CN1373008A - Metallocene catalyst and its preparing process, application and selective hydrogenation process - Google Patents
Metallocene catalyst and its preparing process, application and selective hydrogenation process Download PDFInfo
- Publication number
- CN1373008A CN1373008A CN 01104879 CN01104879A CN1373008A CN 1373008 A CN1373008 A CN 1373008A CN 01104879 CN01104879 CN 01104879 CN 01104879 A CN01104879 A CN 01104879A CN 1373008 A CN1373008 A CN 1373008A
- Authority
- CN
- China
- Prior art keywords
- cyclopentadienyl
- bis
- tolyltitanium
- catalyst
- hydrogenation
- 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.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A novel metallocene catalyst, the selective hydrogenation using said catalyst, the process for preparing said catalyst, and the application of said catalyst in polymerizing and isomerizing olefine and hydrogenating conjugated diolofine and its copolymer are disclosed.
Description
The present invention relates to a metallocene catalyst and a preparation method thereof, and to a selective hydrogenation method of a conjugated diene-containing polymer using the catalyst.
There are many types of metallocene catalysts, such as titanocene catalysts, which are useful for olefin polymerization, isomerization, and hydrogenation of conjugated dienes and copolymers thereof. Documents which may be mentioned in the prior art relating to the preparation of metallocene catalysts herein are EP 0,601,953 a 1; GB 2,159,819 a; CN 1,163,275A; U.S. Pat. No. 4,501,857, etc. EP 0,601,953A 1 synthesizes compounds of the structure Cp2Ti(PhOR)2And Cp2TiR′2With Cp being a cyclopentadienyl group and Ph being a phenyl group OR1Is C1-C4R' is diphenyl methylene phosphino (-CH)2PPh2) For example, the catalyst biscyclopentadienylbis (4-methylphenoxy) titanium is prepared by adding Cp at-78 ℃ with 4-iodomethoxybenzene under argon protection2TiCl2The prepared bis-cyclopentadienyl bis (diphenyl methylene phosphino) titanium is prepared by reacting LiCH at-78 ℃ in an argon atmosphere2PPh2XTMEDA and CpTiCl2And reacting to obtain the product. Although the catalyst can effectively hydrogenate conjugated diene and the copolymer thereof, the preparation is complex, and the catalyst is particularly prepared at the temperature of minus 78 ℃, so the catalyst is limited in practical use. Preparation of GB 2,159,819AA catalyst of the structural formula prepared by reacting an alkyl-substituted bromobenzene:
CN 1,163,275A synthesizes a structural formula ofAnd for the hydrogenation of conjugated dienes and copolymers thereof, A1，A2Are identical or different optionally substituted indenyl groups, L1，L2Is the same or different hydrogen, halogen, alkyl, aryl substituted aryl, alkoxyAryl, aryloxy. USP 4,501,857 prepares a catalyst having the structural formula:
wherein R is1，R2Are the same or different C1-C2Alkyl or alkoxy of, C6-C8Aryl, aryloxy, cycloalkyl, halogen, carbonyl and the like.
Metallocene catalysts have been widely used in the industrial fields of olefin polymerization, isomerization, and selective hydrogenation of unsaturated polymers since their advent. For example, the use of metallocene catalysts, such as titanocene catalysts, for carrying out selective hydrogenation of conjugated diene polymers is knownin the art. As found in USP 4,980,421; USP 4,501,857; CN 1,067,898A; US 5,132,372; EP 0,601,953 a 1; USP 4,673,714 and the like. The above patents have their respective characteristics, but have their disadvantages. For example, when USP 4,980,421 is used for hydrogenation of butadiene-styrene block copolymer, titanocene compound is used as main catalyst, at least one alkoxy lithium compound RO-Li (such as alkoxy lithium or phenoxy lithium) and at least one organic metal compound (such as organic aluminium, organic magnesium, organic zinc, etc.) are added simultaneously, Li/Ti is 0.5-20: 1, and the molar ratio of Ti to organic metal compound is 1: 0.5-20. EP 0601953A1 with Cp2Ti(PhOR1)2Or Cp2TiR′2As the main catalyst for hydrogenation, Cp is cyclopentadienyl, Ph is phenyl, OR1Is C1-C4R' is diphenyl methylene phosphino (-CH)2PPh2) Although the patent has less catalyst consumption (less than 0.2mmol/100g polymer), the patent has higher reaction temperature (90℃)) 2, 6-2 tert-butyl-4 methyl phenol is required to be added into the active polymer for deactivation, and the preparation process of the catalyst is complex (the preparation temperature is-78 ℃), so that the method has certain practical limitation. USP 4,673,714 uses a hydrogenation catalyst of (C)5H5)2Ti(R1R2R3-Ph)(R4R5R6Ph), the catalyst preparation of which is not very complicated and does not require additional addition of organic alkali metal or organic metal oxide, which is a technological advance, but the hydrogenation reaction temperature is high (-100 ℃) at a low catalyst dosage (0.1mmol/100g polymer), which easily causes crosslinking of the polymer and consumes a lot of energy. USP 4,501,875 emphasizes that the use of titanocene compound as main catalyst and the addition of lithium alkoxide as cocatalyst, the Li/Ti ratio is at least 1:1, but the catalyst dosage is larger (>0.2mmol/100g polymer) when high hydrogenation degree is required (>98%). CN 1,067,898A and CN 1,166,498A do not need to be added into polymer glue solutionThe original agent directly utilizes active Li which is not terminated in the polymerization process of the conjugated diene to reduce the titanocene catalyst, and then introduces substances with polarity or polar groups, such as alcohols, esters, carboxylic acids, aldehydes, aromatic compounds with two or more ester groups or hydroxyl functional groups, as a cocatalyst. The process is obviously complicated and not beneficial to industrial production
Therefore, the invention aims to provide a novel titanocene catalyst and a synthesis method thereof, and the structural formula of the catalyst is as follows:
wherein R is1，R2Is the same or different straight-chain alkyl, cycloalkyl, aryl or substituted aryl containing 1-8 carbon atoms, R3，R4Is the same or different aryl, substituted aryl, alkyl, alkoxy or aryloxy containing 6 to 12 carbon atoms, and M is a transition metal with 2 to 4 valences (such as Ti, Zr, Hf, etc.).
The catalyst of the present invention may be used in the copolymerization and isomerization of olefin, and the hydrogenation of conjugated diene and its copolymer, especially the hydrogenation of styrene-conjugated diene copolymer (such as SBS, SIS, etc.).
The catalyst of the invention is a new type metallocene catalyst, it is the object of the invention to provide a method for preparing this metallocene catalyst too, this preparation method generally includes cyclopentadiene and is chosen from straight-chain alkane, naphthene, arene and substituted arene containing 1-8 carbon atoms to carry on the substitution reaction, get and substitute cyclopentadiene, and further react with n-BuLi and produce and substitute cyclopentadienyl lithium, then react with hydrochloric acid compound of transition metal and separate and get its complex crystal containing di (substituted cyclopentadienyl); the crystal is reacted with organic lithium with 1-12C alkyl, alkoxyl, aryl, substituted aryl and aryloxy as organic part to obtain metallocene catalyst,
in one embodiment, the synthetic route is as follows:
cyclopentadiene is first reacted with ketone compound containing certain substituent to produce (substituted) cyclopentadiene, which reacts with n-BuLi to produce (substituted) cyclopentadienyl lithium, and then reacted with TiCl42THF reaction to produce bis (cyclopentadienyl) titanium dichloride, separation to obtain their crystals;
reacting the obtained crystal with two equivalents of ArLi to obtain the hydrogenation catalyst required by the invention, wherein Ar represents aryl or substituted aryl,
another object of the present invention is to provide a novel hydrogenation catalyst and a selective hydrogenation method. The method is a hydrogenation method of conjugated diene polymer composed of aromatic hydrocarbon compound containing vinyl and conjugated diene containing 4-6 carbon atoms, which comprises terminating the newly generated active polymer in a solution system, such as a solution system using one or a mixture of two or more of cyclohexane, hexane, toluene and the like as a solvent with hydrogen, and then hydrogenating the terminated active polymer in the presence of metallocene catalyst, such as titanium catalyst, and is characterized in that: the selective hydrogenation is carried out in the presence of a metallocene catalyst having the structureUnder the conditions of (a):
the metallocene main catalyst is one or a mixture of more than one of the compounds with the structure, wherein R1，R2Are identical or different straight-chain alkyl, cycloalkyl, aryl or substituted aryl radicals having from 1 to 8 carbon atoms, R3，R4The same or different aryl, substituted aryl, alkyl, alkoxy and aryloxy containing 6-12 carbon atoms, the hydrogenation reaction temperature is 20-80 ℃, the pressure is 0.2-3.0MPa, the reaction time is 1.0-2.0 hours, the dosage of the metallocene main catalyst is 0.05-0.6mmol/100g polymer, preferably 0.1-0.4mmol/100g polymer; the molar ratio of LiH to procatalyst is generally from 2 to 60, preferably from 4 to 20. The invention leads hydrogen into the active polymer glue solution to generate lithium hydride as a cocatalyst, does not need to add an organic metal compound and an organic metal oxide additionally, and the cocatalyst and the titanium compound form an efficient hydrogenation catalyst of the conjugated diene polymer, thereby fully saturating double bonds in the diene polymer and ensuring that the hydrogenation reaction time is less than 2 hours. The obtained polymer is coagulated with polar solvent (such as methanol, ethanol, etc.) or coagulated with steam to obtain white solid product, which can omit the hydrogenation catalyst removal process or remove the hydrogenation catalyst by known method. The hydrogenation can be carried out by a continuous process, a batch process or a semi-continuous process.
The conditions generally selected for the hydrogenation of the conjugated diene copolymer are that firstly the active polymer initiated by the alkali metal compound is terminated by hydrogen at a certain temperature to generate LiH, then the catalyst of the invention is added at a certain pressure, the hydrogenation reaction temperature is 20-80 ℃, preferably 50-80 ℃, the pressure is 0.2-3.0MPa, preferably 1.0-2.5MPa, the reaction time is 0.5-4.0 hours, preferably 1.0-2.0 hours, the hydrogenation degree of the conjugated diene section can reach 98%, and the hydrogenation degree of the benzene ring is less than 2%.
The conjugated diene copolymer used for hydrogenation is a copolymer of both aromatic and conjugated diene having vinyl substitution, and specific examples of hydrogenated copolymers providing industrial value are butadiene/styrene copolymer, isoprene/styrene copolymer and butadiene/α -methylstyrene copolymer, which may have a random, progressive and block monomer distribution, the amount of vinyl aromatic is preferably between 15 and 45%, the polymer concentration is 8 to 20%, and the molecular weight is in the range of 5,000-500,000.
The hydrogenation main catalyst is a mixture of one or more of the following compounds:
wherein R is1，R2Is the same or different straight-chain alkyl, cycloalkyl, aryl or substituted aryl containing 1-8 carbon atoms, R3，R4Is the same or different aryl, substituted aryl, alkyl, alkoxy or aryloxy containing 1-12 carbon atoms. Typical compounds of this type are: bis (cyclohexyl)Cyclopentadienyl-cyclopentadienyl) di-p-tolyltitanium, bis (cyclohexyl-cyclopentadienyl) di-m-tolyltitanium, bis (methyl-cyclopentadienyl) di-p-tolyltitanium, bis (methyl-cyclopentadienyl) di-m-tolyltitanium, bis (cyclohexyl-cyclopentadienyl) diphenyltitanium, bis (cyclopentadienyl) di-p-tolyltitanium, bis (cyclopentadienyl) di-m-tolyltitanium, bis (phenyl-cyclopentadienyl) di-p-tolyltitanium, bis (phenyl-cyclopentadienyl) di-m-tolyltitanium, bis (cyclopentadienyl) diphenyltitanium, bis (methyl-cyclopentadienyl) di-p-phenyltitanium.
The preferable technical scheme of the invention is that in the selective hydrogenation process, the main catalyst is used in an amount of 0.05-0.6mmol per 100g of polymer. The molar ratio of LiH to procatalyst is from 2.0 to 60, preferably from 4 to 20. The hydrogenation reaction temperature is 50-80 ℃. The reaction pressure is 1.0-2.5 MPa. The hydrogenation time is 1.0-2.0 hours.
Compared with the prior art, the invention selects a novel hydrogenation catalyst. The catalyst has good stability, and is beneficial to transportation and storage; good hydrogenation selectivity, high activity and short hydrogenation time, and the hydrogenation cocatalyst can be generated by terminating the active polymer with hydrogen. Without the need for additional organometallic compounds and metal alkoxide compounds. The hydrogenation catalyst can be removed from the hydrogenation product without removing the hydrogenation product or by a very simple method. Prevent the chlorine-containing hydrogenation catalyst from corroding equipment and generating adverse effects on products. The production cost of the product is reduced, and the production capacity of the device is effectively improved.
The present invention will be described in more detail below with reference to specific examples. These examples should not be construed as limiting the scope of the invention. EXAMPLE 1 bis- (cyclohexylcyclopentadienyl) di-p-tolyltitanium 1 preparation of ligand cyclohexylcyclopentadiene
Adding 56ml (0.68mol) of freshly steamed cyclopentadiene and 70ml (0.68mol) of cyclohexanone into a 250ml three-necked bottle, dropwise adding 25ml (0.2mol) of methylamine aqueous solution from a constant-pressure dropping funnel at room temperature, and stirring for 5-12 hours to obtain an orange yellow solution. Saturated NH at 100ml4Hydrolyzing with Cl water solution, extracting water phase with 50ml diethyl ether, mixing organic phases, washing with water to neutrality, and collecting anhydrous Na2SO4Drying for 12 hours. The solvent was removed by rotary evaporation, and 77.5 g of a fraction of 60 to 64 ℃ per 0.4mmHg was collected by distillation under reduced pressure. Yellow oil, yield 78.1%.
1000ml three-necked flask with electric stirring, spherical condenser, constant pressure dropping funnel, and argon gas10.8g (0.29mol) of LiAlH are added under protection4750ml of diethyl ether. A solution of 40g (0.27mol) of the above product in 50ml of diethyl ether is added dropwise at 0 ℃. After the dropwise addition is completed within 0.5 hour, the mixture is stirred at room temperature for 1 to 5 hours. Under an ice-water bath, 70ml of water was added dropwise, followed by 50ml of 10% diluted hydrochloric acid. Separating, extracting the water phase with diethyl ether, mixing the organic phases, washing with water to neutrality, and removing anhydrous MgSO4Drying for 12 hours. The solvent was removed by rotary evaporation, and 33g of a fraction of 60 to 62 ℃ under 12mmHg was collected by distillation under reduced pressure. Light yellow oil, yield 82.5%. 2. Preparation of bis (cyclohexyl-cyclopentadienyl) titanium dichloride
A250 ml three-necked flask was charged with a bulb-type condenser and a constant pressure dropping funnel, 3.32g (22.4mmol) of cyclohexylcyclopentadiene and 70ml of THF were added under protection of argon, and 10.8ml (22.4mmol) of n-BuLi/hexane solution was added dropwise in an ice-water bath, whereupon the reaction solution turned brown from pale yellow. Stir at room temperature for 4 hours. 3.74g (11.2mmol) TiCl are introduced42THF was dissolved in 20ml of THF, and the reaction mixture was introduced into the reaction system through a steel tube in an ice-water bath to turn reddish brown. Stirred at room temperature for12 hours. Refluxing for 2-6 hrSolvent, CH, is evacuated2Cl2Extraction, sand-plate filtration, concentration, addition of an appropriate amount of hexane, and freezing in a refrigerator gave the compound bis (cyclohexyl-cyclopentadienyl) titanium dichloride as red crystals 1.29g, in 27.9% yield. 3. Preparation of bis (cyclohexyl-cyclopentadienyl) di-p-tolyl titanium
A50 ml Schlenk flask was charged with 0.62g (1.5mmol) of the compound bis (cyclohexyl-cyclopentadienyl) titanium dichloride under an argon atmosphere and 10ml of diethyl ether, and the resulting p-methylphenyllithium was introduced into the reaction system through a steel tube under an ice-water bath and stirred at room temperature for 12 hours. Filtering with a sand plate, concentrating the filtrate to obtain orange yellow crystals, and recrystallizing to obtain 0.242g of the compound bis (cyclohexyl-cyclopentadienyl) di-p-tolyl titanium with the yield of 30.8%. EXAMPLE 2 Synthesis of several other hydrogenation catalysts
The preparation method of the catalyst, such as bis (cyclohexyl-cyclopentadienyl) di-m-tolyltitanium, bis (methyl-cyclopentadienyl) di-p-tolyltitanium, bis (methyl-cyclopentadienyl) di-m-tolyltitanium, bis (cyclohexyl-cyclopentadienyl) diphenyltitanium, bis (cyclopentadienyl) di-p-tolyltitanium, bis (cyclopentadienyl) di-m-tolyltitanium, bis (phenyl-cyclopentadienyl) di-p-tolyltitanium, bis (phenyl-cyclopentadienyl) di-m-tolyltitanium, bis (cyclopentadienyl) diphenyltitanium, etc., is the same as in example 1, except that the corresponding substituent is changed. Example 3 use of metallocene catalyst in hydrogenation of styrene-butadiene copolymer 1 preparation of Living Polymer Gum
In a 10L polymerization kettle, active polymer is synthesized by taking n-butyllithium as an initiator and cyclohexane as a solvent. The reaction temperature of the polymer is 50 ℃, and the SBS concentrationin the glue solution is 10%. The molecular weight is 60000 and S/B3/7. The vinyl content of the butadiene was 40%. (S-styrene, B-butadiene). 2. Hydrogenation of styrene-butadiene copolymers
200g of the above active polymer liquid cement was put into a 0.5 l hydrogenation reactor with stirring, the inside of the reactor was previously replaced with hydrogen, heated in a constant temperature water bath, and then stirred while heating, and hydrogen bubbling was not stopped, the pressure in the reactor was 1.5MPa, the hydrogen flow rate was 0.8l/min, and hydrogen bubbling was carried out for 1 hour. Adding 0.04mmol of cyclopentadienyl titanium catalyst solution prepared by using dry toluene at the temperature of 70 ℃, stirring and bubbling with hydrogen, keeping the kettle pressure at 1.5MPa in the reaction process, reacting for 2.0 hours, and sampling at regular intervals to analyze the hydrogenation degree of butadiene and benzene rings in the polymer. The hydrogenation results for the various catalyst types are shown in table 1.
TABLE 1 hydrogenation effect of various types of titanocene catalysts
| Serial number | Kind of catalyst | Degree of hydrogenation of conjugated diene in block (％) | Degree of hydrogenation of benzene ring (％) |
| 1 (comparison) | Bis (cyclopentadienyl) di-p-tolyl titanium | 98.1 | ＜2 |
| 2 (comparison) | Bis (cyclopentadienyl) di-m-tolyl titanium | 97.3 | ＜2 |
| 3 | Bis (methyl-cyclopentadienyl) di-p-tolyl titanium | 98.9 | ＜2 |
| 4 | Bis (cyclohexyl-cyclopentadienyl) di-p-tolyl titanium | 99.5 | ＜2 |
| 5 | Bis (methyl-cyclopentadienyl) diphenyltitanium | 96.4 | ＜2 |
| 6 | Bis (cyclohexyl-cyclopentadienyl) diphenyltitanium | 94.5 | ＜2 |
| 7 | Bis (phenyl-cyclopentadienyl) di-p-tolyl titanium | 98.5 | ＜2 |
| 8 | Bis (phenyl-cyclopentadienyl) di-m-tolyl titanium | 99.1 | ＜2 |
| 9 | Bis (phenyl-cyclopentadienyl) diphenyltitanium | 93.1 | ＜2 |
| 10 (comparison) | Bis (cyclopentadienyl) diphenyltitanium | 93.3 | ＜2 |
Note: the amount of the hydrogenation catalyst used was 0.2mmol/100g of the polymer, the activity Li/Ti was 8.2, and the degree of hydrogenation of the conjugated diene was determined by iodometry measurement of the unsaturation degree before and after the hydrogenation in the polymer, which is the same as below.
The iodine value method (iodometry) used for analyzing the degree of hydrogenation of a polymer utilizes the addition of iodine bromide to double bonds, excess iodine bromide is reduced with potassium iodide to precipitate iodine, and back titration is carried out with sodium thiosulfate. The molar iodine value of the iodine added to 1kg of polymer is the unsaturation in the rubber. The reaction formula is as follows:
VoConsumption of sodium thiosulfate solution (ml) for blank titration
V-consumption ofsodium thiosulfate solution (ml) upon titration of the sample
Normality of the sodium N-thiosulfate solution.
W-sample weight (g)
The calculation formula of the hydrogenation degree of the sample is as follows:
as can be seen from Table 1: the hydrogenation catalyst of the invention can effectively hydrogenate the styrene-conjugated diene copolymer. It can also be seen from table 1: 1. the activity of the cyclopentadienyl titanium catalyst with the substituent on the benzene ring is obviously higher than that of the cyclopentadienyl titanium catalyst without the substituent; 2. when the substituents on the benzene rings are the same, the larger the substituent on the cyclopentadienyl group is, the greater the steric hindrance is. In theory, the chance of the catalyst coming into contact with hydrogen is relatively reduced and the rate of formation of the catalytically active central TiH compound should be low. However, in fact, the activity of the catalyst is not reduced but improved, and the hydrogenation degree of the product is also improved, so that the substituent on the cyclopentadienyl stabilizes the active center of the catalyst, thereby improving the hydrogenation degree of the product. EXAMPLES 4 to 17
The living polymer dope was synthesized under the same conditions as in example 3.
200g of the obtained active polymer glue solution is transferred into a 0.5L hydrogenation reaction kettle under the condition of air isolation, the kettle is replaced by hydrogen in advance, the temperature is increased while stirring is carried out, and hydrogen bubbling is not stopped, the hydrogen flow is 0.8l/min, the pressure in the kettle is 1.5MPa, and the hydrogen bubbling is carried out for 1 hour at the temperature of 60 ℃. Adding a metallocene titanium catalyst solution prepared by using dry toluene in advance according to calculated amount at the temperature of 70 ℃, bubbling with hydrogen while stirring, keeping the kettle pressure at 1.5MPa in the reaction process, reacting for 2.0 hours, and sampling at regular intervals to analyze the hydrogenation degree of butadiene and benzene rings in the polymer. Table 2 shows the effect of different catalyst types, amounts and different Li/Ti ratios on the degree of hydrogenation.
TABLE 2 hydrogenation effect of various catalysts under different conditions
*And in addition, n-butyl lithium is added into the glue solution, and the rest is not additionally added with the n-butyl lithium.
| Examples | Kind of catalyst | Amount of catalyst used (mmoleTi/100 g polymer) | Li/Ti | Conjugated diolefin block Degree of hydrogenation (%) | Degree of hydrogenation of benzene ring (％) |
| 4 (comparison) | Bis (cyclopentadienyl) bis P-tolyl titanium | 0.1 | 16.4 | 96.1 | ＜2 |
| 5 (comparison)) | 0.2 | 8.2 | 98.1 | ＜2 | |
| 6 (comparison) | 0.3 | 5.5 | 98.5 | ＜2 | |
| 7 (comparison) | 0.48 | 3.4 | 99.6 | ＜2 | |
| 8 (comparison) | Bis (cyclopentadienyl) bis M-tolyl titanium | 0.2 | 8.2 | 97.3 | ＜2 |
| 9 (comparison) | 0.4 | 4.1 | 98.0 | ＜2 | |
| 10 | Bis (cyclohexyl-cyclopentedi) Alkenyl) di-p-tolyl titanium | 0.1 | 16.4 | 96.5 | ＜2 |
| 11 | 0.2 | 8.2 | 99.5 | ＜2 | |
| 12 | 0.2 | 30* | 95.7 | ＜2 | |
| 13 | Bis (methyl-cyclopentadiene) Yl) di-p-tolyl titanium | 0.1 | 40* | 82.1 | ＜2 |
| 14 | 0.2 | 8.8 | 98.9 | ＜2 | |
| 15 | 0.3 | 5.5 | 99.8 | ＜2 | |
| 16 | Bis (phenyl-cyclopentadiene) Yl) di-p-tolyl titanium | 0.1 | 16.4 | 85.6 | ＜2 |
| 17 | 0.2 | 8.2 | 98.5 | ＜2 |
As can be seen from table 2: the styrene conjugated diene copolymer can be effectively hydrogenated by selecting the proper amount of the catalyst. Meanwhile, it can be seen that butyl lithium is additionally added into the active rubber, so that the hydrogenation of the polymer is not promoted, and even side effects are achieved. Therefore, butyl lithium can be added before hydrogenation reaction.
Examples 18 to 26
The living polymer dope was synthesized under the same conditions as in example 3. 200g of the obtained active polymer glue solution is transferred into a 0.5L hydrogenation reaction kettle under the condition of airisolation, the kettle is replaced by hydrogen in advance, the temperature is increased while stirring is carried out, and hydrogen bubbling is not stopped, the hydrogen flow is 0.8l/min, the pressure in the kettle is 1.5MPa, and the hydrogen bubbling is carried out for 1 hour at the temperature of 60 ℃. Adding a calculated amount of a titanocene catalyst solution prepared by using dry toluene in advance at a certain temperature, stirring and bubbling with hydrogen, maintaining the kettle pressure at a certain pressure in the reaction process, reacting for 2.0 hours, and sampling at certain intervals to analyze the hydrogenation degree of butadiene and benzene rings in the polymer. The effect of different reaction temperatures and pressures on the degree of hydrogenation for the various catalysts is shown in Table 3.
TABLE 3 different reaction temperatures, pressures vs. additionInfluence of the Hydrogen reaction
| Examples | Kind of catalyst | Reaction temperature | Reaction pressure (MPa) | Degree of hydrogenation of conjugated diene block (%) | Degree of hydrogenation of benzene ring (％) | ||
| 1.0hr | 1.5hr | 2.0hr | |||||
| 18 (comparison) | Bis (cyclopentadienyl) bis P-tolyl titanium* | 67 | 1.5 | 96.0 | 98.6 | 99.2 | ＜2 |
| 19 (comparison) | 67 | 2.0 | 99.0 | 99.4 | 99.6 | ＜2 | |
| 20 (comparison) | 67 | 3.0 | 99.1 | 99.5 | 99.8 | ＜2 | |
| 21 (comparison) | 75 | 1.5 | 98.2 | 99.6 | 99.8 | ＜2 | |
| 22 (comparison) | Bis (cyclopentadienyl) bis Para-methyl titanium** | 67 | 1.5 | 92.5 | 96.2 | 98.1 | ＜2 |
| 23 | Bis (cyclohexyl-cyclopentadiene) Yl) di-p-tolyl titanium** | 67 | 1.5 | 92.2 | 97.5 | 99.5 | ＜2 |
| 24 | 67 | 3.0 | 94.5 | 98.2 | 99.6 | ＜2 | |
| 25 | Bis (phenyl-cyclopentadiene) Yl) di-p-tolyl titanium** | 67 | 1.5 | 90.1 | 96.5 | 99.1 | ＜2 |
| 26 | 67 | 3.0 | 90.4 | 96.8 | 99.4 | ＜2 | |
Note:*the amount of catalyst used was 0.4mmol/100g polymer,**the amount of catalyst used was 0.2mmol/100g of polymer
As can be seen from Table 3, the hydrogenation reaction is facilitated by properly increasing the temperature and pressure of the hydrogenation reaction. It can also be seen from Table 3 that when a biscyclopentadienyl-substituted titanium compound is used as the hydrogenation catalyst, the degree of hydrogenation of the conjugated diene portion of the polymer is less than that without the substituent in 1.0 hour at the same catalyst level. However, when the reaction time exceeds 1.0 hour, the hydrogenation degree of the product using the biscyclopentadienyl-substituted titanium compound as the catalyst is higher. Indicating that cyclohexyl and phenyl groups stabilize the catalyst activity.
Examples 27-29, SIS hydrogenation
In a 10L polymerization kettle, taking n-butyllithium as an initiator and cyclohexane as a solvent to synthesize the SIS active polymer. The reaction temperature of the polymer was 50 ℃, the SIS concentration in the dope was 10%, and S/I was 3/7. (S-styrene, I-isoprene).
200g of the above active polymer liquid cement was put into a 0.5 l hydrogenation reactor with stirring, the inside of the reactor was previously replaced with hydrogen, heated in a constant temperature water bath, and then stirred while heating, and hydrogen bubbling was not stopped, the pressure in the reactor was 1.5MPa, the hydrogen flow rate was 0.8l/min, and hydrogen bubbling was carried out for 1 hour. Adding 0.04mmol of cyclopentadienyl titanium catalyst solution prepared by using dry toluene at the temperature of 70 ℃, stirring and bubbling with hydrogen, keeping the kettle pressure at 1.5MPa in the reaction process, reacting for 2.0 hours, and sampling at regular intervals to analyze the hydrogenation degree of butadiene and benzene rings in the polymer. The hydrogenation results for each catalyst are shown in Table 4.
TABLE 4 hydrogenation effect of various catalysts on SIS
| Examples | Kind of catalyst | Li/Ti | Degree of diene hydrogenation (%) | Degree of hydrogenation of benzene ring (%) |
| 27 (comparison) | Bis (cyclopentadienyl) di-p-tolyl titanium | 8.2 | 90.3 | ＜2 |
| 28 | Bis (cyclohexyl-cyclopentadienyl) di-p-tolyl titanium | 8.2 | 91.7 | ＜2 |
| 29 | Bis (phenyl-cyclopentadienyl) di-p-tolyl titanium | 8.2 | 90.2 | ＜2 |
Note: the catalyst dosage is as follows: 0.2mmol/100g of polymer
As can be seen from table 4: the catalyst of the present invention can effectively hydrogenate SIS.
Claims (18)
1. A metallocene catalyst, the catalyst having the structure:
wherein R is1，R2Is the same or different straight-chain alkyl, cycloalkyl, aryl or substituted aryl containing 1-8 carbon atoms, R3，R4Is the same or different alkyl, alkoxy, aryl, substituted aryl or aryloxy containing 6 to 12 carbon atoms, and M is 2 to 4-valent transition metal.
2. A metallocene catalyst as claimed in claim 1, characterised in that the transition metal is Ti, Zr or Hf.
3. The metallocene catalyst according to claim 1, characterized in that the transition metal is ti (iv).
4. The metallocene catalyst of claim 1, selected from one or a mixture of: bis (cyclohexyl-cyclopentadienyl) di-p-tolyltitanium, bis (cyclohexyl-cyclopentadienyl) di-m-tolyltitanium, bis (methyl-cyclopentadienyl) di-p-tolyltitanium, bis (methyl-cyclopentadienyl) di-m-tolyltitanium, bis (cyclohexyl-cyclopentadienyl) diphenyltitanium, bis (cyclopentadienyl) di-p-tolyltitanium, bis (cyclopentadienyl) di-m-tolyltitanium, bis (phenyl-cyclopentadienyl) di-p-tolyltitanium, bis (phenyl-cyclopentadienyl) di-m-tolyltitanium, bis (cyclopentadienyl) diphenyltitanium.
5. A process for producing a metallocene catalyst as claimed in any one of claims 1 to 4, characterized in that cyclopentadiene is subjected to a substitution reaction with any one selected from the group consisting of linear alkanes having 1 to 8 carbon atoms, cyclic alkanes, aromatic hydrocarbons and substituted aromatic hydrocarbons to give substituted cyclopentadiene, and then the substituted cyclopentadiene is reacted withReacting with n-BuLi to generate substituted cyclopentadienyl lithium, reacting with a transition metal hydrochloride, and separating to obtain a complex crystal containing bis (substituted cyclopentadienyl); the crystal is reacted with organic lithium with alkyl, alkoxyl, aryl, substituted aryl and aryloxy containing 6-12 carbon atoms as organic part to obtain metallocene catalyst with the structure as shown,
6. use of a metallocene catalyst as claimed in any one of claims 1 to 5 as a catalyst in the polymerisation of olefins.
7. Use of a metallocene catalyst as claimed in any one of claims 1 to 5 as a catalyst in the isomerisation of olefins.
8. Use of a metallocene catalyst as claimed in any one of claims 1 to 5 as a catalyst in the hydrogenation of a conjugated diene or a copolymer thereof.
9. A process for hydrogenating a conjugated diene polymer composed of an aromatic hydrocarbon compound having a vinyl group and a conjugated diene having 4 to 6 carbon atoms, which comprises terminating a living polymer newly formed in a solution system with hydrogen and then hydrogenating the living polymer by the action of a metallocene catalyst, characterized in that: the selective hydrogenation is carried out in the presence of a metallocene procatalyst having the structure:
the metallocene main catalyst is one or a mixture of more than one of the compounds with the structure, wherein R1，R2Are identical or different straight-chain alkyl, cycloalkyl, aryl or substituted aryl radicals having from 1 to 8 carbon atoms, R3，R4The same or different aryl, substituted aryl, alkyl, alkoxy and aryloxy containing 6-12 carbon atoms, M is 2-4 valent transition metal, the hydrogenation reaction temperature is 20-80 ℃, the pressure is 0.2-3.0MPa, the reaction time is 0.5-2.0 hours, and the metallocene is mainly catalyzedThe amount of agent used is 0.05-0.6mmol per 100g of polymer.
10. Hydrogenation process according to claim 9, characterized in that the transition metal is Ti, Zr or Hf.
11. Hydrogenation process according to claim 9, characterized in that the transition metal is ti (iv).
12. The hydrogenation process of claim 9, wherein said conjugated diene polymer is a styrene-butadiene-styrene copolymer and a styrene-isoprene-styrene copolymer.
13.The hydrogenation process of claim 9, wherein the alkali metal hydride is lithium hydride.
14. The hydrogenation process of claim 9, wherein the molar ratio of alkali metal hydride to metallocene is from 2 to 60.
15. The hydrogenation process of claim 9, wherein the molar ratio of alkali metal hydride to metallocene is from 4 to 20.
16. The hydrogenation process of claim 9, wherein the metallocene catalyst is selected from the group consisting of: bis (cyclohexyl-cyclopentadienyl) di-p-tolyltitanium, bis (cyclohexyl-cyclopentadienyl) di-m-tolyltitanium, bis (methyl-cyclopentadienyl) di-p-tolyltitanium, bis (methyl-cyclopentadienyl) di-m-tolyltitanium, bis (cyclohexyl-cyclopentadienyl) diphenyltitanium, bis (cyclopentadienyl) di-p-tolyltitanium, bis (cyclopentadienyl) di-m-tolyltitanium, bis (phenyl-cyclopentadienyl) di-p-tolyltitanium, bis (phenyl-cyclopentadienyl) di-m-tolyltitanium, bis (cyclopentadienyl) diphenyltitanium.
17. Hydrogenation process according to claim 9, characterized in that the hydrogenation reaction temperature is 50-80 ℃, the pressure is 1.0-2.5MPa and the reaction time is 1.0-2.0 hours.
18. Hydrogenation process according to claim 9, characterized in that the molar ratio of LiH to procatalyst is from 4 to 20 and the amount of procatalyst used is from 0.1 to 0.4mmol per 100g of polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01104879 CN1121274C (en) | 2001-02-28 | 2001-02-28 | Metallocene catalyst and its preparing process, application and selective hydrogenation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01104879 CN1121274C (en) | 2001-02-28 | 2001-02-28 | Metallocene catalyst and its preparing process, application and selective hydrogenation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1373008A true CN1373008A (en) | 2002-10-09 |
| CN1121274C CN1121274C (en) | 2003-09-17 |
Family
ID=4654068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01104879 Expired - Lifetime CN1121274C (en) | 2001-02-28 | 2001-02-28 | Metallocene catalyst and its preparing process, application and selective hydrogenation process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1121274C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492513B (en) * | 2008-01-25 | 2010-12-22 | 中国石油化工股份有限公司 | Hydrogenator and polymer hydrogenation method |
| WO2010149812A1 (en) | 2009-06-22 | 2010-12-29 | Dynasol Elastomeros, S. A. | Catalyst for the hydrogenation of unsaturated compounds |
| CN103080279A (en) * | 2010-07-06 | 2013-05-01 | 道达尔炼油与销售部 | Hydroconversion process for heavy hydrocarbonaceous feedstock |
| CN103080278A (en) * | 2010-07-06 | 2013-05-01 | 道达尔炼油与销售部 | Catalyst preparation reactors from catalyst precursor used for feeding reactors to upgrade heavy hydrocarbonaceous feedstocks |
| CN103097026A (en) * | 2010-07-06 | 2013-05-08 | 道达尔炼油与销售部 | Process for the hydroconversion of a low quality hydrocarbonaceous feedstock |
| CN106366226A (en) * | 2015-07-23 | 2017-02-01 | 中国石油化工股份有限公司 | Transition metal catalyst composition and applications thereof |
| CN106554464A (en) * | 2015-09-24 | 2017-04-05 | 中国石化扬子石油化工有限公司 | A kind of hydrogenation preparation method of Petropols |
| CN106554435A (en) * | 2015-09-24 | 2017-04-05 | 中国石化扬子石油化工有限公司 | A kind of hydrogenation preparation method of Petropols |
| CN107417837A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Transition-metal catalyst composition and bimodal distribution ethene-α rnonoolefin copolymers and preparation method thereof |
| CN111253506A (en) * | 2020-01-20 | 2020-06-09 | 青岛科技大学 | Method for preparing polymer materials with different saturation degrees by solution hydrogenation method |
| CN111686811A (en) * | 2020-07-08 | 2020-09-22 | 陈天然 | Titanium supported catalyst and method for preparing hexamethylene diamine by catalytic hydrogenation of adiponitrile |
-
2001
- 2001-02-28 CN CN 01104879 patent/CN1121274C/en not_active Expired - Lifetime
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492513B (en) * | 2008-01-25 | 2010-12-22 | 中国石油化工股份有限公司 | Hydrogenator and polymer hydrogenation method |
| RU2522429C2 (en) * | 2009-06-22 | 2014-07-10 | Динасол Эластомерос, С.А. | Catalyst for hydrogenation of unsaturated compounds |
| WO2010149812A1 (en) | 2009-06-22 | 2010-12-29 | Dynasol Elastomeros, S. A. | Catalyst for the hydrogenation of unsaturated compounds |
| EP2272588A1 (en) | 2009-06-22 | 2011-01-12 | Dynasol Elastomeros, S.A. | Catalyst for the hydrogenaton of unsaturated compounds |
| US9211532B2 (en) | 2009-06-22 | 2015-12-15 | Dynasol Elastomeros, S.A. | Catalyst for the hydrogenation of unsaturated compounds |
| US9233359B2 (en) | 2010-07-06 | 2016-01-12 | Total Marketing Services | Process for the hydroconversion of a low quality hydrocarbonaceous feedstock |
| KR101778628B1 (en) | 2010-07-06 | 2017-09-14 | 토탈 라피나쥬 프랑스 | Process for the hydroconversion of a low quality hydrocarbonaceous feedstock |
| CN103097026B (en) * | 2010-07-06 | 2015-07-15 | 道达尔炼油与销售部 | Process for the hydroconversion of a low quality hydrocarbonaceous feedstock |
| CN103080278A (en) * | 2010-07-06 | 2013-05-01 | 道达尔炼油与销售部 | Catalyst preparation reactors from catalyst precursor used for feeding reactors to upgrade heavy hydrocarbonaceous feedstocks |
| US9233363B2 (en) | 2010-07-06 | 2016-01-12 | Total Marketing Services | Catalyst preparation reactors from catalyst precursor used for feeding reactors to upgrade heavy hydrocarbonaceous feedstocks |
| CN103080279A (en) * | 2010-07-06 | 2013-05-01 | 道达尔炼油与销售部 | Hydroconversion process for heavy hydrocarbonaceous feedstock |
| US9255229B2 (en) | 2010-07-06 | 2016-02-09 | Total Raffinage Marketing | Hydroconversion process for heavy hydrocarbonaceous feedstock |
| CN103097026A (en) * | 2010-07-06 | 2013-05-08 | 道达尔炼油与销售部 | Process for the hydroconversion of a low quality hydrocarbonaceous feedstock |
| CN106366226A (en) * | 2015-07-23 | 2017-02-01 | 中国石油化工股份有限公司 | Transition metal catalyst composition and applications thereof |
| CN106366226B (en) * | 2015-07-23 | 2019-11-12 | 中国石油化工股份有限公司 | A kind of transition-metal catalyst composition and its application |
| CN106554435A (en) * | 2015-09-24 | 2017-04-05 | 中国石化扬子石油化工有限公司 | A kind of hydrogenation preparation method of Petropols |
| CN106554435B (en) * | 2015-09-24 | 2018-12-11 | 中国石化扬子石油化工有限公司 | A kind of hydrogenation preparation method of Petropols |
| CN106554464B (en) * | 2015-09-24 | 2018-12-11 | 中国石化扬子石油化工有限公司 | A kind of hydrogenation preparation method of Petropols |
| CN106554464A (en) * | 2015-09-24 | 2017-04-05 | 中国石化扬子石油化工有限公司 | A kind of hydrogenation preparation method of Petropols |
| CN107417837A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Transition-metal catalyst composition and bimodal distribution ethene-α rnonoolefin copolymers and preparation method thereof |
| CN111253506A (en) * | 2020-01-20 | 2020-06-09 | 青岛科技大学 | Method for preparing polymer materials with different saturation degrees by solution hydrogenation method |
| CN111686811A (en) * | 2020-07-08 | 2020-09-22 | 陈天然 | Titanium supported catalyst and method for preparing hexamethylene diamine by catalytic hydrogenation of adiponitrile |
| CN111686811B (en) * | 2020-07-08 | 2023-02-17 | 宁波柏湖管理咨询合伙企业(有限合伙) | Titanium supported catalyst and method for preparing hexamethylene diamine by catalytic hydrogenation of adiponitrile |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1121274C (en) | 2003-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2322324C (en) | Integrated process for preparation of diene complexes | |
| Erker et al. | Hydroboration of Bis (alkenylcyclopentadienyl) zirconium Dichlorides | |
| US20050090383A1 (en) | Metal complex compositions and their use as catalysts to produce polydienes | |
| JP2002526548A (en) | Crosslinked metal complex | |
| JPH05271326A (en) | Hydrogenation of olefinic unsaturated polymer and hydrogenation catalyst | |
| JPH05271325A (en) | Hydrogenation of olefinic unsaturated polymer and hydrogenation catalyst | |
| MXPA02000311A (en) | Hydrogenation of unsaturated polymers using divalent diene-containing bis-cyclopentadienyl group iv metal catalysts. | |
| CN1373008A (en) | Metallocene catalyst and its preparing process, application and selective hydrogenation process | |
| CN1248979A (en) | Process for polymerizing olefins | |
| Sedláček et al. | Controlled and living polymerizations induced with rhodium catalysts. A Review | |
| EP0601953B1 (en) | Process of hydrogenation in solution of the double bonds of polymers of conjugated dienes, and hydrogenated block copolymer produced | |
| US5708101A (en) | Stereospecific olefin polymerization catalysts | |
| JPH0352487B2 (en) | ||
| EP0900228B1 (en) | A method for producing octahydrofluorenyl metal complexes | |
| EP0784639A1 (en) | Syndiotactic prochiral olefin polymerization process | |
| US20040082727A1 (en) | Process for hydrogenation of conjugated diene polymer | |
| RU2522429C2 (en) | Catalyst for hydrogenation of unsaturated compounds | |
| CA2355236A1 (en) | Ligands and catalysts for producing elastomeric propylene polymers | |
| DE69723636T2 (en) | Process for the hydrogenation of olefins or polymers using a catalyst based on a Ti, Zr or Hf complex | |
| JP4912519B2 (en) | Efficient method for hydrogenating conjugated diene polymers | |
| JPH11292925A (en) | Hydrogenation of conjugated diene polymer | |
| Forens | Tuning polybutadiene microstructure using multi-metallic initiation systems by anionic polymerization | |
| JP2004161760A (en) | New transition metal compound, olefin polymerization catalyst and method for producing polyolefin | |
| JPH08245715A (en) | Catalyst component for polymerization alpha-olefin and its use | |
| JPH0725811B2 (en) | Hydrogenation method for olefin compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| C10 | Entry into substantive examination | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20030917 |