Method of obtaining modified titanium-magnesium nanocatalyst

FIELD: chemistry.

SUBSTANCE: invention relates to production of polymers, specifically metal complex polymerisation catalysts, and can be used to produce trans-1,4-polyisoprene. Described is a method of obtaining a modified titanium-magnesium nanocatalyst for polymerisation of isoprenate by reacting magnesium with titanium tetrachloride and butyl chloride in volume ratio of 1/(63-190), followed by washing and further modification with phosphine of general formula R3P, where R=aryl, alkyl or a thiol of general formula R1SR2, where R1, R2=aryl, alkyl or carbon disulphide. In the nanocatalyst, the ratio phosphorus/titanium in the case of phosphine or sulphur/titanium in the case of thiol or carbon disulphide ranges from 1 to 20 mol/mol.

EFFECT: high stereospecificity of the catalyst with respect to isoprene and reduced amount of low molecular weight fractions in polyisoprene.

3 cl, 15 ex

 

The invention relates to the production of polymers, namely: a metal-complex catalysts of polymerization, and can be used to obtain TRANS-1,4-polyisoprene.

A method of obtaining titanium-magnesium catalyst for the polymerization of isoprene by the following method: charged to the reactor magnesium turnings, a solvent, n-butyl chloride (1/5 of the total number) and a crystal of iodine, the temperature was raised to 65-70°C and gradually add the remainder of the butyl chloride, the reaction leads 4 hours, after cooling the suspension, the solvent is decanted and the precipitate washed with solvent from unreacted n-butyl chloride, then with solvent and at 60-70°C add the titanium tetrachloride, after 5-6 hours the reactor is cooled, the solvent is decanted, the resulting titanium-magnesium catalyst is washed from an excess of titanium tetrachloride (Patent RF 2196782). This method is sequential and requires considerable time for synthesis.

Closest to the proposed invention is a method of obtaining titanium-magnesium of nanocatalysts (co)polymerization of alpha-olefins and conjugated dienes (RF patent 2425059). The interaction of magnesium metal with n-butyl chloride occurs in a single phase with the direct participation in the reaction of titanium tetrachloride. When this happens its restoration mA the of and cocrystallization formed of magnesium dichloride and trichloride titanium. The content of the butyl chloride is 6.0-8.7 ml per 1 g of magnesium, the volumetric ratio of titanium tetrachloride to the butyl chloride is 1/(47-67).

These synthesis methods allow to obtain a catalyst for the polymerization of isoprene in the TRANS-1,4-polyisoprene with a content of TRANS-1,4-units 92% srednekamennogo molecular weight of up to 20,000 g/mol, the mass-average molecular weight of 50,000 g/mol. At the same time there is a problem of increasing molecular mass and a content of TRANS-1,4-units in the isoprene.

The technical problem of the invention to provide a new method for the synthesis of titanium-magnesium of nanocatalysts, allowing to obtain TRANS-1,4-polyisoprene with a molecular mass of more than 50,000 g/mol and a content of TRANS-1,4-units of more than 92%.

The technical result of the invention is to improve stereospecificity action of the catalyst with respect to isoprene and reduce the amount of low molecular weight fractions in the polyisoprene.

This technical result is achieved by introducing into the composition of the titanium-magnesium of nanocatalysts modifying additives on the basis of the phosphines of General formula R3P (R = aryl, alkyl) or thiols of the General formula R1SR2, (R1, R2= aryl, alkyl), or carbon disulphide, and the change of the volume ratio of titanium tetrachloride to the butyl chloride.

Modifica is consistent titanium-magnesium catalyst for the polymerization of isoprene produced by the interaction of magnesium with titanium tetrachloride and butyl chloride with their volumetric ratio of 1/(63-190), then rinse and additional modification of a phosphine of General formula R3P (R = aryl, alkyl) or a thiol of General formula R1SR2, (R1, R2= aryl, alkyl), or carbon disulphide.

The ratio of modifier and titanium, namely phosphorus/titanium in the case of additives on the basis of the said phosphine or sulfur/titanium in the case of additives on the basis of the said thiol or disulfide is from 1 to 20 mol/mol.

The synthesis of the modified titanium-magnesium catalyst is carried out at the following ratios: 1 g of the magnesium content of the butyl chloride is 9-15 ml volumetric ratio of titanium tetrachloride and butyl chloride is 1/(63-190).

By electron transmission microscopy revealed that the obtained catalyst is a nanoparticles (15-35 nm).

The following examples 1-7 illustrate the proposed method of obtaining modified titanium-magnesium of nanocatalysts.

Example 1

In a reactor with a stirrer in an atmosphere of inert gas (argon, nitrogen) loads simultaneously 2.4 g of magnesium shavings, 21 ml of n-butyl chloride and 0.33 ml of titanium tetrachloride. The volumetric ratio of titanium tetrachloride and butyl chloride is 1/63,6. The reaction is carried out at 78-80°C for 4 hours. The precipitate of the catalyst is washed twice with hot hexane, and then into the reactor until ablaut 1,83 g triallylamine. The mixture is stirred at 60°C, cooled. The ratio of phosphorus/titanium is 2 mol/mol.

Example 2

In a reactor with a stirrer in an atmosphere of inert gas (argon, nitrogen) loads simultaneously 2.4 g of magnesium shavings, 21 ml of n-butyl chloride and 0.33 ml of titanium tetrachloride. The volumetric ratio of titanium tetrachloride and butyl chloride is 1/63,6. The reaction is carried out at 78-80°C for 4 hours. The precipitate of the catalyst is washed twice with hot hexane, and then into the reactor add 6 ml of tributylphosphine. The mixture is stirred at 60°C, cooled. The ratio of phosphorus/titanium is 8 mol/mol.

Example 3

In a reactor with a stirrer in an atmosphere of inert gas (argon, nitrogen) loads simultaneously 3.6 g of magnesium shavings, to 31.5 ml of n-butyl chloride and 0.17 ml of titanium tetrachloride. The volumetric ratio of titanium tetrachloride and butyl chloride is 1/190. The reaction is carried out at 75°C for 6 hours. The precipitate of the catalyst is washed twice with hot hexane, and then the reactor is added to 4.2 g tricyclohexylphosphine. The mixture is stirred at 60°C, cooled. The ratio of phosphorus/titanium is 10 mol/mol.

Example 4

In a reactor with a stirrer in an atmosphere of inert gas (argon, nitrogen) loads simultaneously 3.6 g of magnesium shavings, to 31.5 ml of n-butyl chloride and 0.17 ml of titanium tetrachloride. The volumetric ratio of titanium tetrachloride and butyl chloride which is 1/190. The reaction is carried out at 75-76°C for 4 hours. The precipitate of the catalyst is washed twice with hot hexane, and then into the reactor type of 0.79 g of triphenylphosphine. The mixture is stirred at 60°C, cooled. The ratio of phosphorus/titanium is 2 mol/mol.

Example 5

In a reactor with a stirrer in an atmosphere of inert gas (argon, nitrogen) loads simultaneously 1.2 g of magnesium shavings, and 10.5 ml of n-butyl chloride and 0,065 ml of titanium tetrachloride. The reaction is carried out at 78-80°C for 4 hours. The volumetric ratio of titanium tetrachloride and butyl chloride is 1/161,5. The precipitate of the catalyst is washed twice with hot hexane, and then into the reactor type of 1.39 ml of carbon disulfide. The mixture is stirred at 60°C, cooled. The ratio of sulfur/titanium is 19 mol/mol.

Example 6

In a reactor with a stirrer in an atmosphere of inert gas (argon, nitrogen) loads simultaneously 2.4 g of magnesium shavings, 21 ml of n-butyl chloride and 0.33 ml of titanium tetrachloride. The reaction is carried out at 78-80°C for 4 hours. The volumetric ratio of titanium tetrachloride and butyl chloride is 1/63,6. The precipitate of the catalyst is washed twice with hot hexane, and then into the reactor type of 1.59 ml of tetrahydrothiophene. The mixture is stirred at 60°C, cooled. The ratio of sulfur/titanium is 6 mol/mol.

Example 7

In a reactor with a stirrer in an atmosphere of inert gas (argon, nitrogen loads simultaneously 2.4 g of magnesium shavings, 21 ml of n-butyl chloride and 0.33 ml of titanium tetrachloride. The reaction is carried out at 78-80°C for 4 hours. The volumetric ratio of titanium tetrachloride and butyl chloride is 1/63,6. The precipitate of the catalyst is washed twice with hot hexane, and then into the reactor add 0,81 ml phenylalaline. The mixture is stirred at 60°C, cooled. The ratio of sulfur/titanium is 2 mol/mol.

The obtained modified titanium-magnesium catalyst can be used in various catalytic systems for the polymerization of conjugated dienes and alpha-olefins.

Example 8 illustrates the effect of nanocatalysts without modifying additives described in the patent of the Russian Federation 2425059.

Examples 9-15 illustrate the effect of modified nanocatalysts obtained by the described method, the polymerization of isoprene, but do not limit its application.

Example 8

Polymerizate isoprene is carried out in a glass reactor with a stirrer in an atmosphere of inert gas.

Charged to the reactor 40 ml of a mixture of isoprene from isopentane content of isoprene 15 wt.%, 4,7 ml triisobutylaluminum in the form of a solution in hexane with aluminium concentration of 0.8 mol/l, 2.2 ml of a suspension of unmodified titanium-magnesium of nanocatalysts with the concentration of titanium 0.5 mol/liter Polymerization is conducted for two hours at 25°C, then stopping the pad from sliding the t introduction 5 ml of ethanol. Conversion of isoprene is 98.8%, the content of TRANS-1,4-units in the isoprene is of 92.1%, Mn=19000, Mw=43000.

Example 9

In the reactor load of 13.8 ml of isoprene, 60 ml of hexane, 1.7 ml of triisobutylaluminum in the form of a solution in hexane with aluminium concentration of 1.2 mol/l and 1.8 ml suspension of titanium-magnesium of nanocatalysts prepared according to example 1. The polymerization is carried out in four hours at 25°C, then stopped by introducing 5 ml of ethanol. Conversion of isoprene is of 92.6%, a content of TRANS-1,4-units in the isoprene is 94,4%, Mn=180000, Mw=437000.

Example 10

In the reactor load of 13.8 ml of isoprene, 60 ml of hexane, 1.7 ml of triisobutylaluminum in the form of a solution in hexane with aluminium concentration of 1.2 mol/l and 1.8 ml suspension of titanium-magnesium of nanocatalysts prepared according to example 2. The polymerization is carried out in four hours at 25°C, then stopped by introducing 5 ml of ethanol. Conversion of isoprene is 90%, the content of TRANS-1,4-units in the isoprene is 96.8%, Mn=194000, Mw=662000.

Example 11

In the reactor load of 13.8 ml of isoprene, 60 ml of hexane, 1.7 ml of triisobutylaluminum in the form of a solution in hexane with aluminium concentration of 1.2 mol/l and 1.8 ml suspension of titanium-magnesium of nanocatalysts prepared according to example 3. The polymerization is carried out in four hours at 25°C, then stopped by the introduction of a 5 ml this is Ola. Conversion of isoprene is 84,5%, the content of TRANS-1,4-units in the isoprene is 94,1%, Mn=92000, Mw=182000.

Example 12

In the reactor load of 13.8 ml of isoprene, 60 ml of hexane, 1.7 ml of triisobutylaluminum in the form of a solution in hexane with aluminium concentration of 1.2 mol/l and 1.8 ml suspension of titanium-magnesium of nanocatalysts prepared according to example 4. The polymerization is conducted for two hours at 25°C, then stopped by introducing 5 ml of ethanol. Conversion of isoprene or 97.7%, a content of TRANS-1,4-units in the isoprene is 97,0%, Mn=292000, Mw=709000.

Example 13

In the reactor load of 13.8 ml of isoprene, 60 ml of hexane, 1.7 ml of triisobutylaluminum in the form of a solution in hexane with aluminium concentration of 1.2 mol/l and 1.8 ml suspension of titanium-magnesium of nanocatalysts prepared according to example 5. The polymerization is conducted for five hours at 25°C, then stopped by introducing 5 ml of ethanol. Conversion of isoprene is to 97.1%, a content of TRANS-1,4-units in the isoprene is 97.3%, Mn=520000, Mw=934000.

Example 14

In the reactor load of 13.8 ml of isoprene, 60 ml of hexane, 1.7 ml of triisobutylaluminum in the form of a solution in hexane with aluminium concentration of 1.2 mol/l and 1.8 ml suspension of titanium-magnesium of nanocatalysts prepared according to example 6. The polymerization is conducted for two hours at 25°C, then stopped by introducing 5 ml of ethanol. To the version of isoprene is 88%, the content of TRANS-1,4-units in the isoprene-91.7%, Mn=172000, Mw=611000.

Example 15

In the reactor load of 13.8 ml of isoprene, 60 ml of hexane, 1.7 ml of triisobutylaluminum in the form of a solution in hexane with aluminium concentration of 1.2 mol/l and 1.8 ml suspension of titanium-magnesium of nanocatalysts prepared according to example 7. The polymerization is conducted for two hours at 25°C, then stopped by introducing 5 ml of ethanol. Conversion of isoprene is to 89.5%, a content of TRANS-1,4-units in the isoprene is 93.0%, Mn=74000, Mw=291000.

These examples show that with some decrease in the rate of polymerization, expressed in the increase of time of polymerization to achieve the conversion of isoprene greater than 90%, the modified titanium-magnesium nano-catalysts described in examples 1-3, can significantly improve bulk and srednekamennogo molecular weight, as well as to increase the content of TRANS-1,4-units in the isoprene.

1. The method of obtaining modified titanium-magnesium of nanocatalysts for the polymerization of isoprene by the interaction of magnesium with titanium tetrachloride and butyl chloride, characterized in that the interaction is carried out at a volume ratio of titanium tetrachloride and butyl chloride 1/(63-190), then rinse and additional modification of a phosphine of General formula R3P, where R is ar is l, alkyl, or a thiol of General formula R1SR2where R1, R2aryl, alkyl, or carbon disulphide.

2. The method according to claim 1, wherein when the modification of nanocatalysts specified phosphine ratio of phosphorus/titanium in nanocatalysts is from 1 to 20 mol/mol.

3. The method according to claim 1, wherein when the modification of nanocatalysts specified thiol or disulfide ratio sulfur/titanium in nanocatalysts is from 1 to 20 mol/mol.



 

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1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to petrochemical industry. Described is a method of preparing a titanium catalyst for stereospecific polymerisation of isoprene in the presence of a catalyst system TiCl4-Al(i-C4H9)3-diphenyloxide-piperylene by mixing toluene solutions of titanium tetrachloride, which contains phenyl oxide, and triisobutylaluminium, which contains piperylene, in molar ratio of the titanium and aluminium components of the catalyst to diphenyl oxide and piperylene of 1:0.15, at temperature of (-20)-(-10)°C, followed by circulation of the catalyst on an outer loop with collection of isoprene for polymerisation, wherein a small tubular turbulent reactor with a diffuser-confusor design is mounted at the step for circulation on the outer mixing loop.

EFFECT: method enables to reduce consumption of the titanium catalyst during isoprene polymerisation.

1 tbl, 4 ex

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EFFECT: formation of copolymers with a controlled composition, the lowest compositional and fractional non-uniformity and preventing simultaneous formation of homopolymers.

1 tbl, 11 ex

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11 cl, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention provides reactor thermoplastic polyolefins having high fluidity and excellent surface quality, which contain (A) a matrix of a propylene homo- or copolymer whose weight ratio ranges from 40 to 90% with ISO 1133 MFR index (230°C, nominal load of 2.16 kg)≥200 g/10 min, and (B) an elastomeric copolymer of ethylene and propylene whose weight ratio ranges from 2 to 30%, with characteristic viscosity of IV (according to ISO 1628 in decalin as a solvent)≤2.8 dl/g with weight ratio of ethylene ranging from more than 50 to 80% and (C) an elastomeric copolymer of ethylene and propylene whose weight ratio ranges from 8 to 30%, with characteristic viscosity IV (according to ISO 1628 in decalin as a solvent) ranging from 3.0 to 6.5 dl/g and with weight content of propylene ranging from 50 to 80%. The reactor thermoplastic polyolefins are obtained in a process by multistep polymerisation, involving at least 3 successive steps, in the presence of a catalyst comprising (i) a Ziegler-Natta procatalyst which contains a product of transesterification of a lower alcohol and a phthalic ester of complex acids, (ii) an organometallic cocatalyst and (iii) an external donor of formula (I), Si(OCH2CH3)3(NR1R2), where values of R1 and R2 are given in the claim. The invention also discloses a multistep process of producing said polyolefins, involving either a combination of one loop reactor and two or three gas-phase reactors, or a combination of two loop reactors and two gas-phase reactors, connected in series. Disclosed polyolefins are used to produce articles for the automobile industry by pressure casting. The invention also relates to articles moulded from the reactor thermoplastic polyolefins.

EFFECT: polyolefins can be used for pressure casting large profiles for which no ripple marks appear and which simultaneously demonstrate good balance of impact viscosity, rigidity and high fluidity.

15 cl, 3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: catalyst composition contains: one or more Ziegler-Natta procatalyst compositions having one or more transition metal compounds and one or more internal electron donors in form of esters of aromatic dicarboxylic acid, one or more aluminium-containing cocatalysts and a selectivity control agent (SCA) which contains a mixture of (i) a first alkoxy silane and a second alkoxy silane and (ii) an ester of C4-C30-aliphatic acid, and the molar ratio of aluminium to total SCA ranges from 0.5:1 to 4:1.

EFFECT: catalyst composition improves polymerisation productivity and polymer production rate, the composition is self-extinguishing.

9 cl, 15 tbl, 10 dwg

FIELD: chemistry.

SUBSTANCE: catalyst composition contains: one or more Ziegler-Natta procatalyst compositions having one or more transition metal compounds and one or more internal electron donors in form of esters of aromatic dicarboxylic acid, one or more aluminium-containing cocatalysts and a selectivity control agent (SCA) which contains a mixture of (i) a first alkoxy silane and a second alkoxy silane and (ii) an ester of C4-C30-aliphatic acid, and the molar ratio of aluminium to total SCA ranges from 0.5:1 to 4:1.

EFFECT: catalyst composition improves polymerisation productivity and polymer production rate, the composition is self-extinguishing.

9 cl, 15 tbl, 10 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining cis-1,4-(co)polymers of conjugated dienes and can be used in production of synthetic rubber, and obtained materials - in tire and rubber industry. Method of obtaining cis-1,4-(co)polymers of conjugated dienes is realised by polymerisation of conjugated dienes or their copolymerisation with each other in medium of hydrocarbon solvent in presence of molecular weight (MW) regulator under action of catalytic complex, consisting of neodymium compound, halogen-free aluminium-organic compound, conjugated diene, necessary for formation of catalytic complex, and halogen source, catalytic complex is obtained in medium of hydrocarbon solvent by interaction of neodymium compound with conjugated diene, necessary for catalytic complex formation, with further fractional addition of halogen-free aluminium-organic compound with further supply of halogen source, of halogen-free aluminium-organic compound being selected from group of compounds, which contains trialkylaluminium, dialkylaluminium hydride, alkylalumoxane.

EFFECT: achieved technical result lies in reduction of consumption norms of catalytic system components due to increase of its activity, as well as in reduction of (co)polymerisation reaction time.

13 cl, 2 tbl, 26 ex

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