KR830000169B1 - Organopolysiloxane composition - Google Patents

Abstract

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Description

Non-Flowable Organopolysiloxane Compositions

The present invention relates to a non-flowing organopolysiloxane composition.

Viscous compositions of liquid organopolysiloxanes, in particular dimethylpolysiloxanes and microparticulate silica filters, at room temperature may include release agents, lubricants, electrical insulation, antifoaming agents, sealants, and sealants. It is also widely used as a raw material for liquid silicone rubber.

However, since the viscous composition consisting of liquid organopolysiloxane and microparticulate silica filler only at room temperature has magnetic fluidity, it is expanded to a place other than the place to be applied when used as the material, and the function at the place of application is performed. At the same time, there is a drawback that it causes obstacles such as pollution in other places that have spread.

In particular, when used as a raw material for liquid silicone rubber, the place of application is extremely limited due to the magnetic fluidity. For example, it cannot be applied to vertical or sloped surfaces.

In order to solve this problem, Japanese Unexamined Patent Publication No. 39-22438 discloses a composition in which boric acid or alkyl borate is added. However, when it is used as a raw material for the defect and liquid silicone rubber, the effect is insufficient if it is not heat treated. There is a drawback that there is a tendency to inhibit).

Japanese Unexamined Patent Publication No. 49-5510 discloses a non-flowable composition composed of liquid organopolysiloxane, hydrophobic silica and organic liquid above a certain vapor pressure. However, the organic liquid has flammability, toxicity, and volatility. There is a drawback to causing various problems.

The present inventors have reached the present invention as a result of studying to develop a non-flowable organopolysiloxane composition without such a defect.

That is, the present invention

(A) 100 parts by weight of liquid organopolysiloxane at room temperature

(B) 2-60 parts by weight of non-particulate silica filler

(C) relates to a non-flowable organopolysiloxane composition comprising 0.1-40% by weight of the total amount of the liquid alcohol-modified organopolysiloxane and / or carboxylic acid-modified organopolysiloxane (A) (b) component at room temperature. .

The present invention provides a mixture of (a) component, (b) component and organopolysiloxane having an alcoholic hydroxyl group or carboxyl group of (poly) component to be non-flowable simply by mixing, and there is no drawback as in the known example. Based on the confirmation.

The component (a) is a component constituting the composition of the present invention, and when the liquid phase is formed at room temperature, the degree of polymerization, molecular structure and substituent are irrelevant.

However, organopolysiloxane such as (C) component should be excluded. Normal temperature means the temperature of the atmosphere in which the composition of the present invention is actually used, that is, -10 ° C to 40 ° C.

The degree of polymerization is generally referred to as polysiloxane, i.e., from 10 or more, generally from 5,000 to 6,000 or less industrially manufacturable.

狀), 분지쇄상(分枝

狀), 환상(環狀), 망상의 어느것이라도 좋으나, 직쇄상이 가장 일반적이다.In particular, the characteristic of this invention is expressed more in the case of the polymerization degree which the viscosity in 25 degreeC shows 50 centistokes-100,000 centistokes. The molecular structure is linear

Branched branching

I) Any one of annular and delusional forms may be used, but linear is most common.

The substituent may be any of conventionally known substituents of organopolysiloxane, such as an alkyl group, an alkenyl group, an aryl group, a halogenated alkyl group, and the like. However, the combined organic group of the hydroxyl group and the combined organic group of the carboxyl group are excluded.

The methyl group, vinyl group, phenyl group, 3,3,3-trifluoropropyl group, 2-phenylethyl group, octyl group, dodecyl group and the like are common.

Especially methyl groups are common. As a substituent, a few reactive groups, such as a hydroxyl group, a hydrogen atom, an acyloxy group, an alkoxy group, and a ketoxime group, may exist. When the vinyl group or the reactive group thereof is present at the terminal of the linear or branched organopolysiloxane, the composition of the present invention is useful as a raw material of the non-flowable liquid silicone rubber.

나

로 표시되는 액상 메틸폴리실록산이 있다.As an example, dimethyl polysiloxane, dimethyl whose sock end is sealed by the trimethyl siloxy group, the dimethyl vinyl siloxy group, the dimethylphenyl siloxy group, the dimethyl hydro diene siloxy group, the dimethyl hydroxy siloxy group, the dimethyl ethoxy siloxy group, the methyl diacetoxy siloxy group, etc. Siloxane-methylvinylsiloxane copolymer, dimethylsiloxane-methylphenylsiloxane copolymer, dimethylsiloxane-niphenylsiloxane copolymer, dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymer, dimethylsiloxane-methyl ( 2-phenylethyl) siloxane copolymer, dimethylsiloxane-methyloctylsiloxane copolymer, dimethylsiloxane-methylhydrodiene siloxane copolymer, or methylhydrodienepolysiloxane, the branched methyl of which the terminal is substituted with a trimethylsiloxy group or a dimethylhydroxy group Polysiloxane, methylphenylpolysiloxane, methylbitylpolysiloxane, average unit formula

I

There is a liquid methyl polysiloxane represented by.

(B) A component is a microparticle filler which has a silica as a main component, and makes it the composition of this invention viscous, and is a component for making it non-flowable by the synergy with (c) component.

When using this composition as a raw material of liquid silicone rubber, it is also a component for enlarging the mechanical characteristic after hardening. Specific examples include dry silica (also called fumed silica), wet silica (also called precipitated silica), dry silica or precipitated silica with trimethylsiloxylated hydroxyl groups on the surface of silicon atoms, and low-polymerization dimethyl on the surface. Dry process silica hydrophobized with polysiloxane, precipitated silica, and a dry method filler containing silica and silica as a main component, and other metals such as titanium and aluminum as secondary components.

Although the addition amount of this component is 2-60 weight part with respect to 100 weight part of (A) components, when it is too small, it will be difficult to make it non-flowable, and when too much, kneading itself will be difficult or it will work as a composition. This is because the sex is degraded.

Dry silica particles rather than wet silica, the surface area is larger, and the filler surface is hydrophobized.

(C) component is a component which comprises the characteristic of this invention, and makes the composition of this invention non-flowable by synergy with (B) component. This function is expressed by an alcoholic hydroxyl group or a carboxyl group. Other organic groups are necessary to improve compatibility with the (a) component.

(Justice)

In the present invention, "alcohol-modified organopolysiloxane" means "organopolysiloxane" having an organic group bonded to a hydroxyl group, and "carboxyl-modified organopolysiloxane" means "organopolysiloxane having an organic group bonded to a carboxyl group". .

It is common that the combined organic group of the hydroxyl group or the combined organic group of the carboxyl group is present in the range of 0.2% -50% of the total number of whole organic groups. The organic group combined with the organic group of the hydroxyl group or the carboxyl group may exist anywhere in the molecule.

It may exist in the middle part, terminal part, or both ends of a coupling chain. It is common to be present at the middle, end, or both ends of the binding chain.

As a specific example of the combined organic group of the hydroxyl group,

,

,-CH ₂ OH, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH,

,

,

,-CH₂CH₂COOCH₂CH₂OH ,

-(CH ₂ ) ₆ -OH,

, -CH ₂ CH ₂ COOCH ₂ CH ₂ OH,

In particular, the alkyl group which couple | bonded with the hydroxyl group at the terminal is preferable.

As a specific example of the combined organic group of a carboxyl group,

-CH₂CH₂CH₂COOH ,

, -(CH₂)₈-COOH가 있다.-CH ₂ CH ₂ COOH,

-CH ₂ CH ₂ CH ₂ COOH,

,-(CH ₂ ) ₈ -COOH.

Also in this case, the alkyl group which couple | bonded with the carboxyl group at the terminal is preferable.

The molecular structure of this component may be any of linear, branched, cyclic and reticulated.

The polymerization degree may be 2 or more, and the upper limit which shows a liquid state at normal temperature is not limited.

As an organic group other than the combined organic group of the hydroxyl group of this component, or the combined organic group of a carboxyl group, any of the conventionally well-known substituents of organopolysiloxane, such as an alkyl group, an alkenyl group, an aryl group, and a halogenated alkyl group, may be sufficient.

The methyl group, vinyl group, phenyl group, 3,3,3-trifluoropropyl group, 2-phenylethyl group, octyl group, dodecyl group and the like are common. Especially methyl groups are common.

The present component is, for example, an alcohol, vinylphenol, unsaturated fatty acid or polyhydric alcohol partial ester thereof having a vinyl group, added to the hydrogen atom of the silicon atom bond of organohydrodiene polysiloxane by using a platinum catalyst, or halogenated organopolysiloxane. Produced easily by substituting a halogen of a hydroxyl group.

The less the molecular weight and the larger the number of hydroxyl groups or carboxyl groups, the lower the compounding amount. However, if the amount is too small, the effect of making it non-flowable is insignificant, and even if it is too large, it ends insignificantly and is 0.1-40 of the total amount of the component (A). Wt% is blended. Preferably it is 0.5-10 weight% compounding.

The composition of the present invention can be easily prepared by mixing the (A)-(C) components until they are uniform.

Moreover, you may mix and mix 2 or more types, not only 1 type for every component. In order to make non-flowability larger, it is preferable to mix (a) component and (a) component first, and to mix (b) component next.

In the composition of the present invention, other components such as diatomaceous earth, extender fillers such as quartz fine powder, pigments such as carbon black, titanium oxide, zinc oxide, and alumina, and thickeners such as boric acid and alkyl borate are provided within the range that does not impair their non-fluidity. Agents, flame retardants, plasticizers, and the like can be added. In particular, when the component (A) has a reactive substituent of a silicon atom bond, for example, a hydroxyl group, tetraethoxysilane, methyltrimethoxysilane, methyltri (methylethylketoxime) silane, methyltriacetoxysilane, vinyltriacetoxysilane , Crosslinking agents such as methyltri (N, N-diethylaminooxy) silane, methyltri (N-butylyl) silane or methylhydrogenpolysiloxane, and curing such as diorganotin carboxylate or alkyl titanate, if necessary By adding a catalyst, room temperature curable liquid silicone rubber can be produced.

When having a vinyl group, methylhydrogenpolysiloxane and a platinum catalyst can be added to produce room temperature to heat-curable liquid silicone rubber.

For example, dimethyl polysiloxane is selected as the component (A), microparticulate silica filler is selected as the component (B), and polysiloxane composed of a methyl group and a hydroxyalkyl group as the component (C) is selected and blended to prepare a transparent composition. You can do it.

In the present invention, the composition has no magnetic fluidity, so it remains in the place where it is applied, does not diffuse to the periphery and contaminates, and because of its excellent stability, it is applied as a release agent, a lubricant, an electric insulator, a sealing agent, etc., to a vertical plane, a slope, a plane. You can do it.

In particular, when used as a raw material for room temperature moisture-curable liquid silicone rubber, it is possible to produce room temperature moisture-curable liquid silicone rubber of non-sag property, that is, it does not sag even when applied to a vertical surface. have.

Although an Example is enumerated next, all the parts in an Example mean a weight part, and all the viscosity is a value in 25 degreeC.

The slump test was based on 6.3 slump of Japanese JIS-A-5757 "Performance of the sealing material for construction". It is only the value at 25 degreeC of atmospheric temperature.

Me in the formula means methyl group and ø means phenyl group.

Example 1-3

-히드록시알킬)메틸폴리실록산 3부를 혼합하고, 뒤이어 표면적 200㎡/gr의 건식법실리카 10부를 소량씩 첨가 혼합하고 균일한 조성물로 하였다. 이 조성물은 어느것이나 약간 백탁하고 있으나 투명하였다. 이 조성물의 혼합직후와 7일후에 있어서의 슬럼프를 측정하고, 제 1표에 표시하였다.100 parts of α, ω-dihydroxy dimethyl polysiloxane having a viscosity of 12,000 centistokes and

3 parts of -hydroxyalkyl) methylpolysiloxane were mixed, followed by addition and mixing of 10 parts of dry method silica having a surface area of 200 m 2 / gr in small portions to obtain a uniform composition. All of these compositions were slightly cloudy but clear. The slump immediately after mixing and after 7 days of this composition was measured, and it showed in the 1st table | surface.

As a comparative example, only (γ-hydroxyalkyl) methylpolysiloxane was added but the others were prepared under the same conditions and the same slump was measured and shown in the first table.

TABLE 1

Degassing 100 parts of the composition of each of the above Examples and Comparative Examples, 8.0 parts each of methyltri (methyl ethyl ketoxime) silane and 0.02 parts each of dibutyl tin dilaurate or 7.0 parts each of methyltriacetoxysilane in the absence of moisture When 0.02 parts of each part and dibutyl tin dilaurate were added and mixed until it became uniform, it became liquid silicone rubber which hardened in the absence of moisture and hardened at room temperature in the presence of moisture.

In each of the examples described above, the slump was extremely small as in the first table, but the composition of the comparative example was scale-over and incapable of measuring.

Example 4-8

100 parts of organopolysiloxane of Table 2 and the following structural formula

1.0 part of ((beta) -hydroxyethyl) methyl polysiloxane was mixed, and 23 parts of dry silica of the surface area of 130 m <2> / gr which trimethyl-siloxylated the hydroxyl group of the silicon atom bond of the surface were added little by little, and it was set as the uniform composition.

The slump immediately after mixing and after 7 days of this composition was measured and shown in the 2nd table | surface.

As a comparative example, only ((beta) -hydroxyethyl) methylpolysiloxane was added, the other was made under the same conditions, and the slump was measured.

TABLE 2

Defoaming 100 parts of the composition of Example 7 and adding 7 parts of vinyltrimethoxysilane and 0.3 parts of tetrabutyl ortho titanate in the absence of moisture and mixing until uniform, as a result of not curing in the absence of moisture and at room temperature in the presence of moisture It became the liquid silicone rubber to harden.

Its slump was 0.1 mm.

However, the slump of the liquid silicone rubber made under the same conditions in the composition of the comparative example was incapable of measuring the scale over.

In addition, 100 parts of the composition of Example 8 was degassed, 34 parts of vinyl tri (methylethylketoxime) silane in the absence of moisture was added, and the slump of the room temperature moisture-curable silicone resin produced by mixing until uniform was 0.4 mm.

The slump of the room temperature moisture-hardenable silicone resin made by the composition of the comparative example was incapable of measuring due to scaleover.

Example 9-13

80 parts of α, ω-dihydroxydimethylpolysiloxane having a viscosity of 76,000 centistokes and 20 parts of α, ω-bis (trimethylsiloxy) dimethylpolysiloxane having a viscosity of 1,000 centistokes and (γ-hydroxypropyl) methylphenyl having the following structural formula 5 parts of polysiloxanes were mixed, and the microparticle silica filler of the 3rd table | surface was then added-mixed little by little, and it was set as the uniform composition.

The slump just after mixing of this composition and after 7 days was measured and shown in the 3rd table | surface.

As a comparative example, only ((gamma) -hydroxypropyl) methylphenylpolysiloxane was not added, others made the composition on the same conditions, and measured slump similarly, but it was impossible to measure by either scale-over.

TABLE 3

Four parts of methyl tri (N, N-dimethylaminooxy) silane were added to each of 100 parts of the composition of Example 8 and Example 9, it mixed quickly, and the slump was measured.

The former was 0.4 mm and the latter was 0 mm. After 90 minutes, both the surface and the interior were almost uniform and were in a rubber state.

Example 14-16

100 parts of α, ω-dihydroxydimethyl polysiloxane having a viscosity of 5,000 centistokes and 2 parts of carboxylic acid-modified methylpolysiloxane of the fourth table are mixed, and then 10 parts of dry method silica having a surface area of 200 m ² / gr are added and mixed in small amounts to obtain uniform mixing. The composition was made.

The slump in 7 days after mixing of this composition was measured and shown in the 4th table | surface.

As a comparative example, only the carboxylic acid-modified methylpolysiloxane was added but the others were prepared under the same conditions, and the slump was measured in the same manner.

TABLE 4

Claims (1)

(A) 100 parts by weight of liquid organopolysiloxane at room temperature, (B) 2-60 parts by weight of fine particulate silica filler, (C) alcohol-modified organopolysiloxane and / or carboxylic acid-modified organopolysiloxane, (A) A non-flowing organopolysiloxane composition comprising 0.1-40% by weight of the total amount of the component (b).