CN106167628A - 用于制备经聚合物包封的TiO2颗粒的方法 - Google Patents
用于制备经聚合物包封的TiO2颗粒的方法 Download PDFInfo
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- CN106167628A CN106167628A CN201610292910.0A CN201610292910A CN106167628A CN 106167628 A CN106167628 A CN 106167628A CN 201610292910 A CN201610292910 A CN 201610292910A CN 106167628 A CN106167628 A CN 106167628A
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- tio
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- 239000008187 granular material Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 93
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
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- 239000000203 mixture Substances 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000001117 sulphuric acid Substances 0.000 claims description 16
- 235000011149 sulphuric acid Nutrition 0.000 claims description 16
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- 150000003839 salts Chemical class 0.000 claims description 14
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- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 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 4
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 3
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- 239000000454 talc Substances 0.000 description 3
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- PBUQZKXKYSAJDO-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxycarbonyl]benzoic acid Chemical compound CC(C)(C)OC(=O)C1=CC=CC=C1C(O)=O PBUQZKXKYSAJDO-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- GQTFHSAAODFMHB-UHFFFAOYSA-N 2-prop-2-enoyloxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOC(=O)C=C GQTFHSAAODFMHB-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 1
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
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- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
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- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
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- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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Abstract
本发明涉及一种用于制备经聚合物包封的TiO2颗粒的水分散体的方法，其包含多阶段聚合步骤，所述步骤包括相对大量的低Tg第一单体和相对少量的高Tg第二单体，所述第二单体包含相对高含量的酸单体。经包封TiO2颗粒的所述分散液相比于不包括用本文所述的第二单体分级的现有技术方法示出了显著改进的冻融稳定性。
Description
背景技术
本发明涉及一种用于制备经聚合物包封的TiO2颗粒的水分散体(TiO2复合材料)的方法，其可用于塑料和涂料配制物中。
遮光颜料(如TiO2)提供用于涂料以及用于塑料的不透明性(遮盖力)以隐藏下表面。据信颜料的功效与在涂料或塑料中的颜料粒子的间距有关。间距的改进可(例如)通过使用硫酸官能的聚合物作为用于与至少部分包封颜料的其它聚合物组合的颜料的分散剂来实现，如公开于美国专利公开20100/298483中。功效的改进(通过其可制备这些TiO2复合材料)公开于美国专利公开2014/0011943中。尽管如此，对这些复合材料的持续关注点为冻融稳定性的减弱。因此希望寻找一种制备具有改进的冻融稳定性的TiO2复合物的方式。
发明内容
本发明通过提供用于制备经聚合物包封的TiO2颗粒的水分散体的方法解决在本领域中的需要，所述方法包含以下步骤：
a)形成以下各项的混合物：i)TiO2颗粒和硫酸官能化聚合物或其盐的水分散体；ii)阴离子表面活性剂；以及iii)氧化还原引发剂系统；然后
b)在一个或两个阶段中使混合物与第一单体接触，所述第一单体包含i)甲基丙烯酸甲酯、苯乙烯或乙烯基酯或其组合以及；ii)丙烯酸丁酯、丙烯酸乙酯、丙烯酸2-乙基己酯或丙烯酸2-丙基庚酯或其组合；然后
c)在一个阶段或两个依序阶段中聚合第一单体以形成包封TiO2颗粒的第一共聚物的水分散体；然后
d)将第二单体添加到步骤c)的水分散体，所述第二单体包含i)以第一单体和第二单体的重量计，0.01至5重量％的羧酸单体；以及ii)以第二单体的重量计，50至99.5重量％的甲基丙烯酸甲酯或苯乙烯或其组合；
e)聚合第二单体以形成包封TiO2颗粒的共聚物的水分散体；
其中第一聚合物的计算的Tg在-30℃至30℃的范围内；
其中第二聚合物的计算的Tg在50℃至120℃的范围内；以及
以第一单体和第二单体的重量计，第二单体的含量为0.2至20重量％。
本发明的方法形成在涂料应用中具有改进的冻融稳定性的TiO2复合材料。
具体实施方式
本发明通过提供用于制备经聚合物包封的TiO2颗粒的水分散体的方法解决在本领域中的需要，所述方法包含以下步骤：
a)形成以下各项的混合物：i)TiO2颗粒和硫酸官能化聚合物或其盐的水分散体；ii)阴离子表面活性剂；以及iii)氧化还原引发剂系统；然后
b)在一个或两个阶段中使混合物与第一单体接触，所述第一单体包含i)甲基丙烯酸甲酯、苯乙烯或乙烯基酯或其组合以及；ii)丙烯酸丁酯、丙烯酸乙酯、丙烯酸2-乙基己酯或丙烯酸2-丙基庚酯或其组合；然后
c)在一个阶段或两个依序阶段中聚合第一单体以形成包封TiO2颗粒的第一共聚物的水分散体；然后
d)将第二单体添加到步骤c)的水分散体，所述第二单体包含i)以第一单体和第二单体的重量计，0.01至5重量％的羧酸单体；以及ii)以第二单体的重量计，50至99.5重量％的甲基丙烯酸甲酯或苯乙烯或其组合；
e)聚合第二单体以形成包封TiO2颗粒的共聚物的水分散体；其中
第一聚合物的计算的Tg在-30℃至30℃的范围内；
第二聚合物的计算的Tg在50℃至120℃的范围内；以及
以第一单体和第二单体的重量计，第二单体的含量为0.2至20重量％。
在本发明的方法的第一步中，将TiO2颗粒和硫酸官能化聚合物或其盐的水分散体与阴离子表面活性剂和氧化还原引发剂系统混合。硫酸官能化聚合物或其盐通过硫酸单体或其盐的聚合或与一种或多种其它单体共聚(优选与丙烯酸酯或甲基丙烯酸酯单体共聚)制备。合适的硫酸单体的实例包括丙烯酸磺乙基酯、甲基丙烯酸磺乙基酯、丙烯酸磺丙基酯、甲基丙烯酸磺丙基酯、苯乙烯磺酸、乙烯基磺酸、2-丙烯酰胺基-2-甲基丙磺酸以及2-甲基丙烯酰胺基-2-甲基丙磺酸及其盐，其中2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和甲基丙烯酸磺乙基酯是优选的。
硫酸官能化聚合物或其盐可进一步包含由硫酸单体或其盐与胺单体的共聚产生的胺基，其中的实例包括甲基丙烯酸二甲氨基乙基酯、丙烯酸二甲氨基乙基酯、二甲氨基丙基甲基丙烯酰胺、二甲氨基丙基丙烯酰胺、甲基丙烯酸叔丁基氨基乙基酯以及丙烯酸叔丁基氨基乙基酯。硫酸官能化聚合物或其盐还可包含由硫酸单体或其盐与一种或多种水可溶单体(如丙烯酸羟基乙基酯、甲基丙烯酸羟基乙基酯、丙烯酰胺、甲基丙烯酰胺、丙烯酸或甲基丙烯酸或其组合)共聚产生的官能团。
在一个优选实施例中，硫酸官能化聚合物或其盐包含丙烯酸酯或甲基丙烯酸酯基团或这两者，胺官能团以及由水可溶单体产生的官能团。甲基丙烯酸二甲氨基乙基酯(DMAEMA)为优选的胺单体。
TiO2和硫酸官能化聚合物或其盐的分散体有利地通过将TiO2的水分散体缓慢添加(其中伴随研磨)到聚合物的水分散体来制备。以TiO2、聚合物和水的重量计，TiO2/两性聚合物分散体的优选的固体含量在70至80重量％的范围内。
将TiO2/聚合物分散体添加到容器并且与a)阴离子表面活性剂(优选与水混合)接触。合适的阴离子表面活性剂的实例包括C4-C20烷基苯磺酸盐(如十二烷基苯磺酸盐)、聚氧化乙烯C8-C20醚磷酸酯(如十三烷基醚磷酸酯)以及碱金属C10-C20α-烯烃磺酸盐(如C14-C16α-烯烃磺酸盐)。
TiO2/聚合物分散体还可与苯乙烯磺酸钠，优选苯乙烯磺酸钠的溶液，更优选如以水和苯乙烯磺酸钠的重量计，5至20重量％的溶液接触。然后氧化还原引发剂系统与此混合物接触以引发聚合。如本文所用，术语“氧化还原引发剂系统”是指还原剂、氧化剂和金属离子催化剂的组合。合适的氧化剂的实例包括过硫酸盐(如铵和碱金属过硫酸盐)；氢过氧化物(如叔丁基氢过氧化物和异丙苯氢过氧化物)；过氧化物(如过氧化苯甲酰、过氧化辛酰以及二-叔丁基过氧化物)；过酸酯(如过乙酸叔丁酯、过邻苯二甲酸叔丁酯以及过苯甲酸叔丁酯)；过碳酸盐；以及过磷酸盐；其中叔丁基氢过氧化物是优选的。
合适的还原剂的实例包括抗坏血酸、异抗坏血酸、苹果酸、乙醇酸、草酸、乳酸和硫代乙醇酸；碱金属次硫酸盐(例如次硫酸钠)；硫代硫酸盐(例如硫代硫酸钾)；或偏亚硫酸氢盐(例如偏亚硫酸氢钾)；和甲醛合次硫酸氢钠。
合适的金属离子催化剂包括以少量使用的钴、铁、镍和铜的卤化物、硫酸盐以及硝酸盐。优选的氧化还原引发剂系统的实例为叔丁基氢过氧化物/异抗坏血酸/Fe+2。优选地，在添加氧化剂和还原剂之前添加金属离子催化剂。进一步优选地，随时间推移添加氧化剂和还原剂，以在单体添加过程期间维持相对均等水平的自由基通量。
优选地，在氧化还原引发剂系统的还原剂和氧化剂与第一单体的添加开始之间的等待时间段的范围为30秒至约10分钟，更优选地为1分钟至5分钟。
在添加氧化还原引发剂之后的步骤中，第一单体与表面活性剂(优选十二烷基苯磺酸钠或十二烷基烯丙基磺基琥珀酸酯)一起作为水分散体有利地添加。第一单体优选甲基丙烯酸甲酯和丙烯酸丁酯或丙烯酸2-乙基己酯或其组合的组合。优选地，在第一步中制备的共聚物的Tg(如通过福克斯方程式(Fox equation)计算)为-5℃至20℃。
在单个阶段中或在两个阶段中，第一单体与TiO2颗粒、硫酸官能化聚合物或其盐的水分散体，阴离子表面活性剂以及氧化还原引发剂系统的混合物接触。当经两个阶段进行单体添加和聚合时，第一阶段第一单体的组合物(所选的浓度以及特定单体)可与第二阶段第一单体的组合物相同或不同。优选地，单体组合物是不同的。
第一单体可包括一种或多种附加单体，如其中包括丙烯酸、甲基丙烯酸和2-亚甲基丁二酸的羧酸单体实例；多烯键系不饱和单体(包括二乙烯基苯和甲基丙烯酸烯丙基酯)；以及硫酸单体(如苯乙烯磺酸钠和AMPS)。
在本发明方法的优选实施例中，将包含50至65重量％的丙烯酸丁酯、35至45重量％的甲基丙烯酸甲酯和0.2至2重量％的甲基丙烯酸的第一阶段第一单体混合物共聚以形成第一阶段第一聚合物。然后将包含35至45重量％的苯乙烯、55至65重量％的丙烯酸丁酯、0.2至2重量％的甲基丙烯酸或丙烯酸和0.1至1重量％的苯乙烯磺酸钠的第二阶段第一单体混合物共聚以形成包封TiO2颗粒的第一共聚物的水分散体。
当第一单体在两个依序阶段中共聚时，在第二阶段中的单体与在第一阶段中的单体的重量：重量比优选从1∶1，更优选从2∶1，最优选从3∶1，至10∶1，更优选至8∶1，最优选至6∶1。
在后续步骤中，将包含羧酸单体和50至95重量％的甲基丙烯酸甲酯或苯乙烯或乙烯基酯或其组合的第二单体添加到第一共聚物包封的TiO2颗粒的水溶液。优选地，以第二单体的重量计，第二单体包含从0.5重量％，更优选地从1重量％并且最优选从2重量％的羧酸单体至20重量％，更优选地至15重量％并且最优选至10重量％的羧酸单体。优选地，以第一单体和第二单体的重量计，第二单体包含从0.05重量％，更优选从0.2重量％并且更优选从1重量％的羧酸单体至3重量％，更优选至2重量％的羧酸单体。
优选地，第二单体包含从60重量％，更优选从70重量％，至95重量％，更优选至90重量％的甲基丙烯酸甲酯或苯乙烯或其组合。第二单体可进一步包含其它单体(例如)高达40重量％，优选高达20重量％的丙烯酸丁酯、丙烯酸2-乙基己酯或丙烯酸2-丙基庚酯或其组合。
优选地，以第一单体和第二单体的重量计，第二单体的含量为从0.5重量％，更优选从1重量％至优选15重量％，更优选地至10重量％。
然后聚合第二单体以形成包封TiO2颗粒的共聚物的水分散体。这些共聚物是多相的，其中第一单体形成成膜相并且第二单体形成硬、非成膜相。
本发明的复合材料可用于涂料配制物中并且可与其它材料(如分散剂、消泡剂、表面活性剂、溶剂、附加粘合剂、增稠剂、扩链剂、聚结剂、杀生物剂以及着色剂)掺混。已出人意料地发现，相对少量的第二单体与相对高含量的羧酸单体的添加和共聚相比于在此最终阶段中无酸单体的情况下制备的复合材料产生具有优越冻融稳定性的TiO2复合材料。实际上，已发现当将酸单体用于第一单体的聚合时，后续涂料调配物的冻融稳定性的改进基本上较小。
实例
在以下实例中，TiO2聚合物复合材料浆液基本上如美国专利公开20100/298483，第7页，第0053段中所公开的制备。
比较实例1-无第三阶段制备经聚合物包封的TiO2
单体乳液1(ME1)通过将水(11.25g)、Polystep A-16-22阴离子表面活性剂(2.183g)、丙烯酸丁酯(BA，30.375g)、甲基丙烯酸(MAA，0.502g)以及甲基丙烯酸甲酯(MMA，19.33g)混合来制备。
单体乳液2(ME2)通过将水(56.25g)、Polystep A-16-22阴离子表面活性剂(15.094g)、苯乙烯(Sty，104.152g)、MAA(2.671g)、BA(158.898g)以及苯乙烯磺酸钠(1.335g)混合来制备。
向配备有机械浆式搅拌器、热电偶、氮气入口以及回流冷凝器的4颈2-L圆底烧瓶中添加TiO2聚合物复合材料浆液(365.83g)和水(38g)。在N2下将混合物加热至30℃；向烧瓶中连续添加Polystep A-16-22阴离子表面活性剂(2.7g在21g水中)的预混合水溶液、苯乙烯磺酸钠(2.138g在20g水中)的预混合水溶液、叔丁基过氧化氢(0.428g在5g水中)的水溶液、异抗坏血酸(0.238g在5g水中)的水溶液、七水硫酸铁(10.688g，0.15％铁)的水溶液以及乙二胺四乙酸(EDTA，0.27g，1％)水溶液的混合物。将共进料催化剂(含4.27g叔丁基过氧化氢的50g水)和共进料活化剂(含2.363g异抗坏血酸酸的50g水)以0.4g/min的速率进料至烧瓶。在3分钟后，以3.22g/min的速率将ME1进料至反应器，并且使烧瓶温度放热至50℃。在完成ME1添加后，将单体乳液容器用5g去离子水冲洗，所述去离子水添加到烧瓶。共进料催化剂和活化剂持续进料3min，然后停止，并且将烧瓶保持在50℃下。在18分钟后，以0.4g/min的速率恢复添加共进料催化剂和活化剂；在恢复后2分钟，以3.7g/min的速率将ME2进料至反应器，其中将烧瓶温度控制在68℃下。在完成ME2添加后，将单体乳液容器用5g去离子水冲洗，所述去离子水添加到烧瓶。持续进料共进料催化剂和活化剂直至完成。在所有进料完成之后，将烧瓶冷却到室温。当烧瓶温度达到45℃时，将ACRYSOLTM ASE-60(4.838g在9g水中)的水溶液以0.5g/min的速率添加到烧瓶，接着以0.84g/min的速率添加29％水性氢氧化铵(3.6g)和水(9g)的溶液。在烧瓶冷却到室温之后，过滤内含物以去除任何凝胶。发现经过滤的分散体的固体含量为57.4％，其中pH为9。
实例1-制备具有高Tg第三阶段含酸单体的包封TiO2的聚合物
ME1通过将水(11.25g)、Polystep A-16-22阴离子表面活性剂(2.25g)、丙烯酸丁酯(30.825g)、甲基丙烯酸(0.54g)以及甲基丙烯酸甲酯(19.688g)混合来制备。
ME2通过将水(56.25g)、Polystep A-16-22阴离子表面活性剂(15.075g)、苯乙烯(104.152g)、甲基丙烯酸(2.475g)、丙烯酸丁酯(153.225g)以及苯乙烯磺酸钠(11.294g)混合来制备。
单体乳液3(ME3)通过将水(2.5g)、甲基丙烯酸甲酯(6.563g)、甲基丙烯酸(0.938g)以及丙烯酸丁酯(1.875g)混合来制备。
向配备有机械浆式搅拌器、热电偶、氮气入口以及回流冷凝器的4颈2-L圆底烧瓶中添加TiO2聚合物复合材料浆液(365.83g)和水(38g)。在N2下将混合物加热至30℃；向烧瓶连续添加Polystep A-16-22阴离子表面活性剂(2.7g在21g水中)的预混合水溶液，苯乙烯磺酸钠(2.138g在20g水中)的预混合水溶液，叔丁基过氧化氢(0.428g在5g水中)的水溶液，异抗坏血酸(0.238g在5g水中)的水溶液，七水硫酸铁(10.688g，0.15％铁)的水溶液以及乙二胺四乙酸(EDTA，0.27g，1％)水溶液的混合物。将共进料催化剂(4.27g叔丁基过氧化氢在50g水中)和共进料活化剂(2.363g异抗坏血酸酸在50g水中)以0.4g/min的速率进料至烧瓶。在3分钟后，以3.22g/min的速率将ME1进料至反应器，并且使烧瓶温度放热至50℃。在完成ME添加后，将单体乳液容器用5g去离子水冲洗，所述去离子水添加到烧瓶。共进料催化剂和活化剂持续进料3min，然后停止，并且将烧瓶保持在50℃下。在18分钟后，以0.4g/min的速率恢复进料共进料催化剂和活化剂；在恢复2分钟后，以3.7g/min的速率将ME2进料至反应器，其中将烧瓶温度控制在68℃下。在完成ME2添加后，将单体乳液容器用5g去离子水冲洗，所述去离子水添加到烧瓶。
在冲洗后，停止共进料添加，于是将ME3添加到烧瓶，接着添加叔丁基过氧化氢(0.1g在1.25g水中)的水溶液以及异抗坏血酸酸(0.075g在1.25g水中)的水溶液。恢复添加共进料并且持续到完成。在所有进料完成之后，烧瓶冷却到室温。当烧瓶温度达到45℃时，将ACRYSOLTMASE-60(4.838g在9g水中)以0.5g/min的速率添加到烧瓶，接着以0.84g/min的速率添加29％水性氢氧化铵(3.6g)和水(9g)的溶液。在烧瓶冷却到室温之后，过滤内含物以去除任何凝胶。发现经过滤的分散体的固体含量为58％，其中pH为9。
实例2至6基本上如实例1所描述的制备，不同之处在于ME3的不同，如总单体(ME1+ME2+ME3)的百分比以及ME3单体概况。
ME3的组份如下：
实例1至实例3-20BA、70MMA、10MAA；
实例4-90MMA、10MAA
实例5-17BA、80MMA以及3MAA
实例6-20BA、70Sty以及10MAA；
表1示出由实例制备的涂料的调配物。在此表中，NaPP是指Calgon 322新型多磷酸钠；消泡剂是指Foamaster NXZ消泡剂；分散剂是指TAMOLTM945分散剂；QP 30000是指CELLOSIZETM QP 30000HEC；滑石是指Mistron 353滑石；CaCO3是指Omyacarb 2CaCO3；AMP-95是指AMPTM-95胺；消泡剂是指Byk-022消泡剂；CF-10是指TRITONTM CF-10表面活性剂；复合材料是指聚合物/TiO2复合材料；CM-219EF是指PRIMALTM CM-219EF(50％)共聚物分散体；OP是指ROPAQUETM Ultra E不透明聚合物；RM-2020是指ACRYSOLTM RM-2020流变改质剂。(TAMOL、CELLOSIZE、AMP、TRITON、PRIMAL、ROPAQUE和ACRYSOL均是陶氏化学公司(The DowChemical Company)或其附属公司的商标。)
表1-具有包封TiO2的聚合物的涂料调配物
| 成分(％) | C1 | 1 | 2 | 3 | 4 | 5 | 6 |
| 水 | 5.65％ | 5.65％ | 5.65％ | 5.65％ | 5.65％ | 5.65％ | 5.65％ |
| NaPP | 0.03％ | 0.03％ | 0.03％ | 0.03％ | 0.03％ | 0.03％ | 0.03％ |
| 消泡剂 | 0.16％ | 0.16％ | 0.16％ | 0.16％ | 0.16％ | 0.16％ | 0.16％ |
| 分散剂 | 0.14％ | 0.14％ | 0.14％ | 0.14％ | 0.14％ | 0.14％ | 0.14％ |
| 丙二醇 | 4.00％ | 4.00％ | 4.00％ | 4.00％ | 4.00％ | 4.00％ | 4.00％ |
| QP 30000 | 0.21％ | 0.21％ | 0.21％ | 0.21％ | 0.21％ | 0.21％ | 0.21％ |
| 滑石 | 6.36％ | 6.36％ | 6.36％ | 6.36％ | 6.36％ | 6.36％ | 6.36％ |
| Omyacarb 2 | 5.30％ | 5.30％ | 5.30％ | 5.30％ | 5.30％ | 5.30％ | 5.30％ |
| AMP-95 | 0.05％ | 0.05％ | 0.05％ | 0.05％ | 0.05％ | 0.05％ | 0.05％ |
| 消泡剂 | 0.11％ | 0.11％ | 0.11％ | 0.11％ | 0.11％ | 0.11％ | 0.11％ |
| CF-10 | 0.19％ | 0.19％ | 0.19％ | 0.19％ | 0.19％ | 0.19％ | 0.19％ |
| 研磨剂小计 | 22.19％ | 22.19％ | 22.19％ | 22.19％ | 22.19％ | 22.19％ | 22.19％ |
| 复合材料 | 62.08％ | 61.43％ | 61.91％ | 61.75％ | 61.30％ | 62.75％ | 61.65％ |
| CM-219EF | 3.25％ | 3.26％ | 2.85％ | 3.08％ | 3.26％ | 3.23％ | 3.24％ |
| 不透明聚合物 | 9.62％ | 9.62％ | 9.62％ | 9.62％ | 9.62％ | 9.62％ | 9.62％ |
| 丁基卡必醇 | 1.22％ | 1.22％ | 1.22％ | 1.22％ | 1.22％ | 1.22％ | 1.22％ |
| RM-2020 | 0.30％ | 0.30％ | 0.30％ | 0.30％ | 0.30％ | 0.30％ | 0.30％ |
| AMP-95 | 0.09％ | 0.09％ | 0.09％ | 0.09％ | 0.09％ | 0.09％ | 0.09％ |
| 水 | 1.24％ | 1.88％ | 1.82％ | 1.75％ | 2.02％ | 0.60％ | 1.69％ |
| 总计 | 100％ | 100％ | 100％ | 100％ | 100％ | 100％ | 100％ |
表2示出了使用包封TiO2样品的聚合物制备的涂料的冻融稳定性。在-15℃下进行冻融研究18h，随后至少4h融化。ME3％是指用于制备包封聚合物的总单体的ME3的重量百分比；KUo是指初始KU(以克雷布斯(Krebs)单位为单位)；KU1d是指在1天后的KU；KUFT1是指在第一冻融周期后的KU；KUFT2是指在第二冻融周期后的KU；并且KUFT3是指在第三冻融周期后的KU。将所有样品的pH调节至8.8至8.9之间。
表2-包封TiO2样品的聚合物的冻融稳定性
出人意料地发现，与在无此第三阶段的情况下制备包封聚合物相比，在相对少量的高TgME3中的相对大量的酸单体经三个循环产生优异的冻融稳定性。进一步发现，在无此第三阶段的情况下，需要在第二阶段中添加显著较高浓度的酸单体以产生可接受的冻融稳定性。
Claims (8)
1.一种用于制备经聚合物包封的TiO2颗粒的水分散体的方法，其包含以下步骤：
a)形成以下各项的混合物：i)TiO2颗粒和硫酸官能化聚合物或其盐的水分散体；ii)阴离子表面活性剂；以及iii)氧化还原引发剂系统；然后
b)在一个或两个阶段中使所述混合物与第一单体接触，所述第一单体包含i)甲基丙烯酸甲酯、苯乙烯或乙烯基酯或其组合以及；ii)丙烯酸丁酯、丙烯酸乙酯、丙烯酸2-乙基己酯或丙烯酸2-丙基庚酯或其组合；然后
c)在一个阶段或两个依序阶段中聚合所述第一单体以形成包封所述TiO2颗粒的第一共聚物的水分散体；然后
d)将第二单体添加到步骤c)的所述水分散体，所述第二单体包含i)以第一单体和第二单体的重量计，0.01至5重量％的羧酸单体；以及ii)以所述第二单体的重量计，50至99.5重量％的甲基丙烯酸甲酯或苯乙烯或其组合；
e)聚合所述第二单体以形成包封所述TiO2颗粒的共聚物的水分散体；其中
所述第一聚合物的计算的Tg在-30℃至30℃的范围内；
所述第二聚合物的计算的Tg在50℃至120℃的范围内；以及
以所述第一单体和所述第二单体的重量计，所述第二单体的含量为0.2至20重量％。
2.根据权利要求1所述的方法，其中在步骤b)中，在两个阶段中所述混合物与第一阶段第一单体和第二阶段第一单体接触。
3.根据权利要求2所述的方法，其中所述第一阶段第一单体包含丙烯酸丁酯和甲基丙烯酸甲酯，并且所述第二阶段第一单体包含丙烯酸丁酯和苯乙烯。
4.根据权利要求2所述的方法，其中所述第一阶段第一单体包含50至65重量％的丙烯酸丁酯、35至45重量％的甲基丙烯酸甲酯和0.2至2重量％的甲基丙烯酸；并且所述第二阶段第一单体包含35至45重量％的苯乙烯、55至65重量％的丙烯酸丁酯、0.2至2重量％的甲基丙烯酸或丙烯酸，和0.1至1重量％的苯乙烯磺酸钠，其中所述第一聚合物的所述计算的Tg为-5℃至20℃。
5.根据权利要求4所述的方法，其中以所述第二单体的重量计，所述第二单体包含0.5至20重量％的所述羧酸单体；并且其中以所述第一单体和所述第二单体的重量计，所述第二单体的含量为0.5至15重量％。
6.根据权利要求5所述的方法，其中以所述第二单体的重量计，所述第二单体包含：i)1至15重量％的所述羧酸单体；以及ii)；60至95重量％的甲基丙烯酸甲酯或苯乙烯或其组合；并且其中以所述第一单体和所述第二单体的重量计，所述第二单体的含量为2至10重量％。
7.根据权利要求2到6中任一权利要求所述的方法，其中第二阶段第一单体与第一阶段第一单体的重量：重量比为1∶1至10∶1。
8.根据权利要求1所述的方法，其中在步骤b)中，在一个阶段中所述混合物与包含甲基丙烯酸甲酯或苯乙烯或其组合；以及丙烯酸丁酯的第一单体接触。
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| CN111793330A (zh) * | 2020-08-12 | 2020-10-20 | 汕头市邦腾科技有限公司 | 一种遮光性改性塑料及其制备方法和应用 |
| CN112292423A (zh) * | 2018-07-10 | 2021-01-29 | 陶氏环球技术有限责任公司 | 多阶段聚合物颗粒的水性分散体和其制备方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891971A (zh) * | 2009-05-19 | 2010-11-24 | 罗门哈斯公司 | 不透明颜料颗粒 |
| CN103391975A (zh) * | 2011-02-23 | 2013-11-13 | 罗门哈斯公司 | 聚合物包封的二氧化钛颗粒 |
| CN103582682A (zh) * | 2011-06-03 | 2014-02-12 | 罗门哈斯公司 | 水性涂料组合物 |
| CN103965392A (zh) * | 2013-02-04 | 2014-08-06 | 罗门哈斯公司 | 丙烯酸类胶乳粘合剂及其制备方法 |
| CA2869161A1 (en) * | 2013-11-15 | 2015-05-15 | Rohm And Haas Company | Freeze-thaw stable paint formulation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101891971A (zh) * | 2009-05-19 | 2010-11-24 | 罗门哈斯公司 | 不透明颜料颗粒 |
| CN103391975A (zh) * | 2011-02-23 | 2013-11-13 | 罗门哈斯公司 | 聚合物包封的二氧化钛颗粒 |
| CN103582682A (zh) * | 2011-06-03 | 2014-02-12 | 罗门哈斯公司 | 水性涂料组合物 |
| CN103965392A (zh) * | 2013-02-04 | 2014-08-06 | 罗门哈斯公司 | 丙烯酸类胶乳粘合剂及其制备方法 |
| CA2869161A1 (en) * | 2013-11-15 | 2015-05-15 | Rohm And Haas Company | Freeze-thaw stable paint formulation |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112292423A (zh) * | 2018-07-10 | 2021-01-29 | 陶氏环球技术有限责任公司 | 多阶段聚合物颗粒的水性分散体和其制备方法 |
| CN112292423B (zh) * | 2018-07-10 | 2022-11-04 | 陶氏环球技术有限责任公司 | 多阶段聚合物颗粒的水性分散体和其制备方法 |
| CN111793330A (zh) * | 2020-08-12 | 2020-10-20 | 汕头市邦腾科技有限公司 | 一种遮光性改性塑料及其制备方法和应用 |
| CN111793330B (zh) * | 2020-08-12 | 2023-01-31 | 疆合材料科技（苏州）有限公司 | 一种遮光性改性塑料及其制备方法和应用 |
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| CA2929412A1 (en) | 2016-11-19 |
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