FR2595364A1 - Silicone copolymer - Google Patents

Abstract

Silicone copolymer of formula in which m and n are integers, R3 to R6 are alkyls and A is a repeat unit derived from an unconjugated cyclic diene. Plastics industry.

Description

Silicone copolymer.

Background of the invention (1) Field of the invention.

 This invention relates to a novel silicone copolymer containing Si-C bonds in the main chains of molecules. More particularly, the invention relates to a new silicone copolymer which is prepared by copolymerizing a non-conjugated cyclic diene and a polysiloxane by what is called hydrosilation.

(2) Description of the prior art.

It is well known up to now, under the name of hydrosilation, which can additively fix hydrosilanes having hydrosilyl groups to olefins, in the presence of a catalyst. This reaction takes place according to the following reaction equation

 This hydrosilation is carried out in the presence of several catalysts, such as peroxide-based catalysts (Sommers et al., J. Amer. Chem.

Soc., 69, 188 (1947)), catalysts based on platinum derivatives (G.G. Wagner et al., British Patent No. 670,617; and Speier et al., J. Amer.

Chem. Soc., 29, 974 (1957)) or azo-based catalysts (R.V. Lipscomb, United States Patent No. 2,570,462).

 However, attempts to obtain organic polymers of silicon by hydrosilation have so far been unsuccessful. In particular, polymers prepared by hydrosilation of a cyclic diene not conjugated with a polysiloxane are still not known.

 However, resins containing silicon, such as silicone polymers, are prepared on an industrial scale because they have excellent physical properties such as good thermal stability. Furthermore, it is believed that polymers whose main chains have a cyclic hydrocarbon structure also have good thermal properties. However, hitherto no polymers are known which have these desirable properties.

Brief summary of the invention.

 The invention therefore essentially relates to a new linear thermally stable polymer, which is prepared by hydrosilating a cyclic unconjugated diene with a polysiloxane.

 The polymer is prepared, according to the present invention, by copolymerizing, in the presence of a catalyst, a polysiloxane represented by the following developed formula (I) and any one of the non-conjugated cyclic dienes B1 to B6 represented by the developed formulas following (II) to (VII), respectively.

dans laquelle les radicaux R3 à R6 sont des groupes alcoyle identiques ou différents en C1 à C5 tels que des groupes méthyle, éthyle et propyle. En outre, m est un nombre entier de 1 à 1000. Cependant, si la masse moléculaire du polysiloxane est trop élevée, les propriétés du copolymère obtenu deviennent moins bonnes, de sorte que l'on préfère que le nombre entier m soit compris entre 1 et 50 et, mieux encore, entre 1 et 5.Polysiloxane

in which the radicals R3 to R6 are identical or different C1 to C5 alkyl groups such as methyl, ethyl and propyl groups. In addition, m is an integer from 1 to 1000. However, if the molecular weight of the polysiloxane is too high, the properties of the copolymer obtained become less good, so that it is preferred that the integer m is between 1 and 50 and, better still, between 1 and 5.

Unconjugated cyclic diene B1

Diène cyclique non conjugué B3

Unconjugated cyclic diene B2

Unconjugated cyclic diene B3

Unconjugated cyclic diene B

Unconjugated cyclic diene B

formules (II) à (VII) dans lesquelles les radicaux
R7 à R14 sont des atomes d'hydrogène ou des groupes alcoyle.Unconjugated cyclic diene B6

formulas (II) to (VII) in which the radicals
R7 to R14 are hydrogen atoms or alkyl groups.

dans laquelle m est un nombre entier de 1 à 1000, n est un nombre entier dgal à 1 ou supérieur à 1, de préférence allant jusqu'à 50, et le groupe A du motif de répétition est un radical qui dérive de l'un quelconque des diènes cycliques non conjugués B1 à B6 mentionnés ci-dessus. Les groupes d'extrémité R1 et
R2 sont des radicaux provenant du polysiloxane correspondant ci-dessus dans le motif de répétition ou de ceux provenant de l'un quelconque des diènes cycliques non conjugués mentionnés ci-dessus que sont B B
Description détaillée de l'invention.The polymer according to the present invention is therefore a silicone copolymer having the repeating units represented by the following structural formula (VIII)

in which m is an integer from 1 to 1000, n is an integer equal to 1 or greater than 1, preferably up to 50, and group A of the repeating unit is a radical derived from one any of the non-conjugated cyclic dienes B1 to B6 mentioned above. The end groups R1 and
R2 are radicals from the corresponding polysiloxane above in the repeat unit or from any of the above-mentioned unconjugated cyclic dienes that are BB
Detailed description of the invention.

 According to the present invention, the polysiloxanes which are represented by the above structural formula (I) are, for example, 1,1,3,3tetramethyldisiloxane, 1,1,3,3-tetraethyldisiloxane and 1,1, 3,3,5,5-hexamethyltrisiloxane. There is a much larger molecular weight polysiloxane such as a hydride-terminated polydimethylsiloxane (hydrogen) prepared by Ventron GmbH in the Federal Republic of Germany.

The B1 mentioned above as an unconjugated cyclic diene is, for example, norbornadiene and methylnorbornadiene; B2 is, for example, dicyclopentadiene, methyldicyclopentadiene and dimethyldicyclopentadiene; B3 is, for example, 4-vinylcyclohexane and 4-vinylmethylcyclohexene
B4 is, for example vinylbicyclo [2.2.î3heptene-2
B5 is, for example, 5-ethylidenebicycloC2.2.11-heptene-2; and B6 is, for example, tetrahydroindene.

 The organic silicon polymer is prepared, according to the present invention, by copolymerizing the polysiloxanes mentioned above and the non-conjugated cyclic dienes mentioned above.

 The copolymerization of polysiloxanes and unconjugated dienes can be carried out under conventional conditions known for a hydrosilation reaction.

 In particular, this reaction is catalyzed by metals from Group VIII of the Periodic Table of the Elements or by mineral or organic derivatives, such as their complexes among these metals, mention may be made in particular of platinum, palladium, ruthenium, rhodium and iridium.

 It is recommended to use platinum which can be introduced in the form of elementary platinum deposited on various supports such as alumina, silica or activated carbon or, preferably, in the form of its chloride such than chloroplatinic acid.

 Chloroplatinic acid is also known as "platinum chloride". It is a commercially available substance and its preferred and most available form is the hexahydrate form, i.e. H2PtCl6,6H20. It is a crystalline substance which can be used, according to the invention, either in its pure form or in the form of a solution. It is well soluble in polar solvents, in particular alcohols such as isopropyl alcohol, water and various glycols and esters. In order to facilitate the handling and the measurement of the relatively small quantities which are required in this case, it is preferred to use a solution of chloroplatinic acid. As only small quantities are required, the possible reactivity of the catalyst solvent on one of the reagents is of no particular importance.

In addition, platinum chloride can be modified by bringing it into contact with particular organic compounds. Mention may be made, for example, of a platinum compound which contains one or more organic groups and in which the platinum forms one or more bonds with atoms chosen from Groups IVa, Va and VIa of the Classification
Periodic. An organic group can be attached to the platinum atom or to any of the chosen atoms, as described> in the Periodic Table.

The platinum compound may contain halogen atoms attached directly to the platinum. Suitable organic groups include hydrocarbon groups derived from alkyl, alkoxy and aryl groups, such as methyl, acetylisopropoxy or phenyl groups, and alkenes or alkynes groups such as ethylene, cyclohexene and dimethylmethylhexyne groups.

 Examples of suitable platinum catalysts include bis (diethylsulfide) dichloroplatin, bis (2-dimethyl-5-methylhex-3-yne) dichlor chlorodiplatin, bis (propionitrile) dichloroplatin, bis (tripropylphosphine) dithiocyano -V-dichloro-cyanodiplatin, (p-toluidine) ethylenedichloroplatin, bis (triethylphosphine) diphenylplatin, bis (benzonitrile) dichloroplatin, bis (dipropylsulfide) dichlorora-dichloroplatin, bis (triethylarsine) dimethylplatin, and bis (triethylarsatin) ) dichloro-V-ethylmercaptylchlorodiplatin.

 Mention may also be made, on the other hand, of the complexes formed between platinum chlorides and olefins, phosphines or alkyl sulfides.

 The quantity of these catalysts introduced into the hydrosilation system is not limited, but it is preferable to use them at a rate of 1 to 10,000 ppm, and preferably from 1 to 1000 ppm and, better still, from 10 to 500 ppm (as the weight of the metal in the catalyst) relative to the reactant constituted by the polysiloxane.

 The hydrosilation reaction can also be carried out in the form of a polyaddition in the absence of any solvent. In the case where the solvent is used, it can be used, to be better able to control the reaction and to prevent any premature solidification and precipitation of the polymers, various solvents, for example cyclic ethers such as tetrahydrofuran and dioxane and aliphatic or aromatic ethers.

 The temperature of the hydrosilation reaction is not particularly limited.

It can be chosen from a wide range depending on other reaction conditions and, in general, the reaction temperatures are between room temperature and 250 ° C.

 The reaction time can also vary widely. However, it is preferred to carry out the reaction for a fairly long period, because it is possible to obtain polymers of fairly high molecular mass, this period generally ranging from 10 minutes to 50 hours.

 The polymers according to the present invention will now be described in more detail having the above structural formula (VIII).

 The polymers of the following developed formulas are prepared by copolymerization, by hydrosilation using 1,1,3,3-tetramethyldisiloxane serving as polysiloxane of any of norbornadiene, dicyclopentadiene, 4-vinylcyclohexane, 2-vinylbicyclo [ 2.2.1] heptene-2, 5-ethylidenebicycloL2.

2.1] heptene-2 and tetrahydroindene.

 In the above formulas, each n is an integer equal to one or greater than one and, preferably, from 1 to 50.

ou un atome d'hydrogène Dans la formule (X) R1 et R2 sont

ou un atome d'hydrogène
Dans la formule (XI) R1 et R2 sont

ou un atome d'hydrogène
Dans la formule (XII) R1 et R2 sont:

ou un atome d'hydrogène
5 10 15 20 25 30 35
Dans la formule (XIII) R1 et R2 sont:

ou un atome d'hydrogène
Dans la formule (XIV) R1 et R2 sont

ou un atome d'hydrogène
Dans les formules ci-dessus, quand n est 1, l'un au moins de R1 et R2 n'est pas un atome d'hydrogène.In addition, the end groups R1 and R2
in the previous formulas are as follows
In formula (IX) R1 and R2 are

or a hydrogen atom In the formula (X) R1 and R2 are

or a hydrogen atom
In formula (XI) R1 and R2 are

or a hydrogen atom
In formula (XII) R1 and R2 are:

or a hydrogen atom
5 10 15 20 25 30 35
In formula (XIII) R1 and R2 are:

or a hydrogen atom
In formula (XIV) R1 and R2 are

or a hydrogen atom
In the above formulas, when n is 1, at least one of R1 and R2 is not a hydrogen atom.

 The nature of the end groups of the polymer according to the present invention is chosen as a function of the molar ratio of the reactants loaded to the reaction system. This means that when polysiloxane is loaded in a larger amount than the other reactant, namely the unconjugated cyclic diene, the end groups derived from the polysiloxane are formed to give a polymer having hydrosilyl groups as groups of end. On the other hand, when the quantity of the non-conjugated cyclic diene is greater than that of the polysiloxane, the end groups derived from the non-conjugated cyclic diene are formed to give a polymer having unsaturated double bonds at its ends. When the two reactants are loaded in equimolar amounts, the end groups of the polymer are those derived from the two reactants. To obtain a high polymer, it is best to load reagents in equimolar amount into the reaction system.

 The polymers obtained by the process described above are in liquid to solid form, have thermal stability, electrical characteristics, transparency and other properties which are excellent.

 The polymers according to the invention can therefore be used as insulating materials from the electrical point of view, if they are solids, and as insulating oils from the electrical point of view, as lubricating oils, as media. heat transfer, etc., if they are liquids.

 Furthermore, since the polymers according to the present invention have end olefinic double bonds or hydrosilyl groups, they can be used as reaction intermediates or as prepolymers, taking advantage of the reactivity of the end functional groups of the polymers.

 The following examples illustrate the invention.

Example 1-1
Without using a reaction medium, 1.84 g (3.076 moles / liter) of norbornadiene (nonconjugated cyclic diene B1) are mixed with 2.68 g (3.076 moles / liter) of 1,1,3,3-tetramethyldisiloxane and 0.08 ml of the catalyst solution in isopropyl alcohol (0.025 x 10 2 moles / liter of hexachloroplatinic acid).

 This mixture is brought to 580C for 24 hours to obtain a polymer in a yield of 100%, this polymer being very viscous at room temperature.

 The analytical data of the polymer obtained are mentioned below.

(Analytical data)
Number average molecular weight: 5,000
(vapor pressure method)
1 H NMR spectrum (medium: CC14)
0.05 ppm (12 H, s, Me-Si)
IR spectrum (solvent-free)
An absorption of -SiH is observed at 2120 cm 1
Elementary analysis
C (%) H (%) SiH (%)
Values found 57.81 9.17 1.01
Example 1-2
The copolymerization of norbornadiene (unconjugated cyclic diene B1) and of 1,1,3,3-tetraethyldisiloxane is carried out in the same way as in Example 1-1. A highly viscous polymer is obtained at room temperature in a yield of 98%.

(Analytical data)
Number average molecular weight i 4,000
(Vapor pressure process)
1 H NMR spectrum (medium: Ce14)
1.0 ppm (20 H, m, Et-Si)
IR spectrum (solvent-free)
An absorption of -SiH is observed at 2120 cm 1.

Elementary analysis:
C (%) H (%) SiH (%)
Values found 7, 98 9.87 0.88
Example 2-1
Copolymerization of dicyclopentadiene (unconjugated cyclic diene B2) and 1,1,3,3-tetramethyldisiloxane is carried out in the same way as in Example 1-1, to obtain a liquid polymer which is very viscous at room temperature. . The yield is 100%.

(Analytical data)
Number average molecular weight. 510
(Vapor pressure process)
1 H NMR spectrum (medium: CC14)
0.05 ppm (12 H, s, Me-Si)
IR spectrum (solvent-free)
An absorption of -SiH is observed at 2120 cm 1
Elementary analysis
C (%) H (%) SiH (%)
Values found 62.13 10.00 5.71
Example 2-2
Copolymerization of dimethyldicyclopentadiene (unconjugated cyclic diene B2) and 1,1,3,3-tetramethyldisiloxane is carried out in the same way as in Example 1-1 to obtain a polymer which is very viscous at room temperature. The yield is 100%.

(Analytical data)
Number average molecular weight: 550
(Vapor pressure process)
1 H NMR spectrum (medium: CC14)
0.05 ppm (12 H, s, Me-Si)
IR spectrum (solvent-free)
An absorption of -SiH of 2120 cm 1 is observed.

Elementary analysis
C (%) H (%) SiH (%)
Found value 65.91 9.98 5.01
Example 3
A copolymerization of 4-vinylcyclohexene (unconjugated cyclic diene B3) and 1,1,3,3-tetramethyldisiloxane is carried out in the same way as in Example 1, to obtain a polymer which is very viscous at room temperature. . The yield is 98%.

(Analytical data)
Number average molecular weight: 610
(Vapor pressure process)
1 H NMR spectrum (medium: CC14)
0.05 ppm (12 H, s, Me-Si)
IR spectrum (solvent-free):
We observe an absorption of -SiH of 2120 cm 1
Elementary analysis:
C (%) H (%) SiH (%)
Values found: 58.93 10.82 4.87
Example 4-1
A copolymerization of 5-vinyl bicycloL2.2.îjheptene-2 (unconjugated cyclic diene) is carried out
B4) and 1,1,3,3-tetramethyldisiloxane in the same way as in Example 1-1, to obtain a solid polymer in a yield of 100%.

(Analytical data)
Number average molecular weight 7,000
(Vapor pressure process)
Thermal stability (DTG): In an atmosphere
of nitrogen, no change in
weight up to 400 to 4500C.

1 H NMR spectrum (medium: CC14)
0.05 ppm (12 H, s, Me-Si)
IR spectrum (solvent-free)
An absorption of -SiH is observed at 2120 cm ~ l.

Elementary analysis:
C (%) H (%) SiH (%)
Values found 61.63 10.74 0.04
Example 4-2
Copolymerization of 5-vinyl bicyclo [2.2. Heptene-2 (unconjugated cyclic diene B4) and 1,1,3,3-tetraethyldisiloxane is carried out in the same way as in Example 1-1, to obtain a solid polymer in 100% yield.

(Analytical data)
Number average molecular weight: 6,500
<Vapor pressure process)
Thermal stability (DTG): In an atmosphere
of nitrogen, no change in
weight up to 400 to 4500C.

H NMR spectrum (medium: CC14)
1.0 ppm <20 H, m, Et-Si)
IR spectrum (solvent-free)
An absorption of -SiH is observed at 2120 cm 1.

Elementary analysis
C (%) H (%) SiH (%)
Values found 66.13 11.21 0.36
Example 4-3
Copolymerization of 5-vinyl bicycloL2.2.1 # heptene-2 (unconjugated cyclic diene) is carried out
B4) and of a hydride-terminated polydimethylsiloxane (hydrogen) (PS, 537, of molecular mass equal to 400, prepared by Ventron, GmbH, Federal Republic of Germany) in the same way as in Example 1-1 , to obtain a polymer in a yield of 100%.

(Analytical data)
Number average molecular weight: 7,000
(Vapor pressure process)
Thermal stability (DTG): In an atmosphere
of nitrogen, no change in
weight up to 400 to 4500C.

1 H NMR spectrum (medium: CC14)
0.05 ppm (s, Me-Si)
IR spectrum (solvent-free)
An absorption of -SiH is observed at 2120 cl 1.

Elementary analysis
C (%) H (%) SiH (%)
Values found s 45.51 9.32 0.31
Example 5
Copolymerization of 5-ethyleneenebicycloL 2.2.1 Jheptene-2 (unconjugated cyclic diene B5) and 1,1,3,3-tetramethyldisiloxane is carried out in the same way as in Example 1-1 to obtain a polymer very viscous at room temperature, in a yield of 98%.

(Analytical data)
Number average molecular weight: 500
(Vapor pressure method)
1 H NMR spectrum (medium: CC14)
6
0.05 ppm (12 H, s, Me-Si)
IR spectrum (solvent-free)
Absorption of -SiH is observed at 2120 cm-1.

Elementary analysis
C (%) H (%) SiH (%)
Found 59.98 10.15 5.97
Example 6
A copolymerization of the tetra hydroindene (nonconjugated cyclic diene B6) and of 1,1,3,3-tetramethyldisiloxane is carried out in the same way as in Example 1-1, in order to obtain a highly viscous polymer at room temperature, in a yield of 61%.

(Analytical data)
Number average molecular weight: 590
(Vapor pressure process)
1 H NMR spectrum (medium: CC14):
6
0.05 ppm (12 H, s, Me-Si)
IR spectrum (solvent-free)
An absorption of -SiH is observed at 2120 cm-1.

Elementary analysis
C () H (%) SiH (%)
Values found 60.07 9.99 5.16

Claims (1)

CLAIM  1. Silicone copolymer having repeating units represented by the following structural formula

 in which each of m and n is an integer equal to 1 or greater than 1, the radicals R3 to R6 are identical or different alkyl groups having from 1 to 5 carbon atoms, the group A of the repeating unit being a radical which is derived from any of the unconjugated cyclic dienes represented by the following developed formulas

  in which the radicals R7 to R14 are respectively the same as those mentioned above.

 in addition, the end groups R1 and R2 are identical or different and each of them is a hydrogen atom or an end group represented by the following developed formulas, in which if the n mentioned previously is 1, at least one of the end groups R1 and R2 is not a hydrogen atom  in which each of the radicals R7 to R14 is a hydrogen atom or a methyl group,