CN1219922A - 韧性的建筑材料 - Google Patents

韧性的建筑材料 Download PDF

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CN1219922A
CN1219922A CN97194882A CN97194882A CN1219922A CN 1219922 A CN1219922 A CN 1219922A CN 97194882 A CN97194882 A CN 97194882A CN 97194882 A CN97194882 A CN 97194882A CN 1219922 A CN1219922 A CN 1219922A
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赖因哈德·黑奇舍尔
克里斯托夫·哈纳
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Abstract

本发明涉及基于无机粘结剂和一种或多种乙烯基酯－乙烯共聚物的韧性的塑料改性的建筑材料,其特征在于,该建筑材料包含保护胶体稳定的乙烯基酯－乙烯共聚物,所述共聚物可通过下列单体的自由基水乳液聚合而得到:a)15－80%重量的乙酸乙烯酯,b)5－35%重量的乙烯,c)5－60%重量的一种或多种含有5－18个碳原子的末支化或支化羧酸的乙烯基酯,和d)0－10%重量的其它可共聚的烯属不饱和单体。

Description

韧性的建筑材料
本发明涉及韧性的、塑料改性的建筑材料，另外还涉及用于韧性建筑材料的、由保护胶体稳定的乙烯基酯-乙烯共聚物的用途。
对于建筑领域的某些应用，例如在密封浆液或建筑粘结剂的应用中，需要高度韧性的混凝土或灰浆混合物。根据种种标准，例如密封浆液的标准，使用由乳化剂稳定的丙烯酸酯分散体改性的灰浆混合物。WO-A92/07804(AU-A9186679)描述了用于韧性建筑材料的粘结剂，所述粘结剂包含聚酯树脂和苯乙烯-丙烯酸酯共聚物乳液的混合物。EP-A558980(US-A5348993)披露了作为建筑材料添加剂的乳化剂稳定的苯乙烯-丙烯酸酯的分散体和乙烯基酯-丙烯酸酯的分散体。在存在这些添加剂的情况下，通过聚合物组份和用于稳定乳液的乳化剂而取得了韧性。有关韧性建筑材料现有技术状态的综述见于下面的文章中：Volkwein,A；Petri,R.；Springenschmid,R；“Protecting concrete by flexible waterproofing slurries”,Betonwerk-Fertihteil-Tech.(1988),54(8)30-36,54(9)72-78。
先前使用的乳化剂稳定的苯乙烯-丙烯酸酯分散体的缺点在于：它们只能用于双组份体系(组份1=干灰浆，组份2=分散体)，而且当使用包含当前体系(乙酸乙烯酯-乙烯共聚物)的可再分散的分散体粉末(在单组份体系中)时，不能取得足够的韧性。然而，与分散体相比，分散体粉末突出的优点在于，可生产出只需在建筑现场与水混合的干灰浆混合物。这将产生许多优点，如配方可靠性、安全加工性以及容器的容易处理性都得到提高。迄今为止，尚没有就韧性而言能与苯乙烯-丙烯酸酯共聚物分散体相比的基于乳化剂稳定的乙烯基酯共聚物分散体的体系。
DE-A 4206429(US-A5348993)披露了用于改善基于丙酸乙烯酯-VeoVa9(VeoVa10)乳液聚合物的建筑材料韧性的粘结剂，所述乳液聚合物是在包含环氧乙烷-环氧丙烷-聚醚、乙氧基化烷基酚和乙氧基化多糖的乳化剂混合物的存在下制备的。其缺点在于，例如当用于密封浆液中时，不能获得足够的伸长率。
EP-A527322披露了用于水泥混合物的添加剂，所述混合物中含有在乳化剂和保护胶体的存在下通过乳液聚合法制备的乙烯-乙酸乙烯酯-新戊酸乙烯酯共聚物。与乙酸乙烯酯-乙烯共聚物相比，显著地改善了耐碱性。其缺点在于，当用于韧性建筑材料时其伸长率不够。
EP-A518406披露了乙烯、乙酸乙烯酯以及含有5或9个碳原子的α-支化叔羧酸的乙烯基酯的共聚物的制备方法，其中用新戊酸乙烯酯(VeoVa5)替代VeoVa9进行聚合，从而改善乙烯的掺合程度。EP-A295727涉及含有带有9或10个碳原子的α-支化叔羧酸(VeoVa9)或(VeoVa10)的乙烯-乙酸乙烯酯的共聚物，为了使涂料降低粘性，建议用含有VeoVa9的共聚物替代含有VeoVa10的共聚物。在EP-A518406和EP-A295727中均未讨论有关建筑材料的韧性。
本发明的目的是提供基于乙烯基酯共聚物的共聚物，所述共聚物不仅适于水分散体的形式，而且优选适于可由这些分散体生产的可再分散的分散粉末的形式，以便生产高度韧性的建筑材料，尤其是密封浆液。这些共聚物应满足下列要求，即相应的共聚物分散体具有至少等于常规苯乙烯-丙烯酸酯分散体的强度和韧性，但相应的分散粉末的韧性作用将比常规乙酸乙烯酯-乙烯分散粉末好得多。
业已令人惊奇地发现，通过添加用保护胶体稳定的乙酸乙烯酯、乙烯和含有5-18个碳原子的末支化或支化羧酸的乙烯基酯的共聚物，提供了高度韧性的建筑材料，其中所述的共聚物是利用保护胶体的稳定化作用、由乳液聚合法制得的，所述建筑材料具有良好的强度，以及比基于乙酸乙烯酯-乙烯的粉末改性的建筑材料明显更高的伸长性。
本发明提供基于无机粘结剂和一种或多种乙烯基酯-乙烯共聚物的韧性的塑料改性的建筑材料，其特征在于，该建筑材料包含保护胶体稳定的乙烯基酯-乙烯共聚物，所述共聚物可通过下列单体的自由基水乳液聚合而得到：
a)15-80％重量的乙酸乙烯酯，
b)5-35％重量的乙烯，
c)5-60％重量的一种或多种含有5-18个碳原子的末支化或支化羧酸的乙烯基酯，和
d)0-10％重量的其它可共聚的烯属不饱和单体。
另外，本发明还提供保护胶体稳定的乙烯基酯-乙烯共聚物在生产基于无机粘结剂的韧性建筑材料中的用途；其中所述共聚物可通过下列单体的自由基水乳液聚合而得到：
a)15-80％重量的乙酸乙烯酯，
b)5-35％重量的乙烯，
c)5-60％重量的一种或多种含有5-18个碳原子的末支化或支化羧酸的乙烯基酯，和
d)0-10％重量的其它可共聚的烯属不饱和单体。
在所有场合，重量百分比均以共聚物的总重量计。
优选的共聚单体c)是月桂酸乙烯酯，硬脂酸乙烯酯，2-乙基己酸乙烯酯和含有5至11个碳原子的α-支化叔羧酸的乙烯基酯，例如VeoVa5,VeoVa9,VeoVa10和VeoVa11(带有5,9,10或11个碳原子，得自Shell的versatic酸的乙烯基酯)。特别优选的是：含有9-11个碳原子的α-支化叔羧酸的乙烯基酯，例如VeoVa9,VeoVa10或VeoVa11。
合适的共聚单体d)是，例如起稳定化作用的辅助单体，如α,β-单烯属不饱和单羧酸和二羧酸及其酰胺或腈类，例如，丙烯酸，甲基丙烯酸，丙烯酰胺；烯属不饱和磺酸或其盐，优选乙烯基磺酸，2-丙烯酰氨基丙磺酸酯；N-乙烯基吡咯烷酮。
特别优选的是，包含如下单体组份的乙烯基酯-乙烯共聚物：a)40-70％重量的乙酸乙烯酯，b)10-30％重量的乙烯和c)20-40％重量的一种或多种含有5,9,10或11个碳原子的α-支化叔羧酸的乙烯基酯。
所述的保护胶体稳定的乙烯基酯-乙烯共聚物是通过自由基，水乳液聚合法而制得的，其中使用保护胶体进行稳定作用。所使用的介质优选是水；另外也能使用水和可与水混溶的液体的混合物。在用或不用种子胶乳下，利用初装反应混合物的所有组份或各别组份，或部分初装反应混合物的组份然后计量加入反应混合物的其它各个组份，或者在没有初装下通过原料流法，可间歇或连续地进行聚合作用。优选对所有组份进行计量添加，以便与各组份的消耗相符。
聚合通常在20-95℃，优选在25-65℃下进行。乙烯的压力在10和85巴之间。利用常用于乳液聚合的水溶性自由基引发剂，进行引发，所述的这些引发剂以单体总重量计，其用量优选从0.01-5.0％重量。这些引发剂的例子是过氧化氢、过氧化叔丁基；烷基过氧化氢如叔丁基过氧化氢；过硫酸钾、过硫酸钠和过硫酸铵；偶氮化合物如偶氮二异丁腈或偶氮二氰基戊酸。以单体的总重量计，优选以已知的方法将0.01-1.0％重量的上述自由基引发剂与还原剂结合。合适的还原剂的例子是甲醛合次硫酸氢碱金属盐，羟甲基亚磺酸，亚硫酸钠和抗坏血酸。在氧化还原引发中，优选在聚合期间计量加入一种或多种氧化还原催化剂组份。此外，可通过添加能以多种氧化态存在的金属离子而增加引发剂体系的活性。优选使用铁(Ⅱ)离子，例如硫酸铁(Ⅱ)的形式。
用于使聚合混合物稳定的分散剂，在不添加乳化剂下优选只是保护胶体；特别优选的是以单体总重量计1-20％重量的保护胶体。合适的保护胶体是，例如，纤维素如羟乙基纤维素，羟丙基纤维素和羧甲基纤维素；聚乙烯醇，聚乙二醇，聚乙烯吡咯烷酮，聚(甲基)丙烯酸；优选使用部分皂化的聚乙烯醇。特别优选的是，水解度从75-95摩尔％，郝普勒粘度(20℃时4％的水溶液)从4-35mPas的部分皂化的聚乙烯醇。如果使用乳化剂的话，其用量应低于1.0％重量(以单体总重量计)。
在完成聚合之后，将分散体的固含量调节至30-65％重量，优选从45-55％重量。保护胶体稳定的乙烯基酯-乙烯共聚物能以其水分散体的形式或优选以可再分散于水中的分散粉末的形式添加至建筑材料中。
优选通过喷雾干燥生产分散粉末。在此，用常规的喷雾干燥装置进行干燥，而雾化可通过单流体、双流体或多流体喷嘴，或通过转盘而进行。
在喷雾干燥之前，优选将在乳液聚合后得到的保护胶体稳定的乙烯基酯-乙烯共聚物分散体的固含量调节至20-60％重量。该固含量取决于在干燥步骤中添加的其它添加剂的种类和用量。例如，可将优选为乙烯基酯-乙烯共聚物的重量的2-20％的上述保护胶体作为雾化助剂添加至分散体中。
在雾化时，业已发现，以共聚物计至多1.5％重量的消泡剂含量是有用的。液体消泡剂通常在干燥之前添加至分散体中，固体消泡剂可混入干燥分散粉末组合物中。
分散粉末颗粒的平均粒径通常从10-400微米。将粉末再分散于水中，从而得到粒径在0.1和5.0微米之间的分散体。
为了通过改善防结块性而增加贮存期限，将得到的粉末与防结块剂混合，所述防结块剂的用量以聚合组份的总重量计优选从3-25％重量。防结块剂的例子是细碎的硅酸铝，硅藻土，胶体硅胶，热解二氧化硅，沉淀二氧化硅，超细二氧化硅(microsilica)，轻晶石，高岭土，滑石，水泥，碳酸镁和/或碳酸钙或硅酸氢镁。
在优选的实施方案中，存在于分散粉末组合物中的另外的组份例如是：染料、填料、泡沫稳定剂和防水剂。这些组份可在喷雾干燥之前或之后添加。
保护胶体稳定的乙烯基酯-乙烯共聚物呈水分散体形式，或优选呈分散粉末组合物的形式，它们用来改善基于无机粘结剂的建筑材料，所述粘结剂如水泥、石膏或石灰浆。与同样可应用的水分散体相比，优选使用分散粉末，由此可使用干燥灰浆混合物，所述混合物只需在建筑工地与水混合。
无机粘结剂的例子是水泥，如卜特兰水泥，铝酸盐水泥，粗面凝灰炭水泥，Hullen水泥，镁氧水泥，磷酸盐水泥，石膏，如呈建筑石膏状、灰泥石膏状或模型石膏状的硫酸钙水合物和/或石灰，如氢氧化钙。除无机粘结剂和水以外，对于每次应用而言，建筑材料还包含通常粒径和用量的填料，如砂，例如石英砂或石英粉，二氧化硅，碳酸钙，白云石，轻晶石。填料的另外的例子是纤维，如丙烯酸酯纤维，聚乙烯纤维或纤维素纤维。
用于建筑材料组合物中另外常用的添加剂是增稠剂，例如有机增稠剂如纤维素醚，以及无机增稠剂，如膨润土，颜料，湿润剂，分散助剂，固化剂，消泡剂，成膜助剂，防冻剂。
优选将保护胶体稳定的乙烯基酯-乙烯共聚物用于制备高韧性密封浆液、建筑粘结剂、填缝灰浆、修补灰浆或修补裂缝的灰泥中。最优选的是用来制备高韧性、可胶接的密封浆液。密封浆液典型的干配方如下：
10-50重量份水泥，
10-50重量份石英砂，
1.0-10重量份纤维，
0.1-1.0重量份水泥增塑剂，
0.1-1.0重量份消泡剂。
将保护胶体稳定的乙烯基酯-乙烯共聚物用来改善建筑材料的韧性，以干配方总重量计共聚物部分优选从10-50％重量。可使用的建筑材料通过与水混合而制得，其中优选这样来计量水用量，以100重量份干配方计，使用25-60重量份水。
当使用保护胶体稳定的乙烯基酯-乙烯共聚物的水分散体时，可利用建筑工业中常用于混合灰浆的搅拌机来混合该分散体。合适的首先是用必需量的搅拌水稀释分散体，然后，添加由水泥，填料以及另外的添加剂组成的混合物。当使用分散粉末时，将该分散粉末与干配方组分进行混合，然后再将该混合物与计算量的搅拌水进行搅拌。
根据本发明使用的保护胶体一稳定的乙烯基酯-乙烯共聚物首先是用来改善基于乙酸乙烯酯-乙烯共聚物的建筑材料的弹性，当本发明的共聚物呈水分散体形式时，至少可与苯乙烯/丙烯酸酯分散体相匹敌，但作为干粉时，相应的伸长性将明显超过保护胶体稳定的苯乙烯-丙烯酸酯粉末和乙酸乙烯酯-乙烯粉末。迄今为止，对于这种应用而言，常用的乙酸乙烯酯-乙烯聚合物只显示出不充分的伸长性和韧性；其原因在于，迄今为止，在这种应用中，只使用苯乙烯/丙烯酸酯分散体(参见Volkwein,A等)。
实施例
本发明使用的分散体和分散粉末：分散体1
用3％重量的聚乙烯醇(水解度为88％，郝普勒粘度(20℃时4％的水溶液)为4mPas)稳定水分散体，所述分散体包含：固含量为51.5％重量的乙酸乙烯酯-乙烯-VeoVa10共聚物，该共聚物包含56％重量的乙酸乙烯酯，20％重量的乙烯，24％重量的VeoVa10，并且Tg为-13℃。分散体2
用3％重量的聚乙烯醇(水解度为88％，郝普勒粘度(20℃时4％的水溶液)为4mPas)稳定水分散体，所述分散体包含：固含量为48％重量的乙酸乙烯酯-乙烯-VeoVa10共聚物，该共聚物包含46％重量的乙酸乙烯酯，23％重量的乙烯，31％重量的VeoVa10，并且Tg为-15℃。分散粉末1和2：
为制备分散粉末，分别向上述分散体1和2中添加以聚合物计为10％重量的聚乙烯醇(水解度为88％，郝普勒粘度为8mPas)和以聚合物计为0.3％重量的消泡剂。通过双流体喷嘴将该混合物进行喷射。然后将得到的粉末与10％重量市售的防粘剂进行混合。
不根据本发明使用的对比分散体和对比分散粉末：分散体A：
乳化剂稳定的水分散体，包含55％重量的苯乙烯-丙烯酸酯-共聚物(Tg为-7℃)。分散体B：
乳化剂稳定的水分散体，包含50％重量的苯乙烯-丙烯酸酯-共聚物(Tg为-7℃)。分散体C：
乳化剂稳定的水分散体，包含53％重量的苯乙烯-丙烯酸酯-共聚物(Tg为-40(℃)。分散粉末A至D：
为制备分散粉末A-D，向相应的水分散体中添加以聚合物计为10％重量的聚乙烯醇(水解度为88％，郝普勒粘度为8mPas)和以聚合物计为0.3％重量的消泡剂。通过双流体喷嘴将该混合物进行喷射。然后将得到的粉末与10％重量市售的防粘剂进行混合。分散粉末A：
基于聚乙烯醇稳定的苯乙烯-丙烯酸酯共聚物(Tg为-7℃)的分散粉末。分散粉末B：
基于聚乙烯醇稳定的苯乙烯-丙烯酸酯共聚物(Tg为-18℃)的分散粉末。分散粉末C：
基于聚乙烯醇稳定的苯乙烯-丙烯酸酯共聚物(Tg为-40℃)的分散粉末。分散粉末D：
基于聚乙烯醇稳定的乙酸乙烯酯-乙烯共聚物(Tg为-7℃)的分散粉末。工业应用试验：
在下列配方Ⅰ和Ⅲ的密封浆液组合物中，对分散粉末进行试验。在配方Ⅱ的密封浆液组合物中，对分散体进行试验。配方                       Ⅰ          Ⅱ          Ⅲ
                     (重量份)    (重量份)    (重量份)卜特兰水泥PZ35             350         350         350石英砂F36                  285         285         185Arbocell BC 1000(纤维)     20          20          20Melment F 10(水泥增塑剂)   3           3           3Tixoton CV 15(增稠剂)      37          37          37Agitan P800(消泡剂)        5           5           5分散粉末                   300         -           400分散体(50％固含量)         -           600         -水                         350         50          350
将上述配方组成在灰浆混合机中干混3分钟。然后添加水，在配方Ⅱ的情况下，先添加分散体和水，然后再混合2分钟。在熟化10分钟之后，将灰浆混合30秒钟，然后，滴加至聚四氟乙烯模板上以形成2mm厚的密封浆液层，干燥后，从模板上取下，并根据表1,2和3中的参数进行储存。
储存之后，对由密封浆组成的肩状板条进行冲压成形，并根据DIN53504，在拉伸速度为10mm/min的Instron-拉伸机上进行的拉伸试验中，测量裂断强度和裂断伸长。各测量系列的平均值列于表1-3中。
在这些表中：
d=以天计的储存时间；’=以分钟计的储存时间；
NK=在23℃,50％相对湿度的标准状态储存；
Naβ=在23℃的水中湿态储存；
0℃=在0℃,50％相对湿度的状态储存。
测量值列于下面的表格中：
裂断伸长率[％]/裂断强度[N/mm2]
  表1(配方I的粉末)：
储存     A           B         C          D           1            2
28d NK 5.6/2.2    5.1/2.8    4.5/-     13.3/4.3    30.7/3.4     32.4/2.1
28d NK 5.5/2.1    5.9/1.1    7.2/0.8   12.9/4.9    12.4/1.2     14.6/0.9
7d Naβ
28d NK 1.5/4.4    3.5/3.7    2.1/3.9    9.8/0.9    23.0/3.8     18.5/3.5
14d Naβ
14d NK
28d NK  -/-       5.4/10.5   2.1/11.0     -/-       6.3/10.4    14.9/6.8
30’0℃
当在恒定的裂断强度下与聚乙烯醇稳定的苯乙烯-丙烯酸酯粉末(粉末A,B,C)或聚乙烯醇稳定的乙酸乙烯酯-乙烯粉末(粉末D)相比时，用粉末1和2(聚乙烯醇稳定的乙酸乙烯酯-乙烯聚合物)改性的密封浆液显示出明显更好的裂断伸长率。
表Ⅱ(配方Ⅲ的粉末)：储存        A         B           C         D           1           228dNK    9.9/2.0   10.2/2.7    8.7/-     19.4/3.9    57.2/3.4    67.1/1.928dNK    9.0/1.9    9.8/0.9   11.2/0.7   21.3/0.6    48.3/1.0    47.2/0.87dNa828dNK    2.6/4.4    5.9/3.9    3.3/4.1   14.4/3.8    63.8/3.5    62.6/3.314dNaβ14dNK28dNK      -/-     10.8/10.7   4.1/11.7     -/-      18.1/10.7   29.6/7.630’0℃
通过该试验得到了与表1类似的结果：
当在恒定的裂断强度下与聚乙烯醇稳定的苯乙烯-丙烯酸酯粉末(粉末A,B,C)或聚乙烯醇稳定的乙酸乙烯酯-乙烯粉末(粉末D)相比时，用粉末1和2(聚乙烯醇稳定的乙酸乙烯酯-乙烯聚合物)改性的密封浆液显示出明显更好的裂断伸长率。
表3(配方Ⅱ的分散体)储存         A          B           C           1             214dNK    62.2/2.5    35.1/3.9    37.5/2.0    115.0/2.5    113.0/1.614dNK    39.4/0.7    39.3/0.7    36.7/5.7     34.1/-       44.3/0.67dNaβ14dNK    59.4/2.5    27.2/5.1    27.4/2.1     58.1/2.8     80.8/1.87dNaβ7dNK
本发明使用的保护胶体稳定的乙烯基酯-乙烯共聚物(呈水分散体形式)(分散体1和2)起到了改善建筑材料弹性的作用，其相应的伸长性至少与传统的、乳化剂稳定的苯乙烯-丙烯酸酯一分散体(分散体A)相匹敌，或者明显地好于所述的分散体(分散体B,C)。

Claims (10)

1．一种基于无机粘结剂和一种或多种乙烯基酯-乙烯共聚物的韧性的塑料改性的建筑材料，其特征在于，该建筑材料包含保护胶体稳定的乙烯基酯-乙烯共聚物，所述共聚物可通过下列单体的自由基水乳液聚合而得到：
a)15-80％重量的乙酸乙烯酯，
b)5-35％重量的乙烯，
c)5-60％重量的一种或多种含有5-18个碳原子的末支化或支化羧酸的乙烯基酯，和
d)0-10％重量的其它可共聚的烯属不饱和单体。
2．一种保护胶体稳定的乙烯基酯-乙烯共聚物在生产基于无机粘结剂的韧性建筑材料中的用途；其中所述共聚物可通过下列单体的自由基水乳液聚合而得到：
a)15-80％重量的乙酸乙烯酯，
b)5-35％重量的乙烯，
c)5-60％重量的一种或多种含有5-18个碳原子的末支化或支化羧酸的乙烯基酯，和
d)0-10％重量的其它可共聚的烯属不饱和单体。
3．如权利要求1或2，其中，共聚单体c)是月桂酸乙烯酯，硬脂酸乙烯酯，2-乙基己酸乙烯酯和含有5至11个碳原子的α-支化叔羧酸的乙烯基酯。
4．如权利要求1或2，其中共聚单体c)是含9、10或11个碳原子的支化羧酸的乙烯基酯。
5．如权利要求1-4，其中的乙烯基酯-乙烯共聚物是：包含如下单体组分的乙烯基酯-乙烯共聚物：a)40-70％重量的乙酸乙烯酯，b)10-30％重量的乙烯和c)20-40％重量的一种或多种含有5、9、10或11个碳原子的α-支化叔羧酸的乙烯基酯。
6．如权利要求1-5，其中保护胶体包括：水解度为75-95摩尔％，郝普勒粘度(20℃时4％的水溶液)为4-35mPas的部分皂化的聚乙烯醇。
7．如权利要求1-6，其中，将由保护胶体稳定的、呈水分散体形式的乙烯基酯-乙烯共聚物添加至建筑材料中。
8．如权利要求1-6，将由保护胶体稳定的、呈可再分散于水中的分散粉末形式的乙烯基酯-乙烯共聚物添加至建筑材料中。
9．如权利要求1-8，其中所述的建筑材料包括：密封浆液，建筑粘结剂，填缝灰浆，修补灰浆或修补裂缝的灰泥。
10．如权利要求1-9，其中，所述的建筑材料包含保护胶体稳定的乙烯基酯-乙烯共聚物，以干配方总重量计共聚物部分优选占10-50％重量。
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EP0902769A1 (de) 1999-03-24
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