CN100519603C - Cross-linking type fluorine-containing acrylic resin - Google Patents
Cross-linking type fluorine-containing acrylic resin Download PDFInfo
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- CN100519603C CN100519603C CNB2007100237591A CN200710023759A CN100519603C CN 100519603 C CN100519603 C CN 100519603C CN B2007100237591 A CNB2007100237591 A CN B2007100237591A CN 200710023759 A CN200710023759 A CN 200710023759A CN 100519603 C CN100519603 C CN 100519603C
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Abstract
The invention relates to a crosslinking type fluorine-containing acrylic resin, which is obtained by the heating and polymerization of more than one acrylic acid type monomer under initiator. The invention is characterized in that: the amount of each monomer applied in polymerization reaction is according to weight portions: methyl methacrylate 5-10 portions, alkyl acrylate monomer 10-20 portions, functional acrylic acid monomer 5-10 portions, fluorine-containing acrylic monomer 10-25 portions, organic solvent 40-60 portions; the fluorine-containing acrylic monomer is either or both of trifluoroethyl methacrylate and trifluoroethyl acrylate; the content of the fluorine-containing acrylic monomer takes 20-50 percent of the total weight of all monomer applied in the polymerization reaction. The resin can be crossingly cured at normal temperature and low medium temperature and has the wide application. Coating produced with the resin, comprehensive performance of which is close to fluorocarbon coatings maintains performance price ratio advantage of the acrylic resin.
Description
Technical field
The present invention relates to a kind of cross-linking type fluorine-containing acrylic resin.More specifically say, the present invention relates to a kind of superiority of effectiveness that keeps acrylic resin, price is low and cross-linking type fluorine-containing acrylic resin that over-all properties and fluorocarbon resin are suitable.
Background technology
Unique fluoro-carbon bond that the fluorocarbon resin molecular structure has has been given the excellent properties such as weathering resistance, chemical resistance, anti-staining property and self-cleaning of fluorocarbon resin coating overlength.But traditional fluorocarbon resin (for example, Teflon series fluorocarbon resin, polyvinylidene fluoride resin) crystallinity height, poorly soluble, poor with matrix adhesive force, particularly need high bake fusion film forming, to using material choice such as base material and color stuffing particular requirement is arranged all, limited using and promoting of fluorocarbon resin.The cross-linking type fluorocarbon resin of recent exploitation, for example the copolymer resins of fluoroolefin and vinyl ether or vinyl ester (be called for short FEVE resin) is formed by trifluorochloroethylene or tetrafluoroethylene and vinyl monomer copolymerization, major advantage is to have excellent weather resistance, and has enlarged the range of application of fluorocarbon resin coating; Shortcoming is that the copolyreaction that forms resin needs high pressure, the difference selected of while comonomer kind, if in molecular resin, can not produce the alternating copolymerization structure, the weathering resistance of fluorocarbon resin coating with its preparation is suitable with common acrylic resin paint, and its price is expensive a lot of than acrylic resin paint, in addition, choice of Solvent also is subjected to certain limitation in the use.Application number is that 200510021181.7 Chinese patent application is a kind of single component thermoplastics type's fluorocarbon coating, fluoroacrylic resin wherein is the fluorine-containing trifluoroethyl methacrylate monomer synthetic by mass percent less than 10%, molecular weight 168 with trifluoroethyl methacrylate calculates, the content of fluorine atom about 3% in the resin, be difficult to from reaching in fact and the akin performance of fluorocarbon resin coating by its coatings formulated, in addition, be subjected to the limitation of thermoplastics type's fluorocarbon resin self proper property, particularly various patience are not as heat cured resin.Application number is that 200610052014.3 Chinese patent application is that to adopt (methyl) vinylformic acid hexafluoro butyl ester be fluorochemical monomer, and synthetic fluorin modified crylic acid resin is applied to helicopter skining paint.Though in helicopter skining paint, obtain to use, but, because the consumption of the fluorochemical monomer methacrylic acid hexafluoro butyl ester that is adopted accounts for 5～15% of whole synthon total amount, difficulty provides effectively " shielding protection " effect to the high-polymer molecular segment, and the weather resistance of resin, the anti-performance that stains all can not fully show; The unexpectedly poly-rate (Q-e value) of other acrylate monomers that used fluorochemical monomer and copolymerization are used differs bigger, is unfavorable for forming the resin that ideal has alternating structure; Ester alkoxyl group in the used isobornyl methacrylate monomer structure partly is huge nonpolar bicyclic alkyl; the space steric effect of the bicyclic alkyl that this is huge; when Raolical polymerizable to the influence of reactivity ratio; can cause the unbalanced of high-polymer molecular structure; so; the fluorin modified crylic acid resin of this application is easy to form fluorochemical monomer in the two ends enrichment of high-polymer molecular segment, middle local " dumbbell shaped " molecular structure that expose, no fluorochemical monomer " shielding protection " that is.Therefore, it is fluorochemical monomer that this application adopts (methyl) vinylformic acid hexafluoro butyl ester, institute's synthetic fluorin modified crylic acid resin is used for industrial paint spraying, and in paint film medium corrosion resistance energy, weather resistance, the anti-performance that stains, particularly film durability can be difficult to reach actual requirement in the aspect.
Summary of the invention
The objective of the invention is: a kind of superiority of effectiveness that keeps acrylic resin is provided, and price is low and cross-linking type fluorine-containing acrylic resin that over-all properties and fluorocarbon resin are suitable.
The technical scheme that realizes the object of the invention is: a kind of cross-linking type fluorine-containing acrylic resin, heated polymerizable obtains in the presence of initiator by more than one acrylic monomer, be characterized in, used each the monomeric quantity of polyreaction is as follows by mass parts: 5～10 parts of methyl methacrylates, 10～20 parts of alkyl acrylate monomers, 5～10 parts of functional Acrylic Acid Monomers, 10～25 parts of fluoro-acrylate monomers; 40～60 parts of organic solvents;
Described fluoro-acrylate monomer is one or both in trifluoroethyl methacrylate, the vinylformic acid trifluoro ethyl ester;
The consumption of described fluoro-acrylate monomer accounts for 20～50% of the used monomer total mass of polyreaction part.
In the above-mentioned thermoset cross-linked type fluoroacrylic resin, described functional Acrylic Acid Monomer is any one or a few in methacrylic acid, vinylformic acid, N hydroxymethyl acrylamide, Propylene glycol monoacrylate, Hydroxyethyl acrylate, Rocryl 410, the hydroxyethyl methylacrylate;
The consumption of described functional Acrylic Acid Monomer accounts for 10～20% of the used monomer total mass of polyreaction part.
In the above-mentioned cross-linking type fluorine-containing acrylic resin, described alkyl acrylate monomer is any one or a few in Jia Jibingxisuanyizhi, ethyl propenoate, butyl methacrylate, the butyl acrylate;
The consumption of described alkyl acrylate monomer accounts for 20～40% of the used monomer total mass of polyreaction part.
In the above-mentioned cross-linking type fluorine-containing acrylic resin, described organic solvent is any one or a few in toluene, dimethylbenzene, vinyl acetic monomer, N-BUTYL ACETATE, butanols, butyl glycol ether, pimelinketone, the butanone.
Technique effect of the present invention: the fluoro-acrylate monomer that the present invention uses copolymerization and other monomeric species and consumption have carried out appropriate selection, make between each monomer more coupling; Adopt with comparatively approaching (methyl) vinylformic acid trifluoro ethyl ester of Q value, the e value of other acrylate monomers of participating in reaction as fluorochemical monomer, help fluorochemical monomer and Acrylic Acid Monomer in Raolical polymerizable, form the polymkeric substance of alternating copolymerization molecular structure, fluorochemical monomer is evenly distributed on the molecular chain, and coating excellent comprehensive performance is provided; Cross-linking type fluorine-containing acrylic resin of the present invention; the consumption of its (methyl) vinylformic acid trifluoro ethyl ester accounts for 50% of the used monomer total mass of polyreaction part, and molfraction is greater than 20%; consumption is moderate, has guaranteed the shielding protection effect of fluorine-containing side chain to the high-polymer molecular main chain.With reference to HG/T3792-2005 " cross-linking type fluorine resin coating " national sector standard, specific embodiment of the invention product is carried out Performance Detection, satisfy standard-required, particularly the artificial weathering ageing resistance, paint film did not have efflorescence in 2500 hours, and variable color is less than 1 grade (seeing Table 4).Therefore, success of the present invention in the acrylic resin polymer architecture, introduce fluoro-containing group, make the acrylic resin paint performance boost, near fluorocarbon coating, the superiority of effectiveness that keeps acrylic resin has again improved simultaneously the weather resistance of paint film, the anti-over-all propertieies such as performance, resistant to chemical media corrosive nature, heat resistance that stain effectively.
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, but is not limited to this.
Used raw material among the embodiment unless otherwise indicated, is the commercially available product that meets the coating raw material standard.
(1) preparation cross-linking type fluorine-containing acrylic resin
The proportioning raw materials of each embodiment sees Table 1, and " part " among each embodiment and the table 1 is " mass parts "; During preparation, equipment used is the used conventional equipment of synthetic resins.
Embodiment 1
In conversion unit, add 15 parts of dimethylbenzene in advance, be warming up to 130 ℃, with 7.5 parts of methyl methacrylates, 7.5 parts of butyl methacrylate, 5.5 parts of ethyl propenoates, 0.5 part of methacrylic acid, 6.5 parts of Propylene glycol monoacrylates, 22.5 parts of trifluoroethyl methacrylates, 0.6～1.2 parts of initiator benzoyl peroxides, 20 parts of dimethylbenzene mix, Dropwise 5 h at the uniform velocity, be warmed up to 135 ℃ of insulation 3h after dropwising, cooling, be blended into 10 parts of butanone, 5 parts of pimelinketone, the after-filtration discharging that stirs makes the cross-linking type fluorine-containing acrylic resin that product is a solids content 50%.
Embodiment 2
In conversion unit, add 15 parts of dimethylbenzene in advance, be warming up to 130 ℃, with 10 parts of methyl methacrylates, 7.5 parts of Jia Jibingxisuanyizhis, 6 parts of butyl acrylates, 3 parts of N hydroxymethyl acrylamides, 6 parts of hydroxyethyl methylacrylates, 12.5 parts of trifluoroethyl methacrylates, 0.6～1.4 parts of initiator benzoyl peroxides, 20 parts of dimethylbenzene mix, Dropwise 5 h at the uniform velocity, be warmed up to 135 ℃ of insulation 3h after dropwising, cooling, be blended into 10 parts of N-BUTYL ACETATEs, 10 parts of pimelinketone, the after-filtration discharging that stirs makes the cross-linking type fluorine-containing acrylic resin that product is a solids content 45%.
Embodiment 3
In conversion unit, add 15 parts of toluene in advance, be warming up to 110 ℃, with methyl methacrylate 8,5 parts, 8.5 parts of butyl methacrylate, 6.5 parts of butyl acrylates, 0.5 part in vinylformic acid, 5.5 parts of Rocryl 410s, 10.5 parts of trifluoroethyl methacrylates, 10 parts of vinylformic acid trifluoro ethyl esters, 0.6～1.2 parts of initiator Diisopropyl azodicarboxylates, 20 parts of toluene mix, Dropwise 5 h at the uniform velocity, insulation 3h, cooling, be blended into 10 parts of N-BUTYL ACETATEs, 5 parts of 1-Methoxy-2-propyl acetates, the after-filtration discharging that stirs makes the cross-linking type fluorine-containing acrylic resin that product is a solids content 50%.
Embodiment 4
In conversion unit, add 20 parts of toluene in advance, be warming up to 110 ℃, 9.5 parts of methyl methacrylates, 8.5 parts of ethyl propenoates, 9 parts of butyl methacrylate, 0.5 part in vinylformic acid, 7 parts of hydroxyethyl methylacrylates, 20.5 parts, 0.6～1.2 part initiator Diisopropyl azodicarboxylate of vinylformic acid trifluoro ethyl ester, 15 parts of butanols are mixed, Dropwise 5 h at the uniform velocity, insulation 3h, cooling, be blended into 5 parts of butyl glycol ethers, 5 parts of N-BUTYL ACETATEs, the after-filtration discharging that stirs makes the cross-linking type fluorine-containing acrylic resin that product is a solids content 55%.
Table 1 embodiment 1～4 proportioning raw materials
| Component | Raw material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Methyl methacrylate | Methyl methacrylate | 7.5 part | 10 parts | 8.5 part | 9.5 part |
| Alkyl acrylate | 1. 2. 3. 4. ethyl propenoate of butyl acrylate of Jia Jibingxisuanyizhi of butyl methacrylate | 7.5--5.5 parts of parts | -7.5 parts 6 parts- | 8.5-6.5 parts- | 9 parts--8.5 parts |
| Functional Acrylic Acid Monomer | 1. 2. 3. 4. 5. 6. 7. hydroxyethyl methylacrylate of Rocryl 410 of vinylformic acid of Hydroxyethyl acrylate of N hydroxymethyl acrylamide of Propylene glycol monoacrylate of methacrylic acid | 0.5 parts 6.5 parts----- | --3 parts 6 parts--- | ----0.5 parts 5.5 parts- | ----0.5 parts-7 parts |
| Fluoro-acrylate monomer | 1. 2. vinylformic acid trifluoro ethyl ester of trifluoroethyl methacrylate | 22.5 part- | -12.5 parts | 10.5 10 parts of parts | -20.5 parts |
| Initiator | 1. 2. Diisopropyl azodicarboxylate of benzoyl peroxide | 0.6～1.2 parts- | 0.6～1.2 parts- | -0.6～1.2 parts | -0.6～1.4 parts |
| Solvent | 1. 2. 3. 4. 5. 6. 7. 8. 1-Methoxy-2-propyl acetate of butyl glycol ether of N-BUTYL ACETATE of butanols of toluene of pimelinketone of butanone of dimethylbenzene | 35 parts 10 parts 5 parts----- | 35 parts-10 parts--10 parts-- | 35 parts-10 parts-5 parts of--- | 20 parts 15 parts 5 parts 5 parts of---- |
| Resin solid part % | - | 50 | 45 | 50 | 55 |
In the fluoroacrylic resin of embodiment 1～4, the fluoro-acrylate monomer consumption, proportion sees Table 2 in the used monomer total amount of polyreaction.
Table 2
| Cross-linking type fluorine-containing acrylic resin | Mass percent, % | Molecular fraction, % |
| Embodiment 1 resin | 45 | 35.9 |
| Embodiment 2 resins | 27.8 | 21.9 |
| Embodiment 3 resins | 41 | 34.6 |
| Embodiment 4 resins | 37.3 | 30.4 |
(2) preparation coating
The product unification of embodiment 1～4 is mixed with white paint;
Used white pigment is the R-960 of an E.I.Du Pont Company Rutile type Titanium Dioxide, and resin-pigment ratio is 35/65; The resin curing agent of specific embodiment 1,3 adopts the N-3390 of Beyer Co., Ltd product ,-OH/-NCO=1/1; Specific embodiment 2,4 solidifying agent adopt the special R-717 of the company aminoresin of cyanogen, and proportioning is embodiment resin/R-717=8/2 (Gu Gu/, mass ratio), and R-717 aminoresin solid part is in 84%; Mixed solvent is dimethylbenzene/N-BUTYL ACETATE=1/1.
The white paint prescription sees Table 3, and wherein each raw material consumption is all in mass parts.
Table 3 white paint prescription
| Raw material | Coating 1 | Coating 2 | Coating 3 | Coating 4 |
| Embodiment 1 resin | 109 | / | / | / |
| Embodiment 2 resins | / | 115.6 | / | / |
| Embodiment 3 resins | / | / | 113.3 | / |
| Embodiment 4 resins | / | / | / | 94.5 |
| Titanium dioxide R-960 | 35 | 35 | 35 | 35 |
| Solidifying agent | 11.7 | 15.5 | 9.3 | 15.5 |
| Mixed solvent | 44.3 | 33.9 | 42.4 | 55 |
| Add up to | 200 | 200 | 200 | 200 |
| Solids coatings | 50％ | 50％ | 50％ | 50％ |
(3) coating property detects
With reference to HG/T3792-2005 " cross-linking type fluorine resin coating " national sector standard, the specific embodiment product is carried out Performance Detection, the results are shown in Table 4.
Table 4 performance test results
| Project | Index | Coating 1 | Coating 2 | Coating 3 | Coating 4 |
| Condition in container | Stir evenly no lump of back | Qualified | Qualified | Qualified | Qualified |
| Appearance of film | Normally | Smooth smooth | Smooth smooth | Smooth smooth | Smooth smooth |
| Recoatability | Recoat is accessible | Qualified | Qualified | Qualified | Qualified |
| Shock-resistance/cm | 50 | ≥50 | ≥50 | ≥50 | ≥50 |
| Sticking power/level≤ | 1 | 0 | 0 | 0 | 0 |
| Resistance to bend(ing)/mm≤ | 2 | 1 | 1 | 1 | 1 |
| Acid resistance (168h) | No abnormal | Qualified | Qualified | Qualified | Qualified |
| Alkali resistance (168h) | No abnormal | Qualified | Qualified | Qualified | Qualified |
| Oil-proofness (168h) | No abnormal | Qualified | Qualified | Qualified | Qualified |
| Water tolerance (168h) | No abnormal | Qualified | Qualified | Qualified | Qualified |
| Moisture-proof cold cycling (10 times) | No abnormal | Qualified | Qualified | Qualified | Qualified |
| Stain resistance | By | By | By | By | By |
| Anti-staining property (white) a/％≤ | 10 | Qualified | Qualified | Qualified | Qualified |
| The wiping of anti-the butanone/time 〉= | 100 | 150 | ≥200 | 150 | 160 |
| Humidity resistance | 1000h is non-foaming, non-corrosive, do not come off | Qualified | Qualified | Qualified | Qualified |
| Salt fog resistance | 1000h is non-foaming, non-corrosive, do not come off | Qualified | Qualified | Qualified | Qualified |
| Artificial weathering ageing resistance's efflorescence/level≤variable color/level≤loss of gloss/level≤ | 2500h is non-foaming, non-corrosive, do not ftracture, do not come off 122 | 0～1 0 1 | / | / | 0～1 0 1 |
By table 4 data as seen, cross-linking type fluorine-containing acrylic resin of the present invention institute coatings formulated, anti-artificial weathering after 2500 hours paint film do not have efflorescence, variable color is less than 1 grade, its over-all properties keeps the acrylic resin superior price-performance preferably near fluorocarbon resin.Application Areas can relate to the marine building of maintenance, weather and the environment harshness of chemical industry, anticorrosion, deep layer building slab, aircraft skin and the geographic architectural finish of seagoing vessel, industrial city and acid rain and the maintenance etc. of carrier.
Claims (3)
1, a kind of cross-linking type fluorine-containing acrylic resin, heated polymerizable obtains in the presence of initiator by more than one acrylic monomer, it is characterized in that, used each the monomeric quantity of polyreaction is as follows by mass parts: 5～10 parts of methyl methacrylates, 10～20 parts of alkyl acrylate monomers, 5～10 parts of functional Acrylic Acid Monomers, 10～25 parts of fluoro-acrylate monomers; 40～60 parts of organic solvents;
Described fluoro-acrylate monomer is one or both in trifluoroethyl methacrylate, the vinylformic acid trifluoro ethyl ester;
The consumption of described fluoro-acrylate monomer accounts for 20～50% of the used monomer total mass of polyreaction part;
Described functional Acrylic Acid Monomer is any one or a few in methacrylic acid, vinylformic acid, N hydroxymethyl acrylamide, Propylene glycol monoacrylate, Hydroxyethyl acrylate, Rocryl 410, the hydroxyethyl methylacrylate;
The consumption of described functional Acrylic Acid Monomer accounts for the used monomer total mass of polyreaction part 10～20%.
2, cross-linking type fluorine-containing acrylic resin according to claim 1 is characterized in that, described alkyl acrylate monomer is any one or a few in Jia Jibingxisuanyizhi, ethyl propenoate, butyl methacrylate, the butyl acrylate;
The consumption of described alkyl acrylate monomer accounts for the used monomer total mass 20～40% of polyreaction.
3, cross-linking type fluorine-containing acrylic resin according to claim 1 is characterized in that, described organic solvent is any one or a few in toluene, dimethylbenzene, vinyl acetic monomer, N-BUTYL ACETATE, butanols, butyl glycol ether, pimelinketone, the butanone.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100237591A CN100519603C (en) | 2007-07-07 | 2007-07-07 | Cross-linking type fluorine-containing acrylic resin |
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| CNB2007100237591A CN100519603C (en) | 2007-07-07 | 2007-07-07 | Cross-linking type fluorine-containing acrylic resin |
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| CN101619116B (en) * | 2009-07-27 | 2011-09-07 | 中国海洋石油总公司 | Thermoplastic fluorine-containing acrylic resin and preparation method thereof |
| CN102153902B (en) * | 2011-03-11 | 2013-05-29 | 安徽嘉智信诺化工有限公司 | Fluorocarbon anti-shrinkage flatting agent for coating ink |
| CN102585108A (en) * | 2012-01-17 | 2012-07-18 | 杭州日耀科技有限公司 | Polyester-modified organic fluorine-silicon acrylic resin and preparation method thereof as well as paint using resin |
| CN104231821B (en) * | 2013-06-24 | 2016-10-05 | 郎溪县鑫泽涂料有限公司 | Super-weathering resistance acrylic anodic electrophoretic coating |
| CN104072662B (en) * | 2014-07-07 | 2016-09-14 | 黄山金质丽科技有限公司 | The artificial color sand preparation preparation method of color sand acrylic resin modified, artificial |
| CN105254904A (en) * | 2015-09-30 | 2016-01-20 | 中国海洋石油总公司 | Fluorinated hydroxy acrylic resin aqueous dispersion and preparation method thereof |
| CN105255324A (en) * | 2015-11-25 | 2016-01-20 | 蓬莱蔚阳新材料有限公司 | Hydrophobic and oleophobic coating with super-long durable corrosion resistance and low surface energy and preparation process of hydrophobic and oleophobic coating |
| CN107629165B (en) * | 2017-10-16 | 2020-07-07 | 六安捷通达新材料有限公司 | Hydroxyl type solid acrylic extinction resin and preparation method thereof |
| CN107793513B (en) * | 2017-10-25 | 2020-03-27 | 杭州海维特化工科技有限公司 | Wood-grain paper coating latex capable of being used for digital inkjet printing and preparation method thereof |
| CN113372483A (en) * | 2021-05-18 | 2021-09-10 | 清远慧谷新材料技术有限公司 | Water-based fluorine-containing acrylic resin, preparation method thereof and application thereof in coating |
| CN113789654A (en) * | 2021-09-16 | 2021-12-14 | 深圳市联星服装辅料有限公司 | Pretreatment liquid based on polyester fabric ink jet, polyester fabric and treatment method thereof |
| CN115386036B (en) * | 2021-09-30 | 2023-06-30 | 浙江金质丽新材料有限公司 | Fluorine-containing acrylic resin for woodware seal primer and preparation method thereof |
| CN113861334B (en) * | 2021-10-11 | 2023-04-07 | 广西民族大学 | Acrylic acid hydrogenated rosin alcohol ester modified fluorocarbon resin and preparation method thereof |
| CN114231111B (en) * | 2021-12-08 | 2024-05-17 | 东来涂料技术（上海）股份有限公司 | Reworkable primer and preparation method thereof |
| CN114213578B (en) * | 2021-12-28 | 2023-03-14 | 天津市新丽华色材有限责任公司 | Defoaming agent suitable for curtain coating of mirror back coating, preparation method of defoaming agent and mirror back coating |
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Owner name: CNOOC CHANGZHOU PAINT + COATINGS INDUSTRY RESEARCH Free format text: FORMER OWNER: CHANGZHOU INST OF PAINT CHEMICAL, CHINESE CHEMICAL BUILDING CORP. Effective date: 20120910 |
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Effective date of registration: 20120910 Address after: 213016 Changzhou Zhong Road, Jiangsu Province, No. 22 Longjiang Road Patentee after: CNOOC Changzhou Paint & Coatings Industry Research Institute Address before: 213016, Jiangsu City, Changzhou province Bell Tower West Ring Road North intersection Patentee before: Changzhou Inst of Paint Chemical, Chinese Chemical Building Corp. |