CN101384646A - 制造阳离子稳定化且水可再分散的聚合物粉末组合物的方法 - Google Patents
制造阳离子稳定化且水可再分散的聚合物粉末组合物的方法 Download PDFInfo
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- CN101384646A CN101384646A CNA2007800054368A CN200780005436A CN101384646A CN 101384646 A CN101384646 A CN 101384646A CN A2007800054368 A CNA2007800054368 A CN A2007800054368A CN 200780005436 A CN200780005436 A CN 200780005436A CN 101384646 A CN101384646 A CN 101384646A
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- 150000005690 diesters Chemical class 0.000 description 1
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- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 1
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
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- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
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- 108090000623 proteins and genes Proteins 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
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- CAAIULQYGCAMCD-UHFFFAOYSA-L zinc;hydroxymethanesulfinate Chemical compound [Zn+2].OCS([O-])=O.OCS([O-])=O CAAIULQYGCAMCD-UHFFFAOYSA-L 0.000 description 1
Classifications
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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
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
- C08F226/04—Diallylamine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/006—Removal of residual monomers by chemical reaction, e.g. scavenging
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
- C04B2111/00517—Coating or impregnation materials for masonry
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
- C04B2111/00672—Pointing or jointing materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/60—Flooring materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/60—Flooring materials
- C04B2111/62—Self-levelling compositions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
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Abstract
本发明涉及制造阳离子稳定化且水可再分散的聚合物粉末组合物的方法,其中在任选存在非离子保护胶体和/或非离子乳化剂的情况下,使一种或多种烯键式不饱和单体在水性介质中进行自由基聚合,随后实施干燥,其特征在于,在存在阳离子保护胶体作为干燥助剂的情况下对所获得的含水聚合物分散体实施干燥。
Description
技术领域
本发明涉及制造阳离子稳定化且水可再分散的聚合物粉末组合物的方法,其中在任选存在非离子保护胶体和/或非离子乳化剂的情况下,一种或多种烯键式不饱和单体在水性介质中进行自由基聚合,随后实施干燥。
背景技术
含水聚合物分散体的稳定化可以通过分散剂实现,所述分散剂具有使分散体在界面处具有活性的性能。保护胶体或乳化剂形式的水溶性化合物具有该功能。在此,可以通过例如非离子聚合物和乳化剂之间的空间相互作用,或者通过聚合物或乳化剂中的阴离子或阳离子官能团之间发生的静电相互作用,或者通过它们适当的组合实现稳定化。
在制造单体基(monomer base)为乙烯基酯、氯乙烯、(甲基)丙烯酸酯单体、苯乙烯、丁二烯和/或乙烯的可再分散的分散体粉末时,在聚合及干燥期间优选使用聚乙烯醇作为保护胶体,因为聚乙烯醇使粉末对颗粒的先期聚结具有有效的稳定性,所述可再分散的分散体粉末用于许多应用,例如用作各种不同基底的涂料组合物或粘合剂组合物。但是如果在最终应用中使用较大量的分散体粉末,则聚乙烯醇含量可能具有负面作用。例如,由于高的粘合性和高的粘度,对基于水泥或石膏的聚合物改性的水固性砂浆组合物的可加工性具有负面影响。高的聚乙烯醇含量还导致用所述砂浆组合物制得的粘合剂的柔韧性低。
替代聚乙烯醇用作干燥助剂的可能的选择是三聚氰胺磺酸的甲醛缩合物(DE-A 2049114)、萘磺酸的甲醛缩合物(DE-A 2445813)、酚磺酸的甲醛缩合物(EP-A 407889)、或者二羟基联苯基磺酸的脂族醛缩合物(WO-A2005/080478)。此外,还使用木素磺酸盐(EP-A 149098)或用阴离子基团官能化的聚电解质(EP-A 073807、EP-A 982351)。这些选择的缺点是,干燥助剂的使用量大,而为了得到耐结块且可快速再分散的粉末,该量是需要的。此外,在某些应用中由磺酸甲醛缩合物或木素磺酸盐产生砂浆组合物的棕色变色是非期望的。
现有技术中已述及阳离子稳定化的分散体粉末:WO-A 00/05275公开了一种方法,其中阳离子单体在水性介质中进行聚合,并在原位形成所得聚合物存在的情况下聚合其它单体。然后对如此获得的聚合物分散体在存在聚乙烯醇的情况下进行喷雾干燥。WO-A 00/05283描述了一种与此相似的方法,其中控制该方法,使得形成具有异质形态的共聚物颗粒。但该方法的缺点是,为了通过喷雾干燥初始得到的聚合物分散体来制造分散体粉末,需要大量聚乙烯醇作为喷雾干燥保护胶体,结果出现上述大量使用粉末时的缺点。
EP-A 0770640描述了一种制造可再分散的聚合物粉末的方法,其中对含水聚合物分散体实施干燥,所述分散体的分散聚合物颗粒具有负电表面电荷或正电表面电荷,所选择的干燥助剂包含表面电荷与所述分散聚合物颗粒相反的聚离子。该方法的缺点是,在喷雾干燥过程之前混合分散体与保护胶体的过程中可能发生聚合物颗粒部分凝结,因此所获得的粉末可能具有较差的可再分散性。
WO-A 98/13411描述了可再分散的分散体粉末的制造,所述分散体粉末是通过用两性聚合物,优选酪蛋白或酪蛋白酸钠,对含有阴离子基团,优选COOH基的乳液聚合物实施喷雾干燥而获得的。在喷雾干燥过程中保护胶体的使用量为2-10重量%,但是直到达到10重量%才获得完全不粘且可流动的粉末。酪蛋白作为保护胶体的缺点是其天然来源以及与此相关的不定的产品质量,这可能使粉末的品质不稳定。此外,像所有蛋白质一样,酪蛋白在碱性条件下释放氨,这导致VOC(挥发性有机化合物)污染。
发明内容
在此背景下,本发明的目的在于开发一种分散体粉末,其利用了聚乙烯醇本身作为粘合剂的优点,但在使用较大量的该分散体粉末时,降低了可加工性方面的缺点并使水固性组合物中的柔韧性提高。
本发明涉及制造阳离子稳定化且水可再分散的聚合物粉末组合物的方法,其中在任选存在非离子保护胶体和/或非离子乳化剂的情况下,将一种或多种烯键式不饱和单体在水性介质中进行自由基聚合,随后实施干燥,其特征在于,在存在阳离子保护胶体作为干燥助剂的情况下对所得含水聚合物分散体实施干燥。
合适的阳离子保护胶体是具有阳离子电荷的聚合物。这些聚合物的实例在E.W.Flick,Water-Soluble Resins-an Industrial Guide,NoyesPublications,Park Ridge,N.J.,1991中有描述。优选包含阳离子单体单元的聚合物,特别优选具有季铵基、锍基及鎓基的单体单元。最优选一种或多种选自以下组中的阳离子单体的均聚物或共聚物:二烯丙基二甲基氯化铵(DADMAC)、二烯丙基二乙基氯化铵(DADEAC)、(3-甲基丙烯酰氧基)丙基三甲基氯化铵(MPTAC)、(3-甲基丙烯酰氧基)乙基三甲基氯化铵(METAC)、(3-甲基丙烯酰胺基)丙基三甲基氯化铵(MAPTAC)、甲基丙烯酸2-二甲氨基乙酯或3-二甲氨基丙基甲基丙烯酰胺(pH≤5的DMAEMA或DMAPMA,质子化的物质)。
基于阳离子保护胶体的总重量,所述阳离子保护胶体通常含有20-100重量%,优选50-100重量%,特别优选100重量%的阳离子单体单元。合适的可共聚合的非离子单体是在羧酸基中具有1-15个碳原子的乙烯基酯,如乙酸乙烯酯、丙酸乙烯酯、十二烷酸乙烯酯;丙烯酰胺、(甲基)丙烯酸羟乙基酯、(甲基)丙烯酸羟丙基酯、甲基丙烯酸及丙烯酸与具有4-13个碳原子的醇的酯、具有C2-C4亚烷基单元且分子量为350-2000g/mol的聚亚烷基二醇(甲基)丙烯酸酯、以及N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、丙烯酰氧基丙基三烷氧基硅烷和甲基丙烯酰氧基丙基三烷氧基硅烷、乙烯基三烷氧基硅烷和乙烯基甲基二烷氧基硅烷和/或所述非离子共聚单体的混合物。
阳离子保护胶体可以利用本领域技术人员已知的聚合方法制备,例如通过在水溶液中、在溶剂混合物中或在存在盐的情况下进行自由基聚合,例如还在沉淀聚合方法中,例如通过在溶液或溶剂混合物中类似聚合物的反应,例如在悬浮液中,或例如通过反相乳液聚合。在此情况下,引发剂可为水溶性或油溶性的,并且可来源于过硫酸盐、过氧化氢、偶氮化合物或者氧化/还原引发剂对。特别是通过最后所述的反相乳液聚合或油包水聚合的方法得到分子量大于5,000,000g/mol的极高分子量的阳离子聚合物。在利用类似聚合物的反应制备阳离子保护胶体时,使对应的非离子保护胶体与阳离子化合物反应以获得阳离子单体单元。其实例是用阳离子醛对聚乙烯醇的缩醛化。
最优选在固体含量低(优选≤40重量%)的水中在存在水溶性引发剂如偶氮引发剂或氧化还原引发剂的情况下,任选在存在分子量调节剂如巯基丙酸或2-巯基乙醇的情况下通过溶液聚合来制备。
优选阳离子保护胶体的K值(通过根据DIN 53726的方法,在水中1重量%,25℃,Ubbelohde粘度计进行测定)为10-250,特别优选为25-130。用于在Ubbelohde粘度计中测定PVC粘度的标准DIN 53726的改变在于,用水代替环己酮作为溶剂。阳离子保护胶体的粘度为1-50mPas,优选为1-25mPas,最优选为1-15mPas(均是根据DIN53015用Hppler法在20℃下测定)。
适合于制备成膜基础聚合物的含水聚合物分散体的单体是具有1-15个碳原子的非支链或支链烷基羧酸的乙烯基酯、具有1-15个碳原子的醇的甲基丙烯酸酯或丙烯酸酯、乙烯基芳烃、烯烃、二烯烃或卤乙烯。
优选的乙烯基酯是乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、乙酸1-甲基乙烯酯、新戊酸乙烯酯以及具有9-13个碳原子的α-分支单羧酸的乙烯基酯,如或(Resolution的商品名)。特别优选乙酸乙烯酯。优选的甲基丙烯酸酯或丙烯酸酯是丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸降冰片基酯。特别优选丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯及丙烯酸2-乙基己酯。烯烃和二烯烃的实例是乙烯、丙烯和1,3-丁二烯。合适的乙烯基芳烃是苯乙烯及乙烯基甲苯。合适的卤乙烯是氯乙烯。
基于主要聚合物的总重量,任选还可共聚合0.05-50重量%,优选1-10重量%的辅助单体。辅助单体的实例是:烯键式不饱和单羧酸和二羧酸,优选为丙烯酸、甲基丙烯酸、富马酸和马来酸;烯键式不饱和酰胺和烯键式不饱和腈,优选为丙烯酰胺及丙烯腈;富马酸和马来酸的单酯和二酯,如二乙基酯和二异丙基酯,及马来酸酐;烯键式不饱和磺酸及其盐,优选为乙烯基磺酸、2-丙烯酰胺基-2-甲基丙烷磺酸。其它的实例有预交联的共聚单体,如烯键式多不饱和共聚单体,如己二酸二乙烯酯、马来酸二烯丙酯、甲基丙烯酸烯丙酯或氰尿酸三烯丙酯;或后交联的共聚单体,如丙烯酰胺基羟基乙酸(AGA)、甲基丙烯酰胺基羟基乙酸甲酯(MAGME)、N-羟甲基丙烯酰胺(NMA)、N-羟甲基甲基丙烯酰胺(NMMA)、N-羟甲基氨基甲酸烯丙酯;烷基醚,如N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺及N-羟甲基氨基甲酸烯丙酯的异丁氧基醚或酯。环氧基官能的共聚单体也是合适的,如甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯。其它的实例有硅官能的共聚单体,如丙烯酰氧基丙基三(烷氧基)硅烷和甲基丙烯酰氧基丙基三(烷氧基)硅烷、乙烯基三烷氧基硅烷和乙烯基甲基二烷氧基硅烷,其中可存在的烷氧基的实例为甲氧基、乙氧基和乙氧基丙二醇醚基。还可述及具有羟基或CO基的单体,例如甲基丙烯酸羟烷基酯和丙烯酸羟烷基酯,如丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯或甲基丙烯酸羟丁酯,以及诸如双丙酮丙烯酰胺及乙酰基乙酰氧基乙基丙烯酸酯或乙酰基乙酰氧基乙基甲基丙烯酸酯的化合物。其它适合的共聚单体是乙烯基烷基醚,如乙烯基甲基醚、乙烯基乙基醚、乙烯基异丁基醚、乙烯基十八烷基醚。
适合作为主要聚合物的均聚物和共聚物的实例是乙酸乙烯酯均聚物、乙酸乙烯酯与乙烯的共聚物、乙酸乙烯酯与乙烯及一种或多种其它乙烯基酯的共聚物、乙酸乙烯酯与乙烯及丙烯酸酯的共聚物、乙酸乙烯酯与乙烯及氯乙烯的共聚物、苯乙烯-丙烯酸酯共聚物、苯乙烯-1,3-丁二烯共聚物。
优选如下:
乙酸乙烯酯均聚物;乙酸乙烯酯与1-40重量%乙烯的共聚物;乙酸乙烯酯与1-40重量%乙烯及1-50重量%的一种或多种选自以下组中的其它共聚单体的共聚物:在羧酸基中具有1-15个碳原子的乙烯基酯,如丙酸乙烯酯、十二烷酸乙烯酯,具有9-13个碳原子的α-分支羧酸的乙烯基酯,如 乙酸乙烯酯、1-40重量%乙烯及优选1-60重量%丙烯酸酯的共聚物,该丙烯酸酯是具有1-15个碳原子的非支链或支链醇的丙烯酸酯,尤其是丙烯酸正丁酯或丙烯酸2-乙基己酯;
以及含有以下单体的共聚物:30-75重量%乙酸乙烯酯、1-30重量%月桂酸乙烯酯或具有9-13个碳原子的α-支链羧酸的乙烯基酯、以及1-30重量%的具有1-15个碳原子的非支链或支链醇的丙烯酸酯,该丙烯酸酯尤其是丙烯酸正丁酯或丙烯酸2-乙基己酯,该共聚物还含有1-40重量%的乙烯;
含有乙酸乙烯酯、1-40重量%乙烯、以及1-60重量%氯乙烯的共聚物;其中这些聚合物还可含有所述量的所述辅助单体,而且重量百分比数据相加之和均为100重量%。
优选的还有如下:
(甲基)丙烯酸酯聚合物,如丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚物、或甲基丙烯酸甲酯与丙烯酸正丁酯和/或丙烯酸2-乙基己酯及任选的乙烯的共聚物;
含有一种或多种选自以下组中的单体的苯乙烯-(甲基)丙烯酸酯共聚物:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯;
含有一种或多种选自以下组中的单体的乙酸乙烯酯-(甲基)丙烯酸酯共聚物:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯及任选的乙烯;
苯乙烯-1,3-丁二烯共聚物;其中这些聚合物还可含有所述量的所述辅助单体,而且重量百分比数据相加之和均为100重量%。
选择单体和/或选择共聚单体的重量份使得通常玻璃态转变温度Tg为-50℃至+50℃,优选为-30℃至+10℃。这些聚合物的玻璃态转变温度Tg可利用差示扫描量热法(DSC)由已知的方式测得。Tg也可利用Fox方程进行近似计算。依照Fox T.G.,Bull.Am.Physics Soc.1,3,page 123(1956):
1/Tg=x1/Tg1+x2/Tg2+…+xn/Tgn
其中xn代表单体n的质量分数(重量%/100),而Tgn为单体n的均聚物的玻璃态转变温度,以开尔文计。均聚物的Tg值记载于“聚合物手册(Polymer Handbook)”,第二版,J.Wiley & Sons,New York(1975)。
所述均聚物和共聚物优选通过乳液聚合法制备,聚合温度通常是,但并非必须,低于100℃。
不管何种聚合方法,聚合可以在使用或不使用晶种格子(seed lattices)的情况下进行,初始加入反应混合物的所有成分或单独成分,或者初始加入部分,后来加入部分反应混合物的成分或单独成分,或者通过没有初始加入的加料方法。可以初始加入所有这些共聚单体来制备分散体(分批法),或者初始加入部分单体,在进料剩余的(半分批法)。
利用乳液聚合常用的水溶性引发剂或氧化还原引发剂组合引发聚合。水溶性引发剂的实例是过氧二硫酸的钠盐、钾盐及铵盐、过氧化氢、过氧化叔丁基、氢过氧化叔丁基、过氧二磷酸钾、过氧新戊酸叔丁酯、氢过氧化异丙苯、单氢过氧化异丙基苯、偶氮二异丁腈。均基于单体的总重量,所述引发剂的使用量通常为0.001-0.02重量%,优选为0.001-0.01重量%。所用的氧化还原引发剂包括所述引发剂与还原剂的混合物。合适的还原剂是碱金属及铵的亚硫酸盐和亚硫酸氢盐,如亚硫酸钠;次硫酸衍生物,如甲醛合次硫酸锌或碱金属甲醛合次硫酸盐,如羟基甲烷亚磺酸钠;及抗坏血酸。均基于单体的总重量,还原剂的量通常为0.001-0.03重量%,优选为0.001-0.015重量%。
为了控制分子量,可以在聚合期间使用调节物质。若使用调节剂,则其基于待聚合的单体,其用量通常为0.01-5.0重量%,他们通常单独加入或预先与反应成分混合。这些物质的实例是正十二烷基硫醇、叔十二烷基硫醇、巯基丙酸、巯基丙酸甲酯、异丙醇和乙醛。
聚合优选在存在非离子保护胶体的情况下进行。合适的非离子保护胶体是聚乙烯醇;聚乙烯醇缩醛;聚乙烯基吡咯烷酮;水溶性多糖,如淀粉(直链淀粉和支链淀粉)、纤维素及它们的甲基衍生物、羟乙基衍生物、羟丙基衍生物;聚(甲基)丙烯酰胺。
优选的是水解度为80-100摩尔%的部分水解或完全水解的聚乙烯醇,尤其是水解度为80-95摩尔%且在4%浓度的水溶液中的粘度为1-30mPas(法,在20℃下,DIN 53015)的部分水解的聚乙烯醇。优选的还有水解度为80-95摩尔%且在4%浓度的水溶液中的粘度为1-30mPas的部分水解的、疏水改性的聚乙烯醇。其实例是乙酸乙烯酯与疏水性共聚单体的部分水解的共聚物,所述疏水性共聚单体例如乙酸异丙烯酯、新戊酸乙烯酯、乙基己酸乙烯酯、具有5个或9-13个碳原子的饱和α-支链单羧酸的乙烯基酯、马来酸二烷基酯和富马酸二烷基酯如马来酸二异丙酯和富马酸二异丙酯、氯乙烯、乙烯基烷基醚如乙烯基丁基醚、烯烃如乙烯和癸烯。基于部分水解的聚乙烯醇的总重量,该疏水性单元的含量优选为0.1-10重量%。还可使用所述聚乙烯醇的混合物。
最优选的是水解度为85-94摩尔%且在4%浓度的水溶液中的粘度为3-15mPas(法,在20℃下,DIN 53015)的聚乙烯醇。所述保护胶体可利用本领域技术人员所熟知的方法获得,基于单体的总重量,在聚合期间保护胶体的总添加量通常为1-20重量%。
聚合还可在存在非离子乳化剂或者存在所述非离子保护胶体与非离子乳化剂的组合的情况下实施。合适的非离子乳化剂是表面活性剂,如具有8-40个环氧烷烃单元的烷基聚乙二醇醚或烷基芳基聚乙二醇醚。优选被C2-C4环氧烷烃,尤其是环氧乙烷和环氧丙烷或其混合物烷氧基化的C8-C16链烷醇。基于单体的总重量,在聚合期间该非离子乳化剂的添加量通常为0.05-10重量%。
聚合结束之后,可采用已知的方法实施后聚合以去除残留单体,通常使用的方法是氧化还原催化剂引发的后聚合。挥发性残留单体还可利用蒸馏来去除,优选在减压下,并且任选同时使空气或水蒸汽或惰性夹带气体如氮气流经或流过。由此获得的含水分散体的固体含量为30-75重量%,优选为50-60重量%。
为了制备水可再分散的聚合物粉末,在添加阳离子保护胶体作为干燥助剂之后,对含水分散体实施干燥。在此情况下,所述阳离子保护胶体还可与非离子保护胶体组合使用,或者与非离子乳化剂组合使用。适合于此的的非离子保护胶体和非离子乳化剂是上述适合于聚合的非离子保护胶体和非离子乳化剂。
举例来说,干燥方法为流化床干燥、冷冻干燥或喷雾干燥。优选对该分散体实施喷雾干燥。在常规的喷雾干燥装置内实施该喷雾干燥,可利用单相喷嘴、两相喷嘴或多相喷嘴进行雾化或可用转盘。取决于装置和想要的干燥程度,出料温度通常被选定为45℃-120℃,优选为60℃-90℃。
均基于分散体的聚合物成分,阳离子保护胶体任选与非离子保护胶体和/或非离子乳化剂一起使用的总用量通常为0.1-20重量%,优选为1-7重量%。
已反复证实,基于主要聚合物,含量高至2重量%的消泡剂在干燥过程中是有利的。所得粉末可含有给予聚合物成分的总重量优选高至30重量%的抗结块剂,以通过提高抗结块性来提高存储稳定性,特别是对于具有低玻璃态转化温度的粉末。抗结块剂的实例是碳酸钙、碳酸镁、滑石、石膏、二氧化硅、高岭土、偏高岭土、硅酸盐,其粒径优选为10nm-100μm。
通过固体含量来调节待雾化和待干燥的混合物的粘度,使得到的值为小于1000mPas(20rpm和23℃下的Brookfield粘度),优选小于500mPas,特别优选小于250mPas。该待雾化的混合物的固体含量应大于30重量%,优选大于40重量%。
为提高性能,可在干燥之前、期间或之后加入其它添加剂。在分散体粉末组合物的优选实施方案中包含的其它组分的实例有颜料、填料、泡沫稳定剂、疏水化剂、增塑剂。
阳离子稳定化且水可再分散的聚合物粉末组合物可用于其典型的应用领域。还可使用阳离子稳定化的分散体粉末与传统分散体粉末的混合物。
例如用于任选与水固性粘结剂,如水泥(波特兰水泥、高铝水泥、火山灰水泥、矿渣水泥、镁氧水泥、磷酸盐水泥)、石膏灰泥及水玻璃相结合的建筑用化学产品,用于制造建筑粘合剂,尤其是砖瓦粘合剂(如高柔韧性粘合剂)及外墙外保温体系粘合剂、粉刷头道浆(venders)、抹光化合物、地板抹平组合物、流平组合物、密封泥浆、接缝砂浆及油漆。优选的应用领域是密封泥浆和砖瓦粘合剂,尤其是木质基底的砖瓦粘合剂。其它可能的应用是用于粘合剂领域和涂料领域,后者例如用于纸张和纺织品。
在根据本发明的方法中惊人地获得含有优选1-7重量%的少量阳离子聚合物作为干燥助剂的分散体粉末,其产生具有非常好的可再分散性的抗结块性粉末。惊人地发现,该阳离子聚合物不仅对聚合物改性的组合物,如密封泥浆、砖瓦粘合剂、粉刷头道浆中的可加工性具有积极作用,而且还提高了这些组合物的柔韧性,例如聚合物改性的密封泥浆的断裂拉伸应变。
具体实施方式
实施例
分散体1(D1):
分散体2(D2):
分散体3(D3):
分散体4(D4):
所用的起始分散体包括利用水解度为88摩尔%且粘度为4mPas的2.5重量%聚乙烯醇制备的固体含量为51重量%且Tg为-13℃的丙烯酸乙基己酯-甲基丙烯酸甲酯共聚物分散体。
分散体5(D5):
分散体6(D6):
所用的起始分散体包括利用水解度为88摩尔%且粘度为4mPas的10重量%聚乙烯醇制备的固体含量为55重量%且Tg为5℃的乙酸乙烯酯-乙烯-VeoVa10共聚物分散体。
分散体7(D7):
保护胶体1(PC1):(聚METAC)
将由795g水和201g 2-甲基丙烯酰氧基乙基三甲基氯化铵组成的混合物初始装入聚合反应容器中,并加热至73℃。在180分钟内,将20.12g 10%浓度的引发剂溶液(VA-044:2,2′-偶氮双[2-(2-咪唑啉-2-基)丙烷]二氢氯化物)连续计量加入混合物中。在73℃下再搅拌反应溶液30分钟,然后冷却。获得pH值为3.1的19.8重量%淡黄色透明溶液。1%浓度的聚合物水溶液的K值为75.9。4%浓度的水溶液的粘度为7.8mPas。
保护胶体2(PC2):(聚MAPTAC)
将由988g水和6.8g 50%浓度的乙酸水溶液组成的混合物加热至80℃。一旦达到温度平衡,在180分钟内,将96g 7%浓度的引发剂溶液(VA-044:2,2′-偶氮双[2-(2-咪唑啉-2-基)丙烷]二氢氯化物)以及910g 50%浓度的2-甲基丙烯酰胺基丙基三甲基氯化铵水溶液连续同时计量加入混合物中。在80℃下再搅拌反应溶液60分钟,然后冷却。获得pH值为3.4的25.4重量%淡黄色透明溶液。1%浓度的聚合物水溶液的K值为29。4%浓度的水溶液的粘度为1.9mPas。
保护胶体3(PC3):(聚DMAEMA/METAC)
将由778g水、179g2-二甲氨基乙基甲基丙烯酸酯和18g2-甲基丙烯酰氧基乙基三甲基氯化铵组成的混合物预先装入聚合反应容器中,并加热至73℃。在180分钟内,将22.1g10%浓度的引发剂溶液(VA-044:2,2′-偶氮双[2-(2-咪唑啉-2-基)丙烷]二氢氯化物)连续计量加入混合物中。在73℃下再搅拌反应溶液30分钟,然后冷却。获得pH值为9.2的18.2重量%淡黄色透明溶液。1%浓度的聚合物水溶液的K值为48.1。4%浓度的水溶液的粘度为5.8mPas。
保护胶体4(PC4):
保护胶体5(PC5):
粉末:
将起始分散体D1-D7与保护胶体PC1-PC5以表1中给出的重量比例混合并添加基于成膜聚合物的固体含量0.5重量%的消泡剂,搅拌30分钟并过滤。表1中所示的混合物中均未形成凝结物。添加基于分散体固体含量12重量%的抗结块剂,对混合物进行喷雾干燥得到粉末P1-P11。
对比例1(P12):
将9重量%的水解度为88摩尔%且粘度为4mPas的聚乙烯醇与起始分散体D2混合。在添加0.5重量%消泡剂之后,搅拌该混合物30分钟,并过滤。添加基于分散体固体含量12重量%的抗结块剂,对该混合物进行喷雾干燥。
对比例2(P13):
所用起始分散体(D8)包括利用12重量%的 CS制备的固体含量为49重量%且Tg为-5℃的乙酸乙烯酯-乙烯共聚物分散体。制造具有小于10重量%的少量保护胶体的分散体的尝试失败。将6重量%的水解度为88摩尔%且粘度为4mPas的聚乙烯醇与该分散体(D8)混合。在添加0.5重量%消泡剂之后,搅拌该混合物30分钟,并过滤。添加基于分散体固体含量12重量%的抗结块剂,对该混合物进行喷雾干燥。未获得具有抗结块性的粉末。
对比例3(P14):
所用起始分散体包括利用6重量%的水解度为88摩尔%且粘度为4mPas的聚乙烯醇制备的固体含量为55重量%且Tg为10℃的乙酸乙烯酯-乙烯共聚物分散体(D9)。将8重量%的水解度为88摩尔%且粘度为4mPas的聚乙烯醇与该分散体混合。搅拌混合物30分钟,并过滤。添加基于分散体固体含量12重量%的抗结块剂,对该混合物进行喷雾干燥得到粉末P14。
测试:
测试所得粉末的粉末性能及它们在密封泥浆中的可加工性。
测定抗结块性(BR):
为了测定抗结块性,将分散粉末放入带螺纹的铁管中,然后用金属柱塞进行装填。将材料在负载下的干燥箱中在50℃下储存16小时。冷却至室温后,将粉末从管中取出,并通过压碎粉末定性测定抗结块性。对抗结块性分级如下:
1=非常好的抗结块性,不形成团块
2=良好的抗结块性
3=合格的抗结块性
4=无抗结块性,粉末在压碎之后不再具有流动性测定沉积特性(管沉积,TS):
再分散体的沉积特性用作粉末的可再分散性的测量标准。通过强剪切力的作用在水中产生50%浓度的再分散体。
然后对稀释的再分散体(固体含量为0.5%)测定沉积特性。将100ml该分散体装入刻度管中,并测量沉积的固体的高度。24小时后以mm沉积物记录数据。大于7的数值表明粉末的再分散不足。
分散体粉末的抗结块性(BR)及沉积特性(TS)的测试结果汇总于表1中。
表1:
粉末编号 | 分散体 | 保护胶体 | BR | TS |
P1 | D1 | 5重量%SK1 | 2 | 2 |
P2 | D2 | 6重量%SK1 | 2 | 1.8 |
P3 | D2 | 6重量%SK2 | 1-2 | 1.4 |
P4 | D1 | 3.5重量%SK4 | 2 | 1.5 |
P5 | D2 | 3.5重量%SK4 | 1 | 1.6 |
P6 | D3 | 2重量%SK4 | 2 | 3.0 |
P7 | D4 | 4重量%SK4 | 2 | 2.5 |
P8 | D1 | 5重量%SK5 | 1 | 1.1 |
P9 | D5 | 5重量%SK4 | 1 | 1.6 |
P10 | D6 | 5重量%SK4 | 1-2 | 1.0 |
P11 | D7 | 5重量%SK4 | 1 | 1.4 |
P12(对比例) | D2 | 9重量%PVA | 2 | 0.7 |
P13(对比例) | D8 | 6重量%PVA | 4 | 7 |
P14(对比例) | D9 | 8重量%PVA | 2 | 1.8 |
对比例P13表明,在聚合反应期间使用阳离子保护胶体的方法获得的产物不可再分散,并且没有抗结块性。
采用以下混合料制造似水泥的密封泥浆:
石英砂 665份
波特兰水泥 50份
纤维素 5份
分散体粉末 280份
水 400份
在混合干燥组分与水期间评估可加工特性(W)。
密封泥浆的可加工性是使用者的主观感觉。对可加工性分级如下:
1=非常好,易成型,无涂抹粘合性
2=有点难以加工,轻微的涂抹粘合性
3=可加工性不足,高度胶粘
借助于间隙宽度为2毫米的刮板,将似水泥的密封泥浆拉成膜,并将该膜在标准温度和湿度条件(23℃,50%相对湿度)下干燥7天。评估所得膜的柔韧性和可变形性。对它们分级如下:
1=均匀、光滑的膜,非常好的可变形性
2=光滑的膜,良好的可变形性
3=光滑的膜,小的可变形性
4=易碎的膜,差的可变形性
通过DIN53455拉伸测试测定试样的极限拉伸强度(UTS,MPas)和断裂拉伸应变(TSB,%)。
在标准温度和湿度条件下储存28天之后的可加工性、柔韧性以及极限拉伸强度和断裂拉伸应变列于表2中。
表2
粉末编号 | W | 柔韧性 | UTS(MPa) | TSB(%) |
P4 | 1-2 | 1 | 1.6 | 100 |
P5 | 1 | 1 | 1.4 | 105 |
P7 | 1-2 | 2 | 1.5 | 92 |
P12(对比例) | 3 | 3 | 1.6 | 41 |
采用以下混合料制造似水泥的高柔韧性粘合剂:
石英砂 576份
水泥(由波特兰水泥和高铝水泥组成的混合物) 300份
纤维素醚 4份
分散体粉末 120份
水 240份
在混合干燥组分与水期间评估可加工性(W,级别如上所述),并列于表3中。
根据DIN 12004(EN1348测试标准)测定以N/mm2计的拉伸粘接强度。
储存A:标准温度和湿度条件下28天;
储存B:标准温度和湿度条件下7天/水中储存21天;
储存C:标准温度和湿度条件下14天/70℃下水中储存14天/标准温度和湿度条件下1天;
储存D:标准温度和湿度条件下7天/水中储存21天/25次结冰-解冻循环5天
结果列于表3中。
根据EN 12002测定以mm计的可变形性。各种分散体粉末的结果列于表3中。
表3
由这些数据可以看出,在制造根据本发明的产品时,没有在制造分散体和阳离子保护胶体和添加剂的混合物期间产生凝结的问题。此外,即使非常少量的阳离子保护胶体仍获得具有非常好的在分散性能的抗结块性粉末。此外,即使在聚合物含量高的情况下,例如在密封泥浆混合料或砖瓦粘合剂混合料中仍获得非常好的可加工特性。
表2和表3表明,与仅用聚乙烯醇稳定化的传统粉末如P12和P14相比,根据本发明所制的粉末在大量使用分散体粉末的应用中,表现出提高的弹性和可加工性。
Claims (10)
1、制造阳离子稳定化且水可再分散的聚合物粉末组合物的方法,其中在任选存在非离子保护胶体和/或非离子乳化剂的情况下,使一种或多种烯键式不饱和单体在水性介质中进行自由基聚合,随后实施干燥,其特征在于,在存在阳离子保护胶体作为干燥助剂的情况下对所得到的含水聚合物分散体实施干燥。
2、根据权利要求1所述的方法,其特征在于,所使用的阳离子保护胶体包括包含具有季铵基团的单体单元的聚合物。
3、根据权利要求2所述的方法,其特征在于,使用一种或多种选自以下组中的阳离子单体的均聚物或共聚物:二烯丙基二甲基氯化铵(DADMAC)、二烯丙基二乙基氯化铵(DADEAC)、(3-甲基丙烯酰氧基)丙基三甲基氯化铵(MPTAC)、(3-甲基丙烯酰氧基)乙基三甲基氯化铵(METAC)、(3-甲基丙烯酰胺基)丙基三甲基氯化铵(MAPTAC)、2-二甲氨基乙基甲基丙烯酸酯或3-二甲氨基丙基甲基丙烯酰胺(DMAEMA或DMAPMA)。
4、根据权利要求1至3之一所述的方法,其特征在于,所使用的阳离子保护胶体的K值(由根据DIN 53726的方法,在水中1重量%,25℃,Ubbelohde粘度计测定)为10-250。
6、根据权利要求1至5之一所述的方法,其特征在于,基于所述含水聚合物分散体的聚合物成分,所述阳离子保护胶体的使用量为0.1-20重量%。
7、根据权利要求1至6之一所述的方法,其特征在于,所述聚合的烯键式不饱和单体包括一种或多种选自以下组中的单体:具有1-15个碳原子的非支链或支链烷基羧酸的乙烯基酯、具有1-15个碳原子的醇的甲基丙烯酸酯和丙烯酸酯、乙烯基芳烃、烯烃、二烯烃和卤乙烯。
8、阳离子稳定化且水可再分散的聚合物粉末组合物,其是如下制得的:在任选存在非离子保护胶体和/或非离子乳化剂的情况下,在水性介质中自由基聚合一种或多种烯键式不饱和单体,随后在存在阳离子保护胶体作为干燥助剂的情况下对所得含水聚合物分散体进行干燥。
9、根据权利要求8所述的阳离子稳定化且水可再分散的聚合物粉末组合物在用于制造建筑粘合剂、粉刷头道浆、抹光化合物、地板抹平组合物、流平组合物、密封泥浆、接缝砂浆及油漆的建筑用化学产品中的用途。
10、根据权利要求8所述的阳离子稳定化且水可再分散的聚合物粉末组合物在粘合剂领域和涂料领域中的用途。
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PCT/EP2007/051209 WO2007093551A1 (de) | 2006-02-16 | 2007-02-08 | Verfahren zur herstellung von kationisch stabilisierten und in wasser redispergierbaren polymerpulverzusammensetzungen |
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CN112601785A (zh) * | 2018-09-06 | 2021-04-02 | 瓦克化学股份公司 | 在水中可再分散的聚合物粉末组合物 |
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CN110582203A (zh) * | 2017-05-03 | 2019-12-17 | 瓦克化学股份公司 | 与非离子结合剂结合的抗微生物非织造湿巾 |
CN112601785A (zh) * | 2018-09-06 | 2021-04-02 | 瓦克化学股份公司 | 在水中可再分散的聚合物粉末组合物 |
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