JPS5859260A - Organopolysiloxane composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which exhibits long-term shelf stability at room temperature and can be rapidly cured by heating, by incorporating an alkinyl alcohol as a preservative. CONSTITUTION:The titled compsn. contains an alkenyl group-contg. organopolysiloxane (A) having an organosiloxane unit of formulaI[wherein R<1> is a 2- 4C alkenyl; R<2> is a (substd.) monovalent hydrocarbon group; a is 1-3; b is 0-2; a+b<=3]such as dimethylvinylsiloxy-terminated polydimethylsiloxane, an organohydrogen polysiloxane (B) having an organohydrogensiloxane unit of formula II[wherein R<3> is a (substd.) mobovalent hydrocarbon group; c is 1-3; d is 0-2; c+d<=3]such as dimethylhydrogensiloxy-terminated dimethylsiloxymethyl hydrogensiloxy-copolymerized polysiloxane, platinum or its, compd. (C) and an alkenyl alcohol (D) of formula III (wherein Ar is aryl; R<4> is H, a 1-15C monovalent org. group; Ar and R<4> may be bonded to each other) such as 3-phenylpropargyl alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organopolysiloxane composition containing a storage stabilizer with a specific structure, which exhibits good storage stability for a long period of time at room temperature and exhibits an addition-resistance type property when heated. The present invention relates to organopolysiloxane compositions that are rapidly cured by a crosslinking reaction of organopolysiloxanes containing conventional vinyl groups.

Regarding organopolysiloxane compositions that contain organohydrogenpolysiloxane and a platinum-based catalyst as main components, and which cure by accelerating the addition reaction by adding a stabilizer to increase storage stability, 4! r
A seed version has been proposed (U.S. Pat. No. 3,383,356).
No. 3445420, No. 3461185,
Japanese Patent Publication No. 51-28119, Japanese Patent Publication No. 53-35983, and Japanese Patent Publication No. 54-3774), all of the components of such compositions are mixed in advance. Can be stored for a long time in the condition.

It is believed that curing occurs only after heating. Among them, carbon-carbon double bonds.

Alternatively, compounds with carbon-carbon triple bonds were used as storage stabilizers. Addition-curable organopolysiloxane compositions are interesting in that addition reactions themselves and the compounds used as stabilizers. Typical examples of compounds used as stabilizers include ethylene tetrachloride (U.S. Pat. No. 3,383,356) and 3-methyl-1-butyn-3-ol' (U.S. Pat. No. 3,445,420). I can do it. The electron density of unsaturated bonds in these compounds is extremely high, and this is thought to suppress the addition reaction catalytic activity of platinum or platinum-based compounds. however.

The activity of these compounds is still insufficient, and addition-curing organopolysiloxanes using them as storage stabilizers tend to gradually increase in viscosity when stored for a long period of time, and in order to completely suppress thickening, large amounts are required. When used for this purpose, there were disadvantages such as insufficient compatibility and release, and curing (requiring quite high temperatures).

The present invention provides a composition that solves these drawbacks, and in particular, as a storage stabilizer, it has a chemical structure that further increases the electron density of unsaturated bonds, that is, an aryl group, an ethynyl group, and a hydroxyl group on one carbon atom. Alkynyl alcohol with a specific structure that requires a group to be bonded,
It is characterized by using /shi.

That is, the present invention has the following formula: R'aR2bSi04-a-b (wherein R1 is an alkenyl group having 2 to 4 carbon atoms, R2 is a substituted or unsubstituted m hydrocarbon group, and a is an integer of 1 to 3.

An alkenyl group-containing organopolysiloxane having an organosiloxane unit where b is an integer of θ to 2, where a+b≦3).

(b) Formula HcR3d 5iq8□'', (in the formula R
3 is Ifm or an unsubstituted monovalent hydrocarbon group, C is 1 to 3
An organohydrogenpolysiloxane having an organohydrogensiloxane base represented by an integer of , d is an integer of θ to 2, where c+d≦3.

(c) platinum or a platinum-based compound; and) general formula Ar HC:C-C-OH (wherein Ar is an aryl group).

The present invention relates to an organopolysiloxane composition characterized in that it consists of an alkynyl alcohol represented by an organic group of

The organopolysiloxane composition obtained by the present invention is characterized by extremely high temperature dependence during curing, which is unlike any conventional technology.For example, although no increase in viscosity is observed for more than half a year at room temperature It can be quickly cured by external heating to provide elastic resin-like materials, gel-like materials, and foamed materials.

2R'aR'' as the component (a) used in the present invention
b An alkenyl group-containing organopolysiloxane having as an essential unit an organosiloxane unit represented by SiO(1) (in the formula, R' + R2+ ae b is the same as Ii above) is an organopolysiloxane represented by formula (9) (1). It may be composed only of siloxane units, or may also contain other organosiloxane units. The structure of the alkenyl group-containing organopolysiloxane is linear, nine-branched, and cyclic.

It can be any type of network, and its degree of polymerization is 2 or more, and the upper limit is allowed to be a degree of polymerization (usually 10,000). The alkenyl group constituting R1 is a subsubstituted saturated hydrocarbon group. R2 is the same or different substituted or unsubstituted monovalent hydrocarbon group, specifically a methyl group, an ethyl group, a propyl group, Butyl75. Unsubstituted octyl group, phenyl group, phenylethyl group, phenylpropyl group, etc.
3-chloropropyl group, 2-methyl-3-chloro, in which some or all of the hydrogen atoms of a valent hydrocarbon group or these groups are substituted with carbon or an atom other than hydrogen, such as a halogen atom such as fluorine or chlorine atom Propyl group, 3,3.
A substituted-valent hydrocarbon group such as a 3-trifluoropropyl group, and the carbon atoms in these substituted or unsubstituted monovalent hydrocarbon groups are usually 1 to 2011! It is. a is an integer of 1 to 3, b is an integer of 0 to 2, provided that a+b≦3, but a
==1b=0. a=1b=1. The combination a=1b=2 has 4 general characteristics.

Although the present invention is not limited to specific organosiloxane units other than the organosiloxane unit of formula (1), R2 of formula H1 may be an alkyl group such as octyl, a phenyl group, phenyl-ethyl, It may be a substituent containing a fluorinated alkyl group such as phenylpropyl, a nitrogen atom such as fluoropropyl, chloropropyl, chlorobutyl, etc. Examples include dimethylsiloxane and methyl. Phenylsiloxane, diphenylsiloxane, methyloctylsiloxane.

Diorganosiloxanes such as methyl(3,3,3-)lifluoropropyl)siloxane, methyl(3-chloropropyl)siloxane, methyl(2-methyl-3-chloropropyl)siloxane.

trimethylsiloxane, dimethylphenylsiloxane,
Triorganosiloxanes such as dimethyl(L&3-trifluoropropyl)siloxanes, methylsiloxanes,
Propylsiloxane.

There are monoorganosiloxanes such as phenylsiloxane, 3,3.3-trifluoropropylsiloxane, 3-chloropropylsiloxane, 2-methyl-3-chloro-logropylsiloh f7. Specific examples of siloxane include:

Examples include dimethylvinylsiloxy end-blocked polydimethylsiloxane, phenylmethylvinylsiloxy endblocked diphenylsiloxane, roxydimethylsiloxy copolymerized polysiloxane, trimethylsiloxy endblocked methylvinylsiloxy dimethylsiloxy co-electropolysiloxane, etc.
It goes without saying that the alkenyl group-containing organopolysiloxanes that can be used in the present invention are not limited to these.

The organohydrogenpolysiloxane having an organohydrogensiloxane unit represented by (as described above) as an essential position may be composed only of organosiloxane units represented by formula (2).

It may also contain organosiloxane units such as Ti and other organosiloxane units. The structure of the organohydrogenpolysiloxane may be linear, monobranched, cyclic, or network-like, and the degree of polymerization is 2 or more, with the limit being an acceptable degree of polymerization (usually 10
060) is allowed.

R3 is the same or different substituted or non-1d monovalent hydrocarbon group, specifically a methyl group like R2.

Ethyl group, propy/L/ group, butyl group, octyl group.

Unsubstituted-valent hydrocarbon groups such as phenyl group, phenylethyl group, phenylpropyl group, or some or all of the hydrogen atoms of these groups are carbon.

3-Chlorpropyl 4.2- which is modified with an atom other than hydrogen, for example a halogen atom such as fluorine or chlorine atom
Methyl-3-chloropropyl group.

OC is a substituted-valent hydrocarbon group such as 3,3.3-trifluoropropyl group, and the number of carbon atoms in the substituted or unsubstituted monovalent hydrocarbon group is usually 1 to 20. 1~
An integer of 3, d is an integer of 0 to 2.

However, c+d≦3, but c=1d=0. c=1d=
1. The most common combination is c=1d=2.

Examples of the organic groups constituting the organosiloxane units other than the organohydrogensiloxane unit of formula (2) and examples of the organosiloxane units are based on the examples given in the explanation of component (A).

Specific examples of the organohydrogenpolysiloxane used in the present invention include dimethylhydrogensiloxy end-blocked dimethylsiloxymethylhydrogensiloxy copolymerized polysiloxane, trimethylsiloxy endblocked dimethylsiloxymethylhydrogensiloxy copolymerized polysiloxane, and cyclic methylhydrogenpolysiloxane. Examples include siloxane, but are not limited to these. Component (a) and component (b) react in the presence of platinum or a platinum-based compound, which is component (c), which will be described in detail later, to increase the molecular weight by 1 and give a product, but the product has a very high molecular weight. In order to obtain a product, it is preferable that component (a) contains a small number of elementary groups per molecule on average. Also.

Components (a) and (b) can be mixed in a desired ratio, but usually component (b) is mixed in a ratio equivalent to 0.2 to 5 times the amount of hydrogen groups to the alkenyl groups in component (a). 0 added
If the amount is less than 0.2 times, curing will be insufficient, and if the amount is more than 5 times, hydrogen gas will bubble, resulting in a lack of stability. However, in the case of a composition whose purpose is to obtain a silicone foam, the amount may exceed 5 times. In the composition of the present invention, components (a) and (b) are sufficiently compatible with each other. It is preferable to use a material that is soluble; if a material with poor compatibility is used, poor curing or uneven curing is likely to occur.

The platinum or platinum-based compound as component (iii) used in the present invention may be any known platinum compound commonly used in hydrosilylation, such as fine particulate platinum.

Particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complex of chloroplatinic acid, coordination compound of chloroplatinic acid and vinylsilokinine, platinum black, tetrakis (triphenylphosphine) Examples include haladium, halasium black, and even rhodium catalysts.

The amount used should be sufficient to cure the composition consisting of components (a) and (b), and in the case of a homogeneous platinum catalyst, 0% of the total amount of components (a) and (b). 1
It is preferable to use the amount in the range of ppm to 100 ppm, and in the case of a platinum-black-nato unbound catalyst, in the range of 20 ppm to 11,000 ppm.

As a component) used in the present invention, the general formula HC-
=C-C-OHt3) (wherein eArsR' is 4 as described above).

It is an important component as a storage stabilizer (addition reaction inhibitor) of this composition. Here, the aryl group represented by Ar is defined as a residue from which one hydrogen atom has been removed from the aromatic ring of an aromatic compound, and includes those having atoms other than carbon and hydrogen. Examples of the aryl group represented by Ar include phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, anthonyl group, phenanthryl group,
Examples include chlorphenyl group, furyl group, and pyridyl group. Also, R4 is hydrogen.

Or, it is a one-stroke organic group having 1 to 15 carbon atoms, and this -valent organic group includes the above-mentioned aryl group. Methyl group, ethyl group.

It may be an alkyl group such as a propyl group, and also includes an arylated alkyl group. These aryl groups, alkyl groups, and arylated alkyl groups may be further substituted with atoms such as oxygen, nitrogen, and halogen. ))) Examples of typical alkynyl alcohols are:

3-Phenylglopargyl alcohol 3-furylpropargyl alcohol 3-phenyl-1-butyn-3-ol 3,3-cyphenylglobargyl alcohol 3-tolyl-1-butyn-3-ol H3 1 3-naphthyl- 1-Butyn-3-ol H3 H3 3-phenyl-1-pentyn-3-ol C2)! 5 etc. can be mentioned. Further, the alkynyl alcohol as the component (2) may be of a type in which Ar and R4 in the general formula (3) are connected to each other at the other end. for example.

That is, an aryl group on one carbon atom.

It is essential that the alkynyl alcohol has a structure in which an ethiniλ group and a hydroxyl group are bonded, and an alkynyl alcohol having such a specific structure exhibits an excellent effect as a storage stabilizer in the present composition. These include 3-methyl-1-butyn-3-ol and 3-methyl-1-butyn-3-ol, which are conventionally known as storage stabilizers.
．． Compared to alkyvinyl alcohols having only alkyl groups as substituents such as 5-dimethyl-1-hexyn-3-ol and arylalkynes such as 3-phenyl-1-j'4-ol, Since the stabilizing effect is dramatically improved, the thickening suppressing effect can be seen even when the amount of storage stabilizer is reduced. Therefore, insufficient compatibility, which has conventionally been a problem when mixing organic compounds into siloxane, does not become a problem. Further 9 aryl groups used in the present invention [#t8! j! Compared to conventional alkyl-substituted alkynyl alcohols, alkynyl alcohols release the inhibition of thickening more quickly when heated, and therefore have the characteristic that it takes less time to cure one composition. There is.

(b) The amount of the component to be used can be almost arbitrarily selected as long as it is uniformly dispersed in the polysiloxane of the component (a) and the component (b). Preferably, they are used in a ratio of 2 to 10,000 moles.

The composition of the present invention has various properties including a reduction in thermal shrinkage during curing, a reduction in the coefficient of thermal expansion of the elastomer obtained by curing, thermal stability, weather resistance, chemical resistance, *flammability, and mechanical strength. Also for the purpose of improving.

Fillers and additives may be included to reduce gas permeability, such as quartz powder, glass fibers, carbon black, alumina, metal oxides such as iron oxide, titanium oxide, etc. metal carbonates such as carbonate, calcium carbonate, and magnetum carbonate. Furthermore, it is also possible to add a suitable pigment, dye blowing agent, antioxidant, etc. within a range that does not inhibit curing. Furthermore, the composition may be diluted with an appropriate organic solvent such as xylene or toluene depending on the use and purpose.

The compositions according to the invention can be cured to give elastomers, gels or foams, and their use applies to all applications in which conventional curable organoborial xane compositions are used. be able to. For example,
Botting materials for the IT/electronic industry, coating materials and molded products, and general industrial potting materials. coating materials, coating materials and molded products, rubber for molding matrices, penetrations for civil engineering and construction, joint sealing materials, medical molded products, dental impression materials,
Liquid injection molding materials, etc.

Next, I will give an example of the present invention.

All parts are by weight.

Viscosity & (cp: centiboise) is the value at 25°C.

Furthermore, Me represents a methyl group, and vi represents a vinyl group.

Example 1 Dimethylvinylsiloxy end-capped dimethylpolysiloxane with a viscosity of 500 cp (containing vinyl groups 410.5% polymerization)
) and 4 parts of average composition formula ganohydrogenpolysiloxane, and further.

After adding 0.02 part of 3-phenyl-1-buty/-3-ol and mixing uniformly, add a vinylsiloxane complex of chloroplatinic acid so that the platinum value is 5 ppm based on the total amount, and mix uniformly. Mixed. The viscosity at this time was 320 cp. When the mixture was left at 25° C., the viscosity increased by only about 10 cp after 4 weeks. 150°
OK /711 When heated, it will completely harden after about 30 seconds.

Comparative Example 1 For comparison, the same vinyl group-containing organopolysiloxane and organohydrogenpolysiloxane as in Example 1 were used to form a mixture of Example 1 and open coat.

After adding and mixing uniformly, the same amount of platinum complex as in Example 1 is obtained! It was added at a concentration of 5 ppm and mixed uniformly.

This mixture was left for 25' (3 minutes).

After two weeks, the viscosity increased to 500 cp, and after three weeks, it had hardened.

Comparative Example 2゜ Similarly, using the same vinyl group-containing organopolysiloxane and organohydrogen polysiloxane as in Example 1, Example 1
and 3-phenyl-1-butyne 0.02
After adding the same platinum complex as in Example 1 so that the amount of platinum was 5 ppm, the mixture was uniformly mixed. When this mixture was left to stand at 25°C, it was cured after 3 days.

Comparative Example 3 In the case of Example 1 without adding the storage stabilizer, it was cured at 25° C. for 7 to 8 minutes.

Example 2 Dimethylvinylsiloxy-terminated dimethylpolysiloxane with a viscosity of 2000 cp (0.2% by weight of vinyl group-containing ring)
) 109 parts and 1 part trimethylsiloxy end-capped methylhydrogen polysiloxane having a viscosity of 10 cp.

Furthermore, 3-phenyl-1-7'tin-3-ol 0.0
After 4 parts were mixed uniformly, a vinylsiloxane complex of chloroplatinic acid was added so that the platinum amount was 5 ppm based on the total amount, and the mixture was uniformly mixed. The viscosity at this time was 1900 cp. When the above mixture was left at 25'O, no increase in viscosity was observed even after 4 weeks. This material was heated to 150° C. and cured after about 30 seconds.

Comparative Example In Raw Example 2, 3-phenyl-1,-butyne-3-
A mixture under the same conditions was left at 25°C, except that 3''-methyl-1-butyn-3-ol was used as a storage stabilizer instead of ol.

It was completely cured after 4 weeks.

Example 3 Dimethylvinylsiloxy end-capped dimethylsiloxyphenylmethylsiloxy copolymerized organopolysiloxane (feral methylsiloxane units 10 moles 5) having a viscosity of 2000 cp was mixed with iootIA and 5 parts of Luganohydrogenpolysiloxane having an average composition, and further K 3.3 - 0.03" part of diphenylpropargyl alcohol was added and mixed uniformly. A vinyl siloxane complex of chloroplatinic acid was added so that the amount of platinum was 5 ppm per 1 part, and mixed uniformly.

The viscosity was 1800 c,p. The above mixture was heated at 25°C.
When I left it for two months, the viscosity increased by about 50 cp.
'I just did it. When heated to 150°C, it was completely cured after about 30 seconds.

Comparative Example 5 In Example 3, 3-methyl-1-butyn-3-ol was used as a storage stabilizer instead of 3,3-diphenylpropargyl alcohol.
When left at 5°C.

After 4 weeks the viscosity exceeded 2000 cp' and after 6 weeks it was cured.

Implemented fallen hair Me2Vi 5i034 unit 20 mol%, Me3S
Toluene soluble organopolysiloxane resin 35 consisting of i034 AA Si mole and 5iOH unit omega mole
part to 100 parts of toluene, and the viscosity was 2000c.
After mixing with 65 parts of dimethylvinylsiloxy end-capped dimethylpolysiloxane of P, the toluene was distilled off. 6 parts of the organohydrogen polysiloxane used in Example 1 were mixed into the mixture, and 3-phenyl-1-butyne-3-
After adding 0.01 part of all and mixing uniformly, the amount of platinum is 5% of the total amount of vinyl siloxane of chloroplatinic acid.
It was added so as to give ppm and mixed uniformly. The viscosity was 3400 ep, and when it was left at 25° C., almost no increase in viscosity was observed even after 3 days. This product cured in 50 seconds when heated to 120°C.Except that 3-methyl-1-butyn-3ol was used in place of 3-phenyl-1-butyn-3ol used in comparative examples and practical hair removal. A gap experiment was conducted on the mixture under exactly the same conditions as in Example 4, and when it was left at 25°C, there was almost no increase in viscosity after 3 days, but the curing time was 1 when heated to 120°C. It took minutes and 10 seconds.

Claims (1)

[Claims] 4=a-b (wherein, R1 is an alkenyl group having 2 to 4 carbon atoms, B2 is a substituted or unsubstituted monovalent carbide or hydrogen group, and a is an integer of 1 to 3., b An alkenyl group-containing organopolysiloxane having organosiloxane units represented by an integer of 0 to 2, provided that a, +b≦3). (b) Formula HeR”d 5i04-c-(1(f, middle), R3 is a substituted or unsubstituted monovalent hydrogen group, C is 1
an integer of ~3, d is an integer of 0-2, provided that c+d≦3) has an organowater-unsiloxane unit represented by (c) platinum or platinum± compound, and (d) general formula Ar 1 ゛HC=C- An organopolysiloxane characterized by consisting of an alkynyl alcohol represented by C-OH (in the formula ', Ar is an aryl group, an organic group of I 4 or M and R 4 interconnected at the other end) Composition.