CN114806360A - Waterproof material - Google Patents
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- CN114806360A CN114806360A CN202210446705.0A CN202210446705A CN114806360A CN 114806360 A CN114806360 A CN 114806360A CN 202210446705 A CN202210446705 A CN 202210446705A CN 114806360 A CN114806360 A CN 114806360A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/325—Polyamines containing secondary or tertiary amino groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/02—Polyureas
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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Abstract
The invention discloses a waterproof material, which comprises a base body, an anti-sticking layer and an adhesive layer for bonding the base body and the anti-sticking layer, wherein the adhesive layer is prepared from a photo-curing polyurea coating; the photo-curing polyurea coating comprises a first component and a second component, wherein the first component comprises an isocyanate polyurea prepolymer and acrylic acid modified polyurea resin; the second component comprises amino-terminated polyether, amine chain extender, plasticizer, photoinitiator and auxiliary agent; the acrylic modified polyurea resin is prepared from the isocyanate polyurea prepolymer and reactive acrylate, wherein the reactive acrylate is acrylate containing hydroxyl or amino. The photocuring polyurea coating in the waterproof material is in a two-component form, the isocyanate polyurea prepolymer in the first component reacts firstly to form an initial molecular crosslinking framework, and the acrylic acid modified polyurea resin can be quickly cured to form a film, so that the final strength is achieved, the curing time is short, and no special requirement is imposed on the curing temperature.
Description
The application is a divisional application of an invention patent application with the application date of 2021, 2 and 4, and the application number of 2021101530414, and the invention name of the invention is 'photo-curing polyurea coating and a preparation method thereof and a waterproof material'.
Technical Field
The invention relates to the technical field of waterproof materials, in particular to a waterproof material with an adhesive layer formed by curing a photo-curing polyurea coating.
Background
As in patent application No. CN201910546432.5, entitled: a single-component photocuring polyurea waterproof coating and a Chinese invention patent application of a preparation process thereof disclose the single-component photocuring polyurea waterproof coating. Although the polyurea coating improves the low-temperature flexibility, the bonding strength, the weather resistance and the mechanical property of the polyurea coating to a certain extent, the polyurea coating also has the problems of dependence on the environment temperature for curing and crosslinking, time for deep curing and strength, low construction efficiency and the like. There are many limitations in using it in a waterproof coating material.
Disclosure of Invention
In view of the above, in order to overcome the defects of the prior art, the present invention aims to provide a waterproof material, wherein an improved photo-curable polyurea coating is adopted, the curing time is short, no special requirement is imposed on the curing temperature, and the construction efficiency is high.
In order to achieve the purpose, the invention adopts the following technical scheme:
a photo-curing polyurea coating comprises a first component and a second component, wherein the first component comprises an isocyanate polyurea prepolymer and an acrylic acid modified polyurea resin; the second component comprises amine-terminated polyether, an amine chain extender, a plasticizer, a photoinitiator and an auxiliary agent, and the weight ratio of the first component to the second component in the photocuring polyurea coating is 1: 0.2-2. The mass ratio of the isocyanate polyurea prepolymer to the acrylic acid modified polyurea resin in the first component is 1:0.5 to 2; the mass ratio of the amine-terminated polyether to the amine chain extender in the second component is 1: 0.5-2.
According to some preferred embodiments of the present invention, the isocyanate polyurea prepolymer is prepared from a secondary hindered amine and an isocyanate, wherein the secondary hindered amine is a compound having the following general formula:
wherein X is an alkyl group having 1 to 3 carbon atoms, and R is 1 、R 2 、R 3 、R 4 Are each a linear or branched alkyl group having 2 to 8 carbon atoms.
The cohesive strength and the permanent viscosity of the material can be improved by introducing a large number of urea bonds. The bi-component polyurea has rapid reaction, high material crosslinking density and short strength time reaching the end point, and can improve the efficiency of on-site glue preparation. It has high permeability and hydrophilicity, and can slowly permeate into various base materials, strengthen chemical and physical anchoring and raise the adhesion to various base materials.
In some preferred embodiments of the present invention, the isocyanate is selected from one, a combination of two or more of diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), Xylylene Diisocyanate (XDI), hydrogenated diphenylmethane diisocyanate, and the like.
According to some preferred embodiments of the present invention, the acrylic-modified polyurea resin is prepared from the isocyanate polyurea prepolymer and a reactive acrylate, which is an acrylate containing a hydroxyl group or an amino group. The double bond of acrylic acid can realize cross-linking curing reaction under the action of photoinitiator, and acrylic acid is grafted to the main chain of polyurea to realize end capping and provide cross-linking points.
In some preferred embodiments of the present invention, the reactive acrylate is selected from the group consisting of hydroxyethyl acrylate (HeA), hydroxyethyl methacrylate (HeMA), and hydroxyacrylic resins. Wherein the hydroxy acrylic resin can be selected from hydroxy acrylic resin HAR863, hydroxy acrylic resin HAR864, hydroxy acrylic resin HAR865, hydroxy acrylic resin HAR867, hydroxy acrylic resin HAR869, hydroxy acrylic resin HAR887, hydroxy acrylic resin HAR960, and hydroxy acrylic resin HAR 970.
The reactive acrylate is obtained by polymerizing an acrylic monomer, and in some preferred embodiments of the present invention, the acrylic monomer is selected from one, a combination of two or more of methyl methacrylate, 2-phenoxyethyl acrylate (PHEA), Lauryl Acrylate (LA), Stearyl Acrylate (SA), ethoxyethoxyethyl acrylate (EOEOEOEA), tetrahydrofurfuryl acrylate (THFA), tetrahydrofurfuryl methacrylate (THFMA), isopropylidene methacrylate (IBOMA), isobornyl acrylate (IBOA), cyclotrimethylolpropane formal acrylate (CTFA), Lauryl Methacrylate (LMA), Stearyl Methacrylate (SMA), methoxypolyethylene glycol (340) acrylate (MPEG (340) A), and o-phenylphenoxyethyl acrylate.
According to some preferred embodiments of the invention, the amine chain extender in the second component is a compound having the following general formula:
wherein X is an alkyl group having 1 to 3 carbon atoms, and R is 1 、R 2 、R 3 、R 4 Are each a linear or branched alkyl group having 2 to 8 carbon atoms.
In some preferred embodiments of the invention, the amine chain extender may remain the same compound as the secondary hindered amine, or a different compound may be used but conforming to the general formula described above.
According to some preferred embodiments of the invention, the amino-terminated polyether is a primary amino polyether or a secondary amino polyether.
In some preferred embodiments of the present invention, the amino-terminated polyether is a primary amino polyether such as D230, D400, D2000, D4000, T403, T3000, T5000, etc. from Hensman, or a secondary amino polyether such as SD231, SD401, SD2001, etc. from Hensman.
In some preferred embodiments of the present invention, the photoinitiator is selected from one or a combination of two or more of fluorinated diphenyltitanocene and bis (pentafluorophenyl) titanocene, benzophenone derivatives, thioxanthone derivatives, alkyl aryl ketone derivatives, and benzil derivatives. Such as Tianjin Jiu Xin material JRCure-1055, JRCure-1065, JRCure-1103, JRCure-1104, JRCure-1107, JRCure-1108, JRCure-1110, JRCure-1112, JRCure-1113, JRCure-1114, JRCure-1116.
In some preferred embodiments of the present invention, the plasticizer is selected from at least one of naphthenic oil, chlorinated paraffin, DINP (diisononyl phthalate), DIDP (diisodecyl phthalate), DOTP (dioctyl terephthalate), vegetable fat, and the like.
In some preferred embodiments of the present invention, the auxiliary agent comprises conventional agents such as antifoaming agents, antioxidants, and the like, which may be selected according to the actual situation.
Wherein the defoaming agent is one or the combination of two or more of physical defoaming agents such as polysiloxane defoaming agent and/or silicone defoaming agent, and chemical defoaming agents such as calcium oxide, magnesium oxide, calcium hydroxide, oxazolidine latent curing agent and ketimine latent curing agent.
The antioxidant is one or two or more selected from 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether and tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
The invention also provides a preparation method of the photocuring polyurea coating, which comprises the following steps:
preparing an isocyanate polyurea prepolymer: adding isocyanate into sterically hindered secondary amine with the moisture content of below 300ppm for reaction, sampling and testing the mass fraction of NCO to reach a preset value, and finishing the reaction to obtain a polyurea prepolymer;
preparing acrylic acid modified polyurea resin: mixing the isocyanate polyurea prepolymer, reactive acrylate and a polymerization inhibitor, reacting, sampling, determining that the mass fraction of NCO reaches a preset value, and finishing the reaction to obtain acrylic acid modified polyurea resin;
preparing a first component: mixing the isocyanate polyurea prepolymer and the acrylic acid modified polyurea resin to obtain the first component;
preparing a second component: and mixing and dehydrating the amino-terminated polyether, the amine chain extender and the plasticizer until the moisture content is below 300ppm, adding the photoinitiator and the auxiliary agent, and uniformly stirring to obtain the second component.
According to some preferred embodiments of the present invention, in the step of preparing the isocyanate polyurea prepolymer, the preset value of the mass fraction of NCO of the reaction system is 1 to 5%; in the step of preparing the acrylic modified polyurea resin, the preset value of the mass fraction of NCO of the reaction system is 0%, that is, all the isocyanates in the system are reacted at the time of preparing the acrylic modified polyurea resin.
According to some preferred embodiments of the present invention, the dehydration temperature for the preparation of the isocyanate polyurea prepolymer and the second component is 115-130 ℃. In some preferred embodiments of the invention, the dehydration temperature is preferably 120 ℃.
In some embodiments of the present invention, the method for preparing a photocurable polyurea coating specifically comprises the steps of:
1) preparation of isocyanate polyurea prepolymer
Dehydrating sterically hindered secondary amine at 120 ℃ until the water content is below 300ppm, then dropwise adding isocyanate, reacting for 2-4h at 70-100 ℃, sampling to test that the mass fraction of NCO reaches a preset value, and finishing the reaction to obtain the isocyanate polyurea prepolymer.
2) Preparation of acrylic acid-modified polyurea resin
Mixing the isocyanate polymerization prepolymer prepared in the step 1) with reactive acrylate, polymerization inhibitor and the like in a reaction kettle according to a ratio, reacting for 4-6h at 70-100 ℃, sampling to determine that the mass fraction of NCO reaches a preset value, and finishing the reaction to obtain the acrylic acid modified polyurea resin.
3) Preparation of the first component
Mixing the isocyanate polyurea prepolymer prepared in the step 1) and the acrylic acid modified polyurea resin prepared in the step 2) to obtain a first component.
4) Preparation of the second component
Dewatering the amine-terminated polyether, the amine chain extender and the plasticizer at 120 ℃ until the water content is below 300ppm, then cooling to 55 ℃, adding the photoinitiator, the auxiliary agent, the color paste and the like, stirring uniformly and defoaming for 30min to obtain the second component. And (4) sealing and storing the second component in dark.
For convenience of description and understanding, the steps are distinguished and numbered, and in actual preparation, the steps such as the preparation of the isocyanate polyurea prepolymer and the acrylic acid modified polyurea resin in the first component, the preparation of the second component and the like can be carried out simultaneously or sequentially.
The invention also provides a waterproof material which comprises a base body, an anti-sticking layer and an adhesive layer for bonding the base body and the anti-sticking layer, wherein the adhesive layer is prepared from the photocuring polyurea coating. The photocuring polyurea coating is used on a waterproof coiled material, so that the cohesiveness and ultraviolet resistance of a waterproof material and the adhesive holding capacity of self-healing of a coating can be improved.
According to some preferred embodiments of the present invention, the waterproof material is obtained by mixing and reacting the first component and the second component, applying the mixture onto the substrate, and irradiating the substrate with ultraviolet rays to obtain the adhesive layer. Specifically, a first component and a second component are added into a reaction kettle, the reaction is carried out for 1-3 hours at 20-60 ℃, after the materials are fully reacted, the materials are coated on a substrate through a coater or naturally flow to the substrate to be uniformly spread, then the materials enter an ultraviolet irradiation box, and other bonding layers or anti-sticking layers are attached after photocuring and shaping, so that the finished coiled material can be formed.
In some preferred embodiments of the present invention, the substrate may be a tire base or another release layer, and the tire base is a PET polyester film, a cross-laminated film, a PE film, a PVC sheet, a PE sheet, a TPO sheet, a composite sheet, a polyester non-woven tire base, a fiberglass tire, a copper tire base, a composite tire base, or the like.
In some preferred embodiments of the present invention, the anti-adhesion layer may be natural sand, machine-made sand or other fine powder, a silicone oil film, an emulsion, or the like.
In some embodiments of the invention, when the substrate is a release layer, the waterproofing material is free of a matrix, and in its simplest form, has a polyurea tie layer between two release layers formed using the photocurable polyurea coating described above.
In some preferred embodiments of the present invention, other adhesive layers may be disposed between the base and the release layer in addition to the adhesive layer prepared from the photocurable polyurea coating; other adhesive layers can be asphalt glue, epoxy glue, butyl glue, hot-melt pressure-sensitive glue, polyurethane glue and other glue materials.
Compared with the prior art, the invention has the advantages that: the adhesive layer in the waterproof material is formed by the photo-cured polyurea coating, the photo-cured polyurea coating is in a two-component form, when the waterproof material is used, after the first component and the second component are mixed, the isocyanate polyurea prepolymer in the first component can react with the amino material (amine-terminated polyether and amine chain extender) in the second component to form an initial molecular crosslinking framework, then, after the ultraviolet irradiation of carbon-carbon double bond in the acrylic acid modified polyurea resin, the quick deep drying and curing can be realized to form a film, the final strength can be reached through the quick crosslinking and curing, the curing time is short, no special requirement is made on the curing temperature, and the construction aging rate is high; also has excellent cohesiveness and self-repairing and self-healing performance.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic sectional view of a waterproof material according to preferred embodiment 1 of the present invention;
FIG. 2 is a schematic sectional view of a waterproof material according to preferred embodiment 2 of the present invention;
FIG. 3 is a schematic sectional view of a waterproof material according to preferred embodiment 3 of the present invention;
FIG. 4 is a schematic sectional view of a waterproof material according to preferred embodiment 4 of the present invention;
FIG. 5 is a schematic sectional view of a waterproof material according to preferred embodiment 5 of the present invention;
FIG. 6 is a schematic sectional view of a waterproof material according to preferred embodiment 6 of the present invention;
FIG. 7 is a schematic sectional view of a waterproof material according to preferred embodiment 7 of the present invention;
fig. 8 is a schematic sectional view of a waterproof material according to preferred embodiment 8 of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not a whole embodiment. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The photocurable polyurea coating in this example included a first component and a second component in a 1:2 weight ratio when used.
The first component comprises isocyanate polyurea prepolymer and acrylic acid modified polyurea resin; the second component comprises amine-terminated polyether, amine chain extender, plasticizer, photoinitiator, color paste, antioxidant and defoamer.
The preparation method of the photo-curing polyurea coating in the embodiment comprises the following steps:
1) preparation of isocyanate polyurea prepolymer
Dehydrating 200g of hindered secondary amine at 120 ℃ until the water content is below 300ppm, then dropwise adding 200g of diphenylmethane diisocyanate, reacting for 3 hours at 80 ℃, sampling and testing the NCO mass fraction to reach a preset value of 5%, and finishing the reaction to obtain the isocyanate polyurea prepolymer.
The secondary sterically hindered amine in this example is a compound of the formula:
wherein X is-CH 2 -，R 1 、R 2 、R 3 、R 4 is-CH 2 CH 3 。
2) Preparation of acrylic acid-modified polyurea resin
Mixing 200g of isocyanate polymerization prepolymer prepared in the step 1), 200g of hydroxy acrylic resin and 0.8g of polymerization inhibitor in a reaction kettle, reacting for 4 hours at 70 ℃, sampling and determining that the mass fraction of NCO reaches a preset value of 0, namely, the isocyanate in the system completely reacts, and finishing the reaction to obtain the acrylic modified polyurea resin.
3) Preparation of the first component
Mixing 250g of the isocyanate polyurea prepolymer prepared in the step 1) and 250g of the acrylic acid modified polyurea resin prepared in the step 2) to obtain a first component.
4) Preparation of the second component
And (3) dehydrating 100g of amine-terminated polyether, 150g of amine chain extender and 248g of plasticizer at 120 ℃ until the water content is below 300ppm, then cooling to 55 ℃, adding 0.5g of photoinitiator, 1g of antioxidant, 0.5g of defoaming agent and 1g of color paste, uniformly stirring and defoaming for 30min to obtain the second component. And (4) sealing and storing the second component in dark.
In this example, the amino-terminated polyether in the second component was D230 primary amino polyether from hensman, and the amine chain extender was a compound having the same structural formula as the hindered secondary amine.
Example 2
The photocurable polyurea coating in this example included a first component and a second component in a 1:1 weight ratio when used.
The first component comprises isocyanate polyurea prepolymer and acrylic acid modified polyurea resin; the second component comprises amine-terminated polyether, amine chain extender, plasticizer, photoinitiator, color paste, antioxidant and defoamer.
The preparation method of the photo-curing polyurea coating in the embodiment comprises the following steps:
1) preparation of isocyanate polyurea prepolymer
Dehydrating 200g of hindered secondary amine at 120 ℃ until the water content is below 300ppm, then dropwise adding 200g of toluene diisocyanate, reacting for 2 hours at 100 ℃, sampling and testing the NCO mass fraction to reach a preset value of 2.5%, and finishing the reaction to obtain the isocyanate polyurea prepolymer.
The secondary sterically hindered amine in this example is a compound of the formula:
wherein X is-CH 2 CH 2 -，R 1 、R 2 、R 3 、R 4 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 。
2) Preparation of acrylic acid-modified polyurea resin
Mixing 200g of isocyanate polymerization prepolymer prepared in the step 1), 200g of hydroxyethyl acrylate and 0.8g of polymerization inhibitor in a reaction kettle, reacting for 4 hours at the temperature of 100 ℃, sampling and determining that the mass fraction of NCO reaches a preset value of 0, namely, the isocyanate in the system completely reacts, and finishing the reaction to obtain the acrylic modified polyurea resin.
3) Preparation of the first component
Mixing 100g of the isocyanate polyurea prepolymer prepared in the step 1) and 400g of the acrylic acid modified polyurea resin prepared in the step 2) to obtain a first component.
4) Preparation of the second component
And (3) dehydrating 100g of amine-terminated polyether, 150g of amine chain extender and 248g of plasticizer at 120 ℃ until the water content is below 300ppm, then cooling to 55 ℃, adding 0.5g of photoinitiator, 1g of antioxidant, 0.5g of defoaming agent and 1g of color paste, uniformly stirring and defoaming for 30min to obtain the second component. And (4) sealing and storing the second component in dark.
In this example, the amino-terminated polyether in the second component was a T3000 primary amino polyether from hensman, and the amine chain extender was a compound of the same formula as the sterically hindered secondary amine.
Example 3
The photocurable polyurea coating in this example included a first component and a second component in a weight ratio of 1:0.5 when used.
The first component comprises isocyanate polyurea prepolymer and acrylic acid modified polyurea resin; the second component comprises amine-terminated polyether, amine chain extender, plasticizer, photoinitiator, color paste, antioxidant and defoamer.
The preparation method of the photo-curing polyurea coating in the embodiment comprises the following steps:
1) preparation of isocyanate polyurea prepolymer
200g of sterically hindered secondary amine is dehydrated at 120 ℃ to the water content of below 300ppm, then 200g of hexamethylene diisocyanate is dripped into the dehydrated hindered secondary amine, the reaction is carried out for 4 hours at 70 ℃, the mass fraction of NCO reaches 0.5 percent of a preset value after sampling and testing, and the reaction is finished to obtain the isocyanate polyurea prepolymer.
The secondary sterically hindered amine in this example is a compound of the formula:
wherein X is-CH 2 CH 2 CH 2 -，R 1 、R 2 、R 3 、R 4 Is CH 3 CH 2 C(CH 3 )CH(CH 3 )CH 2 CH 3 。
2) Preparation of acrylic acid-modified polyurea resin
Mixing 200g of isocyanate polymerization prepolymer prepared in the step 1), 200g of hydroxyethyl methacrylate and 0.8g of polymerization inhibitor in a reaction kettle, reacting for 6 hours at 70 ℃, sampling and determining that the mass fraction of NCO reaches a preset value of 0, namely, the isocyanate in the system completely reacts, and finishing the reaction to obtain the acrylic modified polyurea resin.
3) Preparation of the first component
Mixing 400g of the isocyanate polyurea prepolymer prepared in the step 1) and 100g of the acrylic acid modified polyurea resin prepared in the step 2) to obtain a first component.
4) Preparation of the second component
And (3) dehydrating 100g of amine-terminated polyether, 150g of amine chain extender and 248g of plasticizer at 120 ℃ until the water content is below 300ppm, then cooling to 55 ℃, adding 0.5g of photoinitiator, 1g of antioxidant, 0.5g of defoaming agent and 1g of color paste, uniformly stirring and defoaming for 30min to obtain the second component. And (4) sealing and storing the second component in dark.
In this example, SD2001 secondary amino polyether from hensman was used as the amino-terminated polyether in the second component, and a compound having the same structural formula as the sterically hindered secondary amine was used as the amine-based chain extender.
Example 4
Referring to fig. 1, the waterproof material in this embodiment sequentially includes a first anti-sticking layer, a first polyurea bonding layer, a base, a second polyurea bonding layer, and a second anti-sticking layer from top to bottom. The first polyurea bonding layer and the second polyurea bonding layer were formed from the photocurable polyurea coatings of examples 1-3.
When the waterproof material is prepared, the first component and the second component are added into a reaction kettle in proportion, the reaction is carried out for 2 hours at 40 ℃, after the materials are fully reacted, the materials are coated on a substrate through a coater, then the substrate enters an ultraviolet irradiation box, and the substrate is formed into a finished coiled material after being subjected to photocuring and shaping and then being attached with a first anti-sticking layer or a second anti-sticking layer.
The base member in this embodiment is the TPO sheet, and first antiseized layer and second antiseized layer are the silicon oil film. In other embodiments, the substrate may be a tire base or another release layer, the tire base being a PET polyester film, a cross laminated film PE film, a PVC sheet, a PE sheet, a TPO sheet, a composite sheet, a polyester non-woven tire base, a fiberglass tire, a copper tire base, a composite tire base, or the like; the anti-sticking layer can be natural sand, machine-made sand or other fine powder, silicon oil film, emulsion, etc.
In other embodiments, if the second polyurea bonding layer and the second release layer are removed, a water repellent material having a structure as shown in fig. 2 is formed.
In another embodiment of the present application, the flashing material is devoid of a base and has a polyurea tie layer formed from a photocurable polyurea coating between two release layers, as shown in fig. 3. As shown in fig. 8, other adhesive layers are further provided between the polyurea adhesive layer and the anti-sticking layer, the other adhesive layers can be asphalt glue, epoxy glue, butyl glue, hot-melt pressure-sensitive glue, polyurethane glue and other glue materials, and no tire base exists in the whole waterproof material.
In another embodiment of the present application, as shown in fig. 4 and 5, there is another bonding layer between the tire base and the polyurea bonding layer, and the other bonding layer can be asphalt glue, epoxy glue, butyl glue, hot melt pressure sensitive glue, polyurethane glue, etc.
In another embodiment of the present application, as shown in fig. 6 and 7, there is another adhesive layer between the polyurea adhesive layer and the release layer, and the other adhesive layer can be asphalt glue, epoxy glue, butyl glue, hot melt pressure sensitive glue, polyurethane glue, etc.
Comparative example 1
The photocurable polyurea coating in this comparative example is different from example 1 in that the first component contains only the acrylic modified polyurea resin, and does not contain the isocyanate polyurea prepolymer, and the other components are the same as example 1.
Comparative example 2
The photocurable polyurea coating in this comparative example is different from example 1 in that the first component contains only the isocyanate polyurea prepolymer, and does not contain the acrylic modified polyurea resin, and the other components are the same as those in example 1.
Comparative example 3
The photocurable polyurea coating in this comparative example differs from example 1 in that the second component does not contain a photoinitiator, and the other components are the same as in example 1.
Testing and analysis
Referring to GB/T23457-2017 pre-paved waterproof coiled material and a relevant method in GB/T19250-2013 polyurethane waterproof coating standard, the photo-curable polyurea coatings in examples 1-3 and comparative examples 1-3 are applied to the waterproof coiled material and subjected to a relevant performance test, and the results are shown in Table 2.
TABLE 1 formulation Table (in parts by mass) of photocurable polyurea coatings of examples and comparative examples
TABLE 2 test results of the properties of the waterproof rolls prepared from the polyurea coatings of examples 1 to 3 and comparative examples 1 to 3
As can be seen from the test data in Table 2, the performance of the waterproof roll obtained by applying the polyurea coating in the examples 1-3 is obviously better than that of the waterproof roll obtained by applying the polyurea coating in the comparative examples 1-3, and the ratio of the polyurea prepolymer to the acrylic acid modified polyurea prepolymer needs to reach about 1 to 1 so as to exert the best effect. If the coating does not contain the isocyanate polyurea prepolymer, the peel strength is poor; the system does not contain an initiator, the performance is greatly influenced by insufficient curing of the material, and the material which is not cured by light has no self-healing capability.
Compared with the prior art, the invention has the following advantages:
1. the coating that polyurea coating formed of this application belongs to glutinous elastomer, and similar non-curing rubber asphalt coating is the same, never solidified state, product 100% solid content, and the environmental protection does not have pungent smell, and the coiled material environmental protection that makes does not have pungent smell.
2. The waterproof material is faster in speed of photocuring during molding and is more thoroughly cured.
3. Compared with asphalt sizing materials, the polyurea coating material has more excellent compatibility with base materials, is less prone to oil migration, and has excellent adhesion with asphalt materials.
4. The polyurea coating has the advantages that initial viscosity and lasting viscosity of the polyurea coating are improved by one grade compared with hot-melt pressure-sensitive adhesive, and the polyurea coating has stronger cohesive force and can resist the influence of high temperature on deformation of a tire base.
5. The polyurea coating has excellent cohesiveness and excellent self-repairing and self-healing performance.
6. The polyurea coating has excellent bonding force with a wet concrete base surface or a mortar base surface.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. The waterproof material is characterized by comprising a base body, an anti-sticking layer and an adhesive layer for bonding the base body and the anti-sticking layer, wherein the adhesive layer is prepared from a photocuring polyurea coating; the photo-curing polyurea coating comprises a first component and a second component, wherein the first component comprises an isocyanate polyurea prepolymer and acrylic acid modified polyurea resin; the second component comprises amino-terminated polyether, amine chain extender, plasticizer, photoinitiator and auxiliary agent; the acrylic modified polyurea resin is prepared from the isocyanate polyurea prepolymer and reactive acrylate, wherein the reactive acrylate is acrylate containing hydroxyl or amino.
2. The waterproof material according to claim 1, wherein the adhesive layer is prepared by a method comprising: and mixing and reacting the first component and the second component of the photocuring polyurea coating, coating the mixture on the substrate, and irradiating the mixture by ultraviolet rays to form the bonding layer by the photocuring polyurea coating.
3. The waterproof material according to claim 1, wherein the waterproof material is prepared by a method comprising: adding the first component and the second component of the photocuring polyurea coating into a reaction kettle, reacting for 1-3h at 20-60 ℃, coating the mixture on the substrate through a coater or naturally flowing the mixture onto the substrate to be uniformly spread, then entering an ultraviolet irradiation box, and attaching other bonding layers or anti-sticking layers after photocuring and shaping to form the finished coiled material.
4. The waterproof material of claim 3, wherein said other adhesive layer is an asphalt mastic, an epoxy, a butyl, a hot melt pressure sensitive adhesive, or a polyurethane adhesive.
5. The waterproof material according to claim 1, wherein the anti-sticking layer is natural sand, machine-made sand, a silicone oil film or an emulsion; the substrate is a PET polyester film, a cross laminated film, a PE film, a PVC sheet, a PE sheet, a TPO sheet, a composite sheet, a polyester non-woven fabric tire base, a glass fiber tire, a copper tire base or a composite tire base.
6. The waterproof material according to claim 1, wherein the photocurable polyurea coating material comprises the first component and the second component in a weight ratio of 1: 0.2-2; the mass ratio of the isocyanate polyurea prepolymer to the acrylic acid modified polyurea resin in the first component is 1:0.5 to 2; the mass ratio of the amine-terminated polyether to the amine chain extender in the second component is 1: 0.5-2.
7. The waterproof material according to claim 1, wherein the isocyanate polyurea prepolymer is prepared from hindered secondary amine and isocyanate, and the hindered secondary amine and/or the amine chain extender in the second component are compounds having the following general formula:
wherein X is an alkyl group having 1 to 3 carbon atoms, and R is 1 、R 2 、R 3 、R 4 Are each a linear or branched alkyl group having 2 to 8 carbon atoms.
8. The waterproof material according to claim 7, wherein the isocyanate is one kind or a combination of two or more kinds selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like.
9. The waterproof material according to claim 1, wherein the reactive acrylate is obtained by polymerizing an acrylic monomer, and the acrylic monomer is one or a combination of two or more selected from the group consisting of methyl methacrylate, 2-phenoxyethyl acrylate, lauryl acrylate, stearyl acrylate, ethoxyethoxyethyl acrylate, tetrahydrofurfuryl methacrylate, isopropylidene methacrylate, isobornyl acrylate, cyclotrimethylolpropane formal acrylate, lauryl methacrylate, stearyl methacrylate, methoxypolyethylene glycol (340) acrylate, and o-phenylphenoxyethyl acrylate.
10. The waterproof material according to claim 1, wherein the photocurable polyurea coating is prepared by the following method:
preparing an isocyanate polyurea prepolymer: adding isocyanate into sterically hindered secondary amine with the moisture content of below 300ppm for reaction, sampling and testing the mass fraction of NCO to reach a preset value, and finishing the reaction to obtain a polyurea prepolymer;
preparing acrylic acid modified polyurea resin: mixing the prepared isocyanate polyurea prepolymer, reactive acrylate and a polymerization inhibitor, reacting, sampling, determining the mass fraction of NCO to reach a preset value, and finishing the reaction to obtain acrylic acid modified polyurea resin;
preparing a first component: mixing the isocyanate polyurea prepolymer and the acrylic acid modified polyurea resin to obtain the first component;
preparing a second component: and (3) mixing and dehydrating the amine-terminated polyether, the amine chain extender and the plasticizer until the moisture content is below 300ppm, adding the photoinitiator and the auxiliary agent, and uniformly stirring to obtain the second component.
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