CN1019497B - 异戊二烯的聚合方法 - Google Patents
异戊二烯的聚合方法Info
- Publication number
- CN1019497B CN1019497B CN86103812A CN86103812A CN1019497B CN 1019497 B CN1019497 B CN 1019497B CN 86103812 A CN86103812 A CN 86103812A CN 86103812 A CN86103812 A CN 86103812A CN 1019497 B CN1019497 B CN 1019497B
- Authority
- CN
- China
- Prior art keywords
- component
- compound
- isoprene
- halogen
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 239000004411 aluminium Substances 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- -1 aluminum compound Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 125000005843 halogen group Chemical group 0.000 abstract description 2
- 239000012190 activator Substances 0.000 abstract 2
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 230000000737 periodic effect Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 7
- 239000000178 monomer Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229920001195 polyisoprene Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000005662 Paraffin oil Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical group CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QIONYIKHPASLHO-UHFFFAOYSA-N 2,2,2-tribromoacetic acid Chemical class OC(=O)C(Br)(Br)Br QIONYIKHPASLHO-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MASXONVJEAXEIV-UHFFFAOYSA-N butyl 2,2-dichloroacetate Chemical compound CCCCOC(=O)C(Cl)Cl MASXONVJEAXEIV-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000011928 denatured alcohol Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/08—Isoprene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
通过在一种催化剂体系存在下和无溶剂时进行聚合的方法制造异戊二烯聚合物和共聚物，该催化剂体系包含(a)至少一种属于周期表三副族的元素或该元素的化合物，(b)至少一种铝的烷基衍生物，(c)至少一种有机卤素衍生物或至少一种能以两种以上价态存在的元素的卤化物(以较最低价态高的价态与卤素结合)或至少一种卤素或至少一种氢卤酸，(d)至少一种含有一个或多个羟基且羟基上的氢可被取代的化合物，组分(b)与组分(a)之比等于或小于20。
Description
本发明涉及一种制备异戊二烯聚合物及共聚物的方法，该方法在设有或基本没有稀释剂的情况下，使用包括下列组分的催化剂体系：（a）至少一种属于周期表三副族的元素或其化合物，（b）至少一种烷基铝衍生物，（c）至少一种有机卤素衍生物或至少一种能以两种以上价态存在的元素的卤化物，该卤化物的价态高于最低态，和（d）至少一种含有一个或多个羟基且羟基上的氢能被取代的化合物，组分（b）与组分（a）之比应等于或少于20。
由属于周期表三副族的元素制得的催化剂对共轭二烯羟的聚合被认为是很有效的。
例如，美国专利3，297，667和3，794，604中叙述的带一价或二价二卤有机配位体的镧系化合物的应用和联邦德国专利2，830，080和2，848，964中叙述的与单价单卤配位体络合的镧。
并不是所提及的各种化合物都是稳定或易于获得的;其制备通常包括大量反应和困难的制备过程。
上述联邦德国专利通过使所述化合物与其他烷基铝等有机类化合物结合而完成避免出现象氧、水、醇类或羧酸类等通常用来使催化剂减活的化合物。
本申请人是使用某些涉及共轭二烯烃聚合和共聚方法的意大利专利申请的权利所有人，这些方法中的一些介绍了使用催化剂体系的工艺方法，奇怪的是，它与上述工艺说明推断的技术不相同。
尤其是1983年10月26日欧洲专利申请文件号（theEuropean Pat.Applns.Publ.）00092270号和第009221号中介绍的使共轭二烯烃聚合物或共聚合成具有基本上全部为1，4顺式结构的线性产物的方法，这些方法包括各单体与多组分催化剂体系接触，该多组分催化剂体系含有下列化合物，（a）至少一种三副族元素或该元素的衍生物，（b）至少一种有机铝衍生物，（c）至少一种有机卤素衍生物和与上述已知工艺不相同的（d）至少一种含有一个或多个可成盐的羟基的化合物。因此，水、醇类或羧酸类都起明显的助催化作用。
这些聚合方法既可在适当反应介质存在时，也可在完全没有稀释剂时完成。在这两种情况下，如果在制造过程中在变化的各组分间小心地加入催化剂使其保持一定比例，反应将按这种控制方法进行。组分（c）与组分（a）之比大于0.1，组分（d）与组分（a）之比大于1，组分（b）与组分（a）之比大于20，最好在30和200之间。
这种催化体系在丁二烯聚合中有明显的优点，例如，通过适当地选择过渡金属和这种金属（或其衍生物）与前述铝化合物之比，可获得具有良好的线性结构，1，4顺式结构单元的含量达到或超过98%的聚丁二烯，其熔点可达曾经观测到的最高值之列。
虽然丁二烯在溶液中与在无稀释剂时聚合没有明显差别，但如果按上述两个专利申请的方法不用稀释剂使异戊二烯聚合，虽然也能获得满意的结果，但不能制取高分子量的聚合物。为避免聚合物受到通常的机械作用时产生的分子量降低而引起的有关的缺陷，高分子量是很重要的，由此可见这是不利的。
本申请者现在已发现本发明的主题，即通过简单方法和较通常溶液聚合明显减少的反应时间生产有申请意义的产品，即顺式含量高（＞96%）、分子量高（门尼粘度＞75）和无凝胶的聚异戊二烯。这可在没有稀释剂的情况下，使用前面所定义的催化剂体系，通过实现异戊二烯的聚合（或共聚合）来制成，催化剂体系中铝化合物与周期表三副族的元素或其衍生物之比值较低。
比值小于或等于20时，可获得具有门尼粘度高于75的高转化率的（≥60%）聚异戊二烯，聚合时间范围为10至40分钟;而以溶液聚合方法，因为稀释剂存在，需4至5小时，使产率进一步降低。
通过将溶解在异戊二烯中的终止剂和稳定剂混入反应体系而使反应结束，过量单体在常规的脱溶剂挤压机中脱除。
因此，本发明提供一种制备异戊二烯聚合物或共聚物的方法，特别是制造顺式含量高的聚异戊二烯的方法，在没有或基本没有稀释剂的条件下，使一种或多种单体与催化剂体系接触，所用催化剂体系包括：
（a）至少一种周期表三副族、原子序号在57和71之间的元素，或至少一种这种元素的化合物;
（b）至少一种化学式为AlR2R′的铝化合物，其中R是烷基，环烷基或烷芳基，且R′是R或氢;
（c）至少一种选自下列物质的化合物：有机卤素衍生物，至少能以两种价态存在的元素的卤化物（以比最低价态高的价态与卤素结合），卤素和氢卤酸;
（d）至少一种含有一个或多个可成盐的羟基的化合物，如水，醇类和羧酸类;
其中组分（b）与组分（a）之比等于或小于20。
组分（a）可以是金属元素，这时它们必须处于非常活泼的状态，并因此有利于在10-1到10-6托尔残压下通过真空蒸发使它们分离，并使它们在-20℃至-200℃的低温下冷凝到组分c形成的载体上，组分（c）既可是纯净态，也可以用饱和或不饱和脂肪烃稀释。（a）和（c）之间的反应可在室温下完成，或根据（c）的性质升高悬浮液温度（如超过100℃）几分钟来完成。
这些元素最好是钕、镨、它们的混合物或它们与镧的混合物。
也可使用这些元素的衍生物，其中最好是氧化物、醇化物和有机酸酯类。
组分（c）可具有有机性质或无机性质，尤其适合的有机卤素衍生物是烯丙基氯和溴化物，丁烯基氯和溴化物，甲代烯丙基氯和溴化物，苄基氯和溴化物，苯甲酰氯和溴化物，叔丁基氯和溴化物，三氯甲烷和三溴乙酸盐，二氯乙酸丁酯，一氯乙酸乙酯等等。
能以一种以上价态存在的元素的卤代物包括四氯化锡，五氯化锑和磷、磷酰基、砜基的氯化物和溴化物等等。
组分（b）与组分（a）之比为小于或等于20时，催化剂体系含有下列比值的各种组分：（c）/（a）大于0.1且最好在1至3之间;（d）/（a）大于1且最好在3和10之间。在组分（d）中，尤其要指出的是使用水时，尽管水在脂肪烃中的溶解性差，但在液态二烯烃中的溶解性还是很好的。
聚合温度可在很宽的范围内选择，如在0℃至130℃除反应动力学，平均分子量，分子量分布和顺式含量外，这基本上不会影响聚合物的特性。对于这些因素来说，较好的范围是40℃至80℃之间。
如上所述，按照本发明的方法不仅能得到1，4顺式含量较高的聚异戊二烯，而且还能得到异戊二烯与第二种共轭二烯烃的共聚物。而且在后一种情况下，所述共聚物的特征在于具有几乎全部是1，4顺式类型的微观结构。如果聚合转化率仅限于中等水平如50～60%，则只在普通的均匀搅拌反应器中就可按本发明的方法实现聚合反应。如果需要较高的转化率，则因为产生非常粘稠的聚合物产物，所以最好使用长形聚合反应器，混合产物可按柱塞式运动形式在反应器中滑动。因此各种挤压机正适合于这种目的，在挤压机中，聚合体由自洁式单螺杆或双螺杆搅拌器推出。
所获得产物的其他特性和一些操作细节通过阅读下列实施例将会明了，这些实施例仅用来说明本发明，而不是以任何形式限制本发明的范围。
实施例1
催化剂的制备：
将一块涂有聚四氟乙烯的金属片置于瓶壁结实的容量约100ml的玻璃瓶中，然后按所述顺序加入下列物质：
三氧化二钕（Nd2O3）（工业产品，95%） 4.04克
环烷酸类（酸值200） 19.8克
石蜡油（凡士林油） 45毫升
将瓶子用一个打了孔的顶盖和一个氯丁二烯橡胶密封垫塞住，并将其置于一个温度控制在80℃的水浴中。以旋转磁铁驱动其中的金属片作旋转运动。
5分钟后，用一个有皮下注射针头的微量调节注射器向反应混合物中加入0.08毫升的37%的盐酸水溶液。
20分钟后，溶液颜色由灰变棕，同时有水生成。在80℃反应2小时后，可获得一种粘稠的溶液，在室温中冷却，同时在搅拌下将粘稠溶液缓慢地移入一个玻璃烧瓶中，该烧瓶中装有0.97摩尔的（iC4H9）2AlH（DIBAH，异丁基氢合铝）的石蜡油溶液471毫升，并以一大气压的干燥氮气保护。
1小时后，向同一烧瓶滴加8.5毫升叔丁基氯，紧接着滴加5毫升异戊二烯。
用此方法获得的催化剂溶液在使用前以同样条件保护下于室温放置24小，元素分析表明下列摩尔浓度：
Nd 0.0426 克原子/升
Al 0.849 克原子/升
Cl 0.126 克原子/升
异戊二烯的聚合反应：
用机械真空泵将一个耐压釜抽成真空，然后抽入500克（约735毫升，绝对大气压）异戊二烯，耐压釜是一个竖直安装的不锈钢圆柱形罐，带有一个磁力驱动机械搅拌器，一个冷却至0℃的顶部冷凝器和一个电加热的或沿釜壁以水流动冷却的夹套。
在以氮气压力向釜内加入10.4毫升所述催化剂的石蜡油溶液之前，将耐压釜的温度控制在70℃（内部受到搅拌的液体温度）。
反应热的散失，一部分由沸腾和回流产生内部冷却来达到，一部分由器壁的热传导来实现。聚合体的温度保持在70℃至75℃之间，反应开始10分钟后，由于未反应单体迅速蒸发，而使反应终止，蒸发出来的单体被收集在一个与耐压釜相连的冷却瓶中。
将获得的聚合物撕碎后浸入溶有1%A02246的变性乙醇中几小时，然后将其真空干燥。
由此获得345克（转化率74.2%）1，4顺式结构单位的含量为97.1%（由13C-核磁共振摄谱仪测定）和门尼粘度为89（1+4，100℃）的干燥产物。
实施例2
重复实施例1中所述聚合反应，但做如下改动;
温度50℃（代替70℃），
使用13.5毫升催化剂溶液（代替15.3），
将搅拌下的反应时间延长至22分钟，其间温度在50℃至58℃之间波动。
由此可获得322克（转化率64.4%）顺式含量为97.8%。和门尼粘度为85的干燥的聚合体。
实施例3
催化剂的制备
涉及Nd2O3和环烷酸于80℃反应的制备法的起始阶段按实施例1所述方法进行。
将所获得的粘稠溶液在所给条件下与373毫升的0.97摩尔浓度的DIBAH的石蜡油溶液进行反应，1小时后，再与8.5毫升叔丁基氯反应。
使用前应将以这种方法制得的催化剂在室温放置24小时。元素分析给出下列各浓度：
Nd 0.052 克原子/升
Al 0.823 克原子/升
Cl 0.157 克原子/升
异戊二烯聚合反应
用一个装有速度可变的机械搅拌器和安了阀门的钢盖的容积为1升的玻璃反应器，首先加入300克异戊二烯，然后将其置于控温水浴加热到70℃后，再加入上述催化剂溶液5.77毫升。
将反应延长至28分钟，其间用热电偶测量内部温度，温度应在70℃至80℃之间波动。
把产品移至含1%A02246防老剂的200毫升乙醇中终止此试验。
于30℃真空干燥聚合物，得到212克干燥产物（转化率70.6%）。
顺式含量为97.7%，门尼粘度为76。
实施例4
按类似于实施例3的方法操作，用较少量的催化剂，即只用4.8毫升来代替原来的5.7毫升，使异戊二烯聚合。
在用醇终止该反应以前，应在70℃至71℃之间反应40分钟。得到182克门尼粘度为85的干燥聚合物。
Claims (1)
1、一种于实际无溶剂无稀释剂环境中使用一催化体系使异戊二烯聚合的方法，催化体系包括(a)氧化钕；(b)至少一种有机金属化的烷基、环烷基或烷芳基取代的铝化合物；(c)至少一种卤素的化合物，和(d)至少一种选自水、醇和羧酸的含羟基化合物，其特征在于催化体系中铝与钕的克原子比不超过20∶1和其均聚合反应在50至75℃下进行10至40分钟。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2103TA/85 | 1985-06-05 | ||
| IT21037/85A IT1186730B (it) | 1985-06-05 | 1985-06-05 | Procedimento per la polimerizzazione di isoprene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86103812A CN86103812A (zh) | 1986-12-03 |
| CN1019497B true CN1019497B (zh) | 1992-12-16 |
Family
ID=11175753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86103812A Expired CN1019497B (zh) | 1985-06-05 | 1986-06-05 | 异戊二烯的聚合方法 |
Country Status (22)
| Country | Link |
|---|---|
| US (1) | US4696984A (zh) |
| EP (1) | EP0204373B1 (zh) |
| JP (1) | JPH0784483B2 (zh) |
| KR (1) | KR910004606B1 (zh) |
| CN (1) | CN1019497B (zh) |
| AR (1) | AR241120A1 (zh) |
| AU (1) | AU587038B2 (zh) |
| BR (1) | BR8602758A (zh) |
| CA (1) | CA1250695A (zh) |
| CS (1) | CS271335B2 (zh) |
| DD (1) | DD245437A5 (zh) |
| DE (1) | DE3676743D1 (zh) |
| EG (1) | EG18887A (zh) |
| ES (1) | ES8801323A1 (zh) |
| IE (1) | IE59083B1 (zh) |
| IN (1) | IN167341B (zh) |
| IT (1) | IT1186730B (zh) |
| PL (1) | PL147662B1 (zh) |
| PT (1) | PT82706B (zh) |
| TR (1) | TR22663A (zh) |
| YU (1) | YU45333B (zh) |
| ZA (1) | ZA863994B (zh) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1265049B1 (it) * | 1993-08-06 | 1996-10-28 | Eniricerche Spa | Complessi alogenati dei lantanidi e loro uso nella polimerizzazione di monomeri insaturi |
| US5665827A (en) * | 1996-11-07 | 1997-09-09 | Bridgestone Corporation | Synthesis of multiblock polymers using group IIA and IIB metal cyclic organometallic initiators |
| US6197713B1 (en) | 1997-12-19 | 2001-03-06 | Bridgestone Corporation | Use of Lewis acids for the breakdown of gelatinous rare earth compounds in hydrocarbon solutions |
| GB2382817B (en) * | 2001-10-19 | 2004-04-21 | Goodyear Tire & Rubber | Clean rubber for use in articles,such as baby bottle nipples |
| US20030139548A1 (en) * | 2001-12-21 | 2003-07-24 | Hochgesang Paul J. | Solventless liquid EPDM compounds |
| US6852805B2 (en) * | 2001-12-21 | 2005-02-08 | Freudenberg-Nok General Partnership | Solventless liquid FKM compounds |
| US6812294B2 (en) | 2001-12-21 | 2004-11-02 | Freudenberg-Nok General Partnership | Solventless liquid nitrile compounds |
| US7335807B2 (en) * | 2001-12-21 | 2008-02-26 | Freudenberg-Nok General Partnership | Solventless liquid isoprene compounds |
| US7879958B2 (en) * | 2007-08-07 | 2011-02-01 | Bridgestone Corporation | Polyhydroxy compounds as polymerization quenching agents |
| US7741418B2 (en) * | 2007-12-31 | 2010-06-22 | Bridgestone Corporation | Process for producing polydienes |
| US7825201B2 (en) * | 2007-12-31 | 2010-11-02 | Bridgestone Corporation | Process for producing polydienes |
| US7902309B2 (en) | 2009-02-23 | 2011-03-08 | Bridgestone Corporation | Process and catalyst system for polydiene production |
| US8623975B2 (en) | 2009-06-24 | 2014-01-07 | Bridgestone Corporation | Process for producing polydienes |
| CN101608003B (zh) * | 2009-07-27 | 2012-05-16 | 中国科学院长春应用化学研究所 | 本体聚合制备中低分子量液体聚异戊二烯橡胶的方法 |
| EP2619233B1 (en) | 2010-09-23 | 2014-08-20 | Bridgestone Corporation | Process for producing polydienes |
| US9000107B2 (en) | 2011-01-31 | 2015-04-07 | Bridgestone Corporation | Process for producing polydienes |
| KR101963474B1 (ko) | 2011-11-17 | 2019-03-28 | 가부시키가이샤 브리지스톤 | 폴리디엔을 생산하는 방법 |
| JP6231997B2 (ja) | 2012-02-27 | 2017-11-15 | 株式会社ブリヂストン | 高シスポリジエンを調製する方法 |
| EP2825574B1 (en) | 2012-03-14 | 2016-02-24 | Bridgestone Corporation | Process for producing polydienes |
| EP3077455B1 (en) | 2013-12-03 | 2020-08-12 | Bridgestone Corporation | Process for preparing blends of cis-1,4-polybutadiene and syndiotactic 1,2-polybutadiene |
| RU2563844C1 (ru) * | 2014-06-27 | 2015-09-20 | Федеральное государственное унитарное предприятие "Ордена Ленина и ордена Трудового Красного Знамени научно-исследовательский институт синтетического каучука имени академика С.В. Лебедева" | Способ полимеризации изопрена в массе в малообъёмных ячейках |
| WO2016057985A1 (en) | 2014-10-10 | 2016-04-14 | Bridgestone Corporation | Polymerization catalyst composition and method of employing same |
| US10316121B2 (en) | 2015-01-28 | 2019-06-11 | Bridgestone Corporation | Cis-1,4-polydienes with improved cold flow resistance |
| EP3250616B1 (en) | 2015-01-28 | 2019-01-23 | Bridgestone Corporation | Aged lanthanide-based catalyst systems and their use in the preparation of cis-1,4-polydienes |
| US10202474B2 (en) | 2015-09-11 | 2019-02-12 | Bridgestone Corporation | Process for producing polydienes |
| RU2617411C1 (ru) * | 2016-01-11 | 2017-04-25 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный технологический институт (технический университет)" | Устройство для полимеризации изопрена в массе |
| US10730985B2 (en) | 2016-12-19 | 2020-08-04 | Bridgestone Corporation | Functionalized polymer, process for preparing and rubber compositions containing the functionalized polymer |
| CN111630075B (zh) | 2017-12-15 | 2023-04-28 | 株式会社普利司通 | 官能化聚合物、用于制备该官能化聚合物的方法和含有该官能化聚合物的橡胶组合物 |
| WO2019133633A1 (en) | 2017-12-30 | 2019-07-04 | Bridgestone Corporation | Composition including multiple terminally functionalized polymers |
| US11584808B2 (en) | 2019-12-30 | 2023-02-21 | Bridgestone Corporation | Polymerization catalyst composition and method of employing same |
| JP2024509164A (ja) * | 2021-03-03 | 2024-02-29 | ライフスタイルズ ヘルスケア プライベート リミテッド | 希土類触媒化ポリイソプレン製品 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3803053A (en) * | 1968-05-08 | 1974-04-09 | Atlantic Richfield Co | Lanthanide oligomerization catalyst |
| DE2830080A1 (de) * | 1978-07-08 | 1980-01-17 | Bayer Ag | Katalysator, dessen herstellung und verwendung zur loesungspolymerisation von butadien |
| CA1223396A (en) * | 1981-06-29 | 1987-06-23 | Tooru Shibata | Process for producing conjugated diene polymer |
| IT1151543B (it) * | 1982-04-15 | 1986-12-24 | Anic Spa | Procedimento per la polimerizzazione di diolefine coniugate e mezzi adatti allo scopo |
| IT1151542B (it) * | 1982-04-15 | 1986-12-24 | Anic Spa | Procedimento per la polimerizzazione di diolefine coniugate e mezzi adatti allo scopo |
| IT1191612B (it) * | 1985-05-15 | 1988-03-23 | Enichem Elastomers | Procedimento migliorato per la polimerizzazione o copolimerizzazione del butadiene |
-
1985
- 1985-06-05 IT IT21037/85A patent/IT1186730B/it active
-
1986
- 1986-05-22 US US06/866,147 patent/US4696984A/en not_active Expired - Lifetime
- 1986-05-28 ZA ZA863994A patent/ZA863994B/xx unknown
- 1986-05-29 IN IN421/MAS/86A patent/IN167341B/en unknown
- 1986-05-30 DE DE8686200943T patent/DE3676743D1/de not_active Expired - Lifetime
- 1986-05-30 EP EP86200943A patent/EP0204373B1/en not_active Expired - Lifetime
- 1986-06-02 AU AU58250/86A patent/AU587038B2/en not_active Ceased
- 1986-06-03 YU YU947/86A patent/YU45333B/xx unknown
- 1986-06-03 ES ES556309A patent/ES8801323A1/es not_active Expired
- 1986-06-04 CS CS864111A patent/CS271335B2/cs unknown
- 1986-06-04 IE IE148386A patent/IE59083B1/en not_active IP Right Cessation
- 1986-06-04 KR KR1019860004437A patent/KR910004606B1/ko not_active IP Right Cessation
- 1986-06-04 EG EG34586A patent/EG18887A/xx active
- 1986-06-04 PT PT82706A patent/PT82706B/pt not_active IP Right Cessation
- 1986-06-04 CA CA000510837A patent/CA1250695A/en not_active Expired
- 1986-06-04 PL PL1986259869A patent/PL147662B1/pl unknown
- 1986-06-04 DD DD86290960A patent/DD245437A5/de not_active IP Right Cessation
- 1986-06-05 TR TR28596/86A patent/TR22663A/xx unknown
- 1986-06-05 CN CN86103812A patent/CN1019497B/zh not_active Expired
- 1986-06-05 JP JP61129343A patent/JPH0784483B2/ja not_active Expired - Lifetime
- 1986-06-05 BR BR8602758A patent/BR8602758A/pt not_active IP Right Cessation
- 1986-09-19 AR AR304247A patent/AR241120A1/es active
Also Published As
| Publication number | Publication date |
|---|---|
| PT82706A (en) | 1986-07-01 |
| IE59083B1 (en) | 1994-01-12 |
| TR22663A (tr) | 1988-03-01 |
| EG18887A (en) | 1994-11-30 |
| YU45333B (en) | 1992-05-28 |
| US4696984A (en) | 1987-09-29 |
| AR241120A2 (es) | 1991-11-15 |
| JPS61283608A (ja) | 1986-12-13 |
| ES8801323A1 (es) | 1988-01-01 |
| BR8602758A (pt) | 1987-02-10 |
| PL147662B1 (en) | 1989-07-31 |
| EP0204373A1 (en) | 1986-12-10 |
| IT8521037A0 (it) | 1985-06-05 |
| CS411186A2 (en) | 1989-12-13 |
| PT82706B (pt) | 1988-12-15 |
| AU587038B2 (en) | 1989-08-03 |
| EP0204373B1 (en) | 1991-01-09 |
| CN86103812A (zh) | 1986-12-03 |
| ES556309A0 (es) | 1988-01-01 |
| DE3676743D1 (de) | 1991-02-14 |
| CS271335B2 (en) | 1990-09-12 |
| AR241120A1 (es) | 1991-11-15 |
| AU5825086A (en) | 1986-12-11 |
| IT1186730B (it) | 1987-12-16 |
| DD245437A5 (de) | 1987-05-06 |
| KR870000363A (ko) | 1987-02-18 |
| IE861483L (en) | 1986-12-05 |
| JPH0784483B2 (ja) | 1995-09-13 |
| YU94786A (en) | 1987-10-31 |
| IN167341B (zh) | 1990-10-13 |
| ZA863994B (en) | 1987-01-28 |
| CA1250695A (en) | 1989-02-28 |
| KR910004606B1 (ko) | 1991-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1019497B (zh) | 异戊二烯的聚合方法 | |
| CN1276931C (zh) | 高反应性聚异丁烯的生产方法 | |
| CA1113915A (en) | Polymerizing and copolymerizing diolefines, and means therefor | |
| EP0201962B1 (en) | Improved process for the polymerization or copolymerization of butadiene | |
| KR890004068B1 (ko) | 부타디엔을 중합 또는 공중합하는 개량된 제조방법 | |
| US4444903A (en) | Process for polymerizing conjugate diolefins, and means suitable for this purpose | |
| JP2536750B2 (ja) | 重合法 | |
| RU2701930C1 (ru) | Способ получения диеновых сополимеров | |
| US6482906B1 (en) | Process for preparing and using neodymium neodecanoate | |
| CN1043999C (zh) | 丁二烯本体聚合方法 | |
| JP5241989B2 (ja) | 希土類元素系触媒の存在下における分岐したポリジエンの製造方法 | |
| RU2345092C1 (ru) | Способ получения катализатора полимеризации бутадиена и сополимеризации бутадиена с изопреном | |
| CN1210311C (zh) | α－烯烃的预聚合方法 | |
| CN1044710C (zh) | 弹性体乙烯共聚物的制备方法 | |
| US3475395A (en) | Catalyst compositions,polymerization process,and products produced thereby | |
| CN1255442C (zh) | 中低相对分子质量反式－1,4－聚异戊二烯蜡和反式－1,4－聚丁二烯蜡的合成 | |
| CN1006365B (zh) | 供高浓度聚合物体系进行聚合反应的反应器 | |
| CN87102324A (zh) | α-烯烃聚合用的球形催化剂载体及其催化剂 | |
| US3594360A (en) | Quaternary catalyst system for butadiene polymerization | |
| RU2072362C1 (ru) | Способ получения синдиотактического 1,2-полибутадиена | |
| SU735171A3 (ru) | Способ получени транс-1,4-полибутадиена | |
| US3408313A (en) | Process for polymerizing 1, 2-epoxides with an anionic initiator | |
| SU384358A1 (ru) | Способ получени цис -1,4-полибутадиеновоно каучука | |
| RU2028309C1 (ru) | Способ получения цис-полибутадиена | |
| SU528749A1 (ru) | Способ получени 1,4-цис-полиизопрена |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |