JP3308977B2 - Reactive organopolysiloxane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to reactive organopolysiloxanes, 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 has excellent weather resistance, heat resistance and durability.

[0002]

2. Description of the Related Art An organopolysiloxane having a polyoxyalkylene group and an organic reactive functional group in one molecule is disclosed in U.S. Pat. No. 4,184,004. Also, 1
An organopolysiloxane having an alkoxysilyl group and an organic reactive functional group in a molecule is disclosed in British Patent No. 140974.
No. 1. However, when these organopolysiloxanes are used as an adhesion modifier between two materials (particularly, between an organic material and an inorganic material such as an inorganic filler), a paint modifier, a fiber surface modifier, etc. However, there was a defect that the reactivity with the substrate was poor, and the latter could not control the hydrophilicity.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned drawbacks, and it is an object of the present invention to provide an adhesive property modifier between materials (particularly, between an organic material and an inorganic material such as an inorganic filler), and a paint reforming agent. When used as a filler, fiber surface modifier, etc.
An object of the present invention is to provide a novel reactive organopolysiloxane having excellent weather resistance, heat resistance and durability.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have at least included, in one molecule, at least an organic reactive functional group, a condensable silylalkyl group and a polyoxyalkylene group directly bonded to a silicon atom. The present inventors have found that the above problem can be solved by a reactive organopolysiloxane having one, and have completed the present invention.

That is, the present invention relates to a method in which one molecule is directly bonded to a silicon atom in one molecule. A) The following formula: -R ¹ -X (wherein R ¹ is a direct bond or a group having 1 to 20 carbon atoms)
X represents a glycidyloxy group,
A minoethylimino group [—NH (CH ₂ ) ₂ NH ₂ ],
Amino group, hydroxyl group, carboxyl group, acyl group, mercap
Group, methacryloxy group, isocyanate group, ureide
Group, vinyl group, amide group, imide group, imino group, aldehyde
Hyd group, nitro group, nitrile group, oxime group, azo group or
Represents an organic reactive functional group selected from hydrazone groups ), and b) an organic reactive functional group (Y group) represented by the following formula: (Wherein, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a represents 2 or 3 a condensable silyl group (Z group) represented by integer is), c) the _{formula: - (CH 2) l -O-} (C 2 H 4 O) m - (C 3 H 6 O) n -R ⁵ (wherein, R ⁵ represents a hydrogen atom, an acyl group or a monovalent hydrocarbon group, 1 is 0 or a positive integer, and m and n are 0 or a positive integer of 150 or less, Where m + n
Is an integer of 1 to 150), and a reactive organopolysiloxane having at least one polyoxyalkylene group (Q group) represented by the following formula:

The present invention particularly relates to the following formula: [In the formula, R independently represents a hydrogen atom, a monovalent hydrocarbon group or a halogenated alkyl group, and Y represents the following formula: -R ¹ -X (wherein, R ¹ is a direct bond or a group having 1 carbon atom. Or 20
X represents a glycidyloxy group,
A minoethylimino group [—NH (CH ₂ ) ₂ NH ₂ ],
Amino group, hydroxyl group, carboxyl group, acyl group, mercap
Group, methacryloxy group, isocyanate group, ureide
Group, vinyl group, amide group, imide group, imino group, aldehyde
Hyd group, nitro group, nitrile group, oxime group, azo group or
Represents an organic reactive functional group selected from hydrazone groups ), and Z represents the following formula: (Wherein, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a represents 2 or 3 Q is a condensable silylalkyl group represented by the following formula: — (CH ₂ ) ₁ —O— (C ₂ H ₄ O) _m — (C ₃ H ₆ O) _n —R ⁵ (Wherein, R ⁵ represents a hydrogen atom, an acyl group or a monovalent hydrocarbon group, 1 is 0 or a positive integer, and m and n are 0 or a positive integer of 150 or less, provided that m + n
Represents an integer of 1 to 150), M represents a group selected from the above R, Y, Z and Q, o is an integer of 0 to 500, and p is Q is an integer of 0 to 200;
R is an integer of 0 to 200, provided that when p is 0, M is Y, and both q and r are integers of 1 or more; Is Z
And p and r are each an integer of 1 or more;
Is 0, M is Q, and p and q are each an integer of 1 or more.]

In the above formula, R is independently a hydrogen atom,
Monovalent hydrocarbon groups such as methyl, ethyl, propyl, butyl, octyl, dodecyl, phenyl,
A phenethyl group or the like or a halogenated alkyl group such as a trifluoropropyl group and a chloropropyl group is preferable, but a monovalent hydrocarbon group, particularly 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 -, -
_{CH (CH 3) CH 2 -} , - (CH 2) 4 -, - (CH
_{2) 6 -, - (CH} 2) 8 -, - CH 2 CH 2 C 6 H 4
_{-, - (CH 2) 12} -, - (CH 2) 16 - a and,
Preferably it is a propylene group. X in the Y group is a functional group having organic reactivity, for example, a glycidyloxy group,
Minoechiruimino group [-NH _{(CH 2) 2} NH _2], an amino group, a hydroxyl group, a carboxyl group, an acyl group, a mercapto group, a methacryloxy group, an isocyanate group, a ureido group, a vinyl group, an amide group, an imide group, an imino group, aldehyde Group, nitro group, nitrile group, oxime group, azo group,
It is 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, And the like, but are not limited thereto.

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 - and the like, preferably an 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 a methyl group. Or an ethyl group. a is an integer of 2 or 3, but 3 is preferred from the viewpoint of reactivity. Specific examples of Z groups, -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 ) _{2 and the} like, but are not limited thereto.

R ⁵ in the Q group is a hydrogen atom, an acyl group such as acetyl or propionyl, or a monovalent hydrocarbon group such as methyl, ethyl, propyl, butyl, phenyl or vinyl. , 1 is 0 or a positive integer, and m and n are 0 or a positive integer of 150 or less, provided that m + n is an integer of 1 to 150.

Specific examples of the reactive organopolysiloxane of the present invention include the following.
Of course, they are not limited to these:

The reactive organopolysiloxanes of the present 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 And CH ₂ ＣＨCHSi (OCH ₃ ) ₃ To an addition reaction 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 And CH ₂ ＣＨCHSi (OC ₂ H ₅ ) ₃ and CH ₂ ＣＨCHC
It can be obtained by performing an addition reaction with H ₂ O (C ₂ H ₄ O) ₁₂ CH _{3 in} the presence of a platinum-based catalyst. Furthermore, in the case of the compound represented by the formula _{(3), CH 2 = CHCH} 2 OH and CH ₂ = CHSi (OCH ₃₎ in the corresponding methylhydrogenpolysiloxane ₃ To an addition reaction in the presence of a platinum-based catalyst. In the case of the compound represented by the above formula (4), the corresponding methyl hydrogen polysiloxane has C
H ₂ ＣＨCHCH ₂ Cl and CH ₂ ＣＨCHSi (OCH ₃ )
It can be obtained by performing an addition reaction between ₃ and CH ₂ CHCH ₂ O (C ₂ H ₄ O) ₁₆ CH _{3 in} the presence of a platinum-based catalyst, and then reacting the obtained product with ethylenediamine.

The reactive organopolysiloxane of the present invention can be used, for example, as an adhesive modifier between two materials (particularly, between an organic material and an inorganic material such as an inorganic filler), and can be used as a natural rubber or a styrene-based material. Synthetic rubbers 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 -Compounded with rubber-based adhesives, urethane-based adhesives, epoxy-based adhesives, etc. used for bonding between synthetic resins such as butadiene-styrene copolymer and polystyrene or between these and other rubbers and 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 the mixing of rubber and 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, Even when bonding with an inorganic filler such as carbon black or an inorganic material such as glass, it exhibits excellent adhesive strength, and a reinforced plastic or a high-strength elastomer having high weather resistance and heat resistance can be obtained. In addition, as a paint modifier, it is blended with paint resins such as polyester resin and acrylic resin,
It enables coating with excellent weather resistance, durability and heat resistance on wood and concrete. Further, as a fiber surface modifier, natural fibers such as wool, silk, hemp, cotton, asbestos, regenerated fibers such as rayon, cupra, acetate, polyester, polyester ether,
Any fibers such as organic synthetic fibers such as polyacrylonitrile, vinylon, polyvinylidene chloride, polyvinyl chloride, polyethylene, and polypropylene, glass fibers, inorganic synthetic fibers such as carbon fibers, and woven fabrics, knitted fabrics, nonwoven fabrics, and resins The surface of the fiber can be treated in any form, such as a work cloth, and the fiber is given weather resistance and durability. Accordingly, 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, and more particularly to the organopolysiloxane of the present invention. Siloxane is suitably used as an adhesion modifier between an organic material and an inorganic material.

[0014]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 In a 1000 ml three-necked flask equipped with a mechanical stirrer, condenser, thermometer and nitrogen inlet, the following formula: Methyl hydrogen polysiloxane 80 represented by
g, toluene 200 g, and a 10% ethanol solution of chloroplatinic acid so that the platinum content was 20 ppm. 22.8 g of vinyltrimethoxysilane and 35.1 g of γ-glycidoxy-1-propene are gradually added to the mixture at such a rate as to maintain the temperature at 80 to 100 ° C., and the mixture is stirred for 2 hours while maintaining the temperature. And the reaction was allowed to proceed. In addition, the reaction is added to the reaction at a rate such that the temperature is maintained at 80-100 ° C .: 230 g of allyl polyether represented by the formula was gradually added. The end of this reaction was determined by the negative value of the AgNO ₃ test for SiH. The reaction mixture is then washed with NaHCO
Neutralize with ₃ , filter and 5 with a rotary evaporator
Removing the solvent at 0 ° C./1 mmHg yields the following formula: 312 g of an organopolysiloxane represented by the formula was obtained.

Example 2 The following formula: Methyl hydrogen polysiloxane 300 represented by
g, toluene 200 g, vinyltrimethoxysilane 1
1.6 g, γ-glycidoxy-1-propene 3.6 g,
Allyl polyether represented by the following formula: CH ₂ ＣＨCHCH ₂ O (C ₂ H ₄ O) ₇ CH ₃ 14.3 g, platinum content 20
When the same operation as in Example 1 is performed using a 10% ethanol solution of chloroplatinic acid to give the following formula: 309 g of an organopolysiloxane represented by the following formula was obtained.

Example 3 The following formula: Methyl hydrogen polysiloxane 91 represented by
g, toluene 200 g, vinyltrimethoxysilane 10
0 g, 12 g of allyl alcohol represented by the following formula: CH ₂ 2CHCH ₂ OH, the following formula: 175 g of allyl polyether represented by
When the same operation as in Example 1 is performed using a 10% ethanol solution of chloroplatinic acid to give the following formula: 330 g of an organopolysiloxane represented by the formula was obtained.

Example 4 The following formula: Methyl hydrogen polysiloxane 100 represented by
g, toluene 200 g, vinyltriethoxysilane 55
g, allyl methacrylate 73 g, the following formula: CH ₂ CH
The same operation as in Example 1 is performed by using 209 g of allyl polyether represented by CH ₂ O (C ₂ H ₄ O) ₁₂ CH ₃ and a 10% ethanol solution of chloroplatinic acid having a platinum content of 20 ppm. And the following equation: 362 g of an organopolysiloxane represented by the following formula was obtained.

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

Test Example 1 10 g of any of the test compounds of formulas (A) to (F) is added to 100 g of an aqueous solution of isopropyl alcohol (water / isopropyl alcohol = 1/9) and mixed until completely dispersed. 1.0 kg of quartz powder was placed in a Henschel mixer, and while uniformly stirring, the solution of the test compound was added at a rate of 25 to 30 ml / min over several minutes.
Stir and mix for an additional minute. After mixing, the wet quartz powder is taken out and dried in an aluminum drying dish (40 cm × 40 c).
mx 5cm) and spread uniformly to a thickness of 2-3cm,
Dry at 105 ° C. for 1 hour in a forced circulation dryer. 1.0 kg of BAKELITE polyethylene DYNH, 1.0 kg of quartz powder treated as described above, and die cup
(Dicup, made by HERCULES) 30g 1 with 2 rolls
Mix at 21 ° C. Next, compression molding was performed at 177 ° C. for 20 minutes, and the tensile strength of the molded product was measured. The results are shown below,
Those using the organopolysiloxane of the present invention exhibited much higher tensile strength than blanks and controls.

Test Example 2 Bakelite epoxy resin ERL-2774 500
g, methylnadic anhydride (curing agent) 400 g, benzyldimethylamine (catalyst) 2.5 g, test compound 10
g and wollastonite (calcium silicate) 500
g were mixed. Next, the composition was cured at room temperature for 16 hours, further cured 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. The results of the present invention show a higher flexural strength both immediately after curing and after boiling for 72 hours as compared to the blanks and the control, especially 7
Even after boiling for 2 hours, the rate of decrease in bending strength was low.

[0022]

The reactive organopolysiloxane of the present invention has an organic reactive functional group (Y group), a condensable silylalkyl group (Z group) and a polyoxyalkylene group (Q group) directly bonded to its silicon atom. ), Each having at least one of them, and exhibiting sufficient hydrophilicity. Accordingly, the reactive organopolysiloxane of the present invention easily dissolves or disperses in water and a mixture of water and alcohol, and this improves the adhesiveness between materials (particularly, between organic materials and inorganic materials such as inorganic fillers). When used as an agent, a paint modifier, a fiber surface modifier, etc., the organopolysiloxane is surely dispersed between the substrates and imparts excellent weather resistance, heat resistance and durability. In addition, the reactive organopolysiloxane of the present invention is capable of designing various molecules according to each base material to be modified and each application from the variety of synthesis raw materials, and can easily impart the characteristics as designed. is there.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-95228 (JP, A) JP-A-61-127733 (JP, A) JP-A-62-225533 (JP, A) 47841 (JP, A) JP-A-53-55341 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 77/18-77/28 C08G 77/46

Claims (7)

(57) [Claims] 1. A molecule directly bonded to a silicon atom in one molecule a) The following formula: -R ¹ -X (wherein R ¹ is a direct bond or a group having 1 to 20 carbon atoms)
X represents a glycidyloxy group,
A minoethylimino group [—NH (CH ₂ ) ₂ NH ₂ ],
Amino group, hydroxyl group, carboxyl group, acyl group, mercap
Group, methacryloxy group, isocyanate group, ureide
Group, vinyl group, amide group, imide group, imino group, aldehyde
Hyd group, nitro group, nitrile group, oxime group, azo group or
Represents an organic reactive functional group selected from hydrazone groups ), and b) the following formula: (Wherein, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a represents 2 or 3 A condensable silylalkyl group represented by the following formula: c) the following formula: — (CH ₂ ) ₁ —O— (C ₂ H ₄ O) _m — (C ₃ H ₆ O) _n —R ⁵ ( In the formula, R ⁵ represents a hydrogen atom, an acyl group or a monovalent hydrocarbon group, 1 is 0 or a positive integer, and m and n are 0 or a positive integer of 150 or less, provided that m + n
Is an integer of 1 to 150), each having at least one polyoxyalkylene group. 2. The following formula: [In the formula, R independently represents a hydrogen atom, a monovalent hydrocarbon group or a halogenated alkyl group, Y is the following formula: -R ¹ -X (wherein R ¹ is a direct bond or a group having 1 or more carbon atoms) 20
X represents a glycidyloxy group,
A minoethylimino group [—NH (CH ₂ ) ₂ NH ₂ ],
Amino group, hydroxyl group, carboxyl group, acyl group, mercap
Group, methacryloxy group, isocyanate group, ureide
Group, vinyl group, amide group, imide group, imino group, aldehyde
Hyd group, nitro group, nitrile group, oxime group, azo group or
Represents an organic reactive functional group selected from hydrazone groups ), and Z represents the following formula: (Wherein, R ² represents an alkylene group having 2 to 5 carbon atoms, R ³ and R ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a represents 2 or 3 represents condensable silyl group represented by integer is), Q is the _{formula: - (CH 2) l -O-} (C 2 H 4 O) m - (C 3 H 6 O) n -R 5 (Wherein, R ⁵ represents a hydrogen atom, an acyl group or a monovalent hydrocarbon group, 1 is 0 or a positive integer, and m and n are 0 or a positive integer of 150 or less, provided that m + n
Represents an integer of 1 to 150), M represents a group selected from the above R, Y, Z and Q, o is an integer of 0 to 500, and p is Q is an integer of 0 to 200, r is an integer of 0 to 200, provided that when p is 0, M is Y, and both q and r are 1 or more. When q is 0, M is Z, and p and r are both 1.
Where r is 0, M is Q, and p and q are 1
A reactive organopolysiloxane represented by the following formula: 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 fiber surface modifier. 7. The reactive organopolysiloxane according to claim 4, which is used as an adhesion modifier between an organic material and an inorganic material.