CN100586998C - 用保护胶体稳定化的分散粉末 - Google Patents
用保护胶体稳定化的分散粉末 Download PDFInfo
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- CN100586998C CN100586998C CN200610146330A CN200610146330A CN100586998C CN 100586998 C CN100586998 C CN 100586998C CN 200610146330 A CN200610146330 A CN 200610146330A CN 200610146330 A CN200610146330 A CN 200610146330A CN 100586998 C CN100586998 C CN 100586998C
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- Prior art keywords
- polyvinyl alcohol
- vinyl
- weight
- dispersed powders
- multipolymer
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- 239000000843 powder Substances 0.000 title claims abstract description 55
- 239000000084 colloidal system Substances 0.000 title claims abstract description 31
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 59
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 59
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 claims description 39
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000004568 cement Substances 0.000 claims description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 11
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
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- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2623—Polyvinylalcohols; Polyvinylacetates
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- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
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- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
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Abstract
本发明涉及用保护胶体稳定化的分散粉末，其中所述保护胶体包含：(a)至少一种Hppler粘度μ1不超过3毫帕斯卡·秒的聚乙烯醇；和(b)至少一种Hppler粘度μ2在4～25毫帕斯卡·秒的聚乙烯醇；且该保护胶体的加权Hppler粘度μw不超过6毫帕斯卡·秒。
Description
技术领域
本发明涉及水可再分散的分散粉末，该粉末是用保护胶体稳定化的，且含有
粘度不超过3毫帕斯卡·秒的聚乙烯醇；还涉及该粉末的制备及其在水固性***中的使用。
背景技术
基于乙烯基酯、氯乙烯、(甲基)丙烯酸酯单体、苯乙烯、丁二烯及乙烯的聚合物特别以其水分散体的形式或以水可再分散的聚合物粉末的形式用于许多应用领域中，例如作为各种不同基底的涂料或粘合剂。为了稳定化这些聚合物，使用保护胶体或更少用到的低分子量表面活性化合物。通常使用聚乙烯醇作为保护胶体。
聚乙烯醇作为保护胶体有许多优点，尤其它使粉末稳定化，防止其颗粒过早聚结，并且本身可用作粘结剂。另一方面，当分散粉末例如在密封砂浆中大量使用时，聚乙烯醇有时也显现几分不足。这种情况下，聚乙烯醇的牛顿流变学性能成为加工这类混料的不利因素。
按照现有技术使用的聚乙烯醇通常具有至少3毫帕斯卡·秒、甚至常常优选至少4毫帕斯卡·秒的
粘度(根据DIN 53015：1978-09)，并且例如描述在专利文献DE 10162513A1和EP 1262465B1中。对
粘度的要求没有上限。然而，由于粘度增加，超过30毫帕斯卡·秒的值也很少采用。
对低于3毫帕斯卡·秒的
粘度范围研究很少，或者说根本没有，因为至今仍假定这样低分子量的化合物在稳定分散粉末方面不是非常适用。
分散粉末是例如通过如EP1262465B1中所述的喷雾干燥法，或者通过含水胶乳冷冻干燥法来制备的。
这些产品特别是在水固性粘合剂中，例如基于水泥或石膏的砖瓦粘合剂中用作粘结剂。
发明内容
因此，本发明目的是开发一种即使在大量使用时也表现出良好的加工性的分散粉末。
该目的可以通过本发明分散粉末来实现，该分散粉末含有低粘度和较高粘度聚乙烯醇的混合物加以稳定化。
本发明提供由保护胶体稳定化的分散粉末，其中该保护胶体的组成包括：
(a)至少一种
粘度μ1不超过3毫帕斯卡·秒的聚乙烯醇；以及
(b)至少一种
粘度μ2为4至25毫帕斯卡·秒的聚乙烯醇；且该保护胶体的加权
粘度μw不超过6毫帕斯卡·秒。
意想不到的是，根据本发明获得的分散粉末，尽管具有高比例的极低分子量聚乙烯醇，仍能够产生结块稳定的粉末。
还令人惊奇的是，发现低分子量聚乙烯醇不仅对加工性有积极影响，而且也能导致例如与聚苯乙烯粘着性的改善。
根据本发明的粉末包含0.1至10.0重量％的
粘度μ1不超过3毫帕斯卡·秒的聚乙烯醇(a)，优选使用1.0至5.0重量％的该聚乙烯醇(a)。
粘度μ1的优选范围是1.5至2.5毫帕斯卡·秒。
这种由(a)和(b)构成的特定聚乙烯醇优选在干燥形成粉末之前加入分散体，但也可以在起始分散体的聚合期间加入。
低分子量聚乙烯醇(a)与惯用的较高分子量的聚乙烯醇(b)联合使用。但高分子量聚乙烯醇的比例不应太高，因为否则会部分丧失积极作用。基于聚乙烯醇总量，优选使用10至50重量％的较高分子量的聚乙烯醇(b)，特别优选15至35重量％的较高分子量聚乙烯醇(b)。
为了获得积极作用，必须满足下述先决条件。作为保护胶体，联合使用至少一种
粘度μ1不超过3毫帕斯卡·秒的聚乙烯醇(a)和至少一种
粘度μ2为4至25毫帕斯卡·秒的聚乙烯醇(b)。此处(a)、(b)之比的选择应使其加权
粘度μw不超过6毫帕斯卡·秒。
μw可以用等式(1)来描述：
μw＝μ1×X1+μ2×X2+……μi×Xi (1)
式中：
i＝所用聚乙烯醇(a)和(b)的数目，即至少是2；
Xi＝具有粘度μi的相应聚乙烯醇i的质量分数，并且可以采用等式(2)来描述：
Xi＝Wi/(W1+W2+……Wi) (2)
式中：
W＝相应聚乙烯醇的质量，而I具有以上含意。
用保护胶体稳定化的本发明分散粉末的其他组成与现有技术一致。
适合于基础聚合物的乙烯基酯是具有1至15个碳原子的羧酸的乙烯基酯。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至13个碳原子的α-分支单羧酸的乙烯基酯，如VeoVa9R或VeoVa10R(Resolution Europe BV公司的商品名，Hoogvliet，荷兰)。特别优选为乙酸乙烯酯。
适宜的甲基丙烯酸酯或丙烯酸酯是具有1至15个碳原子的非分支或分支型醇的酯，如丙烯酸甲酯、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(norbornyl acrylate)。优选为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯及丙烯酸2-乙基己酯。
烯烃和二烯烃的例子是乙烯、丙烯及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。
基于基础聚合物的总重量，任选还可共聚合0.05至50重量％，优选1至10重量％的辅助单体。辅助单体的实例为：烯键式不饱和单羧酸及二羧酸，优选为丙烯酸、甲基丙烯酸、富马酸及马来酸；烯键式不饱和羧酰胺及腈，优选为丙烯酰胺及丙烯腈；富马酸及马来酸的单酯及二酯，如二乙酯及二异丙酯；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-甲基丙磺酸。其他的实例是预交联共聚单体，如多重烯键式不饱和共聚单体，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脲酸三烯丙酯；或后交联共聚单体，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；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烷基醚，如异丁氧基醚或酯。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及丙烯酸缩水甘油酯。其他的实例是硅官能的共聚单体，如丙烯酰氧基丙基三(烷氧基)硅烷及甲基丙烯酰氧基丙基三(烷氧基)硅烷、乙烯基三烷氧基硅烷及乙烯基甲基二烷氧基硅烷，其中例如可含有甲氧基、乙氧基及乙氧基丙二醇醚基作为烷氧基。还述及具有羟基或CO基的单体，如甲基丙烯酸羟烷基酯及丙烯酸羟烷基酯，如丙烯酸羟乙基酯、丙烯酸羟丙基酯、丙烯酸羟丁基酯、甲基丙烯酸羟乙基酯、甲基丙烯酸羟丙基酯或甲基丙烯酸羟丁基酯，以及诸如双丙酮丙烯酰胺及丙烯酸乙酰基乙酰氧基乙酯或甲基丙烯酸乙酰基乙酰氧基乙酯的化合物。
适宜均聚物和共聚物的例子有：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更多种其他乙烯基酯的共聚物、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。
优选为乙酸乙烯酯均聚物；乙酸乙烯酯与1至40重量％乙烯的共聚物；乙酸乙烯酯与1至40重量％乙烯及1至50重量％的一种或更多种选自以下组中的其他共聚单体的共聚物：在羧酸基中具有1至12个碳原子的乙烯基酯，如丙酸乙烯酯、月桂酸乙烯酯、具有9至13个碳原子的α-分支羧酸的乙烯基酯，如VeoVa9、VeoVa10、VeoVa11，购自ResolutionEurope BV公司，Hoogvliet，荷兰；乙酸乙烯酯与1至40重量％乙烯及优选1至60重量％丙烯酸酯的共聚物，该丙烯酸酯是具有1至15个碳原子的非分支或分支型醇的丙烯酸酯，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至75重量％乙酸乙烯酯、1至30重量％月桂酸乙烯酯或具有9至11个碳原子的α-分支羧酸的乙烯基酯、以及1至30重量％的具有1至15个碳原子的非分支或分支型醇的丙烯酸酯，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至40重量％的乙烯；乙酸乙烯酯、1至40重量％乙烯、以及1至60重量％氯乙烯的共聚物；其中这些聚合物还可含有所述含量的所述辅助单体，而且重量百分比数据相加之和均为100重量％。
优选的还有(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；含有一种或更多种选自以下组中的单体的苯乙烯/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；含有一种或更多种选自以下组中的单体的乙酸乙烯酯/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含量的所述辅助单体，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，通常使得玻璃化转变温度Tg为-50℃至+50℃，优选为-30℃至+40℃。该聚合物的玻璃化转变温度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方程预先进行近似计算。依照Fox T.G.，Bull.Am.Physics Soc.1，3，page123(1956)：
1/Tg＝x1/Tg1+x2/Tg2+…+xn/Tgn (3)
其中xn代表单体n的以重量％/100计的质量分数，而Tgn为单体n的均聚物以开尔文计的玻璃化转变温度。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都采用乳液聚合法制备，但其中起始聚合温度通常并非必须低于100℃。该聚合反应的总转化率的至少60％，优选至少70％，更优选至少80％是在100℃至140℃的温度下发生的。
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反应。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至0.02重量％，优选为0.001至0.01重量％。
作为氧化还原引发剂使用所述引发剂与还原剂的组合。合适的还原剂是碱金属及铵的亚硫酸盐及亚硫酸氢盐，如亚硫酸钠，次硫酸衍生物，如甲醛化次硫酸锌或碱金属甲醛化次硫酸盐，如羟基甲烷亚磺酸钠，及抗坏血酸。均基于单体的总重量，还原剂的含量通常为0.001至0.03重量％，优选为0.001至0.015重量％。
为了控制分子量，可在聚合反应期间使用调节物质。若使用调节剂，则其基于待聚合的单体的使用量通常为0.01至5.0重量％，并且单独地或以预先与反应成分混合的方式按计量添加。这些物质的实例是正十二烷基硫醇、叔十二烷基硫醇、硫醇基丙酸、硫醇基丙酸甲酯、异丙醇及乙醛。
为稳定聚合混合物，可以添加本发明的聚乙烯醇(a)和(b)的混合物。但聚合也可以在其他保护胶体存在下进行。
聚合混合物适用的其他保护胶体有：聚乙烯醇；聚乙烯醇缩醛；聚乙烯吡咯烷酮；水溶性多糖，如淀粉(直链淀粉及支链淀粉)，纤维素及其羧甲基衍生物、甲基衍生物、羟乙基衍生物、羟丙基衍生物；蛋白质，如酪蛋白或酪蛋白酸盐、大豆蛋白、明胶；木质素磺酸盐；合成聚合物，如聚(甲基)丙烯酸、(甲基)丙烯酸酯与羧基官能的共聚单体单元的共聚物、聚(甲基)丙烯酰胺、聚乙烯基磺酸及其水溶性共聚物；三聚氰胺-甲醛磺酸盐、萘-甲醛磺酸盐、苯乙烯/马来酸共聚物及乙烯基醚/马来酸共聚物。
优选的是水解度为80至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至95摩尔％且在浓度为4％的水溶液中的
粘度为1至30毫帕斯卡·秒(
法，在20℃下)的部分水解的聚乙烯醇。优选的还有水解度为80至95摩尔％且在浓度为4％的水溶液中的
粘度为1至30毫帕斯卡·秒的部分水解的经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，该疏水性共聚单体例如是乙酸异丙烯酯、新戊酸乙烯酯、乙基己酸乙烯酯、具有5或9至11个碳原子的饱和α-分支单羧酸的乙烯基酯、马来酸二烷基酯及富马酸二烷基酯，如马来酸二异丙酯及富马酸二异丙酯，氯乙烯、乙烯基烷基醚，如乙烯基丁基醚，烯烃，如乙烯及癸烯。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至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至94摩尔％且在浓度为4％的水溶液中的粘度为3至15毫帕斯卡·秒(法，在20℃下)的聚乙烯醇。所述保护胶体是利用本领域技术人员所熟知的方法制成的，基于单体的总重量，在该聚合反应期间保护胶体的总添加量通常为1至20重量％。
若在存在乳化剂的情况下实施该聚合反应，则基于单体的量，该乳化剂的量为1至5重量％。合适的乳化剂为：阴离子型、阳离子型及非离子型乳化剂，例如阴离子表面活性剂，如链长度为8至18个碳原子的烷基硫酸盐、疏水性基团中具有8至18个碳原子且具有最多40个环氧乙烷单元或环氧丙烷单元的烷基醚硫酸盐或烷基芳基醚硫酸盐、具有8至18个碳原子的磺酸烷基酯或磺酸烷基芳基酯、磺基琥珀酸与一元醇或烷基酚的酯及半酯，或非离子表面活性剂，如具有8至40个环氧乙烷单元的烷基聚二醇醚或烷基芳基聚二醇醚。优选不加乳化剂。
聚合反应结束之后，可采用已知的方法，通常通过由氧化还原催化剂引发的后聚合反应而实施后聚合反应以去除残留单体。挥发性残留单体还可利用蒸馏加以去除，优选在减压下，并任选使诸如空气、氮气或水蒸汽的惰性夹带气体流经或流过产物。由此获得的含水分散体的固体含量为30至75重量％，优选为50至60重量％。
如果在其他保护胶体存在下进行所述聚合反应，则要在干燥之前添加本发明的聚乙烯醇(a)和(b)混合物。
为了生产水可再分散的聚合物粉末，含水分散体任选在添加作为干燥助剂的保护胶体后例如通过流化床干燥、冷冻干燥或喷雾干燥进行干燥。分散体优选喷雾干燥。喷雾干燥在常规的喷雾干燥装置中进行，采用单流体、双流体或多流体喷嘴或转盘均能实施雾化。出口温度一般在45至120℃，优选60至90℃，取决于干燥装置、树脂的Tg和要求的干燥程度。
通常，干燥助剂也是保护胶体，以该分散体的聚合物成分为基准，其总使用量通常为3至30重量％。也就是说，以聚合物成分为基准，该干燥过程之前保护胶体的总使用量应为3至30重量％，更优选以聚合物成分为基准为5至20重量％。
如果聚合采用本发明聚乙烯醇(a)和(b)的混合物进行，也可以使用其他合适的保护胶体作为干燥助剂。
其他适宜的干燥助剂有：部分水解的聚乙烯醇；聚乙烯吡咯烷酮；水溶性多糖，如淀粉(直链淀粉及支链淀粉)，纤维素及其羧甲基衍生物、甲基衍生物、羟乙基衍生物及羟丙基衍生物；蛋白质，如酪蛋白或酪蛋白酸盐、大豆蛋白、明胶；木质素磺酸盐；合成聚合物，如聚(甲基)丙烯酸、(甲基)丙烯酸酯与羧基官能的共聚单体单元的共聚物、聚(甲基)丙烯酰胺、聚乙烯基磺酸及其水溶性共聚物；三聚氰胺-甲醛磺酸盐、萘-甲醛磺酸盐、苯乙烯/马来酸共聚物及乙烯基醚/马来酸共聚物。优选不使用除聚乙烯醇以外的其他保护胶体作为干燥助剂，其中聚乙烯醇优选用作保护胶体，还优选用作干燥助剂。
已反复证实，基于基础聚合物，含量最高为1.5重量％的消泡剂在雾化期间是有利的。为通过提高结块稳定性以提高存储稳定性，特别是在具有低玻璃化转变温度的粉末的情况下，以聚合物成分的总重量为基准，所得粉末可混入优选最高30重量％的抗结块剂或抗成块剂。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、硅酸盐，其粒径优选为10纳米至10微米。
由固体含量调节待雾化物料的粘度，使得(于20转及23℃下以Brookfield粘度测得的)数值小于500毫帕斯卡·秒，优选小于250毫帕斯卡·秒。该待雾化的分散体的固体含量为至少35％，优选为至少40％。
为提高应用技术中的特性，可在雾化作用期间添加其他添加剂。在优选的具体实施方案中包含的分散粉末组合物的其他组分是：颜料、填料、泡沫稳定剂、疏水化剂。
根据本发明的分散粉末的制备方法是如下进行的：在水性介质中进行自由基聚合，随后干燥如此所获得的分散体，并且其特征在于，在聚合反应期间和/或在干燥水性分散体之前添加根据本发明所用的保护胶体。
根据本发明的由保护胶体稳定化的水可再分散的分散粉末可用于其典型的应用领域。例如用于与水固性粘结剂，水泥，如卜特兰水泥、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，及保温粘合剂粉刷头道浆、抹平剂、地板抹平剂、自找平的抹平剂、密封泥浆、接缝砂浆及涂料。优选的应用领域是：用于高层建筑及地下建筑的施工工程的喷射砂浆及混凝土喷浆，以及隧道壁的砌面。
具体实施方式
实施例
采用6重量％水解度为88摩尔％、
粘度为4毫帕斯卡·秒的聚乙烯醇作为起始分散体，制备玻璃化转变温度Tg为-7℃的乙酸乙烯酯-乙烯共聚物分散体。
粉末
该粉末是添加聚乙烯醇后制备的。其分散体采用双流体喷嘴喷雾。以预压缩至4巴的空气作为雾化组分，利用加热至125℃的空气在平行流中对所形成的液滴实施干燥。在获得的干燥粉末中混入10重量％可商购的抗结块剂碳酸钙镁。
粉末P1(按照本发明制备)
起始分散体与2重量％水解度为88摩尔％、
粘度为2毫帕斯卡·秒的聚乙烯醇，和3重量％水解度为88摩尔％、
粘度为13毫帕斯卡·秒的聚乙烯醇，以及2重量％水解度为88摩尔％、
粘度为4毫帕斯卡·秒的聚乙烯醇混合。
聚乙烯醇μ1的重量百分数＝15.4％，μw＝5.8毫帕斯卡·秒。
粉末P2(按照本发明制备)
起始分散体与5重量％水解度为88摩尔％、
粘度为2毫帕斯卡·秒的聚乙烯醇，和3重量％水解度88摩尔％、
粘度为13毫帕斯卡·秒的聚乙烯醇，以及2重量％水解度88为摩尔％、
粘度为4毫帕斯卡·秒的聚乙烯醇混合。
聚乙烯醇μ1的重量百分数＝31.3％，μw＝5.1毫帕斯卡·秒。
粉末V3(未按本发明)
起始分散体与12重量％水解度为88摩尔％、
粘度为2毫帕斯卡·秒的聚乙烯醇，和3重量％水解度为88摩尔％、
粘度为13毫帕斯卡·秒的聚乙烯醇，以及2重量％水解度为88摩尔％、
粘度为4毫帕斯卡·秒的聚乙烯醇混合。
聚乙烯醇μ1的质量百分数＝52.2％，μw＝4.1毫帕斯卡·秒。
粉末V4(未按本发明制备)
起始分散体与2重量％水解度88摩尔％、
粘度2毫帕斯卡·秒的聚乙烯醇，和5重量％水解度88摩尔％、
粘度13毫帕斯卡·秒的聚乙烯醇，以及2重量％水解度88摩尔％、
粘度4毫帕斯卡·秒的聚乙烯醇混合。
聚乙烯醇μ1的质量百分数＝13.3％，μw＝6.7毫帕斯卡·秒。
试验：
考察所获得的粉末，测定其粉末性质、密封浆的加工性以及与Styropor粘合性。
测定抗结块性(BF)：
为了测定抗结块性，将分散粉末装填入一个具有螺栓紧固件的铁管中，然后利用金属柱塞施加压力。施压之后，在干燥箱中于50℃下放置16小时。冷却至室温后，将粉末从管中取出，并通过压碎粉末定量测定抗结块性。以如下方式对抗结块性加以分级：
1～3＝非常好的抗结块性
4～6＝良好的抗结块性
7～8＝合格的抗结块性
9～10＝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(RA)：
再分散体的沉积特性用作粉末的可再分散性的度量。以50％的浓度在强烈的剪切力的作用下在水中形成再分散体。
然后对释释的固体含量为0.5％的再分散体测定沉积特性，为此将100毫升该分散体装入带有刻度的管中，并测量固体沉积物的高度。24小时后以毫米测量沉积数据。大于7的数值表明粉末的再分散作用不足。
测定用再分散粉末改性的含水泥的粘合剂对Styropor的胶粘抗拉强度(HZ)：
按下述配方(聚合物含量3％)试验对Styropor的胶粘抗拉强度(以拉脱百分数表示)：
石英砂 665份
卜特兰水泥 300份
纤维素 5份
再分散粉末 30份
在下述条件储存后再测定胶粘抗拉强度：
7d/21w 7天干燥/21天湿润(湿式储存)
按下述配方定性确定含水泥的密封浆的加工性(VA)：
石英砂 547份
卜特兰水泥 150份
纤维素 3份
再分散粉末 300份
将再分散粉末抗结块性、沉积特性、胶粘抗拉强度以及加工性的试验结果归纳于表1。
表1
| 实施例 | BF | RA | HZ | VA |
| P1* | 4 | 1.9 | 80 | 容易 |
| P2* | 5 | 2.3 | 85 | 容易，需水量较低 |
| V3 | 9 | 6.5 | 15 | 不能加工 |
| V4 | 3 | 2.1 | 78 | 粘稠，难加工 |
*按照本发明
由表1数据可见，本发明产物P1、P2的粉末性质未受到不利影响，其应用数据也获得改善。
Claims (9)
1、一种用保护胶体稳定化的分散粉末，其特征在于，所述保护胶体包含：
(a)至少一种根据DIN 53015的粘度μ1不超过3毫帕斯卡·秒的聚乙烯醇；以及
(b)至少一种根据DIN 53015的
粘度μ2为4至25毫帕斯卡·秒的聚乙烯醇；且该保护胶体的加权
粘度μw不超过6毫帕斯卡·秒，该分散粉末包含0.1至10.0重量％的聚乙烯醇(a)。
2、根据权利要求1所述的分散粉末，其特征在于，μ1为1.5至2.5毫帕斯卡·秒。
3、根据权利要求1或2所述的分散粉末，其特征在于，该分散粉末包含1.0至5.0重量％的聚乙烯醇(a)。
4、根据权利要求1或2所述的分散粉末，其特征在于，其含有选自以下组中的聚合物：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更多种其他乙烯基酯的共聚物、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。
5、制备根据权利要求1至4之一所述的分散粉末的方法，其是通过在水性介质中进行自由基聚合，随后干燥如此所获得的分散体来实施，其特征在于，在所述聚合反应期间和/或在干燥水性分散体之前添加所述保护胶体。
6、根据权利要求1至4之一所述的分散粉末的用途，其是与水固性粘结剂、石膏及水玻璃相结合用于建筑用化学产品中。
7、根据权利要求6所述的用途，其中所述水固性粘结剂为水泥。
8、根据权利要求1至4之一所述的分散粉末的用途，其是用于制造建筑粘合剂、砖瓦粘合剂及保温粘合剂、粉刷头道浆、抹平剂、密封泥浆、接缝砂浆及涂料。
9、根据权利要求1至4之一所述的分散粉末的用途，其是用于高层建筑及地下建筑的施工工程的喷射砂浆及混凝土喷浆，以及隧道壁的砌面。
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| EP2433984B1 (en) * | 2010-09-27 | 2014-06-18 | Dow Global Technologies LLC | Styrene-butadiene based redispersible polymer powders with improved stability in cement applications |
| CN102276181A (zh) * | 2011-05-18 | 2011-12-14 | 江苏名和集团有限公司 | 混凝土用阻泥剂及其制备方法 |
| DE102012203881A1 (de) * | 2012-03-13 | 2013-09-19 | Wacker Chemie Ag | Verwendung von anorganischen Materialien zur Herstellung von Verbundstoffen |
| DE102012209210A1 (de) * | 2012-05-31 | 2013-12-05 | Wacker Chemie Ag | Vinylacetat-Copolymere für hydraulisch abbindende Baustoffmassen |
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| US10988630B2 (en) * | 2014-12-19 | 2021-04-27 | Certainteed Corporation | Coating compositions for building materials and coated building material substrates |
| EP3856844A1 (en) * | 2018-09-27 | 2021-08-04 | Basf Se | Latex styrene butadiene powders and asphalt composition comprising said powder |
| EP3707109B1 (de) * | 2018-11-07 | 2021-01-27 | Wacker Chemie AG | Hydrophobe, in wasser redispergierbare polymerpulver-zusammensetzung |
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