Method of preparing catalyst for polymerisation of norbornene

FIELD: chemistry.

SUBSTANCE: disclosed method relates to preparing a catalyst for addition polymerisation of norbornene to polynorbornene. Described is a method of preparing a catalyst for addition polymerisation of norbornene based on complexes of zero-valent nickel and BF3OEt2 involving use of catalyst systems of the composition (L)nNi(PR3)2/BF3OEt2, where n=1, 2; L=PR3 or ethylene; R=Ph, OC6H4CH3-o combined with a controlled amount of water as a modifying component, and the process is carried out in a medium of organic solvent, e.g. toluene in molar ratio of boron to nickel B: Ni=50:1-600:1, ratio H2O/Ni=2-104 and temperature 10-80°C.

EFFECT: high efficiency of the norbornene polymerisation process.

3 tbl, 8 ex

 

The present invention relates to the field of production of the catalyst for addition polymerization of norbornene (bicyclo[2.2.1]heptan-2) in polynorbornene that are used for the production of coatings in electronics, telecommunications, materials, optical lenses, substrates for plastic displays, photoresistors for the production of chips and displays, dielectrics for semiconductor devices.

Additive polymerization proceeds with the disclosure of the double bond and leads to polymers containing unmodified cyclic structure in the main chain. Such polymers are characterized by good thermal and chemical stability, amorphous, high transparency in the infrared, visible and UV regions, low refractive index, a narrow decomposition temperature, isotropic dielectric properties. This makes them promising for the production of coatings in electronics, telecommunications, materials, optical lenses, substrates for plastic displays, photoresistors for the production of chips and displays, dielectrics for semiconductor devices.

Known catalysts for the addition polymerization of norbornene (NB): (1) single-component Nickel catalyst, presents cationic complexes with bulky counterions /US 6103920 C07F 15/04; C08F 4/06; C08F 4/70, 2000, US 5741869 C08F 4/80; C08F 32/08; C08F 4/00; C08F 32/00, 1998, US 5468819 C08F 4/70; C08F 4/30; C08F 442; C08F 32/00; 1995/; (2) neutral complexes of Nickel (II) in combination with methylaluminoxane (MAO), a combination of triethylaluminum (AlEt3) and Tris(pentafluorophenyl)borate (B(C6F5)3) /US 7247687 C08F 4/06; B01J 31/00; C07F 15/02 2006/, the combination of triisobutylaluminum and B(C6F5)3/US 5629398 C08F 4/54; C08F 4/602; C08F 4/64 1997/; (3) complexes of Nickel (0) in combination with a combination of AlEt3and(C6F5)3/ Y.Jang, H.-K.Sung, Lee, S., SWE, Polymer 46 (2005) 11301-11310/.

The disadvantage of such catalytic systems include the use of expensive, unstable ORGANOMETALLIC complexes of Nickel, boron and alyuminiiorganicheskikh connections.

The closest known solution of an analogous problem to the technical essence is a method of producing a catalyst for polymerization of norbornene by the interaction of tetranitroaniline Nickel (0) with efratom of boron TRIFLUORIDE /G.Myagmarsuren, AU-Yong Jeong, Son-Ki Ihm, Appl. Catal. A: Gen. 255 (2003) 203-209.

However, such catalytic systems are characterized by low reproducibility and spontaneous temperature rise process.

The task of the invention is to increase the efficiency of polymerization of norbornene.

This object is achieved in that in the method of producing a catalyst for addition polymerization of norbornene-based complexes nonvalence Nickel and BF OEt2during use of the catalytic system composition (L)nNi(PR3)2/BF3OEt2(where n=1, 2; L=PR3or ethylene; R=Ph, OC6H4CH3-Oh) in combination with controlled quantities of water as a modifying component and the process is carried out in a medium of an organic solvent, for example toluene, at a molar ratio of boron to Nickel:Ni=50:1-600:1, the ratio of H2O/Ni=2-104, a temperature of 10-80°C.

It is proposed to use catalysts based on compounds nonvalence Nickel in combination with efratom of boron TRIFLUORIDE and controlled quantities of water.

The hallmark of the present invention is the use of catalytic systems based on complexes nonvalence Nickel General formula (L)nNi(PR3)2(where n=1, 2; L=PR3or ethylene; R=Ph, OS6H4CH3-Oh), water and epirate of boron TRIFLUORIDE of formula BF3OEt2.

The method is as follows.

The method consists in the interaction of compounds of Nickel, water and epirate boron TRIFLUORIDE in the environment of an organic solvent, for example toluene. The components are mixed in the following order: a solution of norbornene in an organic solvent is injected with microprism the required amount of water, add a solution of compounds of Nickel (0) of General formula (L)nNi(PR3) (where n=1, 2; L=PR3or ethylene; R=Ph, OC6H4CH3-Oh) in an organic solvent; then enter athirat of boron TRIFLUORIDE. Optimal process conditions: molar ratio of boron to Nickel:Ni=50:1-600:1, preferably In:Ni=200:1-400:1, the ratio of H2O/Ni=2-104, preferably 6-25, the temperature of 10-80°C., preferably 25°C.

Norbornene and toluene previously dehydrated and Tegaserod boiling and subsequent distillation over sodium in the presence of benzophenone in an argon atmosphere.

The characteristic polymer viscosity is determined at 25°C. the solvent is 1,2,4-trichlorobenzene.

Additive patterns obtained polynorbornene confirmed by NMR and IR spectroscopy. The NMR spectrum1N bars are missing from the protons of the double bond. The IR spectrum of the sample polymers are characteristic absorption bands: 2946.95, 2867.12, 1474.04, 1452.52, 1363.38, 1294.36, 1257.71, 1220.05, 1145.55, 1108.23, 978.32, 940.01, 890.81, 813.40 and 774.15 cm-1. Strong absorption bands in the region 1452-1474 cm-1from δH-C-Hdeformation vibrations bridge CH2groups norbornene rings are a sign of additive 2,3-polymerization.

The following examples illustrate the present invention.

Example 1.

In pre-insulated and filled with inert gas (argon) 20 ml flask with a magnetic stir bar was loaded RAS is the thief of norbornene in toluene (80% mole.), containing 4.71 g (0.05 mol) of norbornene, the required amount of toluene (10 ml total reaction mixture)was added to microprism estimated amount of water that given a trace amount of water in the solvent and the norbornene defined by Fisher, was 9·10-5mol H2O, a solution of Ni(PPh3)4in toluene containing 1·10-5mol Ni. Polymerization was initiated by introducing BF3OEt2(4·10-3mol). The molar ratio of NB:B:Ni=5000:400:1. The reaction time was 30 minutes the Reaction was stopped by addition of acidified (HCl, 3% wt.) ethanol, planted the polymer was washed with ethanol three times and dried in vacuum (10 mm Hg) at 80°C for 6 hours, the polymer Yield was 3.00 g or 6383 mol polynorbornene per mole of Ni per hour. Characteristic viscosity in 1,2,4-trichlorobenzene at 25°C was 0.591 DL/g

Examples 2-8.

These examples illustrate the effect of the ratio H2O:Ni output and characteristic viscosity polynorbornene. The reaction was carried out similarly to example 1. The results of the experiments are combined in Table 1.

Table 1
Polymerization of norbornene. The system Ni(PPh3)4+nH2O+400BF3OEt2(NB/Ni=5000. The reaction time is 30 minutes. The number Ni - 1·10sup> -5mol. T=25°C. the Solvent is toluene. Total volume of the mixture -10 ml)
# exampleH2O/NiOutput, gSpeed, mol NB/mol Ni per hour[η] DL/gConversion, %
22*0,15319-3
340,714890,95315
4143,34371130,44371
5193,8581910,42482
6294,187230,44987
7543,95 84040,25484
81043,574470,22674
* - the sample is poorly soluble in 1,2,4-trichlorobenzene

Examples 9-15.

These examples illustrate the influence of the composition of complexes nonvalence Nickel and relationship B/Ni on the output, and the characteristic viscosity polynorbornene. The polymerization was carried out similarly to example 1, the results of the experiments are presented in Tables 2 and 3.

Table 2
Polymerization of norbornene. System (CH2=CH2)Ni(PPh3)2+6H2O+nBF3OEt2(Number Ni - 1·10-5mol. T=25°C. the Solvent is toluene. Total volume of the mixture to 10 ml)
# exampleB/NiOutput, gSpeed, mol NB/mol Ni per hour[η], DL/gConversion, %τ min
925- ---30
1050121280,242130
111001,327660,322830
122003191490,416410
134000,817020,771730

Table 3
Polymerization of norbornene in the system (CH2=CH2)Ni(PR3)2+3H2O+400BF3OEt2NB/Ni=3250. The reaction time is 30 minutes. The number Ni is 1.2·10-5mol. t=25°C. the Solvent is toluene. Total volume of the mixture of 6 ml
# examplePR3Speed, mol NB/mol Ni per hourConversion, %Output, g
14PPh31590240,9
15P(OC6H4CH3-o)3654100,37

Compared to known methods of improving the efficiency of the process of polymerization of norbornene.

A method of producing a catalyst for addition polymerization of norbornene-based complexes nonvalence Nickel and BF3OEt2, characterized in that the process uses catalytic system composition (L)nNi(PR3)2/BF3OEt2where n=1, 2; L - PR3or ethylene; R - Ph, OS6H4CH3-Oh), in combination with controlled quantities of water as a modifying component and the process is carried out in a medium of an organic solvent, for example toluene, at a molar ratio of boron and Nickel:Ni=50:1-600:1, the ratio of H2O/Ni=2-104, a temperature of 10-80°C.



 

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