CN111849232A - Polyurethane resin capable of being cured by low-temperature free radical polymerization and application thereof - Google Patents
Polyurethane resin capable of being cured by low-temperature free radical polymerization and application thereof Download PDFInfo
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- CN111849232A CN111849232A CN202010755762.8A CN202010755762A CN111849232A CN 111849232 A CN111849232 A CN 111849232A CN 202010755762 A CN202010755762 A CN 202010755762A CN 111849232 A CN111849232 A CN 111849232A
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
- B05D7/26—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials synthetic lacquers or varnishes
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a polyurethane resin capable of being cured by low-temperature free radical polymerization, which consists of a component A and a component B; the component A comprises the following components in parts by mass: 20-90 parts of polymer, 2-80 parts of reactable monomer and 0-0.2 part of polymerization inhibitor; the component B comprises 5-60 parts by weight of isocyanate and 0.001-5.0 parts by weight of redox initiator. The polyurethane resin system provided by the invention can be used for construction in a low-temperature environment of room temperature to about 0 ℃.
Description
Technical Field
The invention belongs to the field of organic polymer materials, and particularly relates to polyurethane resin capable of being cured by low-temperature free radical polymerization and application thereof.
Background
The polyurethane resin is the most common basic raw material for printing ink, paint and adhesive, and has the characteristics of good performance, wide application range and the like. Polyurethane applications are AB two-component formulations as the most common form. Two-component polyurethane coating is generally composed of two parts, namely isocyanate (also called curing agent) and resin containing hydroxyl or amino (also called main agent), wherein the two parts usually have the characteristic of high VOC or high viscosity, and especially after the two parts are prepared and mixed, when construction such as spraying and the like is required, a large amount of organic solvent is required to dilute the system to achieve the required viscosity. In general, when polyurethane is constructed, an organic solvent is required to be diluted to a solid content of 40-70% for operations such as spraying, and a large amount of VOC is required to be discharged. In order to reduce VOC, there is a technique proposed to reduce the viscosity of a mixture of a curing agent and a main agent by reducing the molecular weight of the main agent resin; however, the reduction of viscosity achievable by this process is extremely limited and the viscosity cannot be used in smaller coating applications, and the reduction of molecular weight causes serious disadvantages in the properties of the polyurethane. The viscosity of the polyurethane can be reduced after the polyurethane is mixed with the reactive organic compound with double bonds, but the reactive organic compound with double bonds needs a certain temperature when participating in the system reaction, and the reaction is difficult at low temperature, so that the polyurethane is difficult to be cured and molded.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a polyurethane resin capable of being cured by low-temperature free radical polymerization.
The second purpose of the invention is to provide a coating containing the polyurethane resin capable of curing by low-temperature free radical polymerization.
The third purpose of the invention is to propose the application of the polyurethane resin which can be cured by low-temperature free radical polymerization as a coating.
The specific technical scheme for realizing the aim of the invention is as follows:
a low VOC polyurethane resin which can be solidified by low temperature free radical polymerization is composed of a component A and a component B; the component A comprises the following components in parts by mass: 20-90 parts of polymer, 2-80 parts of reactive monomer, 0.001-5 parts of reducing agent and 0-0.2 part of polymerization inhibitor; the component B comprises 5-60 parts by weight of isocyanate and 0.001-5 parts by weight of redox initiator;
the polymer is polyhydroxyacrylate or polyester, or a combination of polyester and polyhydroxyacrylate, the polyester is polyester polyol with the molecular weight of 800-3000, the polyhydroxyacrylate is polyhydroxyacrylate resin with the molecular weight of 1000-5000, and the polyester and the polyhydroxyacrylate independently have the hydroxyl value of 70-220 mgKOH/g.
The redox initiator is one or more of benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropyl peroxydicarbonate, tert-amyl peroxide, tert-amyl hydroperoxide, di-tert-amyl peroxide, tert-butyl hydroperoxide, lauroyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, dicyclohexyl peroxydicarbonate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl acetate and ethyl 3, 3-di (tert-amyl peroxy) butyrate.
Wherein the reactable monomer is a first monomer, or the mass ratio of the first monomer to the second monomer is 2: 4-30, wherein the first monomer is selected from one or more of methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, butyl 2-hydroxypropionate, methyl 3-hydroxypropionate, ethyl 3-hydroxybutyrate, butyl glycolate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and trimethylolpropane triacrylate;
the second monomer is selected from the group consisting of butyl acrylate, octyl acrylate, lauryl acrylate, 2,3 dihydroxy propyl methacrylate, tetrahydrofuran methyl methacrylate, phenoxyethyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, isodecyl acrylate, triethylene glycol divinyl ether, 1, 4-cyclohexyl dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, glyceryl carbonate propenyl ether, dodecyl vinyl ether, methoxypolyethylene glycol monomethacrylate, methoxypolyethylene glycol monoacrylate, methoxypropylene glycol monoacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, propylene glycol diacrylate, mixtures thereof, and mixtures thereof, One or more of tripropylene glycol diacrylate, 1, 4-butylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, methacrylic acid monoester phosphate, methacrylic acid diester, acrylic acid phosphate, acrylic acid dioxacene ester, aliphatic monoacrylate, trifunctional methacrylate, trifunctional acrylate, tertiary amine acrylate, styrene and p-styrene.
Wherein the isocyanate is one or more of Hexamethylene Diisocyanate (HDI), HDI biuret, HDI trimer, isophorone diisocyanate (IPDI), IPDI adduct, IPDI trimer, dicyclohexylmethane diisocyanate (HMDI) and adduct thereof, Toluene Diisocyanate (TDI), TDI adduct, TDI trimer, diphenylmethane diisocyanate (MDI), MDI adduct, Xylylene Diisocyanate (XDI), XDI adduct;
the polymerization inhibitor is one of hydroquinone, p-tert-butyl catechol, benzaldehyde, aromatic amines and p-methoxyphenol. The purpose of the inhibitor is to avoid self-polymerization of the reactable monomers during storage in the polyurethane system. For the condition of on-site preparation of coating material in which the reactive monomer is added on site during construction, the polymerization inhibitor can not be added.
The reducing agent is one or more of naphthenate, isooctoate, tertiary amine compounds, triethylaluminum, triethylboron, triethylzinc, 2-Thiylbenzothiazole (MBT), n-dodecylmercaptan, n-octadecylmercaptan, methyl 3-Thiylpropionate, ethyl 2-Thiylhexadecanoate, sodium metabisulfite and ferrous chloride.
When the reducing agent is naphthenate, naphthenate or isooctoate, a 10% toluene solution is prepared.
The naphthenate is selected from cobalt naphthenate, manganese naphthenate, vanadium naphthenate, zinc naphthenate, iron naphthenate and the like; the naphthanate is selected from cobalt, manganese, vanadium, zinc, iron naphthanate, cuprous naphthanate and the like, and the isooctanoate is selected from manganese isooctanoate, cobalt isooctanoate, potassium isooctanoate, sodium isooctanoate, copper isooctanoate, zinc isooctanoate, nickel isooctanoate, vanadium isooctanoate and the like. The tertiary amine compound may be selected from N, N-dimethylaniline, N-diethylaniline, N-dipropylaniline, N-dibutylaniline, N-dimethyltoluidine, N-bis (2-hydroxyethyl) p-toluidine, etc.
Preferably, the redox initiator is one of methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-amyl hydroperoxide and tert-butyl hydroperoxide;
the reducing agent is one or two of N, N-dimethylaniline, N-diethylaniline, N-dipropylaniline, N-dibutylaniline, N-dimethyl toluidine, N-di (2-hydroxyethyl) p-toluidine, isooctanoate, naphthenate and cobalt naphthenate, preferably a tertiary amine compound and naphthenate in a mass ratio of 1: (0.1-8).
The redox initiator has the use temperature range of about room temperature to 0 ℃, is uniformly decomposed, only forms a free radical, and has no other side reaction. Stable, safe storage in a pure state, easy control of polymerization reaction, no residue in the polymerization process and high product conversion rate.
According to a preferable technical scheme, the polymer is 40-85 parts, and the mass ratio of polyester to polyhydroxyacrylate is 5: 2-60. More preferably, the polymer is a polyester and a polyhydroxyacrylate in a mass ratio of 5: 5 to 40.
The used reactive monomer is used as a part of resin and has a diluting effect, and the effect of low VOC and low viscosity is realized. Because the resin is a coating capable of being cured by low-temperature free radical polymerization, the reactive monomer can react quickly when being heated, thereby avoiding the generation of more volatile substances and having little influence on the environment and operators.
Wherein the isocyanate is one or more of Hexamethylene Diisocyanate (HDI), HDI biuret, HDI trimer, isophorone diisocyanate (IPDI), IPDI adduct, IPDI trimer, dicyclohexylmethane diisocyanate (HMDI) and adduct thereof, Toluene Diisocyanate (TDI), TDI adduct, TDI trimer, diphenylmethane diisocyanate (MDI), MDI adduct, Xylylene Diisocyanate (XDI), XDI adduct.
Wherein the TDI trimer is more effective in reducing coating VOC.
The isocyanate is one of HDI tripolymer, TDI tripolymer, HDI biuret and isophorone diisocyanate (IPDI), and the mass ratio of the isocyanate to the reactive monomer is 1-6: 3.
further preferably, the component A contains the following components in parts by mass: 60-80 parts of polyester and polyhydroxyacrylate, 20-40 parts of a reactive monomer, 0.005-3 parts of a reducing agent and 0-0.2 part of a polymerization inhibitor; the component B comprises 20-60 parts of isocyanate and 0.005-3 parts of initiator.
The coating capable of being cured by low-temperature free radical polymerization comprises the polyurethane resin capable of being cured by low-temperature free radical polymerization, and consists of a first component and a component B of the polyurethane resin capable of being cured by low-temperature free radical polymerization, wherein the component B comprises 5-60 parts by weight of isocyanate and 0.005-3 parts by weight of an initiator;
the first component contains 30-60 parts of the A component of the low VOC polyurethane resin, 3-60 parts of pigment, 4-60 parts of filler, 0-8.5 parts of silicate, 0.2-1 part of flatting agent, 0.1-0.5 part of defoaming agent, 0.2-0.5 part of wetting agent and 0.1-2 parts of organic bentonite.
The components in the paint are conventional products sold in the market, for example, the pigment can be one or more of titanium dioxide and ferric oxide, the filler is one or more of precipitated barium sulfate, white carbon black and nano silicon dioxide, and the silicate is one or more of talcum powder, clay, magnesium silicate and montmorillonite. The leveling agent, the defoaming agent and the wetting agent are all commercially available.
The spraying method for applying the coating curable by the low-temperature free radical polymerization comprises the following operations:
mixing the first component and the B component of the coating, and spraying the mixture on the surface of a device by using a single-component spray gun; curing in an environment above 0 ℃.
Such devices include, but are not limited to, containers, automotive parts, steel structures, and the like. The first component and the B component of the coating may be mixed in a ratio of 100: (10-60).
The invention has the beneficial effects that:
the polyurethane composition system provided by the invention can be used for construction in a low-temperature environment of room temperature to about 0 ℃.
The coating prepared from the polyurethane has extremely low VOC because the reactive monomer participates in the reaction of the resin matrix to become the final composition component of the polyurethane resin. The system has the structural characteristics of typical polyurethane, and the coating has excellent mechanical properties such as adhesive force, impact resistance, flexibility, tensile resistance and the like, and also has excellent corrosion resistance and aging resistance.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention.
The following examples are given to further illustrate the embodiments of the present invention. Unless otherwise specified, all technical means used in the examples are technical means existing in the field.
Example 1
In this example, a polyhydroxyacrylate resin raw material having a mass fraction of 85% was used
The component A comprises: 70 parts of polyhydroxyacrylate resin (hydroxyl value is 70), 0.4 part of N, N-diethylaniline, 2 parts of hydroxypropyl acrylate, 15 parts of octyl acrylate and 13 parts of butyl acrylate.
And B component: HDI curing agent TPA-10017 parts, and benzoyl peroxide 0.6 part.
The preparation method of the polyurethane of the embodiment comprises the following steps: uniformly mixing polyhydroxyacrylate resin, hydroxypropyl acrylate, octyl acrylate, N-diethylaniline and butyl acrylate to obtain a component A; TPA-100 and benzoyl peroxide are mixed to form the component B.
The VOC of the polyurethane prepared in this example was 12% and the pot life at room temperature after mixing of the AB component was over 2 hours. The curing time is 24 hours, and the temperature can be cured at 25 ℃.
The anti-aging test of the obtained coating is carried out according to the standard GB/T14522-2008 fluorescent ultraviolet lamp (UVV) of paint artificial weathering test method for mechanical industrial products, and the QUV test reaches 1000 hours (UVA-340). Adhesion test adhesion was measured to be 8.6MPa according to ASTM D4541-2009, test method for measuring the pull-off strength of a coating by a portable adhesion tester.
The VOC detection method is according to the standard: GB/T34682-2017.
Example 2
The component A comprises: 70 parts of polyester resin (hydroxyl value of 175), 2 parts of hydroxypropyl acrylate, 13 parts of isodecyl acrylate (IDA), 15 parts of butyl acrylate and 0.4 part of cobalt naphthenate.
And B component: HDI trimer N339050 parts and tert-butyl peroxybenzoate 0.5 part.
The preparation method of the polymer coating of this example: uniformly mixing polyester resin, cobalt naphthenate, hydroxypropyl acrylate, isodecyl acrylate and butyl acrylate to obtain a component A; n3390 and benzoyl peroxide are mixed and packaged as component B.
The VOC value of the polyurethane prepared in this example was 9.4%. The pot life of the AB component is more than 1.5 hours at room temperature after mixing. The temperature is 25 ℃ to be cured.
The anti-aging is measured according to fluorescent ultraviolet lamp (GB/T14522-2008) of paint artificial weathering test method for mechanical industry products to obtain a QUV test for 700 hours (UVA-340). The adhesion of the coating was measured to be 8.8MPa according to ASTM D4541-2009, test method for measuring the pull-off strength of a coating by a portable adhesion tester.
Example 3
The component A comprises: 10 parts of polyester resin (hydroxyl value of 175), 55 parts of polyhydroxyacrylate resin (hydroxyl value of 70), 2 parts of hydroxypropyl acrylate, 13 parts of isodecyl acrylate (IDA), 15 parts of butyl acrylate and 0.5 part of N, N-dimethyl-p-methylaniline.
And B component: HDI curing agent TPA-10020 parts, and benzoyl peroxide 0.8 part.
The VOC value of the polyurethane prepared in this example was 9.7%. The pot life of the AB component is more than 1.5 hours at room temperature after mixing. The temperature is 0 ℃ and the curing can be realized.
The ageing resistance is measured according to fluorescent ultraviolet lamp (GB/T14522-2008) of paint artificial weathering test method for mechanical industry products, and the QUV test reaches 1200 hours (UVA-340). The paint of this example showed little discoloration because of the benzene ring contained in the initiation system. Adhesion test adhesion was measured to be 10.3MPa according to ASTM D4541-2009, test method for measuring the pull-off strength of a coating by a portable adhesion tester.
Example 4
The component A comprises: 30 parts of polyester resin (hydroxyl value of 175), 40 parts of polyhydroxyacrylate resin (hydroxyl value of 70), 1 part of hydroxyethyl acrylate, 20 parts of lauryl acrylate, 5 parts of trimethylolpropane triacrylate, 0.2 part of N, N-dimethyl-p-methylaniline and 0.5 part of cobalt isooctanoate.
And B component: TPA-10026 parts
0.65 part of methyl ethyl ketone peroxide.
The preparation method of the polymer coating of this example: uniformly mixing polyhydroxyacrylate resin, hydroxypropyl acrylate, methyl methacrylate and trimethylolpropane triacrylate to obtain a component A; TPA-100 and methyl ethyl ketone peroxide are mixed to form a component B.
The polyurethane prepared in this example had a VOC of 8.5%. The pot life of the AB component is more than 2 hours at room temperature after mixing. The curing time is 32 hours, and the curing temperature is 5 ℃.
The anti-aging is measured by a fluorescent ultraviolet lamp (UVV) test method for paint artificial weathering test for mechanical industrial products of GB/T14522-2008, and the QUV test reaches 1440 hours (UVA-340). Adhesion test adhesion was measured to be 12.5MPa according to ASTM D4541-2009, test method for measuring the pull-off strength of a coating by a portable adhesion tester.
Example 5
The component A comprises: 10 parts of polyester resin (hydroxyl value of 175), 55 parts of polyhydroxyacrylate resin (hydroxyl value of 70), 15 parts of isodecyl acrylate (IDA), 15 parts of butyl acrylate and 0.4 part of N, N-dimethyl-p-methylaniline.
And B component: HDI curing agent TPA-10019 parts. 0.5 part of tert-butyl hydroperoxide.
The VOC value of the polyurethane prepared in this example was 9.7%. The pot life of the AB component is more than 3 hours at room temperature after mixing. The curing can be carried out at the temperature of 10 ℃, and the curing time is 48 hours.
The ageing resistance is tested according to GB/T14522-2008 fluorescent ultraviolet lamp (test method for artificial weathering test of coatings for mechanical industrial products), and the test sample is qualified (UVA-340) when the QUV test is carried out for 1000 hours. Adhesion test adhesion was measured to be 6.2MPa according to ASTM D4541-2009, test method for measuring the pull-off strength of a coating by a portable adhesion tester.
Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art will appreciate that various modifications and alterations can be made to the present invention without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A polyurethane resin capable of being cured by low-temperature free radical polymerization consists of a component A and a component B; the composition is characterized in that the component A comprises the following components in parts by mass: 20-90 parts of polymer, 2-80 parts of reactable monomer and 0-0.2 part of polymerization inhibitor; the component B comprises 5-60 parts by weight of isocyanate and 0.001-5.0 parts by weight of redox initiator;
the polymer is polyhydroxyacrylate or polyester, or a combination of polyester and polyhydroxyacrylate, the polyester is polyester polyol with the molecular weight of 800-3000, the polyhydroxyacrylate is polyhydroxyacrylate resin with the molecular weight of 1000-5000, and the polyester and the polyhydroxyacrylate independently have the hydroxyl value of 70-220 mgKOH/g;
the redox initiator is one or more of benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropyl peroxydicarbonate, tert-amyl peroxide, tert-amyl hydroperoxide, di-tert-amyl peroxide, tert-butyl hydroperoxide, lauroyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, dicyclohexyl peroxydicarbonate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl acetate and ethyl 3, 3-di (tert-amyl peroxy) butyrate.
2. The low-temperature radical polymerization-curable polyurethane resin according to claim 1, wherein the reactable monomer is a first monomer or a second monomer, or the first monomer and the second monomer are mixed in a mass ratio of 2: (4-30), wherein the first monomer is selected from one or more of methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, butyl 2-hydroxypropionate, methyl 3-hydroxypropionate, ethyl 3-hydroxybutyrate, butyl glycolate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and trimethylolpropane triacrylate;
the second monomer is selected from the group consisting of butyl acrylate, octyl acrylate, lauryl acrylate, 2,3 dihydroxy propyl methacrylate, tetrahydrofuran methyl methacrylate, phenoxyethyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, isodecyl acrylate, triethylene glycol divinyl ether, 1, 4-cyclohexyl dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, glyceryl carbonate propenyl ether, dodecyl vinyl ether, methoxypolyethylene glycol monomethacrylate, methoxypolyethylene glycol monoacrylate, methoxypropylene glycol monoacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, propylene glycol diacrylate, mixtures thereof, and mixtures thereof, One or more of tripropylene glycol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, methacrylic acid monoester phosphate, methacrylic acid diester, acrylic acid phosphate, acrylic acid dioxacene ester, aliphatic monoacrylate, trifunctional methacrylate, trifunctional acrylate, tertiary amine acrylate, styrene and p-styrene.
3. The low-temperature radical polymerization-curable polyurethane resin according to claim 1, wherein the isocyanate is one or more of hexamethylene diisocyanate, HDI biuret, HDI trimer, isophorone diisocyanate, IPDI adduct, IPDI trimer, dicyclohexylmethane diisocyanate, HMDI adduct, toluene diisocyanate, TDI adduct, TDI trimer, diphenylmethane diisocyanate, MDI adduct, xylylene diisocyanate, XDI adduct;
the polymerization inhibitor is one of hydroquinone, p-tert-butyl catechol, benzaldehyde, aromatic amines and p-methoxyphenol.
4. The low temperature free radical polymerization curable polyurethane resin according to claim 1, wherein the reducing agent is one or more of naphthenate, isooctoate, tertiary amine, triethylaluminum, triethylboron, triethylzinc, 2-thiobenzothiazole, n-dodecylmercaptan, n-octadecylmercaptan, 3-thiopropionic acid methyl ester, 2-thiohexadecanoic acid ethyl ester, sodium metabisulfite, and ferrous chloride;
when the reducing agent is naphthenate, naphthenate or isooctoate, a 10% toluene solution is prepared.
5. The low-temperature radical polymerization-curable polyurethane resin according to claim 1, wherein the redox initiator is one of methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, t-amyl hydroperoxide, and t-butyl hydroperoxide;
the reducing agent is one or more than two of N, N-dimethylaniline, N-diethylaniline, N-dipropylaniline, N-dibutylaniline, N-dimethyl toluidine, N-di (2-hydroxyethyl) p-toluidine, isooctanoate, naphthenate and naphthenate, preferably a tertiary amine compound and naphthenate with the mass ratio of 1: (0.1-8).
6. The polyurethane resin capable of being cured by low-temperature free radical polymerization according to claim 1, wherein the polymer is 40-85 parts by mass of polyester and polyhydroxyacrylate, and the mass ratio of the polyester to the polyhydroxyacrylate is 5: 2-60; preferably, the polymer is polyester and polyhydroxyacrylate in a mass ratio of 5: 5 to 40.
7. The polyurethane resin capable of being cured by low-temperature free radical polymerization according to claim 1, wherein the isocyanate is one or more of HDI trimer, TDI trimer, HDI biuret and isophorone diisocyanate, and the mass ratio of the isocyanate to the reactive monomer is 1-6: 3.
8. the polyurethane resin capable of being cured by low-temperature free radical polymerization according to any one of claims 1 to 7, wherein the component A comprises the following components in parts by mass: 60-80 parts of polyester and polyhydroxyacrylate, 20-40 parts of a reactive monomer, 0.005-3 parts of a reducing agent and 0-0.2 part of a polymerization inhibitor; the component B comprises 20-60 parts of isocyanate and 0.005-3 parts of initiator.
9. A low-temperature free radical polymerization curable coating material comprising the low-temperature free radical polymerization curable polyurethane resin according to any one of claims 1 to 8, wherein the coating material is composed of a first component and a B component of the low-temperature free radical polymerization curable polyurethane resin, wherein the B component comprises 5 to 60 parts by weight of isocyanate and 0.005 to 3.0 parts by weight of a redox initiator;
the first component contains 30-60 parts of the A component of the low VOC polyurethane resin, 3-60 parts of pigment, 4-60 parts of filler, 0-8.5 parts of silicate, 0.2-1 part of flatting agent, 0.1-0.5 part of defoaming agent, 0.2-0.5 part of wetting agent and 0.1-2 parts of organic bentonite.
10. A spray coating method using the low temperature radical polymerization curable coating material according to claim 9, characterized by comprising the operations of:
mixing the first component and the B component of the coating, and spraying the mixture on the surface of a device by using a single-component spray gun; curing in an environment above 0 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812645A (en) * | 2021-01-19 | 2021-05-18 | 上海贝能环保科技有限公司 | Bio-based waterproof environment-friendly coating and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2914640A1 (en) * | 2012-10-31 | 2015-09-09 | Lubrizol Advanced Materials, Inc. | Thermoplastic polyurethanes with crystalline chain ends |
| CN107722235A (en) * | 2017-09-28 | 2018-02-23 | 西安天元化工有限责任公司 | A kind of low VOC polyurethane resins |
| CN110066538A (en) * | 2019-04-10 | 2019-07-30 | 西安天元化工有限责任公司 | A kind of UV solidifies and commonly solidify the urethane composition of combination |
| CN110372823A (en) * | 2019-07-12 | 2019-10-25 | 万华化学集团股份有限公司 | A kind of single-component thermosetting polyurethane combined material |
| CN111116857A (en) * | 2020-01-06 | 2020-05-08 | 华东理工大学华昌聚合物有限公司 | Vinyl resin and preparation method thereof |
| CN111440432A (en) * | 2020-04-10 | 2020-07-24 | 烟台瑞特橡塑有限公司 | Low-temperature-resistant high-strength polyurethane tire and preparation process thereof |
-
2020
- 2020-07-31 CN CN202010755762.8A patent/CN111849232A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2914640A1 (en) * | 2012-10-31 | 2015-09-09 | Lubrizol Advanced Materials, Inc. | Thermoplastic polyurethanes with crystalline chain ends |
| CN107722235A (en) * | 2017-09-28 | 2018-02-23 | 西安天元化工有限责任公司 | A kind of low VOC polyurethane resins |
| CN110066538A (en) * | 2019-04-10 | 2019-07-30 | 西安天元化工有限责任公司 | A kind of UV solidifies and commonly solidify the urethane composition of combination |
| CN110372823A (en) * | 2019-07-12 | 2019-10-25 | 万华化学集团股份有限公司 | A kind of single-component thermosetting polyurethane combined material |
| CN111116857A (en) * | 2020-01-06 | 2020-05-08 | 华东理工大学华昌聚合物有限公司 | Vinyl resin and preparation method thereof |
| CN111440432A (en) * | 2020-04-10 | 2020-07-24 | 烟台瑞特橡塑有限公司 | Low-temperature-resistant high-strength polyurethane tire and preparation process thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812645A (en) * | 2021-01-19 | 2021-05-18 | 上海贝能环保科技有限公司 | Bio-based waterproof environment-friendly coating and preparation method thereof |
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