CN1484657A - 催化体系与使用此体系制备弹性体的方法 - Google Patents
催化体系与使用此体系制备弹性体的方法 Download PDFInfo
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- CN1484657A CN1484657A CNA018215963A CN01821596A CN1484657A CN 1484657 A CN1484657 A CN 1484657A CN A018215963 A CNA018215963 A CN A018215963A CN 01821596 A CN01821596 A CN 01821596A CN 1484657 A CN1484657 A CN 1484657A
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- Prior art keywords
- catalytic system
- salt
- rare earth
- alkylating agent
- catalytic
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Links
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- 239000002168 alkylating agent Substances 0.000 claims abstract description 31
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- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
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Images
Classifications
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- 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
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
-
- 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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers 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
- C08F136/04—Homopolymers 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
-
- 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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers 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
- C08F136/04—Homopolymers 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
- C08F136/08—Isoprene
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- 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)
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Abstract
Description
分析的盐试样 | 通过配位滴定测定的Nd百分数 | 通过ICP/AES测定的Nd百分数 | 两种方法之间的相对偏差 |
磷酸钕盐[[RO]2P(O)O]3Nd | 12.8(9) | 12.8(3) | 0% |
磷酸钕盐[[RO]2P(O)O]3Nd | 12.8(4) | 12.6(3) | 1.6% |
磷酸钕盐[[RO]2P(O)O]3Nd | 12.7(6) | 12.2(4) | 4% |
磷酸钕盐[[RO]2P(O)O]3Nd | 12.6(6) | 12.5(4) | 0.8% |
乙酰丙酮钕“对照” | 31.7(6) | 32.4(4) | 2.2% |
草酸钕“对照” | 37.7(3) | 38.0(3) | 0.8% |
催化体系 | 聚合 | 聚异戊二烯 | ||||||||||||
序号 | 溶剂化(溶剂/时间/T) | Bd/Ndmol | Al/Ndmol | 烷基化(时间/T) | Cl/Ndmol | 成型时间/T | NdμMcm | S/MT | 反应时间(min.) | 转化率(%) | ηinhdl/g | 100℃的ML(1+4) | Mn(g/mol)IP(SEC) | 顺式-1,4(%) |
t | MCH30min.30℃ | 30 | 1,8 | 15min.30℃ | 2,6 | 2h60℃ | 300 | 950℃ | 204060120 | 0000 | ||||
t’ | MCH30min.30℃ | 30 | 1,8 | 15min.30℃ | 2,6 | 2h60℃ | 300 | 950℃ | 204060120 | 0000 | ||||
1 | MCH30min.30 ℃ | 50 | 2,0 | 15min.30℃ | 3,0 | 2h60℃ | 260 | 950℃ | 204060120 | 578698100 | 3,984,04 | 98,0** | ||
2 | 正庚烷30min.30℃ | 50 | 2,0 | 15min.30℃ | 3,0 | 2h60℃ | 260 | 950℃ | 204060120 | 5989100100 | 3,873,89 | 98,0** | ||
3 | MCH30min.30℃ | 50 | 1,8 | 15min.30℃ | 2,6 | 2h60℃ | 250 | 950℃ | 204060120 | 608799100 | 4,144,28 | 98,1*98,0** | ||
4 | MCH30min.30℃ | 50 | 1,8 | 15min.30℃ | 2,6 | 2h60℃ | 300 | 950℃ | 204060120 | 669299100 | 4,364,364,48 | 425000/2,17 | 98,0** | |
5(1) | MCH30min.30℃ | 25 | 1,8 | 15min.30℃ | 2,6 | 2h60℃ | 300 | 950℃ | 204060120 | 6790100100 | 4,144,29 | 443000/2,25 | 98,1** | |
5(2) | MCH30min.30℃ | 25 | 1,8 | 15min.30℃ | 2,6 | 2h60℃ | 240255260285315345 | 950℃ | 120 | 100 | 4,404,504,304,154,103,80 | 838180767166 | 490000/2,10 | 98,0**97,9**98,0**98,0**98,0**98,0** |
5(3) | MCH30min.30℃ | 25 | 1,8 | 15min.30℃ | 2,6 | 2h60℃ | 375450460495540600 | 930 ℃ | 120 | 100 | 5,004,604,604,404,204,10 | 898180767265 | 457000/2,28 | 98,4**98,5**98,4**98,4**98,4**98,4** |
6 | MCH30min.30℃ | 30 | 1,8 | 15min.30℃ | 2,6 | 2h60℃ | 300 | 950℃ | 204060120 | 6896100100 | 4,494,46 | 98,0** |
催化体系 | 聚合 | 聚异戊二烯 | ||||||||||||
序号 | 溶剂化(溶剂/时间/T) | Bd/Ndmol | Al/Ndmol | 烷基化(时间/T) | Cl/Ndmol | 成型时间/T | NdμMcm | S/MT | 反应时间(min.) | 转化率(%) | ηinhdl/g | 100℃ML(1+4) | Mn(g/mol)IP(SEC) | 顺式-1,4(%) |
7 | 正庚烷30min.30℃ | 30 | 1,8 | 15min.30℃ | 2,6 | 2h60℃ | 300 | 950℃ | 204060120 | 6595100100 | 4,844,83 | 98,1** | ||
8 | MCR30min.30℃ | 50 | 2,0 | 15min.30℃ | 3,0 | 2h60℃ | 245 | 950℃ | 204060120 | 628699100 | 3,883,90 | 98,0** | ||
9 | MCH30min.30℃ | 50 | 1,8 | 15min.30℃ | 3,0 | 2h60℃ | 200 | 950℃ | 204060120 | 528192100 | 3,994,31 | 98,0** | ||
10 | MCH30min.30℃ | 30 | 1,8 | 30min.30℃ | 2,6 | 2h60℃ | 380 | 950℃ | 204060120 | 75100100100 | 4,304,27 | 98,0** | ||
11 | MCH30min.30℃ | 30 | 1,8 | 30min.30℃ | 2,6 | 1h60℃ | 270 | 950℃ | 204060120 | 70100100100 | 4,314,25 | 98,1** | ||
12 | MCH30min.30℃ | 30 | 1,5 | 30min.30℃ | 2,6 | 2h60℃ | 540 | 950℃ | 204060120 | 87100100100 | 4,354,30 | 98,1** | ||
13 | MCH30min.30℃ | 30 | 1,3 | 30min.30℃ | 2,6 | 2h60℃ | 760 | 950℃ | 204060120 | 96100100100 | 4,334,39 | 80 | 98,1** | |
14 | 油,CH4h60℃ | 50 | 4,5 | 15min.30℃ | 3,0 | 2h60℃ | 90 | 950℃ | 50100150 | 558195,5 | 3,87 | 98,0** | ||
15 | 油,CH4h60℃ | 50 | 3,4 | 15min.30℃ | 3,0 | 2h60℃ | 110 | 950℃ | 50100150 | 7194100 | 3,89 | 98,0** | ||
16 | 油,CH4h60℃ | 50 | 2,2 | 15min.30℃ | 3,0 | 2h60℃ | 160 | 950℃ | 50100150 | 85100100 | 3,88 | 98,0** |
催化体系 | 聚合 | 聚丁二烯 | |||||||||||
序号 | 溶剂化(溶剂/时间/T) | Bd/Ndmol | Al/Ndmol | 烷基化(时间/T) | Cl/Ndmol | 成型时间/T | NdμMcm | S/MT | 反应时间(min) | 转化率(%) | ηinhdl/g | Mn(g/mol)Ip(SEC) | 顺式-1,4(%) |
14 | 油,CH4h60℃ | 50 | 4,5 | 15min.30℃ | 3 | 2h60℃ | 250 | 730℃ | 15253547 | 387186100 | --2,572,71(*)2,77(**) | 1850001,42 | 98,9 |
15 | 油,CH4h60℃ | 50 | 3,4 | 15min.30℃ | 3 | 2h60℃ | 350 | 730℃ | 7152232 | 2567,593100 | --2,542,68(*)2,80(**) | 1850001,44 | 98,1 |
16 | 油,CH4h60℃ | 50 | 2,2 | 15min.30℃ | 3 | 2h60℃ | 560 | 730℃ | 591317 | 34,57194100 | --2,522,57(*)2,68(**) | 1780001,47 | 97,7 |
17 | 油,CH4h60℃ | 50 | 4 | 15 min.30℃ | 3 | 2h60℃ | 250 | 950℃ | 81114 | 7394100 | 2,362,722,87 | 1940001,76 | 96,2 |
18 | 油,CH4h60℃ | 50 | 4 | 15min.30℃ | 3 | 2h60℃ | 250 | 950℃ | 81114 | 7396,5100 | 2,342,682,81 | 1850001,63 | 95,7 |
催化体系 | 聚合 | 聚丁二烯 | |||||||||||
序号 | 溶剂化(溶剂/时间/T) | Bd/Ndmol | Al/Ndmol | 烷基化(时间/T) | Cl/Ndmol | 成型时间/T | NdμMcm | S/MT | 反应时间(min) | 转化率(%) | ηinhdl/g | Mn(g/mol)Ip(SEC) | 顺式-1,4(%) |
19 | 油,CH4h60℃ | 50 | 4 | 15min.30℃ | 3 | 2h60℃ | 250 | 950℃ | 81114 | 7895100 | 2,412,752,84 | 1850001,65 | 96,4 |
20 | 油,CH4h60℃ | 50 | 4 | 15min.30℃ | 3 | 2h60℃ | 250 | 950℃ | 81114 | 76,597100 | 2,502,732,82 | 1890001,63 | 95,7 |
21 | 油,CH4h60℃ | 50 | 4 | 15min30℃ | 3 | 2h60℃ | 300 | 930℃ | 11203045 | 286187100 | --2,772,95 | ||
22 | 油,MCH4h60℃ | 50 | 4 | 15min.30℃ | 3 | 2h60℃ | 300 | 930℃ | 11203045 | 29638698 | --2,833,05 | ||
23 | 油,CH4h60℃ | 50 | 4 | 15min.30℃ | 3 | 2h60℃ | 300 | 930℃ | 11203045 | 306589100 | --2,822,99 | ||
24 | 油,CH4h60℃ | 50 | 3,9 | 15min.30℃ | 3 | 2h60℃ | 300 | 730℃ | 10203040 | 29708999 | --2,622,74(*)2,79(**) | 1950001,43 | 98,7 |
25 | 油,CH4h60℃ | 50 | 2,8 | 15min.30℃ | 3 | 2h60℃ | 420 | 730℃ | 5101520 | 225389,598 | --2,532,65(*)2,73(**) | 1810001,45 | 98,2 |
26 | 油,CH4h60℃ | 50 | 1,7 | 15min.30℃ | 3 | 2h60℃ | 680 | 730℃ | 591316,5 | 40,58097100 | --2,752,80(*)2,98(**) | 1890001,60 | 98,5 |
27 | CH4h60℃ | 50 | 4 | 15min.30℃ | 3 | 2h60℃ | 300 | 930℃ | 11203045 | 38729298 | 2,863,12 | ||
28 | CH2h60℃ | 50 | 4 | 15 min30℃ | 3 | 2h60℃ | 520 | 760℃ | 15 | 100 | 2,50 | ||
520 | 760℃ | 15 | 100 | 2,61 | |||||||||
460 | 760℃ | 15 | 100 | 2,58 | |||||||||
29 | MCH30min.30℃ | 30 | 1,8 | 30min30℃ | 2,6 | 2h60℃ | 2000 | 930℃ | 15 | 100 | 2,99 |
序号 | 溶剂化(溶剂/时间/T) | Bd/Ndmol | Al/Ndmol | 烷基化(时间/T) | Cl/Ndmol | 成型时间/T | NdμMcm | S/MT | 反应时间(min) | 转化率(%) | ηinhdl/g | ML(1+4) | IP(SEC) |
28 | CH2h60℃ | 50 | 4 | 15min.30℃ | 3 | 2h60℃ | 520 | 760℃ | 15 | 100 | 2,50 | 43 | 1,85 |
520 | 760℃ | 15 | 100 | 2,61 | 50 | 1,92 | |||||||
460 | 760℃ | 15 | 100 | 2,58 | 45 | 1,79 | |||||||
29 | MCH30min.30℃ | 30 | 1,8 | 30min.30c | 2,6 | 2h60℃ | 2000 | 930℃ | 15 | 100 | 2,99 | 59 | 1,86 |
1,92 | |||||||||||||
1,90 |
附录1:所获得弹性体的微观结构的测定。 |
附录2:通过尺寸排阻色谱法(SEC)测定所获得弹性体的分子量的分布。 |
Claims (15)
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- 2001-11-07 EP EP01993635A patent/EP1355960B1/fr not_active Expired - Lifetime
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101291722B (zh) * | 2005-10-19 | 2013-02-27 | 米其林集团总公司 | 连续制备用于聚合共轭二烯的催化体系的方法以及实施该方法的装置 |
CN101525396A (zh) * | 2007-12-31 | 2009-09-09 | 株式会社普利司通 | 用于生产聚二烯烃的本体聚合方法 |
WO2012075964A1 (zh) | 2010-12-09 | 2012-06-14 | 中国石油化工股份有限公司 | 钕系均相稀土催化剂及其应用 |
CN103772772A (zh) * | 2014-01-21 | 2014-05-07 | 大连理工大学 | 采用稀土聚异戊二烯胶液直接制备胶乳的方法 |
CN106589195A (zh) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | 一种制备聚异戊二烯的方法 |
CN106589195B (zh) * | 2015-10-19 | 2018-11-02 | 中国石油化工股份有限公司 | 一种制备聚异戊二烯的方法 |
CN108192002A (zh) * | 2016-12-08 | 2018-06-22 | 中国石油化工股份有限公司 | 一种制备聚异戊二烯的方法 |
CN108192002B (zh) * | 2016-12-08 | 2020-07-24 | 中国石油化工股份有限公司 | 一种制备聚异戊二烯的方法 |
Also Published As
Publication number | Publication date |
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KR20030048467A (ko) | 2003-06-19 |
MXPA03004070A (es) | 2004-04-20 |
BR0115238A (pt) | 2004-02-17 |
RU2268268C2 (ru) | 2006-01-20 |
JP2008239996A (ja) | 2008-10-09 |
BR0115238B1 (pt) | 2011-09-20 |
CA2427984A1 (fr) | 2002-05-16 |
EP1355960B1 (fr) | 2008-12-03 |
KR100882742B1 (ko) | 2009-02-10 |
US20040009870A1 (en) | 2004-01-15 |
DE60136856D1 (de) | 2009-01-15 |
WO2002038636A1 (fr) | 2002-05-16 |
ES2317952T3 (es) | 2009-05-01 |
EP1355960A1 (fr) | 2003-10-29 |
JP5396040B2 (ja) | 2014-01-22 |
JP2004513999A (ja) | 2004-05-13 |
ZA200303543B (en) | 2003-11-13 |
JP4820529B2 (ja) | 2011-11-24 |
US6838534B2 (en) | 2005-01-04 |
ATE416203T1 (de) | 2008-12-15 |
CN100558767C (zh) | 2009-11-11 |
AU2002217006A1 (en) | 2002-05-21 |
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