RU2570703C1 - Method for addition polymerisation of norbornene - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method includes polymerisation of norbornene using a catalyst obtained by reacting a cationic palladium complex and boron trifluoride etherate in an organic solvent medium in the presence of norbornene. Components are mixed in the following order: adding, to a norbornene solution in an organic solvent, e.g. methylene chloride, a solution of a cationic palladium complex in an organic solvent, e.g. methylene chloride, and then adding boron trifluoride etherate in pure form or in the form of a solution in an organic solvent, e.g. methylene chloride. The catalyst components used are palladium tetrafluoroborate (acetylacetonato)(α-diimine) of general formula [(acac)Pd(N^∧N)]BF₄, where acac is acetylacetonate, N,N are α-diimine ligands, such as bis[N-(phenyl)imino]acenaphthene, bis[N-(2,6-dimethylphenyl)imino]acenaphthene, N,N-(1,2-diphenylethane -1,2-diilydene)bis(2,6-dimethylaniline), bis[N-(2,6-diisopropylphenyl)imino]acenaphthene, N,N-(2,3-butanediilydene)bis(2,6-dimethylaniline), N,N-(2,3-butanediilydene)bis(2,6-diisopropylaniline). Optimum process conditions: molar ratio of boron to palladium, B:Pd=15:1-50:1, preferably B:Pd=25:1, with molar ratio of norbornene to palladium, NB/Pd=10000:1-50000:1, preferably NB/Pd=20000, at temperature 20-45°C.

EFFECT: simple method for addition polymerisation of norbornene in the presence of complexes of transition metals with α-diimine ligands.

1 tbl, 23 ex

Description

The present invention relates to the field of production of norbornene addition polymers (bicyclo [2.2.1] hepten-2) under the action of catalytic systems based on cationic complexes of palladium and boron trifluoride etherate. Additive polymerization proceeds with the opening of a double bond and leads to polymers containing unchanged cyclic structures in the main chain. Such polymers are characterized by good thermal and chemical stability, amorphous properties, high transparency in the IR, visible and UV regions, low refractive index, narrow decomposition temperature, and low dielectric coefficient. This makes them promising for the production of coatings in electronics, telecommunications materials, optical lenses, substrates for plastic displays, photoresistors, dielectrics for semiconductors.

Known in the literature are methods for producing additive norbornene (NB) polymers under the influence of palladium catalysts: (1) one-component palladium catalysts consisting solely of palladium-organic cationic complexes with bulk counterions (US 5468819, B. L. Goodall, GM Benedikt, LH Mcintosh III, DA Barnes, November 21, 1995; JP Mathew, A. Reinmuth, J. Melia, N. Swords, W. Risse // Macromolecules 29, 1996, 2755-2763); (2) neutral palladium complexes in combination with methylaluminoxane (MAO), triethylaluminum (AlEt3) or triisobutylaluminum (Al (i-Bu) 3) (EP 0445755, N. Maezawa, J. Matsumoto, H. Aiura, S, Asahi, June 17, 1998); (3) neutral palladium complexes in combination with tris (pentafluorophenyl) borate (B (C6F5) 3) and aluminum triethyl (US 6031058, LH Mcintosh III, L. Goodall, RA Shick, S. Jayaraman, February 29, 2000; PG Lassahn, C. Janiak, Jae-Seung Oh, Macromol. Rapid. Commun., 23, 2002, 16-20); (4) catalysts based on (1,5-cyclooctadiene) Pd (CH3) Cl in combination with PR3 and Na + [(3,5- (CF3) 2C6H3) 4B] - (A.D. Hennis, JD Polley, GS Long , A. Sen, D. Yandulov, J. Lipian, GM Benedikt, LF Rhodes, J. Huffman, Organometallics, 20, 2001, 2802-2812). The disadvantages of such catalytic systems include the use of expensive, unstable organometallic complexes of palladium, organoboron and aluminum compounds.

Also known are methods of additive polymerization of norbornene under the action of catalytic systems based on cationic complexes of palladium, nickel and boron etherate trifluoride: (1) Pat. 2383556 RF, IPC C08F 32/08, C08F 4/06, B01J 23/44. A method of obtaining additive polymers of norbornene / B.C. Weaver, D.S. Suslov, G. Myagmarsuren, F.K. Schmidt applicant and patentee Irkut. state un-t - No. 2007127169; declared 07/16/2007; publ. 03/10/2010. (2) Pat. 2315064 Russian Federation, IPC C08F 32/08, B01J 23/44, C08F 4/26. A method of obtaining a catalyst for the polymerization of norbornene / B.C. Weaver, G. Myagmarsuren, D.S. Suslov, F.K. Schmidt applicant and patentee Irkut. state un-t - No. 2006128296; declared 08/03/2006; publ. 01/20/2008. (3) Pat. 2414965 RF, IPC B01J 37/00, C07F 15/04, C07F 5/04, C08F 4/06, C08F 32/08. A method of obtaining a catalyst for the polymerization of norbornene / B.C. Weaver, D.S. Suslov, O.V. Gubaidulina, M.V. Bykov, O.I. Mysko; applicant and patentee Irkut. state un-t - No. 2009149724/04; declared 12/30/2009; publ. 03/27/2011.

The closest analogue of the proposed method is a method of additive polymerization of norbornene (Appukuttan V. Influence of type and positioning of N-aryl substituents on vinyl polimerisation of norbornene by Ni (II) α-diimine complexes / Appukuttan Vinukrishnan, Jin Hyuk Kim, Chang Sik Ha, Il Kim // Korean J. Chem. Eng. - V. 25 (3). - PP. 423-425. - 2008). In this example, the polymerization reaction is carried out in the presence of a nickel complex with α-diimine ligands, Br ₂ Ni (R ₂ BIAN), as a catalyst (where R = H, 2,6-Me ₂ , 2,6-Et ₂ , 2,6 -iPr ₂ , 2,3-Me ₂ , 2,4-Me ₂ , 2,5-Me ₂ , 3,5-Me ₂ , 2,4,6-Me ₃ ), methylaluminoxane (MAO) as a cocatalyst and toluene as a solvent under the following conditions: T = 30 ° C, Al / Ni = 2000, t = 30 min, [Cat] = 2.0-10 ^-4 M, [NB] = 1.59 M. The yields are from 14 to 71% . The disadvantage of this method is the use of self-inflammable in air organoaluminum compounds (MAO) as a cocatalyst, which significantly increases the risk and, therefore, complicates the process, and also requires the use of instruments and equipment for implementing the process in an inert atmosphere for implementing the process.

The present invention is to simplify the method of additive polymerization of norbornene in the presence of complexes of transition metals with α-diimine ligands.

The task is achieved in that cationic acetylacetonate complexes of palladium with α-diimine ligands are used as catalyst components, non-self-inflammable stable Lewis acid in air: boron etherate trifluoride, BF ₃ · OEt ₂ , and methylene chloride as a solvent. The reaction is carried out at room temperature. This implementation of the process greatly simplifies the achievement of the technical result due to the fact that there is no need to use instruments and equipment to implement the process in an inert atmosphere, in addition, the safety of the process is increased. In this case, tetrafluoroborate (acetylacetonato) (α-diimine) palladium of the general formula [(acac) Pd (N ^∧ N)] BF ₄ , where asac-acetylacetonate, N ^∧ N are α-diimine ligands, such as bis, are used as catalyst components [N- (phenyl) imino] acenaphthene (Ph ₂ BIAN), bis [N- (2,6-dimethylphenyl) imino] acenaphthene ((2,6-MePh) _2- BIAN), bis [N- (2,6 -diisopropylphenyl) imino] acenaphthene ((2,6- ⁱ PrPh) _2- BIAN), N, N- (2,3-butanediylidene) bis (2,6-dimethylaniline) ((2,6-MePh) ₂ DABMe ₂ ), N, N- (2,3-butanediylidene) bis (2,6-diisopropylaniline) ((2,6- ⁱ PrPh) ₂ DABMe ₂ ), N, N- (1,2-diphenylethane-1,2- diylidene) bis (2,6-dimethylaniline) ((2,6-MePh) ₂ DABPh ₂ ), N, N- (1,2-diphenylethan-1,2-diylide m) bis (2,6-diisopropylaniline) ((2,6- ⁱ PrPh) ₂ DABPh ₂ ).

The method is as follows.

A solution of norbornene in methylene chloride is poured into the flask, a solution of the palladium complex in a similar solvent is poured. Mix, pour the solution of socialization, the reaction is carried out for 30 minutes Polynorbornene is planted with ethanol.

The structure of the obtained polynorbornene was confirmed by IR spectroscopy. In the IR spectrum, no bands are observed in the region of 1620-1680 cm ^-1 from double bonds, but there are strong absorption bands in the region of 1452-1474 cm ^-1 from deformation vibrations of the bridging -CH ₂ - group of the norbornene ring.

The following examples illustrate the present invention.

EXAMPLE 1

A 5 ml solution of norbornene in methylene chloride containing 3.77 g (40 mmol) of norbornene was loaded into a 10 ml flask, then a solution of the complex (acetylacetonato-κ ² O, O ′) (bis [N- (phenyl) imino] acenaphthene) palladium tetrafluoroborate was added in methylene chloride (0.1 ml containing 0.002 mmol Pd). The polymerization was initiated by the introduction of a solution of boron trifluoride etherate in methylene chloride (0.1 ml of a solution with a concentration of C = 0.3 mol / L). The molar ratio of NB: B: Pd = 20,000: 25: 1, reaction time 30 min. The reaction was interrupted by the addition of ethanol, the precipitated polymer was washed three times with ethanol and dried in vacuum (1 mmHg) at 60 ° C for 6 h. The polymer yield was 3.755 g (99.6%).

EXAMPLES 2-6

These examples illustrate the effect of the B: Pd molar ratio on the polynorbornene yield. The reactions were carried out analogously to example 1. The results of the experiments are combined in Table 1.

Table 1 The effect of the molar ratio B: Pd on the yield of polynorbornene in the presence of the system: [(acac) Pd ((2,6- ⁱ PrPh) ₂ DABPh ₂ )] BF ₄ + nBF ₃ OEt ₂ (temperature 25 ° C, reaction time 30 min, 3.77 g NB, total volume 5.2 ml) No. B: Pd
rel. HB: Pd
rel. Amount of catalyst
10 ⁶ mol Exit,
% TOF
h ^-1 2 5 20,000 2.11 traces traces 3 fifteen 20,000 2.11 63.2 25200 four 25 20,000 2.11 72.3 28900 5 fifty 20,000 2.11 80.2 32000 6 one hundred 20,000 2.11 90.0 36000

EXAMPLES 7-9

These examples illustrate the effect of the NB / Pd ratio on polynorbornene yield. The polymerization was carried out analogously to example 1, the results of the experiments are presented in Table 2.

table 2 The effect of the NB / Pd ratio on the polynorbornene yield in the presence of the system: [(acac) Pd ((2,6- ⁱ PrPh) ₂ DABPh ₂ )] BF ₄ + 25BF ₃ OEt ₂ (temperature 25 ° C, 3.77 g NB, total volume 5.2 ml) reaction time,
min B: Pd
rel. HB: Pd
rel. Amount of catalyst
10 ⁶ mol Exit,
% TOF
h ^-1 7 60 25 50,000 0.844 62.1 31000 8 thirty 25 20,000 2.11 73.2 29300 9 2 25 10,000 4.33 82.2 246700

EXAMPLES 10-19.

These examples illustrate the effect of the nature of the α-diimine ligand on the yield of polynorbornene. The polymerization was carried out analogously to example 1, the results of the experiments are presented in Table 3.

Table 3 The effect of the nature of the α-diimine ligand on the yield of polynorbornene (temperature 25 ° C, reaction time 30 min, 3.77 g NB, total volume 5.2 ml) No. Diimin B: Pd
rel. NB: Pd
rel. Amount of catalyst
10 ⁶ mol Exit
% TOF
h ^-1 10 (2,6-MePh) ₂ DABPh ₂ 25 20000 2.11 37.6 15,000 eleven (2,6- ⁱ PrPh) ₂ DABMe ₂ 25 20000 2.11 9.1 3600 12 (2,6-MePh) ₂ DABMe ₂ 25 20000 2.11 Traces - 13 Ph ₂ DABMe ₂ 25 20000 2.11 6.6 2600 fourteen (2,6-MePh) ₂ DABH ₂ 25 20000 2.11 Traces - fifteen (2,6- ⁱ PrPh) ₂ DABH ₂ 25 20000 2.11 Traces - 16 (2,6-MePh) ₂ BIAN 25 20000 2.11 71.0 28,400 17 (2.6- ⁱ PrPh) ₂ BIAN 25 20000 2.11 Traces - eighteen (2,6-MePh) ₂ DABMe ₂ * 25 10,000 4.33 53.3 2600 19 (2,6- ⁱ PrPh) ₂ DABMe ₂ * 25 10,000 4.33 58.0 2900 twenty (2.6- ⁱ PrPh) ₂ BIAN * 25 10,000 4.33 13.5 700 * reaction time - 120 min

EXAMPLES 21-23

These examples illustrate the effect of reaction temperature on the yield of polynorbornene. The polymerization was carried out analogously to example 1, the results of the experiments are presented in Table 4.

Table 4 Effect of reaction temperature on the yield of polynorbornene (reaction time 30 min, 3.77 g NB, B / Pd = 15) No. Diimin Τ
° C HB: Pd
rel. Amount of catalyst
106 mol Exit,
% TOF
h ^-1 21 Ph ₂ BIAN 7 20,000 1.95 7.5 3000 22 Ph ₂ BIAN twenty 20,000 1.95 25.2 10080 23 Ph ₂ BIAN 45 20,000 1.95 60.7 24280

Claims (1)

The method of additive polymerization of norbornene by carrying out a reaction in an organic solvent in the presence of catalyst components — a transition metal complex with diimine ligands and a cocatalyst — Lewis acid, characterized in that palladium tetrafluoroborate (acetylacetonato) (α-diimine) of the general formula [ (acac) Pd (N ^∧ N)] BF ₄ , where acac is acetylacetonate, N ^∧ N are α-diimine ligands such as bis [N- (phenyl) imino] acenaphthene, bis [N- (2,6-dimethylphenyl ) imino] acenaphthene, N, N- (1,2-diphenylethan-1,2-diylide N) bis (2,6-dimethylaniline), as cocatalyst - boron trifluoride etherate, BF ₃ OEt Formula _2, the process is carried out in methylene chloride at a molar ratio of boron to palladium, B: Pd = 15: 1-50: 1, with a molar ratio of norbornene to palladium, NB / Pd = 10000: 1-50000: 1 and at a temperature of 20-45 ° C,
or as a catalyst, tetrafluoroborate (acetylacetonato) (α-diimine) palladium of the general formula [(acac) Pd (N ^∧ N)] BF ₄ , where acac is acetylacetonate, N ^∧ N are α-diimine ligands such as bis [N - (2,6-diisopropylphenyl) imino] acenaphthene, N, N- (2,3-butanediylidene) bis (2,6-dimethylaniline), N, N- (2,3-butanediylidene) bis (2,6-diisopropylaniline ), as a cocatalyst, boron trifluoride etherate of the formula BF ₃ OEt ₂ , the process is carried out in methylene chloride at a molar ratio of boron to palladium, B: Pd = 25: 1, at a molar ratio of norbornene to palladium, NB / Pd = 10000: 1 and at temperature 20-45 ° C.