CN88102180A - 稳定的共聚物组合物 - Google Patents
稳定的共聚物组合物 Download PDFInfo
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/132—Phenols containing keto groups, e.g. benzophenones
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- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C08K5/00—Use of organic ingredients
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08K5/3492—Triazines
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Abstract
一种包括由乙烯和一氧化碳共聚物以及0.03～5.0％(重)的稳定化合物的组合物，该稳定化合物选自二芳基胺、羟基二苯甲酮以及带有位阻酚取代基的苯并三唑或苯并三嗪。
Description
本发明涉及包括特定添加剂及一种由一氧化碳和一种烯属不饱和化合物（例如乙烯）生成的共聚物的组合物。该共聚物的特征在于其中含有重复结构-（A-CO）n，其中A从烯属不饱和化合物衍生而来。名词“共聚物”也包括其中的某些A是由另外一种烯属不饱和化合物衍生而来的三元共聚物。例如乙烯、一氧化碳和丙烯（或丁烯）的共聚物就是适宜的三元共聚物。
该交替共聚物及他们的制备方法是已知的，如US-A3694412，EP-A121965和EP-A181014所述，虽然该共聚物具有良好的物理和机械性能，例如良好的屈服应力、拉伸强度、冲击强度和弯曲模量，但是这些共聚物的抗光化降解的稳定性还有待于改进。
本申请人发现，很多在聚酰胺、聚烯烃、聚丙烯酸酯、聚苯乙烯和其他很多热塑性塑料及工程热塑性塑料中起到有效作用的防紫外线剂商品在交替烯烃/CO共聚物中却不能达到令人满意的效果。令人吃惊的是有一些定义很窄的添加剂能使防紫外线的效果获得令人满意的改进。
本发明提供了一种共聚物组合物，它包括一种由一氧化碳、烯属不饱和化合物（最好是乙烯）和（根据需要任选的）另外一种烯属不饱和化合物生成的交替共聚物及0.03～5.0%（重）的选自下列化合物的添加剂：
a）式（Ⅰ）的化合物
式中，R1是氢或羟基、R2是羟基（在R1为氢时）或氢（R1为羟基时），R3是羟基、C1-12烷基或C1-12烷氧基，
b）式（Ⅱ）的化合物
式中，R4和R5各自独立地代表氢或囟原子，R6为C1-16烷基，R7为氢、羟基、C1-8烷基、C7-17烷芳基、C7-17芳基或C7-17芳烷基，
c）式（Ⅲ）的化合物
式中，R8和R9各自独立地代表氢、C1-12烷基、苯基或其亚甲基上可能带有一个或两个选自C1-8烷基的取代基的苄基，
d）式（Ⅳ）的化合物
式中，R10和R11各自独立地代表C1-14烷基和C1-14烷硫基，R12为氢或羟基，R13为羟基（当R12为氢时）或氢（当R12为羟基时），R14和R15为氢或C1-16烷基，但是，当R12为羟基时，至少R14应为烷基，当R13为羟基时，至少R14或R15应为烷基。
合适的化合物a）有如2′，4-二羟基二苯甲酮，2-羟基二苯甲酮，2′，4，6-三羟基二苯甲酮，2-羟基-4-甲基二苯甲酮，2-羟基-4-甲氧基二苯甲酮，2，2′-二羟基-4，n-己氧基二苯甲酮，2-羟基-4，n-辛氧基二苯甲酮和2，2′-二羟基-4，n-十一烷氧基二苯甲酮。
推荐的二苯甲酮类化合物为其中的R1为氢及R2为羟基的该类化合物，另一类推荐的二苯甲酮化合物是其中的R2为羟基及R3是含6～10个碳原子的n-烷氧基的该类化合物，最好的二苯甲酮是2-羟基-4，n-辛氧基二苯甲酮。
合适的化合物b）有如
2-（2′-羟基-4′-苯基苯基）苯并三唑，
2-（2′-羟基-4′n-己基苯基）苯并三唑，
2-（2′-羟基-3′，5′-二叔丁基苯基）苯并三唑，
2-（2′-羟基-3′-叔丁基-5′-甲基苯基）苯并三唑，
2-（2′-羟基-3′-叔丁基-4′-辛氧基苯基）苯并三唑，
2-（2′-羟基-3′-异丙基-5′-n-丁基苯基）-5，7-二氯苯并三唑，
2-（2′-羟基-3′，5′-二叔丁基苯基）-7-氯苯并三唑，
2-（2′-羟基-3′-叔丁基苯基）-5-氯苯并三唑，
2-（2′-羟基-3′-乙基苯基）-5-氯苯并三唑，
2-（2′，4′-二羟基-3′，5′-二叔丁基苯基）-5，7-二氯苯并三唑，
2-（2′-羟基-3′-异戊基-1，5′-苄基苯基）-5，7-二溴苯并三唑。
推荐的化合物b）为其中R4是氯的该类化合物，另一类推荐的b）化合物是其中R6为引起位阻的烷基的该类化合物，最好的b）化合物是2-（2′-羟基-3′-叔丁基-5′-甲基苯基）-5-氯苯并三唑。
合适的化合物c）是二苯基胺，二（4-甲基-苯基）胺，二（6-己基苯基）胺，二（4-苄基苯基）胺，二（4-α，α-二正丙基苄基苯基）胺，二（4-α-乙基苄基苯基）胺，二（4-苄基苯基）胺，二（4-丙基苄基苯基）胺，二（4′-环己基苄基苯基）胺，以及二（4-壬基苯基）胺。
推荐的化合物c）为其中R8和1或R9是α，α-二烷基苄基的该类化合物，另一类推荐的化合物c）是其中R8或R9为含6～10个碳原子的n-烷基的该类化合物。最好的化合物c）是二（4-α，α-二甲基苄基苯基）胺
合适的化合物d）有如
6-（2′-羟基-3′-丙基苯胺基）-2，4-二甲基-1，3，5-三嗪，
6-（4′-羟基-5′-叔丁基苯胺基）-2，4-二己硫基-1，3，5-三嗪，
6-（2′，4′-二羟基-3′，5′-二叔丁基苯胺基）-2-己基-4-乙硫基-1，3，5-三嗪，
6-（2′-羟基-3′-叔丁基-5′-甲基苯胺基）-2，4-二环己基-1，3，5-三嗪，
6-（4′-羟基-3′，5′-二异丙基苯胺基）-2-环己基-4-环己硫基-1，3，5-三嗪，
6-（4′-羟基-3′，5′-二叔丁基苯胺基）-2，4-二庚硫基-1，3，5-三嗪。
推荐的化合物d）是其中R14（R15也可）为可引起位阻的烷基。在苯胺取代基中，推荐的羟基的位置是R13的位置，同时在此情况下R宜为氢。推荐的取代基R10和R11含6～10个碳原子的n-烷硫基。最好的化合物d）是6-（4′-羟基-3′，5′-二叔丁基苯胺基）-2，4-二辛硫基-1，3，5-三嗪。
本发明对于使聚合物链中C2H4单元和C3H6单元的比例至少为3∶1且至多15∶1的乙烯、丙烯和一氧化碳的交替三元共聚物稳定来说特别重要。推荐的乙烯/丙烯/一氧化碳三元共聚物是晶体熔点在215～240℃之间的该类聚合物。另一类推荐的共聚物是乙烯和一氧化碳的共聚物。
本发明所采用的共聚物的重均分子量应至少为2000，最好为至少6000。
本发明的改进的组合物可以通过诸如熔化抽丝、挤出、共挤出、吹塑、压塑、注塑及固相压力成型等通常加工技术加工成各种产品，如纤维、薄片，薄膜，层压板，容器，管子，管道和具有复杂形状的产品。本发明对于提高本发明共聚物和三元共聚物的长使用期光稳定性来说是特别重要的。本发明的稳定的共聚物组合物还可以包括其他添加剂，例如碳黑、矿物填料、染料、着色剂和增塑剂。同样，该共聚物组合物可与其他热塑性塑料混合在一起。
实施例
测定下述化合物的稳定功能
a）2-羟基-4-n-辛氧基二苯甲酮，
b）2-（2′-羟基-3′-叔丁基-5′-甲基苯基）-5-氯苯并三唑，
c）4，4′-双（α，α-二甲基苄基）二苯胺，
d）6-（4′-羟基-3′，5′-二叔丁基苯胺基）-2，4-双（n-辛硫基）-1，3，5-三嗪，
e）（（3，5-双（1，1-二甲基乙基）-4-羟基苯基）甲基）丁基-双（1，2，2，6，6-五甲基-4-哌啶基）酯
f）聚（（2，2，6，6-四甲基-1，4-亚哌啶基）氧基-（1，4-二氧代-1，4-亚丁烷）氧基-1，2-亚乙基）
g）癸二酸双（2，2，6，6-四甲基-4-哌啶基）酯
添加剂a）～d）是本发明的添加剂，e），f），g）是广泛应用的稳定剂商品，这是用来作对比。
在250℃下通过压塑由乙烯、丙烯和一氧化碳的三元共聚物来制备一个1mm厚的试样，该三元共聚物具有交替结构，结晶熔点为218℃，特性粘度为1.6dl/g。所有的稳定剂的使用浓度都为1.0%（重）。在测试前，将试样在23℃，50%相对湿度下平衡72小时。
将试样放在老化试验机中使其暴露在下列条件下：氙灯，水冷硅硼玻璃进样器，光强0.6w.m-2（340×10-9m），黑色板温度为55～60℃，空气温度为30℃，相对湿度50%，干燥周期为120分，潮湿周期为18分。在20毫米/分的伸长速速率下测定拉伸强度。
实验结果列于表中，用于热塑性塑料（特别是聚烯烃）的许多其他稳定剂商品的实验结果，最好也只是与对比添加剂e和f的结果相似，大部分的结果都比添加剂e和f差。
表
最大拉伸强度 断裂伸长率 E-模量
（MPa） （%） （GPa）
稳定剂 几天后 几天后 几天后
0 1 3 0 1 3 0 1 3
无 78 50 19 470 24 2 1.02 1.12 1.25
a） 76 53 50 452 304 253 0.98 0.92 1.01
b） 82 55 52 462 296 228 1.00 0.99 0.98
c） 83 55 49 459 303 98 0.95 1.03 1.04
d） 80 48 47 476 238 55 0.96 0.98 1.07
e）＊ 81 48 27 472 28 6 1.05 1.08 1.23
f）＊ 81 49 18 482 35 3 1.14 1.10 1.14
g）＊ 71 48 19 385 21 4 1.04 1.01 1.10
＊对比用
Claims (11)
1、共聚物组合物，其中包括一种由一氧化碳、一种烯属不饱和化合物和(根据需要任选的)另一种烯属不饱和化合物生成的交替共聚物以及0.03～5.0%(重)的一种添加剂，该添加剂选自：
a)式(I)的化合物
式中，R1是氢或羟基，R2是羟基(在R1为氢时)或氢(R1为羟基时)，R3是羟基、C1-12烷氧基或C1-12烷氧基，
b)式(Ⅱ)的化合物
式中，R4和R5各自独立地代表氢或囟原子，R6为C1-16烷基，R7为氢、羟基、C1-8烷基、C7-17芳基或C7-17芳基或C7-17芳烷基，
c)式(Ⅲ)的化合物
式中，R8和R9各自独立地代表氢、C1-12烷基、苯基或其亚甲基上可能带有一个或两个选自C1-8烷基的取代基的苄基，
d)式(Ⅳ)的化合物
式中，R10和R11各自独立地代表C1-14烷基和C1-14烷硫基，R12为氢或羟基，R13为羟基(当R12为氢时)或氢(当R12为羟基时)，R14和R15为氢或C1-16烷基，但是，当R12为羟基时，至少R14应为烷基，当R13为羟基时，至少R14或R15应为烷基。
2、权利要求1所述的组合物，其中R2是羟基，R1是氢。
3、权利要求1或2所述的组合物，其中R3是C6-10正-烷基。
4、权利要求1所述的组合物，其中R4是氯。
5、权利要求1或4所述的组合物，其中R6是引起位阻的烷基。
6、权利要求1所述的组合物，其中R8和1或R9是2，2-二烷基苄基。
7、权利要求1所述的方法，其中R8或R9是C6-10烷基。
8、权利要求1所述的组合物，其中R14是引起位阻的烷基。
9、权利要求1或8所述的组合物，其中R10、R11为C6-10正烷硫基。
10、权利要求1～9中任何一项所述的组合物，其中的共聚物是乙烯和一氧化碳的共聚物。
11、权利要求1～9中任何一项所述的组合物，其中的聚合物是乙烯、丙烯和一氧化碳的三聚物，其中乙烯单元和丙烯单元的比例是3∶1～15∶1。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB878709488A GB8709488D0 (en) | 1987-04-22 | 1987-04-22 | Copolymer composition |
| GB8709488 | 1987-04-22 |
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| Publication Number | Publication Date |
|---|---|
| CN88102180A true CN88102180A (zh) | 1988-12-28 |
| CN1021456C CN1021456C (zh) | 1993-06-30 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88102180A Expired - Fee Related CN1021456C (zh) | 1987-04-22 | 1988-04-20 | 稳定的共聚物组合物 |
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| Country | Link |
|---|---|
| US (1) | US5019614A (zh) |
| EP (1) | EP0288124B1 (zh) |
| JP (1) | JP2594612B2 (zh) |
| KR (1) | KR960005625B1 (zh) |
| CN (1) | CN1021456C (zh) |
| AT (1) | ATE108194T1 (zh) |
| AU (1) | AU599479B2 (zh) |
| BR (1) | BR8801875A (zh) |
| CA (1) | CA1319219C (zh) |
| DE (1) | DE3850516T2 (zh) |
| DK (1) | DK214888A (zh) |
| ES (1) | ES2056097T3 (zh) |
| GB (1) | GB8709488D0 (zh) |
| NO (1) | NO172056C (zh) |
| ZA (1) | ZA882764B (zh) |
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| US4684688A (en) * | 1986-08-25 | 1987-08-04 | Gaf Corporation | UV stabilizer for polyacetylenic recording media |
| US4761448A (en) * | 1987-09-29 | 1988-08-02 | Shell Oil Company | Stabilized crystalline polymers |
| GB8801756D0 (en) * | 1988-01-27 | 1988-02-24 | Shell Int Research | Copolymer composition |
| CA1340630C (en) * | 1988-01-29 | 1999-07-06 | Johannes Leopold Marie Syrier | Thermal stabilization of carbon monoxide copolymers |
| EP0339745B1 (en) * | 1988-04-29 | 1995-01-18 | Shell Internationale Researchmaatschappij B.V. | Polyketone polymer composition |
| JP2909143B2 (ja) * | 1989-04-27 | 1999-06-23 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | ポリケトン重合体組成物 |
| GB2253399A (en) * | 1991-03-04 | 1992-09-09 | Shell Int Research | Stabilized polymer composition |
| US5362881A (en) * | 1993-05-27 | 1994-11-08 | Fairmount Chemical Company, Inc. | Coupled benzotriazole and benzophenone UV absorbers |
| ATE224928T1 (de) * | 1995-04-19 | 2002-10-15 | Shell Int Research | Polyketonpolymer-zusammensetzung |
| US6147170A (en) * | 1998-08-17 | 2000-11-14 | E. I. Du Pont De Nemours And Company | UV stabilized ethylene copolymers |
| US7290146B2 (en) * | 2004-05-03 | 2007-10-30 | Fargo Electronics, Inc. | Managed credential issuance |
| US7968001B2 (en) * | 2007-12-19 | 2011-06-28 | Air Products And Chemicals, Inc. | Stabilizers for the stabilization of unsaturated hydrocarbon-based precursor |
| CA3004917A1 (en) * | 2015-12-11 | 2017-06-15 | General Cable Technologies Corporation | Conductive compositions for jacket layers and cables thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2495286A (en) * | 1949-06-08 | 1950-01-24 | Du Pont | Interpolymers of carbon monoxide and method for preparing the same |
| GB1081304A (en) * | 1965-03-23 | 1967-08-31 | Ici Ltd | Improvements in or relating to chemical compounds |
| US3505225A (en) * | 1966-04-07 | 1970-04-07 | Uniroyal Inc | Derivatives of diphenylamine and the phenylnaphthylamines as antioxidants and as synergists with dialkyl 3,3'-thiodipropionates |
| GB1362363A (en) * | 1970-04-27 | 1974-08-07 | Univ Toronto | Photodegradable polymers |
| US3694412A (en) * | 1971-03-04 | 1972-09-26 | Shell Oil Co | Process for preparing interpolymers of carbon monoxide in the presence of aryl phosphine-palladium halide complex |
| US3817914A (en) * | 1971-07-02 | 1974-06-18 | Ciba Geigy Corp | Sulfur containing derivatives of dialkyl-4-hydroxyphenyltriazine |
| US3786021A (en) * | 1972-02-10 | 1974-01-15 | Phillips Petroleum Co | Polymers of 1-olefins protected against ultraviolet light |
| US3978074A (en) * | 1973-11-21 | 1976-08-31 | Uniroyal Inc. | Method of making hydroxyarylbenzotriazoles and their N-oxides |
| US4024104A (en) * | 1975-06-13 | 1977-05-17 | Atlantic Richfield Company | Stabilized ethylene-carbon monoxide copolymers |
| US3929727A (en) * | 1975-06-18 | 1975-12-30 | Atlantic Richfield Co | Stabilized ethylene-carbon monoxide copolymers |
| JPS54158484A (en) * | 1978-05-19 | 1979-12-14 | Sekisui Chem Co Ltd | Fiber-reinforced unsaturated polyester resin molded article |
| DE3119385A1 (de) * | 1981-05-15 | 1982-12-09 | Basf Ag | Ethoxylierte diphenylamine als lichtschutzmittel |
| JPS57159828A (en) * | 1982-02-13 | 1982-10-02 | Seikou Kagaku Kk | Antideteriorant for rubber |
| DE3480845D1 (de) * | 1983-04-06 | 1990-02-01 | Shell Int Research | Verfahren zur herstellung von polyketonen. |
| NL8403035A (nl) * | 1984-10-05 | 1986-05-01 | Shell Int Research | Werkwijze ter bereiding van polyketonen. |
| JPS6218443A (ja) * | 1985-07-17 | 1987-01-27 | Adeka Argus Chem Co Ltd | 安定化高分子材料組成物 |
| US4786672A (en) * | 1986-07-31 | 1988-11-22 | Ciba-Geigy Corporation | Anilinotriazines and the use thereof |
-
1987
- 1987-04-22 GB GB878709488A patent/GB8709488D0/en active Pending
-
1988
- 1988-03-14 US US07/167,801 patent/US5019614A/en not_active Expired - Fee Related
- 1988-04-12 CA CA000563867A patent/CA1319219C/en not_active Expired - Fee Related
- 1988-04-19 AT AT88200742T patent/ATE108194T1/de not_active IP Right Cessation
- 1988-04-19 EP EP88200742A patent/EP0288124B1/en not_active Expired - Lifetime
- 1988-04-19 DE DE3850516T patent/DE3850516T2/de not_active Expired - Fee Related
- 1988-04-19 ES ES88200742T patent/ES2056097T3/es not_active Expired - Lifetime
- 1988-04-20 ZA ZA882764A patent/ZA882764B/xx unknown
- 1988-04-20 KR KR1019880004498A patent/KR960005625B1/ko not_active IP Right Cessation
- 1988-04-20 CN CN88102180A patent/CN1021456C/zh not_active Expired - Fee Related
- 1988-04-20 JP JP63098031A patent/JP2594612B2/ja not_active Expired - Lifetime
- 1988-04-20 NO NO881694A patent/NO172056C/no unknown
- 1988-04-20 BR BR8801875A patent/BR8801875A/pt not_active IP Right Cessation
- 1988-04-20 DK DK214888A patent/DK214888A/da not_active Application Discontinuation
- 1988-04-20 AU AU14783/88A patent/AU599479B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| DK214888D0 (da) | 1988-04-20 |
| ZA882764B (en) | 1988-10-21 |
| EP0288124B1 (en) | 1994-07-06 |
| EP0288124A3 (en) | 1990-02-14 |
| DK214888A (da) | 1988-10-23 |
| KR960005625B1 (ko) | 1996-04-30 |
| NO172056C (no) | 1993-06-02 |
| US5019614A (en) | 1991-05-28 |
| ATE108194T1 (de) | 1994-07-15 |
| AU599479B2 (en) | 1990-07-19 |
| JPS63314273A (ja) | 1988-12-22 |
| BR8801875A (pt) | 1988-11-22 |
| CN1021456C (zh) | 1993-06-30 |
| KR880012695A (ko) | 1988-11-28 |
| GB8709488D0 (en) | 1987-05-28 |
| CA1319219C (en) | 1993-06-15 |
| NO172056B (no) | 1993-02-22 |
| ES2056097T3 (es) | 1994-10-01 |
| DE3850516D1 (de) | 1994-08-11 |
| NO881694D0 (no) | 1988-04-20 |
| NO881694L (no) | 1988-10-24 |
| DE3850516T2 (de) | 1994-10-27 |
| AU1478388A (en) | 1988-10-27 |
| EP0288124A2 (en) | 1988-10-26 |
| JP2594612B2 (ja) | 1997-03-26 |
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