CN102549021B - 聚氯丁二烯胶乳的制造方法、聚氯丁二烯胶乳、及使用其的粘接剂 - Google Patents
聚氯丁二烯胶乳的制造方法、聚氯丁二烯胶乳、及使用其的粘接剂 Download PDFInfo
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- CN102549021B CN102549021B CN201080037181.5A CN201080037181A CN102549021B CN 102549021 B CN102549021 B CN 102549021B CN 201080037181 A CN201080037181 A CN 201080037181A CN 102549021 B CN102549021 B CN 102549021B
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- chloroprene
- polychloroprene latex
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- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/14—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
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Abstract
本发明提供粘接物性极为优异的聚氯丁二烯胶乳。本发明为在添加有小于临界胶束浓度(CMC)的表面活性剂和由芳香族磺酸甲醛缩合物的金属盐形成的高分子分散剂的水性介质中使氯丁二烯、或者氯丁二烯和可与氯丁二烯共聚的单体聚合的聚氯丁二烯胶乳的制造方法。该高分子分散剂优选使用芳香族磺酸甲醛缩合物的金属盐。所得聚氯丁二烯胶乳可以用作粘接剂。
Description
技术领域
本发明涉及通过在水性介质中聚合而制造聚氯丁二烯胶乳的方法及使用其的粘接剂。
背景技术
以聚氯丁二烯为基础的粘接剂以溶于甲苯、己烷、乙酸乙酯、甲乙酮、环己烷等有机溶剂的溶剂型为主流,因此被指出存在环境污染等问题。因此,不使用有机溶剂的所谓水系粘接剂的开发正在积极进行中,然而,在现有的聚氯丁二烯胶乳中存在粘接性、耐水性不充分的问题。
在聚氯丁二烯胶乳的制造中使用所谓的乳液聚合法。乳液聚合法中,使用松香酸皂、烷基硫酸钠、高级醇硫酸酯钠、聚氧乙烯烷基醚、烷基胺盐、季铵盐、聚乙烯醇等乳化剂,使氯丁二烯、或者氯丁二烯和可与氯丁二烯共聚的单体在水中乳化后,添加过硫酸钾等自由基引发剂而使氯丁二烯聚合。然而,由于该聚合方法中通常需要大量的乳化剂,会妨碍聚氯丁二烯原本的粘接性,因此有时得到的粘接剂的粘接物性、耐水性会显著降低。于是,进行了各种尝试来制造乳化剂含量减少的聚氯丁二烯胶乳。
在氯丁二烯的乳液聚合中,从分散稳定地进行聚合、提高各种物性的目的出发,有时会将高分子分散剂与各种表面活性剂组合添加。高分子分散剂通常尽管表面活性较低,但多具有分散性、聚集性、可溶化性等特征,较低分子量的高分子分散剂会像乳化剂那样形成胶束,但高分子量的高分子分散剂其自身具有胶束那样的大小,因此认为不有助于胶束形成。作为氯丁二烯的乳液聚合中使用的高分子分散剂,芳香族磺酸甲醛缩合物的金属盐是特别常用的,因其具有强分散能力而被广泛使用。
但是,在使用以芳香族磺酸甲醛缩合物的金属盐为代表的高分子分散剂时,必须与过量的表面活性剂(包含具有乳化能力的聚合物)组合添加到水性介质中,无法避免所得粘接剂的粘接物性的降低(例如专利文献1、专利文献2、专利文献3)。
现有技术文献
专利文献
专利文献1:日本特开2008-222736号公报
专利文献2:日本特开2007-297502号公报
专利文献3:日本特开2006-199932号公报
发明内容
发明要解决的问题
如上所述,迫切需要开发出初始强度等粘接物性得到改善的新型聚氯丁二烯胶乳及使用其的粘接剂,本发明以解决这一问题为课题。
用于解决问题的方案
本发明人等对上述问题进行了深入研究,结果发现在具有小于临界胶束浓度的表面活性剂物种的水性介质中添加由芳香族磺酸甲醛缩合物的金属盐形成的高分子分散剂来制造聚氯丁二烯胶乳的方法。进而,使用该聚氯丁二烯胶乳的粘接剂可以大幅改善初始粘接力等现有的问题,由此完成了本发明。
即,本发明提供一种聚氯丁二烯胶乳的制造方法,所述方法在添加有小于临界胶束浓度(CMC)的表面活性剂和由芳香族磺酸甲醛缩合物的金属盐形成的高分子分散剂的水性介质中使氯丁二烯、或者氯丁二烯和可与氯丁二烯共聚的单体聚合。
所述高分子分散剂可以在氯丁二烯聚合前初期添加而不在氯丁二烯的聚合途中添加。另外,在添加该高分子分散剂而未添加表面活性剂的水性介质中进行氯丁二烯的聚合时,会进一步提高粘接剂的品质。该高分子分散剂的用量相对于100重量份水性介质为0.01重量份以上且0.1重量份以下是理想的。
进而,本发明还提供使用通过上述制造方法制造的聚氯丁二烯胶乳的粘接剂。
发明的效果
根据本发明,在聚合工序中不需要大量的表面活性剂,通过添加芳香族磺酸甲醛缩合物的金属盐,对聚合中的分散稳定有很大帮助,可以得到基本上没有附着物产生、初始粘接力等粘接物性极为良好的聚氯丁二烯胶乳。进而,聚合时间缩短,可以对生产率的提高带来很大帮助。本发明得到的聚氯丁二烯胶乳不使用妨碍粘接力的各种表面活性剂物种、或者只添加极少量妨碍粘接力的各种表面活性剂物种,因此容易获得氯丁二烯原本的初始粘接力,初始粘接力等粘接性显著改善,适用于纸、木材、布、乔赛、皮革、革、橡胶、塑料、发泡体(foam)、陶器、玻璃、水泥基质和金属等同类或不同类的接合。
具体实施方式
对本发明所使用的表面活性剂没有特别限制,作为公知的表面活性剂,可列举阴离子性表面活性剂、非离子性表面活性剂、阳离子性表面活性剂等,例如,作为阴离子性表面活性剂,可列举松香酸盐、高级脂肪酸盐、烯基琥珀酸盐、烷基硫酸钠、高级醇硫酸酯钠、烷基苯磺酸盐、烷基二苯醚二磺酸盐、高级脂肪酸酰胺的磺酸盐、高级脂肪酸烷基醇酰胺的硫酸酯盐、烷基磺基甜菜碱等,作为非离子性表面活性剂,可列举聚氧乙烯烷基醚、聚氧乙烯山梨糖醇酐脂肪酸酯、高级脂肪酸烷醇酰胺、聚乙烯醇等,作为阳离子性表面活性剂,可列举烷基胺盐、季铵盐等。
另外,对本发明所使用的芳香族磺酸甲醛缩合物的金属盐也没有特别限制,例如可列举出萘磺酸甲醛缩合物的钠盐、甲基萘磺酸甲醛缩合物的钠盐、其他特殊芳香族系磺酸甲醛缩合物的钠盐等,特别适宜的是常用的萘磺酸甲醛缩合物的钠盐。
本发明中,表面活性剂是指,添加量增加时会在水性介质中形成胶束(表面活性剂的集合体)的乳化剂。另外,芳香族磺酸甲醛缩合物的金属盐由于其本身具有胶束那样的大小,因此即使增加添加量也不会对水性介质中的胶束形成带来帮助。
本聚合的特征在于,在水性介质中表面活性剂物种小于CMC(包括添加量为0的情况)的条件下,添加芳香族磺酸甲醛缩合物的金属盐进行聚合。为了进一步提高初始粘接强度,不添加表面活性剂是理想的,优选的是,相对于100重量份水性介质添加0.5重量份以下的芳香族磺酸甲醛缩合物的金属盐。更优选的是,不添加表面活性剂且相对于100重量份水性介质添加0.01~0.1重量份芳香族磺酸甲醛缩合物的金属盐。
此外,在本发明中A~B是指A以上且B以下的意思,在A没有附加单位时,设A的单位与B的单位(重量份等)相同。
CMC是指在纯水中的CMC,例如十二烷基苯磺酸钠(DBS)的CMC在60℃纯水中为1.2mmol/dm3H2O(利用电导率法测定),十二烷基硫酸钠(SDS)的CMC在50℃纯水中为8.1mmol/dm3H2O(利用表面张力法测定)。
在本发明中,与实际使用水性介质时的温度无关,采用50℃纯水的CMC(利用表面张力法)。在实际使用的水性介质包含水以外的物质的情况下,将水性介质假定为纯水,使水性介质中的表面活性剂浓度小于50℃纯水中的CMC。例如,在表面活性剂为SDS的情况下,SDS的CMC在50℃纯水中为8.1mmol/dm3H2O,因此,使1dm3水性介质(包括水、其他溶剂)中含有不足8.1mmol的SDS。
还可以含有两种以上表面活性剂,该情况下,将所添加的表面活性剂物种中的CMC最低的表面活性剂的CMC作为总表面活性剂添加量的上限。即,使水性介质中的表面活性剂含量的总和不足该CMC。例如,在使用CMC为1mmol/dm3 H2O的表面活性剂A和CMC为2mmol/dm3 H2O的表面活性剂B的情况下,使表面活性剂A、B的总浓度不足1mmol/dm3 H2O。
本发明中使用的水性介质是含有50重量%以上水的介质,可以添加醇等有机溶剂,但优选水性介质中水的含量为90重量%以上。有机溶剂的添加量为10重量%以上、水的含量不足90重量%时,会对氯丁二烯胶乳的性质带来不良影响。
在本发明中,对表面活性剂以及由芳香族磺酸甲醛缩合物的金属盐形成的高分子分散剂的添加方法没有特别限制,在聚合前初期添加的方法、在聚合中分批添加的方法等任意方法皆可。从提高生产率、并得到特别是初始粘接强度大的聚氯丁二烯胶乳的目的出发,不添加表面活性剂物种而仅在聚合前初期添加芳香族磺酸甲醛缩合物的金属盐的方法是适宜的。
在本发明中,氯丁二烯是指氯丁二烯的单体(chloroprenemonomer),具体而言为2-氯-1,3-丁二烯。而且,可与氯丁二烯共聚的单体(monomer)例如可列举:2,3-二氯-1,3-丁二烯、2-氰基-1,3-丁二烯、1-氯-1,3-丁二烯、1,3-丁二烯、异戊二烯等1,3-丁二烯类,苯乙烯、α-甲基苯乙烯、对氯甲基苯乙烯、对氰基苯乙烯、对乙酰氧基苯乙烯、对苯乙烯磺酰氯、对苯乙烯磺酸乙酯、对丁氧基苯乙烯、4-乙烯基苯甲酸、3-异丙烯基-α,α′-二甲基苄基异氰酸酯等苯乙烯类,甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸-2-羟丙酯、甲基丙烯酸-4-羟丁酯、甲基丙烯酸-2-(二甲基氨基)乙酯、甲基丙烯酸-2-(二乙基氨基)乙酯、甲基丙烯酸-3-(二甲基氨基)丙酯、甲基丙烯酸-2-(异氰酸根合)乙酯、甲基丙烯酸-2,4,6-三溴苯酯、甲基丙烯酸2,2,3,3-四氟丙酯、甲基丙烯酸-2,2,2-三氟乙酯、甲基丙烯酸-2,2,3,3,3-五氟丙酯、甲基丙烯酸-2,2,3,4,4,4-六氟丁酯等甲基丙烯酸酯类,丙烯酸丁酯、丙烯酸乙酯、丙烯酸-2-乙基己酯、丙烯酸-2-乙氧基乙酯、丙烯酸-2-丁氧基乙酯、丙烯酸环己酯、丙烯酸-3-(三甲氧基甲硅烷基)丙酯、丙烯酸-2,2,3,3-四氟丙酯、丙烯酸-2,2,2-三氟乙酯、丙烯酸-2,2,3,3,3-五氟丙酯、丙烯酸-2,2,3,4,4,4-六氟丁酯等丙烯酸酯类,以及丙烯腈、甲基丙烯腈、丙烯酸-α-氰基乙酯、马来酸酐、马来酸、柠康酸酐、乙烯基乙酸、马来酸酯、富马酸酯、巴豆酸、衣康酸、富马酸、单2-(甲基丙烯酰氧基)乙基邻苯二甲酸酯、单2-(甲基丙烯酰氧基)乙基琥珀酸酯、单2-(丙烯酰氧基)乙基琥珀酸酯、甲基丙烯酸、丙烯酸、丙烯醛、双丙酮丙烯酰胺、乙烯基甲基酮、乙烯基乙基酮、二丙酮甲基丙烯酸酯等。其中,从与氯丁二烯的自由基共聚性比较高的方面考虑,优选2,3-二氯-1,3-丁二烯、2-氰基-1,3-丁二烯、1-氯-1,3-丁二烯、苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸、甲基丙烯酸缩水甘油酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯、甲基丙烯酸-4-羟基丁酯、α-氰乙基丙烯酸酯、马来酸酐、马来酸。与氯丁二烯的共聚性最高的2,3-二氯-1,3-丁二烯更为适宜。另外,还可以根据需要组合使用2种以上这些单体。
氯丁二烯和可与氯丁二烯共聚的单体的添加量相对于100重量份水性介质优选为1~50重量份,在该范围内时,可获得特别稳定的聚氯丁二烯胶乳。
对氯丁二烯的添加方法没有特别限定,在欲加快聚合速度而提高生产率的情况下,优选在聚合过程中将氯丁二烯的一部分连续地或间断地添加到聚合体系内的方法。例如,将100重量份氯丁二烯中的10~50重量份添加到聚合体系内,引发聚合,在其转化率达到1~40%的时刻至聚合终止的期间内,将保持为较聚合温度更低的温度的剩余的单体连续地添加到聚合体系内,进行聚合即可。该情况下,在本发明中,在聚合开始后无需变更水性介质,且即使不进行中和等调整也可以使氯丁二烯聚合。即,本发明可使氯丁二烯在同一水性介质中连续地聚合而获得氯丁二烯系聚合物胶乳。
本发明中的聚氯丁二烯胶乳是指氯丁二烯的均聚物、氯丁二烯和可与其共聚的单体的共聚物。聚氯丁二烯胶乳的凝胶含有率可通过控制使氯丁二烯聚合时使用的链转移剂的用量、聚合温度、聚合率而进行调整,为了提高凝胶含有率,采用使链转移剂的用量减少、提高聚合温度、提高聚合率等手段即可。
作为链转移剂,只要是在聚氯丁二烯的制造中通常使用的链转移剂即没有特别限制,例如可以使用正十二烷基硫醇、辛基硫醇、己基硫醇、叔丁基硫醇、巯基乙酸、硫代苹果酸、硫代水杨酸等硫醇类,二硫化二异丙基黄原酸酯、二硫化二乙基黄原酸酯、二硫化二乙基秋兰姆等硫醚类,碘仿等卤代烃,二苯乙烯、对氯二苯乙烯、对氰基二苯乙烯、α-甲基苯乙烯二聚物、硫等公知的链转移剂。
作为聚氯丁二烯的聚合中使用的催化剂,例如可使用:过氧化苯甲酰、过氧化月桂酰、叔丁基过氧化氢、萜烷过氧化氢(p-menthane hydroperoxide)、过氧化二异丙苯、过硫酸钾、过硫酸铵等过氧化合物,2,2′-偶氮双(4-甲氧基-2,4-二甲基戊腈)、2,2′-偶氮双(2,4-二甲基戊腈)、2,2′-偶氮双(2-甲基丙腈)、2,2′-偶氮双(2-甲基丁腈)、1,1′-偶氮双(环己烷-1-腈)、1-[(1-氰基-1-甲基乙基)偶氮]甲酰胺、2,2′-偶氮双(2-甲基丙酸)二甲酯、4,4′-偶氮双(4-氰基戊酸)、2,2′-偶氮双(2,4,4-三甲基戊烷)、2,2′-偶氮双{2-甲基-N-[1,1′-双(羟甲基)-2-羟乙基]丙酰胺}、2,2′-偶氮双{2-(2-咪唑啉-2-基)丙烷]二盐酸盐、2,2′-偶氮双{2-(2-咪唑啉-2-基)丙烷]二硫酸盐二水合物、2,2′-偶氮双{2-[1-(2-羟乙基)-2-咪唑啉-2-基)丙烷]}二盐酸盐、2,2′-偶氮双(1-亚氨基-1-吡咯烷基-2-甲基丙烷)二盐酸盐、2,2′-偶氮双(2-甲基丙脒)二盐酸盐、2,2′-偶氮双[N-(2-羧乙基)-2-甲基丙脒]四水合物等偶氮化合物。在它们当中,特别是从进行稳定的聚合的方面考虑,优选使用过硫酸钾。
它们的用量可适当决定,优选相对于100重量份氯丁二烯为0.01重量份以上且不足10重量份左右。添加10重量份以上的离子性引发剂时,离子强度变得过高,颗粒容易变得不稳定化。另外,作为这些催化剂的添加方法,没有特别限制,可列举出一次性添加、滴加添加、分批添加、或它们的组合等添加方法。
为了提高氯丁二烯的聚合中使用的催化剂的活性,还可以组合添加例如亚硫酸钠、硫酸亚铁、蒽醌-β-磺酸钠、甲脒磺酸、L-抗坏血酸等。
为了使氯丁二烯的聚合停止,例如还可以添加如下的聚合抑制剂:硫化二苯胺、二乙基羟胺、对苯二酚、对叔丁基邻苯二酚、1,3,5-三羟基苯、对苯二酚甲基醚、2,6-二-叔丁基-4-甲基苯酚、2,2-亚甲基双(6-叔丁基-4-甲基苯酚)、4,4-亚丁基双(6-叔丁基-3-甲基苯酚)、亚乙基双(氧亚乙基)双[3-(5-叔丁基-4-羟基-间甲苯基)丙酸酯]、十八烷基-3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯、季戊四醇四[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯]等。
关于聚合温度,从聚合控制方面考虑,优选在0~55℃的范围。另外,为了使聚合反应更顺利且安全地进行,特别优选使聚合温度为30~50℃。另外,聚合时间可根据目的而适当调整,并无特别的限定,通常为0.5~10小时左右。
聚氯丁二烯胶乳的固体成分浓度可通过浓缩或水稀释而调整为必要的浓度。通过设定为更高的固体成分浓度,可形成干燥速度快、初始强度优异的胶乳。另外,关于固体成分浓度,还可以根据聚合时与单体的比率而调整。
聚氯丁二烯胶乳在刚聚合完后是酸性的,可以用pH调整剂等自由地调整pH。作为pH调整剂,优选为弱酸的盐,例如有:碳酸钠、碳酸钾、磷酸钠、磷酸氢二钠、磷酸钾、磷酸氢二钾、柠檬酸钾、柠檬酸氢二钾、柠檬酸钠、柠檬酸氢二钠、乙酸钠、乙酸钾、四硼酸钠等无机盐。另外,pH调整剂也可以是氢氧化钠、氢氧化钾,还可以是二乙醇胺等碱性物质等。pH调整剂的添加方法并不受到特别限制,可以直接添加pH调整剂粉末或者用水将pH调整剂粉末稀释为任意比例来添加。
本发明中所得的聚氯丁二烯胶乳是稳定的,但为了使聚氯丁二烯胶乳的基本特性进一步稳定化,还可以在聚合所使用的聚合釜的内表面及聚合釜的附带设备内表面涂布阻垢剂而形成涂膜。阻垢剂可使用具有羟基萘化合物的化合物,例如有作为市售品的CIRS公司制造的NOXOL WSW、NOXOL ETH、NOXOLETH/S等。
阻垢剂的涂布方法有使用辊、毛刷等的涂布,使用喷雾器、蒸汽喷射器等公知雾化装置的喷雾等。作为涂布量,考虑到其效果、经济性,以阻垢剂的固体成分计在0.001~0.5g/m2、优选在0.003~0.3g/m2的范围即可。为了形成牢固的涂膜,也可以以50℃~150℃的温度进行加热。在涂布时,当预知在聚合釜内表面存在妨碍涂膜形成的某些污染物质的情况下,优选预先实施使用有机溶剂、洗涤剂等的表面清洗、利用纯水的冲洗操作等,使清洁的金属面等露出。
在形成涂膜后,通过用纯水冲掉残留在聚合釜内表面的剩余物质,可使效果更佳。通过1次涂布可以在其效果减弱之前进行1次以上的聚合操作。涂布的频率因使用条件而异,优选在效果减弱之前实施再涂布。另外,涂膜形成优选在氮气、氩气等非活性气体气氛下进行。聚合釜的材质为不锈钢等,也可以设置玻璃衬里、橡胶衬里。
实施例
为了对本发明进行更具体的说明而例示以下实施例,但本发明不受这些实施例限制。此外,实施例和比较例中的重量份在没有特别说明的情况下为相对于100重量份氯丁二烯的份数。
作为本发明中的聚合反应器,使用通常使用的安装有1500ml的玻璃制四口烧瓶、斜叶浆、温度计、冷凝管、氮气通气管的反应器。搅拌叶片使用安装有4片板状挡板的搅拌叶片。
<实施例1>
在具有三通活栓的1500ml的玻璃烧瓶中装入918.5重量份添加有0.02重量份(该添加量是以NEOPELEX G-65计的添加量,并非DBS纯品换算)十二烷基苯磺酸钠(以下简称为DBS,商品名:NEOPELEX G-65、花王株式会社产品)和0.500重量份β-萘磺酸甲醛缩合物的钠盐(商品名:Demore N、以下简称为Demore N)的纯水。
接着,进行充分的氮气鼓泡之后,装入100重量份氯丁二烯,在300rpm的搅拌条件下,升温至内温40℃。升温后,接着一次性添加包含4.44重量份过硫酸钾(以下简称为KPS)、0.178重量份蒽醌β磺酸钠和217.5重量份纯水的引发剂水溶液引发聚合。聚合开始2小时时,氯丁二烯的聚合转化率达到81%。回收胶乳时,基本未发现附着物等的产生。用旋转蒸发器将未反应单体除去而获得聚氯丁二烯胶乳。此外,该实施例中DBS的CMC为约0.4重量份(用100重量份50℃的纯水换算为约0.04重量份)。
得到的胶乳未进行粘度调整而进行以下的测定。
〔粘接试验〕
用刮刀分别在两张帆布(25×150mm)上涂布150g(固体成分)/m2的粘接剂组合物,在室温下放置10分钟,然后在完全湿润的状态下将涂布面贴合,用手压辊(hand roller)往复5次进行压接。对其进行以下的粘接力评价试验。
〔初始剥离强度〕
在室温下,于辊压接后花费10分钟的固化时间(set time)后,使用拉伸试验机,以200mm/min的拉伸速度测定180°剥离强度。将实施例1的测定结果示于下述表1中。
<实施例2>
在具备三通活栓的1500ml的玻璃烧瓶中装入458.3重量份添加有0.229重量份Demore N的纯水,进行充分的氮气鼓泡,然后装入0.596重量份正辛基硫醇和100重量份氯丁二烯,在充分的搅拌条件下,升温至内温40℃。接着,一次性添加包含0.25重量份过硫酸钾和12.5重量份纯水的引发剂水溶液引发聚合。聚合开始3小时时,氯丁二烯的聚合转化率达到88%。回收胶乳时,基本上没有发现附着物的产生。用旋转蒸发器除去未反应单体,获得聚氯丁二烯胶乳。与实施例1同样地进行初始剥离强度的测定。将实施例2的测定结果示于下述表1。
<实施例3>
在具备三通活栓的1500ml的玻璃烧瓶中装入333.3重量份添加有0.167重量份Demore N的纯水,进行充分的氮气鼓泡,然后装入0.27重量份正辛基硫醇和45.5重量份氯丁二烯,在充分的搅拌条件下,升温至内温40℃。接着,一次性添加包含0.19重量份过硫酸钾和9.1重量份纯水的引发剂水溶液引发聚合。在聚合开始1小时后,分批添加0.33重量份正辛基硫醇和54.5重量份氯丁二烯。聚合开始3小时时,氯丁二烯的聚合转化率达到90%,基本上没有发现附着物等的产生。用旋转蒸发器除去未反应单体,得到聚氯丁二烯胶乳。与实施例1同样地进行初始剥离强度的测定。将实施例3的测定结果示于下述表1。
<比较例1>
在具备三通活栓的1500ml的玻璃烧瓶中装入918.5重量份纯水。接着,进行充分的氮气鼓泡,装入100重量份氯丁二烯,在300rpm的搅拌条件下,升温至内温40℃。升温后,接着,一次性添加包含2.22重量份KPS、0.089重量份蒽醌β磺酸钠和108.7重量份纯水的引发剂水溶液引发聚合。但是,在聚合开始18小时左右时,在聚合釜内确认到过剩的附着物,因此使聚合停止。
<比较例2>
在具备三通活栓的1500ml的玻璃烧瓶中装入919.2重量份添加有0.72重量份DBS和0.500重量份Demore N的纯水,接着,进行充分的氮气鼓泡,然后装入100重量份氯丁二烯,在300rpm的搅拌条件下,升温至内温40℃。升温后,一次性添加包含4.44重量份KPS、0.178重量份蒽醌β磺酸钠和217.5重量份纯水的引发剂水溶液引发聚合。聚合开始1小时时,氯丁二烯的聚合转化率达到90%。在回收胶乳时,基本上没有发现附着物等的产生。用旋转蒸发器除去未反应单体得到聚氯丁二烯胶乳。
其中,该实施例中DBS的CMC为约0.4重量份(用100重量份50℃的纯水换算为约0.04重量份)。与实施例1同样地进行初始剥离强度的测定。比较例2的测定结果示于下述表1。
<比较例3>
使用具备三通活栓的1500ml的玻璃烧瓶,在氮气气流下装入100重量份纯水、4.0重量份歧化松香酸、1.0重量份氢氧化钾、0.8重量份β-萘磺酸甲醛缩合物的钠盐,溶解后,边搅拌边添加100重量份氯丁二烯和0.1重量份正十二烷基硫醇。使用过硫酸钾作为引发剂,在氮气气氛下,在10℃的温度下进行聚合。聚合开始5小时时,氯丁二烯的聚合转化率达到90%。用旋转蒸发器除去未反应单体得到聚氯丁二烯胶乳。
其中,该实施例中歧化松香酸的CMC为约0.43重量份(用100重量份50℃的纯水换算也为约0.43重量份)。与实施例1同样地进行初始剥离强度的测定。比较例3的测定结果示于下述表1。
[表1]
Claims (4)
1.一种聚氯丁二烯胶乳的制造方法,其在相对于100重量份水性介质添加有0.01重量份以上且0.1重量份以下的高分子分散剂的水性介质中,使氯丁二烯、或者氯丁二烯和可与氯丁二烯共聚的单体聚合,所述高分子分散剂由芳香族磺酸甲醛缩合物的金属盐形成,
其中,所述水性介质不添加表面活性剂。
2.根据权利要求1所述的聚氯丁二烯胶乳的制造方法,其特征在于,在氯丁二烯聚合之前初期添加所述高分子分散剂。
3.一种聚氯丁二烯胶乳,其是通过权利要求1~2中的任一项所述的制造方法得到的。
4.一种粘接剂,其特征在于,其含有权利要求3所述的聚氯丁二烯胶乳。
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