CN1151170A - 发泡方法 - Google Patents

发泡方法 Download PDF

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CN1151170A
CN1151170A CN95193749A CN95193749A CN1151170A CN 1151170 A CN1151170 A CN 1151170A CN 95193749 A CN95193749 A CN 95193749A CN 95193749 A CN95193749 A CN 95193749A CN 1151170 A CN1151170 A CN 1151170A
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styrene polymer
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P·J·史密斯
B·J·克罗斯
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Mitsubishi Chemical UK Ltd
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    • C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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Abstract

一种制备具有封闭微孔结构的泡沫制品无须使用卤代发泡剂的方法。在该方法中，含有按重量计至少为50％的苯乙烯聚合物和按重量计多达50％具有低于苯乙烯聚合物平均分子量90％的平均分子量的丙烯酸聚合物的聚合物共混物和烃发泡剂被供应给加热过的挤压机，在此处形成共混物，再加入发泡剂以生成熔融混合物，在它由挤压机中放出时形成泡沫制品。

Description

发泡方法
本发明涉及一种由苯乙烯聚合物和至少一种丙烯酸聚合物的共混物形成泡沫制品的制备方法。
众所周知很容易通过各种方法包括挤压法使聚苯乙烯发泡。这样的工业生产聚苯乙烯泡沫的密度，不经任何特殊的处理一般数量级为32kg.m-3。
GB2146941公开了用挤压法制备聚苯乙烯泡沫。
EP 0411 923的目的在于使用挤压法制备密度在32-160kg.m-3的聚苯乙烯泡沫，其中用液体二氧化碳作为发泡剂来代替常规的卤代烃发泡剂。正如众所周知的，使用这种卤代烃对环境存在着某种危险因而日益变得不受欢迎。然而，使用二氧化碳作发泡剂的方法因需要致冷液体二氧化碳而伴随着复杂化。
使用既非卤代烃也非液体二氧化碳的物理发泡剂来制备正常密度到低密度聚苯乙烯泡沫、即密度为32kg.m-3或以下的泡沫，达到此目的是困难的。
US 3554932的目的在于使用烃发泡剂的同时使用成核剂(nucleating agents)来改进各种聚合物，包括苯乙烯均聚物的发泡。苯乙烯泡沫的密度约为64kg.m-3。为了由这样一种原料制备正常密度的泡沫，通常必须使原料直接在低于一个大气压下的环境中发泡，否则就必须使原料经过某种可控再膨胀成型的处理，例如US 4552904公开了通过挤压过的泡沫再膨胀制备低于32kg.m-3密度的聚苯乙烯泡沫。这样的要求条件既增加了发泡制造工艺的复杂性也增加了烃发泡泡沫的费用。
本发明的目的是采用烃发泡剂使用常规的挤压发泡工艺提供正常密度或低密度的聚苯乙烯泡沫，而无须使用再膨胀或其它的这种技术。
因此，本发明第一方面是提供制成具有封闭微孔结构的泡沫制品的方法，该制品含有(a)聚合物共混物和(b)烃发泡剂，该聚合物共混物至少含有按重量计50％的苯乙烯聚合物和按重量计多达50％的丙烯酸聚合物，丙烯酸聚合物具有比苯乙烯聚合物平均分子量90％低的平均分子量，所述方法包括向加热过的挤压机中供应苯乙烯聚合物和丙烯酸聚合物，加热和混合挤压机中的苯乙烯聚合物和丙烯酸聚合物以便形成熔融的聚合物共混物，把烃发泡剂加到挤压机内的熔融聚合物共混物中以形成熔融混合物，并在此之后把该熔融混合物从挤压机中放出，以便引起发泡剂去使熔融混合物膨胀形成泡沫制品。
本发明第二方面是提供具有封闭微孔结构的泡沫制品，该制品含有(a)聚合物共混物和(b)烃发泡剂，该聚合物共混物含有按重量计至少50％的苯乙烯聚合物和按重量计多达50％的丙烯酸聚合物，丙烯酸聚合物具有比苯乙烯聚合物平均分子量90％低的平均分子量。
苯乙烯聚合物可以是均聚物或苯乙烯、甲基苯乙烯、丙烯腈中至少一种的共聚物。优选苯乙烯聚合物至少有50％的单体单元是由苯乙烯产生的，尤其是苯乙烯聚合物是苯乙烯的均聚物。
适当的是，苯乙烯聚合物具有的平均分子量从180000到250000，优选180000-230000，例如约200000。
丙烯酸聚合物可以是均聚物或至少一种C1-8烷基(C1-4烷基)的丙烯酸酯，例如甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯和丙烯酸丁酯的共聚物。优选丙烯酸聚合物是共聚物，特别是含甲基丙烯酸酯，例如甲基丙烯酸甲酯、和如丙烯酸甲酯或丙烯酸乙酯的丙烯酸酯的共聚物。丙烯酸聚合物优选含有按重量计50-100％，特别是80-95，尤其是90-95来源于甲基丙烯酸酯，例如甲基丙烯酸甲酯的单体单元，其单体单元的剩余部分来源于至少一种丙烯酸酯。
丙烯酸聚合物具有低于苯乙烯聚合物平均分子量90％，优选低于80％，特别是低于75％而尤其是50-60％的平均分子量。合适的是，丙烯酸聚合物具有的平均分子量为50000-180000，优选50000-150000，特别是80000-140000。
泡沫制品具有封闭微孔结构。通常封闭的微孔壁厚范围为100-1000μ，特别是100-900μ，尤其是100-600μ。
泡沫制品的密度与仅用常规卤代烃作发泡剂的苯乙烯聚合物制成的类似泡沫制品可比或低于其密度。可以相信烃发泡剂与在共混物中的丙烯酸聚合物要比苯乙烯聚合物更相容，并且还可相信由于使用丙烯酸聚合物与通用的相比能有更多的烃发泡剂加入，由此导致较低密度的泡沫。
泡沫制品的性能，如热传导性，自然可与仅由苯乙烯聚合物制成的类似泡沫制品的性能相比，尽管一贯低些。泡沫制品有代表性的热传导性在制造后紧接着就在20-24mW.(mk)-1变动，例如约21mW.(mk)-1而在与环境平衡后升至25-27mW.(mk)-1，例如约26mW.(mk)-1。同样泡沫苯乙烯聚合物按测量具有约24mW.(mk)-1的热传导性，该热传导性随时间升至约27mW.(mk)-1。
泡沫制品的抗压强度随丙烯酸聚合物含量的提高降低。然而，在50％或以下的丙烯酸聚合物含量时，抗压强度可保持在150-260kPa。
使用时泡沫制品可层压在任何适当的载体材料上，例如灰泥板、木材或其它塑料结构，以便制成绝缘的建筑材料等。
泡沫制品可在常规的挤压装置上制成。当如此制成时，在整个标准的泡沫制品的横截面中，相对挤压轴密度的变化呈现典型的“浴缸(bath-tub)”型曲线，即泡沫制品中心处致密程度低于表面处。尽管浴缸型曲线是挤压泡沫材料的典型，但是至今只是通过常规苯乙烯聚合物在真空下或通过再膨胀，例如在空气中或在水蒸汽中加热才可得到所观察到的密度，其中在后面情况下浴缸型曲线是倒转的。
合适的烃发泡剂是现有技术中有代表性的那些。优选发泡剂选自丙烷、丁烷、戊烷、异戊烷、环戊烷和庚烷。使用的发泡剂数量至少部分取决于聚合物共混物的组成和所要求的泡沫制品的密度。通常，在特定的聚合物共混物中可接纳的发泡剂烃较卤代烃少些。因此通常每100kg的聚合物使用的烃发泡剂浓度为2-10kg，优选4-8kg。用下列实施例进一步说明本发明。
实施例1
在本例中，使用的丙烯酸聚合物是甲基丙烯酸甲酯与5％的平均分子量为129000的丙烯酸乙酯(EA)的共聚物。然后使用22％w/w的这种丙烯酸聚合物连同78％的平均分子量约200000的苯乙烯均聚物制成聚合物共混物。该聚合物共混物在常规的挤压机内被加热，再往该挤压机内加发泡剂，之后经尺寸为3mm×300mm的模缝把聚合物的混合物挤压至大气中。
密度差异是相对由苯乙烯均聚物采用R22作发泡剂在相同的设备上制备泡沫制品而论的。
实施例    ％发泡剂  密度差异(％)  发泡剂
 1a         13        -17           R22
      1b       5.7      -1     丁烷
由此可以证实烃发泡剂可以用来生产正常密度的泡沫，先决条件是苯乙烯聚合物要经含有丙烯酸聚合物改性。

Claims (10)

1、一种制备具有封闭微孔结构并含有(a)聚合物共混物和(b)烃发泡剂的泡沫制品的方法，所述聚合物共混物含有按重量计至少50％的苯乙烯聚合物和按重量计多达50％的丙烯酸聚合物，它具有的平均分子量比苯乙烯聚合物平均分子量的90％低，所述方法包括向加热过的挤压机中供应苯乙烯聚合物和丙烯酸聚合物，加热和混合挤压机内的苯乙烯聚合物和丙烯酸聚合物以便形成熔融的聚合物共混物，把烃发泡剂加到挤压机内的熔融聚合物共混物中以形成熔融混合物，并在此之后把该熔融混合物由挤压机放出以便引起发泡剂去使熔融混合物膨胀形成泡沫制品。
2、按权利要求1所述的方法，其中至少50％的苯乙烯聚合物的单体单元来源于苯乙烯。
3、按权利要求2所述的方法，其中苯乙烯聚合物是苯乙烯的均聚物。
4、按权利要求1-3中任一项所述的方法，其中苯乙烯聚合物具有180000-250000的平均分子量。
5、按权利要求1-4中任一项所述的方法，其中丙烯酸聚合物含有按重量计来源于甲基丙烯酸酯的50-100％的单体单元，单体单元剩余部分来源于至少一种丙烯酸酯。
6、按权利要求1-5中任一项所述的方法，其中丙烯酸聚合物具有的平均分子量比苯乙烯聚合物平均分子量的90％低。
7、按权利要求1-6中任一项所述的方法，其中封闭微孔壁厚的范围为100-1000μ。
8、按权利要求1-7中任一项所述的方法，其中发泡剂选自丙烷、丁烷、戊烷、异戊烷、环戊烷和庚烷。
9、按权利要求1-8中任一项所述的方法，其中烃发泡剂通常使用的含量为每100kg聚合物混合物2-10kg。
10、一种能通过权利要求1-9中任一项所述方法制成的具有封闭微孔结构的泡沫制品，该制品含有(a)聚合物共混物和(b)烃发泡剂，所述聚合物共混物含有至少按重量计50％的苯乙烯聚合物和按重量计多达50％的丙烯酸聚合物，其平均分子量比苯乙烯聚合物平均分子量的90％低。
CN95193749A 1994-06-24 1995-06-07 发泡方法 Expired - Fee Related CN1066752C (zh)

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DE69508243T2 (de) 1999-09-09
DE69508243D1 (de) 1999-04-15
CN1066752C (zh) 2001-06-06
WO1996000257A1 (en) 1996-01-04
EP0766711A1 (en) 1997-04-09
JPH10502117A (ja) 1998-02-24
WO1996000256A1 (en) 1996-01-04
DE69505381D1 (de) 1998-11-19
ES2122622T3 (es) 1998-12-16
CN1151171A (zh) 1997-06-04
EP0766710A1 (en) 1997-04-09
EP0766711B1 (en) 1999-03-10
EP0766710B1 (en) 1998-10-14
ATE172218T1 (de) 1998-10-15
DE69505381T2 (de) 1999-04-08
US6063485A (en) 2000-05-16
JPH10502118A (ja) 1998-02-24
AU2625795A (en) 1996-01-19
CN1071355C (zh) 2001-09-19
GR3029652T3 (en) 1999-06-30
AU2677595A (en) 1996-01-19
US5898039A (en) 1999-04-27
CA2192168A1 (en) 1996-01-04
CA2192169A1 (en) 1996-01-04
ES2128738T3 (es) 1999-05-16
ATE177453T1 (de) 1999-03-15

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