CN1109693C - 由α-β-不饱和单体和不饱和脂肪酸形成的树脂 - Google Patents
由α-β-不饱和单体和不饱和脂肪酸形成的树脂 Download PDFInfo
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Abstract
一种由约85-96重量%的α-β-不饱和单体与约4-15重量%的有10-30个碳原子的不饱和脂肪酸的混合物形成的聚合物。
Description
技术领域
本发明提出了α-β-不饱和化合物,如(甲基)丙烯酸酯、乙烯基化合物、苯乙烯和取代的苯乙烯单体在不饱和脂肪酸存在下的聚合反应。在树脂组合物中加入部分这类不饱和化合物,可以降低熔融粘度,以致使树脂可以在不加入共溶剂下合成,而与聚合方法无关。本发明中提出的组合物不同于现有技术的组合物,因为目前所有的组合物在聚合之前要求加入共溶剂,而共溶剂随后或与聚合物反应,或被除去。但是,由于操作的限制和非定量的转化和/或除去,制得的聚合物仍含有明显数量的加入的共溶剂。
背景技术
一般采用间歇式或连续式操作来生产羧基官能的(甲基)丙烯酸和/或苯乙烯/(甲基)丙烯酸树脂。这些材料固有的高熔融粘度使处理困难。为防止发生这样的问题,一般都加入共溶剂。加入的共溶剂然后部分除去或与聚合物反应,在材料中留下2-10%的挥发性化合物。然后这些材料用碱性水中和,根据聚合物的羧化作用,形成水溶液或分散液。制得的水中的树脂可以配入含挥发性有机内容物(VOC)的胶乳、涂料、印刷油墨和罩印清漆中。
本发明中讨论的这类组合物的独特性是能制备低熔融粘度的聚合物,这使该聚合物的聚合反应可以不加入共溶剂。这有利于生产无VOC的胶乳、涂料、印刷油墨和罩印清漆。
尽管本发明直接的兴趣涉及具有不同的羧基含量的可水溶或水分散的树脂及用连续反应器法对它们进行制备,但是这一技术可通用于任何α-β-不饱和树脂及其合成,而与工艺无关。在各种情况中,在不饱和脂肪酸存在下的α-β-不饱和单体的聚合降低了制得的聚合物的熔融粘度,有助于能在没有溶剂存在下进行操作。
发明内容
本发明描述了在不饱和脂肪酸存在下,由α-β-不饱和化合物,诸如(甲基)丙烯酸酯、乙烯基化合物、苯乙烯和取代的苯乙烯单体制备的聚合物。一般脂肪酸的用量在4-15重量%(以单体总重量为基准),较好的为5-12重量%。不饱和脂肪酸由10-30个碳原子,较好的为12-20个碳原子组成。可以在没有有机溶剂存在下,采用连续式、间歇式或半连续式工艺合成上面组成的聚合物。
具体实施方式
在此,除非特别指出,单体、脂肪酸和引发剂的百分数均是相对于单体总重量的百分数。
本发明中讨论的聚合物一般由高达96重量%(甲基)丙烯酸单体、高达80重量%的苯乙烯单体和高达50重量%的其它α-β-不饱和化合物或取代的苯乙烯单体组成。根据本发明,典型的聚合物含有至少约10重量%的(甲基)丙烯酸单体。根据本发明典型的聚合物含有至少约5重量%的苯乙烯或取代的苯乙烯单体。
对本发明有用的(甲基)丙烯酸单体的例子包括但不限于:(甲基)丙烯酸和其酯衍生物,例如甲基丙烯酸酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸异丁酯、丙烯酸2-乙基己酯、丙烯酸羟基乙酯、丙烯酸羟基丙酯、丙烯酸羟基丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸异冰片酯、甲基丙烯酸羟基乙酯、甲基丙烯酸羟基丙酯、甲基丙烯酸月桂酯和甲基丙烯酸硬脂基酯。
对本发明有用的苯乙烯单体包括但不限于:苯乙烯、α-甲基苯乙烯、乙烯基甲苯和叔丁基苯乙烯。对本发明有用的其它乙烯基单体包括但不限于;乙烯醇和其酯衍生物,如乙酸乙烯酯和2-乙基己酸乙烯基酯、巴豆酸和马来酸酐。
在根据本发明的聚合材料中被部分加入的脂肪酸必须具有至少一个碳-碳双键。如果存在多个碳-碳双键,不要求它们是共轭的。另外,脂肪酸不必用其游离酸,但是可以在聚合反应之前或期间,用各种醇酯化。不饱和脂肪酸的合适例子如下,但不限于下面,月桂烯酸、肉豆蔻脑酸、棕榈油酸、油酸、蓖麻油酸、亚油酸、亚麻酸、桐酸、laconic acid、顺(式)9-二十碳烯酸、花生四烯酸、芥酸、4,7,11-二十二碳烯三烯-18炔酸和尼生酸。
可通过自由基机理生产本发明中所述的聚合物材料。因此,必须使用自由基引发剂,其类型和量取决于单体混合、温度、压力和时间的反应参数。通常引发剂量为单体重量的1-10%。对本领域熟练的技术人员而言,自由基引发剂的例子是显而易见的。本发明涉及了下面的例子,但不限于这些,1,1-二-(叔丁基过氧)-3,3,5-三甲基环己烷、2,2-二[4,4-二-(叔丁基过氧环己基)]丙烷、3,5,5-三甲基过己酸叔丁酯、2-甲基过苯甲酸叔丁酯、2,2-二-(叔丁基过氧)丁烷、叔丁基过氧异丙基碳酸酯、过乙酸叔丁酯、过苯甲酸叔丁酯、过氧化二枯烯、二叔丁基过氧化物、二异丙基苯单过氧氢和枯基过氧氢。
典型的聚合反应工艺中,α-β-不饱和单体、不饱和脂肪酸和引发剂在注入反应器之前混合在一起。反应器加热至能提供引发剂充分分解速度的温度。一旦聚合反应开始,反应器可能温升约50-100℃,必须注意不能使温度超过250℃。例如,当使用二叔丁基过氧化物时,反应器可能被加热至155-165℃,温升会使温度升高至200-220℃。
最终的聚合物的物性取决于单体含量、引发剂类型和量、以及反应时间和温度。所述的树脂的数均分子量一般在1500-10000范围,较好的在3000-5000范围。还可以根据要求的水溶性和分散性改变聚合物的酸值。树脂的酸值一般在80-275的范围,在125-250的范围较佳,最好在150-200的范围。但是,本发明所述的不饱和脂肪酸改性树脂不管其分子量或酸值都是能应用的。用上述的树脂简单地与水和碱的溶液混合就可以制备水溶液或水分散液。为加快这一过程,可采用升高温度至低于水/碱的沸点。制得的聚合物溶液可配制到无VOC的颜料分散体、胶乳、涂料、印刷油墨或罩印清漆中。
由下面的实施例详细说明本发明。
实施例1
*2-乙基过己酸叔丁酯(tert-butyl peroxy-2-ethyl hexanote)**过氧化二叔丁基
重量% | |
单体原料 | |
苯乙烯 | 48.0 |
α-甲基苯乙烯 | 15.0 |
丙烯酸 | 22.5 |
粘度改进剂 | |
油酸 | 9.5 |
接种引发剂 | |
TBPEH* | 0.7 |
本体引发剂 | |
DTBP** | 4.3 |
实施例2
*2-乙基过己酸叔丁酯**过氧化二叔丁基
重量% | |
单体原料 | |
苯乙烯 | 48.0 |
α-甲基苯乙烯 | 15.0 |
丙烯酸 | 22.5 |
粘度改进剂 | |
亚油酸 | 9.5 |
接种引发剂 | |
TBPEH* | 0.7 |
本体引发剂 | |
DTBP** | 4.3 |
实施例1和2的程序
在反应釜中加入单体原料的约15%。搅拌该混合物,通入氮气吹扫,并加热至95℃。一旦达到要求的聚合反应温度,将接种引发剂溶解在5克单体原料中并加入加料釜。让反应升温并在120℃保持10分钟。之后将反应混合物加热至165℃。加热时将粘度改进剂和本体引发剂加至剩余的单体原料中。将产生的混合物花3个小时加入反应釜中。一旦添加结束,将混合物保持30分钟,然后从反应釜取出树脂。冷却后的树脂为脆性固体。
实施例3
*过氧化二叔丁基
重量% | |
粘度改进剂 | |
油酸 | 8.2 |
单体原料 | |
甲基丙烯酸甲酯 | 58.2 |
丙烯酸乙酯 | 4.3 |
丙烯酸丁酯 | 4.3 |
丙烯酸 | 7.8 |
甲基丙烯酸 | 7.8 |
油酸 | 5.1 |
DTBP* | 4.3 |
实施例4
*过氧化二叔丁基
重量% | |
粘度改进剂 | |
亚油酸 | 8.2 |
单体原料 | |
甲基丙烯酸甲酯 | 58.2 |
丙烯酸乙酯 | 4.3 |
丙烯酸丁酯 | 4.3 |
丙烯酸 | 7.8 |
甲基丙烯酸 | 7.8 |
亚油酸 | 5.1 |
DTBP* | 4.3 |
实施例3和4的程序
将粘度改进剂加入反应釜进行搅拌、通入氮气吹扫并加热至165℃。一旦达到要求的聚合反应温度,将单体原料花4个小时加到该反应釜中。一旦添加结束,保持30分钟,然后从反应釜取出树脂。冷却后的树脂为脆性固体。
实施例5
*过氧化二叔丁基
组分 | 重量% |
苯乙烯 | 53.5 |
丙烯酸 | 30.7 |
油酸 | 10.2 |
DTBP* | 5.6 |
实施例5的程序
以140公斤/小时的速度和15-20分钟的停留时间,输入单体和引发剂的混合物通过连续流动式反应器。反应器在165℃开始输入单体/引发剂原料,发热升温至220℃。完全冷却后该固体聚合物用于制备如下的碱性聚合物溶液。
组分 | 重量% |
树脂 | 30.0 |
去离子水 | 8.9 |
NH4OH(30%溶液) | 61.1 |
水溶解程序
在反应烧瓶中加入固体树脂和去离子水,迅速搅拌并在20分钟内滴加氢氧化氨。将该混合物缓慢加热至80℃,保持该温度直到树脂全部溶解。冷却该聚合物溶液,从反应烧瓶中取出。其物性为pH在7.9-8.9,粘度在450-1500cps,非挥发物为29-32%。
Claims (6)
1.一种聚合物,该聚合物通过在没有共溶剂存在下的自由基聚合,由85-96重量%的选自丙烯酸、甲基丙烯酸和苯乙烯的α-β-不饱和单体与4-15重量%的有10-30个碳原子的不饱和脂肪酸的混合物形成,所述聚合物的数均分子量范围为1500-10000。
2.如权利要求1所述的聚合物,其特征还在于所述的脂肪酸有12-20个碳原子。
3.一种生产提供85-96重量%的选自丙烯酸、甲基丙烯酸和苯乙烯的α-β-不饱和单体与4-15重量%的有10-30个碳原子的不饱和脂肪酸的混合物的聚合物的方法,通过在没有共溶剂存在下的自由基聚合反应聚合所述的单体。
4.如权利要求3所述的方法,其特征还在于实现连续式聚合反应操作。
5.如权利要求3所述的方法,其特征还在于实现间歇式聚合反应操作。
6.如权利要求3所述的方法,其特征还在于实现半连续式聚合反应操作。
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US08/880,479 | 1997-06-23 | ||
US08/880,479 US5830957A (en) | 1997-06-23 | 1997-06-23 | Resins formed from alpha-beta-unsaturated monomers and unsaturated fatty acids |
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US (1) | US5830957A (zh) |
EP (1) | EP0887361B1 (zh) |
CN (1) | CN1109693C (zh) |
AU (1) | AU702303B2 (zh) |
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US6967227B1 (en) | 2003-07-09 | 2005-11-22 | Meadwestvaco Corporation | Carboxyester-modified vinylic polymeric compositions |
FI119431B (fi) * | 2006-03-06 | 2008-11-14 | Upm Kymmene Oyj | Luonnonrasvahappopohjainen akrylaattihybridipolymeeri ja menetelmä sen valmistamiseksi |
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GB996774A (en) * | 1962-11-07 | 1965-06-30 | Internat Synthetic Rubber Comp | Improvements for emulsion polymerizations |
US4186116A (en) * | 1977-06-24 | 1980-01-29 | Bayer Aktiengesellschaft | Air-drying and oven-drying acrylate lacquer binders |
US5504162A (en) * | 1993-01-06 | 1996-04-02 | Hoechst Aktiengesellschaft | Salts of copolymers of ethylenically unsaturated carboxylic acids and ethylenically unsaturated fatty acid derivatives |
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US5399275A (en) * | 1992-12-18 | 1995-03-21 | The Lubrizol Corporation | Environmentally friendly viscosity index improving compositions |
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Publication number | Priority date | Publication date | Assignee | Title |
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GB996774A (en) * | 1962-11-07 | 1965-06-30 | Internat Synthetic Rubber Comp | Improvements for emulsion polymerizations |
US4186116A (en) * | 1977-06-24 | 1980-01-29 | Bayer Aktiengesellschaft | Air-drying and oven-drying acrylate lacquer binders |
US5504162A (en) * | 1993-01-06 | 1996-04-02 | Hoechst Aktiengesellschaft | Salts of copolymers of ethylenically unsaturated carboxylic acids and ethylenically unsaturated fatty acid derivatives |
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EP0887361B1 (en) | 2005-01-26 |
AU702303B2 (en) | 1999-02-18 |
AU6377698A (en) | 1998-12-24 |
DE69828721T2 (de) | 2005-06-30 |
EP0887361A2 (en) | 1998-12-30 |
CN1203239A (zh) | 1998-12-30 |
SG81930A1 (en) | 2001-07-24 |
DE69828721D1 (de) | 2005-03-03 |
EP0887361A3 (en) | 1999-09-15 |
US5830957A (en) | 1998-11-03 |
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