CN1074417C - 呈现出高水解稳定性的固体非晶态稳定剂组合物及其制法 - Google Patents
呈现出高水解稳定性的固体非晶态稳定剂组合物及其制法 Download PDFInfo
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- 239000000203 mixture Substances 0.000 claims abstract description 48
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- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 14
- 150000003018 phosphorus compounds Chemical class 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 10
- -1 ammediol phosphorous acid ester Chemical class 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
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- 238000000034 method Methods 0.000 claims description 7
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
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- 239000000654 additive Substances 0.000 abstract description 2
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- 239000003963 antioxidant agent Substances 0.000 abstract 1
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- 239000002585 base Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 4
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 4
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- WAOPGHCXGUXHKF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-1,1-diphenylpropane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.C1(=CC=CC=C1)C(O)(C(CO)(CO)CO)C1=CC=CC=C1 WAOPGHCXGUXHKF-UHFFFAOYSA-N 0.000 description 1
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- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
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- IFTZOWKEQLZNMT-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite 3-ethyl-2,2-bis(hydroxymethyl)pentane-1,3-diol Chemical class OP(O)OP(O)O.C(C)C(O)(C(CO)(CO)CO)CC IFTZOWKEQLZNMT-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000001624 naphthyl group Chemical group 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical class C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
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- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/10—Phosphatides, e.g. lecithin
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- C07—ORGANIC CHEMISTRY
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/025—Purification; Separation; Stabilisation; Desodorisation of organo-phosphorus compounds
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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
- C08K5/17—Amines; Quaternary ammonium compounds
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
提供一种固体非晶态亚磷酸酯稳定剂组合物,它具有高水解稳定性。优选让该稳定剂组合物含有从10%到99.9%重量的一种亚磷化合物,选自亚磷酸酯类和亚膦酸酯类,并且优选含量从0.1%到10%重量的一种脂族多胺。该稳定剂组合物表现出高水解稳定性,并且以粉末或片状的形式为好。该稳定剂组合物作为抗氧剂稳定剂,用作聚合物树脂的添加剂。
Description
本发明涉及固体亚磷酸酯稳定剂组合物,更具体地说涉及呈现高水解稳定性的固体亚磷酸酯稳定剂组合物。
胺化合物一直是与亚磷酸酯类,特别是亚磷酸季戊四醇酯共同使用,用于提高亚磷酸酯抗水解的能力,见York的美国专利4116926,1978年9月26公开。据York所言,在与胺化合物和亚磷酸酯共用以提高稳定性时,仍然发现,在长期曝露于室温下的潮湿条件下时,组合物的水份仍然重量增加。因此,有必要提供表现出高水解抗力的亚磷酸季戊四醇酯组合物。
本发明涉及一种非结晶(玻璃状的,非晶体)固体亚磷酸酯稳定剂组合物,具有高水解稳定性,包括一有机亚磷酸酯和一脂族多胺的熔混体,更优选的是一种结晶亚磷酸酯和一种脂族伯二胺的熔混体。与含有亚磷酸酯和三异丙醇胺的熔混体组合物相比,以及与磨细的亚磷酸酯和脂族多胺的混合物相比,这种熔混体具有人惊异的和出乎预料的超高水解稳定性。这种固体稳定剂组合物用作为抗热氧化降解的稳定聚合组分的添加剂是有用的。
适用的亚磷化合物包括亚磷酸酯类和亚膦酸酯类(phosphonites)。适用的亚磷酸酯类包括从下面通式中选出的那些: 其中,R1、R2、R3和每个R4表示或者相同或者相异的烃基基团,既可以是烷基、环烷基、芳基、烷芳基,也可以是芳烷基;R5可以是氢、烷基、环烷基、芳基、烷芳基或芳烷基。亚磷酸酯类也可选自下面的通式:适宜的亚膦酸酯类包括通式:其中R7和R8分别地代表既可以是烷基,环烷基,芳基,烷芳基,也可以是芳烷基。
亚磷酸酯类优选为一亚磷酸季戊四醇酯,它可以从由下式化合物(a)组成的组中选取:其中,R7是含有1至大约20个碳原子的脂族基团,5到约8个碳原子的环烷基,或6到14个碳原子的芳基、烷芳基或芳烷基,或从下式(b)化合物中选取:式中:R7的定义如前。这些化合物的例子为,R7是一脂族基团;R7可以是(a)一烷基基团,例如甲基、乙基、异丙基、正丁基、正己基、2-乙己基、正十二烷基,正十四基、正十八烷基、等等,(b)含2到约20个碳原子的一种烷氧烷基,例如,甲氧乙基、乙氧乙基、乙氧丙基等等,和(c)含2到约20个碳原子的烷氧羰烷基,例如,甲氧羰乙基、丙氧羰乙基、癸氧羰乙基,等等。当R7是一环烷基时,R7的例子包括:环戊基、环己基、环辛基、等等。当R7是一芳基时,其例子有苯基和萘基。芳基可以是卤化的,如溴苯基。最后,当R7是7到约14个碳原子的烷芳基时,即一烷基取代的苯或萘基团时,其例子有:甲苯基、叔-丁苯基、壬苯基、等等;当R7是含碳7到大约14个碳原子的芳烷基时,即芳基取代的烷基,例子有苄基和苯乙基。烷芳基或芳烷基可以是卤化的,例如2-氯乙基苯基团。最优选的亚磷酸酯是纯净(天然)状态的结晶体。
所限定的亚磷酸季戊四醇酯类的例子有:二甲基季戊四醇二亚磷酸酯,二乙基季戊四醇二亚磷酸酯,二-十二基季戊四醇二亚磷酸酯,二-十八基季戊四醇二亚磷酸酯,二苯基季戊四醇二亚磷酸酯,二甲苯基季戊四醇二亚磷酸酯,二-对-氯苯基季戊醇亚磷酸酯,二苄基季戊四醇二亚磷酸酯等等。美国专利2847443,2961,454,3000850,3205250和3737485还公开了更多的所定义的化合物的例子。
更优选的是让R7基团为1至20个碳原子的烷基、环己基、苯基或苄基、最优选让R7为一含6到大约20碳原子的高级烷基,例如正己基、正辛基、正癸基、2-乙基己基,正-癸基,正十四烷基、正十八烷基,等。
优选的脂族多胺沸点大于175℃,更优选大于190℃,最优选大于200℃。脂族多胺可以包括伯、仲或叔胺。优选使胺基为伯胺基。多胺可以含2、3或多个胺基,换言之,可以是二胺、三胺或高级多胺。优选的多胺是具有下式的脂族伯二胺:
N2N-R10-NH2式中,R10从C6至C10二价烷基中选出,而更优选的二胺从1,6-二氨基己烷和1,10-二氨基癸烷中选出。适用的脂族仲二胺可以用下面的通式表示:式中,R11从C1到C10二价烷基中选择,而R12从C1到C10单价烷基中选择。适用的脂族叔二胺用下面的通式表示:式中,R11和R12的限定如前。最优选的多胺是脂族伯二胺。
本发明也涉及一种方法,涉及一种结晶亚磷酸酯和一种多胺熔融混合以形成一种熔混体,再冷却该熔混体形成非晶态固体亚磷酸酯组合物的方法。该方法还涉及存贮亚磷酸酯,在室温下(在相对湿度大于60%的可能的湿度下)贮存期超过10天,然后使该亚磷酸酯组合物与一热塑性聚合物诸如聚烯烃化合,例如与聚丙烯化合以提高其热氧化稳定性。
本发明的稳定剂组合物包括10%到99.9%重量的亚磷酸酯,以稳定剂组合物的全部重量为基计算,较优选的为90%到99.8%(重量),更优选从96%到99.5%(重量),最优选从97%到99%(重量)。多胺的含量优选从0.1%到10%重量,以稳定剂组合物的全部重量计,较优选为从0.2%到5%重量,更优选从0.5%到4%重量,最优选的含量为从1%到3%重量。稳定剂组合物为非晶态(非结晶的)颗粒,例如粉末和小片状。稳定剂组合物优选含有少于10%重量的其它材料,例如聚合物材料和其他有机材料,例如蜡,干燥的合成的或石油润滑油和润滑脂;动物油脂,例如脂肪、牛脂、猪脂、鳕鱼肝油、鲸蜡油;植物油,例如蓖麻油、亚麻子油、花生油,鳕鱼籽(cod seed)油等等;燃料油,柴油、汽油,等。另外,稳定剂组合物优选基本上不含有其它材料,换言之,含有不超过1%的其它有机材料,优选不含有其它有机材料。优选使稳定剂组合物基本上不含有单胺,例如,三异丙胺。本发明的组合物优选非晶态以保证组合物的均一性。该组合物优选以熔混合而不是简单地机械混合或溶液混合方法,并且令人惊异和出乎预料地,用熔混方法制成的组合物表现出超高水解稳定性,超过用简单的机械(干)混或溶液混合方法所制的相似的组合物。
实施例A-H是对比例。实施例1和2是说明本发明的例子。实施例A是结晶双(2,4-二-叔-丁基苯基)季戊四醇二亚磷酸酯(Phos1)。实施例B是99%重量的Phos1和1%重量的三异丙醇胺(TIPA)的研磨(机械的干式混合)混合物。实施例C是99%重量的Phos1和1%重量TIPA的玻璃状(非晶态)的熔混体。实施例D是99%重量的Phos1和1%的1,10-二氨基癸烷(DAD)的研磨混合物。实施例1是99%重量的Phos1和1%重量DAD的非晶态熔混体。注意实施例1的性能超过实施例A-D。实施例E是晶体状态,是下式的一种亚磷酸酯:实施例F是玻璃状的Phos2。实施例G是99%Phos2和1%重量的Tinuvin770(双(2,2,6,6-四-甲基哌啶基)癸二酸酯)的非晶态熔混体。实施例H是含有99%重量Phos2和1%三辛基胺的非晶态熔混体。实施例2是含有99%重量的Phos2和1%的1,10-二氨基癸烷的非晶态熔混体。注意实施例2的性能超过实施例E-H的性能。各试样在室温下(约70°F)在75%公称相对湿度下曝露相当长的时间,水解稳定性的这些不同的等级,用重量%增加表示,在给定曝露时间长度下重量增加的百分数越低,表明水解稳定性的等级越高。
实施例3是99份重量的(pbw)双(2,4-二-叔-丁苯基)季戊四醇二亚磷酸酯和1份重量的1,6-二氨基己烷的一种非晶态固体(熔混体)。实施例Ⅰ是双(2,4-二-叔-丁苯基)季戊四醇二亚磷酸酯的一种结晶。实施例J是双(2,4-二-叔-丁苯基)季戊四醇二亚磷酸酯的非晶态固体。实施例K是双(2,4-二-叔-丁苯基)季戊四醇二亚磷酸酯(99pbw)与1份重量(pbw)的十八烷基胺的混合物。实施例L是双(2,4-二-叔-丁苯基)季戊四醇二亚磷酸酯(95.4pbw)与十八烷基胺(4.6pbw)的非晶体固体(熔混体)。实施例L所用的胺的碱当量与实施例3的相等。实施例I-L是对比实施例。注意实施例3实质上的抵抗水分重量增加能力超越对比例I-L。其抗性的实质性的增大既令人吃惊,又出人意料。
表1在室温下在75%公称相对湿度下老化试样小时 实施例A 实施例B 实施例C 实施例D 实施例10 0.00 0.00 0.00 0.00 0.0024 #N/A 0.74 0.12 0.45 0.0148 #N/A 1.16 0.16 0.43 0.0296 0.94 #N/A 0.46 0.87 0.02120 1.09 #N/A 0.61 1.14 0.09168 #N/A #N/A 0.98 1.74 0.07216 #N/A #N/A 1.64 2.63 0.07288 #N/A #N/A 3.10 5.49 0.09336 #N/A #N/A #N/A #N/A 0.06360 #N/A #N/A #N/A #N/A 0.08384 #N/A #N/A #N/A #N/A 0.13456 #N/A #N/A #N/A #N/A 0.12480 #N/A #N/A #N/A #N/A 0.08528 #N/A #N/A #N/A #N/A 0.03552 #N/A #N/A #N/A #N/A 0.03624 #N/A #N/A #N/A #N/A 0.05672 #N/A #N/A #N/A #N/A 0.06720 #N/A #N/A #N/A #N/A 0.05
表1(续)小时 实施例A 实施例B 实施例C 实施例D 实施例1792 #N/A #N/A #N/A #N/A 0.06840 #N/A #N/A #N/A #N/A 0.06888 #N/A #N/A #N/A #N/A 0.09960 #N/A #N/A #N/A #N/A 0.151008 #N/A #N/A #N/A #N/A 0.181054 #N/A #N/A #N/A #N/A 0.161128 #N/A #N/A #N/A #N/A 0.231176 #N/A #N/A #N/A #N/A 0.291224 #N/A #N/A #N/A #N/A 0.361296 #N/A #N/A #N/A #N/A 0.541344 #N/A #N/A #N/A #N/A 0.67
表2在室温下在75%公称相对湿度下老化的试样小时 实施例G 实施例H 实施例2 实施例F 实施例E72 0.10 0.05 0.07 0.04 0.03144 0.14 0.13 0.14 0.10 0.29168 0.12 0.19 0.10 0.12 0.62240 0.11 0.10 0.12 0.29 2.30312 0.13 0.12 0.1 3 0.59 #N/A456 0.13 0.09 0.12 1.82 #N/A504 0.14 0.09 0.16 2.39 #N/A576 0.13 0.08 0.14 #N/A #N/A840 0.16 0.14 0.20 #N/A #N/A936 0.18 0.20 0.13 #N/A #N/A1080 0.40 0.56 0.14 #N/A #N/A1248 1.26 1.94 0.18 #N/A #N/A1416 #N/A #N/A 0.18 #N/A #N/A1584 #N/A #N/A 0.21 #N/A #N/A1776 #N/A #N/A 0.24 #N/A #N/A2112 #N/A #N/A 0.26 #N/A #N/A2280 #N/A #N/A 0.20 #N/A #N/A2496 #N/A #N/A 0.26 #N/A #N/A
表2(续)小时 实施例G 实施例H 实施例2 实施例F 实施例E2952 #N/A #N/A 0.21 #N/A #N/A3312 #N/A #N/A 0.28 #N/A #N/A3528 #N/A #N/A 0.22 #N/A #N/A3936 #N/A #N/A 0.26 #N/A #N/A4608 #N/A #N/A 0.4 #N/A #N/A
表3小时 实施例1 实施例J 实施例3 实施例K 实施例L0 0 0 0 0 048 0.27 0.1 0.32 0.65 0.0372 0.3 0.82 0.21 1.3 0.0796 0.3 3.43 0.14 2.93 0.55168 0.45 #N/A 0.09 #N/A 1.43336 1.38 #N/A 0.13 #N/A #N/A384 #N/A #N/A 0.13 #N/A #N/A
Claims (9)
1.一种呈现出高水解稳定性的固体非晶态稳定剂组合物,它包括:
(A)一种亚磷化合物,以稳定剂组合物的总重量计,所述亚磷化合物的重量百分含量为90%到99.9%,所述亚磷化合物选自由下面的通式所代表的亚磷酸酯类和亚膦酸酯类化合物:式中每个R1、R4、R7和R8基团分别选自:烷基、环烷基、芳基、烷芳基或芳烷基基团,R5可以是氢、烷基、环烷基、芳基、烷芳基或芳烷基;和
(B)一种脂族多胺,以组合物的总重量计,其含量为0.1%至10%重量;所述多胺选自下式基团:H2N-R10-NH2,R12-NH-R11-NH-R12和R12-N(R12)-R11-N(R12)-R12,其中R10选自C6-C10二价烷基,R11选自C1-C10二价烷基,以及R12选自C1-C10一价烷基。
2.根据权利要求1的稳定剂组合物,其中,以组合物总重量计,所述亚磷化合物的含量为90%至99.8%重量。
3.根据权利要求1的稳定剂组合物,其中,以组合物总重量计,所述亚磷化合物的含量为96%至99.5%重量。
4.根据权利要求1的稳定剂组合物,其中,所述稳定剂组合物由所述亚磷化合物和所述多胺构成。
5.根据权利要求1的组合物,其中,所述亚磷化合物是2,4,6-三-叔-丁苯基2-丁基-2-乙基-1,3-丙二醇亚磷酸酯。
6.根据权利要求1的组合物,其中,所述亚磷化合物是双(2,4-二-叔-丁苯基)季戊四醇二亚磷酸酯。
7.根据权利要求1的组合物,其中,所述组合物是粉末状的,其平均粒径尺寸从10毫微米到2毫米之间选定。
8.根据权利要求1的稳定剂组合物,其中,所述组合物是片状的。
9.一种制造具有高水解稳定性的稳定剂组合物的方法,所述方法包括:
(a)熔融混合一种亚磷化合物和一种脂族多胺;以组合物的总重量计,所述组合物含有90%到99.9%重量的所述亚磷化合物和从0.1%到10%重量的所述多胺,所述多胺选自下式基团:H2N-R10-NH2,R12-NH-R11-NH-R12和R12-N(R12)-R11-N(R12)-R12,其中R10选自C6-C10二价烷基,R11选自C1-C10二价烷基,以及R12选自C1-C10一价烷基;所述亚磷化合物选自由下面的通式所代表的亚磷酸酯类和亚膦酸酯类化合物:式中每个R1、R4、R7和R8基团分别选自:烷基、环烷基、芳基、烷芳基或芳烷基基团,R5可以是氢、烷基、环烷基、芳基、烷芳基或芳烷基。
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US08/325,726 US5468895A (en) | 1994-10-19 | 1994-10-19 | Amine stabilized amorphous phosphite |
US325726 | 2001-09-28 |
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CN (1) | CN1074417C (zh) |
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-
1994
- 1994-10-19 US US08/325,726 patent/US5468895A/en not_active Expired - Lifetime
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1995
- 1995-07-24 TW TW084107644A patent/TW279882B/zh active
- 1995-09-21 HU HU9502764A patent/HUT72433A/hu unknown
- 1995-09-28 CA CA002159369A patent/CA2159369A1/en not_active Abandoned
- 1995-10-04 ZA ZA958363A patent/ZA958363B/xx unknown
- 1995-10-13 CZ CZ952682A patent/CZ268295A3/cs unknown
- 1995-10-16 AT AT95307321T patent/ATE212045T1/de not_active IP Right Cessation
- 1995-10-16 JP JP26654795A patent/JP4195730B2/ja not_active Expired - Lifetime
- 1995-10-16 EP EP95307321A patent/EP0708138B1/en not_active Expired - Lifetime
- 1995-10-16 DE DE69525010T patent/DE69525010T2/de not_active Expired - Fee Related
- 1995-10-17 NO NO954127A patent/NO954127L/no unknown
- 1995-10-18 KR KR1019950035934A patent/KR100377296B1/ko not_active IP Right Cessation
- 1995-10-19 CN CN95119922A patent/CN1074417C/zh not_active Expired - Fee Related
- 1995-11-16 US US08/559,585 patent/US5674927A/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3553298A (en) * | 1967-10-20 | 1971-01-05 | Hooker Chemical Corp | Hydrolytic stabilized phosphite esters |
US3737485A (en) * | 1971-12-30 | 1973-06-05 | Weston Chemical Corp | Tripentaerythritol tetraphosphite |
US4116926A (en) * | 1975-08-11 | 1978-09-26 | Borg-Warner Corporation | Stabilizer for polymers |
Also Published As
Publication number | Publication date |
---|---|
DE69525010D1 (de) | 2002-02-21 |
CZ268295A3 (en) | 1996-06-12 |
NO954127D0 (no) | 1995-10-17 |
HU9502764D0 (en) | 1995-11-28 |
US5468895A (en) | 1995-11-21 |
KR100377296B1 (ko) | 2003-06-02 |
DE69525010T2 (de) | 2002-09-12 |
NO954127L (no) | 1996-04-22 |
TW279882B (zh) | 1996-07-01 |
CN1130187A (zh) | 1996-09-04 |
ZA958363B (en) | 1996-04-26 |
CA2159369A1 (en) | 1996-04-20 |
US5674927A (en) | 1997-10-07 |
JPH08245958A (ja) | 1996-09-24 |
KR960014144A (ko) | 1996-05-22 |
EP0708138B1 (en) | 2002-01-16 |
JP4195730B2 (ja) | 2008-12-10 |
HUT72433A (en) | 1996-04-29 |
EP0708138A1 (en) | 1996-04-24 |
ATE212045T1 (de) | 2002-02-15 |
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