CN114395351A - Environment-friendly water-based resin for replacing self-adhesive PE (polyethylene) film of waterproof coiled material and preparation method thereof - Google Patents

Environment-friendly water-based resin for replacing self-adhesive PE (polyethylene) film of waterproof coiled material and preparation method thereof Download PDF

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CN114395351A
CN114395351A CN202210197425.0A CN202210197425A CN114395351A CN 114395351 A CN114395351 A CN 114395351A CN 202210197425 A CN202210197425 A CN 202210197425A CN 114395351 A CN114395351 A CN 114395351A
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parts
emulsifier
stirring
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water
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安吕
程昌华
郭伟
汪晓华
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Jiangsu Changhua Chemical Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • C08F290/068Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

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Abstract

The invention discloses an environment-friendly water-based resin for replacing a self-adhesive PE film of a waterproof coiled material and a preparation method thereof, wherein a monomer, an emulsifier, a pH value regulator, a seed emulsion, an initiator and adipic acid dihydrazide are added into soft water, and are stirred and mixed uniformly to prepare a pre-emulsion; adding soft water, a pH value regulator, a chain extender, a seed emulsion, an emulsifier and an initiator into a polymerization kettle, replacing air in the polymerization kettle with nitrogen, heating for reaction, dropwise adding the pre-emulsion, adding the monoacrylate terminated polysiloxane when dropwise adding is started, and carrying out heat preservation reaction after dropwise adding is finished to obtain the acrylic ester terminated polysiloxane modified polypropylene material. The water-based resin can be used for preparing a waterproof coiled material isolating membrane, replaces a PE membrane which is commonly used at present, is soft and non-sticky, has good adhesive force and stripping property, achieves the characteristic of easy stripping at various production and construction temperatures, and greatly improves the production and construction performance of the waterproof coiled material.

Description

Environment-friendly water-based resin for replacing self-adhesive PE (polyethylene) film of waterproof coiled material and preparation method thereof
Technical Field
The invention relates to a water-based resin, in particular to an environment-friendly water-based resin for replacing a self-adhesive PE (polyethylene) film of a waterproof coiled material and a preparation method thereof. Belongs to the technical field of waterproof coiled materials.
Background
The waterproof coiled material mainly comprises an asphalt waterproof coiled material and a high-molecular waterproof coiled material. The self-adhesive waterproof coiled material is one of asphalt waterproof coiled materials, is the best waterproof, moistureproof and sealing material for subways, tunnels and incombustible fields, and is also suitable for waterproof and anticorrosion engineering of pipelines. It has the elasticity of rubber, excellent tensile strength and excellent low temperature resistance.
In fact, the self-adhesive waterproof coiled material has good acid resistance, alkali resistance and chemical corrosion resistance, has excellent aging resistance in various environments, has a characteristic self-healing function, can automatically heal smaller puncture damages, can automatically integrate with objects when being punctured or embedded by hard objects, and keeps good waterproof performance. It is completely suitable for water proofing of roofs, basements, indoor rooms, municipal works and other places of industrial and civil buildings.
From the development condition of the building engineering in China, the self-adhesive waterproof coiled material is a novel waterproof material with development prospect; from the perspective of the environmental protection called for by our country, the self-adhesive waterproof coiled material is a novel material which has low-temperature flexibility, high construction speed and meets the environmental protection requirement.
South China, especially Guangdong and Hainan, is affected by tropical and subtropical climates, is in a high-temperature and rainy state all year round, and is mostly frozen, cold and windy and sandy in north China. This requires that the manufacturers of self-adhesive waterproof rolls and the construction methods of waterproof works cannot be practiced simply by using the same self-adhesive waterproof roll and the same construction method in all areas.
When the self-adhesive waterproof roll is used, the waterproof material is made of synthetic rubber, so that the waterproof material also has rubber elasticity, and the extensibility of the waterproof material is very good, so that the waterproof roll can be completely used on a building, and the condition that a building base layer is not deformed or cracked is ensured.
The self-adhesive waterproof roll has excellent adhesive force to a base layer, the adhesive force is generally better than that of other waterproof rolls, and the self-adhesive waterproof roll can be tightly lapped and has no gap when in use.
Besides the main material, the polyethylene film of the waterproof roll also has relatively excellent waterproof strength. Therefore, compared with the waterproof roll, the waterproof roll has double safety, and is more convenient and safer to use
PE isolating film, which is generally used on the self-adhesive coiled material; the polyester fiber is used as the isolating material for spraying the silicon oil on the lower surface of the tire body and aluminizing the upper surface, and the isolating material has the main functions of preventing the self-adhesive material from being adhered to equipment during processing, preventing the self-adhesive asphalt mixture from being adhered to a package of the self-adhesive asphalt mixture before construction during storage, transportation and use, and tearing off the membrane during waterproof construction.
However, due to the reason that the environmental temperature and the discharge temperature are too high, the isolation film is easy to deform and melt, so that a lot of isolation films are left in the process of using the coiled material, and the performances of the waterproof coiled material, such as the sealing property, the waterproofness and the like, are affected.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an environment-friendly water-based resin for replacing a self-adhesive PE film of a waterproof coiled material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of environment-friendly water-based resin for replacing a self-adhesive PE film of a waterproof coiled material comprises the following specific steps in parts by weight:
(1) firstly, 100 parts of monomer, 0.8-1 part of emulsifier, 0.02-0.03 part of pH value regulator, 10-20 parts of seed emulsion, 0.5-0.8 part of initiator and 1-2 parts of adipic acid dihydrazide are added into 80-90 parts of soft water, and are stirred and mixed uniformly to prepare pre-emulsion;
(2) adding 80-90 parts of soft water, 0.01-0.02 part of pH value regulator, 2-10 parts of chain extender, 2-4 parts of seed emulsion, 0.08-0.1 part of emulsifier and 0.05-0.07 part of initiator into a polymerization kettle, replacing air in the polymerization kettle with nitrogen, heating to 65-75 ℃, carrying out heat preservation reaction for 1-2 hours, heating to 84-86 ℃, dropwise adding the pre-emulsion obtained in the step (1), adding 2-5 parts of monoacrylate terminated polysiloxane when dropwise adding is started, carrying out heat preservation reaction for 1-1.5 hours after dropwise adding is finished, vacuumizing to remove residual monomers, cooling to 35-40 ℃, and filtering to obtain the water-based resin;
the monomer comprises two parts of a main monomer and an auxiliary monomer, wherein the main monomer is methyl methacrylate, butyl acrylate or isooctyl acrylate, and the auxiliary monomer is vinyl unsaturated carboxylic acid or vinyl unsaturated amide.
Preferably, the emulsifier is a mixture of an anionic emulsifier and a nonionic emulsifier, and the mass ratio of the anionic emulsifier to the nonionic emulsifier is 0.3-3: 0.1-1.5, wherein the anionic emulsifier is selected from one or more of sulfate, succinate, sulfonate or phosphate anionic emulsifier, and the nonionic emulsifier is selected from alkylphenol ethoxylates or fatty alcohol polyoxyethylene ether.
Preferably, the pH regulator is a sodium bicarbonate solution with the mass concentration of 5%, the chain extender is any one of hydroxyethyl methacrylate, hydroxyethyl acrylate or butylene glycol, and the initiator is potassium persulfate or ammonium persulfate.
Preferably, the preparation method of the seed emulsion comprises the following steps in parts by weight:
(A) adding 8-9 parts of potassium hydroxide into 400 parts of isopropanol, heating to reflux, steaming 350 parts of isopropanol, adding 140-150 parts of octamethylcyclotetrasiloxane, stirring at 110-120 ℃ for reaction for 100-120 minutes, cooling to 70-80 ℃, adding 9-11 parts of glacial acetic acid, keeping the temperature and stirring for 55-65 minutes, vacuumizing, and filtering to obtain an organic silicon prepolymer;
(B) then, 6-7 parts of deionized water and 0.2-0.3 part of glacial acetic acid are dropwise added into 70-80 parts of ethyl orthosilicate, stirred and reacted for 60-70 minutes at 85-95 ℃, vacuumized, added with the organic silicon prepolymer obtained in the step (A), heated to 135-145 ℃, stirred and reacted for 150-160 minutes, vacuumized, and cooled to room temperature, so that silicon dioxide nanoparticles with the surfaces coated with the organic silicon prepolymer are obtained;
(C) and (3) finally, stirring and mixing 220-240 parts of deionized water, 4-5 parts of sodium dodecyl sulfate and 0.3-0.5 part of initiator, adding 110-120 parts of methacrylic acid, 10-15 parts of double-bond grafted nano boron fiber and 8-10 parts of silica nanoparticles coated with organic silicon prepolymer obtained in the step (B), stirring and heating to 70-75 ℃, and preserving heat and stirring for 40-50 minutes to obtain the seed emulsion.
Further preferably, in the step (C), the preparation method of the double-bond grafted nano boron fiber comprises the following steps: adding 5-7 parts of gamma- (methacryloyloxy) propyl trimethoxy silane into 20-25 parts of absolute ethyl alcohol, uniformly stirring, adding 2-3 parts of nano boron fiber, stirring and heating until reflux, keeping the temperature and stirring for 8-10 hours, cooling, centrifuging and taking precipitate to obtain the double-bond grafted nano boron fiber.
Preferably, the ethylenically unsaturated carboxylic acid is selected from any one or more of acrylic acid, methacrylic acid, itaconic acid or maleic anhydride, and the ethylenically unsaturated amide is selected from any one or more of diacetone acrylamide, methacrylamide, dimethylacrylamide, methylolacrylamide or methylolmethacrylamide.
The environment-friendly water-based resin obtained by the preparation method can replace the self-adhesive PE film of the waterproof coiled material.
The environment-friendly water-based resin is applied to preparing the isolating membrane of the waterproof coiled material.
The invention has the beneficial effects that:
firstly, adding a monomer, an emulsifier, a pH value regulator, a seed emulsion, an initiator and adipic dihydrazide into soft water, and uniformly stirring to prepare a pre-emulsion; adding soft water, a pH value regulator, a chain extender, a seed emulsion, an emulsifier and an initiator into a polymerization kettle, replacing air in the polymerization kettle with nitrogen, heating for reaction, dropwise adding the pre-emulsion, adding the monoacrylate terminated polysiloxane when dropwise adding is started, and carrying out heat preservation reaction after dropwise adding is finished to obtain the water-based resin. The water-based resin can be used for preparing a waterproof coiled material isolating membrane, replaces a PE membrane which is commonly used at present, is soft and non-sticky, has good adhesive force and stripping property, achieves the characteristic of easy stripping at various production and construction temperatures, and greatly improves the production and construction performance of the waterproof coiled material.
The monomer comprises two parts of a main monomer and an auxiliary monomer, wherein the main monomer is methyl methacrylate, butyl acrylate or isooctyl acrylate, and the auxiliary monomer is vinyl unsaturated carboxylic acid or vinyl unsaturated amide. The obtained water-based resin is a silicone-acrylate emulsion, and has small particle size, high surface tension and excellent performance.
The preparation method of the seed emulsion comprises the following steps: adding potassium hydroxide into isopropanol, heating to reflux, steaming 350 parts of isopropanol, adding octamethylcyclotetrasiloxane, stirring for reaction, adding glacial acetic acid, stirring for reaction, vacuumizing, and filtering to obtain an organic silicon prepolymer; then, dropwise adding deionized water and glacial acetic acid into tetraethoxysilane, stirring for reaction, vacuumizing, then adding an organic silicon prepolymer, heating for reaction, vacuumizing, and cooling to room temperature to obtain silicon dioxide nanoparticles with surfaces coated with the organic silicon prepolymer; and finally, stirring and mixing deionized water, sodium dodecyl sulfate and an initiator, adding methacrylic acid, double-bond grafted nano boron fiber and silicon dioxide nano particles with the surfaces coated with the organic silicon prepolymer, stirring and heating for reaction to obtain the seed emulsion. The addition of the seed emulsion further improves various properties of the obtained water-based resin.
Detailed Description
The present invention will be further illustrated by the following examples, which are intended to be merely illustrative and not limitative.
Example 1:
a preparation method of environment-friendly water-based resin comprises the following specific steps:
(1) firstly, 100kg of monomer, 0.8kg of emulsifier, 0.03kg of pH value regulator, 10kg of seed emulsion, 0.8kg of initiator and 1kg of adipic acid dihydrazide are added into 90kg of soft water, and are stirred and mixed uniformly to prepare pre-emulsion;
(2) adding 80kg of soft water, 0.02kg of pH value regulator, 2kg of chain extender, 4kg of seed emulsion, 0.08kg of emulsifier and 0.07kg of initiator into a polymerization kettle, replacing the air in the polymerization kettle with nitrogen, heating to 65 ℃, carrying out heat preservation reaction for 2 hours, heating to 84 ℃, dropwise adding the pre-emulsion obtained in the step (1), adding 5kg of monoacrylate-terminated polysiloxane (silok 3821F 3) when dropwise adding is started, carrying out heat preservation reaction for 1 hour after dropwise adding is finished, vacuumizing to remove residual monomers, cooling to 40 ℃, and filtering to obtain the water-based resin;
the monomer comprises a main monomer and an auxiliary monomer, wherein the main monomer is a monomer prepared from the following components in a mass ratio of 1: 1 butyl acrylate and isooctyl acrylate, and the auxiliary monomer is methacrylic acid.
The emulsifier is a mixture of an anionic emulsifier and a nonionic emulsifier, and the mass ratio of the anionic emulsifier to the nonionic emulsifier is 0.3: 1.5, wherein the anionic emulsifier is sodium dodecyl benzene sulfonate, and the nonionic emulsifier is alkylphenol ethoxylates.
The pH regulator is sodium bicarbonate solution with the mass concentration of 5%, the chain extender is hydroxyethyl methacrylate, and the initiator is potassium persulfate.
The preparation method of the seed emulsion comprises the following steps:
(A) adding 8kg of potassium hydroxide into 400kg of isopropanol, heating to reflux, steaming out 350kg of isopropanol, adding 150kg of octamethylcyclotetrasiloxane, stirring and reacting at 110 ℃ for 120 minutes, cooling to 70 ℃, adding 11kg of glacial acetic acid, keeping the temperature and stirring for 55 minutes, vacuumizing, and filtering to obtain an organic silicon prepolymer;
(B) then, 6kg of deionized water and 0.3kg of glacial acetic acid are dripped into 80kg of ethyl orthosilicate, stirred and reacted for 70 minutes at the temperature of 85 ℃, vacuumized, added with the organic silicon prepolymer obtained in the step (A), heated to 135 ℃, stirred and reacted for 160 minutes, vacuumized and cooled to room temperature to obtain silicon dioxide nano particles with the surfaces coated with the organic silicon prepolymer;
(C) and (3) finally, stirring and mixing 220kg of deionized water, 5kg of sodium dodecyl sulfate and 0.3kg of initiator, adding 120kg of methacrylic acid, 10kg of double-bond grafted nano boron fiber and 10kg of silicon dioxide nano particles coated with the organic silicon prepolymer obtained in the step (B), stirring and heating to 70 ℃, and preserving heat and stirring for 50 minutes to obtain the seed emulsion.
In the step (C), the preparation method of the double-bond grafted nano boron fiber comprises the following steps: firstly, adding 5kg of gamma- (methacryloyloxy) propyl trimethoxy silane into 25kg of absolute ethyl alcohol, uniformly stirring, then adding 2kg of nano boron fiber, stirring and heating until reflux, keeping the temperature and stirring for 10 hours, cooling, centrifuging and taking precipitate to obtain the double-bond grafted nano boron fiber.
Example 2:
a preparation method of environment-friendly water-based resin comprises the following specific steps:
(1) firstly, 100kg of monomer, 1kg of emulsifier, 0.02kg of pH value regulator, 20kg of seed emulsion, 0.5kg of initiator and 2kg of adipic acid dihydrazide are added into 80kg of soft water, and are stirred and mixed uniformly to prepare pre-emulsion;
(2) adding 90kg of soft water, 0.01kg of pH value regulator, 10kg of chain extender, 2kg of seed emulsion, 0.1kg of emulsifier and 0.05kg of initiator into a polymerization kettle, replacing the air in the polymerization kettle with nitrogen, heating to 75 ℃, carrying out heat preservation reaction for 1 hour, heating to 86 ℃, dropwise adding the pre-emulsion obtained in the step (1), adding 2kg of monoacrylate-terminated polysiloxane (silok 3821F 3) when dropwise adding is started, carrying out heat preservation reaction for 1.5 hours after dropwise adding is finished, vacuumizing to remove residual monomers, cooling to 35 ℃, and filtering to obtain the water-based resin;
the monomer comprises a main monomer and an auxiliary monomer, wherein the main monomer is a monomer prepared from the following components in a mass ratio of 1: 1, and the auxiliary monomer is diacetone acrylamide.
The emulsifier is a mixture of an anionic emulsifier and a nonionic emulsifier, and the mass ratio of the anionic emulsifier to the nonionic emulsifier is 3: 0.1, wherein the anionic emulsifier is dihexyl sodium sulfosuccinate, and the nonionic emulsifier is fatty alcohol-polyoxyethylene ether.
The pH regulator is a sodium bicarbonate solution with the mass concentration of 5%, the chain extender is hydroxyethyl acrylate, and the initiator is ammonium persulfate.
The preparation method of the seed emulsion comprises the following steps:
(A) adding 9kg of potassium hydroxide into 400kg of isopropanol, heating to reflux, steaming out 350kg of isopropanol, adding 140kg of octamethylcyclotetrasiloxane, stirring and reacting at 120 ℃ for 100 minutes, cooling to 80 ℃, adding 9kg of glacial acetic acid, keeping the temperature and stirring for 65 minutes, vacuumizing, and filtering to obtain an organic silicon prepolymer;
(B) then 7kg of deionized water and 0.2kg of glacial acetic acid are dripped into 70kg of ethyl orthosilicate, stirred and reacted for 60 minutes at 95 ℃, vacuumized, added with the organic silicon prepolymer obtained in the step (A), heated to 145 ℃, stirred and reacted for 150 minutes, vacuumized and cooled to room temperature to obtain silicon dioxide nano particles with the surfaces coated with the organic silicon prepolymer;
(C) and (3) finally, stirring and mixing 240kg of deionized water, 4kg of sodium dodecyl sulfate and 0.5kg of initiator, adding 110kg of methacrylic acid, 15kg of double-bond grafted nano boron fiber and 8kg of silicon dioxide nano particles coated with the organic silicon prepolymer obtained in the step (B), stirring and heating to 75 ℃, and preserving heat and stirring for 40 minutes to obtain the seed emulsion.
In the step (C), the preparation method of the double-bond grafted nano boron fiber comprises the following steps: adding 7kg of gamma- (methacryloyloxy) propyl trimethoxy silane into 20kg of absolute ethanol, uniformly stirring, adding 3kg of nano boron fiber, stirring and heating until reflux, keeping the temperature and stirring for 8 hours, cooling, centrifuging and taking precipitate to obtain the double-bond grafted nano boron fiber.
Example 3:
a preparation method of environment-friendly water-based resin comprises the following specific steps:
(1) firstly, 100kg of monomer, 0.9kg of emulsifier, 0.025kg of pH value regulator, 15kg of seed emulsion, 0.7kg of initiator and 1.5kg of adipic acid dihydrazide are added into 85kg of soft water, and are stirred and mixed uniformly to prepare pre-emulsion;
(2) adding 85kg of soft water, 0.015kg of pH value regulator, 7kg of chain extender, 3kg of seed emulsion, 0.09kg of emulsifier and 0.06kg of initiator into a polymerization kettle, replacing the air in the polymerization kettle with nitrogen, heating to 70 ℃, carrying out heat preservation reaction for 1.5 hours, heating to 85 ℃, dropwise adding the pre-emulsion obtained in the step (1), adding 4kg of monoacrylate-terminated polysiloxane (silok 3821F 3) when dropwise adding is started, carrying out heat preservation reaction for 1.5 hours after dropwise adding is finished, vacuumizing to remove residual monomers, cooling to 38 ℃, and filtering to obtain the water-based resin;
the monomer comprises two parts of a main monomer and an auxiliary monomer, wherein the main monomer is methyl methacrylate, butyl acrylate and isooctyl acrylate, and the mass ratio of the methyl methacrylate to the butyl acrylate to the isooctyl acrylate is 11: 3: 4, the auxiliary monomer is methacrylic acid, maleic anhydride and hydroxymethyl acrylamide, and the mass ratio of the methacrylic acid to the maleic anhydride to the hydroxymethyl acrylamide is 1: 1: 1.
the emulsifier is a mixture of an anionic emulsifier and a nonionic emulsifier, and the mass ratio of the anionic emulsifier to the nonionic emulsifier is 2: 1, wherein the anionic emulsifier is dihexyl sodium sulfosuccinate and phosphate ester anionic emulsifier, and the mass ratio of the dihexyl sodium sulfosuccinate to the phosphate ester anionic emulsifier is 1: 1, the nonionic emulsifier is alkylphenol polyoxyethylene.
The pH regulator is sodium bicarbonate solution with the mass concentration of 5%, the chain extender is hydroxyethyl methacrylate, and the initiator is potassium persulfate.
The preparation method of the seed emulsion comprises the following steps:
(A) adding 8.5kg of potassium hydroxide into 400kg of isopropanol, heating to reflux, steaming out 350kg of isopropanol, adding 145kg of octamethylcyclotetrasiloxane, stirring and reacting at 115 ℃ for 110 minutes, cooling to 75 ℃, adding 10kg of glacial acetic acid, keeping the temperature and stirring for 60 minutes, vacuumizing, and filtering to obtain an organic silicon prepolymer;
(B) then, 6.5kg of deionized water and 0.25kg of glacial acetic acid are dropwise added into 75kg of ethyl orthosilicate, stirred and reacted for 65 minutes at 90 ℃, vacuumized, added with the organic silicon prepolymer obtained in the step (A), heated to 140 ℃, stirred and reacted for 155 minutes, vacuumized and cooled to room temperature to obtain silicon dioxide nanoparticles with the surfaces coated with the organic silicon prepolymer;
(C) and finally, stirring and mixing 230kg of deionized water, 4.5kg of sodium dodecyl sulfate and 0.4kg of initiator, adding 115kg of methacrylic acid, 12kg of double-bond grafted nano boron fiber and 9kg of silicon dioxide nano particles coated with the organic silicon prepolymer obtained in the step (B), stirring and heating to 72 ℃, and preserving heat and stirring for 45 minutes to obtain the seed emulsion.
In the step (C), the preparation method of the double-bond grafted nano boron fiber comprises the following steps: firstly, adding 6kg of gamma- (methacryloyloxy) propyl trimethoxy silane into 22kg of absolute ethyl alcohol, uniformly stirring, then adding 2.5kg of nano boron fiber, stirring and heating until reflux, keeping the temperature and stirring for 9 hours, cooling, centrifuging and taking precipitate to obtain the double-bond grafted nano boron fiber.
Comparative example
A preparation method of environment-friendly water-based resin comprises the following specific steps:
(1) firstly, 100kg of monomer, 0.8kg of emulsifier, 0.03kg of pH value regulator, 10kg of seed emulsion, 0.8kg of initiator and 1kg of adipic acid dihydrazide are added into 90kg of soft water, and are stirred and mixed uniformly to prepare pre-emulsion;
(2) adding 80kg of soft water, 0.02kg of pH value regulator, 2kg of chain extender, 4kg of seed emulsion, 0.08kg of emulsifier and 0.07kg of initiator into a polymerization kettle, replacing the air in the polymerization kettle with nitrogen, heating to 65 ℃, carrying out heat preservation reaction for 2 hours, heating to 84 ℃, dropwise adding the pre-emulsion obtained in the step (1), adding 5kg of monoacrylate-terminated polysiloxane (silok 3821F 3) when dropwise adding is started, carrying out heat preservation reaction for 1 hour after dropwise adding is finished, vacuumizing to remove residual monomers, cooling to 40 ℃, and filtering to obtain the water-based resin;
the monomer comprises a main monomer and an auxiliary monomer, wherein the main monomer is a monomer prepared from the following components in a mass ratio of 1: 1 butyl acrylate and isooctyl acrylate, and the auxiliary monomer is methacrylic acid.
The emulsifier is a mixture of an anionic emulsifier and a nonionic emulsifier, and the mass ratio of the anionic emulsifier to the nonionic emulsifier is 0.3: 1.5, wherein the anionic emulsifier is sodium dodecyl benzene sulfonate, and the nonionic emulsifier is alkylphenol ethoxylates.
The pH regulator is sodium bicarbonate solution with the mass concentration of 5%, the chain extender is hydroxyethyl methacrylate, and the initiator is potassium persulfate.
The preparation method of the seed emulsion comprises the following steps: stirring and mixing 220kg of deionized water, 5kg of sodium dodecyl sulfate and 0.3kg of initiator, adding 120kg of methacrylic acid, stirring and heating to 70 ℃, preserving heat and stirring for 50 minutes to obtain the seed emulsion.
Test examples
The performance of the aqueous resins obtained in examples 1-3 and comparative example was tested, and the results are shown in Table 1.
Wherein, the solid content is detected according to GB/T1725-2007, the viscosity is detected by a viscometer, and the peel strength is detected according to GB/T2790-1995.
TABLE 1 Performance test results
Solid content (%) Viscosity (mpa.s) Peel strength (kN/m)
Example 1 43.5 470 0.31
Example 2 43.9 473 0.30
Example 3 51.2 500 0.18
Comparative example 35.3 424 0.96
As can be seen from Table 1, the waterborne resin obtained in the examples 1-3 has high solid content, high viscosity and low peel strength, which indicates that the waterborne resin has good adhesive force and is easy to peel, and the production and construction performance of the waterproof roll are greatly improved.
The comparative example omits double bond grafted nano boron fiber and silicon dioxide nano particle with surface coated with organic silicon prepolymer when preparing the seed emulsion, and all performances are obviously poor, thus showing that the preparation of the specific seed emulsion of the invention determines all performances of the finally obtained water-based resin.
Although the present invention has been described with reference to the specific embodiments, it is not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.

Claims (8)

1. The preparation method of the environment-friendly water-based resin for replacing the self-adhesive PE film of the waterproof coiled material is characterized by comprising the following specific steps in parts by weight:
(1) firstly, 100 parts of monomer, 0.8-1 part of emulsifier, 0.02-0.03 part of pH value regulator, 10-20 parts of seed emulsion, 0.5-0.8 part of initiator and 1-2 parts of adipic acid dihydrazide are added into 80-90 parts of soft water, and are stirred and mixed uniformly to prepare pre-emulsion;
(2) adding 80-90 parts of soft water, 0.01-0.02 part of pH value regulator, 2-10 parts of chain extender, 2-4 parts of seed emulsion, 0.08-0.1 part of emulsifier and 0.05-0.07 part of initiator into a polymerization kettle, replacing air in the polymerization kettle with nitrogen, heating to 65-75 ℃, carrying out heat preservation reaction for 1-2 hours, heating to 84-86 ℃, dropwise adding the pre-emulsion obtained in the step (1), adding 2-5 parts of monoacrylate terminated polysiloxane when dropwise adding is started, carrying out heat preservation reaction for 1-1.5 hours after dropwise adding is finished, vacuumizing to remove residual monomers, cooling to 35-40 ℃, and filtering to obtain the water-based resin;
the monomer comprises two parts of a main monomer and an auxiliary monomer, wherein the main monomer is methyl methacrylate, butyl acrylate or isooctyl acrylate, and the auxiliary monomer is vinyl unsaturated carboxylic acid or vinyl unsaturated amide.
2. The preparation method according to claim 1, wherein the emulsifier is a mixture of an anionic emulsifier and a nonionic emulsifier, and the mass ratio of the anionic emulsifier to the nonionic emulsifier is 0.3-3: 0.1-1.5, wherein the anionic emulsifier is selected from one or more of sulfate, succinate, sulfonate or phosphate anionic emulsifier, and the nonionic emulsifier is selected from alkylphenol ethoxylates or fatty alcohol polyoxyethylene ether.
3. The preparation method according to claim 1, wherein the pH regulator is a 5% sodium bicarbonate solution, the chain extender is any one of hydroxyethyl methacrylate, hydroxyethyl acrylate or butylene glycol, and the initiator is potassium persulfate or ammonium persulfate.
4. The method of claim 1, wherein the seed emulsion is prepared by the following steps in parts by weight:
(A) adding 8-9 parts of potassium hydroxide into 400 parts of isopropanol, heating to reflux, steaming 350 parts of isopropanol, adding 140-150 parts of octamethylcyclotetrasiloxane, stirring at 110-120 ℃ for reaction for 100-120 minutes, cooling to 70-80 ℃, adding 9-11 parts of glacial acetic acid, keeping the temperature and stirring for 55-65 minutes, vacuumizing, and filtering to obtain an organic silicon prepolymer;
(B) then, 6-7 parts of deionized water and 0.2-0.3 part of glacial acetic acid are dropwise added into 70-80 parts of ethyl orthosilicate, stirred and reacted for 60-70 minutes at 85-95 ℃, vacuumized, added with the organic silicon prepolymer obtained in the step (A), heated to 135-145 ℃, stirred and reacted for 150-160 minutes, vacuumized, and cooled to room temperature, so that silicon dioxide nanoparticles with the surfaces coated with the organic silicon prepolymer are obtained;
(C) and (3) finally, stirring and mixing 220-240 parts of deionized water, 4-5 parts of sodium dodecyl sulfate and 0.3-0.5 part of initiator, adding 110-120 parts of methacrylic acid, 10-15 parts of double-bond grafted nano boron fiber and 8-10 parts of silica nanoparticles coated with organic silicon prepolymer obtained in the step (B), stirring and heating to 70-75 ℃, and preserving heat and stirring for 40-50 minutes to obtain the seed emulsion.
5. The preparation method according to claim 4, wherein in the step (C), the double-bond grafted nano boron fiber is prepared by the following steps in parts by weight: adding 5-7 parts of gamma- (methacryloyloxy) propyl trimethoxy silane into 20-25 parts of absolute ethyl alcohol, uniformly stirring, adding 2-3 parts of nano boron fiber, stirring and heating until reflux, keeping the temperature and stirring for 8-10 hours, cooling, centrifuging and taking precipitate to obtain the double-bond grafted nano boron fiber.
6. The method according to claim 1, wherein the ethylenically unsaturated carboxylic acid is selected from any one or more of acrylic acid, methacrylic acid, itaconic acid, and maleic anhydride, and the ethylenically unsaturated amide is selected from any one or more of diacetone acrylamide, methacrylamide, dimethylacrylamide, methylolacrylamide, and methylolmethacrylamide.
7. The environment-friendly water-based resin obtained by the preparation method of any one of claims 1 to 6 replaces a self-adhesive PE film of a waterproof coiled material.
8. Use of the environment-friendly aqueous resin according to claim 7 for preparing a waterproofing membrane separator.
CN202210197425.0A 2022-03-02 2022-03-02 Environment-friendly water-based resin for replacing self-adhesive PE (polyethylene) film of waterproof coiled material and preparation method thereof Pending CN114395351A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117728110A (en) * 2024-02-07 2024-03-19 盐城博盛新能源有限公司 Preparation method of sodium ion battery diaphragm

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117728110A (en) * 2024-02-07 2024-03-19 盐城博盛新能源有限公司 Preparation method of sodium ion battery diaphragm
CN117728110B (en) * 2024-02-07 2024-04-09 盐城博盛新能源有限公司 Preparation method of sodium ion battery diaphragm

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