CN1113657A - 加工塑料用助剂、制造助剂的方法及制造具有抑制单体组分挥发性特性的不饱和聚酯树脂的方法 - Google Patents
加工塑料用助剂、制造助剂的方法及制造具有抑制单体组分挥发性特性的不饱和聚酯树脂的方法 Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
塑料制造助剂主要用于降低不饱和聚酯树脂中苯乙烯的挥发性。该助剂是具有通式BOOC-A-COOB′的化合物(式中A代表通式(1)的基团、B代表式CH3(CH2)x的基团(其中X=1—23)和B′代表松香分子失去氢后的基团),以每100份用2—50份的用量与长链脂肪酰胺和/或二价金属盐、长链脂肪酸酯和/或分子量为300—5000的聚乙烯蜡的混合物。还可添加0.1—7.0份(重量)石蜡。也公开了制造能降低苯乙烯挥发性的不饱和聚酯树脂的方法。
Description
本发明涉及加工塑料的助剂和制备该助剂的方法以及涉及具有能抑制单体组分挥发性特征、能具体用于制造聚酯-玻璃纤维层压板的不饱和聚酯树脂的制造方法。
本发明涉及制造助剂的方法并包括主要成分的化学合成及含该成分与酰胺和/或高级脂肪酸二价金属盐和/或脂肪酸酯和/或聚乙烯蜡的混合物的组合物。
塑料加工涉及用作增滑剂的羟基酯或环氧酯,这类增滑剂常具有低熔点或高熔点,但与塑料相容性差。
波兰专利No.121438和125545公开了具有增滑性能、用作抑制不饱和聚酯树脂中苯乙烯挥发的添加剂的羟基酯。这些众所熟知的羟基酯是长链脂肪酸与环氧化合物(主要是二烷环氧树脂)的加成产物,它们的特点在于在有机溶剂中的溶解度有限,因而用于塑料加工时不能方便地配制成有机溶剂浓溶液。
波兰专利Nos.141789和141790已公开了在有机溶剂(主要在芳族烃)中更容易溶解的助剂,这类助剂是由长链脂肪酸及树胶松香酸与环氧化合物加成产物所构成的环氧酯。
上述发明的缺点是除主要组分外还需加入熔点为45°-60℃的石蜡以帮助主要组分产生其主要功能,即在工业加工条件下树脂在加工过程中基本上能抑制不饱和聚酯树脂中苯乙烯的挥发。该功能也与聚酯-玻璃纤维层压板层间粘附力的降低有关,尤其是用干湿交替(wet-on-dry)法制造的层压板,已经观察到由此法制造的层压板在造船和船坞工业中的使用期限延长了。
令人意外地发现可通过采用通式为BOOC-A-COOB′的化合物(式中A代表通式1的基团、B代表基团CH3(CH2)x,其中x=11-23,B′代表由枞酸、左旋海松酸、新枞酸及长叶松酸混合物组成的松香在分子中失去氢后所形成的基团),
式1
BOOC-A-COOB′
B:CH3-[-CH2-]x x=11÷23
与酰胺和/或脂肪酸二价金属盐和/或脂肪酸酯和/或分子量为300-5000的聚乙烯蜡的混合物所组成的助剂可有效地抑制不饱和聚酯树脂中苯乙烯的挥发。加入量为每100份BOOC-A-COOB′化合物(式中A、B和B′的含义如上规定)加入2-50份酰胺和/或长链脂肪酸二价金属盐和/或脂肪酸酯和/或聚乙烯蜡。
根据本发明的助剂既与不饱和聚酯树脂相容也溶解于有机溶剂中。它们能有效地抑制苯乙烯的挥发,并不降低聚酯-玻璃纤维层压板的机械性能,具体说不会损害层压板的层间粘附力。
根据本发明的助剂是由松香和化合物CH3(CH2)xCOOH(x=11-23)与环氧树脂经加成反应制备的。反应在高温和胺催化剂存在下进行,接着加入酰胺和/或C11-18脂肪酸的二价金属盐和/或分子量为300-5000的聚乙烯蜡。
通式为CH3(CH2)xCOOH的化合物基团包括饱和脂肪酸如硬脂酸和月桂酸是优选选用的,不饱和的脂肪酸也可采用,优选油酸。
对于环氧树脂主要采用环氧数为0.21-0.51的二烷环氧树脂,能采用的脂族环氧树脂和缩水甘油基酯,如1,4-丁二醇二环氧甘油醚、二甘醇二环氧甘油醚和甲基丙烯酸缩水甘油酯。
对于脂肪酰胺主要采用亚乙基二硬脂酰胺。
对于脂肪酸衍生物和二价金属盐最常用的是硬脂酸铅、镉和锌盐。
对于高级脂肪酸酯主要采用三硬脂酸甘油酯。
对于聚乙烯蜡采用分子量为300-5000的烃。
根据本发明的方法,各反应物可以任何顺序加入,通过保持脂肪酸对松香的重量比为0.1∶1.0至5.0∶1.0制得通式为BOOC-A-COOB′的化合物。
环氧树脂量对脂肪酸和松香总量的比率是固定的,而环氧化合物的环氧数与羧基的比率保持在0.5∶1.0至1.5-1.0范围之内。
具有一系列优选性能的助剂是通过将BOOC-A-COOB′与2-50份(重量)的酰胺和脂肪酸二价金属盐和/或脂肪酸酯和/或分子量为300-5000的聚乙烯蜡经混合并熔融的方法制备的。向所得组合物添加0.1-7.0份(重量)的石蜡,在添加后1小时内在实验室条件下、对不饱和聚酯树脂进行试验,表明石蜡已经完全抑制了不饱和聚酯树脂中苯乙烯的挥发。
令人意外地发现能制造出其特征在于苯乙烯挥发性很低的不饱和聚酯树脂。这类树脂能用于制造具有很好层间粘附力的聚酯-玻璃纤维层压板,即使前层已经成型并固化而随后的叠层被搁置达7-14天,只要不饱和聚酯树脂含有适当选择的化合物的混合物。
这样的组合物混合物其特点在于具有良好和长久的稳定性并没有发现先有技术方法中改性剂在溶液中产生分层的趋向。此外,该组合物既可采用邻苯二甲酸及间苯二甲酸不饱和聚酯树脂,也可采用乙烯基酯型树脂。
根据本发明的方法中,向100份(重量)不饱和聚酯树脂加入0.05-5.0份(重量)、优选0.5-2.0份(重量)通式为BOOC-A-COOB′的化合物(式中A表示通式1的基团、B表示CH3(CH2)x基团,其中x=11-23和B′表示由枞酸、左旋海松酸、新枞酸和长叶松酸混合物组成的松香的分子中失去氢后所形成的基团),与酰胺和/或脂肪酸二价金属盐和/或脂肪酸酯和/或分子量为300-5000的聚乙烯蜡的混合物,酰胺和/或长链脂肪酸二价金属盐和/或脂肪酸酯和/或聚乙烯蜡的用量是每100份(重量)通式为BOOC-A-COOB′的化合物(式中A、B和B′的含义如上规定)为2-50份(重量)。
根据本发明的助剂与不饱和聚酯树脂具有良好相容性,并在有机溶剂中可溶。
添加添加剂的特别方便的方式是利用这些添加剂在有机溶剂(包括二甲苯、甲苯、石油溶剂及它们的混合物)中有良好的溶解性,因此能以含高浓度改性剂甚至其浓度高达90%(重量)的糊状形态添加到聚酯树脂中。提出的添加剂也与所有已知的聚酯树脂是相容的,在延长的储存期中没有分层的趋向。
被引入到聚酯树脂中的添加剂是在高温和胺催化剂存在下将通式为CH3(CH2)xCOOH(x=11-23)的化合物和松香与环氧树脂进行加成反应制造的,接着加入酰胺和/或C11-C18脂肪酸二价金属盐和/或脂肪酸酯和/或分子量为300-5000的聚乙烯蜡。
根据本发明的方法中,不饱和聚酯树脂包括作为主要交联单体组分的苯乙烯;但是,所述添加剂也可添加到含这种交联单体(如单一的苯乙烯衍生物、丙烯酸低聚酯和甲基丙烯酸低聚酯或它们的混合物)的不饱和聚酯树脂中。
构成这些树脂的不饱和聚酯包括马来酸或富马酸残基与二元醇残基,如乙二醇、二甘醇、1,2-丙二醇、二丙二醇、1,3-丁二醇、新戊二醇、二溴新戊二醇和氯甲基乙二醇和2,2-二(对羟丙氧基苯基)丙烷、表氯醇与二元羧酸残基如邻苯二甲酸、间苯二甲酸、对苯二甲酸、已二酸和癸二酸残基及酸类即马来酸酐与环戊二烯、六氯代环戊二烯的二烯加成物的衍生物、β-萘酚或蒽与马来海松酸残基。
根据本发明的不饱和聚酯树脂也可包括某些熟知的添加剂如阻聚剂如氢醌;触变剂如活性二氧化硅;阻燃剂如五溴乙基苯;矿物填料如白垩、高岭土、滑石或短切玻璃纤维;增稠剂如氧化镁及烟雾抑制剂。
树脂可通过已知技术固化,特别是用玻璃纤维织成的布、席或粗纱经浸渍后可添加过氧化物或过氧化氢固化剂及促进剂(如脂族-芳族叔胺或钴或钒化合物)进行固化。也可通过其它熟知的方法如采用适当的敏化剂用紫外或可见光辐照或用γ射线或电子束照射进行固化。
根据本发明的主要优点是抑制苯乙烯从加工的聚酯树脂中挥发并使其降至最少、改性剂在所有熟知的有机溶剂中有很好的溶解度以及一开始就提到的能以包括干湿交替法在内的任何方法制造聚酯-玻璃纤维层压板的可能性。
实施例1
在装有搅拌器、冷却器和温度计的反应器中在130℃,和0.3g三乙醇胺催化剂存在下加热70.0g Epidian 5二烷环氧树脂(环氧值0.52)与45.0g松香及44.0g硬脂酸,反应持续3小时直到酸值达到10mgKOH/g;在55℃下向反应产物添加32.0g亚乙基二硬脂酰胺和16.5g聚乙烯蜡(Mn=1000),冷却后制得的组合物成为固体,m.p.46℃。
实施例2
在110℃、在0.5g三乙醇胺存在下加热100.0g1,4-丁二醇二环氧甘油醚与75.0g油酸及80.0g松香。反应持续2小时直到酸值达到8mgKOH/g。在50℃下向反应产物添加45.0g三硬脂酸甘油酯、15.0g亚乙基二硬脂酰胺及15.0g聚乙烯蜡(Mn=400),将制得的混合物溶于120.8g二甲苯中,冷却后,组合物为糊状粘稠体,储存期间不会沉析。
实施例3
在0.1g N,N′-二甲基苄基胺存在下加热100.0g 2,2-双(4-羟苯基)丙烷-表氯醇树脂(环氧值为0.40)与75.2g软脂酸及42.2g松香1小时,向熔融的反应产物添加22.8g三硬脂酸甘油酯和32.5g聚乙烯蜡(Mn=1500),将制得的混合物溶于78.8g甲苯中,冷却后混合物为糊状粘稠体容易导入到不饱和聚酯树脂中。
实施例4
在150℃,在三乙醇胺存在下加热35.2g 2,2-双(4-羟苯基)丙烷-表氯醇环氧树脂(环氧值0.35)与16.5g硬脂酸及15.2g松香5小时,在5小时内反应产物的酸值达到3mgKOH/g,在60℃下向反应产物添加32.5g亚乙基二硬脂酰胺和35.8g聚乙烯蜡(Mn=400),冷却后该组合物的熔点为39℃、在聚酯树脂中是相容的,没有产生混浊的迹象。
实施例5
在120℃在0.3g三乙醇胺存在下加热100g二甘醇二环氧甘油醚与78.5g松香和65.7g硬脂酸,酸值达到5mgKOH/g后,于55℃下添加20.0g亚乙基二硬脂酰胺、38.0g聚乙烯蜡(Mn=1000)和15.7g单硬脂酸甘油酯-硬脂酸钙混合物,冷却后该组合物的熔点为41℃并易溶于芳烃中。
实施例6
在120℃在0.3g三乙醇胺存在下加热100.0g 2,2-双(4-羟苯基)丙烷-表氯醇树脂(环氧值0.40)与75.2g硬脂酸和42.2g松香3小时。向熔融的反应产物中添加32.0g亚乙基二硬脂酰胺和16.5g聚乙烯微晶蜡,将10.3g混合物溶解于含33%(重量)苯乙烯的1000g马来酸(富马酸)-邻苯二甲酸-亚丙基聚酯树脂中,将溶液倾倒在表面积为95cm2侧壁高10mm的Petri盘子中,将盘子放置在流速为0.4m/s、温度为22℃的空气流中。盘子在挥发试验开始前和试验开始后60分钟内分别称重,为比较起见用不含添加剂的树脂进行平行试验。
添加剂的效能(E%)用下式评价:
E= (mo-m)/(mo) ×100%
式中mo和m分别为不含添加剂的树脂和含添加剂的树脂的失重。
在本实施例中得到的效能E=99.8%。
层间粘合力的评价按Plastics Review(British Industrial Plastics)1981,No.11,4中所述方法对玻璃纤维织物与不含纤维的树脂层之间形成的接头作目测评价。
在本实施例中层间粘合力是很好的:“干”的玻璃纤维沿着整个撕开的表面积被拉出而没有明显的层间分离,否则应在分离的表面上留下光滑的区域。因此使用该法评估结果得到最高标志,即在3点标尺上的值为“3”(在第一层涂敷后第二叠压层被放置7天)。
实施例7
在装有搅拌器、冷却器和温度计的反应器中,在130℃和0.1gN,N′-二甲基苄基胺存在下加热70.0g Epidian 5二烷环氧树脂(环氧值0.52)与45.0g软脂酸及45.0g松香直至酸值达到10mgKOH/g,在55℃下向反应产物添加22.8g三硬脂酸甘油脂和17.0g亚乙基二硬脂酰胺,将得到的产物溶于120.0g二甲苯中,冷却后该组合物为糊状粘稠体,在储存期间不会沉析。
将15.5g该糊状组合物溶解于1000g含50%苯乙烯的马来酸(富马酸)一丙氧基-2,2-双(4-羟苯基)丙烷聚酯树脂中,用实施例6所述方法试验添加剂效能,得到的效能为E=99.5%。
用新式Du Pont冲击试验机对上述改性树脂制备的层压板进行冲击试验来检验层间粘附力,在该方法中用面积测量方法对所制得的层压板在7天间隔内评价其分层的表面积。试验结果得到分层的表面积为178mm2,作为比较,用来改性树脂制的层压板试验所得面积为175mm2,由此可见,添加剂没有降低单独搁置的叠压层的粘附力。
实施例8
在150℃和0.1g三乙醇胺存在下加热100g二甘醇二环氧甘油醚与78.5g松香和65.7g硬脂酸4小时,在酸值达到5mg/KOH/g后,在50℃添加20.0g亚乙基二硬脂酰胺、38.0g聚乙烯蜡(Mn=600)和15.7g单硬脂酸甘油酯-硬脂酸钙混合物,冷却后该组合物的m.p.41℃并且溶于芳烃中且与聚酯树脂相容。将制得的15.0g组合物溶解于1000g马来酸(富马酸)-邻苯二甲酸-表氯醇聚酯树脂中。引入的添加剂效能以实施例6所述方法进行检验。
用实施例6所述方法对用干湿交替法制备的层压板在12天间隔内检验其层间粘附力。结果为该层压板达到按三点目测标尺的最高标志。
Claims (8)
1、加工塑料用助剂,主要为了抑制不饱和聚酯树脂中苯乙烯的挥发,其特征在于该助剂是由通式BOOC-A-COOB′(式中A代表通式1的基团、B代表CH3(CH2)x基团,x=11-23,B′代表由枞酸、左旋海松酸、新枞酸及长叶松酸混合物组成的松香分子失去氢后所形成的基团)
式1
BOOC-A-COOB′
其中
B:CH3-[-CH2-]x- x=11÷23的化合物与酰胺和/或高级脂肪酸二价金属盐和/或高级脂肪酸酯和/或分子量为300-5000的聚乙烯蜡组成的混合物,混合物中胺和/或高级脂肪酸二价金属盐和/或高级脂肪酸酯和/或分子量300-5000的聚乙烯蜡的用量以每100份(重量)BOOC-A-COOB′化合物(A、B和B′如上规定)为2-50份(重量)以及必要时含0.1-7.0份(重量)石蜡。
2、制造加工塑料用并主要为抑制不饱和聚酯树脂中苯乙烯挥发的助剂的方法,其特征在于在高温和有胺催化剂存在下由饱和的或必要时不饱和的脂肪酸和松香与环氧树脂进行加成反应,其后导入酰胺和/或C11-C18脂肪酸的二价金属盐和/或高级脂肪酸酯和/或分子量为300-5000的聚乙烯蜡,或必要时的石蜡。
3、权利要求2的方法,其特征在于采用硬脂酸作为饱和酸。
4、权利要求2的方法,其特征在于采用月桂酸作为饱和酸。
5、权利要求2的方法,其特征在于采用油酸作为不饱和酸。
6、制造能抑制苯乙烯挥发的不饱和聚酯树脂,(具体地说用于制造聚酯-玻璃纤维层压板)的方法,并包括用特殊添加剂改性该树脂的方法,其特征在于苯乙烯挥发的抑制剂同时也可用作在干湿交替法制造聚酯-玻璃纤维层压板时的改性剂,该抑制剂采用由每100份(重量)聚酯树脂及0.05-5.0份(重量)的通式为BOOC-A-COOB′的化合物(式中A代表式1的基团、B代表CH3(CH2)x基团,x=11-23,B′代表由枞酸、左旋海松酸、新枞酸及长叶松酸混合物组成的松香分子失去氢后形成的基团)
式1BOOC-A-COOB′
与酰胺和/或高级脂肪酸二价金属盐和/或高级脂肪酸酯和/或分子量为300-5000的聚乙烯蜡的混合物所构成的混合物,混合物中酰胺和/或高级脂肪酸二价金属盐和/或高级脂肪酸酯和/或分子量为300-5000的聚乙烯蜡的用量以每100份(重量)BOOC-A-COOB′化合物(式中A、B和B′按上规定)为2-50份(重量)以及必要时含0.7-7.0份(重量)石蜡。
7、权利要求6的方法,其特征在于混合物的各个组分能以熔融状态或分别地添加到树脂中。
8、权利要求6的方法,其特征在于混合物的各个组分在溶解于单一溶剂中或溶于有机溶剂混合物中后添加到树脂中。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL30013093A PL172079B1 (pl) | 1993-08-18 | 1993-08-18 | Środek pomocniczy do przetwórstwa tworzyw sztucznych |
PL300130 | 1993-08-18 | ||
PL30048493A PL172081B1 (pl) | 1993-09-24 | 1993-09-24 | Sposób wytwarzania nienasyconych żywic poliestrowych o zmniejszonej emisji monomeru, zwłaszcza do laminatów poliestrowo-szklanych |
PL300484 | 1993-09-24 |
Publications (2)
Publication Number | Publication Date |
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CN1113657A true CN1113657A (zh) | 1995-12-20 |
CN1062876C CN1062876C (zh) | 2001-03-07 |
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CN94190615A Expired - Fee Related CN1062876C (zh) | 1993-08-18 | 1994-08-18 | 抑制单体组分挥发的不饱和聚酯树脂的制造方法 |
Country Status (6)
Country | Link |
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US (1) | US5719213A (zh) |
EP (1) | EP0664817B1 (zh) |
KR (1) | KR100340131B1 (zh) |
CN (1) | CN1062876C (zh) |
DE (1) | DE59409310D1 (zh) |
WO (1) | WO1995005410A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103408792A (zh) * | 2013-08-15 | 2013-11-27 | 常州市华润复合材料有限公司 | 一种苯乙烯挥发抑制剂及含有其的不饱和聚酯 |
CN107903601A (zh) * | 2017-12-21 | 2018-04-13 | 吴江市强塑阀门管件厂 | 一种抗老化塑料管材的制备方法及其应用 |
CN108659603A (zh) * | 2018-06-12 | 2018-10-16 | 淮北宇鑫新型材料有限公司 | 一种不饱和树脂挥发性单体的挥发抑制剂及其制备方法 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19902403A1 (de) * | 1999-01-22 | 2000-08-03 | Bayer Ag | UV-härtende Bindemittel, sowie deren Verwendung zur Erzeugung hochglänzender Beschichtungen |
US6348270B1 (en) | 1999-09-01 | 2002-02-19 | Reichhold Inc. | High performance polyetherester containing laminating resin compositions |
DE102004059883A1 (de) * | 2004-12-10 | 2006-06-14 | Brandenburger Patentverwertung Gbr (Vertretungsberechtigte Gesellschafter Herr Joachim Brandenburger | Herstellung eines harzgetränkten Faserschlauches zur Innenauskleidung von Kanälen und Rohrleitungen |
CN102731729B (zh) * | 2012-07-10 | 2014-11-26 | 常州华日新材有限公司 | 二次粘结不饱和聚酯树脂的制备方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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PL141771B1 (en) * | 1984-10-01 | 1987-08-31 | Inst Chemii Przemyslowej | Auxiliary agent for processing plastics and method of obtaining it |
PL141789B1 (en) * | 1984-10-01 | 1987-08-31 | Inst Chemii Przemyslowej | Auxiliary agent for processing plastics and method of obtaining it |
DE4028628A1 (de) * | 1990-09-08 | 1992-03-12 | Hoechst Ag | Ungesaettigte haertbare polyesterharzmassen mit verringerter styrolemission und verbesserter eigenhaftung auf ihrer ausgehaerteten masse |
-
1994
- 1994-08-18 KR KR1019950701479A patent/KR100340131B1/ko not_active IP Right Cessation
- 1994-08-18 CN CN94190615A patent/CN1062876C/zh not_active Expired - Fee Related
- 1994-08-18 EP EP94923838A patent/EP0664817B1/de not_active Expired - Lifetime
- 1994-08-18 WO PCT/PL1994/000017 patent/WO1995005410A1/de active IP Right Grant
- 1994-08-18 DE DE59409310T patent/DE59409310D1/de not_active Expired - Fee Related
-
1997
- 1997-01-23 US US08/788,052 patent/US5719213A/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103408792A (zh) * | 2013-08-15 | 2013-11-27 | 常州市华润复合材料有限公司 | 一种苯乙烯挥发抑制剂及含有其的不饱和聚酯 |
CN107903601A (zh) * | 2017-12-21 | 2018-04-13 | 吴江市强塑阀门管件厂 | 一种抗老化塑料管材的制备方法及其应用 |
CN108659603A (zh) * | 2018-06-12 | 2018-10-16 | 淮北宇鑫新型材料有限公司 | 一种不饱和树脂挥发性单体的挥发抑制剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE59409310D1 (de) | 2000-05-31 |
WO1995005410A1 (de) | 1995-02-23 |
EP0664817B1 (de) | 2000-04-26 |
EP0664817A1 (de) | 1995-08-02 |
KR950703591A (ko) | 1995-09-20 |
CN1062876C (zh) | 2001-03-07 |
US5719213A (en) | 1998-02-17 |
KR100340131B1 (ko) | 2002-10-31 |
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