PL194663B1 - Novel poly(silylene-methylene-vinylene) polymers and method of obtaining them - Google Patents

Abstract

1. New poly (silylene-methylene- -vinyl) of the general formula I, where for n = 2 m = 36, for n = 3 m = 41, and for n = 4 m = = 42. 2. The method of obtaining new polymers poly (silylene-methylene-vinylene) of general formula 1, where for n = 2 m = 36, for n = 3 m = 41, and for n = 4 m = 42, characterized in that divinyl substituted organosilicon monomer of general formula II, where n has the meaning given above is subjected to deetification polycondensation in the presence of bis (di-m- -chlorotris (carbonyl) ruthenium (II)) as a catalyst at 80 to 100 ° C.

Description

Description of the invention

The present invention relates to new poly (silylene-methylene-vinylene) polymers and a method of their preparation.

Metathetic polymerization of acyclic diene (ADMET Polymerization) presents a versatile path towards the synthesis of linear, well-defined, unsaturated organosilicon polymers (KJ. Ivin, JC Mol, Olefin metathesis and Metathesis Polymerization, Acad. Press, New York, 1997, Chapter 8; KB Wagener) , JM Boncella, JG Nel, Macromolecules, 24, 2647, 1991).

This reaction takes place in the presence of highly active tungsten and molybdenum matathesis catalysts of the type [(CF3) 2Me (CO)] 2 (ArN-M = CH (t-Bu), where M = Mo or W (RR Schrock, JS Murdzanek, GC Bazan, J. Robbinson, M. Dimare, M. O'Regan, J. Am.Chem. Soc. 112, 3875, 1990) and in the presence of the ruthenium carbene RuCh (= CHPh) (PCy3) 2 (P. Schwab , MB France, JW Ziller, RH Grubbs, Angew. Chem., Int. Ed. English. Ed., 34, 2039, 1995).

This reaction is very important from an industrial point of view (A. Mortreux, in: Principles and Advances in Molecular Catalysis, B. Marciniec, J. Ziółkowski (ed.), Publishing House of Wrocławski, Poznań-Wrocław, 1993).

However, divinyl-substituted organosilicon compounds do not undergo this reaction. ADMET polymerization of silicon-containing dienes, such as, for example, dialkenylsilanes and siloxanes (except divinylsubstituted organosilicon compounds), provides a variety of unsaturated organosilicon polymers, including carbosilanes and carbosiloxanes (K.B. Wagener,

D. W. Smith, Macromolecules, 24, 6073, 1991, D.W. Smith, K.B. Wagener, Macromolecules, 26, 3533, 1993). However, the unsaturated organosilicon polymers obtained by metathetic polymerization are primarily poly (silylene-methylene-alkenylene) polymers (KR Brzezińska, R. Schitter, KB Wagener, J. Polym. Sci, Part A: Polym. Chem., 38, 1544, 2000).

On the other hand, Finkel'shtein and colleagues reported that the ADMET metathetic polymerization reaction of di (allyl-butenyl) silanes and silacyclobutanes and siloxanes, as well as diallyltetramethyldisiloxane in the presence of heterogeneous Re2O7 / AhO3 + SnR4 (or PbR4) catalysts (ES Finkel'shtein, EB Portnykh, IV Antigova, BM Vdivin, Izv Akad. Nauk SSSR, Ser. Khim., 1358, 1989;

E. S. Finkel'shtein, N. V. Ushakov, E. B. Portnykh, J. Mol. Catal. 76, 133, 1992; E.S. Finkel'shtein, N.V.Ushakov, E.B. Portnykh, B. Marcmiec, in R.G. Jones ed. Silicon-Containing Polymers, Royal Soc. Chem., 29, 1995) largely leads to a mixture of cyclic and linear polysilylene alkenyl polymers.

However, also in this case, in the presence of heterogenized rhenium complexes, the polymerization reaction of divinyl-substituted organosilicon compounds is ineffective.

Recent literature reports concern metathetic polymerization, or rather oligomerization of tetravinyl- and divinyl-substituted silanes in the presence of a heterogenized rhenium catalyst of the Re2O7 / AhO3 + SnR4 (or PbR4) type. However, on the basis of GPC chromatographic studies, the formation of oligomers with a very low yield was found (T. Kawai, K. Shiga, T. Suzuki, T. lyoda, J. Mol. Catal. 140, 287, 1999; T. Kawai, K. Shiga) , T. Suzuki, T. lyoda, J. Mol. Catal. 160, 173, 2000).

Contrary to the lack of catalytic activity of metalacarbene complexes in the metathetic polymerization of acyclic divinyl-substituted organosilicon compounds, examples of copolymerization of divinyl-substituted silanes with alkadienes can be found (K.B. Wagener, D. W. Smith, Macromolecules, 24, 6073, 1991).

Unfortunately, vinyl-substituted organosilicon compounds, which have spectacular industrial importance, are completely passive in the homometathesis reaction with the use of metalacarbene complexes as reaction catalysts.

The only effective catalytic system in the polycondensation process of vinyl-substituted organosilicon compounds are ruthenium and rhodium complexes, which enable oligomers to be obtained by insertion-elimination of methyl divinylsilanes and divinylsiloxanes (B. Marciniec, M. Lewandowski, J. Inorg. Organometal, 115, Polym., 5. 1995).

The essence of the invention are new poly (silylene-methylene-vinylene) polymers of the general formula 1, in which for n = 2 m = 36, for n = 3 m = 41, and for n = 4 m = 42.

The essence of the invention is also a method of obtaining new poly (silylene-methylene-vinylene) polymers of the general formula 1, in which n and m are as defined above, by means of deetencing polycondensation of divinyl-substituted organosilicon monomers of general formula

In formula 2, in which n is as defined above. The reaction is carried out in the presence of bis (di-m-chlorotris (carbonyl) ratene (II)) as a catalyst at a temperature of 80 to 100 ° C.

The compounds of the invention are stereoregular polymers having exclusively trans-1,2-bis (silyl) ethene moieties. They are obtained in the presence of ruthenium catalysts with a yield of 82-85%, with 100% monomer conversion.

The prior art showed that by using carbene complexes of tungsten and molybdenum it was possible to obtain organosilicon polysilylene-methylene-alkenyl polymers containing trans and cis units in their structure. The use of bis (di-m-chlorotris (carbonyl) ruthenium (II) as a catalyst allowed to obtain new stereoregular poly (silylene-methylene-vinylene) polymers.

The compounds of the invention have potential wide application in the polymer industry. The structures of these polymers, confirmed by spectroscopic tests, have only the trans-substituted ethene group, are characterized by high purity of the material, which determines their potential properties as pre-ceramic materials, which are an interesting subject of research in the technology of new polymer materials, as starting materials for the synthesis of membranes or cross-linking .

The following examples illustrate the invention.

P r z k ł a d I

The reaction vessel was 0.5 cm ³ (2.13 mmol) of 1,2-bis (winylodimetylosililo) ethane, and 5.46 mg (2.13 x 10 ⁵ mol) of bis (di-m-chlorotris (carbonyl) ruthenium (II) ) as a catalyst for the reaction. The reaction was carried out in a 5 cm3 reactor equipped with a reflux condenser, placed in a thermostatic oil bath allowing the desired temperature to be kept constant at 90 ° C for a period of 10 days. After 70 hours, GPC analysis showed 100% monomer conversion.

After completion of the reaction, the polymer was isolated by precipitation with CH3OH from the reaction mixture. The polymer layer was separated and treated with hexane to precipitate the remainder of the catalyst. After filtration, the solution was applied to a silica gel column using hexane as eluent. The hexane was then distilled off and the end product was purified by dissolving in methylene chloride and reprecipitating in methanol.

The polymer is very soluble in chloroform, tetrahydrofuran and benzene.

The compound was analyzed by standard methods:

¹ IH ^nmr ( ³⁰⁰ C ₆ D ₆ ), ^d ( ^pp m): ⁰ - ⁰ . ^21, m (-C ^{H 3, p} y ^{y y} outer ^et RZN c ^h internal ^et RZN ^y c ^h silicon atoms), 0.54 m (-CH 2, in methylene bridges between the outer silicon atoms), 0.60 m (-CH 2, in methylene bridges in the polymer chain), 5.67-5.79, m (= CH2, in the outer vinyl group), 5.94-6.03, m (= CH, in the outer vinyl group), 6.14-6.29, m (= CH, in the inner vinyl group) vinyl), ¹³ C ^NMR ( ^{75 M} Hz, C ₆ D ₆ ), ^d ( ^pp m): - ³ . ⁸⁰ - ^1.42, m (-C ^{H 3, p} y ^{y y} outer ^et RZN c ^h internal ^et RZN ^y c ^h silicon atoms) 7.28, m (-CH 2, in methylene bridges between the outer silicon atoms), 10.28 - 10.86 m (-CH2, in polymer chain methylene bridges), 131.95, m (= CH2, in outer vinyl), 139.03, (= CH, in outer vinyl), 150.89, m (= CH, in inner vinyl).

Elemental analysis for (OH ^ Si;): C 56.47, H 10.59.

Measured: C 55.79, H 12.21.

P r z x l a d II

In a reaction vessel provided 0.5 cm3 (1.69 mmol) of 1,3-bis (winylodimetylosililo) propane and 4.32 mg (1.69 x 10 ⁵ mol) of bis (di-m-chlorotris (carbonyl) ruthenium (II)) as a catalyst for the reaction. The reaction was carried out in a 5 cm3 reactor equipped with a reflux condenser, placed in a thermostatic oil bath allowing the desired temperature to be kept constant at 90 ° C for a period of 10 days. After 100 hours, GPC analysis showed 100% monomer conversion.

After completion of the reaction, the polymer was isolated by precipitation with CH3OH from the reaction mixture. The polymer layer was separated and treated with hexane to precipitate the remainder of the catalyst. After filtration, the solution was applied to a silica gel column using hexane as eluent. The hexane was then distilled off and the end product was purified by dissolving in methylene chloride and reprecipitating in methanol.

The polymer is very soluble in chloroform, tetrahydrofuran and benzene.

PL 194 663 B1

The compound was analyzed by standard methods:

¹ H NMR (300 MHz, C6D6) ^d (ppm): 0-0.27 m (-CH3, ^{Getting et} RZN external ^and internal ^y ch ^et RZN ^y ch silicon atoms), 0.65-0.69 m (-CH 2, linked to the outer silicon atoms), 0.70-0.79, m (-CH2, linked to the outer silicon atoms in the chain), 1.41-1.58, m (-CH2, central methylene group in the outer group), 1.59-1.61, m (-CH2 , central methylene group in the inner group), 5.66-5.76, m (= CH2, in the outer vinyl group), 5.92-6.01, m (= CH, in the inner vinyl group), 6.14-6.49, m (= CH, in the outer vinyl group) vinyl group), ¹³ C ^NMR ( ^{75 M} Hz, C ₆ ^D 6), ^d ( ^pp m): - ² . ⁷² - ¹ . ^83, m (-C ^{H 3, p} y ^{y y} outer ^et RZN c ^h internal ^et RZN ^y c ^h silicon atoms), 18.74 m (-CH 2, in methylene bridges between the outer silicon atoms), 19.18 m (-CH 2, in methylene bridges in the polymer chain), 20.62, m (-CH2, central methylene group in the inner group), 23.76, m (-CH2, central methylene group in the inner group), 132.07, m (= CH2, in the outer vinyl group) , 138.82, (= CH, in the inner vinyl group), 151.34, m (= CH, in the inner vinyl group).

Elemental analysis for (CgH2cSi2): C 58.70, H 10.87.

Measured: C 60.14, H 12.47.

P r z x l a d III

0.5 cm3 (1.83 mmol) 1,4-bis (vinyl-dimethylsilyl) butane and 4.69 mg (1.83 x 10 ⁵ mol) bis (di-a-chlorotris (carbonyl) ruthenium (II) were placed in the reaction vessel. )) as a catalyst for the reaction. The reaction was carried out in a 5 cm3 reactor equipped with a reflux condenser, placed in a thermostatic oil bath allowing the desired temperature to be kept constant at 90 ° C for a period of 10 days. After 120 hours, GPC analysis showed 100% monomer conversion.

After completion of the reaction, the polymer was isolated by precipitation with CH3OH from the reaction mixture. The polymer layer was separated and treated with hexane to precipitate the remainder of the catalyst. After filtration, the solution was applied to a silica gel column using hexane as eluent. The hexane was then distilled off and the end product was purified by dissolving in methylene chloride and reprecipitating in methanol.

The polymer is very soluble in chloroform, tetrahydrofuran and benzene.

The compound was analyzed by standard methods:

¹ IH ^nmr ( ^{300 M} Hz, C ₆ ^D 6), ^d ( ^pp m): ⁰ - ⁰ . ^17, m (-C ^{H 3, p} y ^{y y} outer ^et RZN c ^h internal ^et RZN ^y c ^h silicon atoms), 0.53-0.62, m (-CH2 connected to the outer silicon atoms), 0.90-0.92 m (- CH2, linked to the outer silicon atoms in the chain), 1.31-1.36, m (-CH2, middle methylene groups in the outer group), 1.38-1.46, m (-CH2, middle methylene groups in the inner group), 5.64-5.73, m (= CH2, in the outer vinyl group), 5.91-5.98, m (= CH, in the inner vinyl group), 6.11-6.23, m (= CH, in the outer vinyl group), ¹³ C ^NMR ( ^{75 M} Hz, C ₆ ^D 6), ^d ( ^pp m): - ³ . ⁰¹ - ⁰ . ^87, m (-C ^ ^p y ^{y y} outer ^et RZN c ^h internal ^et RZN ^s cli silicon atoms), 14.58 m (-CH 2, in methylene bridges between the outer silicon atoms), 15.57-15.71 m (-CH 2, in methylene bridges in the polymer chain), 27.85, m (-CH2, middle methylene groups in the inner group), 28.22-28.25, m (-CH2, middle methylene groups in the inner group), 131.62, m (= CH2, in the outer group vinyl), 139.40, (= CH, in the outer vinyl group), 150.83, m (= CH, in the inner vinyl group).

Elemental analysis for (C 1 H22Si2 _0): C 60.61, H 11.11.

Measured: C 57.16, H 14.09.

Claims (2)

Patent claims 1. New poly (silylene-methylene-vinylene) polymers of the general formula 1, in which for n = 2 m = 36, for n = 3 m = 41, and for n = 4 m = 42. 2. The method of obtaining new poly (silylene-methylene-vinylene) polymers of the general formula 1, where for n = 2 m = 36, for n = 3 m = 41, and for n = 4 m = 42, characterized in that a divinyl-substituted organosilicon monomer of the general formula II, in which n is as defined above, is subjected to a deetening polycondensation in the presence of bis (di-chlorotris (carbonyl) ruthenium (II)) as a catalyst at a temperature of 80 to 100 ° C.