JP3133389B2 - Polymerization-reactive linear silicone oligomer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polymerization-reactive linear silicone oligomer and a method for producing the same, and more particularly, to acrylamide or methacrylamide (hereinafter referred to as (meth) acrylamide) at one end of the molecule. The present invention relates to a novel polymerization-reactive linear silicone oligomer having one vinyl polymerization-reactive functional group having a controlled molecular weight and a controlled molecular weight distribution, and a method for producing the same.

[0002]

2. Description of the Related Art Polymerization-reactive silicone oligomers are conventionally known to be of the acrylate type, and include polymer films such as various films, plastics, rubbers and waxes, and paper products. , Used as a surface treatment agent for glass, etc., and as a modifier for shampoos, rinses, hair setting agents, etc. Furthermore, these products have water repellency, antifouling properties, non-adhesive properties, heat resistance, friction resistance, etc. It is used for the purpose of giving the function of.

Heretofore, such polymerization-reactive silicone oligomers are mainly produced by hydrolyzing polychlorinated silanes or modifying silicone oligomers obtained by living polymerization of cyclic siloxanes with compounds having a (meth) acryloyloxy group. (For example, Japanese Patent Publication 2-341
7).

[0004] However, among these, in the production method by hydrolysis, it is difficult to control the molecular weight of the polymerization-reactive silicone oligomer produced, and regioselectivity of the functional group is almost impossible except for modification of both terminals. Since only those having a wide molecular weight distribution can be obtained, there is a disadvantage that a polymerization-reactive silicone oligomer having a controlled structure cannot be obtained.

On the other hand, living polymerization of cyclic siloxane can be easily carried out under an inert gas atmosphere.
A linear silicone oligomer having a controlled molecular weight and molecular weight distribution can be obtained. For example, an average molecular weight of 10,
If it is about 000 or less, the polydispersity (Mw / M
Compounds with n) of 1.3 or less can be synthesized relatively easily.

However, the polymerization-reactive silicone oligomers obtained by these conventional synthetic methods can easily undergo a hydrolysis reaction because the bond between the vinyl polymerization-reactive functional group and the linear silicone oligomer portion is an ester bond. It has been practically impossible to use the polymer containing the polymerization-reactive silicone oligomer under high humidity or under such a condition that the polymer is exposed to moisture for a long time.

Therefore, development of a stable polymerization-reactive silicone oligomer having a controlled molecular weight and molecular weight distribution has been desired.

[0008]

Means for Solving the Problems Under such circumstances, the present inventors have conducted intensive studies and as a result, have found that a (meth) acrylamide-type vinyl polymerization reactive functional group is provided at one end of a molecule represented by the following general formula (1). The present inventors have found that a novel polymerization-reactive linear silicone oligomer having the above-mentioned object solves the above problems, and have completed the present invention.

That is, the present invention provides the following general formula (1)

[0010]

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It is intended to provide a polymerization-reactive linear silicone oligomer represented by the formula (1) and a method for producing the same.

The alkyl group represented by R ¹ or R ² in the polymerization-reactive linear silicone oligomer (1) of the present invention includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and a sec-butyl group. And a t-butyl group.

The polymerization-reactive linear silicone oligomer (1) of the present invention is prepared by subjecting a cyclic siloxane (3) to anion living polymerization using a compound (2) as an initiator and a compound (4) according to, for example, the following reaction formulas A to E. ), The anionic living polymerization reaction is stopped by the chlorosilane derivative (5), and then the obtained silicone oligomer (6) having one end of a Si-H group and (meth) having a double bond at one end. The compound (8) is reacted with an allylamine analog (7) to give a compound (8). When R ⁸ and / or R ^{9 in} the compound of the general formula (8) is a trimethylsilyl group, this is solvolyzed to form a protecting group. Production by reacting (meth) acrylic acid or its reactive derivative (10) with one-terminal amino-modified silicone oligomer (9) obtained by removing. Can be.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[Wherein R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , m and n have the same meaning as described above, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a trimethylsilyl group, and R ⁹ represents a hydrogen atom or a trimethylsilyl group.

In order to avoid the formation of a cyclic oligomer, lithium trialkylsilanolate or alkyllithium represented by the general formula (2) is used as an initiator of the anionic living polymerization reaction represented by the formula A in the production method of the present invention. Used. Specific examples include trimethylsilanolate, triethylsilanolate, tripropylsilanolate, tributylsilanolate, methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium.
-Butyllithium or lithium trimethylsilanolate is particularly preferred.

The cyclic siloxane represented by the general formula (3) includes hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaethylcyclotrisiloxane, octaethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, Octaphenylcyclotetrasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and the like, among which hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane are preferable, and among them, hexamethylcyclotrisiloxane is particularly preferable. preferable.

The degree of polymerization of the living polymer obtained by the anionic living polymerization reaction is determined by the molar ratio of the initiator (2) and the cyclic siloxane (3), and the molar ratio is determined by the initiator (2) / cyclic siloxane. (3)
Is preferably 0.01 to 0.2.

The anionic living polymerization is carried out in the presence of a suitable solvent. As the solvent, ethers such as tetrahydrofuran, ethyl ether and dioxane are preferred, and tetrahydrofuran is particularly preferred.
In addition, when it is difficult to use ethers due to other reaction factors, a solvent such as hexane, benzene, or toluene can be used as appropriate. In this case, a polar solvent such as HMPTA (hexamethylphosphoric triamide) is used as a cosolvent. More preferably, it is added.

The reaction temperature is preferably from -78 to 30 ° C, particularly preferably from -10 to 20 ° C. If the temperature is lower than -78 ° C, the polymerization reaction tends to be slow, and if the temperature exceeds + 30 ° C, the molecular weight distribution of the produced living polymer tends to be wide. Further, the polymerization time varies greatly depending on the reaction temperature,
In the case of 0 ° C., about 1 to 20 hours is appropriate.

In the anionic living polymerization termination reaction represented by the formula B, the chlorosilane derivative represented by the general formula (5) is used in an amount of 1 to 10 moles per mol of the anion living polymerization initiator (2). Preferably, 1.
More preferably, it is 1 to 5 moles. The reaction solvent and the reaction temperature may be the same as those in the case of the anionic living polymerization, and the reaction time of about 30 minutes to 1 hour is sufficient.

In the hydrosilylation reaction represented by the above formula C, the amount of the (meth) allylamine analog having a double bond at the terminal represented by the general formula (7) is determined by the amount of the Si— It is preferably 1 to 100 times mol based on the silicone oligomer having an H group at one end,
Especially 1.1 to 20 times mol is preferable.

This reaction is preferably carried out in the presence of a catalyst. As the catalyst, platinum-based or rhodium-based catalysts are used, and chloroplatinic acid is particularly preferably used.
The reaction temperature is preferably from 20 to 120 ° C, and from 40 to 8 ° C.
0 ° C. is more preferred. The reaction solvent is not particularly necessary, but when the viscosity of the reaction system is extremely high, for example, toluene,
Tetrahydrofuran or the like can be used as appropriate.

The solvolysis reaction represented by the formula D is carried out, for example, in an alcohol solvent. The alcohol used here is not particularly limited, but preferably includes methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, butyl alcohol and the like, and methyl alcohol is particularly preferable. In this reaction, if necessary, another solvent can be used in combination with the alcohol solvent, as long as it is compatible with the alcohol and the compound represented by the general formula (8). Not something.

The reactive derivatives of (meth) acrylic acid represented by the general formula (10) used in the reaction represented by the formula E include (meth) acrylic acid chloride and (meth) acrylic anhydride. , (Meth) acrylic acid esters. Of these, (meth) acrylic acid esters are preferably alcohol esters having 1 to 4 carbon atoms such as methyl ester, ethyl ester, propyl ester, butyl ester and hydroxyethyl ester of (meth) acrylic acid.

The amount of (meth) acrylic acid or its reactive derivative (10) used in this reaction is preferably 1 to 10 times the mol of the amino-modified silicone oligomer at one end represented by the general formula (9). , Especially 1.1 to
Three times mole is preferred. Further, as a reaction solvent, toluene, chloroform, dichloromethane, hexane, TH
F, ethyl acetate and the like are used, and the reaction temperature is 0 to 100 ° C.
Is preferable, and particularly preferably 15 to 40 ° C. In addition, a tertiary amine or the like may be added for the purpose of promptly completing the reaction.

The polymerization-reactive linear silicone oligomer (1) of the present invention is obtained by adding a compound to the silicone oligomer (6) having a Si—H group at one end obtained by the above reaction according to the following reaction formula F: It can also be produced by reacting (11).

[0032]

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(Wherein R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , m and n have the same meaning as described above)

The general formula (11) used in this reaction
The amount of the compound represented by the formula is preferably 1 to 100 times, and particularly preferably 1.1 to 2 times, the mol of the silicone oligomer having the Si-H group represented by the general formula (6) at one end.
0-fold molar is preferred. The reaction solvent is not particularly limited, but toluene, THF, or the like is appropriately used, and the reaction temperature is preferably 20 to 120 ° C, particularly preferably 40 to 120 ° C.
80 ° C. is preferred.

The thus obtained polymerization-reactive linear silicone oligomer (1) of the present invention has a number average molecular weight of 1,000
It has a terminal vinyl functional group number of 0.9 to 1.0 per molecule from 0 to 50,000, and exhibits a liquid or paste state depending on its molecular weight. In addition, it is generally soluble in ordinary organic solvents, but can be precipitated and collected by using a poor solvent such as methyl alcohol.

The polymerization-reactive linear silicone oligomer (1) of the present invention can be prepared by reacting other monomers such as (meth) acrylamide, (meth) acrylic ester in the same manner as general (meth) acrylamide monomers. , Acrylonitrile, styrene, etc., resulting in a graft polymer having a silicone moiety as a branch. In the graft polymer thus obtained, the number of branches is controlled by the charge ratio of the polymerization-reactive linear silicone oligomer (1) and the other comonomer, the length of the branches is also controlled, and there is no crosslinking. It does not contain homopolymers consisting of only the branch or trunk components. Thus, by using the polymerization-reactive linear silicone oligomer (1) of the present invention, a graft copolymer having a clear structure can be easily obtained.

When a small amount of the graft copolymer having this structure is added to another polymer, a silicone site is precipitated on the surface of the polymer due to the surface activity of the silicone, and the surface alone is modified, that is, repellent. Properties such as aqueous properties, non-adhesiveness, low friction properties, and antifouling properties can be imparted. The polymer thus obtained does not lose its properties even under high humidity conditions or under long-term exposure to water.

[0038]

The polymerization-reactive linear silicone oligomer (1) of the present invention has one (meth) acrylamide-type vinyl polymerizable functional group at one end of the molecule, and has a controlled molecular weight and molecular weight distribution. And excellent in hydrolysis resistance.

The use of this polymerization-reactive linear silicone oligomer makes it possible to easily produce a graft copolymer having a clear structure and high moisture resistance and high water resistance. It is useful as a modifier which can stably maintain its surface modification characteristics.

[0040]

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

Example 1 (1) Preparation of linear silicone oligomer having one end functionalized with Si—H group: dried tetrahydrofuran 200
To a solution obtained by adding 23.0 mmol of n-butyllithium to 100 ml of a solution, 105 g of hexamethylcyclotrisiloxane (4
(70 mmol) in 500 ml of dry tetrahydrofuran was added, and the mixture was polymerized at 0 ° C. for 6 hours under a nitrogen atmosphere. Then, 8.8 g (93.0 mmol) of chlorodimethylsilane was added, and the mixture was stirred for 1 hour to terminate the polymerization.
After the formed precipitate of lithium chloride was separated by filtration, the precipitate was washed with ion-exchanged water, methyl alcohol was added to precipitate the formed oligomer, and the precipitate was purified by reprecipitation of a tetrahydrofuran-methyl alcohol system.
A linear silicone oligomer having a -H group was obtained. The number average molecular weight of the obtained oligomer was as follows. Calculated value 4600, GPC method (polystyrene conversion) 496
0. The polydispersity Mw / Mn by GPC is 1.2.
It was 0. The IR spectrum of this compound shows 213
At 5 cm ⁻¹ , characteristic absorption derived from the Si—H bond was observed. Under the above polymerization conditions, the polymerization was carried out by changing the amount of n-butyllithium to 5.8 to 46.0 mmol, and the polymerization was terminated using dimethylchlorosilane. The molecular weight of the silicone oligomer obtained by the GPC method was obtained. According to the measurement results, the calculated value from the cyclic siloxane / initiator molar ratio and ± 5
%, And the polydispersity Mw / Mn is 1.10.
１．２1.25. From this result, it is understood that the polymerization proceeds in a living manner under the above-mentioned polymerization conditions. IR (cm ^-1 ) 2960 (s, S) 2135 (br, W) 1260 (s, S) 1100 (s, S) 1030 (s, S) 915 (s, W) 800 (s, S) NMR ( _{ppm) 0.0 (Si-CH 3} ), s 0.45 (CH 2), m 0.80 (CH 2), m 1.24 (CH 3), m 1.50 (CH 2), s 4 .63 (Si-H), m

(2) Method for producing a linear silicone oligomer having one end functionalized with a 3-aminopropyl group: (1)
A solution prepared by dissolving 9 mg of chloroplatinic acid hexahydrate in 0.09 g of isopropyl alcohol was added to 100 g (18.2 mmol) of a linear silicone oligomer whose one end was functionalized with a Si-H group. Further, 12.9 g (100 mmol) of trimethylsilyl allylamine is added dropwise. After completion of the dropwise addition, the reaction temperature is adjusted to 60 to 65 ° C., and the reaction is carried out for about 12 hours. After completion of the reaction, the reaction temperature was lowered to room temperature, and methyl alcohol / tetrahydrofuran (1/1 v
ol), and the mixture was reacted under reflux with heating for about 3 hours to carry out solvolysis and deprotection. Activated carbon was added, the platinic acid was adsorbed, and after filtration under reduced pressure, low-boiling substances such as a solvent were distilled off under reduced pressure using an evaporator. A colorless transparent oil was obtained almost quantitatively. Oil and fat analysis result, total amine value, calculated value 10.2, measured value 10.7 partial amine value, calculated value = 0, measured value 0.3> IR (cm ⁻¹ ) 2960 (s, S) 1420 (s, S) W) 1260 (s, S) 1090 (s, S) 1020 (s, S) 800 (s, S) NMR (ppm) 0.0 (Si-CH 3), s 0.45 (CH 2), m 0.80 (CH ₂ ), m 1.23 (CH ₂ + CH ₃ ), m 1.50 (CH ₂ + NH ₂ ), s 2.60 (N-CH ₂ ), t, (J = 6.3 Hz)

(3) Production of a vinyl polymerization-reactive linear silicone oligomer having a methacryloyl group introduced through an amide bond: a linear silicone oligomer synthesized in (2), wherein one end is functionalized with a 3-aminopropyl group. 10
200 g of toluene, 2.3 g (21.6 mmol) of methacryloyl chloride and 2.2 g (21.6 mmol) of triethylamine are added to 0 g (18.0 mmol), and the mixture is reacted at room temperature for about 12 hours. After the completion of the reaction, the resultant was washed with ion-exchanged water and dried with anhydrous sodium sulfate. When a low-boiling substance such as a solvent was distilled off under reduced pressure using an evaporator, a pale yellow transparent oil was obtained almost quantitatively. Oil and fat analysis result, total amine value, calculated value = 0, measured value 0.3
The vinyl-polymerizable linear silicone oligomer having a methacryloyl group introduced by an amide bond synthesized in the present example exhibits almost or slightly lower polymerization reactivity than a normal methacrylamide monomer having the same terminal vinyl group. Was. IR (cm ^-1 ) 2960 (s, S) 1685 (br, W) 1640 (br, W) 1420 (s, m) 1260 (s, S) 1100 (br, S) 1020 (br, S) 800 ( br, S) NMR (ppm) 0.0 (Si-CH 3), s 0.48 (CH 2), m 0.83 (CH 2), m 1.24 (CH 2 + CH 3), m 1. _{55 (CH 2 + NH 2)} , s 1.89 (= C-CH 3), s 3.21 (N-CH 2), m 5.40 (H 2 C = C), d, (J = 78. 2H
z)

[Brief description of the drawings]

FIG. 1 is a drawing showing an infrared absorption spectrum of a linear silicone oligomer having one terminal functionalized with a Si—H group obtained in Example 1 (1).

FIG. 2 is a drawing showing a nuclear magnetic resonance spectrum of a linear silicone oligomer having one end functionalized with a Si—H group obtained in Example 1 (1).

FIG. 3 is a drawing showing an infrared absorption spectrum of a linear silicone oligomer having one terminal functionalized with a 3-aminopropyl group obtained in Example 1 (2).

FIG. 4 is a drawing showing a nuclear magnetic resonance spectrum of a linear silicone oligomer having one end functionalized with a 3-aminopropyl group obtained in Example 1 (2).

FIG. 5 is a drawing showing an infrared absorption spectrum of a vinyl polymerization-reactive linear silicone oligomer obtained in Example 1 (3).

FIG. 6 is a drawing showing a nuclear magnetic resonance spectrum of a vinyl polymerization reactive linear silicone oligomer obtained in Example 1 (3).

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 77/388 C08F 299/08 C08G 77/06

Claims (6)

(57) [Claims] 1. The following general formula (1): A polymerization reactive linear silicone oligomer represented by the formula: 2. The following general formula (9): The one-terminal amino-modified silicone oligomer represented by the following general formula (10): 2. The method for producing a linear silicone oligomer according to claim 1, wherein (meth) acrylic acid or a reactive derivative thereof represented by the formula: wherein R ⁶ represents a hydrogen atom or a methyl group. 3. The following general formula (6): A silicone oligomer having a Si—H group at one terminal represented by the following general formula (7): Wherein R ⁵ represents a hydrogen atom or a methyl group, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a trimethylsilyl group, R ⁹ represents a hydrogen atom or a trimethylsilyl group, and n represents 1 to The compound is reacted with a (meth) allylamine analog having a double bond at one end represented by the following general formula (8): Wherein R ¹ , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , m and n have the same meanings as described above, and R ^{8 in} the compound of the general formula (8) And / or when R ⁹ is a trimethylsilyl group, it is solvolyzed to obtain the following general formula (9): [Wherein R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹ , R ³ , R ⁴ , R ⁵ , m and n have the same meaning as described above] The modified silicone oligomer has the following general formula (10): 2. The method according to claim 1, wherein (meth) acrylic acid represented by the formula: wherein R ⁶ represents a hydrogen atom or a methyl group, or a reactive derivative thereof. Method. 4. The following general formula (6): A silicone oligomer having a Si—H group at one terminal represented by the following general formula (11): Wherein R ⁵ and R ⁶ represent a hydrogen atom or a methyl group;
R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
n represents a number of 1 to 8], and the reaction is carried out. 5. The following general formula (2): R ¹ -Li (2) Using a compound represented by the following formula as an initiator, the following general formula (3): Wherein R ³ represents a methyl group, an ethyl group or a phenyl group, and p is 3 or 4. Anionic living polymerization of the cyclic siloxane represented by the following general formula (4): Wherein m represents a number of ³ to 1,000, and R ¹ and R ³ have the same meaning as described above.
The following general formula (5) [Wherein R ⁴ represents a methyl group, an ethyl group or a phenyl group] to terminate the anionic living polymerization reaction with a chlorosilane derivative represented by the following general formula (6): [Wherein R ¹ , R ³ , R ⁴ and m have the same meaning as described above] and a silicone oligomer having a Si—H group at one end represented by the following general formula (7): Wherein R ⁵ represents a hydrogen atom or a methyl group, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a trimethylsilyl group, R ⁹ represents a hydrogen atom or a trimethylsilyl group, and n represents 1 to And a (meth) allylamine analog having a double bond at one end represented by the following general formula (8): Wherein R ¹ , R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , m and n have the same meanings as described above, and R ^{8 in} the compound of the general formula (8) And / or when R ⁹ is a trimethylsilyl group, it is solvolyzed to obtain the following general formula (9): [Wherein R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹ , R ³ , R ⁴ , R ⁵ , m and n have the same meaning as described above] The modified silicone oligomer has the following general formula (10): 2. The method according to claim 1, wherein (meth) acrylic acid represented by the formula: wherein R ⁶ represents a hydrogen atom or a methyl group, or a reactive derivative thereof. Method. 6. The following general formula (2): R ¹ -Li (2) Using a compound represented by the following formula as an initiator, the following general formula (3): Wherein R ³ represents a methyl group, an ethyl group or a phenyl group, and p is 3 or 4. Anionic living polymerization of a cyclic siloxane represented by the following general formula (4): Wherein m represents a number of ³ to 1000, and R ¹ and R ³ have the same meanings as described above, and then a compound represented by the following general formula (5): [Wherein R ⁴ represents a methyl group, an ethyl group or a phenyl group], the anionic living polymerization reaction is stopped by a chlorosilane derivative represented by the following general formula (6): [Wherein R ¹ , R ³ , R ⁴ and m have the same meaning as described above] to a silicone oligomer having a Si—H group at one end, represented by the following general formula (11): Wherein R ⁵ and R ⁶ represent a hydrogen atom or a methyl group;
R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
n represents a number of 1 to 8], and the reaction is carried out.