CN1376176A - 耐伽玛辐射的聚碳酸酯组合物 - Google Patents
耐伽玛辐射的聚碳酸酯组合物 Download PDFInfo
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- JHUWODOJJBBFNF-UHFFFAOYSA-N bis(2,3-dihydroxyphenyl)methanone Chemical compound OC1=CC=CC(C(=O)C=2C(=C(O)C=CC=2)O)=C1O JHUWODOJJBBFNF-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1565—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
公开了一种改善了耐γ-辐射引起的泛黄性的热塑性聚碳酸酯模塑组合物。该组合物含有某一添加量的结构符合式(I)的起稳定作用的甘油单酯的环状缩醛,式中R1代表C1-30烷基,R2代表芳基。
Description
本发明涉及透明热塑性模塑组合物,更具体地说,涉及改善了耐γ-辐射引起的泛黄性的聚碳酸酯模塑组合物。
发明概述
发明背景
聚碳酸酯树脂因其物理和机械性能优异而被发现特别适用于医学领域中的各种用途。然而,这些用途都要求通过暴露于离子辐射来进行消毒,而聚碳酸酯易于泛黄,从而显示出高的雾度,因此存在问题。已注意到相关技术包括美国专利4,624,972,该专利公开了含有芳族多羧酸的酯和聚二醇的单烷基或单芳基醚的耐γ-辐射的聚碳酸酯组合物。该专利中公开了含有基于伯醇的酯的相关组合物的性能。
美国专利4,873,271公开了一种含有聚环氧烷烃的酯作为稳定剂的耐γ-辐射的聚碳酸酯组合物。另一些相关技术是下列美国专利:5,187,211、4,804,692、4,963,598、4,874,802、5,006,572、5,187,208、5,274,009和5,214,078,所有这些专利都涉及通过加入稳定剂来赋予耐γ-辐射性的聚碳酸酯组合物。最后,美国专利5,280,050公开了一种含有聚环氧烷烃低聚物和伯醇的卤代芳族苯二甲酸酯的聚碳酸酯组合物。已注意到美国专利5,145,751公开了一种磁记录介质,其中包含一种非磁性基材和涂布在该基材上的磁记录层。该磁记录层含有包含本发明的稳定剂的化合物。
发明详述
本发明的热塑性组合物包含一种聚碳酸酯树脂的相对于该聚碳酸酯的重量而言,约0.1-2%,优选0.1-1%的符合下式的起稳定作用的化合物:式中R1代表C1-30烷基,R2代表芳基。
适用于制备本发明的聚碳酸酯树脂是均聚碳酸酯和共聚碳酸酯以及其混合物。
该聚碳酸酯的重均分子量一般为10,000-200,000,优选为15,000-80,000,其按ASTM D-1238在300℃测定的熔体流动速率为约1-约95克/10分钟,优选约2-15克/10分钟。该聚碳酸酯可通过例如已知的二相界面法由碳酸衍生物如光气和二羟基化合物进行缩聚来制备(参见德国公开专利2,063,050、2,063,052、1,570,703、2,211,956、2,211,957和2,248,817,法国专利1,561,518,以及H.Schnell的专题论文《聚碳酸酯的化学与物理学》,Interscience出版公司,纽约,1964,所有这些文献均并入本文作为参考)。
e和g均代表0-1的数;
Z代表F、Cl、Br或C1-C4烷基,且如果几个Z基团是在1个芳基中的取代基,则它们彼此可以相同或不同;
d代表1个0-4的整数;以及
f代表1个0-3的整数。
可用于实施本发明的二羟基化合物是氢醌、雷琐酚、二羟苯基烷烃、二羟苯基醚、二羟苯基酮、二羟苯基亚砜、二羟苯基硫醚、二羟苯基砜、二羟基二苯基环烷烃,和α,α-二羟苯基-二异丙基苯及其核上烷基化的化合物。这些和进一步适用的芳族二羟基化合物公开于例如美国专利5,227,458、5,105,004、5,126,428、5,109,076、5,104,723、5,086,157、3,028,356、2,999,835、3,148,172、2,991,273、3,271,367和2,999,846中,所有这些专利均并入本文作为参考。
适用的双酚的进一步的例子是2,2-二(4-羟基苯基)-丙烷(双酚A)、2,4-二(4-羟基苯基)-2-甲基-丁烷、1,1-二(4-羟基苯基)-环己烷、α,α′-二(4-羟基苯基)-对二异丙基苯、2,2-二(3-甲基4-羟基苯基)-丙烷、2,2-二(3-氯-4-羟基苯基)-丙烷、二(3,5-二甲基-4-羟基苯基)-甲烷、2,2-二(3,5-二甲基-4-羟基苯基)-丙烷、二(3,5-二甲基-4-羟基苯基)-硫醚、二(3,5-二甲基-4-羟基苯基)-亚砜、二(3,5-二甲基-4-羟基苯基)-砜、二羟基二苯甲酮、2,4-二(3,5-二甲基-4-羟基苯基)-环己烷、α,α′-二(3,5-二甲基-4-羟基苯基)-对二异丙基苯、4,4′-磺酰基联苯酚和1,1-二(4-羟基苯基)-3,3,5-三甲基环己烷。
特别优选的芳族双酚的例子是2,2-二(4-羟基苯基)-丙烷、2,2-二(3,5-二甲基-4-羟基苯基)-丙烷、1,1-二(4-羟基苯基)-环己烷和1,1-二(4-羟基苯基)-3,3,5-三甲基环己烷。
最优选的双酚是2,2-二(4-羟基苯基)-丙烷(双酚A)。
本发明的聚碳酸酯结构中必须有从一种或多种适当的双酚衍生的结构单元。
适用于实施本发明的树脂是酚-酞基聚碳酸酯、共聚碳酸酯和三元共聚碳酸酯,如美国专利3,036,036和4,210,741中所述的那些,这两篇专利均并入本文作为参考。
本发明的聚碳酸酯也可以是支化的,这可通过在其中缩合少量,例如0.05-2.0%(摩尔)(相对于双酚而言)的多羟基化合物来实现。
这种类型的聚碳酸酯已公开于例如德国公开专利1,570,533、2,116,974和2,113,374,英国专利885,442和1,079,821以及美国专利3,544,514中。下面列举的是可用于此目的的多羟基化合物的一些例子:间苯三酚、4,6-二甲基-2,4,6-三(4-羟基苯基)-庚烷、1,3,5-三(4-羟基苯基)-苯、1,1,1-三(4-羟基苯基)-乙烷、三(4-羟基苯基)-苯基甲烷、2,2-二〔4,4-(4,4′-二羟基二苯基)〕-环己基-丙烷、2,4-二(4-羟基-1-异亚丙基)-苯酚、2,6-二(2′-二羟基-5′-甲基苄基)-4-甲基-苯酚、2,4-二羟基苯甲酸、2-(4-羟基苯基)-2-(2,4-二羟基苯基)-丙烷和1,4-二(4,4′-二羟基三苯基甲基)-苯。其它一些多官能化合物是2,4-二羟基-苯甲酸、1,3,5-苯三酸、氰脲酰氯和3,3-二(4-羟基苯基)-2-氧代-2,3-二氢吲哚。
除了上述的缩聚法之外,制备本发明的聚碳酸酯的其它方法是均相缩聚和酯交换。适合的方法公开于美国专利3,028,365、2,999,846、3,153,008和2,991,273中,这些专利均并入本文作为参考。
制备聚碳酸酯的优选方法是界面缩聚法。
也可以采用其它合成方法来形成本发明的聚碳酸酯,例如美国专利3,912,688中所述的方法,该专利并入本文作为参考。
适用的聚碳酸酯树脂有市售品,例如Makrolon 2400、Makrolon2600、Makrolon 2800和Makrolon 3100树脂,所有这些树脂均为基于双酚的均聚碳酸酯树脂,只有各自的分子量不同而已,其特征在于按ASTM D-1238测定的熔体流动指数(MFR)分别为约16.5-24、13-16、7.5-13.0和3.5-6.5克/10分钟。尤其适合的是Makrolon2500,其MFR值为14-17克/10分钟。这些都是宾夕法尼亚州匹兹堡的拜耳公司的产品。
适用于实施本发明的聚碳酸酯树脂是已知的,其结构及制备方法已公开于例如美国专利3,030,331、3,169,121、3,395,119、3,729,447、4,255,556、4,260,731、4,369,303和4,714,746中,所有这些专利均并入本文作为参考。
本发明上下文中所述的稳定剂符合下面的结构:式中R1代表C1-30烷基,R2代表芳基。芳基可以是有取代的,其取代基包括线型或支化的烷基、环烷基和烷氧基,以及卤原子。优选的芳基是选自下列的基团:苯基、萘基、蒽基、菲基和联苯基。
本发明的组合物中还可以加入传统的添加剂用于技术上已知的用途。添加剂包括染料、阻燃剂、脱模剂、增塑剂、热稳定剂、水解稳定剂、UV稳定剂、抗氧化剂、填料以及增强剂等。可以有利地加入到本发明的稳定化组合物中的有用的热稳定剂是受阻酚、膦、亚磷酸酯、磷酸酯和硫化物。在一个优选的具体实施方案中,本发明的组合物不含任何类型的磁性组分。
下列实施例进一步说明本发明,但无意用来限制本发明。实施例中所有份数和百分数均指重量,但另有指明除外。
本发明的稳定化组合物的制备方法是传统的方法。
实验
按上述方法通过使甘油单硬脂酸酯与苯甲醛在酸催化剂的存在下进行反应制备了按照本发明的稳定剂(下称“稳定剂”)。制备方法叙述如下:
往装配有迪安斯达克分水器和冷凝器的250ml圆底烧瓶中加入10g(27.80mmol)甘油单硬脂酸酯、75ml无水甲苯、0.09g(~1%)对甲苯磺酸一水合物和3.4ml(34mmol)苯甲醛。在搅拌和回流下进行反应直至通过迪安斯达克分水器收集到理论量的水(~0.5ml)为止。反应一旦完成,通过蒸馏除去溶剂。将残留的熔融物料加入到280ml甲醇中,并让其冷却至室温使产物沉淀。为确保全部物料沉淀,慢慢加入70ml DI-H2O(制成20%溶液)。然后通过真空过滤收集产物,并在减压下进行干燥。
本发明组合物的制备:
将稳定剂掺入到重均分子量约2600的基于双酚A的均聚碳酸酯树脂(PC)中,然后按传统方法模制物品。按照ASTM D 1925所述程序评价试样的泛黄指数(YI)和雾度。将试样暴露于5M拉德离子化辐射(Co-60放射源)环境中,持续457分钟,照射后的试样贮存于暗处,按指出的时间间隔评估其泛黄指数和雾度。评估结果示于下表中:
组分 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 |
聚碳酸酯,wt% | 100 | 99.75 | 99.50 | 99.25 | 99.00 |
稳定剂,wt% | 0 | 0.25 | 0.50 | 0.75 | 1.0 |
性能 | |||||
泛黄指数 | |||||
照射前 | 3.5 | 2.85 | 2.69 | 3.53 | 6.35 |
照射后0天 | 26.36 | 22.16 | 17.85 | 16.40 | 17.74 |
照射后2天 | 26.00 | 21.86 | 17.74 | 16.40 | 17.70 |
照射后7天 | 26.08 | 21.95 | 18.56 | 17.26 | 18.50 |
照射后14天 | 24.42 | 20.77 | 17.59 | 16.21 | 17.57 |
泛黄指数* | 1.94 | 1.39 | 0.26 | 0.19 | 0.17 |
*泛黄指数YI是指照射后0天与14天的YI之差。
所得泛黄指数之差表明本发明的稳定剂对改善该组合物耐γ-辐射引起的泛黄性的效果。
虽然上面为了说明的目的已对本发明作了详细的叙述,但应理解的是,这样的详述只是为了说明的目的,本领域中的技术人员可以作出各种变换而不会背离本发明的精神和范围。本发明的范围只受权利要求书的限制。
Claims (8)
2.权利要求1的热塑性模塑组合物,其中所述稳定剂的含量为0.1-1.0%。
3.权利要求1的热塑性模塑组合物,其中所述聚碳酸酯的重均分子量为15,000-80,000。
5.权利要求1的热塑性模塑组合物,其中所述聚碳酸酯是从至少一种选自下列一组的成员衍生的:2,2-二(4-羟基苯基)-丙烷、2,4-二(4-羟基苯基)-2-甲基-丁烷、1,1-二(4-羟基苯基)-环己烷、α,α′-二(4-羟基苯基)-对二异丙基苯、2,2-二(3-甲基4-羟基苯基)-丙烷、2,2-二(3-氯4-羟基苯基)-丙烷、二(3,5-二甲基-4-羟基苯基)-甲烷、2,2-二(3,5-二甲基-4-羟基苯基)-丙烷、二(3,5-二甲基-4-羟基苯基)-硫醚、二(3,5-二甲基-4-羟基苯基)-亚砜、二(3,5-二甲基-4-羟基苯基)-砜、二羟基二苯甲酮、2,4-二(3,5-二甲基-4-羟基苯基)-环己烷、α,α′-二(3,5-二甲基-4-羟基苯基)-对二异丙基苯、4,4′-磺酰基联苯酚和1,1-二(4-羟基苯基)-3,3,5-三甲基环己烷。
6.权利要求1的热塑性模塑组合物,其中所述聚碳酸酯是从2,2-二(4-羟基苯基)-丙烷衍生的一种均聚物。
7.权利要求1的热塑性模塑组合物,其中芳基是有取代的。
8.权利要求1的热塑性模塑组合物,其中芳基是从下列一组中选择的一种:苯基、萘基、蒽基、菲基和联苯基。
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US4576982A (en) * | 1984-09-14 | 1986-03-18 | General Motors Company | Hydrolytically stabilized polycarbonates |
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