JP3383670B2 - Reactive organopolysiloxane - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a reactive organopolysiloxane, and more particularly, to an adhesion modifier between materials,
The present invention relates to a novel reactive organopolysiloxane which is useful as a paint modifier, a fiber surface modifier, etc. and exhibits excellent weather resistance, heat resistance, and durability.

[0002]

Organopolysiloxanes having an alkoxysilyl group and an organic reactive functional group in one molecule are disclosed in British Patent No. 1409741. However, this organopolysiloxane is used as an adhesion modifier between two materials (especially between an organic material and an inorganic material such as an inorganic filler).
When used as a paint modifier, fiber surface modifier, etc.,
There were drawbacks such as poor reactivity with the substrate.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks, and improves the adhesiveness between materials (particularly between organic materials and inorganic materials such as inorganic fillers) and paints. When used as a substance or surface modifier for fibers,
An object of the present invention is to provide a novel reactive organopolysiloxane exhibiting excellent weather resistance, heat resistance and durability.

[0004]

Means for Solving the Problems As a result of earnest research by the present inventors, the reactivity having at least one organic reactive functional group and at least one condensable silylalkyl group directly bonded to a silicon atom in one molecule. The inventors have found that organopolysiloxane can solve the above problems, and have completed the present invention.

That is, the present invention provides, in one molecule, directly bonded to a silicon atom: a) the following formula: -R ¹ -X (wherein R ¹ is a direct bond or has 1 to 20 carbon atoms).
Represents a divalent hydrocarbon group of, X is a glycidyloxy group,
Amino ethyl imino group _{[-NH (CH 2) 2 NH} 2],
Amino group, carboxyl group, acyl group, mercapto group,
Methacryloxy group, isocyanate group, ureido group, vinyl
Nyl group, amide group, imide group, imino group, aldehyde
Groups, nitro groups, nitrile groups, oxime groups, azo groups or
An organic reactive functional group (Y group) represented by a functional group having an organic reactivity selected from a dolazone group , and b) the following formula: (In the formula, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a represents 2 or 3 And an at least one condensable silylalkyl group (Z group) represented by each integer.

The present invention has the following formulas: [In formula, R represents a hydrogen atom, a monovalent hydrocarbon group, or a halogenated alkyl group mutually independently, Y is the following formula: -R ¹ -X (In the formula, R ¹ is a direct bond or has 1 carbon atom. Through 20
Represents a divalent hydrocarbon group of, X is a glycidyloxy group,
Amino ethyl imino group _{[-NH (CH 2) 2 NH} 2],
Amino group, carboxyl group, acyl group, mercapto group,
Methacryloxy group, isocyanate group, ureido group, vinyl
Nyl group, amide group, imide group, imino group, aldehyde
Groups, nitro groups, nitrile groups, oxime groups, azo groups or
Represents a functional group having organic reactivity selected from the dolazone group ), Z represents the following formula: (In the formula, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a represents 2 or 3 Is an integer), M is a group selected from R, Y and Z, p is an integer of 0 to 500, and q is 0 to 2
00 is an integer of 0 to 200, but when q is 0, M is Y, and r is an integer of 1 or more, and when r is 0, M is Z, And q is an integer of 1 or more].

In the above formula, R is independently of each other a hydrogen atom,
Monovalent hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, phenyl group,
A phenethyl group and the like or a halogenated alkyl group such as a trifluoropropyl group and a chloropropyl group, particularly a monovalent hydrocarbon group, especially a methyl group, and a fluoroalkyl group are preferable.

R ¹ in the above Y group is a direct bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, for example, —CH _{2
-, - CH 2 CH 2 -} , - CH 2 CH 2 CH 2 -, - C
_{H (CH 3) CH 2 -} , - (CH 2) 4 -, - (C
_{H 2) 6 -, - (} CH 2) 8 -, - CH 2 CH 2 C 6 H
_{4 -, - (CH 2)} 12 -, - (CH 2) 16 - a, preferably from propylene group. In addition, X of the Y group is a functional group having organic reactivity, such as glycidyloxy.
Group, an amino group, a hydroxyl group, a carboxyl group, an acyl group, a mercapto group, methacrylo alkoxy group, an isocyanate group, a ureido group, a vinyl group, an amide group, an imide group, an imino group,
It is an aldehyde group, a nitro group, a nitrile group, an oxime group, an azo group, or a hydrazone group. Specific examples of the Y group include-
_{(CH 2) 3 OH, -} (CH 2) 3 SH, - (CH 2)
₃ NH ₂ ,-(CH ₂ ) ₇ COOH, However, the present invention is not limited to these.

R ² in the Z group is an alkylene group having 2 to 5 carbon atoms, for example, --CH ₂ CH _2- , --CH _{2
CH 2 CH 2 -, - CH} (CH 3) CH 2 -, - (CH
₂ ) ₄ -,-(CH ₂ ) _5-, etc., preferably ethylene group. R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group or a butyl group, preferably R ³ is a methyl group and R ⁴ is methyl. Group or ethyl group. a is an integer of 2 or 3, but 3 is preferable from the viewpoint of reactivity. Specific examples of the Z group include —CH ₂ CH.
_{2 Si (OCH 3) 3,} -CH 2 CH 2 Si (OC 2 H
_{5) 3, -CH 2 CH 2} Si (CH 3) (OC
_{H 3) 2, -CH 2 CH} 2 Si [OCH (CH _{3) 2]
3, - (CH 2) 3} Si (CH 3) (OC 2 H 5) 2,
_{- (CH 2) 5 Si (} C 2 H 5) (OC 2 H 5) but ₂ and the like, but is not limited thereto.

The following may be mentioned as specific examples of the reactive organopolysiloxane of the present invention.
Of course not limited to:

The reactive organopolysiloxanes of this invention can be prepared by a combination of conventional synthetic methods known per se. For example, in the case of the compound represented by the above formula (1), the corresponding methyl hydrogen polysiloxane is And CH ₂ ═CHSi (OCH ₃ ) _{3 in} the presence of a platinum-based catalyst. Similarly,
In the case of the compound represented by the above formula (2), the corresponding methyl hydrogen polysiloxane is And CH ₂ ═CHSi (OC ₂ H ₅ ) _{3 in} the presence of a platinum-based catalyst. Further, in the case of the compound represented by the above formula (3), CH ₂ ═CHCH is added to the corresponding methyl hydrogen polysiloxane.
It can be obtained by addition reaction of ₂ OH and CH ₂ ═CHSi (OCH ₃ ) _{3 in} the presence of a platinum catalyst. In the case of the compound represented by the above formula (4), CH ₂ ═CHCH is added to the corresponding methyl hydrogen polysiloxane.
₂ Cl and _{CH 2 = CHSi (OCH 3)} 3 and by addition reaction in the presence of a platinum catalyst to be the resulting product is then obtained by reaction with ethylenediamine.

The reactive organopolysiloxane of the present invention can be used, for example, as a modifier for the adhesiveness between two materials (especially between an organic material and an inorganic material such as an inorganic filler), and can be used as a natural rubber or styrene. Synthetic rubber such as butadiene copolymer rubber, butadiene rubber, isobutylene-isoprene copolymer rubber, chloroprene rubber, acrylonitrile-butadiene copolymer rubber, isoprene rubber, ethylene-propylene-diene copolymer rubber, ethylene-propylene copolymer rubber and acrylonitrile -Butadiene-styrene copolymer, compounded with synthetic resins such as polystyrene, or rubber-based adhesives, urethane resin-based adhesives, epoxy resin-based adhesives, etc. used for bonding these to other rubbers or resins Or use this organopolysiloxane as the main component of the adhesive. It can also be. It is also effective as an adhesive at the interface between the compositions in mixing rubber or resin.
Further, the organopolysiloxane of the present invention is an organic material such as the above rubber or resin and metal or silica, quartz, talc, clay, zinc oxide, iron oxide, titanium oxide, aluminum oxide, calcium carbonate, aluminum hydroxide, mica, Excellent adhesive strength is exhibited even when bonded to an inorganic filler such as carbon black or an inorganic material such as glass, and a reinforced plastic or high-strength elastomer having high weather resistance and heat resistance can be obtained. Also, as a paint modifier, it is mixed with paint resins such as polyester resin and acrylic resin, and metal,
It enables coating with excellent weather resistance, durability and heat resistance on wood, concrete, etc. Further, as the surface modifier of the fiber, as its material, natural fiber such as wool, silk, hemp, cotton, asbestos, regenerated fiber such as rayon, cupra and acetate, polyester, polyester ether,
It may be any fiber such as organic synthetic fiber such as polyacrylonitrile, vinylon, polyvinylidene chloride, polyvinyl chloride, polyethylene, polypropylene, etc., glass fiber, inorganic synthetic fiber such as carbon fiber, woven fabric, knitted fabric, non-woven fabric, resin The surface of the fiber can be treated in any form such as a work cloth, and the fiber is provided with weather resistance and durability. Therefore, the present invention relates to the use of the above-mentioned reactive organopolysiloxane according to the present invention as an adhesion modifier between materials, a paint modifier and a surface modifier for fibers, among which the organopolysiloxane of the present invention is used. Siloxane is preferably used as an adhesion modifier between an organic material and an inorganic material.

[0013]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

Example 1 35 g vinyltrimethoxysilane, 80 gamma-glycidoxy-1-propene in a 500 ml three-necked flask equipped with a mechanical stirrer, condenser, thermometer and nitrogen inlet.
g, toluene 100 g, and a 10% ethanol solution of chloroplatinic acid so that the platinum content was 20 ppm. To this mixture, at a rate such that the temperature was maintained at 80-100 ° C., the following formula: Methyl hydrogen polysiloxane represented by 100
g was gradually added, and stirring was continued while maintaining this temperature to allow the reaction to proceed. The end of this reaction was determined by a negative AgNO ₃ test for SiH. Then, the reaction mixture was neutralized with NaHCO ₃ and filtered, and the solvent was removed by a rotary evaporator at 50 ° C./1 mmHg. 204 g of an organopolysiloxane represented by

Example 2 100 g of toluene, 9.3 vinyltrimethoxysilane
g, γ-glycidoxy-1-propene 5.7 g, the following formula: Methyl hydrogen polysiloxane 200 represented by
g and a 10% ethanol solution of chloroplatinic acid having a platinum content of 20 ppm, the same operation as in Example 1 was carried out. 202 g of an organopolysiloxane represented by

Example 3(Reference example) 50 g of toluene, 120 g of vinyltrimethoxysilane,
Next formula: CH_Two= CHCH_TwoAllyl alco represented by OH
23 g, the following formula: Methyl hydrogen polysiloxane represented by 100
g, and chloroplatinic acid having a platinum content of 20 ppm
Using a 10% ethanol solution of
If you do the following formula: 218 g of an organopolysiloxane of
It was

Example 4 50 g of toluene, 60 g of vinyltriethoxysilane, 120 g of allyl methacrylate, the following formula: Methyl hydrogen polysiloxane represented by 100
g and a 10% ethanol solution of chloroplatinic acid having a platinum content of 20 ppm, the same operation as in Example 1 was performed. 250 g of an organopolysiloxane represented by

Formulas (A) to (D) synthesized in Examples 1 to 4
The following tests were carried out using the organopolysiloxanes of the present invention represented by and the organopolysiloxanes represented by the following formulas (E) and (F) as a control for comparison.

Test Example 1 BAKELITE polyethylene DYNH 1.0k
g, quartz powder 1.0 kg, any one of the above test compounds
0 g and 30 g of die cup (Dicup, manufactured by HERCULES) were mixed at 121 ° C. using a double roll. Then 177 ° C
Was subjected to compression molding for 20 minutes, and the tensile strength of the molded product was measured.
The results are shown below, but the one using the organopolysiloxane of the present invention showed extremely high tensile strength as compared with the blank and the control.

Test Example 2 Bakelite Epoxy Resin ERL-2774 500
g, methyl nadic acid anhydride (curing agent) 400 g, benzyldimethylamine (catalyst) 2.5 g, test compound 10
g and wollastonite (calcium silicate) 500
g were mixed. Then, it was cured at room temperature for 16 hours and further at 177 ° C. for 2 hours, and the bending strength was measured immediately after curing and after boiling for 72 hours. The results are shown below, but the one according to the present invention shows higher flexural strength than the blank and the control, both immediately after curing and after boiling for 72 hours, especially 7
Even after boiling for 2 hours, the rate of decrease in bending strength was low.

[0021]

INDUSTRIAL APPLICABILITY The reactive organopolysiloxane of the present invention has at least one organic reactive functional group (Y group) and at least one condensable silylalkyl group (Z group) directly bonded to the silicon atom, Shows sufficient reactivity. Therefore, the reactive organopolysiloxane of the present invention is used as a modifier for the adhesiveness between materials (particularly between organic materials and inorganic materials such as inorganic fillers),
When used as a paint modifier, fiber surface modifier, etc.,
It is highly reactive with base materials and imparts excellent weather resistance, heat resistance and durability to those base materials. In addition, the reactive organopolysiloxane of the present invention is capable of various molecular designs according to each substrate to be modified and each application due to the variety of synthetic raw materials, and can easily impart the properties as designed. is there.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 77/00-77/62

Claims (7)

(57) [Claims] 1. In one molecule, a) directly bonded to a silicon atom: a) the following formula: —R ¹ —X (wherein R ¹ is a direct bond or has 1 to 20 carbon atoms).
Represents a divalent hydrocarbon group of, X is a glycidyloxy group,
Amino ethyl imino group _{[-NH (CH 2) 2 NH} 2],
Amino group, carboxyl group, acyl group, mercapto group,
Methacryloxy group, isocyanate group, ureido group, vinyl
Nyl group, amide group, imide group, imino group, aldehyde
Groups, nitro groups, nitrile groups, oxime groups, azo groups or
Represents an organic-reactive functional group selected from the dolazone groups ), and b) the following formula: (In the formula, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a represents 2 or 3 Which is an integer) and each has at least one condensable silylalkyl group. 2. The following formula: [In formula, R represents a hydrogen atom, a monovalent hydrocarbon group, or a halogenated alkyl group mutually independently, Y is the following formula: -R ¹ -X (In the formula, R ¹ is a direct bond or has 1 carbon atom. Through 20
Represents a divalent hydrocarbon group of, X is a glycidyloxy group,
Amino ethyl imino group _{[-NH (CH 2) 2 NH} 2],
Amino group, carboxyl group, acyl group, mercapto group,
Methacryloxy group, isocyanate group, ureido group, vinyl
Nyl group, amide group, imide group, imino group, aldehyde
Groups, nitro groups, nitrile groups, oxime groups, azo groups or
Represents a functional group having organic reactivity selected from the dolazone group ), Z represents the following formula: (In the formula, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a represents 2 or 3 Is an integer), M is a group selected from R, Y and Z, p is an integer of 0 to 500, and q is an integer of 0 to 200. And r is an integer of 0 to 200, provided that when q is 0, M is Y, and r is an integer of 1 or more, and when r is 0, M is Z and q is 1 The above-mentioned integer is an integer]. 3. The reactive organopolysiloxane according to claim 2, wherein R represents a monovalent hydrocarbon group or a fluoroalkyl group. 4. The reactive organopolysiloxane according to claim 1, which is used as an adhesion modifier between materials. 5. The reactive organopolysiloxane according to claim 1, which is used as a paint modifier. 6. The reactive organopolysiloxane according to claim 1, which is used as a surface modifier for fibers. 7. The reactive organopolysiloxane according to claim 4, which is used as an adhesion modifier between an organic material and an inorganic material.