CN1132851C - Cyclopentadienyl rare-earth metal compound and its preparing process and application - Google Patents

Cyclopentadienyl rare-earth metal compound and its preparing process and application Download PDF

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CN1132851C
CN1132851C CN 01119822 CN01119822A CN1132851C CN 1132851 C CN1132851 C CN 1132851C CN 01119822 CN01119822 CN 01119822 CN 01119822 A CN01119822 A CN 01119822A CN 1132851 C CN1132851 C CN 1132851C
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earth metal
cyclopentadienyl
metal compound
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polymerization
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CN1393476A (en
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钱延龙
巴拉
张�浩
黄吉玲
孙俊全
梁成锋
陈伟
郑刚
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
East China University of Science and Technology
Zhejiang University ZJU
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
East China University of Science and Technology
Zhejiang University ZJU
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Abstract

The present invention relates to a cyclopentadiene rare-earth metal compound which has the general expression formula of Cp<=>2LnCl. 2THF, wherein Ln is selected from lanthanide series metals, Cp<=> is alkenyl substituted cyclopentadienyl, and THF is tetrahydrofuran. Alkenyl substituted cyclopentadienyl sodium salt and LnCl3 are added to tetrahydrofuran according to a molar ratio of 2 to 4:1 under the protection of inert gas for a full reaction at 10 to 100 DEG C, and reaction products are concentrated, washed with an organic solvent and concentrated to obtain the compound. The compound can independently or together with a cocatalyst, such as alkylaluminium, etc., be used for a catalyst of a polymerization reaction of methyl methylacrylate, and a polymerisate with high syndiotacticity can be prepared.

Description

Cyclopentadienyl rare-earth metal compound and its production and application
The present invention is a kind of cyclopentadienyl rare-earth metal compound and preparation method thereof, and the application of this compound aspect the alkyl acrylate catalyzed polymerization.
People, carry out with the anionic catalytic polymerization method in the presence of initiators such as alkali-metal alkylate or alkali-metal alcoholate when particularly preparing methyl methacrylate polymer usually at preparation alkyl-acrylates polymkeric substance.Yet, with initiator (methyl) alkyl acrylate being carried out polymerization and be difficult to obtain the high polymkeric substance of taxis, this is because the cause of secondary reaction takes place earlier at the alpha position of acrylate negatively charged ion, ester group or the hydrogen atom in the reaction process.
In order to address the above problem, EP185641A is an initiator system with butyllithium and lithium chloride, can prepare the acrylate of tertiary alkyl, the polymkeric substance of methyl methacrylate etc.This method further controlled polymerization is done in order to prepare the polymkeric substance that molecular weight is higher, molecular weight distribution is narrower.Yet polyreaction needs to carry out under-78 ℃ low temperature.
EP524054A utilizes alkali-metal butylation thing and a ligand compound, be that alkali-metal alkoxyl group alcoholization thing (alcoxy alcoholate) is made initiator system, (methyl) alkyl acrylate is carried out polymerization, can control the polymerization of (methyl) alkyl acrylate better.
People such as M.Tomoi propose a kind of method of carrying out methyl methacrylate polymerization in the presence of alkali metal alcoholates in " polymkeric substance " (Polymer Journal) magazine (the 6th volume, the 5th phase, 438-444 page or leaf, 1974).Yet this method can only be carried out in some solvent, and can cause the per-cent of the syndiotaxy body in the prepared methyl methacrylate polymer to diminish.
Syndiotaxy body per-cent in the raising methyl methacrylate polymer can improve the second-order transition temperature of polymkeric substance, makes it have higher heat resistance.For this reason, people adopt the catalyzer of coordination compound as methyl methacrylate polymerization.Studies show that traditional Ziegler-Natta catalyst is as TiCl 4/ MgCl 2/ AlR 3System does not have activity substantially to Polymerization of Methyl; Common bis cyclopentadienyl zirconium dichloride catalyst system Cp 2ZrCl 2/ MAO does not have activity to Polymerization of Methyl yet.The article that YanlongQian etc. deliver in " transition metal chemistry " [Transition Met.Chem.21.393-397 (1996)] is to Cp 2ZrCl 2Luxuriant improvement of part, synthesized and contained substituent metallocene dichloride on a series of cyclopentadienyl ligands, the transition metal in this compound is titanium, zirconium or hafnium, the substituting group on part is luxuriant can be the thiazolinyl that contains 4～5 carbon atoms.This article only reports that above-claimed cpd to olefinic polymerization, has catalytic activity as vinyl polymerization, does not report that this compound can be used for the polyreaction of polar monomer.
1991, Later Shen and his colleague reported rare earth compound Y (acac) 3-Al (i-Bu) 3The catalyst system of forming with a small amount of butyllithium can be at room temperature catalyzed polymerization methyl methacrylate expeditiously.From then on, be the catalyst system of main ingredient with the rare earth metal organic compound, bringing into play more and more important effect at the syndiotactic polymerization of methyl methacrylate.
Sun Junquan etc. point out that at the article that " European Polymer Journal 2000,36:11:2375-2380 " delivers general formula is O (C 2H 4C 5H 3CH 3) 2The rare earth metallocene muriate of LnCl can be used for the Polymerization of Methyl catalyzer, and wherein Ln is yttrium, neodymium or samarium.The temperature that this compound is used for methyl methacrylate polymerization is 20～80 ℃, its mass polymerization transformation efficiency is near 80%, the polymkeric substance that obtains has higher molecular weight and narrow molecular weight distribution, but the syndiotactic regularity is lower, normality only is that normality is 58.7% between 61.2%, 80 ℃ of polymerisate between 40 ℃ of polymerisates.
The purpose of this invention is to provide a kind of cyclopentadienyl rare-earth metal compound and preparation method thereof, carry out the acrylic acid alkyl polyisocyanate polyaddition, can obtain normal polymerization product between height with this compound.
It is that catalyzer carries out alkyl acrylate polymeric method that another object of the present invention provides with above-mentioned cyclopentadienyl rare-earth metal compound.
We find, the muriatic part of rare earth metallocene is improved, and introduce the alkenyl group that has carbon-carbon double bond, promptly can be used for the polyreaction of polar monomer, and can obtain normal polymerization product between height.Specifically, cyclopentadienyl rare-earth metal compound provided by the invention has following general expression:
Cp ＝ 2LnCl·2THF
Ln is selected from lanthanide series metal in the formula, preferred samarium, dysprosium, erbium or yttrium;
Cp =Cyclopentadienyl for alkenyl substituted, wherein the carbon-carbon double bond of alkenyl group is positioned on the carbon atom of substituent end position, described thiazolinyl is preferably the chain thiazolinyl with 2～10 carbon atoms, preferably has the chain thiazolinyl of 3～6 carbon atoms, more preferably allyl group or alkene butyl.
THF is a tetrahydrofuran (THF) in the general formula.
The preparation method of cyclopentadienyl rare-earth metal compound of the present invention is included under the protection of inert gas, with the cyclopentadienyl sodium salt and the LnCl of alkenyl substituted 3By 2～4: 1 mol ratio joins in the tetrahydrofuran (THF), 10～100 ℃ of fully reactions, resultant of reaction is concentrated, again with organic solvent washing, concentrated then.
The cyclopentadienyl sodium salt of alkenyl substituted can be with conventional method preparation in the described method, as reacting in organic solvent such as tetrahydrofuran (THF), hexane or ether with the cyclopentadiene of alkenyl substituted and sodium Metal 99.5 and getting.LnCl 3Be the lanthanide rare metal chloride, preferred samarium trichloride, Dysprosium trichloride, Erbium trichloride or Yttrium trichloride.
Among the preparation method of above-mentioned alkenyl substituted cyclopentadienyl rare-earth metal compound, the cyclopentadienyl sodium salt of alkenyl substituted can be joined LnCl 3Tetrahydrofuran solution in, also can be with LnCl 3Join in the tetrahydrofuran solution of cyclopentadienyl sodium salt of alkenyl substituted, wherein cyclopentadienyl sodium salt and LnCl 3Mol ratio preferred 2～3: 1.Preferred 20～50 ℃ of temperature of reaction, the time is 1～48 hour, preferred 20～30 hours.The weight ratio of tetrahydrofuran (THF) and reactant is 2～100: 1.
Above-mentioned reaction product obtains the thick product of buttery after concentrating, this thick product needs with organic solvent washing to remove by product, described organic solvent is selected from ether, benzene, toluene, normal hexane, sherwood oil or their mixture, preferred ether or normal hexane, the weight ratio of washing used organic solvent and thick product is 2～200: 1, preferred 5～20: 1.Washing can be carried out repeatedly, is colourless until cleaning solvent, and thoroughly removing byproduct, but washing times is too much, and product yield is descended.Washing back product promptly gets The compounds of this invention through concentrated after removing organic solvent again.
The preparation of above-claimed cpd needs to carry out under protection of inert gas, and used rare gas element is argon gas or nitrogen.
The compounds of this invention be applicable to general formula be R ' CH=CH (polymerizing catalyst of the alkyl acrylate of COOR "), R ' is selected from hydrogen or methyl in the described general formula, R " is selected from C 1～C 18Alkyl, C 3～C 8Cycloalkyl or trifluoroethyl.Polyreaction is carried out under 20～80 ℃, can be catalyzer with The compounds of this invention separately during polymerization, can also cyclopentadienyl rare-earth metal compound be Primary Catalysts, adding aluminum alkyls or alkylaluminoxane is promotor, and preferred promotor is triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium or methylaluminoxane.It is 5～20: 1 that the dosage of promotor should make wherein Al and the rare earth metal mol ratio in the cyclopentadienyl rare-earth metal compound.
Being suitable for The compounds of this invention is that catalyzer carries out the polymeric monomer and has: methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, the secondary butyl ester of methacrylic acid, the methacrylic tert-butyl acrylate, the methacrylic acid n-pentyl ester, the methacrylic isoamyl valerate, Isooctyl methacrylate, methacrylic acid certain herbaceous plants with big flowers ester, ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, Ethyl acrylate, vinylformic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, lauryl acrylate, the stearyl acrylate ester, 2 ethyl hexyl acrylate, cyclohexyl acrylate, trifluoroethyl methacrylate.Preferred monomer is methyl methacrylate or methyl acrylate.
The cyclopentadienyl rare-earth metal compound of alkenyl substituted provided by the invention, it is simple to have preparation, and separating purifies is easy to advantage, can be separately or cooperate with promotor such as aluminum alkyls and to be used for the methyl methacrylate polymerization catalyst for reaction, and under moderate temperature of reaction, show high polymerization activity.Polymkeric substance with The compounds of this invention preparation has higher molecular weight and narrow molecular weight distribution, and contains more syndiotaxy body, between 40 ℃ of polymerisates normality can reach 67～72%, 60 ℃ of polymerisates between normality reach 62%.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
The preparation expression formula is (CH 2=CHCH 2Cp) 2Two (allyl group cyclopentadienyl) Erbium trichloride tetrahydrofuran (THF) of ErCl2THF.
Under argon shield, with 0.95 gram (3.43 mmole) ErC1 3Be dissolved in 30 milliliters of tetrahydrofuran (THF)s, the sodium salt that adds the cyclopentadiene that the allyl group of 2 times of amounts (6.86 mmole) replaces then, stirring at room was reacted in 24 hours, obtain oily crude product through centrifugation, after concentrating, this thick product is respectively washed twice with 20 milliliters of ether and normal hexane, get limpid yellow oily compd A, its molecular formula: C behind the vacuum concentration 24H 34ErO 2Cl; The analytical test result is as follows:
Ultimate analysis data: actual measurement, C:51.61% H:5.18%
Calculate C:51.61% H:5.70%
Mass spectrum demonstration molecular ion peak 411 (4, M-2THF).
Ir data (cm -1): 3500s, 3080s, 3000m, 2950s, 2920s, 1980w, 1820w, 1715m, 1640s, 1600s, 1530w, 1490w, 1430m, 1410w, 1360m, 1300w, 1260w, 1200w, 1165w, 1040w, 995m, 905m, 850w, 820w, 790s, 680s.
1040cm in the infrared spectra -1And 850cm -1The peak, position is the tetrahydrofuran (THF) characteristic peak.
Example 2
The preparation expression formula is (CH 2=CHCH 2Cp) 2Two (allyl group cyclopentadienyl) samarium trichloride tetrahydrofuran (THF) of SmCl2THF.
Under argon shield, with 0.88 gram (3.43 mmole) SmCl 3Be dissolved in 30 milliliters of tetrahydrofuran (THF)s, add the sodium salt of the cyclopentadiene that the allyl group of 3 times of amounts (10.29 mmole) replaces then, stirring at room was reacted in 24 hours, through centrifugation, concentrate and obtain oily crude product.This thick product respectively washes twice with 20 milliliters of ether and normal hexane, gets limpid yellow oily compd B, its molecular formula: C behind the vacuum concentration 24H 34SmO 2Cl; The analytical test result is as follows:
Ultimate analysis data: actual measurement, C:53.01% H:6.11%
Calculate C:53.43% H:6.37%
Mass spectrum demonstration molecular ion peak 397 (1, M-2THF).
Ir data (cm -1): 3420s, 3080s, 3000m, 2950s, 2920s, 1980w, 1820w, 1715m, 1660s, 1640s, 1600s, 1530w, 1490w, 1430m, 1410w, 1360m, 1300w, 1250w, 1200w, 1165w, 1040w, 995m, 905m, 850w, 820w, 770s, 570s.
Example 3
The preparation expression formula is (CH 2=CHCH 2Cp) 2Two (allyl group cyclopentadienyl) Yttrium trichloride tetrahydrofuran (THF) of YCl2THF.
Under argon shield, with 0.67 gram (3.43 mmole) YCl 3Be dissolved in 30 milliliters of tetrahydrofuran (THF)s, add the sodium salt of the cyclopentadiene that the allyl group of 3 times of amounts (10.29 mmole) replaces then, stirring at room was reacted in 30 hours, through centrifugation, concentrate and obtain oily crude product.This thick product respectively washes twice with 20 milliliters of ether and normal hexane, gets limpid yellow oily Compound C, its molecular formula: C behind the vacuum concentration 24H 34YO 2Cl; The analytical test result is as follows:
Ultimate analysis data: actual measurement, C:59.44% H:6.80%
Calculate C:60.30% H:7.18%
Mass spectrum demonstration molecular ion peak 334 (4, M-2THF).
Ir data (cm -1): 3400s, 3080s, 3000m, 2950s, 2920s, 1980w, 1820w, 1715m, 1660,1640s, 1600s, 1530w, 1490w, 1430m, 1410w, 1360m, 1300w, 1260w, 1200w, 1165w, 1040w, 995m, 905m, 850w, 820w, 770s, 680s.
Example 4
The preparation expression formula is (CH 2=CHCH 2Cp) 2Two (allyl group cyclopentadienyl) Dysprosium trichloride tetrahydrofuran (THF) of DyCl2THF.
Under argon shield, with 0.92 gram (3.43 mmole) DyCl 3Be dissolved in 30 milliliters of tetrahydrofuran (THF)s, add the sodium salt of the cyclopentadiene that the allyl group of 2 times of amounts (6.86 mmole) replaces then, stirring at room was reacted in 24 hours, through centrifugation, concentrate and obtain oily crude product.This thick product respectively washes twice with 20 milliliters of ether and normal hexane, gets limpid yellow oily Compound D, its molecular formula: C behind the vacuum concentration 24H 34DyO 2Cl; The analytical test result is as follows:
Ultimate analysis data: actual measurement, C:52.16% H:5.50%
Calculate C:51.99% H:6.13%
Mass spectrum demonstration molecular ion peak 409 (4, M-2THF).
Ir data (cm -1): 3400s, 3080s, 3000m, 2950s, 2920s, 1980w, 1820w, 1715m, 1660s, 1640s, 1600s, 1530w, 1490w, 1430m, 1410w, 1360m, 1300w, 1260w, 1200w, 1165w, 1040w, 995m, 905m, 850w, 820w, 770s, 680s.
Example 5
The preparation expression formula is (CH 2=CHCH 2CH 2Cp) 2Two (alkene butyl cyclopentadienyl) samarium trichloride tetrahydrofuran (THF) of SmCl2THF.
Under argon shield, with 0.88 gram (3.43 mmole) SmCl 3Be dissolved in 30 milliliters of tetrahydrofuran (THF)s, add the sodium salt of the cyclopentadiene that the alkene butyl of 3 times of amounts (10.29 mmole) replaces then, stirring at room was reacted in 30 hours, through centrifugation, concentrate and obtain oily crude product.This thick product respectively washes twice with 20 milliliters of ether and normal hexane, gets limpid yellow oily compd E, its molecular formula: C behind the vacuum concentration 26H 38Sm0 2Cl; The analytical test result is as follows:
Ultimate analysis data: actual measurement, C:54.77% H:6.23%
Calculate C:54.93% H:6.75%
Mass spectrum demonstration molecular ion peak 425 (1, M-2THF).
Ir data (cm -1): 3400s, 3080s, 3000m, 2980s, 2920s, 2850m, 1820w, 1740m, 1660s, 1640s, 1600s, 1500w, 1450w, 1430m, 1410w, 1360m, 1300w, 1260w, 1200w, 1165w, 1040w, 995m, 905m, 850w, 820w, 770s, 680s.
Example 6
Preparation (CH 2=CHCH 2CH 2Cp) 2Two (alkene butyl cyclopentadienyl) Erbium trichloride tetrahydrofuran (THF) of ErCl2THF.
Under argon shield, with 0.95 gram (3.43 mmole) ErCl 3Be dissolved in 30 milliliters of tetrahydrofuran (THF)s, add the sodium salt of the cyclopentadiene that the alkene butyl of 2 times of amounts (6.86 mmole) replaces then, stirring at room was reacted in 24 hours, through centrifugation, concentrate and obtain oily crude product.This thick product respectively washes twice with 20 milliliters of ether and normal hexane, gets limpid yellow oily compound F 17-hydroxy-corticosterone, its molecular formula: C behind the vacuum concentration 26H 38ErO 2Cl; The analytical test result is as follows:
Ultimate analysis data: actual measurement, C:53.61% H:6.48%
Calculate C:53.52% H:6.52%
Mass spectrum demonstration molecular ion peak 439 (4, M-2THF).
Ir data (cm -1): 3400s, 3080s, 3000m, 2980s, 2920s, 2850m, 1820w, 1740m, 1660s, 1640s, 1600s, 1500w, 1450w, 1430m, 1410w, 1360m, 1300w, 1260w, 1200w, 1165w, 1040w, 995m, 905m, 850w, 820w, 770s, 680s.
Example 7
Polyreaction is carried out in the ampoule of a baking argon filling three times.1 milliliter of methyl methacrylate, and 0.05 milliliter concentration is that the toluene solution of 0.458 mmole/milliliter Compound C is injected in the ampere bottle successively was positioned in the oil bath of constant temperature to 40 in advance ℃ polymerization 24 hours.Stop polyreaction with the ethanol that contains 10%HCl, after filtration, after the carrying out washing treatment, resulting polymers in 50 ℃ of following vacuum-dryings 24 hours to constant weight.Transformation efficiency is 42.7%, and the molecular weight that viscosimetry records polymkeric substance is 141 * 10 3, the weight-average molecular weight that GPC records polymkeric substance is 766 * 10 3, molecular weight distribution has two peaks, first peak Mw/Mn=1.39; Second peak Mw/Mn=2.35.
Example 8
Polyreaction is carried out in the ampoule of a baking argon filling three times.1 milliliter of methyl methacrylate, and 0.07 milliliter concentration is that the toluene solution of 0.66 mmole/milliliter Compound C is injected in the ampere bottle successively was positioned in the oil bath of constant temperature to 40 in advance ℃ polymerization 24 hours.Stop polyreaction with the ethanol that contains 10%HCl, after filtration, after the carrying out washing treatment, resulting polymers in 50 ℃ of following vacuum-dryings 24 hours to constant weight.Transformation efficiency is 100%, and the molecular weight that viscosimetry records polymkeric substance is 727 * 10 3, 1H-NMR records syndiotaxy body 72% in the polymkeric substance, atactic body 28%.
Example 9
Polyreaction is carried out in the ampoule of a baking argon filling three times.1 milliliter of methyl methacrylate, and 0.0175 milliliter concentration is that the toluene solution of 0.66 mmole/milliliter Compound C is injected in the ampere bottle successively was positioned in the oil bath of constant temperature to 40 in advance ℃ polymerization 24 hours.Stop polyreaction with the ethanol that contains 10%HCl, after filtration, after the carrying out washing treatment, resulting polymers in 50 ℃ of following vacuum-dryings 24 hours to constant weight.Transformation efficiency is 26.8%, and the molecular weight that viscosimetry records polymkeric substance is 1661 * 10 3
Example 10
Polyreaction is carried out in the ampoule of a baking argon filling three times.1 milliliter of methyl methacrylate, and 0.035 milliliter concentration is that the toluene solution of 0.66 mmole/milliliter Compound C is injected in the ampere bottle successively was positioned in the oil bath of constant temperature to 80 in advance ℃ polymerization 24 hours.Stop polyreaction with the ethanol that contains 10%HCl, after filtration, after the carrying out washing treatment, resulting polymers in 50 ℃ of following vacuum-dryings 24 hours to constant weight.Transformation efficiency is 65.7%, and the molecular weight that viscosimetry records polymkeric substance is 28.3 * 10 3
Example 11
Carry out the Polymerization of Methyl reaction according to the method for example 10, different is that polymerization temperature is 40 ℃, and the time is 40 hours.Stop polyreaction with the ethanol that contains 10%HCl, after filtration, after the carrying out washing treatment, resulting polymers in 50 ℃ of following vacuum-dryings 24 hours to constant weight.Transformation efficiency is 67.5%, and the molecular weight that viscosimetry records polymkeric substance is 261 * 10 3, wherein the syndiotaxy body 67%, atactic body 28%, isotaxy body 5%.
Example 12
Polyreaction is carried out in the ampoule of a baking argon filling three times.1 milliliter of methyl methacrylate, and 0.05 milliliter concentration is the toluene solution of 0.458 mmole/milliliter Compound C, 0.03 milliliter of triethyl aluminum is injected in the ampere bottle successively, is positioned in the oil bath of constant temperature to 40 in advance ℃ polymerization 24 hours.Stop polyreaction with the ethanol that contains 10%HCl, after filtration, after the carrying out washing treatment, resulting polymers in 50 ℃ of following vacuum-dryings 24 hours to constant weight.Transformation efficiency is 95.3%, and the molecular weight that viscosimetry records polymkeric substance is 727 * 10 3
Example 13
Polyreaction is carried out in the ampoule of a baking argon filling three times.1 milliliter of methyl methacrylate, and 0.05 milliliter concentration is the toluene solution of 0.458 mmole/milliliter Compound C, 0.116 milliliter of triisobutyl aluminium is injected in the ampere bottle successively, is positioned in the oil bath of constant temperature to 40 in advance ℃ polymerization 24 hours.Stop polyreaction with the ethanol that contains 10%HCl, after filtration, after the carrying out washing treatment, resulting polymers in 50 ℃ of following vacuum-dryings 24 hours to constant weight.Transformation efficiency is 75.6%, and the molecular weight that viscosimetry records polymkeric substance is 97 * 10 3
Example 14
Polyreaction is carried out in the ampoule of a baking argon filling three times.1 milliliter of methyl methacrylate, and 0.0134 milliliter concentration is the toluene solution of 0.326 mmole/milliliter compd E, 0.0118 milliliter of triisobutyl aluminium is injected in the ampere bottle successively, is positioned in the oil bath of constant temperature to 60 in advance ℃ polymerization 15 hours.Stop polyreaction with the ethanol that contains 10%HCl, after filtration, after the carrying out washing treatment, resulting polymers in 50 ℃ of following vacuum-dryings 24 hours to constant weight.Transformation efficiency is 44.6%, and the molecular weight that viscosimetry records polymkeric substance is 1462.5 * 10 3, wherein the syndiotaxy body 62%, atactic body 34%, and the weight-average molecular weight that isotaxy body 4%, GPC record is 587 * 10 3, molecular weight distribution has two peaks, first peak Mw/Mn=3.11; Second peak Mw/Mn=1.45.
Example 15
Polyreaction is carried out in the ampoule of a baking argon filling three times.1 milliliter of methyl methacrylate, and 0.0143 milliliter concentration is the toluene solution of 0.326 mmole/milliliter compd E, 0.0118 milliliter of triisobutyl aluminium is injected in the ampere bottle successively, is positioned in the oil bath of constant temperature to 80 in advance ℃ polymerization 15 hours.Stop polyreaction with the ethanol that contains 10%HCl, after filtration, after the carrying out washing treatment, resulting polymers in 50 ℃ of following vacuum-dryings 24 hours to constant weight.Transformation efficiency is 58.3%, and the molecular weight that viscosimetry records polymkeric substance is 1599.3 * 10 3, wherein the syndiotaxy body 62%, atactic body 33%, and the weight-average molecular weight that isotaxy body 5%, GPC record is 336 * 10 3, molecular weight distribution mw/mn=2.81.
Example 16
Polyreaction is carried out in the ampoule of a baking argon filling three times.1 milliliter of methyl methacrylate, and 0.0143 milliliter concentration is the toluene solution of 0.326 mmole/milliliter compd E, 0.0118 milliliter of triisobutyl aluminium is injected in the ampere bottle successively, is positioned in the oil bath of constant temperature to 60 in advance ℃ polyase 13 0 hour.Stop polyreaction with the ethanol that contains 10%HCl, after filtration, after the carrying out washing treatment, resulting polymers in 50 ℃ of following vacuum-dryings 24 hours to constant weight.Transformation efficiency is 70.1%, and the molecular weight that viscosimetry records polymkeric substance is 1653.2 * 10 3, wherein the syndiotaxy body 62%, atactic body 34%, isotaxy body 4%.
Example 17
Polyreaction is carried out in the ampoule of a baking argon filling three times.1 milliliter of methyl methacrylate, and 0.04 milliliter concentration is that the toluene solution of 0.59 mmole/milliliter Compound D is injected in the ampere bottle successively was positioned in the oil bath of constant temperature to 40 in advance ℃ polymerization 24 hours.Stop polyreaction with the ethanol that contains 10%HCl, after filtration, after the carrying out washing treatment, resulting polymers in 50 ℃ of following vacuum-dryings 24 hours to constant weight.Transformation efficiency is 25.3%, and the molecular weight that viscosimetry records polymkeric substance is 48.8 * 10 3
Example 18
Polyreaction is carried out in the ampoule of a baking argon filling three times.1 milliliter of methyl methacrylate, and 0.022 milliliter concentration is the toluene solution of 0.211 mmole/milliliter compound F 17-hydroxy-corticosterone, 0.0117 milliliter of triisobutyl aluminium is injected in the ampere bottle successively, is positioned in the oil bath of constant temperature to 60 in advance ℃ polymerization 15 hours.Stop polyreaction with the ethanol that contains 10%HCl, after filtration, after the carrying out washing treatment, resulting polymers in 50 ℃ of following vacuum-dryings 24 hours to constant weight.Transformation efficiency is 35.3%, and the molecular weight that viscosimetry records polymkeric substance is 1037.8 * 10 3

Claims (12)

1, a kind of cyclopentadienyl rare-earth metal compound has following general expression:
Cp ＝ 2LnCl·2THF
Ln is selected from lanthanide series metal in the formula; C p =Be the cyclopentadienyl of alkenyl substituted, THF is a tetrahydrofuran (THF).
2, according to the described cyclopentadienyl rare-earth metal compound of claim 1, it is characterized in that Cp =The carbon-carbon double bond of middle thiazolinyl is positioned on the carbon atom of substituent end position.
3,, it is characterized in that Ln is samarium, dysprosium, erbium or yttrium according to the cyclopentadienyl rare-earth metal compound of the described alkenyl substituted of claim 1.
4, according to described any one cyclopentadienyl rare-earth metal compound of claim 1～3, it is characterized in that C p =In thiazolinyl be the chain thiazolinyl that 2～10 carbon atoms are arranged.
5, according to the described cyclopentadienyl rare-earth metal compound of claim 4, it is characterized in that Cp =In thiazolinyl be the chain thiazolinyl that 3～6 carbon atoms are arranged.
6, according to the described cyclopentadienyl rare-earth metal compound of claim 4, it is characterized in that Cp =In thiazolinyl be allyl group or alkene butyl.
7, the preparation method of the described cyclopentadienyl rare-earth metal compound of a kind of claim 1 is included under the protection of inert gas, with the cyclopentadienyl sodium salt and the LnCl of alkenyl substituted 3By 2～4: 1 mol ratio joins in the tetrahydrofuran (THF), 10～100 ℃ of fully reactions, resultant of reaction is concentrated, again with organic solvent washing, concentrated then.
8,, it is characterized in that the cyclopentadienyl sodium salt and the LnCl of alkenyl substituted according to the described preparation method of right claim 7 3Mol ratio is 2～3: 1, and temperature of reaction is 20～50 ℃, and the time is 1～48 hour.
9,, it is characterized in that described organic solvent is selected from ether, benzene, toluene, normal hexane, sherwood oil or their mixture according to the described preparation method of right claim 7.
10, a kind of general formula is R ' CH=CH (polymerization process of the alkyl acrylate of COOR "); comprise that with described any one cyclopentadienyl rare-earth metal compound of claim 1～3 be catalyzer; carry out polymerization under 20～80 ℃, R ' is selected from hydrogen or methyl in the described general formula, and R " is selected from C 1～C 18Alkyl, C 3～C 8Cycloalkyl or trifluoroethyl.
11, in accordance with the method for claim 10, also adding aluminum alkyls or alkylaluminoxane when it is characterized in that polymerization is promotor, and it is 5～20: 1 that the dosage of promotor should make wherein Al and the rare earth metal mol ratio in the cyclopentadienyl rare-earth metal compound.
12, in accordance with the method for claim 10, it is characterized in that described alkyl acrylate is methyl methacrylate, methyl acrylate.
CN 01119822 2001-06-29 2001-06-29 Cyclopentadienyl rare-earth metal compound and its preparing process and application Expired - Lifetime CN1132851C (en)

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