CN1210107A - 茂金属钛化合物 - Google Patents
茂金属钛化合物 Download PDFInfo
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- CN1210107A CN1210107A CN 97106585 CN97106585A CN1210107A CN 1210107 A CN1210107 A CN 1210107A CN 97106585 CN97106585 CN 97106585 CN 97106585 A CN97106585 A CN 97106585A CN 1210107 A CN1210107 A CN 1210107A
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- 239000010936 titanium Substances 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 title abstract description 10
- 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 19
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 125000002541 furyl group Chemical group 0.000 claims description 7
- 150000003609 titanium compounds Chemical class 0.000 claims description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 229920010524 Syndiotactic polystyrene Polymers 0.000 abstract description 2
- 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
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- MCJUWBUSIQXMPY-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1 MCJUWBUSIQXMPY-UHFFFAOYSA-N 0.000 description 7
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 7
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical class C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 210000004940 nucleus Anatomy 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 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
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001576 syndiotactic polymer Polymers 0.000 description 1
- 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个碳原子的芳杂环基团。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
本发明涉及茂金属钛化合物。
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问规度在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,工业应用不合宜。
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铁化合物,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个碳原子的芳杂环基团。
上述技术方案中R1的优选范围为为环戊二烯基、五甲基环戊二烯基;R2的优选范围为呋喃基。
本发明的茂金属钛化合物的制备工艺是由相应的茂基三氯化钛与糠醇(
)在氯化氢吸收剂存在下以碳氢化合物为溶剂反应制得的。氯化氢吸收剂可以足各种胺类化合物,其中以三烷基胺为宜,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:将乙胺与糠醇混合溶液慢慢滴加至茂基三氯化钛的苯溶液中,茂基三氯化钛与糠醇的克分子比为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,得到的褶产物用己烷萃取,除去挥发物后,得亮黄色的粘液。
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21.5千克聚合物/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为呋喃基时化合物的质谱图。
图2为R1为环戊二烯基,R2为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为呋喃基时化合物的氢核磁共振图。
其数据分别如下:
元素分析(element analyses)
Calcd for C20H20O6Ti:C:59.42;H:4.99.Found:C:59.84;H:4.64
氢核磁共振谱[1H NMR(CDCl3 TMS intern)]:
δ5.10(s,6H,(OCH2)3),6.20-6.28(m,9H,(CCHCHCHO)3),
6.32-6.36(m,5H,Cp H).
碳13核磁共振谱[13C NMR(CDCCl3)]:
δ69.8(OCH2),154.6(C),110.0(CH-CH),106.9(CH=CH-O),141.4(CH-O),
113.9-114.2(Cp C).
质谱[MS(m/z,%intcnsity)]:
39(100,CH2CCH+),53(70,CH2CCH2CH+),69(40,OCH2CCHO+),
81(75,CH2CHCHCHO+or OTiO+),95(40,OTiOCH2),98(74,OCH2CCHCHCHO+)
112(10,CpTi+),129(3,CpTiO+),169(5,M-(OCH2CCHCHCHO)-(OCCHCHCH)+),
339(5,M-Cp+).
红外光谱(Infrared FTIR)波数 振 动3114 茂环C-H伸缩振动,呋喃环=C-H伸缩振动2903-2846 碳氢键不对称伸缩振动[VasC-H(O-CH2-C)]1602-1503 呋喃环骨架振动1735 附近 茂环的泛频吸收带1447 茂环骨架振动1644 呋喃环的双键伸缩振动(Vc-c)1068-1096 碳氧键伸缩振动[Vc-0(Ti)]1011 茂环上C-H的平面弯曲振动913 885 呋喃环=C-H的面外弯曲振动814-737 呋喃环上三个相邻氢的特征振动589 钛碳键伸缩振动(VTi-c)421 钛氧键伸缩振动(VTi-o)
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2.41g(11.0mmol)茂基三氯化钛装入干燥的、受氮气保护的250ml反应瓶中,加入50ml干燥的苯,再在氮气保护下用滴液漏斗缓慢地滴加50ml含有3.34g(33.0mmol,4.60ml)三乙胺和3.24g(33.0mmol,2.86ml)呋喃甲醇的干燥的苯溶液,让其在18℃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,得金黄色油状产物4.08g,得率92%。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20℃下用真空泵抽1h,除去部分甲苯,再在30℃下抽1h,最后在40℃下将甲苯等挥发物除去,得到13.0g白色固体MAO,产率约32.5%,经测定,甲基铝氧烷(MAO)的平均齐聚度为18。【实施例3】
在经抽真空并充氮气的250ml反应瓶中,依次加入10ml甲苯,10ml苯乙烯,实施例1制备的茂钛化合物0.1ml,实施例2制备的MAO0.24g,在60℃聚合2h,得到4.3g聚合物,催化效率为21.5千克聚合物/克钛,产物的间规度为94%,熔点为260.4℃。【实施例4】
茂钛化合物的制备
将2.12g(9.66mmol)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2.93g(28.9mmol,4.03ml)三乙胺和2.83g(28.9mmol,4.00ml)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,得金黄色油状产物3.55g,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0.12ml,实施例2制备的MAO0.22g,苯乙烯10ml,在70℃聚合1h,得到3.8g聚合物,催化效率为16.8千克聚合物/克钛,产物的间规度为92%,熔点为258℃。
Claims (3)
1、一种茂金属钛化合物,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个碳原子的芳杂环基团。
2、根据权利要求1所述的茂金属钛化合物,其特征在于R1为环戊二烯基、五甲基环戊二烯基。
3、根据权利要求1所述的茂会属钛化合物,其特征在于R2为呋喃基。
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