SU692835A1 - Norbornene derivatives containing triorganylsiloxy group for synthesis of ethylene and propylene copolymers - Google Patents

Description

I

This invention relates to silicon organic chemistry. New norbornene derivatives containing a triorganylsiloxy group of the general formula are proposed.

sn

ns, (cis) p-osiR,

HCv,

sn

where n is 0.1;

R SNZ, SNzSNgSRZ,

for the synthesis of copolymers with ethylene and propylene, capable of producing vulcanizers in mixtures with mineral fillers with high physicomechanical indicators.

Known derivatives of norbornene containing hydroxyl groups of the general formula CH

,

sn

where n 0-3,

for example, norbornenyl carbinol.

However, due to the high reactivity of the hydroxyl group, these norbornene derivatives react strongly with organoaluminum compounds used as catalysts in the synthesis of ethylene-propylene rubbers. Therefore, their use to produce rubber with modified properties requires high catalyst consumption (at least 1.5 mol per 1 mol of monomer), which significantly affects the cost of rubber and increases the risk of work.

In addition, these monomers do not show sufficient activity in the copolymerization with ethylene and propylene and their conversion in this reaction does not exceed 15-209s.

Known derivatives of norbornene containing silicon, of the general formula

CH

.-

CH

where X is chlorine; R is alkyl; n 0-2. However, such npiat compounds in contact with air moisture hydrolyzate with the formation of organosilicon alcohols. This reaction has resulted in HC. Therefore, working with them is associated with great difficulty and safety (it is necessary. It is necessary to comply with safety requirements) during the synthesis, transportation and storage and avoid contact with air. The copolymerization of these monomers with these flax and propylene also requires high costs of aluminum-aluminum compounds (more than 3 mol per 1 mol of monomer), the resulting copolymers contain high hydrolysable groups, therefore, their degradation from polymerization solutions by water degassing will result in cross-linking the macromolecule, which will be applied to the deactivating material. . These copolymers without the use of various expensive techniques for their isolation are not of practical value. The aim of the invention is to increase the hydrolytic stability of norbornene derivatives containing silicon and reduce the consumption of the catalyst during their polymerization. The proposed norbornene derivatives are suitable for use in the synthesis of copolymers with ethylene and propylene. The compounds of the general formula 1 are prepared by reacting i-riorganyl chlorosilane with norbornenol or norbornenyl carbinol. The reaction reagents are taken in stoichiometric ratios and the reaction is carried out in an organic solvent (heptane, benzene, acetone, ethyl acetate) in the presence of a hydrogen chloride acceptor, for example, an amine, at O-UOC-C, to dissolve the target product with limestone, for example, rectification. Example 1. In a three-necked flask equipped with a stirrer, two dropping funnels and a thermometer, load a solution of 6 g of triethylamine in 60 ml of heptane. The contents of the flask are cooled to O-5 ° C. For a period of 1 h, a solution of 20.9 g of norbornenyl carbinol formul is simultaneously fed from the dropping funnels. .;,, , cn, .... HC l i-CHzOH l cg in 60 ml of heptane and a solution of 18.4 g of trimethylchlorosilane (CH3) s5 | C1 in 60 ml of heptane. At the same time, a salt of triethane-Llamine hydrochloride is observed; and heating the reaction mass. Upon termination of supply of reagents to a temperatu-; The reaction mixture was allowed to warm to room temperature and the contents of the flask were stirred for an additional hour. Then the salt of trizthanololine hydrochloride was filtered on a Schott filter and the precipitate was washed with several portions of heptane. Heptane is distilled off from the obtained filtrate and the residue is subjected to distillation under reduced pressure, h. 25.7 g (yield: 78% by weight) of a liqueur-graphically pure norbornenylmethyleneoxytrimethylsilane of the formula, CH, are obtained. . Sf C F - 2-o-Si (CH3) 3 II with% unresponsive The product has the following characteristics: bp. 62 ° C / 3 mmHg; p 1.4561; d 0.9228 MR: 57.72 found; calculated 58.72. Mol.v .: found 186.5; calculated 196.3. Found: C, 66.8; H 10.5; Si 13.6; CH group CH 13.4, Calculated,%: C 67.2; H 10.2; Si 14.2; CH group CH 13.2. The monomer is copolymerized with ethylene and propylene, for which, in a glass reactor filled with dried argon, 0.5 l of Dry, distilled in a stream of argon, heptane is poured from a vessel of Shleyk. The solvent is saturated with a mixture of ethylene and propylene, taken in a volume ratio of 1: 2, respectively. . After saturation with stirring of the contents of the reactor and the constant supply of the gas mixture at a rate of 60 l / h, the solutions of the components of the catalytic system and norbornenylmethylene-xytrimethylsilane are gradually fed from the dispensers connected to the reactor. The copolymerization reaction is carried out at 20 ° C for 1 hour, then the process is interrupted by the addition of ethyl alcohol and the polymer is isolated by water degassing, dried on a roll at 65-75 ° C in the presence of 0.2 wt.% phenyl- / 3 naphtylamine (neozon D). Just the reaction serves 2.04 mol. AI (C2Hs) .Cli 5,0,173 mmol OOS1 and 5.5 mol of norbrynylmethyleneoxytrimethylsilane. 4.3 g of a white amorphous copolymer with intrinsic viscosity jj 1.43 of the following composition are obtained: propylene content 35 mol.%, Si content 1.15 wt.%. The conversion of the monomer in the reaction was 32% by weight, based on the total amount fed. Example2. Under the conditions of example 1, from 8.2 g of norbornenol and 8.1 g of trimethylchlorosilane in the presence of 1.8 g of triethylamine in 100 ml of benzene, 9.7 g (yield 71% by weight) of chromatographically pure norborienyloxitrimethylsilane of the formula o-zisnz) s .fcH2 product has the following characteristics; m.p. 72C / 28 mm Hg; p 1.4534; , 927 MRjj: found 53.20; calculated 54.03. Like, found 189.3; calculated 182.3. Found,%: C 64.9; H 10.1; Si 15.1; CH group CH 13.9. Calculated,%: C 65.7; H 9.9; Si 15.4, CH group CH 14.3. The obtained norbornenipoxitrimethylsilane is used in the copolymerization reaction with ethylene and propylene, which is carried out as described in Example 1. A total of 2.04 mmol AI (CiH5) i, j Cli, s, 0.173 mmol VOCIj and 5.5 mmol monomer are used for the reaction . Obtain 5.6 g of a copolymer with t of 1.6, the content of SzNv 31 mol.% And Si 1.2 wt.%. The monomer conversion in the reaction is 35% by weight. Froze Under the conditions of example 1, from 13 g of norbornenyl carbinol and 37.5 g of tris (3,3,3-trifluoropropyl) chlorosilane in the presence of 11.1 g of triethylamine in 120 ml of heptane, 41.3 g (yield 89%) of chromatographically pure norbornylmethyl-enoxy- grms- (3,3,3-trifluoropropylsilane of the formula CH HC l CH-CHzO Si (CHzCHzCr3) 3 II cis The product has the following characteristics: bp 136-138 ° C / 2 mm Hg; n 1.4064 ; d 1,2742, MR .: found 86,32; 1st were 86.33. Mod.: found 436.4; calculated 442.3. Found: C 45.9; H 5.5; F 38 , 8; Si 6.1; CH group CH 6.1. Calculated: C 46.2; H 5.2; F 38.6; Si 6.3; CH group CH 5.9. The obtained norbornenylmethylenoxy-trns (3.3, 3-Trifluoroylpropyl) chlorosilane is used in the copolymerization reaction with ethylene and propylene, which is carried out according to the procedure described in Example I. The reaction takes 2.04 mmol AKCjHs) t, CI, 5jO, 173 mmol VOCIj and 4.54 mmol monomer . 16.9 g of polymer with an IT of 2.15 are obtained. The content of SEN is 33 mol.%; F content is 2.1 wt.%, Si content is 0.4 wt.% Conversion of the monomer in the reaction is 49.5 wt.%, P p and measures 4. Under conditions of example 1, from 11.7 g of norbornenol and 37.7 g Tris- (3,3,3-trifluoropropyl) chlorosilaia in the presence of P, 2 g of triethylamine in 120 ml of benzene, 40.8 g are obtained. (90% yield) of chromatographically pure norbornenyloxy-tUS- (3,3,3-trifluoropropyl) silane of formula Hc. sn-0 S1 (snngf CFjjj Pen CH) The product has the following characteristics, bp 127 ° C / 5 mm Hg; mp. 39-40 ° C. Mol.: found 417.2; calculated 428.1. Found: C 44.6; H 5.2; Si 6.8; F 39.8; CH group CH 6.3.%: C: 44.8; H 5.1; Si 6.5; F 40.0; CH groups CH 6.1. Norbornenyloxy-Trm- (3,3,3-trifluoropropyl) silane is used to prepare ethylene-propylene copolymer. The copolymerization reaction is carried out as described in Example 1, in 200 ml of heptane. A total of 0.685 mmol of Al (C2H5) i, 5 Cl ,, - 0.0578 mmol of VQCIj and 1.37 mmol of monomer are fed to the reaction, 3.7 g of polymer are obtained with m} 2.9. containing 35 mol.%. CzNv; O, 45 in % Si and 2.02% by weight F. 55% by weight of monomer conversion. Vulcanizates were prepared on the basis of the copolymers obtained. EXAMPLE 5 A preparation of a vulcanizing mixture of the following composition, parts by weight: Copolymer 100 Aerosil A-17530 Zinc Oxide5.0 Dicumyl peroxide 3.0 Sulfur 0,4 Volcanization mode 150 ° C x 60 minutes The properties of the obtained vulcanizates compared to the vulcanizates of similar mixtures of ethylene propylene serial rubber (SKEPT) and a copolymer of ethylene, propylene and norbornyl carbinol, are described in the same section.

A copolymer of ethylene, propylene and norbor

Thus, new norbornene derivatives containing triorganylsiloxy groups are non-hydrolyzable products, in contrast to the known mono-, di-to-trichlorosilyl norbornene derivatives. This is confirmed by elemental analysis and the presence in the copolymers obtained on the basis of these monomers, the same groups as in the initial monomer, and also by X-ray data. Due to this, the monomers are not sensitive to moisture in the air, and working with them is safe and does not require special techniques.

The use of these monomifs to produce ethylene-propylene rubbers allows one to obtain copolymers with modified properties without increasing the decomposition of the organoaluminum compound at a high conversion of monomers in the reaction. .

In the polymerization of known monomers, the consumption of an organoaluminum catalyst is not less than 1.5 mol per 1 mol of monomer; in the case of polymerization of compounds of the general formula 1, the decay of an organoaluminum catalyst is 0.5 mol per 1 mol 25 monomer. In this case, the conversion of the monomer increases 3 times.

Formula of the invention

Norbornene derivatives containing the triorganylsiloxy group of the general formula

sn

sn

where n is 0.1; R SNZ, CF ,,

for the synthesis of a copolymer with ethylene and propylene.