Catalytic system for alternating copolymerization of carbon monoxide and olefins and method for producing alternating copolymers of carbon monoxide and olefins

 

(57) Abstract:

The invention relates to the synthesis of alternating copolymers of carbon monoxide and olefins under the action of catalysts containing phosphine palladium salt and an organic boron salt. Describes a catalytic system for alternating copolymerization of carbon monoxide and olefins on the basis of salts of palladium acetate or palladium acetylacetonate, bodyperformance and organic salts of boron. As the organic boron salt it contains a compound of General formula XB(C6F5)4where X is dialkylanilines or triarylmethyl group, and the molar ratio of organic salts of boron to palladium salt is 0.5 - 10, and the molar ratio of compounds of the phosphine to palladium salt is 1.1 to 2.0. The technical result - the possibility of carrying out the process of copolymerization of carbon monoxide and olefins under conditions of stationary action of the catalyst. The invention can be used in the technical industry for a new generation of functional copolymers. 2 S. and 4 C.p. f-crystals.

The invention relates to the creation of catalytic systems and the synthesis of alternating copolymers of carbon monoxide and olepi the ranks industries for various structural materials, composites ingredients to the materials of organic and inorganic origin. There are various ways to obtain alternating copolymers based on carbon monoxide and various monomers. Enough details are described and analyzed in reviews [Drent, P. H. M. Budzelaar. Chem. Rev. 1996, v.96, R. 663, G. P. Belov. Polymer sciense ser. connections, vol.B. 1998, T. 40, N 3, S. 503].

Known methods for producing alternating copolymers of olefins and carbon monoxide in the liquid phase in the presence of a catalytic system containing a palladium salt, a bidentate phosphine ligand and an acid having a pKa of 2 [E. Drent. EP a) 0121965 A1, 1984. b) 01810l4 A1, 1986. c) 0272728 A1, 1987, E., Chaikin, A. P., Bezruchenko, G. P. Belov. Pat.RF 1636417, B. I., 1991, No. 4, S. 76] .

The main disadvantages of these methods are:

the relatively low outputs copolymers,

- use as a component of the catalyst is highly corrosive acids (for example, CF3COOH [E. Drent. EP a) 0121965 A1, 1984. b) 01810l4 A1, 1986. c) 0272728 A1, 1987] or even carrying out copolymerization process in the environment of glacial acetic acid [E., Chaikin, A. P., Bezruchenko, G. P. Belov. Pat.RF 1636417, B. I., 1991, No. 4, S. 76].

Known methods for producing the above copolymer in the presence of the catalytic system is. The R 0592531 A1, 1996. d) Sommazzi A. et al. EP 0774479 A1, l997. e) Baardmaan F. et al. EP 0702046 Al, 1995. g) Cooly N. A. et al. EP 0619335 A1 and EP 0704471 A1, 1995. f) Conves Z. W. et al.EP 0722968 Al, l995. i) Baardmaan F. et al. EP. 0733660 A1, 1996].

Typically, in these methods, the receiving alternating copolymers of carbon monoxide and olefins (as a double, for example CO - ethylene and a triple, for example ethylene - CO - propylene) in the presence of a pre-prepared catalytic complex based on Pd(CH3COO)2and diphenylphosphinite (for example, diphenylphosphane). The copolymerization process is carried out at a temperature of 20 - 95oC, preferably 70-90oC and the total pressure of a Monomeric mixture of carbon monoxide and olefin 1-200 bar, preferably from 20 to 100 atmospheres, i.e., 2-10 MPa.

Specially the resulting complex is then dissolved in a suitable haloesters solvent (e.g. dichloromethane) and loaded into the reactor in the form of a solution after the reactor is already loaded with the desired amount of solvent (e.g. dichloromethane or methanol), an organic boron salt (for example, (C6F5)3B) in the reactor filed the required pressure of CO (0.1-10 MPa) and ethylene and implemented heating the reaction mass to the desired temperature (preferably 70-90o
unstable in time responsiveness: it is high in the first minutes of the reaction and decreases rapidly in time (after 1 hour, the speed is reduced by 80-90%). This disadvantage can be partly resolved if added to the reactor before the reaction of small amounts previously received alternating copolymer of carbon monoxide and ethylene [Baardmaan F. et al. EP 0733662 A1, 1996].

Closest to the proposed invention is a catalytic system and method described in the patent Baardmaan F. et A1. EP 0733662 A1, 1996.

The process of copolymerization of CO and olefins is carried out similarly to that described above (i.e., at temperatures up to 90oC and pressure up to 5 MPa). The difference is that by replacing haloesters solvent of methanol and the reduction of the molar ratio of boron salt (preferably B(C5F5)3) to the compound of palladium to 1-2 speed copolymerization, at least within one hour remained constant (2,7-3,0 kg/gPdhour), but lower compared with the process in the environment haloesters solvent (10,7-5.4 kg/gPdhours).

The task of the invention is razresheniya alternating copolymers of carbon monoxide and olefins under conditions of stationary action of the catalyst, i.e. when the rate of copolymerization is practically unchanged for several hours.

The problem is solved due to the fact that as a component of a catalytic system containing a salt of palladium and a bidentate phosphine ligand charge of the organic boron compound of General formula XB(C6F5)4where X is dialkylanilines group - R2NH(C6H5), for example dimethyl, diethyl, dipropyl, aminobutiramida, dibutil, Diisobutylene and the like; or organic boron compound, where X is tiarella group, for example triphenylethylene - (C6H5)3C. When the molar ratio of boron salt to the compound of palladium take in the range of from 0.5 to 10, preferably 1-2.

Preferably in this invention take diethylenetriaminepentaacetic - (CH3)2NH(C6H5)B(C6F5)4or triphenylmethylenephosphorane - (C6H5)3CB(C6F5)4.

In addition, the task is solved by the proposed method of obtaining alternating copolymers of carbon monoxide and olefins by the reactions of copolymerization of these monomers in the liquid phase at a temperature of 20-95oC when the ol boron General formula XB(C6F5)4where X is dialkylanilines group or tiarella group, preferably (CH3)2NH(C6H5)B(C6F5)4or (C6H5)3CB(C6F5)4.

The process of alternating copolymerization of carbon monoxide and olefins in the presence of these organic salts of boron helps to make the process of obtaining alternating copolymers of carbon monoxide and olefins, more manageable, because the reaction rate remains almost constant for many hours even before you obtain a very dense suspensions of polymer in the reactor (up to 300 g/l) that cannot be achieved using other well-known from the patent sources salts of boron or other activators.

Carrying out the proposed method of producing alternating copolymers of carbon monoxide and olefin as the olefin can be used: ethylene, propylene, butene-1, penten-1 and cyclopentene, hexene-1, octene-1 and other higher alpha-olefins, preferably ethylene and propylene.

As the reaction medium can be preferably used proton solvents (for example, lower aliphatic alcohols, preferably met themes used:

salts of palladium, preferably can be used Pd(CH3COOH)2or Pd(C5H7O2)2,

- bidentate phosphine ligands, bis-diphenylphosphinoethyl, preferably bis-diphenylphosphinoethyl.

The molar ratio of phosphine to the compound of palladium is preferably 1.1 to 2. The process of copolymerization at a higher or lower molar relationship leads to unstable speed copolymerization and the reduction of the yield of copolymer.

The molar ratio of boron salt to the compound of palladium 0.3 to 3, preferably 1-2.

Thus, the analysis of the existing scientific-technical and patent literature showed that the stated set of characteristics meets the criterion of industrial applicability, and also confirms the compliance of the claimed invention, the criteria of novelty and significant differences.

The invention is illustrated by the following examples.

Example 1 (for comparison, prototype)

A copolymer of carbon monoxide and ethylene was obtained as follows.

In a pre-heated and rolled back the vacuum pump reactor with a volume of 250 ml was loaded solution (C6F5)3B (0.05 mperature 90oC and even added an equimolar mixture of monomers to 40 ATM, and then introduced into the reactor a solution of equimolar mixture of Pd(CH3COO)2(0,025 mmol) (B/Pd= 2) and diphenylphosphane in 20 ml of methanol. The copolymerization reaction of ethylene and begins immediately after the introduction of this solution. The pressure in the reactor is maintained by adding equimolar mixture of monomers from a measuring cylinder. The initial reaction rate was 2.2 kg of copolymer/gPdhour, and after one hour it was equal to 1.8 kg/gPdhour. Thus, the speed reduction occurred by 18.2%.

Example 2

A copolymer of ethylene and carbon monoxide was obtained analogously to example 1, except that as the salt of boron was taken onlinepropecia salt of boron -(CH3)2NH(C6H5)B(C6F5)4. The initial rate of the copolymerization reaction was equal 2,45 kg/gPdhour, and after one hour she remained the same. Only after 4 hours, the rate decreased by 6% and was equal to 2.35 kg/gPdhour, the concentration of the suspension of polymer in the reactor was equal to 240 g/l, i.e., it was already thick enough. Perhaps the observed decrease in the rate of copolymerization primarily due to difficulties ravnomernost.

Example 3

A copolymer of ethylene and carbon monoxide was obtained analogously to example 1, except that as the salt of boron was taken (C6H5)3CB(C6F5)4. The initial rate of copolymerization was 2,38 kg/gPdhour, after one hour there was no speed decrease, and after 4 hours the speed is decreased by 10% and was equal to 2.14 kg/gPdhour.

Example 4

Copolymer of ethylene, carbon monoxide and propylene was obtained analogously to example 2, except that the reactor after loading salt of boron was loaded with 15 g of propylene. The initial rate of the copolymerization 2,32 kg/gPdhour, after one hour it was down 3%, and 4 hours by 11%.

Example 5

A method of producing a copolymer of ethylene and carbon monoxide is carried out analogously to example 2, except that boron salt take in the amount of 0.025 mmol (B/Pd=1). The initial rate of copolymerization was 2.4 kg/gPdhour, and four hours later it dropped to 2.1 kg/gPdhour, i.e. 8.8%.

Example 6

A method of producing a copolymer of ethylene and carbon monoxide is carried out analogously to example 2, except that the temperature of the 50oC and as salts of boron taken the/gPdhour, and after 3 hours it dropped to 1.7 kg/gPdhour, i.e. by 5.6%.

Example 7

A method of producing a copolymer of ethylene and carbon monoxide is carried out analogously to example 2, except that as the salt taken palladium acetylacetonate, palladium - Pd(C5H7O2)2. The initial rate of the copolymerization at 70oC was 1.5 kg/gPdhour, and after 5 hours it dropped to 1.35 kg/gPdhour, i.e. 10%.

Thus, the above examples clearly show that the inventive catalyst system allows for the process of obtaining alternating copolymers of carbon monoxide and olefins in a long time in conditions of stationary action of the catalyst.

1. Catalytic system for alternating copolymerization of carbon monoxide and olefins on the basis of salts of palladium acetate or palladium acetylacetonate, bodyperformance and organic salts of boron, wherein as the organic boron salt it contains a compound of General formula

XB(C6F5)4,

where X is dialkylanilines or triarylmethyl group,

moreover, the molar ratio of the organic boron salt to salt pall is Analiticheskaya system on p. 1, characterized in that as the organic boron salt it contains preferably compounds of the formula

(CH3)2NH(C6H5) B(C6H5)4< / BR>
or

(C6H5)3CB(C6F5)4.

3. The method of obtaining alternating copolymers of carbon monoxide and olefin copolymerization of these monomers in the solvent at a temperature of 20 - 95oIn the presence of catalytic systems on the basis of salts of palladium acetate or palladium acetylacetonate, bodyperformance and organic salts of boron, characterized in that the copolymerization is carried out in the presence of a catalytic system under item 1.

4. The method according to p. 3, characterized in that the copolymerization is carried out in the presence of a catalytic system under item 1, containing as organic salts of boron, preferably compounds of the formula

(CH3)2NH(C6H5) B(C6H5)4< / BR>
or

(C6H5)3CB(C6F5)4.

5. The method according to p. 3, characterized in that the copolymerization is carried out in the presence of a catalytic system under item 1, in which the molar ratio of organic salts of boron to palladium salt is predpochtitelnye alcohols, preferably methanol.

 

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