CN107641409A - 用于制备被磷类酸和光引发剂基团官能化的胶乳的方法 - Google Patents
用于制备被磷类酸和光引发剂基团官能化的胶乳的方法 Download PDFInfo
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- CN107641409A CN107641409A CN201710567226.3A CN201710567226A CN107641409A CN 107641409 A CN107641409 A CN 107641409A CN 201710567226 A CN201710567226 A CN 201710567226A CN 107641409 A CN107641409 A CN 107641409A
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- 239000002253 acid Substances 0.000 title claims abstract description 69
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 59
- 239000011574 phosphorus Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000007306 functionalization reaction Methods 0.000 title claims description 8
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- 229920000126 latex Polymers 0.000 title abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 181
- 238000010276 construction Methods 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 16
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 24
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 17
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 8
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- PHJZTYNBFPIINN-UHFFFAOYSA-N CC(C(=O)O)=C.[P] Chemical compound CC(C(=O)O)=C.[P] PHJZTYNBFPIINN-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
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- 230000000844 anti-bacterial effect Effects 0.000 description 1
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- 210000000481 breast Anatomy 0.000 description 1
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- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- MHZDONKZSXBOGL-UHFFFAOYSA-N propyl dihydrogen phosphate Chemical compound CCCOP(O)(O)=O MHZDONKZSXBOGL-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08F2/22—Emulsion polymerisation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C08F275/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers containing phosphorus, selenium, tellurium or a metal as defined in group C08F30/00
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- C08F8/00—Chemical modification by after-treatment
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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Abstract
本发明是一种用来制备稳定的包含磷类酸单体或其盐的结构单元和光引发剂单体的结构单元的聚合物颗粒的水性分散体的方法。与不具有化学键接到胶乳颗粒的光引发剂的漆相比,含有通过本发明方法制备的胶乳的漆的光泽保持率得到提高。
Description
技术领域
本发明涉及一种用于制备稳定的被磷类酸基团和光引发剂基团官能化的聚合物颗粒的水性分散体(即胶乳)的方法。胶乳可用于用来在外部涂料应用中保持光泽并改进抗污物粘附性的漆。
背景技术
改进丙烯酸漆外部耐用性的最有效方式之一是向漆中加入少量(通常≤1.0%)的二苯甲酮。然而,曝露于外部环境1到2年后(或者在QUV中加速风化~1500小时),大部分漆会丧失大量光泽。此外,二苯甲酮还会受到其它不利因素的影响,包括:1)分类为挥发性有机化合物(VOC);2)随着时间而溶出;以及3)可能的毒性。所以,在外部涂料领域找到不使用具有二苯甲酮不利因素的材料而能在很长时间内保持光泽的方法将会是有利的。
发明内容
本发明旨在通过提供一种方法来解决外部涂料领域的需求,所述方法包含通过多阶段乳液聚合的方式形成稳定的被以聚合物颗粒的重量计0.2到5重量百分比的磷类酸单体的结构单元以及0.05到10重量百分比的光引发剂单体的结构单元官能化的丙烯酸类聚合物颗粒的水性分散体,其磷类酸单体和光引发剂单体的结构单元由同一阶段中磷类酸单体与光引发剂单体的共聚产生。
本发明的方法提供了一种胶乳,其可改进漆组合物在很长时间内的光泽并且不具有VOC、毒性以及与二苯甲酮相关的法规问题。
具体实施方式
本发明是一种方法,其包含通过多阶段乳液聚合的方式形成稳定的被以聚合物颗粒的重量计0.2到5重量百分比的磷类酸单体的结构单元以及0.05到10重量百分比的光引发剂单体的结构单元官能化的丙烯酸类聚合物颗粒的水性分散体,其磷类酸单体和光引发剂单体的结构单元由同一阶段中磷类酸单体与光引发剂单体的共聚产生。
如本文所使用,术语“丙烯酸类聚合物颗粒”是指包含以聚合物颗粒的重量计至少30重量百分比的甲基丙烯酸酯单体和或丙烯酸酯单体的结构单元的聚合物颗粒(包括种子聚合物颗粒)。优选地,丙烯酸类聚合物颗粒包含一种或多种像甲基丙烯酸甲酯、甲基丙烯酸乙酯和脲基丙烯酸甲酯这样的甲基丙烯酸酯单体,以及一种或多种像丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯这样的丙烯酸酯单体的结构单元。丙烯酸类聚合物还可包括像苯乙烯这样的其它单体的结构单元。
如本文所使用,所指单体的术语“结构单元”是指聚合后单体的残余部分。例如,甲基丙烯酸甲酯的结构单元如下所示:
甲基丙烯酸甲酯结构单元
其中虚线表示结构单元与聚合物骨架的连接点。
聚合物颗粒优选包含以聚合物颗粒的重量计40到50重量百分比的甲基丙烯酸甲酯或苯乙烯结构单元;从23、更优选从25重量百分比到33、更优选到30重量百分比的丙烯酸2-乙基己酯结构单元;15到25重量百分比的丙烯酸丁酯结构单元;从0.1、更优选从0.5重量百分比到5、更优选到3、以及最优选到2重量百分比的脲基丙烯酸甲酯结构单元;以及0.05到2重量百分比的甲基丙烯酸或丙烯酸或其盐的结构单元。
聚合物颗粒进一步包含以聚合物颗粒的重量计从0.05、优选从0.1、更优选从0.2、以及最优选从0.5重量百分比到10、优选到5、以及更优选到3重量百分比的光引发剂单体的结构单元;以及以聚合物颗粒的重量计从0.2、优选从0.5、更优选从0.8重量百分比到5、优选3、更优选到2重量百分比的磷类酸单体的结构单元。
多阶段胶乳优选以两阶段制备。在第一阶段,第一聚合物颗粒的水性分散体优选通过单体的乳液聚合制备,所述单体包含a)甲基丙烯酸甲酯或苯乙烯或其组合,优选甲基丙烯酸甲酯;b)一种或多种选自由以下组成的群组的丙烯酸酯:丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯、以及丙烯酸2-乙基己酯,优选丙烯酸丁酯和丙烯酸2-乙基己酯的组合;c)羧酸单体或其盐,例如丙烯酸、甲基丙烯酸、或衣康酸、或其盐。釜可任选地在聚合引发前或在聚合引发过程中用像稀Na2CO3水溶液这样的合适的碱缓冲。
第二阶段也优选地包含甲基丙烯酸甲酯(和/或苯乙烯)、一种或多种前述丙烯酸酯、以及羧酸单体。还发现,优选地以在以第二阶段单体的重量计从0.2、更优选从0.5重量百分比到优选10、更优选到5、以及最优选到3重量百分比的范围内的浓度包括像脲基丙烯酸甲酯这样的脲基官能化的单体是有利的。
光引发剂单体与磷类酸单体在第一阶段或在第二阶段,更优选在第一阶段放置在一起。光引发剂单体和磷类酸单体中的任一种或两者都被包括在多于一个阶段中是可能的,只要两种单体在同一阶段共聚。例如,如果光引发剂单体和磷类酸单体在2-阶段乳液聚合反应的第一阶段共聚,光引发剂单体和磷类酸单体中的任一种或两者都被包括在第二阶段是可能的。优选地,如果光引发剂单体和磷类酸单体两者都在第一阶段共聚,那么第二阶段任选地包括光引发剂单体或磷类酸单体或者两者都包括,条件是第一阶段光引发剂单体与第二阶段光引发剂单体的比例大于2∶1,优选大于5∶1,更优选大于10∶1,以及最优选大于100∶1,并且第一阶段磷类酸单体与第二阶段磷类酸单体的比例大于2∶1,优选大于5∶1,更优选大于10∶1,以及最优选大于100∶1。最优选地,如果第一阶段单体包含光引发剂单体和磷类酸单体,那么第二阶段单体则不包含这些单体。
类似地,如果光引发剂单体和磷类酸单体两者都在第二阶段共聚,那么第一阶段任选地包括光引发剂单体或磷类酸单体或者两者都包括,条件是第二阶段光引发剂单体与第一阶段光引发剂单体的比例大于2∶1,优选大于5∶1,更优选大于10∶1,以及最优选大于100∶1,并且第二阶段磷类酸单体与第一阶段磷类酸单体的比例大于2∶1,优选大于5∶1,更优选大于10∶1,以及最优选大于100∶1。
尽管不受理论的束缚,据信磷类酸单体和光引发剂单体在同一阶段的共聚提供了官能化的光引发剂基团有利地处于胶乳颗粒表面上的机理;此类表面官能化使得能够利用紫外光,其导致由光引发剂基团促进的交联,从而赋予有利的光泽保持率以及改进的抗污物粘附性。
合适的磷类酸单体的实例包括醇的磷酸酯和磷酸二氢酯,其中所述醇含有可聚合的乙烯基或烯烃基团或者被可聚合的乙烯基或烯烃基团取代。优选的磷酸二氢酯是丙烯酸羟基烷基酯或甲基丙烯酸羟基烷基酯的磷酸酯,包括甲基丙烯酸磷酸酯乙酯(PEM)和甲基丙烯酸磷酸酯丙酯。特别优选的磷类酸单体PEM由以下结构表示:
其中R是H或
如本文所使用,术语“光引发剂单体”是指具有苯甲酰基官能团和能够在乳液聚合反应中聚合的烯属不饱和基团的化合物。具有苯甲酰基官能团和烯属不饱和的一类化合物是如下所示的一类可聚合化合物:
其中j是0、1、2、或3;k是0、1、或2;R1和R2各自独立地是C1-C6-烷基、CF3、OH、NH2、COOH、或COOCH3;或者R1和R2以及与其连接的碳原子一起形成桥连S、O、NH、或NH3基团;Y是任选地包含至少一个O、N、或S杂原子的含有有机烃的基团,该基团进一步包含可与丙烯酸类、甲基丙烯酸类、苯乙烯、或乙烯基酯单体共聚的不饱和取代基。
另一类合适的光引发剂单体如下所示:
其中每个R3独立地是CF3、C1-C6-烷基、-O-C1-C6烷基、-COO-C1-C6-烷基、卤素、CN、COOH、或OH;X是C1-C6-烷基;Z是被丙烯酸酯或甲基丙烯酸酯官能化的基团。
优选地,Z是以下分子式:
其中A是O或NR3;n是0或1;p是1到12;并且每个R3独立地是H或CH3。
特定光引发剂单体的实例如下所示:
2-苯甲酰基苯甲酸2-羟基-3-(甲基丙烯酰氧基)丙酯
甲基丙烯酸2-(((4-苯甲酰基苯氧基)羰基)氨基)乙酯
甲基丙烯酸2-(丙烯酰氧基)-3-((9-氧代-9/f-噻吨-2-基)氧基)丙酯
甲基丙烯酸2-(2-(4-苯甲酰基-2,5-二甲基苯氧基)乙氧基)乙酯
4-(4-氯苯甲酰基)苯甲酸2-(甲基丙烯酰氧基)乙酯
甲基丙烯酸4-苯甲酰基苯酯
在一个实施例中,第一阶段与第二阶段的重量/重量比例优选在10∶90到70∶30、更优选20∶80到50∶50、以及最优选25∶75到40∶60的范围内。在另一个实施例中,第二阶段与第一阶段的重量/重量比例优选在10∶90到70∶30、更优选20∶80到50∶50、以及最优选25∶75到40∶60的范围内。优选地,每个阶段包含20到30重量百分比的丙烯酸2-乙基己酯结构单元、15到25重量百分比的丙烯酸丁酯结构单元、40到50重量百分比的甲基丙烯酸甲酯结构单元、0.4到1.2重量百分比的丙烯酸或甲基丙烯酸结构单元。磷类酸单体和光引发剂单体优选在含有小于50%的总单体的阶段共聚。例如,在第一与第二阶段单体的重量/重量比例为30∶70的2-阶段乳液聚合反应中,磷类酸单体和光引发剂单体优选在第一阶段共聚;所述比例为70∶30时,则优选在第二阶段共聚。
聚合物颗粒的水性分散体可用作漆配制物中的粘结剂。相应地,在另一方面,本发明组合物进一步包括一种或多种选自由以下组成的群组的物质:颜料、增稠剂、分散剂、表面活性剂、聚结剂、消泡剂、增粘剂、杀菌剂、以及中和剂。
令人意外地发现,含有本文所述的胶乳的漆的光泽保持率相较于不具有化学键接到胶乳颗粒的光引发剂的漆而言被显著改进。可进一步通过光引发剂不存在任何溶出、降低的毒性、以及比含有二苯甲酮的漆更少的VOC使漆有利。
本发明组合物与其它物质结合来制造漆,然后测试光泽保持率。
实例1–2-阶段胶乳的制备:第一阶段加入光引发剂单体和磷类酸单体
通过将去离子水(195g)、Disponil FES-993表面活性剂(29.2g,30%有活性)、丙烯酸2-乙基己酯(155.0g)、丙烯酸丁酯(99.4g)、甲基丙烯酸甲酯(227.2g)、甲基丙烯酸磷酸酯乙酯(39.2g,60%有活性)、甲基丙烯酸(4.6g)和2-苯甲酰基苯甲酸2-羟基-3-(甲基丙烯酰氧基)丙酯(38.3g)混合来制备第一单体乳液。向配有桨式搅拌器、温度计、氮气入口和回流冷凝器的5-L四颈圆底烧瓶中加入去离子水(929.2g)和Disponil FES-32表面活性剂(11.2g,31%有活性)。将烧瓶内容物在N2下加热到83℃并开始搅拌。然后加入一部分第一单体乳液(112g),接着用去离子水(40g)洗涤。向烧瓶中加入过硫酸铵(3.76g)溶于去离子水(20g)中的溶液,接着用去离子水(5g)洗涤。观察到最大放热后,在将温度保持在85℃的同时在30分钟内以恒定速率加入第一单体乳液的剩余部分。同时在30分钟内分别加入过硫酸铵(3.49g)在去离子水(85g)中的30%的引发剂溶液。一旦加入第一单体乳液,将含有第一单体乳液的烧瓶用去离子水(30g)洗涤并停止添加引发剂溶液。将反应物在85℃保持15分钟。同时,通过将去离子水(337g)、Disponil FES-32表面活性剂(36.0g,31%有活性)、丙烯酸2-乙基己酯(361.8g)、丙烯酸丁酯(235.6g)、甲基丙烯酸甲酯(706.8g)、甲基丙烯酸(10.7g)、脲基丙烯酸甲酯(24.9g)混合来制备第二单体乳液。向引发剂溶液中加入氢氧化铵(13.9g,30%有活性),接着用去离子水(23.0g)洗涤。保持15分钟后,在将温度保持在85℃的同时在80分钟内线性地并且分别地加入第二单体乳液和引发剂溶液的剩余部分。一旦加料结束,将单体乳液釜和引发剂溶液用去离子水(分别为75g和5g)洗涤。将烧瓶内容物冷却到65℃并向烧瓶中加入催化剂/活化剂对以减少残余单体。将聚合物用氢氧化铵(30%有活性)中和到pH 8.5。使用Brookhaven BI 90 Plus颗粒分析器测量的粒径为110-130nm,固体含量为50%。
实例2–2-阶段胶乳的制备:第二阶段加入光引发剂单体和磷类酸单体
通过将去离子水(307g)、Disponil FES-32表面活性剂(20.5g,31%有活性)、丙烯酸2-乙基己酯(206.7g)、丙烯酸丁酯(139.8g)、甲基丙烯酸甲酯(415.2g)、乙基甲基丙烯酸(3.8g)混合来制备第一单体乳液。向配有桨式搅拌器、温度计、氮气入口、以及回流冷凝器的5-L四颈圆底烧瓶中加入去离子水(929.2g)和Disponil FES-32表面活性剂(11.2g,31%有活性)。将烧瓶内容物在N2下加热到83℃并开始搅拌。然后加入一部分第一单体乳液(112g),接着用去离子水(40g)洗涤烧瓶。向烧瓶中加入过硫酸铵(3.76g)溶于去离子水(20g)中的溶液,接着用去离子水(5g)洗涤。观察到最大放热后,在将反应温度保持在85℃的同时在35分钟内以恒定速率加入第一单体乳液的剩余部分。同时在35分钟内分别加入过硫酸铵(3.49g)在去离子水(170g)中的42%的引发剂溶液。一旦加入第一单体乳液,将烧瓶用去离子水(30g)洗涤并停止添加引发剂溶液。将反应物在85℃保持15分钟。同时,通过将去离子水(397g)、Disponil FES-993表面活性剂(58.5g,30%有活性)、丙烯酸2-乙基己酯(310.1g)、丙烯酸丁酯(195.2g)、甲基丙烯酸甲酯(530.3g)、甲基丙烯酸(11.5g)、甲基丙烯酸磷酸酯乙酯(39.2g,60%有活性)、脲基丙烯酸甲酯(24.9g)、2-苯甲酰基苯甲酸2-羟基-3-(甲基丙烯酰氧基)丙酯(38.2g)混合来制备第二单体乳液。保持15分钟后,在将温度保持在85℃的同时在85分钟内线性地并且分别地加入第二单体乳液和引发剂溶液的剩余部分。一旦加料结束,将单体乳液釜和引发剂溶液用去离子水(分别为50g和5g)洗涤。将烧瓶内容物冷却到65℃并向烧瓶中加入催化剂/活化剂对以减少残余单体。聚合物用氢氧化铵(30%有活性)中和到pH 8.5。使用Brookhaven BI 90 Plus颗粒分析器测量的粒径为110-130nm,固体含量为48%。
对比实例1–2-阶段胶乳的制备:第一阶段加入磷类酸单体,未加入光引发剂单体
2-阶段聚合物基本上如实例1所述制备,除了未使用光引发剂单体。第一阶段与第二阶段的w/w阶段比例为30∶70。
用于制备第一阶段单体的相对w/w量是27 2-EHA/19.3 BA/46.2 MMA/6.7 PEM(60%有活性)/和0.8 MAA;用于制备第二阶段单体的相对w/w量是27 2-EHA/19.3 BA/50.8MMA/1.9 UMA/和0.8 MAA。
2-EHA是指丙烯酸2-乙基己酯;BA是指丙烯酸丁酯;MMA是指甲基丙烯酸甲酯;PEM是指甲基丙烯酸磷酸酯乙酯;UMA是指脲基丙烯酸甲酯;MAA是指甲基丙烯酸。此外,对比实例1胶乳包括就胶乳中的总固体而言以重量计0.6%的二苯甲酮。如表1所示,实验胶乳被与其它添加剂一起配制成漆。
表1–漆配制物
TAMOL、ROCIMA和ACRYSOL都是陶氏化学公司(Dow Chemical Company)或其分支机构的商标。
QUV测量
将实验漆涂覆到基底上并使用以下步骤进行加速风化测试。加速风化使用QUV仪器根据ASTM-D 4587的《漆和相关涂料的荧光UV-凝聚曝露的标准实践(Standard Practicefor Fluorescent UV-Condensation Exposures of Paint and Related Coatings)》来进行。周期由在60℃下8小时的UV曝露(0.89W/m2)接着在50℃下4小时的阴暗凝聚期组成。将配制物涂覆到(15密耳厚)经铬酸盐处理的铝板上,并在引发QUV曝露前在受控环境室(25℃,50%RH)内固化7天。光泽使用BYK Gardner micro-TRI-gloss仪在QUV曝露500小时、1500小时和2000小时的间隔测量。表2显示60°光泽变化的结果。在该表中,Δ60实例1是指由包括实例1胶乳的漆制备的涂料的60°光泽变化;Δ60实例2是指由包括实例2胶乳的漆制备的涂料的60°光泽变化;Δ60对比实例1是指由包括对比实例1胶乳的漆制备的涂料的60°光泽变化。
表2–QUV加速风化时的60°光泽单位下的变化
曝露时间(小时) | 0 | 100 | 500 | 1500 | 2000 |
Δ60实例1 | 79 | 76 | 77 | 81 | 82 |
Δ60实例2 | 78 | 72 | 67 | 65 | 66 |
Δ60对比实例1 | 79 | 69 | 74 | 83 | 51 |
数据表明,与由含有被化学键接的二苯甲酮基团官能化的胶乳的漆制备的涂料相比,由包括游离二苯甲酮的漆衍生的涂料在2000小时显示光泽的显著丧失。结果进一步表明PEM与光引发剂在胶乳的第一阶段进行共聚的优点。
实例3–2-阶段胶乳的制备:在第一阶段加入光引发剂单体、磷类酸单体和脲基丙烯酸甲酯
通过将去离子水(139g)、Disponil FES-993表面活性剂(28.2g,30%有活性)、丙烯酸2-乙基己酯(158.8g)、丙烯酸丁酯(96.4g)、甲基丙烯酸甲酯(230.2g)、甲基丙烯酸磷酸酯乙酯(39.2g,60%有活性)、甲基丙烯酸(4.7g)、以及2-苯甲酰基苯甲酸2-羟基-3-(甲基丙烯酰氧基)丙酯(72.6g,54%有活性)混合来制备第一单体乳液。向配有桨式搅拌器、温度计、氮气入口和回流冷凝器的5-L四颈圆底烧瓶中加入去离子水(931g)和Disponil FES-32表面活性剂(11.9g,30%有活性)。将烧瓶内容物在N2下加热到82℃并开始搅拌。然后加入一部分第一单体乳液(116.1g),接着用去离子水(32g)洗涤。向烧瓶中加入过硫酸铵(4.0g)溶于去离子水(26g)中的溶液。然后向第一单体乳液中加入去离子水(15.0g)、Disponil FES-993表面活性剂(3.0g,30%有活性)和脲基丙烯酸甲酯(39.2g,50%有活性)的溶液。观察到最大放热后,在将温度保持在85℃的同时在30分钟内以恒定速率加入第一单体乳液的剩余部分。同时在30分钟内分别加入过硫酸铵(3.7g)在去离子水(118g)中的30%的引发剂溶液。一旦加入第一单体乳液,将含有第一单体乳液的烧瓶用去离子水(15g)洗涤,并停止添加引发剂溶液。将反应物在85℃保持15分钟。同时,通过将去离子水(398g)、Disponil FES-32表面活性剂(39.4g,30%有活性)、丙烯酸2-乙基己酯(370.4g)、丙烯酸丁酯(221.2g)、甲基丙烯酸甲酯(769.4g)、甲基丙烯酸(11.0g)、以及氢氧化铵(14.4g,29%有活性)混合来制备第二单体乳液。保持15分钟后,在将温度保持在85℃的同时在80分钟内线性地并且分别地加入第二单体乳液和引发剂溶液的剩余部分。一旦加料结束,将单体乳液釜和引发剂溶液用去离子水(30g)洗涤。将烧瓶内容物冷却到75℃,并向烧瓶中加入催化剂/活化剂对以减少残余单体。将聚合物用氢氧化铵(29%水溶液)中和到pH 9.0。使用Brookhaven BI 90 Plus颗粒分析器测量的粒径是110-130nm,固体含量是51%。
实例4–2-阶段胶乳的制备:在第一阶段加入光引发剂单体和磷类酸单体
2-阶段聚合物基本上如实例3所述制备,除了未使用脲基丙烯酸甲酯单体。第一阶段与第二阶段的w/w阶段比例为30∶70。用于制备第一阶段单体的相对w/w量是27.02-EHA/16.4 BA/39.2 MMA/6.7 PEM(60%有活性)/6.7 2-苯甲酰基苯甲酸2-羟基-3-(甲基丙烯酰氧基)丙酯/0.8 MAA;用于制备第二阶段单体的相对w/w量是27.0 2-EHA/16.12 BA/56.08MMA/0.8 MAA。
抗污物粘附性的测量
进行了进一步的实验以展示用脲基丙烯酸甲酯官能化胶乳对如Y-反射度测量的抗污物粘附性的作用。胶乳基本上如实例1所述制备,除了第二阶段单体乳液不含有脲基丙烯酸甲酯。漆组合物如表3所述制备,并且将基底用含有实例1胶乳的漆以及含有未被脲基丙烯酸甲酯官能化的类似胶乳的漆涂覆。将漆配制物用5密耳的涂覆器涂覆到经铬酸盐处理的铝板上,并在受控环境室(25℃,50%RH)内干燥过夜。然后将板以45°的角度朝南置于户外6天。户外曝露后,进行初始Y-反射度测量。接着将样品置于气培箱中1.5小时,然后轻拍干燥。刷涂棕色氧化铁浆体,并干燥4小时,在用纱布摩擦的同时用流动的温水将其洗掉。干燥后测量最终的Y-反射度值。保留Y-反射度等于将最终的Y-反射度除以初始Y-反射度再乘以100%。使用BYK Gardner颜色-指导45/0仪进行Y-反射度测量。棕色氧化铁浆体通过将Davis Colors 641棕色氧化铁(125g)分散到水(250g)和TAMOLTM731A分散剂(0.1g)中来制备。发现含有实例1胶乳的漆的保留Y-反射度为95.7%,含有未被脲基丙烯酸甲酯官能化的胶乳的漆的保留Y-反射度为93.2%。表3所示结果表明将脲基丙烯酸甲酯包括到聚合物胶乳中对抗污物粘附性具有正面作用。
表3–0 VOC漆配制物
物质 | 重量(g) | 重量(g) |
水 | 67.36 | 67.19 |
Ti-Pure R-746二氧化钛 | 129.19 | 129.19 |
实例1胶乳 | 285.63 | |
实例1胶乳,无脲基丙烯酸甲酯 | 285.46 | |
BYK-348表面活性剂 | 1.10 | 1.10 |
Rhodoline 643消泡剂 | 1.50 | 1.50 |
Optifilm Enhancer 400聚结剂 | 11.67 | 11.67 |
氨水(28%,在水中) | 0.70 | 0.52 |
ACRYSOLTMRM-2020NPR增稠剂 | 9.00 | 9.00 |
ACRYSOLTMRM-8W增稠剂 | 0.70 | 0.70 |
水 | 0.30 | 0.48 |
总计 | 507.15 | 506.81 |
Claims (9)
1.一种方法,其包含通过多阶段乳液聚合的方式形成稳定的被以聚合物颗粒的重量计0.2到5重量百分比的磷类酸单体的结构单元以及0.05到10重量百分比的光引发剂单体的结构单元官能化的丙烯酸类聚合物颗粒的水性分散体,其所述磷类酸单体和所述光引发剂单体的结构单元通过磷类酸单体和光引发剂单体在同一阶段共聚而产生。
2.根据权利要求1所述的方法,其中所述多阶段乳液聚合是2-阶段反应,其中第一阶段单体包含所述光引发剂单体、所述磷类酸单体、甲基丙烯酸甲酯或苯乙烯或其组合、一种或多种选自由丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯组成的群组的丙烯酸酯、以及羧酸单体或其盐在第一阶段共聚;
其中甲基丙烯酸甲酯或苯乙烯或其组合、一种或多种选自由丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯组成的群组的丙烯酸酯、以及羧酸单体或其盐在第二阶段共聚;
其中所述第二阶段任选地包括所述光引发剂单体或所述磷类酸单体或者两者都包括,条件是所述第一阶段的光引发剂单体与所述第二阶段的光引发剂单体的比例大于2∶1,并且所述第一阶段的磷类酸单体与所述第二阶段的磷类酸单体的比例大于2∶1;
其中第一阶段单体与第二阶段单体的比例在20∶80到50∶50的范围内。
3.根据权利要求2所述的方法,其中0.1到5重量百分比的所述光引发剂单体、0.5到3重量百分比的所述磷类酸单体、40到50重量百分比的甲基丙烯酸甲酯、15到25重量百分比的丙烯酸丁酯、23到33重量百分比的丙烯酸2-乙基己酯、以及0.05到2重量百分比的甲基丙烯酸或其盐在所述第一阶段共聚,其中所有重量都以第一阶段单体的重量计;
其中40到50重量百分比的甲基丙烯酸甲酯、15到25重量百分比的丙烯酸丁酯、23到33重量百分比的丙烯酸2-乙基己酯、0.05到2重量百分比的甲基丙烯酸或其盐在所述第二阶段共聚,其中所有重量都以第二阶段单体的重量计;
其中0.2到5重量百分比的脲基丙烯酸甲酯在所述第一阶段或所述第二阶段共聚;
其中所述第二阶段单体任选地包括所述光引发剂单体或所述磷类酸单体或者两者都包括,条件是所述第一阶段中的光引发剂单体与所述第二阶段中的光引发剂单体的比例大于10∶1,并且所述第一阶段中的磷类酸单体与所述第二阶段中的磷类酸单体的比例大于10∶1。
4.根据权利要求3所述的方法,其中第一阶段单体与第二阶段单体的比例在25∶75到40∶60的范围内,所述第一阶段中的光引发剂单体与所述第二阶段中的光引发剂单体的比例大于100∶1,并且所述第一阶段中的磷类酸单体与所述第二阶段中的磷类酸单体的比例大于100∶1。
5.根据权利要求4所述的方法,其中所述第二阶段单体不包含光引发剂单体或磷类酸单体。
6.根据权利要求1所述的方法,其中所述多阶段乳液聚合是2-阶段反应,其中第一阶段单体包含甲基丙烯酸甲酯或苯乙烯或其组合、一种或多种选自由丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯组成的群组的丙烯酸酯、以及羧酸单体或其盐在第一阶段共聚;
其中所述光引发剂单体、所述磷类酸单体、甲基丙烯酸甲酯或苯乙烯或其组合、一种或多种选自由丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯组成的群组的丙烯酸酯、以及羧酸单体或其盐在第二阶段共聚;并且
其中所述第一阶段任选地包括所述光引发剂单体或所述磷类酸单体或者两者都包括,条件是所述第一阶段中的光引发剂单体与所述第二阶段中的光引发剂单体的比例大于2∶1,并且所述第一阶段中的磷类酸单体与所述第二阶段中的磷类酸单体的比例大于2∶1。
7.根据权利要求6所述的方法,其中40到50重量百分比的甲基丙烯酸甲酯、15到25重量百分比的丙烯酸丁酯、23到33重量百分比的丙烯酸2-乙基己酯、以及0.05到2重量百分比的甲基丙烯酸或其盐在所述第一阶段共聚,所有重量都以第一阶段单体的重量计;
其中,0.1到5重量百分比的所述光引发剂单体、0.5到3重量百分比的所述磷类酸单体、40到50重量百分比的甲基丙烯酸甲酯、15到25重量百分比的丙烯酸丁酯、23到33重量百分比的丙烯酸2-乙基己酯、0.05到2重量百分比的甲基丙烯酸或其盐、以及0.2到5重量百分比的脲基丙烯酸甲酯在所述第二阶段共聚,所有重量都以第二阶段单体的重量计;
其中所述第一阶段单体任选地包括所述光引发剂单体或所述磷类酸单体或者两者都包括,条件是所述第二阶段中的光引发剂单体与所述第一阶段中的光引发剂单体的比例大于10∶1,并且所述第二阶段中的磷类酸单体与所述第一阶段中的磷类酸单体的比例大于10∶1;
其中0.2到5重量百分比的脲基丙烯酸甲酯在所述第一阶段或所述第二阶段共聚;并且
其中第二阶段单体与第一阶段单体的比例在20∶80到50∶50的范围内。
8.根据权利要求7所述的方法,其中第一阶段单体与第二阶段单体的比例在25∶75到40∶60的范围内,所述第一阶段中的光引发剂单体与所述第二阶段中的光引发剂单体的比例大于100∶1,并且所述第一阶段中的磷类酸单体与所述第二阶段中的磷类酸单体的比例大于100∶1。
9.根据权利要求7所述的方法,其中所述第一阶段单体不包含光引发剂单体或磷类酸单体。
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US11479619B2 (en) * | 2017-11-10 | 2022-10-25 | Basf Se | Aqueous polymer dispersions |
AU2019204492B2 (en) | 2018-07-19 | 2023-04-20 | Rohm And Haas Company | Aqueous dispersion of multistage polymer particles |
CN109054487A (zh) * | 2018-07-19 | 2018-12-21 | 大美泰康(天津)生态科技有限公司 | 二氧化钛粉体以及包含其的室内空气净化型多功能无机生态涂料 |
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