CN1052487C - 茂钛化合物 - Google Patents
茂钛化合物 Download PDFInfo
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- CN1052487C CN1052487C CN97106587A CN97106587A CN1052487C CN 1052487 C CN1052487 C CN 1052487C CN 97106587 A CN97106587 A CN 97106587A CN 97106587 A CN97106587 A CN 97106587A CN 1052487 C CN1052487 C CN 1052487C
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- 239000010936 titanium Substances 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 title abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title description 4
- 229910052719 titanium Inorganic materials 0.000 title description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 17
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 17
- MCJUWBUSIQXMPY-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1 MCJUWBUSIQXMPY-UHFFFAOYSA-N 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 150000003609 titanium compounds Chemical class 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 2
- 239000004793 Polystyrene Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229920002223 polystyrene Polymers 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- FCAJYRVEBULFKS-UHFFFAOYSA-N 2-(oxolan-2-yl)ethanol Chemical compound OCCC1CCCO1 FCAJYRVEBULFKS-UHFFFAOYSA-N 0.000 description 5
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 238000007172 homogeneous catalysis Methods 0.000 description 1
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- 238000003801 milling Methods 0.000 description 1
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- 210000003097 mucus Anatomy 0.000 description 1
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- VYNCPPVQAZGELS-UHFFFAOYSA-N toluene;trimethylalumane Chemical compound C[Al](C)C.CC1=CC=CC=C1 VYNCPPVQAZGELS-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Abstract
本发明涉及一种新型结构的茂金属钛化合物,其通式为R1Ti(OCH2R2)3,式中R1为环戊二烯基、取代环戊二烯基,R2为含4~20个碳原子的杂环基团。该化合物和烷基铝氧烷组成的催化剂可用于制备高间规度的聚苯乙烯聚合物,且具有催化活性、催化效率高的特点,可用于工业生产中。
Description
本发明涉及茂钛化合物。
茂钛化合物与助催化剂甲基铝氧烷(MAO)或硼氟化合物组成的均相催化体系,用于苯乙烯聚合可得到间规度在95%以上的间规聚合物。聚合物熔点高(达到270℃左右),分子量分布窄,耐热性、耐化学性及电性能优良,综合性能可与工程塑料相比。间规聚苯乙烯的问世引起了人们对其催化体系,特别是茂钛化合物的关注,并开展了广泛的研究。文献EP210615和US5252693等报导了结构为CpTiCl3和助催化剂MAO组成的催化体系用于苯乙烯间规聚合的情况,但其催化活性及催化效率不高,工业应用不合直。
本发明的目的是为克服上述文献存在的缺点,提供一种新型结构的茂金属钛化合物,该茂金属钛化合物与烷基铝氧烷组成的催化体系,可成功地用于苯乙烯的间规聚合,且具有较高的催化活性及催化效率。
本发明的目的是通过以下的技术方案来实现的:一种茂钛化合物,其结构具有以下通式:
R1Ti(OCH2R2)3
式中R1为环戊二烯基、取代环戊二烯基:
R2为含4~20个碳原子的杂环基团。
上述技术方案中R1的优选范围为环戊二烯基、五甲基环戊二烯基:R2的优选范围为四氢呋喃基。
本发明的茂钛化合物制备工艺是由相应的茂基三氯化钛与四氢呋喃甲醇(HO-)在氯化氢吸收剂存在下以碳氢化合物为溶剂反应制得的。氯化氢吸收剂可以是各种胺类化合物,其中以三烷基胺为直,例如三乙胺。碳氢化合物可以是脂肪烃或芳香烃,使用芳香烃更好,例如苯、甲苯等。具体步骤为:将乙胺与四氢呋喃甲醇混合溶液慢慢滴加至茂基三氯化钛的苯溶液中,茂基三氯化钛与四氢呋喃甲醇的克分子比为1∶3.0~3.5,茂基三氯化钛与三乙胺的克分子比为1∶3.0~3.5,反应温度为0~60℃,反应时间为1~30小时,过滤除去固体,减压蒸馏除去溶剂,得到的粗产物用己烷萃取,除去挥发物后,得红褐色的粘液。
本发明的化合物与烷基铝氧烷一起作为苯乙烯的间规聚合催化剂时,可得到较高的催化效率,其催化效率较高的可达29.0千克聚合物/克钛,取得了较好的效果。同时该化合物还可用作α-烯烃与苯乙烯的共聚。
图1为R1为环戊二烯基,R2为四氢呋喃基时化合物的质谱图。
图2为R1为环戊二烯基,R2为四氢呋喃基时化合物的红外光谱图。
图3为R1为环戊二烯基,R2为四氢呋喃基时化合物的碳核磁共振图。
图4为R1为环戊二烯基,R2为四氢呋喃基时化合物的氢核磁共振图。
元素分析(element analyses)
Calcd for C20H34O6Ti: C:57.42; H:8.19 Found: C:57.30; H:7.90
氢核磁共振谱[1H NMR(CDCl3 TMS intern)]:
δ1.78(m,12H,(C-CH2CH2-C)3),3.85(d,6H,(OCH2C)3),
4.19-4.25(m,9H,(CCHO OCH2)3),6.35-6.37(d,5H,CpH)
碳13核磁共振谱[13C NMR(CDCCl3)]:
δ64.8(Ti-OCH2-),79.2(-CH2CH2-),80.0(-CH-),79.4(CH2-O),114.0(Cp C)
质谱[MS(m/z,%intensity)]:
41(60,CH2CHCH2 +),43(100,CH2CHO+),65(30,C5H5 +),66(32,C5H5 +),
64(10,TiO+),71(100,OCHCH2CH2CH2 +),85(13,CH2CHCH2CH2CH2O+),
113(4,CpTi+),129(28,CpTiO+),165(18,M-Cp-(OCH2CHCH2CH2CH2O)2 +),
213(11,M-(OCH2CHCH2CH2CH2O)2 +),249(18,M-Cp-(OCH2CHCH2CH2CH2O)+),
315(10,M-OCH2CHCH2CH2CH2O+),351(22,M-Cp′).
红外光谱(Infrared FTIR)
波数 振 动
3100 茂环C-H伸缩振动
2966-2868 碳氢健不对称伸缩振动[VasC-H(O-CH2-C)]
1735-1644 茂环的泛频吸收带
1447 茂环骨架振动
1131-1068 碳氧键伸缩振动[Vc-0(Ti)],以及四氢呋喃环骨架振动
990 茂环上C-H的平面弯曲振动
589 钛碳键伸缩振动(VTi-c)
下面就通过实施例对本发明作进一步的阐述【实施例1】
茂钛化合物的制备
将1.51g(6.88mmol)茂基三氯化钛装入干燥的、受氮气保护的250ml反应瓶中,加入40ml干燥的苯,再在氮气保护下用滴液漏斗缓慢地滴加35ml含有2.08g(20.6mmol,2.87ml)三乙胺和2.10g(20.6mmol,2.00ml)四氢呋喃甲醇的干燥的苯溶液,让其在20℃的温度下反应24h,过滤,抽干溶剂,再用干燥的40℃的正己烷萃取,恒温静置2h,将上层清液转移到干燥洁净充氮气的容器中,抽干溶剂,得红褐色油状产物2.52g,得率88%。配成0.02M的甲苯溶液备用。【实施例2】
MAO的制备
装有电磁搅拌的500ml反应器中加入30克经碾磨的Al2(SO4)3·18H2O和70ml甲苯,在-10℃温度下,滴加200ml浓度为3.1M的三甲基铝甲苯溶液。滴加速度为5毫升/分钟,60分钟滴完。然后逐渐提高反应温度,在2h内使温度达到60℃,继续反应24h。反应混和物经过滤除去固体,滤液在30℃下用真空泵抽1h,除去部分甲苯,再在50℃下抽干,将甲苯等挥发物除去,得到12.8g白色固体MAO,产率约32.0%,经测定,甲基铝氧烷(MAO)的平均齐聚度为16。【实施例3】
在经抽真空并充氮气的250ml反应瓶中,依次加入5ml甲苯,5ml苯乙烯,实施例1制备的茂钛化合物0.05ml,实施例2制备的MAO 0.11g,在50℃聚合2h,得到2.0g聚合物,催化效率为20.0千克聚合物/克钛,产物的间规度为95%,熔点为258.2℃。【实施例4】
茂钛化合物的制备
将2.22g(10.1mmol)茂基三氯化钛装入干燥的、受氮气保护的250ml反应瓶中,加入45ml干燥的苯,再在氮气保护下用滴液漏斗缓慢地滴加45ml含有3.08g(30.3mmol,4.25ml)三乙胺和3.10g(30.3mmol,2.94ml)四氢呋喃甲醇的干燥的苯溶液,让其在25℃的温度下反应24h,过滤,抽干溶剂,再用干燥的40℃的正己烷萃取,恒温静置2h,将上层清液转移到干燥洁净充氮气的容器中,抽干溶剂,得红褐色油状产物3.82g,得率91%。配成0.02M的甲苯溶液备用。【实施例5】
在经抽真空并充氮气的250ml反应瓶中,依次加入10ml甲苯,实施例4制备的茂钛化合物0.10ml,实施例2制备的MAO 0.21g,苯乙烯10ml,在60℃聚合2h,得到5.8g聚合物,催化效率为29.0千克聚合物/克钛,产物的间规度为97%,熔点为258.3℃。
Claims (1)
1、一种茂钛化合物,其结构具有以下通式:
R1Ti(OCH2R2)3
式中R1为环戊二烯基或五甲基环戊二烯基;
R2为含四氢呋喃基。
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US5026625A (en) * | 1987-12-01 | 1991-06-25 | Ciba-Geigy Corporation | Titanocenes, the use thereof, and n-substituted fluoroanilines |
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US5026625A (en) * | 1987-12-01 | 1991-06-25 | Ciba-Geigy Corporation | Titanocenes, the use thereof, and n-substituted fluoroanilines |
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