CN101412791B - Epoxy organosilicon phosphoester compound modified acrylic resin - Google Patents

Epoxy organosilicon phosphoester compound modified acrylic resin Download PDF

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CN101412791B
CN101412791B CN 200810227817 CN200810227817A CN101412791B CN 101412791 B CN101412791 B CN 101412791B CN 200810227817 CN200810227817 CN 200810227817 CN 200810227817 A CN200810227817 A CN 200810227817A CN 101412791 B CN101412791 B CN 101412791B
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acrylic resin
epoxy
modified acrylic
compound modified
resin
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CN101412791A (en
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周铭
张玉兴
陈斌
张东阳
李焕
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Changzhou Paint and Coatings Industry Research Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Changzhou Paint and Coatings Industry Research Institute Co Ltd
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Abstract

The invention relates to epoxy silicon phosphate ester composite modified acrylic resin, which is characterized in that epoxy groups, phosphate ester groups and siloxane groups are introduced into acrylic resin; and the weight percentage of resin solid is between 40 and 60 percent, and the balance being a solvent. The acrylic resin comprises the following compositions with the percentage content: as calculated by the total weight of the resin solid, acrylate monomers account for 60 to 96 percent; epoxy resin accounts for 2 to 20 percent; silicon monomers account for 1 to 10 percent; phosphate monomers account for 1 to 10 percent; and an initiator is 0.5 to 1.5 percent of the amount of the acrylate monomers. After the resin is prepared into single-component anticorrosive coating, the anticorrosive property of a film coating is superior to that of the prior single-component anticorrosive coating, and the salt water resistance and the salt fog resistance of the film coating are even superior to those of the prior double-component anticorrosive coating. The epoxy silicon phosphate ester composite modified acrylic resin overcomes the defects of trivial use of the prior double-component coating and poor anticorrosive effect of the single-component coating.

Description

Epoxy organosilicon phosphoester compound modified acrylic resin
Technical field
The present invention relates to a kind of epoxy organosilicon phosphoester compound modified acrylic resin, be particularly suitable for preparing the single component anticorrosive coating.
Background technology
Present anticorrosive coating has two-pack and single component, and the film forming base-material that its two-pack anticorrosive coating is commonly used has epoxy-polyamide resin, acrylate-urethane resin, chlorosulfonated polyethylene resin etc.Had for many years with these resin preparation anticorrosive coatings, its Corrosion Protection is better than the anticorrosive coating of single component greatly, but, before construction, need to weigh in proportion and mix two components, simultaneously arranged after preparation certain working life, in case surpass working life, mechanical property of filming after the film forming and Corrosion Protection all can descend significantly, therefore use very inconvenient; The film forming base-material that the single component anticorrosive coating is commonly used has polyacrylate resin, urethane resin, Resins, epoxy, HCPE, chlorinated rubber or the like, though, do not need to prepare in proportion before use, there is not restriction working life yet, but, the performance of filming for the ease of the preparation of coating and construction and assurance, the molecular weight of these resins all can not be too big, if excessive, just be difficult in the solvent and dissolve, even dissolving forms the solution of low solid content, the performance of film forming matter such as sticking power also can descend greatly, and when loss of adhesion, have the ion of corrosive nature or oxygen to enter paint film easily, cause the ground corrosion.In addition, the molecule of these resins does not have crosslinkable structure basically, and its molecular backbone chain is a linear structure, or at the intermolecular hydrogen bond action that only exists.Because a spot of crosslinking structure will obviously influence its solubleness in solvent, problems such as loss of adhesion can occur equally, and then influence non-corrosibility.Therefore, the film-forming resin of single component anticorrosive coating is compared with the film-forming resin of two-pack anticorrosive coating, very big difference is arranged aspect molecular weight after film forming and the degree of crosslinking, thereby the Corrosion Protection of its corresponding coating often also far is inferior to two-component coating.
Summary of the invention
The objective of the invention is: a kind of epoxy organosilicon phosphoester compound modified acrylic resin that can improve single component anticorrosive coating Corrosion Protection is provided.
The technical scheme that realizes the object of the invention is: a kind of epoxy organosilicon phosphoester compound modified acrylic resin, it is characterized in that, introduced epoxide group, bound phosphate groups and siloxane groups in acrylic resin, the weight percentage of resin solid is 40%~60%, and surplus is a solvent;
Each component and the consumption thereof that constitute acrylic resin are as follows:
By the resin solid gross weight, acrylate monomer accounts for 60%~96%, and Resins, epoxy accounts for 2%~20%, and organosilane monomer accounts for 1%~10%, and phosphate ester monomer accounts for 1%~10%;
Initiator is 0.5%~1.5% of an acrylate monomer consumption.
Above-mentioned epoxy organosilicon phosphoester compound modified acrylic resin, its described acrylate monomer are to contain in the compound with esters of acrylic acid polymerization feature of unsaturated double-bond one or more.For example: for example: one or more of vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, Isooctyl acrylate monomer, butyl methacrylate, butyl acrylate, isopropyl acrylate, isopropyl methacrylate, vinylformic acid n-propyl, n propyl methacrylate etc.
Above-mentioned epoxy organosilicon phosphoester compound modified acrylic resin, its described Resins, epoxy are oxirane value one or more in 0.04~0.56 Resins, epoxy.For example: E12, E14, E31, E44, E51, etc. one or more.
Described epoxy organosilicon phosphoester compound modified acrylic resin, its described organosilane monomer has one of following two kinds of structures:
Figure G2008102278177D00021
Wherein: R 1Be H or C 1~C 10Alkyl; R 2Be C 1~C 10Alkyl; R 3, R 4, R 5Be C 1~C 5Alkyl.For example: KH-570, DL151, DL171 etc.
Above-mentioned epoxy organosilicon phosphoester compound modified acrylic resin, its described phosphate ester monomer has following structure:
Figure G2008102278177D00022
Wherein: R 1Be H or CH 3R 2Be C 1~C 5Alkyl.For example: PM-100, PM-200, PM-300 etc.
Above-mentioned epoxy organosilicon phosphoester compound modified acrylic resin, its described initiator are 10 hour transformation period at 60~130 ℃ radical initiator.For example: benzoyl peroxide, the peroxidation 2-ethylhexyl carbonic acid tert-butyl ester, peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, peroxidation tert-butyl acetate etc.
Above-mentioned epoxy organosilicon phosphoester compound modified acrylic resin, its described solvent are one or more in toluene, dimethylbenzene, N-BUTYL ACETATE, pimelinketone, butanols, ethylene glycol ethyl ether, propylene glycol monomethyl ether, ethylene glycol ether acetate, the 1-Methoxy-2-propyl acetate.
Above-mentioned epoxy organosilicon phosphoester compound modified acrylic resin, the concrete grammar of its synthetic described acrylic resin is: add partial solvent in reaction vessel, be warmed up to 80~140 ℃, add Resins, epoxy, be incubated 0.5~1.0 hour, with part initiator and all acrylate monomer, organosilane monomer and phosphate ester monomer mix and stir after be added in the above-mentioned system, added in 2~5 hours, be incubated 1~2 hour again, to remain then after initiator is dissolved in residual solvent, add in the reaction vessel, add in 1~2 hour, after being incubated 3~5 hours again, cooling, packing promptly makes the epoxy organosilicon phosphoester compound modified acrylic resin product.
Above-mentioned epoxy organosilicon phosphoester compound modified acrylic resin, its described part initiator is 80~85% of an initiator amount; Described partial solvent is 80% of a solvent load.
Technique effect of the present invention is: introduced epoxide group, bound phosphate groups and the siloxane groups of appropriate amount in the epoxy organosilicon phosphoester compound modified acrylic resin of the present invention, wherein the epoxide group of Yin Ruing has improved the resin Corrosion Protection; Hydrolytic crosslinking can take place in siloxane groups in film process, further improved the cross-linking density of resin, and therefore, though the molecular backbone chain of resin of the present invention is a linear structure, formed film forming matter has bigger cross-linking density; Bound phosphate groups can form the phosphatize phosphate coat of passivation with metal substrate, can stop ion or oxygen and metallic contact with corrosive nature.Therefore, resin of the present invention is after making the single component anticorrosive coating, and its Corrosion Protection of filming is better than existing single component anticorrosive coating, aspect resistance to salt water and salt fog resistance, even is better than present some two-pack anticorrosive coating (seeing Table 2).
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, but is not limited to this.
Embodiment and comparative example are unless otherwise indicated raw materials used, are the commercial coating industrial goods, and equipment used is the conventional equipment of coatings industry.
Embodiment 1~6 preparation epoxy organosilicon phosphoester compound modified acrylic resin
(1) the raw material consumption sees Table 1, and wherein consumption is weight part
Table 1
Component Material name Consumption embodiment 1 Consumption embodiment 2 Consumption embodiment 3 Consumption embodiment 4 Consumption embodiment 5 Consumption embodiment 6
Acrylate monomer Methyl methacrylate butyl acrylate Isooctyl acrylate monomer vinylformic acid 30 15 10 5 40 25 12 3 49 30 15 2 30 20 10 5 35 25 12 3 49 30 15 2
Resins, epoxy E12 E44 20 / 10 / 2 / / 20 / 10 / 2
Organosilane monomer KH-570 DL-151 10 / 5 / 1 / / 10 / 5 / 1
Phosphate ester monomer PM-100 10 5 1 5 10 1
Initiator BPO TBEC 0.84 / 1.02 / 1.16 / / 0.84 / 1.02 / 1.16
Solvent The xylylene diacetate butyl ester 100 / 100 / 100 / / 100 / 100 / 100
In the table 1:
Organosilane monomer KH-570 and DL-151 are the product grade of Jiangsu Chenguang Coincident Dose Co., Ltd.,
The KH-570 structure is as follows:
The DL-151 structural formula is as follows:
Figure G2008102278177D00042
Phosphate ester monomer PM-100 is the product grade of French Rhodia, and its structure is as follows:
Figure G2008102278177D00043
Resins, epoxy E12 (oxirane value 0.090.14) and E44 (oxirane value 0.41~0.47) are the name of product of homemade Resins, epoxy, are the coating commercially available product;
Initiator B PO is the abbreviation of benzoyl peroxide; Initiator TBEC is the peroxidation 2-ethylhexyl carbonic acid tert-butyl ester;
(2) synthetic method
In reaction vessel, add 80 gram solvents, be warmed up to 130 ℃, the consumption of pressing table 1 embodiment 1 adds Resins, epoxy, insulation degree 1.0 hours, with 0.7 gram initiator and all acrylate monomer, organosilane monomer and phosphate ester monomer mix and stir after be added in the above-mentioned system, added in 3~3.5 hours, be incubated 1 hour again, to remain then after 0.14 gram initiator is dissolved in 20 gram solvents, add in the reaction vessel, add in 1 hour, after being incubated 3 hours again, cooling, packing promptly makes the epoxy organosilicon phosphoester compound modified acrylic resin product, is numbered Resin A, resin solid content 50% (weight);
In reaction vessel, add 80 gram solvents, be warmed up to 130 ℃, press the consumption of table 1 embodiment 2, use the method identical to make the epoxy organosilicon phosphoester compound modified acrylic resin product, be numbered resin B, resin solid content 50% (weight) with synthetic resins A; Its difference is: with 0.85 the gram initiator mix with all acrylate monomer, organosilane monomer and phosphate ester monomer and stir after be added in the above-mentioned system;
In reaction vessel, add 80 gram solvents, be warmed up to 130 ℃, press the consumption of table 1 embodiment 3, use the method identical to make the epoxy organosilicon phosphoester compound modified acrylic resin product, be numbered resin C, resin solid content 50% (weight) with synthetic resins A; Its difference is: with 0.97 the gram initiator mix with all acrylate monomer, organosilane monomer and phosphate ester monomer and stir after be added in the above-mentioned system;
In reaction vessel, add 80 gram solvents, be warmed up to 130 ℃, press the consumption of table 1 embodiment 4, use the method identical to make the epoxy organosilicon phosphoester compound modified acrylic resin product, be numbered resin D, resin solid content 50% (weight) with synthetic resins A; Its difference is: with 0.7 the gram initiator mix with all acrylate monomer, organosilane monomer and phosphate ester monomer and stir after be added in the above-mentioned system;
In reaction vessel, add 80 gram solvents, be warmed up to 130 ℃, press the consumption of table 1 embodiment 5, use the method identical to make the epoxy organosilicon phosphoester compound modified acrylic resin product, be numbered resin E, resin solid content 50% (weight) with synthetic resins A; Its difference is: with 0.85 the gram initiator mix with all acrylate monomer, organosilane monomer and phosphate ester monomer and stir after be added in the above-mentioned system;
In reaction vessel, add 80 gram solvents, be warmed up to 130 ℃, press the consumption of table 1 embodiment 6, use the method identical to make the epoxy organosilicon phosphoester compound modified acrylic resin product, be numbered resin F, resin solid content 50% (weight) with synthetic resins A; Its difference is: with 0.97 the gram initiator mix with all acrylate monomer, organosilane monomer and phosphate ester monomer and stir after be added in the above-mentioned system.
Embodiment 7 preparation single component anticorrosive coatings
The Resin A that 100 weight part embodiment 1 are made is with after 17.6 weight part iron oxide reds, 6.5 weight part zinc yellows, 6.0 weight part zinc phosphates, 29.1 weight part calcined kaolins, 0.8 weight part wilkinite, 0.6 weight part dispersant B YK-163 and 40 weight part xylene solvents mix, being ground to fineness with sand mill is below 50 microns, promptly make the single component anticorrosive coating, be numbered coating A.
Embodiment 8 preparation single component anticorrosive coatings
The single component anticorrosive coating that makes substantially the same manner as Example 7 is numbered coating B, and its difference is that used resin is the resin B that embodiment 2 makes.
Embodiment 9 preparation single component anticorrosive coatings
The single component anticorrosive coating that makes substantially the same manner as Example 7 is numbered coating C, and its difference is that used resin is the resin C that embodiment 3 makes.
Embodiment 10 preparation single component anticorrosive coatings
The single component anticorrosive coating that makes substantially the same manner as Example 7 is numbered coating D, and its difference is that used resin is the resin D that embodiment 4 makes.
Embodiment 11 preparation single component anticorrosive coatings
The single component anticorrosive coating that makes substantially the same manner as Example 7 is numbered coating E, and its difference is that used resin is the resin E that embodiment 5 makes.
Embodiment 12 preparation single component anticorrosive coatings
The single component anticorrosive coating that makes substantially the same manner as Example 7 is numbered coating F, and its difference is that used resin is the resin F that embodiment 6 makes.
Comparative example 1 preparation epoxy-polymeric amide two-pack anticorrosive coating
35 weight part Resins, epoxy E44 are mixed the back, and to be ground to fineness with sand mill be below 50 microns with 17.6 weight part iron oxide red S130,6.5 weight part zinc yellows, 109,6.0 weight part zinc phosphates, 29.1 weight part calcined kaolins, 0.8 weight part wilkinite, 0.6 weight part dispersant B YK-163 and solvent (30 weight part dimethylbenzene and 10 weight part butanols), promptly makes component 1; During construction, stir with 15 weight part 300# polyamide curing agents again and make comparative example 1 coating, can use as component 2.
Comparative example 2 preparation chlorinated rubber single component anticorrosive coatings
100 weight parts, 50% chlorinated rubber solution is mixed the back, and to be ground to fineness with sand mill be below 50 microns with 17.6 weight part iron oxide red S130,6.5 weight part zinc yellows, 109,6.0 weight part zinc phosphates, 29.1 weight part calcined kaolins, 0.8 weight part wilkinite, 0.6 weight part dispersant B YK-163 and 40 weight part xylene solvents, promptly makes comparative example 2 coating.
Comparative example 3 preparation vinylformic acid single component anticorrosive coatings
Basic identical with comparative example 2, difference is 100 weight parts, the 50% chlorinated rubber solution that replaces comparative example 2 with the common acrylic resin BS-105 (solids constituent 50%) of the non-modified of 100 weight parts, makes comparative example 3 coating.
When preparation the foregoing description and comparative example coating, the raw materials used commercially available industrial goods of coating that are, wherein resin B S-105 is the product grade of Sanmu Group Corp, Jiangsu; Dispersant B YK-163 is the product grade of German BYK company.
By the concerned countries standard of existing coatings industry, the coating that coating A~F that makes with the foregoing description 7~12 and comparative example 1~3 make is made model and is carried out the film performance detection, and it the results are shown in the table 2.
Table 2
Test item Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Comparative example 1 Comparative example 2 Comparative example 3
Sticking power is drawn the circle method, level 1 1 1 1 1 1 1 2 1
Impact cm 50 50 50 50 50 50 50 50 50
Snappiness, mm 1 1 1 1 1 1 1 1.5 1
Water-fast, day >60 >60 >60 >60 >60 >60 >60 50 45
Salt water resistance, day 37 31 27 36 30 27 30 20 15
Salt spray resistance, day 28 23 19 26 21 19 22 14 7
As can be seen from Table 2, with the single component anticorrosive coating that epoxy organosilicon phosphoester compound modified acrylic resin of the present invention makes, its Corrosion Protection obviously is better than the single component anticorrosive coating of comparative example 2 and comparative example 3; During resin preparation single component anticorrosive coating of the present invention that use makes by embodiment 1,2,4 prescription, the Corrosion Protection of its coating even be better than bi-component epoxy-polymeric amide anticorrosive coating (comparative example 1 coating).As seen the present invention is fairly obvious with the effect of epoxy, organosilicon, phosphoester compound modified acrylic resin.

Claims (8)

1. an epoxy organosilicon phosphoester compound modified acrylic resin is characterized in that, has introduced epoxide group, bound phosphate groups and siloxane groups in acrylic resin, and the weight percentage of resin solid is 40%~60%, and surplus is a solvent;
Each component and the consumption thereof that constitute acrylic resin are as follows:
By the resin solid gross weight, acrylate monomer accounts for 60%~96%, and Resins, epoxy accounts for 2%~20%, and organosilane monomer accounts for 1%~10%, and phosphate ester monomer accounts for 1%~10%;
Initiator is 0.5%~1.5% of an acrylate monomer consumption.
2. epoxy organosilicon phosphoester compound modified acrylic resin according to claim 1 is characterized in that, described acrylate monomer is to contain in the compound with esters of acrylic acid polymerization feature of unsaturated double-bond one or more.
3. epoxy organosilicon phosphoester compound modified acrylic resin according to claim 1 is characterized in that, described Resins, epoxy is oxirane value one or more in 0.04~0.56 Resins, epoxy.
4. epoxy organosilicon phosphoester compound modified acrylic resin according to claim 1 is characterized in that, described organosilane monomer has one of following two kinds of structures:
Figure F2008102278177C00011
Wherein: R 1Be H or C 1~C 10Alkyl; R 2Be C 1~C 10Alkyl; R 3, R 4, R 5Be C 1~C 5Alkyl.
5. epoxy organosilicon phosphoester compound modified acrylic resin according to claim 1 is characterized in that, described phosphate ester monomer has following structure:
Figure F2008102278177C00012
Wherein: R 1Be H or CH 3R 2Be C 1~C 5Alkyl.
6. epoxy organosilicon phosphoester compound modified acrylic resin according to claim 1 is characterized in that, described initiator is 10 hour transformation period at 60~130 ℃ radical initiator.
7. epoxy organosilicon phosphoester compound modified acrylic resin according to claim 1, it is characterized in that described solvent is one or more in toluene, dimethylbenzene, N-BUTYL ACETATE, pimelinketone, butanols, ethylene glycol ethyl ether, propylene glycol monomethyl ether, ethylene glycol ether acetate, the 1-Methoxy-2-propyl acetate.
8. epoxy organosilicon phosphoester compound modified acrylic resin according to claim 1, it is characterized in that, the concrete grammar of synthetic described acrylic resin is: add partial solvent in reaction vessel, be warmed up to 80~140 ℃, add Resins, epoxy, be incubated 0.5~1.0 hour, with part initiator and all acrylate monomer, organosilane monomer and phosphate ester monomer mix and stir after be added in the above-mentioned system, added in 2~5 hours, be incubated 1~2 hour again, to remain then after initiator is dissolved in residual solvent, add in the reaction vessel, added in 1~2 hour, be incubated 3~5 hours again after, the cooling, packing promptly makes the epoxy organosilicon phosphoester compound modified acrylic resin product;
Described part initiator is 80~85% of an initiator amount; Described partial solvent is 80% of a solvent load.
CN 200810227817 2008-12-01 2008-12-01 Epoxy organosilicon phosphoester compound modified acrylic resin Expired - Fee Related CN101412791B (en)

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CN103305101B (en) * 2013-07-09 2015-09-30 湖南太子化工涂料有限公司 A kind of quick-dry type is anticorrosion, rust-proofing primer and preparation method thereof
US20150240108A1 (en) * 2014-02-26 2015-08-27 Armstrong World Industries, Inc. Surface coating compositions
CN104804621A (en) * 2015-04-30 2015-07-29 柳州玲通科技有限责任公司 Anticorrosive coating
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