CN103820017A - Epoxy modified polyurethane primer and preparation method thereof - Google Patents

Epoxy modified polyurethane primer and preparation method thereof Download PDF

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Publication number
CN103820017A
CN103820017A CN201410071904.3A CN201410071904A CN103820017A CN 103820017 A CN103820017 A CN 103820017A CN 201410071904 A CN201410071904 A CN 201410071904A CN 103820017 A CN103820017 A CN 103820017A
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component
modified polyurethane
primary coat
epoxy modified
epoxy resin
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CN201410071904.3A
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CN103820017B (en
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刘子康
王新锋
李红英
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Beijing Oriental Yuhong Waterproof Technology Co Ltd
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Beijing Oriental Yuhong Waterproof Technology Co Ltd
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Abstract

The invention discloses an epoxy modified polyurethane primer. The epoxy modified polyurethane primer is bi-component coating comprising an A component and a B component. The A component comprises 20-45 parts by weight of polyisocyanate, prepolymer obtained by reacting 20-40 parts by weight of polyol with 5-15 parts by weight of epoxy resin, and 10-40 parts by weight of a solvent. The B component comprises 5-15 parts by weight of an amino curing agent, 5-30 parts by weight of a hydroxy curing agent and 50-85 parts by weight of a solvent. The epoxy modified polyurethane primer can be used for concrete surfaces and used in an environment with relatively large humidity and relatively low temperature, and has advantages of good pore blocking effects, high construction efficiency, high adhesive force, and the like.

Description

A kind of epoxy modified polyurethane primary coat and preparation method thereof
Technical field
The present invention relates to a kind of epoxy modified polyurethane primary coat, belong to building material field.
Background technology
Polyureas must use special primary coat at concrete surface, and primary coat one is for air and moisture in closed concrete substrate surface pore, avoids occurring bulge and pin-hole phenomena after polyurea coating spraying; The 2nd, can play the effect of sizing agent, improve the cohesive strength of polyurea coating and concrete substrate, improve protection effect.
Primary coat in the market mainly contains following several system:
1, urethane primary coat.Urethane primary coat is generally divided into two components and single-component, and monocomponent polyurethane primary coat is easy to use, but holder is shorter.Compared with dual-component polyurethane primary coat, monocomponent polyurethane primary coat is in use prone to foaming phenomenon, and its cohesive strength of dual-component polyurethane primary coat is lower, is difficult to meet requirement of engineering.
2, epoxy resin primary coat.Epoxy resin primary coat is generally two components, and A component is epoxy resin and epoxide resin reactive diluent and solvent composition, and B component is amino epoxy hardener.Although the relative urethane primary coat of epoxy resin primary coat cohesive strength is good, affected by ambient moisture little, its temperature influence is larger, very fast 15 ℃ of following speed of response reductions, is almost difficult to below solidify at 5 ℃.
Summary of the invention
For the defect of prior art, the invention provides a kind of epoxy modified polyurethane primary coat, under the environment that this primary coat can be larger in relative humidity, temperature is lower, brushing is used for concrete surface, has that plug-hole is effective, operating efficiency is high, a strong adhesion, the advantage such as applied widely.
For achieving the above object, the present invention is achieved through the following technical solutions:
A kind of epoxy modified polyurethane primary coat, is the two-component coating being made up of A component and B component, and wherein A component is to react by polyisocyanates, polyester polyol and epoxy resin the performed polymer and the solvent composition that obtain; B component is made up of amino curing agent, hydroxyl cure agent, solvent and auxiliary agent, and wherein each composition weight umber is as follows:
A component:
Figure BDA0000471052680000011
B component:
Amino curing agent 5~15
Hydroxyl cure agent 5~30
Solvent 50~85.
Accordingly, on the basis of the above, the invention discloses the preparation method of the described epoxy modified polyurethane primary coat for concrete surface:
The preparation method of A component: polyester polyol is added in the reactor that has nitrogen protection, under agitation be heated to 100~120 ℃, constant temperature is evacuated to still internal pressure-0.095MPa and dewaters above 3 hours, vacuum cool-down to 50~60 ℃, pass add the polyisocyanates of respective amount, be heated to 70~90 ℃ of reactions 3 hours, add epoxy resin to continue reaction 1 hour, be cooled to 40~60 ℃, add stirring solvent evenly after discharging and obtaining;
The preparation method of B component: first solvent is joined in reactor, add under then stirring under amino curing agent and hydroxyl cure agent low rate mixing after solidifying agent dissolves completely, add other auxiliary agents mix discharging and obtain.
Above preparation method is only preferably preparation method of the present invention; and unrestricted the present invention only can adopt aforesaid method to make; those skilled in the art change and can't change essence of the present invention Heating temperature, vacuum tightness, reaction times etc. on the basis of the above; just affect accordingly preparation speed and the productive rate of product, within this change is covered by protection domain of the present invention.
Further, the invention also discloses the using method of the described epoxy modified polyurethane primary coat for concrete surface, is that 2: 1~4: 1 ratios are carried out mixing and stirring by two components according to weight ratio, adopts brushing or roller coating mode to construct.
Of the present invention be described in further detail and specifically implement in; the invention discloses the preferred type of various compositions used; so that better, clearer explanation the present invention; but this detailed description does not form special restriction of the present invention; do not rely on these details and adopt other general chemical materials of the technology of the present invention field; as long as it meets the above-mentioned restriction that each moiety title is done of the present invention, still belong to protection scope of the present invention.
In the present invention, described polyisocyanates is selected from tolylene diisocyanate, diphenylmethanediisocyanate, the aromatic polyisocyanates such as polymethine polyphenyl polyisocyanate; Or be selected from the aliphatic polyisocyantes such as cyclohexyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate; Or the mixture of aromatic polyisocyanate and aliphatic polyisocyante.
Preferably, described polyisocyanates is diphenylmethanediisocyanate and/or polymethine polyphenyl polyisocyanate.
In the present invention, described polyvalent alcohol is selected from a kind of in polyether glycol, polyester polyol, polytetrahydrofuran polyvalent alcohol and/or more than one mixture, and its functionality is 2~4, and hydroxyl value equivalent is 500~2000.
Described polyvalent alcohol is preferably polyester polyol, and its functionality is 2~3, and hydroxyl value equivalent is 1000.
In the present invention, described epoxy resin is selected from bisphenol A type epoxy resin and/or bisphenol f type epoxy resin, and its oxirane value is not less than 0.12.
Described epoxy resin is preferably bisphenol A type epoxy resin, and its oxirane value is 0.20~0.56.
In the present invention, described amino curing agent is selected from 3,3 '-bis-chloro-4,4 '-diaminodiphenyl-methane (MOCA), diethyl toluene diamine, dimethythiotoluene diamine, N, N '-dialkyl methyl pentanoic, 4, a kind of in 4 '-diaminodiphenyl-methane and/or more than one mixture, its functionality is 2~4.
Described amino curing agent is preferably 3, and 3 '-bis-is chloro-4,4 '-diaminodiphenyl-methane (MOCA).
In the present invention, described hydroxyl cure agent is selected from a kind of in BDO, glycerine, TriMethylolPropane(TMP), trolamine, tetramethylolmethane and/or more than one mixture, and its functionality is 2~4.
Described hydroxyl cure agent is preferably TriMethylolPropane(TMP) (TMP).
In the present invention, described solvent is selected from a kind of in ethyl acetate, butylacetate, acetone, dimethylbenzene and/or more than one mixture.
Described solvent is preferably the mixture of butylacetate and acetone.
Further, in coating of the present invention, described B component also can comprise that auxiliary agent for example, to improve the multiple performance of coating: in B component, can add as required the auxiliary agents such as defoamer, oxidation inhibitor, ultraviolet absorbers, FLOW IMPROVERS.
Wherein, the parts by weight of auxiliary agent, for other composition, not higher than 5,0~5.It should be noted that, the consumption of describing auxiliary agent has herein used the such numerical expression scope of 0-x, it is the restriction that consumption for expressing specific examples of such components is subject to the upper limit, can play corresponding function as long as add this component in composition, make under normal conditions used additives in order to improve the specified property of certain aspect, but according to the needs that use, it is also feasible not making used additives.
Epoxy modified polyurethane primary coat of the present invention is applied to concrete surface processing, is mainly the processing of the concrete surface of spray polyurea, has suitability widely, applicable to humidity and temperature scope widely.
Embodiment
The invention spirit can better understand the present invention in conjunction with specific embodiments; in following enforcement; provide that the present invention is some preferred embodiment to be formed with material; but the present invention is not limited in and adopts following manner to implement, change that those skilled in the art carry out the present invention on the basis of understanding essence of the present invention, replacement, improvement etc. still belong to protection scope of the present invention.
In the following embodiments, each raw material all can be from market purchasing, for example:
PM-200 polyisocyanates (Yantai Wan Hua urethane company limited)
M20S polyisocyanates (BASF Aktiengesellschaft)
PS-2000 polyester polyol (imported from America)
MOCA amino curing agent (garden, Hunan chemical industry)
E-44, E-51 bisphenol A type epoxy resin (Shanghai Resin Factory's manufacture)
Embodiment 1
40 weight part polyester diol PS-2000 and 5 weight part epoxy resin E-44s are added in the reactor that fills nitrogen, heat to (105~115) ℃, constant temperature is evacuated to still internal pressure-0.095MPa and dewaters above 3 hours, closing vacuum cool-down to (50~60) ℃ adds 20 weight part PM-200, is heated to (70~90) ℃ reaction 3 hours, be cooled to (50~60) ℃, add 35 weight part acetone, after stirring, discharging is A component.B component is to be uniformly mixed and to make in reactor by the catalyzer of 5 weight part MOCA, 5 weight part TMP, 40 weight part acetone, 45 weight part butylacetates, 1 weight part defoamer, 1 weight part flow agent, 1 weight part and 2 weight part adhesion promoters.When use, A: B=2: 1 (mass ratio) mixing and stirring.
Embodiment 2
30 weight part polyester diol PS-2000 and 10 weight part epoxy resin E-44s are added in the reactor that fills nitrogen, heat to (105~115) ℃, constant temperature is evacuated to still internal pressure-0.095MPa and dewaters above 3 hours, closing vacuum cool-down to (50~60) ℃ adds 30 weight part PM-200, is heated to (70~90) ℃ reaction 3 hours, be cooled to (50~60) ℃, add 30 weight part acetone, after stirring, discharging is A component.B component is to be uniformly mixed and to make in reactor by the catalyzer of 10 weight part MOCA, 10 weight part TMP, 40 weight part acetone, 35 weight part butylacetates, 1 weight part defoamer, 1 weight part flow agent, 1 weight part and 2 weight part adhesion promoters.When use, A: B=2: 1 (mass ratio) mixing and stirring.
Embodiment 3
20 weight part polyester diol PS-2000 and 15 weight part epoxy resin E-44s are added in the reactor that fills nitrogen, heat to (105~115) ℃, constant temperature is evacuated to still internal pressure-0.095MPa and dewaters above 3 hours, closing vacuum cool-down to (50~60) ℃ adds 45 weight part PM-200, is heated to (70~90) ℃ reaction 3 hours, be cooled to (50~60) ℃, add 15 weight part acetone, after stirring, discharging is A component.B component is to be uniformly mixed and to make in reactor by the catalyzer of 12 weight part MOCA, 20 weight part TMP, 25 weight part acetone, 35 weight part butylacetates, 1 weight part defoamer, 1 weight part flow agent, 1 weight part and 2 weight part adhesion promoters.When use, A: B=2: 1 (mass ratio) mixing and stirring.
The performance test results of above embodiment is in Table
The performance test results of table 1 embodiment (normal temperature)
Project Embodiment 1 Embodiment 2 Embodiment 3
Surface drying time/h 1.5 1.0 0.5
Do solid work time/h 4 3.5 3
Cohesive strength/MPa 3.8 4.4 4.9
Stripping strength N/mm 7.9 9.5 10.8
Can be found out by above-mentioned experimental data, coating of the present invention is all good by properties under described composition, meets application demand.
Processing by the product of above-described embodiment for the concrete surface under low temperature, having carried out respectively temperature is 12 ℃, humidity 60%, and temperature is the checking under 3 ℃, humidity 75% situation, and result is as shown in following table 2,3:
The performance test results of table 2 embodiment
Project Embodiment 1 Embodiment 2 Embodiment 3
Surface drying time/h 1.5 1.1 0.6
Do solid work time/h 4.1 3.8 3.2
Cohesive strength/MPa 3.5 4.0 4.7
Stripping strength N/mm 7.5 9.5 10.5
The performance test results of table 3 embodiment
Project Embodiment 1 Embodiment 2 Embodiment 3
Surface drying time/h 1.7 1.4 0.7
Do solid work time/h 4.2 3.9 3.5
Cohesive strength/MPa 3.5 4.0 4.5
Stripping strength N/mm 7.5 9.2 10.2
Can find out from above-mentioned data, although slightly reducing has appearred in the performance of coating of the present invention under low temperature, high humidity, still meet building operation demand.
There is rapid drawdown in conventional epoxy resin primary coat performance within the scope of 10-15 ℃, 5 ℃ and following temperature, substantially without the feasibility of constructing, epoxy modified polyurethane primary coat of the present invention has overcome this problem.

Claims (10)

1. an epoxy modified polyurethane primary coat, is characterized in that forming two-component coating by A component and B component, performed polymer and solvent composition that described A component is obtained by polyisocyanates, polyvalent alcohol and epoxy resin reaction; Described B component comprises amino curing agent, hydroxyl cure agent, solvent, and wherein each composition weight umber is as follows:
A component:
Figure FDA0000471052670000011
B component:
Amino curing agent 5~15
Hydroxyl cure agent 5~30
Solvent 50~85.
2. epoxy modified polyurethane primary coat according to claim 1, is characterized in that described polyisocyanates is aromatic polyisocyanate and/or aliphatic polyisocyante.
3. epoxy modified polyurethane primary coat according to claim 2, is characterized in that described polyisocyanates is diphenylmethanediisocyanate and/or polymethine polyphenyl polyisocyanate.
4. epoxy modified polyurethane primary coat according to claim 1, it is characterized in that described polyvalent alcohol is selected from one or more the mixture in polyether glycol, polyester polyol, polytetrahydrofuran polyvalent alcohol, its functionality is 2~4, and hydroxyl value equivalent is 500~2000.
5. epoxy modified polyurethane primary coat according to claim 1, is characterized in that described epoxy resin is bisphenol A type epoxy resin and/or bisphenol f type epoxy resin, and its oxirane value is not less than 0.12.
6. epoxy modified polyurethane primary coat according to claim 1, is characterized in that described epoxy resin is bisphenol A type epoxy resin, and its oxirane value is 0.20~0.56.
7. epoxy modified polyurethane primary coat according to claim 1, it is characterized in that described amino curing agent is selected from 3,3 '-bis-chloro-4,4 '-diaminodiphenyl-methane (MOCA), diethyl toluene diamine, dimethythiotoluene diamine, N, N '-dialkyl methyl pentanoic, 4, the mixture of one or more in 4 '-diaminodiphenyl-methane, its functionality is 2~4.
7, epoxy modified polyurethane primary coat according to claim 1, it is characterized in that described hydroxyl cure agent is selected from 1, the mixture of one or more in 4-butyleneglycol, glycerine, TriMethylolPropane(TMP), trolamine, tetramethylolmethane, its functionality is 2~4.
8. epoxy modified polyurethane primary coat according to claim 1, is characterized in that described solvent is selected from one or more the mixture in ethyl acetate, butylacetate, acetone, dimethylbenzene.
9. epoxy modified polyurethane primary coat according to claim 1, is characterized in that described B component also comprises auxiliary agent, and the parts by weight of auxiliary agent are not higher than 5.
10. the preparation method of above-mentioned arbitrary epoxy modified polyurethane primary coat, is characterized in that:
The preparation method of A component: polyester polyol is added in the reactor that has nitrogen protection, under agitation be heated to 100~120 ℃, constant temperature is evacuated to still internal pressure-0.095MPa and dewaters above 3 hours, vacuum cool-down to 50~60 ℃, pass add the polyisocyanates of respective amount, be heated to 70~90 ℃ of reactions 3 hours, add epoxy resin to continue reaction 1 hour, be cooled to 40~60 ℃, add stirring solvent evenly after discharging and obtaining;
The preparation method of B component: first solvent is joined in reactor, add under then stirring under amino curing agent and hydroxyl cure agent low rate mixing after solidifying agent dissolves completely, add other auxiliary agents mix discharging and obtain.
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CN105153389A (en) * 2015-10-23 2015-12-16 蓝星(成都)新材料有限公司 Polyurethane-epoxy resin material and preparation method thereof
CN106700887A (en) * 2016-12-28 2017-05-24 北京金盾建材有限公司 Bottom coating for basic treatment of low-temperature cured concrete
CN106928809A (en) * 2017-03-21 2017-07-07 新疆科能防水防护技术股份有限公司 A kind of epoxy coating and preparation method thereof
CN107760191A (en) * 2017-09-29 2018-03-06 东来涂料技术(上海)有限公司 A kind of waterborne conductive priming paint applied to automobile carbon fiber and preparation method thereof
CN108841308A (en) * 2018-06-22 2018-11-20 中国石油天然气集团公司管材研究所 A kind of curing agent and preparation method thereof, anticorrosive coating and preparation method thereof
CN111269647A (en) * 2020-03-24 2020-06-12 宜兴市华夏化工材料有限公司 Preparation method and application of epoxy resin modified polyurethane coating agent
CN112980377A (en) * 2021-01-29 2021-06-18 佛山市高明大都化工有限公司 Oil skin nylon treating agent and preparation method thereof
CN115926605A (en) * 2022-11-25 2023-04-07 四川昕悦环保科技有限公司 Film spraying material, preparation method and application thereof
WO2023240946A1 (en) * 2022-06-17 2023-12-21 中车株洲车辆有限公司 Water-based prefabrication primer, coating, and product with coating

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105153389A (en) * 2015-10-23 2015-12-16 蓝星(成都)新材料有限公司 Polyurethane-epoxy resin material and preparation method thereof
CN106700887A (en) * 2016-12-28 2017-05-24 北京金盾建材有限公司 Bottom coating for basic treatment of low-temperature cured concrete
CN106928809A (en) * 2017-03-21 2017-07-07 新疆科能防水防护技术股份有限公司 A kind of epoxy coating and preparation method thereof
CN107760191A (en) * 2017-09-29 2018-03-06 东来涂料技术(上海)有限公司 A kind of waterborne conductive priming paint applied to automobile carbon fiber and preparation method thereof
CN108841308A (en) * 2018-06-22 2018-11-20 中国石油天然气集团公司管材研究所 A kind of curing agent and preparation method thereof, anticorrosive coating and preparation method thereof
CN108841308B (en) * 2018-06-22 2021-02-19 中国石油天然气集团公司管材研究所 Curing agent and preparation method thereof, and anticorrosive paint and preparation method thereof
CN111269647A (en) * 2020-03-24 2020-06-12 宜兴市华夏化工材料有限公司 Preparation method and application of epoxy resin modified polyurethane coating agent
CN112980377A (en) * 2021-01-29 2021-06-18 佛山市高明大都化工有限公司 Oil skin nylon treating agent and preparation method thereof
WO2023240946A1 (en) * 2022-06-17 2023-12-21 中车株洲车辆有限公司 Water-based prefabrication primer, coating, and product with coating
CN115926605A (en) * 2022-11-25 2023-04-07 四川昕悦环保科技有限公司 Film spraying material, preparation method and application thereof
CN115926605B (en) * 2022-11-25 2023-10-13 四川昕悦环保科技有限公司 Spray film material, preparation method and application thereof

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