CN1583917A - Organic silicon modified water double-component polyurethane coating and preparing method thereof - Google Patents
Organic silicon modified water double-component polyurethane coating and preparing method thereof Download PDFInfo
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- CN1583917A CN1583917A CN 200410042723 CN200410042723A CN1583917A CN 1583917 A CN1583917 A CN 1583917A CN 200410042723 CN200410042723 CN 200410042723 CN 200410042723 A CN200410042723 A CN 200410042723A CN 1583917 A CN1583917 A CN 1583917A
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Abstract
This invention involves a kind of orrganic silicon and modifies one pair of component parts of swimming skill is gathered Ammonia ester coating and method of preparing, it is by the following weight shares. The raw materials counted: organic silicon is it include hydroxyl ethylene sour cream to modify, Disappear and steep the pharmaceutical, the wetting-out agent, water is (30), hydrophilic how difference cyanic acid ester does it modifiy, through mixing, Mix and make evenly: stated organic silicon modify and suck the hydroxyl propylene. The acid ester cream is by the raw materials of the following manners of weight: Acrylic acid the single mixture of ester, the organic silicon is single, milk take the pharmaceutical, the intiator, water, buffer. The right amount neutralize is heated and got together, cool neutralization, adjust whole pH value is in 8.5, sieve out the material and have: Advantages of this invention whether. It is easy for this coating to mix, the normal atmospheric temperature is done by oneself, nonpoisonous, no Flavor, the characteristic not polluting the environment, the hardness is high, it is good to able to bear the swimming skill.
Description
Technical field
The present invention relates to a kind of organic silicon modified aqueous bicomponent polyurethane coating and preparation method.
Background technology
Polyurethane paint has the performance of many excellences, as strong adhesion, wear resistance is good, elasticity is adjustable, can be made into and arrive utmost point softish coating extremely firmly, have performances such as excellent acid, alkaline-resisting, high-low temperature resistant, therefore obtained using widely at aspects such as national defence, building, chemical industry, vehicle, woodenware, aircrafts.Traditional polyurethane paint contains to human body and the deleterious volatile organic compounds of environment, as toluene, dimethylbenzene etc.Along with the enhancing of people's Environmental awareness and the foundation of environmental regulation, its application more and more is restricted.
Aqueous polyurethane coating, water have replaced poisonous and hazardous organic solvent, have nontoxic, fire-retardant, free from environmental pollution, save advantage such as the energy, progressively replacing traditional solvent reducible coatings, represented the direction of coating development.Mono-component aqueous polyurethane coating easy construction, but still can not reach the performance of solvent borne polyurethane coating at aspects such as many performances such as water tolerance, solvent resistance, chemical-resistant, wear resistance, hardness; And waterborne two-component polyurethane coating has improved the cross-linking density of coating greatly by using polyisocyanates as the linking agent crosslinking curing, and its performance can compare favourably with the solvent borne polyurethane coating.
Aqueous polyurethane coating with bi component has carried out number of research projects both at home and abroad.Hydroxy-containing component as aqueous polyurethane coating with bi component, patent CA2107957, CN1278539, EP792898, EP1065228, US5387642, US5830938, WO97-35898 etc. have applied for the hydroxyl polyurethane dispersions, patent CN1162964, CN1230971, EP959115, WO99-58589, US6225398, WO99-51658, WO01-04172 etc. have applied for the hydroxy acryl acid dispersion, patent EP562282, EP742239 etc. have applied for the hydroxy acryl acid polyurethane dispersions, these dispersions all exist hardness of paint film low, water resistance is poor, with shortcomings such as hydrophilically modified polyisocyanates compatibility differences, be difficult to reach the performance of solvent based coating.
Summary of the invention
The objective of the invention is to improve the shortcoming of prior art, and provide a kind of organic-silicon-modified hydroxy acryl acid emulsion and its to cooperate the modified aqueous polyurethane coating with bi component that makes its performance reach solvent borne polyurethane coating index with hydrophilically modified polyisocyanates.
Another object of the present invention is to and a kind of preparation method of organic silicon modified aqueous bicomponent polyurethane coating is provided.
For achieving the above object, the present invention takes following design: described organic-silicon-modified hydroxy acryl acid ester emulsion is made up of following materials based on weight:
Acrylate monomer blend 20～50 emulsifying agents 0.2～2
Initiator 0.2～0.5 water 49～79
Buffer reagent 0.1～0.3 neutralizing agent is an amount of
Organosilane monomer 0.5～5
Described acrylate monomer blend, its solid acid number scope is at 5～50mgKOH/g, and solid hydroxyl value scope is at 50～250mgKOH/g; Described an amount of neutralizing agent, its be in right amount make the preparation emulsion the pH value be 7～8.5.Described acrylate monomer blend can with hydroxy acryl acid ester monomer and not the acrylate monomer copolymerization of hydroxyl make.Described hydroxy acryl acid ester monomer is (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate; The acrylate monomer of described not hydroxyl comprises vinylbenzene, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA or other (methyl) higher hydrocarbyl acrylate.The acrylate monomer of described not hydroxyl is (methyl) vinylformic acid also.Described emulsifying agent is the mixing of anionic emulsifier and nonionic emulsifying agent.The mixed weight ratio of described anionic emulsifier and nonionic emulsifying agent is 2: 8～8: 2.Described initiator is water miscible, as Potassium Persulphate or ammonium persulphate etc.Described water is distilled water or deionized water.Described buffer reagent is a sodium bicarbonate.Described neutralizing agent is methyldiethanolamine, dimethylethanolamine, triethylamine or ammoniacal liquor etc.Described organosilane monomer is double bond containing organo-siloxane, as vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane or gamma-methyl allyl acyloxypropyl trimethoxysilane etc.
Described organic-silicon-modified hydroxy acryl acid ester emulsion preparation step is as follows: earlier water, emulsifying agent, buffer reagent sodium bicarbonate etc. are mixed the back and add in the reactor, be warmed up to 65～85 ℃, drip the mixture of the initiator, acrylate monomer and the organosilane monomer that are mixed with the aqueous solution respectively, after in 1～3 hour, dripping off, kept 0.5～1.5 hour, make the complete polymerization of acrylate monomer, be cooled to 40～60 ℃, add neutralizing agent, adjust pH, excessively discharging behind at least 80 eye mesh screens 7～8.5.
The organic silicon modified aqueous bicomponent polyurethane coating of the present invention is made up of following materials based on weight:
Hydroxy-containing component:
Organic-silicon-modified hydroxy acryl acid ester emulsion 100 defoamers 0.05～1
Wetting agent 0.05～1, water 0～30
Curing agent component: hydrophilically modified polyisocyanates 5～50
Organic silicon modified aqueous bicomponent polyurethane coating preparation process is as follows: various raw materials in the hydroxy-containing component are mixed, add curing agent component, by hand or mechanical stirring even, be the inventive method product.
During use, can adopt conventional coating method, this coating is coated on the ground that needs, as timber, metal, plastics or paper etc. as brushing, spraying, roller coat, showering, dip-coating etc.This coating can be used as priming paint, in be coated with and finish paint etc.
Advantage of the present invention is: this coating have mix easily, normal temperature self-drying, characteristics nontoxic, tasteless, free from environmental pollution, hardness height, water-tolerant.
Embodiment
Embodiment 1:
Organic-silicon-modified hydroxy acryl acid ester emulsion is made up of following materials based on weight:
Acrylate monomer blend 50 emulsifying agents 2
Initiator 0.5 water 79
Sodium bicarbonate 0.3 neutralizing agent is an amount of
Organosilane monomer 3
Organic-silicon-modified hydroxy acryl acid ester emulsion preparation step is as follows:
In container, add distilled water, compound emulsifying agent MS-1/OP-10 (1: 1) and buffer reagent sodium bicarbonate, be warming up to 85 ℃, drip the aqueous solution (10%) and acrylate monomer blend (the monomer weight ratio: Rocryl 410 23 of initiator ammonium persulfate, methacrylic acid 3, butyl acrylate 40, methyl methacrylate 34) and organosilane monomer vinyltrimethoxy silane mixture.After in 1 hour, dripping off, kept 1.5 hours, be cooled to 40 ℃, add neutralizing agent ammoniacal liquor, adjust the pH value, excessively discharging behind 80 eye mesh screens 8.5.
Organic silicon modified aqueous bicomponent polyurethane coating is made up of following materials based on weight:
Hydroxy-containing component:
Organic-silicon-modified hydroxy acryl acid ester emulsion 100 defoamers 0.05
Wetting agent 0.1, water 30
Curing agent component: hydrophilically modified polyisocyanates 50
Organic silicon modified aqueous bicomponent polyurethane coating preparation process is as follows: in above-mentioned organic-silicon-modified hydroxy acryl acid emulsion, add defoamer Byk028, wetting agent Byk346, stir evenly the back and add hydrophilic polyisocyanate WT2102, stir, add entry, stir evenly, be product of the present invention.
Embodiment 2:
Organic-silicon-modified hydroxy acryl acid ester emulsion is made up of following materials based on weight:
Acrylate monomer blend 20 emulsifying agents 0.2
Initiator 0.2 water 49
Sodium bicarbonate 0.1 neutralizing agent is an amount of
Organosilane monomer 0.5
Organic-silicon-modified hydroxy acryl acid ester emulsion preparation step is as follows:
In container, add deionized water, compound emulsifying agent sodium lauryl sulphate/OP-10 (6: 4) and buffer reagent sodium bicarbonate, be warming up to 65 ℃, drip the aqueous solution (10%) and acrylate monomer blend (the monomer weight ratio: hydroxyethyl methylacrylate 20 of initiator ammonium persulfate simultaneously, methacrylic acid 3, butyl acrylate 40, methyl methacrylate 37) with the mixture of organosilane monomer vinyltriethoxysilane.After in 2 hours, dripping off, kept 1 hour, be cooled to 50 ℃, add the neutralizing agent methyldiethanolamine, adjust the pH value, excessively discharging behind 100 eye mesh screens 7.
Organic silicon modified aqueous bicomponent polyurethane coating is made up of following materials based on weight:
Hydroxy-containing component:
Organic-silicon-modified hydroxy acryl acid ester emulsion 100 defoamers 0.2
Wetting agent 1 water 10
Curing agent component: hydrophilically modified polyisocyanates 25
Organic silicon modified aqueous bicomponent polyurethane coating preparation process is as follows: in above-mentioned organic-silicon-modified hydroxy acryl acid emulsion, add defoamer Byk028, wetting agent Byk346, stir evenly the back and add hydrophilic polyisocyanate WT2102, stir, add entry, stir evenly, be product of the present invention.
Embodiment 3:
Organic-silicon-modified hydroxy acryl acid ester emulsion is made up of following materials based on weight:
Acrylate monomer blend 30 emulsifying agents 1
Initiator 0.3 water 60
Sodium bicarbonate 0.2 neutralizing agent is an amount of
Organosilane monomer 5
Organic-silicon-modified hydroxy acryl acid ester emulsion preparation step is as follows:
In container, add distilled water, compound emulsifying agent sodium lauryl sulphate/OP-10 (6: 4) and buffer reagent sodium bicarbonate, be warming up to 75 ℃, drip the aqueous solution (10%) and acrylate monomer blend (the monomer weight ratio: hydroxyethyl methylacrylate 20 of initiator potassium persulfate simultaneously, methacrylic acid 3, propyl methacrylate 40, methyl methacrylate 37) with the mixture of organosilane monomer gamma-methyl allyl acyloxypropyl trimethoxysilane.After in 3 hours, dripping off, kept 0.5 hour, be cooled to 60 ℃, add the neutralizing agent triethylamine, adjust the pH value, excessively discharging behind 100 eye mesh screens 8.
Organic silicon modified aqueous bicomponent polyurethane coating is made up of following materials based on weight:
Hydroxy-containing component:
Organic-silicon-modified hydroxy acryl acid ester emulsion 100 defoamers 1
Wetting agent 0.05 water 0
Curing agent component: hydrophilically modified polyisocyanates 5
Organic silicon modified aqueous bicomponent polyurethane coating preparation process is as follows: in above-mentioned organic-silicon-modified hydroxy acryl acid emulsion, add defoamer Byk028, wetting agent Byk346, stir evenly the back and add hydrophilic polyisocyanate WT2102, stir, add entry, stir evenly, be product of the present invention.
Press CNS and detect performance, the paint film property detected result is as follows:
Surface drying: 1 hour
Do solid work: 5 hours
Gloss (60 °): 90
Pencil hardness: 2H
Snappiness: 2mm passes through
Sticking power (cross-hatching): 0
Shock strength: 50Kg.cm
Water-fast: as to pass through in 72 hours
Chemical-resistant (spot corrosion):
10%H
2SO
4By
10%HCl passes through
10%CH
3COOH passes through
Ethanol: by
Dimethylbenzene: by
Methylethylketone: by
Claims (10)
1, a kind of organic silicon modified aqueous bicomponent polyurethane coating, it is characterized in that: it is made up of following materials based on weight:
Hydroxy-containing component:
Organic-silicon-modified hydroxy acryl acid ester emulsion 100 defoamers 0.05～1
Wetting agent 0.05～1 water 0～30
Curing agent component: hydrophilically modified polyisocyanates 5～50
Described organic-silicon-modified hydroxy acryl acid ester emulsion is made up of following materials based on weight:
Acrylate monomer blend 20～50 emulsifying agents 0.2～2
Initiator 0.2～0.5 water 49～79
Buffer reagent 0.1～0.3 neutralizing agent is an amount of
Organosilane monomer 0.5～5
2, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1 is characterized in that: described hydroxy acryl acid ester monomer is (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate.
3, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1 is characterized in that: the acrylate monomer of described not hydroxyl is vinylbenzene, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA or other (methyl) higher hydrocarbyl acrylate.
4, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1 is characterized in that: the acrylate monomer of described not hydroxyl is (methyl) vinylformic acid.
5, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1, it is characterized in that: described emulsifying agent is the mixing of anionic emulsifier and nonionic emulsifying agent, and the mixed weight ratio of described anionic emulsifier and nonionic emulsifying agent is 2: 8～8: 2.
6, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1, it is characterized in that: described initiator is water miscible Potassium Persulphate or ammonium persulphate.
7, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1, it is characterized in that: described organosilane monomer is double bond containing organo-siloxane, as vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane or gamma-methyl allyl acyloxypropyl trimethoxysilane.
8, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1 is characterized in that: the solid acid number scope of described acrylate monomer blend is at 5～50mgKOH/g, and solid hydroxyl value scope is at 50～250mgKOH/g;
9, a kind of organic silicon modified aqueous bicomponent polyurethane coating according to claim 1, it is characterized in that: described neutralizing agent is methyldiethanolamine, dimethylethanolamine, triethylamine or ammoniacal liquor.
10, a kind of preparation method of organic silicon modified aqueous bicomponent polyurethane coating is characterized in that:
Select the organic-silicon-modified hydroxy acryl acid ester emulsion raw material of following portions by weight for use:
Acrylate monomer blend 20～50 emulsifying agents 0.2～2
Initiator 0.2～0.5 water 49～79
Sodium bicarbonate 0.1～0.3 neutralizing agent is an amount of
Organosilane monomer 0.5～5
Prepare organic-silicon-modified hydroxy acryl acid ester emulsion, step is as follows: earlier water, emulsifying agent, sodium bicarbonate etc. are mixed the back and add in the reactor, be warmed up to 65～85 ℃, drip initiator, acrylate monomer blend and the organosilane monomer that is mixed with the aqueous solution respectively, after in 1～3 hour, dripping off, kept 0.5～1.5 hour, make the complete polymerization of acrylate monomer, be cooled to 40～60 ℃, add neutralizing agent, adjust pH 7～8.5, excessively discharging behind at least 80 eye mesh screens;
Select the organic silicon modified aqueous bicomponent polyurethane coating raw material of following portions by weight for use:
Hydroxy-containing component:
Organic-silicon-modified hydroxy acryl acid ester emulsion 100 defoamers 0.05～1
Wetting agent 0.05～1, water 0～30
Curing agent component: hydrophilically modified polyisocyanates 5～50
It is as follows to prepare organic silicon modified aqueous bicomponent polyurethane coating step: various raw materials in the hydroxy-containing component are mixed, add curing agent component, by hand or mechanical stirring even.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410042723 CN1267517C (en) | 2004-05-24 | 2004-05-24 | Organic silicon modified water double-component polyurethane coating and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410042723 CN1267517C (en) | 2004-05-24 | 2004-05-24 | Organic silicon modified water double-component polyurethane coating and preparing method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1583917A true CN1583917A (en) | 2005-02-23 |
| CN1267517C CN1267517C (en) | 2006-08-02 |
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| CN100363447C (en) * | 2005-03-24 | 2008-01-23 | 郑州大学 | Modified water-proof acrylic acid paint |
| CN103031046A (en) * | 2011-09-29 | 2013-04-10 | 上海正欧实业有限公司 | Novel organosilicone acrylic acid bi-component polyurethane coating and preparation method thereof |
| CN103342956A (en) * | 2013-06-27 | 2013-10-09 | 天长市巨龙车船涂料有限公司 | Acrylic acid modified waterborne polyurethane paint and preparation method thereof |
| CN105567045A (en) * | 2016-02-01 | 2016-05-11 | 潘浩升 | Latex coating applied to outer wall |
| CN106916254A (en) * | 2017-03-22 | 2017-07-04 | 中山市千佑化学材料有限公司 | Polymerization of acrylic modified polyurethane emulsion and preparation method thereof |
| CN107573474A (en) * | 2017-08-22 | 2018-01-12 | 广东省石油与精细化工研究院 | A kind of silicone-modified water-soluble polyurethane acrylic resin emulsion and preparation method thereof |
| CN108659650A (en) * | 2018-06-14 | 2018-10-16 | 上海安弗柯林工业科技有限公司 | A kind of aqueous anti-fog coating and preparation method |
| CN108864929A (en) * | 2018-07-27 | 2018-11-23 | 武汉理工大学 | A kind of water-soluble low surface energy resin/nano zine oxide compound anti-fouling paint and preparation method thereof |
| CN109370406A (en) * | 2018-11-20 | 2019-02-22 | 沈左红 | A kind of automobile external coating scratch resistance coating varnish and preparation method thereof |
| CN109852221A (en) * | 2019-01-08 | 2019-06-07 | 中海油常州涂料化工研究院有限公司 | A kind of low VOC and high performance dual-component aqueous polyurethane woodwork coating and preparation method thereof |
| CN110016279A (en) * | 2018-10-30 | 2019-07-16 | 浙江博星化工涂料有限公司 | A kind of enamel effect imitation marble paint |
| CN110396342A (en) * | 2019-08-01 | 2019-11-01 | 苏晓辉 | A kind of self-cleaning coating and its construction technology |
| CN110982323A (en) * | 2019-12-17 | 2020-04-10 | 广东歌丽斯化学有限公司 | Antifouling water-based paint and preparation method and application thereof |
| CN111763287A (en) * | 2019-04-02 | 2020-10-13 | 万华化学集团股份有限公司 | Hydroxyl acrylic emulsion for water-based double-component anti-doodling and anti-sticking coating and preparation method thereof |
| CN112708031A (en) * | 2020-12-25 | 2021-04-27 | 嘉宝莉化工集团股份有限公司 | Water-based hydroxyl acrylic emulsion and preparation method and application thereof |
| CN112961587A (en) * | 2021-02-07 | 2021-06-15 | 三棵树(上海)新材料研究有限公司 | High-stain-resistance glass heat-insulating coating based on cesium tungsten bronze and preparation method thereof |
-
2004
- 2004-05-24 CN CN 200410042723 patent/CN1267517C/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100363447C (en) * | 2005-03-24 | 2008-01-23 | 郑州大学 | Modified water-proof acrylic acid paint |
| CN103031046A (en) * | 2011-09-29 | 2013-04-10 | 上海正欧实业有限公司 | Novel organosilicone acrylic acid bi-component polyurethane coating and preparation method thereof |
| CN103031046B (en) * | 2011-09-29 | 2015-05-27 | 上海正欧实业有限公司 | Novel organosilicone acrylic acid bi-component polyurethane coating and preparation method thereof |
| CN103342956A (en) * | 2013-06-27 | 2013-10-09 | 天长市巨龙车船涂料有限公司 | Acrylic acid modified waterborne polyurethane paint and preparation method thereof |
| CN105567045A (en) * | 2016-02-01 | 2016-05-11 | 潘浩升 | Latex coating applied to outer wall |
| CN106916254A (en) * | 2017-03-22 | 2017-07-04 | 中山市千佑化学材料有限公司 | Polymerization of acrylic modified polyurethane emulsion and preparation method thereof |
| CN107573474A (en) * | 2017-08-22 | 2018-01-12 | 广东省石油与精细化工研究院 | A kind of silicone-modified water-soluble polyurethane acrylic resin emulsion and preparation method thereof |
| CN108659650A (en) * | 2018-06-14 | 2018-10-16 | 上海安弗柯林工业科技有限公司 | A kind of aqueous anti-fog coating and preparation method |
| CN108864929B (en) * | 2018-07-27 | 2019-11-08 | 武汉理工大学 | A kind of water-soluble low surface energy resin/nano zine oxide compound anti-fouling paint and preparation method thereof |
| CN108864929A (en) * | 2018-07-27 | 2018-11-23 | 武汉理工大学 | A kind of water-soluble low surface energy resin/nano zine oxide compound anti-fouling paint and preparation method thereof |
| CN110016279A (en) * | 2018-10-30 | 2019-07-16 | 浙江博星化工涂料有限公司 | A kind of enamel effect imitation marble paint |
| CN109370406A (en) * | 2018-11-20 | 2019-02-22 | 沈左红 | A kind of automobile external coating scratch resistance coating varnish and preparation method thereof |
| CN109852221A (en) * | 2019-01-08 | 2019-06-07 | 中海油常州涂料化工研究院有限公司 | A kind of low VOC and high performance dual-component aqueous polyurethane woodwork coating and preparation method thereof |
| CN109852221B (en) * | 2019-01-08 | 2021-07-13 | 中海油常州涂料化工研究院有限公司 | Low-VOC high-performance double-component waterborne polyurethane wood coating and preparation method thereof |
| CN111763287A (en) * | 2019-04-02 | 2020-10-13 | 万华化学集团股份有限公司 | Hydroxyl acrylic emulsion for water-based double-component anti-doodling and anti-sticking coating and preparation method thereof |
| CN111763287B (en) * | 2019-04-02 | 2023-03-03 | 万华化学集团股份有限公司 | Hydroxyl acrylic emulsion for water-based double-component anti-doodling and anti-sticking coating and preparation method thereof |
| CN110396342A (en) * | 2019-08-01 | 2019-11-01 | 苏晓辉 | A kind of self-cleaning coating and its construction technology |
| CN110982323A (en) * | 2019-12-17 | 2020-04-10 | 广东歌丽斯化学有限公司 | Antifouling water-based paint and preparation method and application thereof |
| CN112708031A (en) * | 2020-12-25 | 2021-04-27 | 嘉宝莉化工集团股份有限公司 | Water-based hydroxyl acrylic emulsion and preparation method and application thereof |
| CN112961587A (en) * | 2021-02-07 | 2021-06-15 | 三棵树(上海)新材料研究有限公司 | High-stain-resistance glass heat-insulating coating based on cesium tungsten bronze and preparation method thereof |
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