SU761485A1 - Method of preparing alternating copolymers - Google Patents

Description

The invention relates to the synthetic rubber industry, in particular to a method for producing alternating copolymers of butadiene with propylene in the presence of a complex catalyst consisting of an organoaluminum compound and a transition metal compound.

The invention may find application in the synthetic rubber industry.

A known method for producing alternating copolymers of butadiene with α-olefins at (—100) - (+ 50DS in hydrocarbon solvents under the influence of a catalyst consisting of ΑΐΚ „λ ₃ _ _η (A), where K is alkyl, aryl or cycloalkyl, and compounds titanium of the formula HRP ₄ '(B), where X' is a halogen, or consisting of A, B and C selected from the following groups of compounds: metal oxides and metalloids, halides, halide compounds such as Lewis acids, acid-base Lewis complexes, organometallic transition compounds metals containing halide, gan s, alkyl halides, metal carbonates, carbonyl compounds,

CO ₂ , phosgene [1].

The disadvantages of this method include:

1. Low temperatures of carrying out the copolymerization [in the examples (—30) ° C and below].

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2. Considerable expenses of the catalyst for the copolymer formed (for example, 0.5 mmol or more A1KpChz-p).

3. The complexity of the catalyst 5 (the best results are obtained on three and

more component catalytic systems).

There is also known a method of producing alternating copolymers of butadiene with a-olefins by copolymerization at (—100) - (+ 50) ° C in an environment of hydrocarbon solvents (hexane, heptane, octane, toluene, etc.) or their halo derivatives (fluoro, chloro , bromo-, iodobenzene, CH ₂ Cl ₂ , CH ₂ Br ₂ , 5 ethylene chloride, etc.) in the presence of an emissator consisting of an organoaluminum compound of the formula A1K _p Xs-p (where K is as defined above, X is Halogen, n = 1–3), vanadium compounds, except US1 ₄ (for example, UR ₄ , UVR ₄ , CA, UOH ₃ , - OS (OK) tHC-t "ΟνΟδΗζΟί) ^ ™, where K 'is alkl, aryl, X - halogen, t - = 1, 2), and element hydroxides with Prichard electronegativity <2.2 [2].

From the disadvantages of this method it should be noted:

1. Low temperatures for carrying out the copolymerization [in the examples, predominantly lower (—30) ° C].

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2. Low molecular weight 'of the obtained copolymers (more than 8Ϊ) weight. % of the obtained copolymers is dissolved in methyl ethyl ketone). The latter dissolves only oligomers. Higher molecular weight fractions of alternating copolymers dissolve in diethyl ether.

3. High costs of the catalyst for the copolymer formed (for example, 0.5 mmol A1KpChz-n and above).

There is also known a method of producing alternating copolymers of butadiene and "-olefins of the general formula CH ₂ = SNK, where K is phenyl, cycloalkyl or alkyl with Οι-β, in a hydrocarbon solvent. Under the influence of a catalytic system consisting of dialkylglu dideluminium of the general formula ACCH ₂ C1 ( where K is alkyl, aryl, cycloalkyl) and a complex compound of vanadium, for example (C ₅ H ₅ ) ₂ US1 ₂ ; (C ₅ H ₇ O ₂ ) OOS1 ₂ ;

, (C ₅ H ₇ O ₂ ) ₃ U, etc., or the vanadium salt of an organic acid, for example

PP (CH ₃ COO) ₂ [3].

Nedbstatkami this method are:

1. Considerable expenses of the catalyst (0.5 mmol 'y above the compounds' of vanadium and 2 mmol and higher ASCH ₂ C1 per 1 g of the copolymer).

2. Low molecular weights of the copolymers obtained at the Utroyteleno-Jaeabioe conversion [η]? //, 0.1 dl / g; conversion 8-30 weight. %

The closest to the invention is a known method for producing alternating copolymers by copolymerizing butadiene with propylene in a hydrocarbon solvent medium in the presence of an organometallic complex catalyst consisting of chloroalkyl aluminum and vanadium compounds of the total ‘formula‘ UO (OK) where 1? - alkyl, cycloalkyl or aryl, n = 1-3 = [4].

The disadvantages of this method are:

1. Low yields of copolymers - from 10 to W (at Polymerization Temperature (—30) - (- 40) ° С.

“2. ^; High catalyst costs (1'mmol and higher of the compound 'Vanadium and' 5 mmol and higher of A1C ₂ C1 per g of copolymer).

‘The purpose of the invention is to 'yield' the yield of the final product as a catalyst unit. —'S

This "goal is achieved by the idea that the catcher, consisting of the aluminum alkyls and the single ones, came to be the ''sb'e'dine'and the transitional M'ethall of the general formula O (Ο8ΐΚ ₂ ) _η 0ΐ4_ _π _ _Π ιΟ „ _Ι)

where <3 — V or Τΐ, K is aryl or CP — C ₄ is alkyl, t = 0—1, n — A — 3, with a molar ratio of aluminum alkyls and transition metal compounds from 2: 1 to 20: 1.

Catalyst 'Prepared at (—100) -

(—30) ° С, preferably (—80) -

(-40) ° C.

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The essence of the method is that alternating copolymerization of butadiene with propylene at their molar ratio in the 4: 1 ^: -1: 4 reaction zone is produced in a hydrocarbon solvent, for example benzene, toluene, gasoline, pentane, isopentane, hexane, heptane, cyclohexane, etc. ., at a temperature of (—100) - (+ 50) ° C under the influence of a catalytic system consisting of one or two organoaluminum compounds of one or two compounds of canadium or titanium, obtained by reacting at a temperature of (—100) - (—30) ° C, preferably (—80) -

(—40) ° C, an organoaluminum compound with a compound of vanadium or titanium, taken in a molar ratio of from 2: 1 to 20: 1, preferably from 2: 1 to 6: 1, respectively.

The copolymer is isolated from the solution, for example, by treating the polymerizate with a precipitant (alcohol) or by water degassing,> and dried, for example, by heating in vacuum.

The microstructure and composition of the copolymers obtained are studied by IR and NMR spectroscopy.

Example 1. To a solution of 0.14 mmol UOS1 ₂ O51 (CH ₃ ) s in 40 ml of toluene is added at a temperature of (—78) ° C 0.3 mmol A1 (1-C ₄ Ne) _3 and the complex formed is maintained at this temperature 20 minutes. Then 0.024 mol of butadiene and 0.093 mol of propylene are added to the solution of the complex. The copolymerization is carried out at a temperature of (+ 20) ° C for 20 h.

The polymer is treated with ethanol acidified with hydrochloric acid. The precipitated copolymer is separated from the mixture of the precipitant with the solvent and dried in vacuo.

The output of the copolymer of 30% of theoretical, in diethyl ether dissolves 86 weight. % copolymer, [η] ® ^ 0.62 DL / g.

Prim'er 2. To a solution of 0.14 mmol UOS1 ₂ 051 (SP ₃ ) s in 40 ml of toluene is added at a temperature of (—78) ° С 0.51 mmol AG (/ - C ₄ Y ₉ ) s and the resulting Complex is maintained 'at this temperature 20 min. The remaining operations are the same as in example.re'1.

The output of the copolymer 43% of theoretical, the solubility in diethyl ether 92 weight. ·% Copolymer, [η] ^ _0Λ 0.32 dl / g.

Example 'W. To a solution of 0.14 mmol UOS1 ₂ 051 (CH ₃ ) s in 40 ml of toluene is added at a temperature of (—78) ° C 1.01 mmol D1 (ί-Ο ₄ Η ₉ ) _3 'and the complex formed is maintained at this temperature 20 min. (The remaining operations are the same as in example 1.

The output of oopolymer'a'68% of theoretical, 'solubility in diethyl ether 96 weight. % copolymer, [η] “^ _{θ / |} 0.315 dl / g.

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Example 4. The conditions are the same as in Example 3, but 0.024 mol of butadiene and 0.067 mol of propylene are added to the complex solution.

The output of the copolymer 70% of theoretical; solubility in diethyl ether of 89 wt. % copolymer, [C]? ” _L at _OL 0.41 dl / g.

Example 5. The conditions are the same as in Example 3, but 0.024 mol of butadiene and 0.024 mol of propylene are added to the complex solution.

The output of copolymer 75% of theoretical; solubility in diethyl ether 93 wt. % copolymer, [c] ^ _L at _0L 0.4 dl / g.

Example 6. To a solution of 0.1 mmol UOS1 ₂ O51 (CH,) s in 40 ml of toluene is added at a temperature of (—78) ° C 1.17 mmol A1 ([- C ₄ H ₉ ) ₃ and the resulting complex is maintained at this temperature 20 min. The remaining operations are the same as in example 1, but the copolymerization is carried out at a temperature of (—35) ° C for 72 hours.

The output of the copolymer of 36% of theoretical, the solubility in diethyl ether 85 weight. % copolymer, [p] ^ _L at _0L 0.4 _DL / g.

Example 7. To a solution of 0.1 mmol UOS1 ₂ O51 (CH3) s in 40 ml of toluene is added at a temperature of (—50) ° C 1.0 mmol A1 (+ C ₄ H ₉ ) ₃ and the complex formed is maintained at this temperature 20 minutes. The remaining operations are the same as in example 1 ·

The output of the copolymer 60% of theoretical; solubility in diethyl ether

93 wt. % copolymer, [C] ^ _L in _OL 0.37 DL / g.

Example 8. The conditions are the same as in example 3, but the copolymerization is carried out ¹ at (+ 40) ° C. The output of the copolymer 52 '% of theoretical, the solubility in diethyl ether 87 weight. % copolymer, [l] „° _L for _OL 0.22 dl / g.

Example 9. The conditions are the same as in example 3, but the copolymerization is carried out at (—60) ° C for 72 hours.

The output of the copolymer 43% of theoretical, solubility in diethyl ether

94 wt. % copolymer, 0,42 DL / g

Example 10. To a solution of 0.1 mmol νθ01 '[05ϊ (CH ₃ ) ₃ ] ₂ in 40 ml of toluene is added at a temperature of (—40) ° C 0.4 mmol A1 (/ - C ₄ H ₉ ) ₃ and the resulting complex at this temperature for 20 min. The remaining operations are the same as in example 1.

The output of the copolymer of 28.5% of theoretical, the solubility in diethyl ether 75 weight. % copolymer, [c] ^ _l y _0l 0.85 dl / g.

Example 11. To a solution of 0.1 mmol

WOS1 [051 (CH ₃ ) h] ₂ in 40 ml of toluene is added at a temperature of (-78) ° С 0.4 mmol

A! (1-С ₄ Н ₉ ) ЗС1 and stand up to form 6 "

Complex at this temperature for 20 minutes. The remaining operations are the same as in example 1.

The output of the copolymer of 15% of theoretical, the solubility in diethyl ether 60 wt. % copolymer, [n]? ° _L at _0L 0.67 dl / g.

Example 12. To a solution of 0.1 mmol UOS11 [O51 (CH3) ₃ ] ₂ in 40 ml of toluene is added at a temperature of (—78) ° C 0.4 mmol A1C ₂ H ₅ SG ₂ and the resulting complex is maintained at this temperature for 20 minutes . The remaining operations are the same as in example 1.

The output of the copolymer of 16% of theoretical, the solubility in diethyl ether 45 weight. % copolymer, [η] ^ ₀ 0,2 0.21 dl / g.

Example 13. To a solution of 0.069 mmol νΟφΟδί (CH ₃ ) s] s in 40 ml of toluene is added at a temperature (—78) ° C 0.14 mmol

A1 (1-C ₄ H ₉ ) s and after 20 min. 0.14 mmol A1 (/ -C ₄ H ₉ ) ₂ C1.

The resulting complex is kept for 20 minutes at a temperature of (—78) ° C. The remaining operations are the same as in example 1.

The output of the copolymer of 10% of theoretical, the solubility in diethyl ether 87 weight. % copolymer, [η] ^ _0Λ 0.61 dl / g.

Example 14. The conditions are the same as in example 13, but AG (/ - C ₄ 9 ₉ ) s are added in the amount of 0.28 mmol and Α1 (ΐ-Ο ₄ Η ₉ ) ₂ Ο1 · -

0.28 mmol.

The output of the copolymer 21% of theoretical; solubility in diethyl ether 93 wt. % copolymer, [n] ^ _L in _OL 0.25 dl / g.

Example 15. At a temperature of (+ 20) ° C p 40 ml of toluene, 0.28 mmol A1 (/ - C ₄ H ₉ ) s and 0.28 mmol A1 (1-C ₄ H ₉ ) ₂ C1 are added and kept 20 min at this temperature. Then, at a temperature of (–78) ° C, 0.069 mmol EO [O51 (CH ₃ ) s] s is added to the resulting solution, the resulting complex is maintained at (–78) ° C for 20 min. The remaining operations are the same as in example 1.

The output of the copolymer 20% of theoretical, the solubility in diethyl ether 95 weight. % copolymer, [n] ^ _L y _OL 0.32 dl / g.

Example 16. To a solution of 0.069 mmol UO [051 (CH ₃ ) s1z in 40 ml of toluene at a temperature of (—78) ° C, 0.57 mmol A1 (/ -C ₄ H ₉ ) ₂ C1 is added and the resulting complex is maintained at this temperature 20 minutes. The remaining operations are the same as in example 1.

The output of the copolymer is 16% of theoretical, the solubility in diethyl ether 84 weight. % copolymer; [p] ® ° _L at _0L 0.17 dl / g.

Example 17. At a temperature of (+ 20) ° C, 0.035 mmol νΟΓΟδί (CH ₃ ) s] and 0.035 mmol UOS1 ₂ O51 (CH ₃ ) s are added to 40 ml of toluene and the mixture is kept at this temperature for 30 minutes. Then at a temperature of (–78) ° C to the resulting solution

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0.21 mmol A1 (1-C ₄ H ₉ ) _{3 is} added. The complex formed at (—78) ° C is kept for 20 min. The remaining operations are the same as in example 1.

The output of the copolymer 49% of theoretical, the solubility in diethyl ether 94 weight. % copolymer, [toluene ^{dl / g} Example 18. The conditions are the same as in example 17, but Α1 (Ϊ- € ₄ Η ₉ ) ₃ add 0.344 mmol.

The output of the copolymer 60% of theoretical, the solubility in diethyl ether 91.4 weight. % copolymer, [d] ® _L Wal ° - ⁴ DL / ^g ·

Example 19. The conditions are the same as in example 17, but A1 (1'-C ₄ H ₉ ), 0.693 mmol is added.

The output of the copolymer 62% of theoretical; solubility in diethyl ether 95.9 weight. % copolymer, [C] ® ° _L at _0L 0.4 _DL / g.

Example 20. The conditions are the same as in example 17, but instead of 40 ml of toluene take 40 ml of hexane.

The output of the copolymer 52% of theoretical, the solubility in diethyl ether

ten

20

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room an example NMR spectroscopy method • IR spectroscopy method The content of propylene units, they say. % The microstructure of the butadiene part of the chain, mol. % 1.2 Cis-1,4 trans-1,4 winlenden one 50.0 2 6 91 one 2 51.3 one eight 89 2 3 50.3 2 eight 88 2 four .. 49.2 2 five 91 2 five 51.0 3 four 92 one 6 52.4 2 3 94 one . 7 48.5 2 7 90 one eight 52.5 7 6 84 3 9 49.5 2 2 94 2 ten 47.5 2 - 96 2 eleven •. 55 2 - ⁹² 6 12 48 2 93 five 13 51.8  - -  14 · 48.4 2 , 7 87 four 15 51.3 . 2 . · -7 85. 6 sixteen ....... 50.3 ' 3 : 6 85 - 17 49,6 five , 9 '86 - 18 . 50.0. five 9 86 - nineteen 51-, 5 ': 3 9 87 · one 20 45.0 18 34 48 -

Example 23. To a solution of 0.035 mmol UOS1 ₂ O51 (CH ₃ ) s in 40 ml of toluene at a temperature of (—78) ° C is added .0.693 mmol A1 (1-C ₄ H ₉ ) ₃ and the complex formed is maintained at this temperature 20 min. The remaining operations are the same as in example 1.

89 wt. % copolymer, [d] ^ ° _L at _0L 0.67 _DL / g.

The composition and microstructure of the copolymers obtained in examples 1-20 are given in table. one.

Example 21. To a solution of 0.6 mmol Τί [Οδί (CH ₃ ) h] C1 ₃ in 20 ml of toluene at a temperature of (—78) ° C add 2 mmol A1 (g – C ₄ Nd) ₃ and maintain the resulting complex at this temperature 40 min. Then, 0.025 mol of butadiene and 0.1 mol of propylene are added to the solution of the complex. The copolymerization is carried out at a temperature of 25 ° C for 24 hours. The remaining operations are the same as in example 1.

The output of copolymer 22% of theoretical, in diethyl ether dissolves

90 weight. % copolymer, [q]? _{) L} at _0L 0.4 _DL / g.

Example 22. The conditions are the same as in example 21, but the copolymerization is carried out at (—30) ° C. The output of the copolymer is 20%, [η] ^ _ol 0.6 dl / g.

Solubility in diethyl ether 60 wt. % copolymer.

Table!

The output of the copolymer is 70% of theoretical, solubility in diethyl ether is 97 wt. % copolymer, [p] ® ° _L y _0L 0.25 dl / g.

Example 24. To a solution of 0.1 mol OOS1 ₂ O51 (CH ₃ ) ₃ in 40 ml of toluene with the same 761485

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1.0 mmol A1 (1-C ₄ H ₉ ) s are added to the experiment (—30) ° C and the resulting complex is kept at this temperature for 20 minutes. The remaining operations are the same as in example 1.

The output of the copolymer 42% of theoretical; solubility in diethyl ether 84 wt. % copolymer, [n] * ° _L at _0L 0.43 dl / g.

Example 25. The conditions are the same as in example 10, but the catalytic complex is formed at a temperature of (–100) ° C and maintained at this temperature for 1 hour.

The output of copolymer 72% of theoretical, the solubility in diethyl ether

98.5 weight. % copolymer; [toluene dl / g.

Example 26. To a solution of 0.13 mmol νθ (31 ₂ Ο5ϊ (CH ₃ ) s in 40 ml of toluene, 0.28 mmol A1 (g-C ₄ H ₉ ) ₃ ) is added at a temperature of (—78) ° C and the resulting complex is maintained At this temperature, 20 minutes Then 0.024 mol of butadiene and 0.093 mol of propylene are added to the complex’s solution.The copolymerization is carried out at (+ 20) ° C for 20 h. The polymer is treated with ethanol and acidified with hydrochloric acid. The precipitated copolymer is separated from the precipitator-solvent mixture and dried in vacuum at a temperature of 30-50 ° C.

The output of the copolymer 53% of theoretical; 88 wt. is dissolved in diethyl ether (DEE). % copolymer, [η] ^ £ _Μ 0.5 dl / g.

The content of propylene units 50,4 mol. %

Example 27. To a solution of 0.07 mmol UOS11 [O81 (CH3) s] ₂ in 40 ml of toluene is added at a temperature of (—40) ° C 0.28 mmol A1 (g – C ₄ H ₉ ) ₃ and the complex formed is maintained at this temperature is 20 min. The remaining operations are the same as in example 1.

The output of the copolymer 67 wt. % of theoretical, solubility in DEE is 91.4% of copolymer, [c] ^ _ol 0.4 dl / g.

The content of propylene units

49.6 mol. %

Example 28. To a solution of 0.1 mmol UOS11 [O51 (CH ₃ ) h] ₂ in 40 ml of toluene is added at a temperature of (–78) ° С 0.475 mmol A1 (1-C ₄ H ₉ ) ₂ C1 and the complex formed is maintained at this temperature is 20 min. The remaining operations are the same as in example 1.

The output of the copolymer of 40.2% of theoretical, the solubility in the DEA 95,8% of the copolymer, [ηΐχ $ _οΛ 0.3 _DL / g

Example 29. The conditions are the same. that in example II, but instead of A1 (1-C ₄ H ₉ ) ₂ C1, 0.475 mmol A1C ₂ H ₅ C1 is added.

The output of the copolymer 60% of theoretical, the solubility in the DEA 60% copolymer,

Lluol °> ²²

Example 30. To a solution of 0.069 mmol

WOS1 [Ο5ΐ (CH ₃ ) s] s in 40 ml of toluene was added

at a temperature of (—78) ° C 0.44 mmol A1 (/ - C ₄ H9) s (A1 / V = 6) and the resulting complex is kept at this temperature for 20 minutes. Then 0.024 mol of butadiene and 0.072 mmol of propylene are added to the solution of the complex. The remaining conditions are the same as in example 1.

The output of the copolymer of 62.3% of theoretical, the solubility in the DEA 95.5% of the copolymer, [t}] Hu _0L 0.32 _DL / g The content of propylene units 51,5 mol. %

Example 31. The conditions are the same as in example 13, but add 0.552 mmol A1 (/ - C ₄ H ₉ ) s (A1 / Y = 8).

The output of the copolymer is 75.8% of theoretical, the solubility in DEE 93% of the copolymer, [< _o ° C _UL 0.33 _DL / g.

The content of propylene units 48 mol. %

Example 32. The conditions are the same as in example 13, but the copolymerization is carried out at a temperature of (—35) ° C.

The output of the copolymer 75% of theoretical, the solubility in the DEA 99% of the copolymer, Vdol 0.29 DL / g

The content of propylene units in ce-. pi 50.9 mol. %

The microstructure of the butadiene part of the chain of the copolymers obtained in Examples 26–32 is given in Table. 2

I

Example 33. The conditions are the same as in example 14, but the copolymerization is carried out at a temperature of (—35) ° C.

The output of the copolymer of 91.2% of theoretical, the solubility in the DEA 99% of the copolymer, [psch _ol 0.33 DL / g

The content of propylene units

52.9 mol. %

The microstructure of the butadiene part of the chain, mol. %:

1,2 cis-1,4 trans-1,4 vinylidene

1 17 82

Example 34. To a solution of 0.5 mmol ΤίΓΟδΐ (CH ₃ ) C1 ₃ in 40 ml of toluene, 0.17 mmol A1 (1-C ₄ Nd) is added at a temperature of (—78) ° C and the resulting complex is maintained at this temperature 40 minutes Then, 0.025 mol of butadiene and 0.1 mol of propylene are added to the solution of the complex.The copolymerization is carried out at 25 ° C for 24 h.

The remaining operations are the same as in example 1.

The output of the copolymer 47% of theoretical, the solubility in the DEA 90% copolymer, MHUOL ° ^{4 dl / g} ·

Thus, the proposed method for producing alternating copolymers of butadiene with propylene can reduce the consumption of catalyst, especially vanadium compounds; per unit weight

eleven

table 2

room an example The microstructure of the butadiene part of the chain, mol. % five 1.2 cis-1,4 t run1,4 vinylidene 26 3 6 91 one 27 five 9 86 - 28 one 7 92 four ten 29 2 - 98 four thirty four· 3 93 one 31 four 21 75 one 32 2 3 95 - 15

Limera (0.02 mmol of vanadium compound per 1 g of the copolymer compared with 0.5 mmol). 20

The possibility of obtaining alternating copolymers with a sufficiently high yield (up to 75% at 20 ° C) at a temperature of copolymerization (+ 20) ° C and higher allows you to reduce the cost of technological design 25 process, since there is no need for expensive low-temperature refrigeration units of high power.

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Claims (1)

Claim The method of obtaining alternating copolymers by copolymerization of butadiene with propylene in the medium of a hydrocarbon solvent in the presence of a complex organometallic catalyst, characterized in that, in order to increase the yield of the final product per unit of catalyst, a catalyst consisting of one or two alkyls of aluminum and one or two transition metal compounds is used formulas O (O51K ₅ ) "C14 — p— _t O _t , where (3 = ν or Τϊ, K is aryl or C] —C ₄ is alkyl, t = 0-1, / g = 1-3, with a molar ratio of aluminum alkyls and transition metal compounds from 2: 1 to 20: 1.