CN108752514A - 一种环氧改性丙烯酸乳液及其制备方法 - Google Patents
一种环氧改性丙烯酸乳液及其制备方法 Download PDFInfo
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- CN108752514A CN108752514A CN201810423237.9A CN201810423237A CN108752514A CN 108752514 A CN108752514 A CN 108752514A CN 201810423237 A CN201810423237 A CN 201810423237A CN 108752514 A CN108752514 A CN 108752514A
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- Prior art keywords
- acrylic acid
- epoxy
- acrylate
- modified acrylic
- parts
- Prior art date
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000006210 lotion Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000839 emulsion Substances 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 239000003822 epoxy resin Chemical group 0.000 claims abstract description 21
- 229920000647 polyepoxide Chemical group 0.000 claims abstract description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003995 emulsifying agent Chemical group 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 125000003368 amide group Chemical group 0.000 claims abstract description 6
- 239000000872 buffer Substances 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical group CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 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 claims description 21
- 238000010792 warming Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- 229930185605 Bisphenol Natural products 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical class CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 claims 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 23
- 239000011248 coating agent Substances 0.000 abstract description 22
- 239000000178 monomer Substances 0.000 abstract description 17
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 7
- 239000003292 glue Substances 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 239000003973 paint Substances 0.000 abstract description 5
- 239000006115 industrial coating Substances 0.000 abstract description 3
- 239000002023 wood Substances 0.000 abstract description 2
- -1 neopelex Chemical compound 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000002994 raw material Substances 0.000 description 11
- 229940051841 polyoxyethylene ether Drugs 0.000 description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 description 10
- 229940106691 bisphenol a Drugs 0.000 description 7
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
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- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
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- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical class CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
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- 238000004383 yellowing Methods 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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Abstract
本发明公开了一种环氧改性丙烯酸乳液及其制备方法,它包括A、B、C三个组份;其A组份由去离子水、乳化剂、环氧树脂、酰胺基化合物、苯乙烯、丙烯酸酯、甲基丙烯酸酯、(甲基)丙烯酸组成;B组份由去离子水、缓冲剂、乳化剂组成;C组份由去离子水、引发剂组成;在乳液体系中还可以包括还原剂、保护胶、功能性单体、中和剂等。所制得的乳液具有颗粒细、弹性好、耐光、耐候、耐水等特点,可以在水性工业涂料、水性建筑涂料、水性木器涂料中应用。采用本发明乳液配制成的水性涂料具有附着力强、力学性能高、固化收缩率低、耐水/油性好、耐温变性好、耐热性好、耐老化性优良、电绝缘性优良、抗化学品性优良等特点。
Description
技术领域
本发明属于树脂与化学合成技术领域,涉及一种环氧改性丙烯酸乳液及其制备方法。
背景技术
丙烯酸树脂作为涂料的成膜基料具有色浅、保色、保光、耐候、耐腐蚀和耐污染等优点。已广泛应用于金属、塑料及木材等基材;金属包括铁、铝、铜、锌、不锈钢等;塑料包括PP、HDPE、PC、ABS、PVC、HIPS、PET等;所涂饰的产品包括汽车、火车、飞机、工程机械、家用电器、五金制品、玩具、家具等。近年来,国内外丙烯酸烯树脂涂料的发展很快,目前已占涂料的1/3以上,丙烯酸树脂在涂料成膜树脂中居于重要地位。
水性丙烯酸树脂涂料的研制和应用始于50年代,70年代初得到了迅速发展,与传统的溶剂型涂料相比,水性涂料具有价格低、使用安全、节省资源和能源,减少环境污染和无公害等优点,因而已成为当前涂料工业发展的主要方向。水性丙烯酸树脂涂料是水性涂料中发展最快、品种最多的无污染型涂料。水性丙烯酸乳液是最重要的乳胶漆基料,具有颗粒细、弹性好、耐光、耐候、耐水的特点,在建筑涂料市场占有重要的应用。但水性丙烯酸乳液在高档工业涂料中的应用受到了很大局限,为了解决这一问题,必须要对其进行改性。
发明内容
本发明所要解决的技术问题是:克服现有丙烯酸乳液存在的不足,提供一种附着力强、力学性能高、固化收缩率低、耐水/油性好、耐温变性好、耐热性好、耐老化性优良、电绝缘性优良、抗化学品性优良的环氧改性丙烯酸乳液及其制备方法。
解决其技术问题所采用的技术方案是:
一种环氧改性丙烯酸乳液,其特征在于它包括A、B、C三个组份,所述的A组份特征在于质量份组成为:去离子水50~80份、乳化剂0.5~2份、环氧树脂2~15份、酰胺基化合物0.5~5份、苯乙烯30~80份、丙烯酸酯30~60份、甲基丙烯酸酯45~75份、(甲基)丙烯酸3~10份;所述的B组份特征在于质量份组成为:去离子水50~100份、缓冲剂0.05~2份、乳化剂0.05~1份;所述的C组份特征在于质量份组成为:去离子水45~90份、引发剂0.5~3份;
所述的环氧改性丙烯酸乳液制备方法为:(1)分别配制A、B、C三个组份,称取相应质量份的物质,依次加入搅拌缸,启动分散机,转速为500~1500r/min,直至形成均象混合物,放到指定位置,待用;(2)将B组份全部加入反应釜,启动搅拌机,转速为150~200r/min,再向反应釜加入质量比为5~20%的A组份,搅拌均匀,升温至60~70℃;(3)搅拌机转速提升至250~400r/min,用5~10min向反应釜滴入质量比为20~40%的C组份;(4)升温至75~85℃反应15~45min,直到体系出现蓝光;(5)用120~210min同时向反应釜滴加完剩余的A、C组份,升温至80~90℃反应60~180min;(6)温度降至45℃以下,停止搅拌、放料、过滤,即得产品。
为了更好的实现本发明:
作为优选,所述的环氧改性丙烯酸乳液可以作为水性工业涂料(金属)、水性建筑涂料、水性木器涂料的成膜物,可以实现常温固化或烘烤固化,固化后的涂层能够形成互穿网络结构。具有优异的物理和化学性能。
作为优选,所述的乳化剂为阴离子型表面活性剂或/和非离子型表面活性剂。阴离子型表面活性剂主要以双电层结构分散、稳定乳液,乳化能力强,主要是因为其亲水端带有负电荷,液滴上的同种电荷层相互排斥,可以阻止液滴间的聚集,起到稳定乳液的作用;非离子型表面活性剂主要以屏蔽效应分散、稳定乳液,可以增加乳液对PH、盐和冻溶的稳定性,主要是因为其亲水链段定向吸附到乳胶粒的表面上,通过氢键作用吸附大量的水,水层的位阻效应也有利于乳液的稳定;阴离子型表面活性剂与非离子型表面活性剂复合使用,可以大大提高乳液的综合性能;其中,阴离子型表面活性剂可以是十二烷基硫酸钠(SDS)、十二烷基磺酸钠、十二烷基苯磺酸钠、烯丙氧基羟基丙磺酸钠、2-丙烯酰胺基-2-甲基丙磺酸钠、琥珀酸二辛酯磺酸钠、壬基酚聚氧乙烯醚琥珀酸单酯磺酸二钠等;非离子型表面活性剂可以是烷基酚聚氧乙烯醚(如OP-4、OP-7、OP-10、OP-15、OP-20等)、壬基酚聚氧乙烯醚(如Igepal CO-630)、辛基酚聚氧乙烯醚(如Igepal CA-630,Triton X-100等)、聚氧乙烯单月桂酸酯等;优选为十二烷基硫酸钠(SDS)、烯丙氧基羟基丙磺酸钠或OP-10。
作为优选,所述的环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、氢化双酚A型环氧树脂、聚氨酯改性环氧树脂中的一种或几种的组合物。双酚A型环氧树脂分子中含有双酚A骨架能够提供强韧性和耐热性,亚甲基链赋予柔软性,醚键赋予耐化学药品性,羟基赋予反应性和粘接性;双酚F型环氧树脂与双酚A型环氧树脂性质相似,黏度较低;氢化双酚A型环氧树脂分子中含有结构对称的环氧基、醚基等,具有粘度低、透明性高、长期不变色、耐热耐侯性好、良好的柔软性、粘结性和耐化学腐蚀性等;聚氨酯改性环氧树脂具有较好的柔韧性、抗老化、光泽高;其中,双酚A型环氧树脂的环氧值应在0.18-0.54eq/100g,如E44、E51、E20、CYD-128、EPON828等;双酚F型环氧树脂的环氧值应在0.4-0.54eq/100g,如F44、F47、F48、F51等;氢化双酚A型环氧树脂可以是泰国ADITYA BIRLA公司生产的YDH-3000、ST-3000、ST-3000H等;聚氨酯改性环氧树脂可以是长沙市原鹏化工科技有限公司生产的YPS-2002A、YPS-2001C等;优选为E44、CYD-128、EPON828、F51、YDH-3000或YPS-2002A。
作为优选,所述的酰胺基化合物为丙烯酰胺、甲基丙烯酰胺、N-羟甲基丙烯酰胺、N-丁氧甲基丙烯酰胺、双丙酮丙烯酰胺、甲基丙烯酸乙酰乙酸乙酯中的一种或几种的组合物。
作为优选,所述的丙烯酸酯为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸环己酯、丙烯酸月桂酯、丙烯酸-2-乙基己酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯中的一种或几种的组合物。
作为优选,所述的甲基丙烯酸酯为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸辛酯、甲基丙烯酸月桂酯、甲基丙烯酸异冰片酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸缩水甘油酯、二甲基丙烯酸乙二醇酯中的两种或两种以上的组合物。
作为优选,所述的缓冲剂为碳酸氢钠、磷酸二氢钠,醋酸钠中的一种。在乳液聚合的过程中,体系的pH值将不断下降,影响引发剂的活性,加入缓冲剂可以使体系的pH值维持相对稳定,使链引发正常进行。
作为优选,所述的引发剂为过硫酸铵、过硫酸钾、过硫酸钠、丙苯过氧化氢、丁基过氧化氢、乙二胺中的一种。
作为优选,在必要的情况下,乳液体系中还包括还原剂或/和保护胶,用量一般为单体质量比的0~6%。还原剂可以是亚铁盐(Fe2+)、亚硫酸氢钠(NaHSO3)、亚硫酸钠(Na2SO3)、连二亚硫酸钠(Na2S2O6)、硫代硫酸钠(Na2S2O3)、吊白粉等;氧化-还原引发体系反应活化能低,在室温或室温以下仍具有正常的引发速率,在乳液聚合后期为避免升温造成乳液凝聚,利用氧化-还原引发体系在50~70℃条件下进行单体的后消除,降低单体残留率。保护胶可以是羟乙基纤维素(HEC)、明胶、阿拉伯胶、海藻酸钠、聚乙烯醇(PVA1788)、聚丙烯酸钠、苯乙烯-马来酸酐交替共聚物单钠盐等;水性高分子的亲油大分子主链吸附到乳胶粒的表面,形成一层保护层,可阻止乳胶粒在聚合过程中的凝聚,另外保护胶提高了体系的粘度,有利于防止粒子的聚并、以及色漆体系贮存过程中颜填料的沉降。
作为优选,在必要的情况下,乳液体系中还包括功能性单体,如有机硅单体、叔碳酸酯类单体、烯类氟单体、己二酰二肼等,用量一般为单体质量比的0~3%。有机硅单体可以是乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷,乙烯基三异丙氧基硅烷,γ-甲基丙烯酰氧基丙基三(β-三甲氧基乙氧基)硅烷等;有机硅单体一般含有两个官能团,其中的环氧基可同树脂上的羟基、羧基或氨基反应,烷氧基硅部分在水解后通过缩聚而交链,有利于提高乳液的耐水耐候等性能,通常作为外加交联剂冷拼使用。叔碳酸酯类单体可以是美国壳牌公司的Veova 10、Veova 9、Veova11等;叔碳酸酯是α-C上带有三个烷基取代基的高度支链化的饱和酯,叔碳酸缩水甘油酯的环氧基有很强的反应性,能与羟基、羧基和胺基反应,能在常规温度下进入聚酯、醇酸、丙烯酸树脂大分子链中,反应几乎是定量的,副反应很少,能制备出分子量分布窄和粘度低的高固体份涂料树脂。烯类氟单体可以是三氟乙烯、偏二氟乙烯、四氟乙烯、氟丙烯酸等;烯类氟单体的加入可以很好的提高涂料的耐候性、耐水性、耐黄变性。双丙酮丙烯酰胺与己二酰二肼复合使用,水分挥发后可以在大分子链间架桥形成交联膜。
作为优选,在必要的情况下,乳液体系中还包括中和剂,如二甲基乙醇胺、2-氨基-2-甲基丙醇等。中和剂的用量应使体系的pH值位于7.0-8.3,不要太高,否则,体系粘度剧增,影响固含量和施工性能。
相对现有技术,本发明的有益效果是:
通过控制投料速率可以方便的控制聚合速率和放热速率,使反应能够比较平稳的进行,无放热高峰出现;单体加入速率小于或等于聚合反应速率,在聚合瞬间单体转化率可达90%以上,饥饿型半连续法乳液聚合可以有效的保证共聚物组成的一致性;乳液聚合的速度快、平均分子量高;体系中单体液滴浓度低,乳胶粒粒度小而均匀;在聚合过程中间断或连续补加一部分乳化剂,进一步提高了乳液聚合及乳液产品的稳定性,有利于提高乳液固含量;水作为分散介质,粘度低且稳定,价格低廉、安全可靠;若采用氧化-还原引发体系,聚合可在较低的温度下进行;本发明合成的乳液具有颗粒细、弹性好、耐光、耐候、耐水等特点。
本发明乳液作为涂料成膜物具有附着力强、力学性能高、固化收缩率低、耐水/油性好、耐温变性好、耐热性好、耐老化性优良、电绝缘性优良、抗化学品性优良等特点。
具体实施方式
下面通过具体实施方式对本发明作进一步说明,但并不意味着对本发明保护范围的限定。根据工程和客户的实际需要,通过调整发明配方,可以获得所需要的性能指标。所用原材料均为市售工业品,可以通过商业渠道购得。
实施例1
(1)配制A、B、C三个组份,各原料的用量(质量份/KG)为:
A组份:去离子水70,十二烷基硫酸钠0.6,烷基酚聚氧乙烯醚(OP-10)0.4,双酚A环氧树脂(E44)6,丙烯酰胺3,苯乙烯60,丙烯酸丁酯50,甲基丙烯酸甲酯35,甲基丙烯酸羟乙酯25,甲基丙烯酸缩水甘油酯2,二甲基丙烯酸乙二醇酯0.5,甲基丙烯酸6;B组份:去离子水90,碳酸氢钠0.3,十二烷基硫酸钠0.12,烷基酚聚氧乙烯醚(OP-10)0.08;C组份:去离子水65,过硫酸钾1.8;
以上各原料依次加入相应搅拌缸,分散机转速为800r/min,直至各组份形成均象混合物,放到指定位置,待用;
(2)将B组份全部(90.5KG)加入反应釜,启动搅拌机,转速为180r/min,再向反应釜加入质量比为10%的A组份(25.85KG),搅拌均匀,升温至65℃;
(3)搅拌机转速提升至300r/min,用10min向反应釜滴入质量比为30%的C组份(20.04KG);
(4)升温至80℃反应40min,直到体系出现蓝光;
(5)用120min同时向反应釜滴加完剩余的A(232.65KG)、C(46.76KG)组份,升温至85℃反应150min;
(6)降温至45℃以下,停止搅拌、放料、用200目滤布过滤,即得产品。
本发明所得环氧改性丙烯酸乳液产品:固含为45%(wt%),粘度为12.5S(涂-4杯),PH值为5.2;应用于水性钢构涂料中,其性能可达:附着力(拉开发)3.5MPa,耐中性盐雾1500h,耐水性240h,耐碱性(10%NaOH)96h,耐油性(120#汽油)120h。
实施例2
(1)配制A、B、C三个组份,各原料的用量(质量份/KG)为:
A组份:去离子水70,十二烷基硫酸钠0.6,烯丙氧基羟基丙磺酸钠0.4,氢化双酚A环氧树脂(YDH3000)6,N-羟甲基丙烯酰胺3,苯乙烯60,丙烯酸甲酯30,丙烯酸环己酯20,甲基丙烯酸丁酯35,甲基丙烯酸羟丙酯25,甲基丙烯酸缩水甘油酯2.5,丙烯酸6;B组份:去离子水90,磷酸二氢钠0.3,十二烷基硫酸钠0.12,烯丙氧基羟基丙磺酸0.08;C组份:去离子水65,过硫酸铵1.8;
以上各原料依次加入相应搅拌缸,分散机转速为600r/min,直至各组份形成均象混合物,放到指定位置,待用;
(2)将B组份全部(90.5KG)加入反应釜,启动搅拌机,转速为150r/min,再向反应釜加入质量比为5%的A组份(12.925KG),搅拌均匀,升温至65℃;
(3)搅拌机转速提升至250r/min,用5min向反应釜滴入质量比为20%的C组份(13.36KG);
(4)升温至75℃反应45min,直到体系出现蓝光;
(5)用180min同时向反应釜滴加完剩余的A(245.575KG)、C(53.44KG)组份和三氟乙烯2KG,然后加入还原剂(亚硫酸钠)0.5KG,保护胶(PVA1788)3KG,升温至90℃反应120min;
(6)降温至45℃以下,用一定量的中和剂AMP-95将乳液体系的PH值调至8.3,停止搅拌、放料、用200目滤布过滤,即得产品。
本发明所得环氧改性丙烯酸乳液产品:固含为45.8%(wt%),粘度为13.2S(涂-4杯),PH值为8.3;应用于水性钢构涂料中,其性能可达:附着力(拉开发)4.2MPa,耐中性盐雾2000h,耐水性240h,耐碱性(10%NaOH)96h,耐油性(120#汽油)120h。
实施例3
(1)配制A、B、C三个组份,各原料的用量(质量份/KG)为:
A组份:去离子水80,烯丙氧基羟基丙磺酸钠2,双酚F环氧树脂(F51)10,N-丁氧甲基丙烯酰胺5,苯乙烯50,丙烯酸丁酯30,丙烯酸月桂酯30,甲基丙烯酸甲酯35,甲基丙烯酸羟乙酯35,二甲基丙烯酸乙二醇酯3,丙烯酸3;B组份:去离子水100,磷酸二氢钠1.5,烯丙氧基羟基丙磺酸1;C组份:去离子水90,过硫酸钠2.5;
以上各原料依次加入相应搅拌缸,分散机转速为500r/min,直至各组份形成均象混合物,放到指定位置,待用;
(2)将B组份全部(102.5KG)加入反应釜,启动搅拌机,转速为200r/min,再向反应釜加入质量比为20%的A组份(56.6KG),搅拌均匀,升温至70℃;
(3)搅拌机转速提升至300r/min,用10min向反应釜滴入质量比为40%的C组份(37KG);
(4)升温至85℃反应15min,直到体系出现蓝光;
(5)用120min同时向反应釜滴加完剩余的A(226.4KG)、C(55.5KG)组份和乙烯基三甲氧基硅烷2.5KG,然后加入还原剂(亚硫酸氢钠)1KG,保护胶(PVA1788)4.5KG,,升温至90℃反应150min;
(6)降温至45℃以下,用一定量的中和剂AMP-95将乳液体系的PH值调至7.5,停止搅拌、放料、用200目滤布过滤,即得产品。
本发明所得环氧改性丙烯酸乳液产品:固含为43.5%(wt%),粘度为12.5S(涂-4杯),PH值为7.5;应用于水性钢构涂料中,其性能可达:附着力(拉开发)3.6MPa,耐中性盐雾1000h,耐水性240h,耐碱性(10%NaOH)96h,耐油性(120#汽油)120h。
实施例4
(1)配制A、B、C三个组份,各原料的用量(质量份/KG)为:
A组份:去离子水50,烷基酚聚氧乙烯醚(OP-10)2,双酚A环氧树脂(EPON828)2,甲基丙烯酰胺0.5,苯乙烯80,丙烯酸丁酯30,甲基丙烯酸甲酯38,甲基丙烯酸羟乙酯5,二甲基丙烯酸乙二醇酯1,甲基丙烯酸缩水甘油酯1,甲基丙烯酸10;B组份:去离子水50,磷酸二氢钠1,烷基酚聚氧乙烯醚(OP-10)1;C组份:去离子水45,过硫酸钠1;
以上各原料依次加入相应搅拌缸,分散机转速为1000r/min,直至各组份形成均象混合物,放到指定位置,待用;
(2)将B组份全部(52KG)加入反应釜,启动搅拌机,转速为150r/min,再向反应釜加入质量比为20%的A组份(43.9KG),搅拌均匀,升温至60℃;
(3)搅拌机转速提升至400r/min,用5min向反应釜滴入质量比为20%的C组份(9.2KG);
(4)升温至75℃反应45min,直到体系出现蓝光;
(5)用210min同时向反应釜滴加完剩余的A(175.6KG)、C(36.8KG)组份,升温至80℃反应180min;
(6)降温至45℃以下,停止搅拌、放料、用200目滤布过滤,即得产品。
本发明所得环氧改性丙烯酸乳液产品:固含为54%(wt%),粘度为14.8S(涂-4杯),PH值为3.9;应用于水性钢构涂料中,其性能可达:附着力(拉开发)3.0MPa,耐中性盐雾800h,耐水性240h,耐碱性(10%NaOH)96h,耐油性(120#汽油)120h。
实施例5
(1)配制A、B、C三个组份,各原料的用量(质量份/KG)为:
A组份:去离子水80,十二烷基硫酸钠0.3,烷基酚聚氧乙烯醚(OP-10)0.2,双酚A环氧树脂(E44)5,聚氨酯改性环氧树脂(YPS-2002A)10,丙烯酰胺1,N-丁氧甲基丙烯酰胺1,苯乙烯30,丙烯酸丁酯15,丙烯酸月桂酯10,甲基丙烯酸甲酯35,甲基丙烯酸羟乙酯35,二甲基丙烯酸乙二醇酯3,甲基丙烯酸缩水甘油酯2,甲基丙烯酸6.5;B组份:去离子水75,碳酸氢钠0.2,十二烷基硫酸钠0.1,烷基酚聚氧乙烯醚(OP-10)0.1;C组份:去离子水90,过硫酸钾3;
以上各原料依次加入相应搅拌缸,分散机转速为1500r/min,直至各组份形成均象混合物,放到指定位置,待用;
(2)将B组份全部(75.4KG)加入反应釜,启动搅拌机,转速为180r/min,再向反应釜加入质量比为20%的A组份(46.8KG),搅拌均匀,升温至70℃;
(3)搅拌机转速提升至400r/min,用10min向反应釜滴入质量比为30%的C组份27.9KG);
(4)升温至80℃反应30min,直到体系出现蓝光;
(5)用210min同时向反应釜滴加完剩余的A(187.2KG)、C(65.1KG)组份,升温至85℃反应120min;
(6)降温至45℃以下,停止搅拌、放料、用200目滤布过滤,即得产品。
本发明所得环氧改性丙烯酸乳液产品:固含为39%(wt%),粘度为12.2S(涂-4杯),PH值为6.2;应用于水性钢构涂料中,其性能可达:附着力(拉开发)4.5MPa,耐中性盐雾1500h,耐水性240h,耐碱性(10%NaOH)96h,耐油性(120#汽油)120h。
上述实施例是为了对本技术方案进行清楚、完整的描述,是本发明的部分实施方式,而不是全部的实施方式。但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、 替代、组合或简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (8)
1.一种环氧改性丙烯酸乳液,其特征在于它包括A、B、C三个组份,所述的A组份特征在于质量份组成为:去离子水50~80份、乳化剂0.5~2份、环氧树脂2~15份、酰胺基化合物0.5~5份、苯乙烯30~80份、丙烯酸酯30~60份、甲基丙烯酸酯45~75份、(甲基)丙烯酸3~10份;所述的B组份特征在于质量份组成为:去离子水50~100份、缓冲剂0.05~2份、乳化剂0.05~1份;所述的C组份特征在于质量份组成为:去离子水45~90份、引发剂0.5~3份;
所述的环氧改性丙烯酸乳液制备方法为:(1)分别配制A、B、C三个组份,称取相应质量份的物质,依次加入搅拌缸,启动分散机,转速为500~1500r/min,直至形成均象混合物,放到指定位置,待用;(2)将B组份全部加入反应釜,启动搅拌机,转速为150~200r/min,再向反应釜加入质量比为5~20%的A组份,搅拌均匀,升温至60~70℃;(3)搅拌机转速提升至250~400r/min,用5~10min向反应釜滴入质量比为20~40%的C组份;(4)升温至75~85℃反应15~45min,直到体系出现蓝光;(5)用120~210min同时向反应釜滴加完剩余的A、C组份,升温至80~90℃反应60~180min;(6)温度降至45℃以下,停止搅拌、放料、过滤,即得产品。
2.根据权利要求1所述的环氧改性丙烯酸乳液,其特征在于所述的乳化剂为阴离子型表面活性剂或/和非离子型表面活性剂。
3.根据权利要求1所述的环氧改性丙烯酸乳液,其特征在于所述的环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、氢化双酚A型环氧树脂、聚氨酯改性环氧树脂中的一种或几种的组合物。
4.根据权利要求1所述的环氧改性丙烯酸乳液,其特征在于所述的酰胺基化合物为丙烯酰胺、甲基丙烯酰胺、N-羟甲基丙烯酰胺、N-丁氧甲基丙烯酰胺、双丙酮丙烯酰胺、甲基丙烯酸乙酰乙酸乙酯中的一种或几种的组合物。
5.根据权利要求1所述的环氧改性丙烯酸乳液,其特征在于所述的丙烯酸酯为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸环己酯、丙烯酸月桂酯、丙烯酸-2-乙基己酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯中的一种或几种的组合物。
6.根据权利要求1所述的环氧改性丙烯酸乳液,其特征在于所述的甲基丙烯酸酯为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸辛酯、甲基丙烯酸月桂酯、甲基丙烯酸异冰片酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸缩水甘油酯、二甲基丙烯酸乙二醇酯中的两种或两种以上的组合物。
7.根据权利要求1所述的环氧改性丙烯酸乳液,其特征在于所述的缓冲剂为碳酸氢钠、磷酸二氢钠,醋酸钠中的一种。
8.根据权利要求1所述的环氧改性丙烯酸乳液,其特征在于所述的引发剂为过硫酸铵、过硫酸钾、过硫酸钠、丙苯过氧化氢、丁基过氧化氢、乙二胺中的一种。
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