based thickener, the defoamer is a modified polysiloxane compound, and the wetting agent is alkyl naphthalene sulfonate and anionic wetting agent in parts by mass Ratio is a mixture of 2:0.5, the film-forming aid is an alcohol ester compound, the leveling agent is a polysiloxane compound, and the dispersant is a polymer-type anionic dispersant, and the model is Hesman dispersant 7040, The antifungal agent is Nipacide DFX/1 antifungal agent from Clariant Company.

Example 8

The self-crosslinking type waterproof emulsion of the present embodiment includes the following raw materials in parts by weight: 40 parts of polyisocyanates, 50 parts of oligomer polyols, 25 parts of chain extenders, 35 parts of end-capping agents, 3 parts of catalysts, comonomers 65 parts, 12 parts of emulsifier, 8 parts of initiator, 10 parts of pH adjuster, 36 parts of deionized water, comonomers are hard monomers, soft monomers and functional monomers in a mass ratio of 43:18: 18 mixes.

Wherein, the capping agent is methyl ethyl ketone oxime. Wherein, the catalyst is a catalyst of organotin compound: dibutyltin dilaurate. Wherein, the emulsifier is a composite emulsifier in which ammonium perfluorooctanoate and sodium lauryl sulfate are mixed at a ratio of 1:1 in parts by mass. Wherein, initiator is potassium persulfate. Wherein, the pH regulator is ammonia water. The oligomer polyol is 1,4-cyclohexanedimethanol, polyethylene adipate, polycarbonate diol and polyoxypropylene triol in a ratio of 1:1.5:2:2.5 in parts by mass mixture. The chain extender includes an alcohol chain extender and a hydrophilic chain extender in a ratio of 1.8:1 in parts by mass. The alcohol chain extender is trimethylolpropane. The hydrophilic chain extender is sodium ethylenediaminoethanesulfonate. The functional monomer is glycidyl methacrylate and silicone active monomer in a ratio of 8:15 by mass. The silicone reactive monomer includes vinyltriethoxysilane.

A preparation method of self-crosslinking type waterproof emulsion, comprising the following steps:

a. Weigh the above-mentioned polyisocyanate in parts by mass, stir and heat up to 70°C, add a chain extender dropwise, react for 3.5h, then raise the temperature to 90°C for 1.5h, then add dropwise the oligomer polyol after vacuum dehydration, and react 1.5h, add end-capping agent, catalyst again, react 1.5h, obtain polyurethane prepolymer;

b. Cool down the polyurethane prepolymer to 40°C, first add 30% of emulsifier, then dropwise add comonomer, and stir rapidly for 0.5h to obtain monomer pre-emulsion;

c. Import the remaining emulsifier and 40% initiator into the reactor, and protect it with nitrogen, add 30% monomer pre-emulsion, raise the temperature to 100°C, stir until the emulsion is slightly blue, add the remaining monomer pre-emulsion dropwise Liquid and 70% initiator aqueous solution, the dropwise addition is completed within 2 hours, and add deionized water to disperse, control the temperature at 85°C, stir for 1.5 hours, then cool, add pH regulator dropwise to adjust the pH value to 8.5, cool down and filter the material , obtained from a cross-linked waterproof emulsion.

The waterproof base film comprises the raw materials of following parts by weight: 20 parts of auxiliary agents, 15 parts of deionized water and 100 parts of self-crosslinking type waterproof emulsion described in claims 1-9, said auxiliary agents include parts by weight It is 2.5 parts of thickener, 0.5 parts of defoamer, 5.5 parts of wetting agent, 6 parts of film-forming aid, 5 parts of leveling agent, 2.5 parts of antifungal agent, and 0.5 part of dispersant. The thickener is TEGOViscoPlus 3030 associative water-based thickener, the defoamer is a modified polysiloxane compound, and the wetting agent is alkyl naphthalene sulfonate and anionic wetting agent in parts by mass The ratio is a mixture of 1:2, the film-forming aid is a mixture of dipropylene glycol butyl ether mixture and alcohol ester compound in a ratio of 0.5:1 by mass and number, and the leveling agent is polysiloxane compound, dispersant It is a polymer-type anionic dispersant: a modified polyacrylic acid ammonium salt dispersant, and the antifungal agent is NipacideDFX/1 antifungal agent from Clariant Company.

Performance Testing

The base film prepared in the above-mentioned Examples 1-8 was tested, and the base film prepared from a self-crosslinking waterproof emulsion containing a single monomer was used as Comparative Example 1 for testing, and the test method used the following method:

Determination of tensile strength and elongation at break of coating film: determined according to the measurement method of IS 7016-2-1981.

Coating film hardness measurement: measured according to the measurement method of GB/T 6739-2006.

Determination of coating film flexibility: determined according to the determination method of GB/T 1731-1993.

Determination of impact resistance of coating film: determined according to the determination method of GB/T 20624.1-2006.

Determination of water resistance of coating film: determined according to the determination method of GB/T 1733-1993.

Anti-seepage pressure of coating film: measured according to the test method of JC/T2217-2014.

The performance test result (1) of table 1 embodiment 1-8 and comparative example 1

Storage time (months) Tensile strength (MPa) Coating impermeability pressure (MPa) Elongation at break (%) Example 1 ≥6 11 1.5 364.7 Example 2 ≥7 10.5 1.6 387.1 Example 3 ≥6 10.3 1.3 384.1 Example 4 ≥9 12.2 1.4 376.2 Example 5 ≥7 11.4 1.5 420.2 Example 6 ≥8 10.6 1.4 370.9 Example 7 ≥7 11.7 1.5 393.6 Example 8 ≥8 12.4 1.4 382.3 Comparative example 1 3-4 7.8 0.7 256.8

The performance test result (two) of table 2 embodiment 1-8 and comparative example 1

hardness water resistance Flexibility/mm Impact resistance/g*cm Example 1 h Soak for 64 hours without foaming and falling off 0.6 500 Example 2 h Soak for 64 hours without foaming and falling off 0.5 500 Example 3 h Soak for 64 hours without foaming and falling off 0.5 500 Example 4 h After soaking for 64 hours, microbubbles on the surface will not fall off 0.6 500 Example 5 h Soak for 64 hours without foaming and falling off 0.5 500 Example 6 h Soak for 64 hours without foaming and falling off 0.6 500 Example 7 h Soak for 64 hours without foaming and falling off 0.5 500 Example 8 h Soak for 64 hours without foaming and falling off 0.6 500 Comparative example 1 B After soaking for 64 hours, the surface will bubble and fall off 0.4 365

As can be seen from Table 1 and Table 2, the self-crosslinking type waterproof emulsion prepared by the present invention has achieved multiple self-crosslinking, high crosslinking density, and a three-dimensional network polymer structure. After film formation, the molecular weight is very large, and its impact resistance, Compared with the ordinary self-crosslinking base film, the tear resistance is stronger, the weather resistance is good, the bonding force with the base surface is strong, the coating impermeability is strong, and it has strong flexibility.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand , the technical solution of the present invention may be modified or equivalently replaced without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

1. A self-crosslinking type waterproof emulsion, characterized in that: comprising the following raw materials in parts by weight: 20-80 parts of polyisocyanate 10-60 parts of oligomer polyol Chain extender 10~30 parts Blocking agent 10~40 parts Catalyst 0.1~5 parts Comonomer 40~90 parts Emulsifier 1~15 parts Initiator 1~10 parts pH adjuster 1~15 parts 5~60 parts of deionized water Wherein, the comonomer is a mixture of hard monomers, soft monomers and functional monomers in a mass fraction ratio of 30-50:10-20:5-20. 2. A kind of self-crosslinking type waterproof emulsion according to claim 1, is characterized in that: comprise the raw material of following parts by weight: 30-70 parts of polyisocyanate 15-50 parts of oligomer polyol Chain extender 10~20 parts Capping agent 20~30 parts Catalyst 0.1~2 parts Comonomer 45~90 parts Emulsifier 1~10 parts Initiator 1~5 parts pH adjuster 1~10 parts 10~50 parts of deionized water. 3. A kind of self-crosslinking type waterproof emulsion according to claim 1, is characterized in that: described oligomer polyol is 1,4-cyclohexanedimethanol, polycaprolactone diol, polyhexamethylene glycol One or more of polyoxypropylene glycol esters, polycarbonate diols, polyoxypropylene diols, polyoxypropylene triols and polyoxypropylene tetraols. 4. A kind of self-crosslinking type waterproof emulsion according to claim 1, is characterized in that: described chain extender comprises alcohol chain extender and hydrophilic chain extender and is 1:1.2-2 by mass and number ratio: 1. 5. A self-crosslinking type waterproof emulsion according to claim 1, characterized in that: the alcohol chain extender is one of trimethylolpropane, glycerol, 1,2,6-hexanetriol species or two or more. 6. A self-crosslinking type waterproof emulsion according to claim 1, characterized in that: said hydrophilic chain extender is diaminobenzoic acid, dimethylolpropionic acid, sodium ethylenediaminoethanesulfonate , 1,4-butanediol-2-sodium sulfonate and one or more of its derivatives. 7. A self-crosslinking type waterproof emulsion according to claim 1, characterized in that: the functional monomer is glycidyl methacrylate and the organic silicon active monomer has a mass fraction ratio of 1-10: 1-20. 8. A self-crosslinking type waterproof emulsion according to claim 1, characterized in that: the silicone active monomer comprises vinyltriethoxysilane, γ-methacryloxypropyltrimethoxy One or more of silane and vinyltrimethoxysilane. 9. the preparation method of a kind of self-crosslinking type waterproof emulsion described in claim 1-8 is characterized in that: comprise the following steps: a. Weigh the above-mentioned polyisocyanate in parts by mass, stir and heat up to 60~80°C, add chain extender dropwise, react for 3h~4h, then raise the temperature to 80-100°C for 1~2h, then add dropwise the low temperature after vacuum dehydration Polymer polyol, react for 1~2h, then add end-capping agent and catalyst, react for 1~2h to obtain polyurethane prepolymer; b. Cool down the polyurethane prepolymer to 40~60℃, add 30-40% emulsifier first, then add comonomer dropwise, and stir rapidly for 0.5~1h to obtain monomer preemulsion; c. Introduce the remaining emulsifier and 30~40% initiator into the reactor, and protect it with nitrogen, add 10~30% monomer pre-emulsion, raise the temperature to 80~100°C, stir until the emulsion is slightly blue, add dropwise Add the remaining monomer pre-emulsion and 60~70% initiator aqueous solution dropwise within 2 hours, add deionized water to disperse, control the temperature at 75~85°C, stir for 1~1.5 hours, then cool, add dropwise to adjust pH agent to adjust the pH value to 6.5-8.5, cool down and filter the material, obtained from cross-linked waterproof emulsion. 10. A waterproof base film, characterized in that: the waterproof base film is made of the following raw materials in parts by weight: 5 to 20 parts of auxiliary agent, 1 to 10 parts of deionized water and the automatic 70-100 parts of cross-linked waterproof emulsion, the additives include 1-3 parts by weight of thickener, 0.1-0.5 parts of defoamer, 2-6 parts of wetting agent, 5-9 parts of film-forming assistant agent, 2-6 parts leveling agent, 0.5-2.5 parts fungicide, 0.1-0.5 parts dispersant.