CN109181473A - 一种高性能双组分水性防腐涂料及其制备方法 - Google Patents
一种高性能双组分水性防腐涂料及其制备方法 Download PDFInfo
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- CN109181473A CN109181473A CN201810899903.6A CN201810899903A CN109181473A CN 109181473 A CN109181473 A CN 109181473A CN 201810899903 A CN201810899903 A CN 201810899903A CN 109181473 A CN109181473 A CN 109181473A
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- 239000003973 paint Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000003822 epoxy resin Substances 0.000 claims abstract description 42
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 42
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 30
- 239000004593 Epoxy Substances 0.000 claims abstract description 29
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 29
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 29
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000839 emulsion Substances 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZTFZSHLWORMEHO-UHFFFAOYSA-A pentaaluminum;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ZTFZSHLWORMEHO-UHFFFAOYSA-A 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 238000007665 sagging Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 14
- 239000003085 diluting agent Substances 0.000 claims description 14
- 238000003801 milling Methods 0.000 claims description 14
- 230000036961 partial effect Effects 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 9
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 9
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000003595 mist Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 5
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 229910052586 apatite Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- -1 cerium hydroxyl phosphorus Chemical compound 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 3
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- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
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- 238000003756 stirring Methods 0.000 claims description 2
- 235000019738 Limestone Nutrition 0.000 claims 1
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- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229920013802 TRITON CF-10 Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
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- 239000010703 silicon Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- CWNOEVURTVLUNV-UHFFFAOYSA-N 2-(propoxymethyl)oxirane Chemical compound CCCOCC1CO1 CWNOEVURTVLUNV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 230000003260 anti-sepsis Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
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- 239000010953 base metal Substances 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 239000005871 repellent Substances 0.000 description 1
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/60—Additives non-macromolecular
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
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- Nanotechnology (AREA)
- Paints Or Removers (AREA)
Abstract
本发明公开了一种高性能双组分水性防腐涂料及其制备方法。该涂料包括甲组分和乙组分,所述的甲组分按质量百分比计,包括:水性环氧树脂乳液45~60%、载铈羟基磷灰石5~10%、球状锌粉15~25%、三聚磷酸铝3~10%、助剂1~4%和水10~15%;所述的乙组分为水性胺类环氧固化剂。本发明提供的双组分水性防腐涂料配比科学,各组分协同发挥较佳的耐水防腐功能。该涂料不仅干燥速度快,施工性能佳,且形成的涂膜平整光滑、无流挂、针孔、开裂、流挂现象,附着力高,不易脱落,膜层致密,具有较佳的机械性能和耐候性,是比较理想的新型水性防腐涂料产品,并且符合环保要求。
Description
技术领域
本发明属于防腐涂料技术领域,具体涉及一种高性能双组分水性防腐涂料及其制备方法。
背景技术
每年,金属腐蚀所导致的经济损失高达8000亿元左右,占到我国GDP的近3%,同样地,在美国、日本等发达国家也面临金属腐蚀相关的问题:美、日等发达国家每年由于腐蚀造成的经济损失约占其GDP的1~4%。金属的腐蚀与防护技术及产品的研发与应用受到了各方的高度重视。在众多的金属防腐措施中,涂料保护是迄今为止最普遍、最经济、最实用的保护措施。传统的防腐蚀涂料多为溶剂型,含有70~80%的有机溶剂,对环境造成污染,并且多含有铅、铬、镉等颜料,如红丹、铅粉、及铈、铅、钡的铬酸盐等,对人体健康造成危害。
水性涂料具有VOC含量较低、无异味、不燃烧且毒性低等优点,已有逐步取代有机溶剂型涂料的趋势。然而由于水的表面张力及蒸发潜热均较大,导致水性防腐涂料的生产、施工、固化及性能等各方面的应用缺陷,尤其是耐水耐腐蚀性不足严重限制水性防腐涂料的应用。
常用的水性防腐蚀涂料主要包括:水性环氧涂料、水性无机富铈涂料、水性丙烯酸涂料和水性聚氨酯涂料四大类。其中水性环氧涂料具有良好的附着力、高涂膜硬度、良好的耐磨性,是工业防腐涂料领域应用最广泛、最重要的涂料品种之一,已逐步替代溶剂型环氧防腐涂料应用于汽车零配件、铁路机车、集装箱、储罐等领域。国内外已商品化的水性环氧防腐涂料品种较多,主要有水性环氧铁红防锈漆、水性环氧富锌漆、水性环氧磷酸锌防锈漆及水性环氧云母防锈漆等,这些产品存在的不足之处主要为:一、水性环氧乳液的稳定性不好,二、水性环氧防腐涂料的性能有待改善,主要为耐水性和耐盐雾性能。目前针对水性环氧涂料改进主要集中于提高环氧树脂乳液的稳定性以及新型固化剂开发。如公开号为CN102020908 A的中国专利申请公开了一种具有优异耐水性和耐盐雾性水性环氧防腐涂料的制备,该发明通过在水性环氧乳化剂分子结构当中引入双酚A链段、羧基、环氧基,使得乳化剂具有较好的乳化能力,用该乳化剂制得的水性环氧乳液粒径较小,稳定性提高;同时乳化剂本身可参与固化反应,消除了乳化剂组分对水性环氧防腐涂料耐水性的影响。公开号为CN 104231866 A的中国专利申请公开了一种水性环氧防腐涂料及其制备方法,该涂料以水性环氧树脂作为成膜物质,以含氨基硅烷改性的纳米二氧化硅和水性环氧固化剂共同作为环氧涂料的固化剂,制备出具有优良的机械性能及防腐性能的水性环氧涂料。
虽然现有技术对水性环氧涂料的改进已获取了不少进步,但仍有必要提供一种新的水性环氧涂料配方,在原来涂料各特点的基础上,扬长避短,进一步提高其各项性能指标,具体为提供给一种不仅具有良好的附着力、耐磨性,还具有优异的耐水性、耐盐雾性、耐化学品性,并且易于施工,稳定性佳的水性防腐涂料,更好地满足市场需求。
发明内容
本发明的目的是提供一种高性能双组分水性防腐涂料及其制备方法,该涂料不仅具有良好的附着力、耐磨性,还具有优异的耐水性、耐盐雾性、耐化学品性,机械性能和防腐蚀性能佳。
本发明是通过以下技术方案予以实现的:
一种高性能双组分水性防腐涂料,包括甲组分和乙组分;所述的甲组分按质量百分比计,包括:水性环氧树脂乳液45~60%、载铈羟基磷灰石5~10%、球状锌粉15~25%、三聚磷酸铝3~10%、助剂1~4%和水10~15%;所述的乙组分为水性胺类环氧固化剂。
所述的载铈羟基磷灰石中铈与羟基磷灰石的摩尔比为1:(2~4);所述的载铈羟基磷灰石的粒径为1~5μm。
所述球形锌粉的粒径<10μm。
此外,本发明还提供一种所述的载铈羟基磷灰石的制备方法,该方法包括以下步骤:
(1)将硝酸铈溶于水,得到硝酸铈水溶液;
(2)将羟基磷灰石粉体加入到步骤(1)的硝酸铈水溶液中,避光浸渍处理6~12h,在真空度低于10-1Pa,温度为20~60℃下烘干,然后置于管式炉内氩气气氛烧结,烧结条件为:采用2℃/min的升温速率从室温加热到150℃,保温3h后,以5℃/min的升温速率加热到650~750℃,保温2h后随炉冷到室温,其中氩气的流速为0.3~0.6L/min,得到粉体;
(3)将步骤(2)得到的粉体加入气流磨制粉机中,在高纯度的惰性气体保护下进行气流磨,已被充分磨碎的微粉随气流通过分选轮的缝隙,而未被充分磨碎的则不能通过,继续进行气流磨,直到粉体的粒径为1~5μm,将其搅拌混匀,得到载铈羟基磷灰石。
上述制备方法中硝酸铈与羟基磷灰石的摩尔比为1:(2~4)。
所述的水性环氧树脂乳液按质量百分比计,包括以下组分:环氧树脂E-51 35~45%、环保稀释剂10~15%、吐温-20 3~5%和去离子水40~50%。其中,环保稀释剂为烯丙基缩水甘油醚与端环氧基硅油以1:0.2~0.3的质量比组成。
水性环氧树脂乳液的制备包括以下步骤:将环氧树脂E-51和环保稀释剂混合,加热至65~70℃,在2000~3000r/min转速下,加入去离子水和吐温-20,分散25~30min,即得水性环氧树脂乳液。
本发明涂料配方中的助剂为分散剂、消泡剂、流平剂、防流挂剂和润湿剂中的至少一种。具体地,所述的分散剂为德国毕克BYK-187、德国毕克BYK-184、德国迪高TEGO 760W或美国陶氏Triton CF-10;所述的消泡剂为聚醚改性有机硅或BYK-045;所述的流平剂为美国气体公司surfynol 420、德国汉高Perenal-3或德国毕克BYK-320;所述的防流挂剂为有机膨润土或气相二氧化硅;所述的润湿剂为雅创X405、美国气体化学surfynol 104或德国迪高TEGO 500。
本发明涂料配方中的水性胺类环氧固化剂为瀚森迈图的Epikure 8538-Y-68、Epikure 8537-WY-60、Epikure 8535-W-50或Epikure 8535-W-53。
此外,本发明还提供一种所述的高性能双组分水性防腐涂料的制备方法,该方法包括以下步骤:
(1)将水、助剂混合搅拌均匀,依次加入载铈羟基磷灰石、球状锌粉、三聚磷酸铝,在1000~2000r/min下分散10~15min;然后降速至100~200r/min,加入水性环氧树脂乳液搅拌均匀1~2h,即得到甲组分;
(2)在使用时按甲组分:乙组分的质量比为1:0.1~0.2,将甲组分与乙组分混合,即得。
上述涂料配方中的球状锌粉粒径较细,颗粒间结合紧密,锌的金属活性较为活泼,在潮湿的大气中发生化学腐蚀,形成白锈,即碱性碳酸盐(2ZnCO3.Zn(OH)2)膜,有一定的保护作用,可以减慢腐蚀速度。三聚磷酸铝中的P3O10 5-具有较佳的化学活性,可与许多金属离子形成络合物,特别对2价或3价铁离子具有很强的络合能力,这样就会在钢铁表面形成三聚磷酸铁保护膜,而且三聚磷酸根离子P3O10 5-会发生解聚反应生成从焦磷酸根离子到正磷酸根离子之类产物,这些离子进一步在金属表面形成坚韧的钝化膜,可使基体金属表面非活性化,阻止基体金属进一步被腐蚀。
所述的载铈羟基磷灰石粒径较细,为1~5μm,均匀分散或包裹在成膜树脂中,固化成膜后在其三维网络交联结构中均匀存在,封闭交联固化时水性涂层中产生的缺陷孔,及含水环境中水性涂层中形成的极性输水通道,一方面增加了涂层的耐水性,另一方面其结构中的羟基可与氯化物、碳酸根等腐蚀性物质发生离子交换,在一定程度上阻碍侵蚀性离子向基体金属渗透。同时,由于载铈羟基磷石中含有铈,减少了羟基磷灰石中钙离子与涂料中的防锈活性金属离子如锌、铝等离子发生交换结合位点,可避免由于防锈活性金属离子游离状态减少所致的防腐蚀效果减弱。且由于铈本身亦具有较活泼的金属性,即使发生离子交换,也可发挥形成钝化膜的防腐效果。
本发明以自制的水性环氧树脂乳液作为成膜材料,与普通市售的水性环氧树脂乳液比较,具有固化速度快,固化交联充分的优点。现有的水性环氧树脂乳液固化速度慢,且含有较大量的醚类环保稀释剂,使环氧树脂乳液的粒径偏大,固化交联不完全。另外,随着固化反应的逐步进行,固化产物的分子量不断增大,导致环氧粒子表层的粘度不断增加,水性环氧产物的玻璃化温度逐步上升,固化剂向环氧树脂内的扩散将变得越来越困难,越不利于固化。本发明人通过大量的试验发现,在环保活性稀释剂中加入一定量的端环氧基硅油,可降低反应过程中的玻璃化温度,并调节环氧粒子表层的粘度,促使固化剂易于向环氧树脂内的扩散,加快固化速度,使水性环氧树脂固化交联达到满意的效果。与此同时,所述的端环氧基硅油分子结构中还带有环氧官能团,可参与固化反应,加快涂料的固化进程。
本发明在水性防腐涂料的制备中加入上述的水性环氧树脂乳液,利用环氧树脂快速固化性能,和优良的粘结性,以及与载锌羟基磷灰石、球状锌粉、三聚磷酸铝等无机材料良好的相容性,缩短了涂层的表干和实干时间,获得较佳的施工性,并形成高交联网状三维结构,形成较为致密的防护层,从而发挥较佳的防腐蚀效果。
与现有技术相比,本发明具有以下有益效果:
本发明提供的双组分水性防腐涂料配比科学,各组分协同发挥较佳的耐水防腐功能。该涂料不仅干燥速度快,施工性能佳,且形成的涂膜平整光滑、无流挂、针孔、开裂、流挂现象,附着力高,不易脱落,膜层致密,具有较佳的机械性能和耐候性,是比较理想的新型水性防腐涂料产品,并且符合环保要求。
具体实施方式
以下实施例是对本发明的进一步说明,而不是对本发明的限制。
实施例1载铈羟基磷灰石的制备
(1)称取434.12g Ce(NO3)3.6H2O溶于水,制成5%m/v的硝酸铈水溶液;
(2)称取3012g羟基磷灰石粉体加入到步骤(1)的硝酸铈水溶液中进行浸渍处理12h,在真空度低于10-1Pa,温度为40℃下烘干,然后置于管式炉内氩气气氛烧结,烧结条件为:采用2℃/min的升温速率从室温加热到150℃,保温3h后,以5℃/min的升温速率加热到750℃,保温2h后随炉冷到室温,其中氩气的流速为0.3L/min,得到粉体;
(3)将步骤(2)得到的粉体加入气流磨制粉机中,在高纯度的惰性气体保护下进行气流磨,已被充分磨碎的微粉随气流通过分选轮的缝隙,而未被充分磨碎的则不能通过,继续进行气流磨,直到粉体的粒径为1~5μm,将其搅拌混匀,得到负载铈羟基磷灰石。
实施例2载铈羟基磷灰石的制备
(1)称取434.12g Ce(NO3)3.6H2O溶于水,制成5%m/v的硝酸铈水溶液;
(2)称取2008g羟基磷灰石粉体加入到步骤(1)的硝酸铈水溶液中进行浸渍处理6h,在真空度低于10-1Pa,温度为50℃下烘干,然后置于管式炉内氩气气氛烧结,烧结条件为:采用2℃/min的升温速率从室温加热到150℃,保温3h后,以5℃/min的升温速率加热到650℃,保温2h后随炉冷到室温,其中氩气的流速为0.5L/min,得到粉体;
(3)将步骤(2)得到的粉体加入气流磨制粉机中,在高纯度的惰性气体保护下进行气流磨,已被充分磨碎的微粉随气流通过分选轮的缝隙,而未被充分磨碎的则不能通过,继续进行气流磨,直到粉体的粒径为1~5μm,将其搅拌混匀,得到载铈羟基磷灰石。
实施例3载铈羟基磷灰石的制备
(1)称取434.12g Ce(NO3)3.6H2O溶于水,制成5%m/v的硝酸铈水溶液;
(2)称取4016g羟基磷灰石粉体加入到步骤(1)的硝酸铈水溶液中进行浸渍处理10h,在真空度低于10-1Pa,温度为50℃下烘干,然后置于管式炉内氩气气氛烧结,烧结条件为:采用2℃/min的升温速率从室温加热到150℃,保温3h后,以5℃/min的升温速率加热到700℃,保温2h后随炉冷到室温,其中氩气的流速为0.6L/min,得到粉体;
(3)将步骤(2)得到的粉体加入气流磨制粉机中,在高纯度的惰性气体保护下进行气流磨,已被充分磨碎的微粉随气流通过分选轮的缝隙,而未被充分磨碎的则不能通过,继续进行气流磨,直到粉体的粒径为1~5μm,将其搅拌混匀,得到载铈羟基磷灰石。
实施例4水性环氧树脂乳液的制备
水性环氧树脂乳液按质量百分比计,包括以下组分:环氧树脂E-51 40%、环保稀释剂10%、吐温-20 4%和去离子水46%,其中环保稀释剂为烯丙基缩水甘油醚与端环氧基硅油以1:0.25的质量比组成。
制备:将环氧树脂E-51和环保稀释剂混合,加热至65℃,在2000r/min转速下,加入去离子水和吐温-20,分散30min,即得水性环氧树脂乳液。
实施例5水性环氧树脂乳液的制备
水性环氧树脂乳液按质量百分比计,包括以下组分:环氧树脂E-51 45%、环保稀释剂10%、吐温-20 5%和去离子水40%,其中环保稀释剂为烯丙基缩水甘油醚与端环氧基硅油以1:0.3的质量比组成。
制备:将环氧树脂E-51和环保稀释剂混合,加热至70℃,在3000r/min转速下,加入去离子水和吐温-20,分散25min,即得水性环氧树脂乳液。
实施例6水性环氧树脂乳液的制备
水性环氧树脂乳液按质量百分比计,包括以下组分:环氧树脂E-51 35%、环保稀释剂15%、吐温-20 3%和去离子水47%,其中环保稀释剂为烯丙基缩水甘油醚与端环氧基硅油以1:0.2的质量比组成。
制备:将环氧树脂E-51和环保稀释剂混合,加热至70℃,在3000r/min转速下,加入去离子水和吐温-20,分散30min,即得水性环氧树脂乳液。
实施例7水性防腐涂料的制备
水性防腐涂料按质量百分比计,包括下表1所示的组分:
表1不同配方的水性防腐涂料
制备:
(1)将水、Triton CF-10、BYK-045、Perenal-3、雅创X405混合搅拌均匀,依次加入载铈羟基磷灰石、球状锌粉、三聚磷酸铝,在2000r/min下分散10min;然后降速至200r/min,加入水性环氧树脂乳液搅拌均匀2h,即得到甲组分;
(2)在使用时按甲组分:乙组分的质量比为1:0.15,将甲组分与乙组分混合,即得。
采用上述各配方制得的水性防腐涂料,使用常规空气喷涂制备样板,底材为冷轧钢板,脱脂清洗烘干后即喷涂防腐涂料,试验样板干膜总厚度平均90±10μm,按照表2所示的标准进行性能检测,结果见表3所示:
表2各项检测指标依据
表3水性防腐涂料质量指标
结果显示,本发明提供的水性防腐涂料在干燥性能、附着力、耐冲击性、柔韧性、耐水性、耐盐雾性、耐酸碱性以及耐湿热性等方面的性能表现是非常优异的,具有优异的施工性能和漆膜性能,防腐蚀效果佳。
实施例8水性防腐涂料的制备
实施例8是保证实施例7配方1中各物质种类不变的情况下,改变各物质含量的投料配方,见下表4所示,按照实施例7的工艺过程制备得到水性防腐涂料。
表4不同配方的水性防腐涂料
由配方6~8制备的得到水性防腐涂料的性能如表5所示,与表3性能对比可知,当涂料配方中各物质的含量超出本发明所公开的范围时,得到的水性防腐涂料的性能显著降低,主要表现为涂层的附着力降低,耐冲击性变差,各方面的耐候性减弱,涂层出现裂纹、开裂现象,防腐蚀效果变差。
表5水性防腐涂料质量指标
对比例1-3水性防腐涂料的制备
对比例1与实施例7的配方1相比,区别仅在于:不含载铈羟基磷灰石,并相应增加水性环氧树脂乳液的含量,按照实施例7的制备方法制得水性防腐涂料。
对比例2与实施例7的配方1相比,区别仅在于:以羟基磷灰石替换载铈羟基磷灰石,按照实施例7的制备方法制得水性防腐涂料。
对比例3与实施例7的配方1相比,区别仅在于:以某市售普通水性环氧乳液(CAS:38891-59-7)替换本发明自制的水性环氧树脂乳液,按照实施例7的制备方法制得水性防腐涂料。
对比例1-3水性防腐涂料的质量指标见表6所示。
表6水性防腐涂料质量指标
结果显示,涂料配方中不含载铈羟基磷灰石,制得的水性防腐涂料耐盐雾性、耐水性、耐湿热性、耐酸碱性变差;配方中含羟基磷灰石而不含载铈羟基磷灰石,制得的水性防腐涂料耐盐雾性、耐酸碱性变差;配方中以某市售普通水性环氧乳液替换本发明自制的水性环氧树脂乳液,制得的水性防腐涂料干燥性能减弱、附着力减弱。
以上仅是本发明的优选实施方式,应当指出的是,上述优选实施方式不应视为对本发明的限制,本发明的保护范围应当以权利要求所限定的范围为准。对于本技术领域的普通技术人员来说,在不脱离本发明的精神和范围内,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种高性能双组分水性防腐涂料,其特征在于,包括甲组分和乙组分;所述的甲组分按质量百分比计,包括:水性环氧树脂乳液45~60%、载铈羟基磷灰石5~10%、球状锌粉15~25%、三聚磷酸铝3~10%、助剂1~4%和水10~15%;所述的乙组分为水性胺类环氧固化剂。
2.根据权利要求1所述的高性能双组分水性防腐涂料,其特征在于,所述的载铈羟基磷灰石中铈与羟基磷灰石的摩尔比为1:(2~4);所述的载铈羟基磷灰石的粒径为1~5μm。
3.根据权利要求1或2所述的高性能双组分水性防腐涂料,其特征在于,所述的载铈羟基磷灰石的制备包括以下步骤:
(1)将硝酸铈溶于水,得到硝酸铈水溶液;
(2)将羟基磷灰石粉体加入到步骤(1)的硝酸铈水溶液中,避光浸渍处理6~12h,在真空度低于10-1Pa,温度为20~60℃下烘干,然后置于管式炉内氩气气氛烧结,烧结条件为:采用2℃/min的升温速率从室温加热到150℃,保温3h后,以5℃/min的升温速率加热到650~750℃,保温2h后随炉冷到室温,其中氩气的流速为0.3~0.6L/min,得到粉体;
(3)将步骤(2)得到的粉体加入气流磨制粉机中,在高纯度的惰性气体保护下进行气流磨,已被充分磨碎的微粉随气流通过分选轮的缝隙,而未被充分磨碎的则不能通过,继续进行气流磨,直到粉体的粒径为1~5μm,将其搅拌混匀,得到载铈羟基磷灰石。
4.根据权利要求3所述的高性能双组分水性防腐涂料,其特征在于,所述的硝酸铈与羟基磷灰石的摩尔比为1:(2~4)。
5.根据权利要求1所述的高性能双组分水性防腐涂料,其特征在于,所述的水性环氧树脂乳液按质量百分比计,包括以下组分:环氧树脂E-51 35~45%、环保稀释剂10~15%、吐温-20 3~5%和去离子水40~50%。
6.根据权利要求5所述的高性能双组分水性防腐涂料,其特征在于,所述的环保稀释剂为烯丙基缩水甘油醚与端环氧基硅油以1:0.2~0.3的质量比组成。
7.根据权利要求5或6所述的高性能双组分水性防腐涂料,其特征在于,所述的水性环氧树脂乳液的制备包括以下步骤:将环氧树脂E-51和环保稀释剂混合,加热至65~70℃,在2000~3000r/min转速下,加入去离子水和吐温-20,分散25~30min,即得水性环氧树脂乳液。
8.根据权利要求1所述的高性能双组分水性防腐涂料,其特征在于,所述的助剂为分散剂、消泡剂、流平剂、防流挂剂和润湿剂中的至少一种。
9.根据权利要求1所述的高性能双组分水性防腐涂料,其特征在于,所述的水性胺类环氧固化剂为瀚森迈图的Epikure 8538-Y-68、Epikure 8537-WY-60、Epikure 8535-W-50或Epikure 8535-W-53。
10.权利要求1-9任一所述的高性能双组分水性防腐涂料的制备方法,其特征在于,包括以下步骤:
(1)将水、助剂混合搅拌均匀,依次加入载铈羟基磷灰石、球状锌粉、三聚磷酸铝,在1000~2000r/min下分散10~15min;然后降速至100~200r/min,加入水性环氧树脂乳液搅拌均匀1~2h,即得到甲组分;
(2)在使用时按甲组分:乙组分的质量比为1:0.1~0.2,将甲组分与乙组分混合,即得。
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