JPH09208628A - Terminal reactive polymer compound and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently and easily obtain a polymer compd. having various reactive functional groups in one terminal by polymerizing a specified α,β-unsatd. carbonyl compd. using a specified alkali metal alcoholate as a polymn. initiator. SOLUTION: An unsatd. carbonyl compd. represented by formula I (wherein R<2> , R<3> , and R<4> represent a 1-10C straight-chain or branched alkyl, aryl, or aralkyl) is polymerized using as a polynm. initiator an alkali metal alcoholate represented by the formula R<1> OM (wherein R<1> represents a 1-15C straight-chain or branched alkyl, aralkyl or an aryl and may contain acetal, cyano, aldehyde, carboxyl, amino, ester bond, amide bond, siloxy, silanol, silylamino or the like; and M represents lithium, sodium, or potassium (e.g. potassium ethoxide) to prepare a polymer compd., having a reactive functional group in its terminal, represented by formula II (wherein (n) is 5 to 10,000).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer compound having various reactive functional groups at one end and a method for producing the same.

[0002]

2. Description of the Related Art Methyl methacrylate (MM
Anionic polymerization of α, β-unsaturated carbonyl compounds represented by A) and the like is important for obtaining a polymer compound whose molecular weight and terminal are regulated, and has been widely studied.
For example, in the anionic polymerization of MMA, an alkali metal alkyl such as butyllithium or naphthalene is generally widely used and has been molecularly designed. However, MMA
Is extremely low in the case of using an oxonium anion such as an alkali metal alcoholate as an initiator, and it cannot be polymerized without various measures such as using a complexing agent such as crown ether. .

In recent years, poly (2-hydroxyethyl methacrylate) (PolyHEMA), which is expected as a hydrogel and a blood-compatible material, is a homologue of an α, β-unsaturated carbonyl compound, but its production is mainly a radical. It was done by polymerization. Nakahama et al. Succeeded in anionic polymerization with an alkali metal alkyl by protecting the hydroxyl group of HEMA with a trimethylsilyl group, and obtained a polymer having a regulated molecular weight. (Macromolecule
S, 19, 1294 (1986)). But in this case,
It is impossible to introduce a polymerizable vinyl group or the like into the initiator fragment to carry out the terminal function of the resulting polymer.

Radical chain transfer polymerization has been used to introduce unsaturated groups and amino groups into the terminals. Okano et al. Used Pol with aminoethanethiol hydrochloride as a chain transfer agent and had a primary amino group at one end by radical polymerization.
y (HEMA) has been successfully synthesized (Polymer
Journal, 10 (5), 477 (1978)).
A polymerizable unsaturated group is introduced at the terminal by condensing methacrylic anhydride or the like to this amino group. However, since this method is based on radical polymerization, there remains a problem in controlling the molecular weight and its distribution. That is, in the polymerization method based on radical polymerization, the distribution of the molecular weight is theoretically 2. Therefore, it is extremely difficult to obtain a polymer compound having a uniform molecular weight.

The present inventor, in the process of examining in detail the anionic polymerization characteristics of a monomer (ProHEMA) in which the hydroxyl group of HEMA is protected by a trialkylsilyl group, the monomer itself acts as a complexing agent, and hence is different from MMA and the like. It has been found that, unlike the above, it is easily polymerized with an alkali metal alcoholate. This makes it possible to introduce the terminal group into PolyHEMA more broadly, which has been conventionally performed only by radical polymerization. Further, as anionic polymerization, anionic polymerization can be performed without using an alkali metal alkyl which is extremely reactive and difficult to handle.

[0006]

The inventor has been
Alkali metal alcoholate, which has been considered to have almost no polymerizability for β-unsaturated carbonyl compounds, is ProH
It was useful for the polymerization of EMA, and its molecular weight and molecular weight distribution were regulated, and it was further successful to quantitatively introduce a functional group at the terminal. According to the present invention, for example, the so-called HEMA macromonomer in which an unsaturated group is introduced into the terminal of PolyHEMA having a uniform molecular weight, which has been difficult so far, can be easily produced. This is extremely useful for molecular design in creating biomaterials, and
Not only unsaturated groups but also various functional groups can be introduced into PolyHEMA having a controlled molecular weight, which is extremely useful as a material. Furthermore, Poly (ProHEMA) having an organosilicon group synthesized in the present invention itself can introduce various functional groups at the terminal, and is therefore useful as a resist material having resistance to oxygen plasma etching.

[0007]

SUMMARY OF THE INVENTION The gist of the present invention is that P having a quantitatively functional group at the terminal represented by the following structural formula (A).
oly (ProHEMA)

[0008]

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(Wherein R ¹ , R ² , R ³ , R ⁴ and n are the same as above), and the following compound (B) is obtained by hydrolyzing this.

[0010]

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(Wherein R ¹ and n are the same as above). Then, the compound (A) of the present invention is converted into the compound (C)

[0012]

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Using the alkali metal alcoholate compound shown in (1) as an initiator, the monomer (D)

[0014]

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It is synthesized by polymerizing. As the monomers (D) used in this reaction, 2- (trimethylsiloxy) ethyl methacrylate, 2- (triethylsiloxy) ethyl methacrylate, 2- (t-butyldimethylsiloxy) ethyl methacrylate and the like are used.

As the initiator (C), methanol, ethanol, propanol, butanol, 2-propanol,
General alcohols such as 2-methyl-2-propanol, alcohols having unsaturated groups such as vinyl alcohol, allyl alcohol, vinylbenzyl alcohol, vinylphenethyl alcohol, hydroxymethylbutadiene, 3.3-dimethoxypropanol, 3.3. -Diethoxypropanol, 3-cyanopropanol, 2- (t
Alkali metal alkoxides of alcohols such as -butoxycarbonyl) ethanol and 2- (trimethylsiloxy) ethanol are used. As the alkali metal, lithium, sodium, potassium, cesium, strontium and the like are used. The amount of these initiators used can be 0.0001 times to 100 times the molar amount of the monomer, and more preferably 0.0001 times to 1 ba times the molar amount. Conversion of an alcohol to an alkali metal alcoholate is prepared by adding an equivalent amount of a corresponding alkali metal hydrogen compound, alkali metal alkyl, alkali metal amide and the like to the alcohol.

This polymerization reaction can be carried out in the absence of a solvent, but it is more preferable to use a solvent. The solvent used is an ether solvent such as tetrahydrofuran, dioxane, diethyl ether or dimethoxyethane, benzene,
Aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as pentane, hexane and cyclohexaneactane,
An aprotic solvent such as dimethyl sulfoxide, N, N-dimethylformamide, hexamethylphosphoric triamide, or the like is used, which is a liquid that does not react with the alkali metal alcoholate under the reaction conditions. Of these, ethers such as tetrahydrofuran are most preferable. The amount of the solvent to be used is preferably 0.1 to 1000 times equivalent by volume of the monomer, more preferably 0.5 to 100 times equivalent. The reaction is generally slower with higher relative amounts of solvent.

The temperature at which the polymerization reaction is carried out in the present invention is not particularly limited, but is preferably -150 ° C to 150 ° C, more preferably -30 ° C to 80 ° C.
The reaction time is not particularly limited, but it is 5 seconds to 100.
Time is preferable, and more preferably 1 minute to 30 minutes. The atmosphere for the polymerization reaction is argon,
Perform in an inert atmosphere such as nitrogen gas. Since the reaction rate varies depending on the reaction conditions and the target substance, it is preferable to determine the reaction time by quantifying the raw materials and products by gas chromatography, liquid chromatography and the like.

The method of hydrolyzing the compound (A) thus obtained to convert it into the compound (B) mainly uses an oxidative water decomposition reaction. Examples of the acid used include hydrochloric acid, sulfuric acid, and the like, as well as nitric acid, acetic acid, phosphoric acid, trifluoroacetic acid, methanesulfonic acid, toluenesulfonic acid, and the like. Also, tetrafluoroammonium fluoride or the like can be used. Since it reacts catalytically, it reacts in very small amounts. Specifically, the molar ratio to siloxy units in the polymer is 0.000001 to 1
It can be used at 0 times, and more preferably 0.0001 to 0.1 times mol. A solvent may be used for the hydrolysis reaction, and the hydrolysis reaction may be carried out by adding the above-mentioned acid to the same solvent after completion of the above-mentioned polymerization. All the above-mentioned polymerization solvents can be used in the hydrolysis reaction. The temperature for carrying out the hydrolysis reaction is not particularly limited, but it is -15
0 ° C to 150 ° C is preferable, and more preferably -30.
° C to 80 ° C. The reaction time is not particularly limited, but is preferably 5 seconds to 100 hours, more preferably 1 minute to 30 minutes.

The compounds (A) and (B) thus obtained have a functional group derived from the initiator fragment at the terminal. When an alkali metal alkoxide of allyl alcohol or vinylbenzyl alcohol is used as an initiator, an unsaturated group can be directly introduced quantitatively at one end, which is a novel PolyHEMA macromonomer.
It is used for the preparation of comb polymers having lyHEMA component and hydrogels having branches. In addition, functional groups such as acetal, cyano group, ester group, siloxy group can be converted into polymer compounds having aldehyde, amino group, carboxyl group, silanol group, etc. at the terminal by acid treatment or reduction, and these are reactive. It is useful as an oligomer.

[0021]

The present invention will be further described below with reference to examples, but these examples do not limit the scope of the present invention in any way. Example 1 The atmosphere in the reaction vessel was replaced with argon, and at room temperature, tetrahydrofuran (15 ml), ethanol (0.06 ml), and potassium naphthalene in a THF solution (3.0 ml) (0.333 mol /
1) is added to form potassium ethoxide. To this solution, 5.4 ml of 2- (t-butyldimethylsiloxy) ethyl methacrylate is added and reacted for 3 minutes. This solution was introduced into a large excess of ethanol to obtain a polymer. The yield of the obtained polymer was 4.07 g (82.5
%). The number average molecular weight and the molecular weight distribution of the polymer determined by GPC were 8800 and 1.59, respectively.
The ¹³ C NMR spectrum of (t-butyldimethylsiloxy) ethyl methacrylate of the obtained polymer is shown in FIG. It was confirmed in FIG. 1 that a signal derived from the ethoxy group of the initiator appeared.

Example 2 The inside of the reaction vessel was replaced with argon, and 0 ml of tetrahydrofuran, 15 ml of tetrahydrofuran, 0.06 ml of ethanol and 3.0 ml of a THF solution of potassium naphthalene (0.333 mol / l).
Is added to produce potassium ethoxide. To this solution is added 5.4 ml of 2- (t-butyldimethylsiloxy) ethyl methacrylate, and the mixture is reacted for 3 minutes. This solution was introduced into a large excess of methanol to obtain a polymer. The yield of the obtained polymer was 4.41 g (89.4).
%). The polymer number average molecular weight and molecular weight distribution determined from GPC were 7300 and 1.43, respectively.

Example 3 The atmosphere in the reaction vessel was replaced with argon, and 15 ml of tetrahydrofuran and 0.134 of vinylbenzyl alcohol were added at room temperature.
g, 3.0 ml of a THF solution of potassium naphthalene (0.
333 mol / l) is added to form potassium alcoholate. To this solution, 5.4 ml of 2- (t-butyldimethylsiloxy) ethyl methacrylate is added and reacted for 5 minutes. This solution was introduced into a large excess of ethanol to obtain a polymer. The yield of the obtained polymer was 4.45 g (88.7%). The number average molecular weight and the molecular weight distribution of the polymer determined from GPC are 8600 and 1.
54. The ¹ HNMR of poly (t-butyldimethylsiloxy) ethyl methacrylate of the obtained polymer is shown in FIG. A signal derived from the vinylbenzyl proton appeared at around 6 to 8 ppm in FIG. 2, and the introduction ratio of the vinylbenzyl group was 94% from the signal of the methyl group of this signal repeating unit.

Example 4 The atmosphere in the reaction vessel was replaced with argon, and at room temperature, tetrahydrofuran (15 ml) and 3.3-diethoxypropanol (0.03) were added.
8ml, THF solution of potassium naphthalene 3.0ml
(0.333 mol / l) is added to form potassium alcoholate. To this solution, 5.4 ml of 2- (t-butyldimethylsiloxy) ethyl methacrylate is added and reacted for 5 minutes. This solution was introduced into a large excess of methanol to obtain a polymer. The yield of the obtained polymer is 4.5.
It was 9 g (91.2%). The number average molecular weight and the molecular weight distribution of the polymer determined by GPC are 750 and 750, respectively.
It was 0 and 1.48. ¹ HNMR of the obtained poly (t-butyldimethylsiloxy) ethyl methacrylate is shown in FIG. A signal derived from acetal methine appeared at around 4.6 ppm in FIG. 3, and the introduction rate of the acetal group was 98% from the signal of the methyl group of this signal repeating unit.

Example 5 The atmosphere in the reaction vessel was replaced with argon, and at room temperature, 15 ml of tetrahydrofuran, 0.16 ml of 2- (t-butoxycarbonylethanol) and 3.0 ml (0.333 mol / l) of a THF solution of potassium naphthalene were added, This produces potassium alcoholate. To this solution, 5.4 ml of 2- (t-butyldimethylsiloxy) ethyl methacrylate
Add and react for 5 minutes. This solution was introduced into a large excess of methanol to obtain a polymer. The yield of the obtained polymer was 4.48 g (89.0%). The number average molecular weight and the molecular weight distribution of the polymer determined by GPC were 7400 and 1.46, respectively. ¹ H NMR 1.
A signal derived from the t-butyl group appeared at around 2 ppm, and the introduction rate of the ester group was 99% from the signal of the methyl group of this signal repeating unit.

Example 6 The reaction vessel was purged with argon, and at room temperature, tetrahydrofuran (15 ml), acetonitrile (0.06 ml) and potassium naphthalene (THF) solution (3.0 ml, 0.333 mol) were used.
/ L) and 0.25 ml of ethylene oxide are added to form potassium-3-cyanopropyl alcoholate. To this solution, 5.4 ml of 2- (t-butyldimethylsiloxy) ethyl methacrylate is added and reacted for 5 minutes. This solution was introduced into a large excess of methanol to obtain a polymer.
The yield of the obtained polymer was 4.50 g (90.
5%). The number average molecular weight and the molecular weight distribution of the polymer determined by GPC were 7700 and 1.48, respectively. A signal derived from cyanomethylene appeared around 13 ppm in ¹³ C NMR, and it was confirmed that the terminal had a cyano group.

Example 7 1.0 g of the polymer obtained in Example 1 was added to 10.
Dissolve in 0 ml of THF, add 3 drops of 1 mol / l hydrochloric acid, and stir for a few minutes. The precipitate formed was filtered off and dried under reduced pressure to obtain a polymer. The yield of the obtained polymer is 0.43.
g (81.1%). In addition, ¹ HNM of polymer
R is shown in FIG. In Figure 4, the 0 ppm seen in Figure 1
It was confirmed that the signal of the nearby silylmethyl group had completely disappeared, and that deprotection had been performed.

Example 8 1.0 g of the polymer obtained in Example 3 was added to 1 part in the reaction solution.
It was dissolved in 0.0 ml of THF, 1 mol / l tetrabutylammonium fluoride was added, and the mixture was stirred for several minutes. The precipitate formed was filtered off and dried under reduced pressure to obtain a polymer. The yield of the obtained polymer was 0.45 g (83.8).
%). ¹ H NMR of this polymer is shown in FIG. FIG.
In Fig. 2, the signal of the vinylbenzyl group of 6 to 8 ppm shown in Fig. 2 remains, but the signal of the silylmethyl group found near 0 ppm disappears completely. From this, it was confirmed that the obtained polymer was a PolyHEMA macromonomer.

Example 9 1.0 g of the polymer obtained in Example 4 was added to 1 part in the reaction solution.
Dissolve in 0.0 ml of THF, 1 mol / l hydrochloric acid 10
Add ml and stir for 2 hours. Extraction with chloroform and drying under reduced pressure gave a polymer. The yield of the obtained polymer was 0.44 g (82.9%). ¹ HN of polymer
The MR is shown in FIG. In FIG. 6, the acetal methine signal disappeared completely at around 4.6 ppm in FIG.
A signal derived from an aldehyde group appeared around 6 ppm. Furthermore, it was confirmed that the signal of the silylmethyl group seen in the vicinity of 0 ppm in FIG.

Example 10 1.0 g of the polymer obtained in Example 5 was added to 1 part in the reaction solution.
Dissolve in 0.0 ml of THF, 1 mol / l hydrochloric acid 10
Add ml and stir for 2 hours. Extraction with chloroform and drying under reduced pressure gave a polymer. The yield of the obtained polymer was 0.45 g (84.9%). ¹ HN of polymer
The MR is shown in FIG. ^The signal derived from the t-butyl group completely disappeared around ¹ ppm of ¹ HNMR. Furthermore, it was confirmed that the signal of the silylmethyl group found in the vicinity of 0 ppm in ¹ H NMR disappeared completely and deprotection was performed.

Example 11 1.0 g of the polymer obtained in Example 6 was added to 1 part in the reaction solution.
It is dissolved in 0.0 ml of THF, 0.10 g of lithium aluminum hydride is added, and the mixture is stirred for 2 hours. 1 mol /
l Hydrochloric acid was added until the pH reached 7, and the mixture was extracted with chloroform and dried under reduced pressure to obtain a polymer. The yield of the obtained polymer was 0.47 g (87.9%). ¹³ CN of polymer
The MR is shown in FIG. In this figure, the signal derived from cyanomethylene disappeared completely at around 13 ppm.
A signal derived from primary aminomethylene appeared around ppm. Furthermore, it was confirmed that the signal of the silylmethyl group found in the vicinity of 0 ppm of ¹³ CNMR in FIG.

[0032]

EFFECTS OF THE INVENTION Although poly (2-hydroxyethyl methacrylate) having various functional groups at its end is expected as its hydrogel and biomedical material, the conventional method is not suitable for molecular weight distribution and introduction of specific functional groups. There were various problems such as limitations. The synthetic method in which various functional groups can be quantitatively introduced as in the present invention and the obtained polymer compound has a narrow molecular weight distribution can be a useful material for designing new biomedical materials in the future. Further, a polymer having a siloxy group in the side chain is expected as a material for lithography having etching resistance.

[Brief description of drawings]

FIG. 1 ¹³ C NMR spectrum of poly (t-butyldimethylsiloxy) ethyl methacrylate polymerized with potassium ethoxide as an initiator.

FIG. 2 ¹ H NMR spectrum of poly (t-butyldimethylsiloxy) ethyl methacrylate polymerized with potassium vinylbenzyl alcoholate as an initiator.

FIG. 3 ¹ H NMR spectrum of poly (t-butyldimethylsiloxy) ethyl methacrylate polymerized with potassium 3.3-diethoxypropyl alkoxide as an initiator.

FIG. 4 ¹ H NMR spectrum after hydrolysis of poly (t-butyldimethylsiloxy) ethyl methacrylate polymerized with potassium ethoxide as initiator.

FIG. 5 ¹ H NMR spectrum after hydrolysis of poly (t-butyldimethylsiloxy) ethyl methacrylate polymerized with potassium vinylbenzyl alcoholate as initiator.

FIG. 6 ¹ H after hydrolysis of poly (t-butyldimethylsiloxy) ethyl methacrylate polymerized with potassium-3.3-diethoxypropyl alkoxide as an initiator.
NMR spectrum

FIG. 7 ¹³ C after reduction and hydrolysis of poly (t-butyldimethylsiloxy) ethyl methacrylate polymerized with potassium-3-cyanopropyl alcoholate as an initiator.
NMR spectrum

Claims (4)

[Claims] 1. A polymer compound having a functional group at one end, which is represented by the following structural formula (A). Embedded image (In the formula, R ¹ represents a linear or side chain alkyl group having 1 to 15 carbon atoms, an aryl group, or an aralkyl group.
It may contain an acetal group, a cyano group, an aldehyde group, a carboxyl group, an amino group, an ester bond, an amide bond, a siloxy group, a silanol group or a silylamino group. R ² , R ³ and R ⁴ represent a chain type or side chain type alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group.
These may be the same or different. n is 5 to 1
Represents an integer of 000. ) 2. A polymer compound having a functional group at one end, which is represented by the following structural formula (B). Embedded image (In the formula, R ¹ and n are the same as above.) 3. An alkali metal alcoholate represented by the following structural formula (C) is used as a polymerization initiator, and (In the formula, R ¹ is the same as above. Further, M represents an alkali metal such as lithium, sodium and potassium.) An α, β-unsaturated carbonyl compound represented by the following structural formula (D) is represented by Polymerize, and (In the formula, R ² , R ³ and R ⁴ are the same as above.) Method for producing a polymer compound represented by the following structural formula (A): (In the formula, R ¹ , R ² , R ³ , R ⁴ and n are the same as above.) 4. An alkali metal alcoholate represented by the following structural formula (C) as a polymerization initiator: (In the formula, R ¹ and M are the same as above.) An α, β-unsaturated carbonyl compound represented by the following structural formula (D) is polymerized, and (In the formula, R ² , R ³ and R ⁴ are the same as above.) Thereafter, a method for producing a polymer compound represented by the following structural formula (B) obtained by hydrolyzing a siloxy bond. Embedded image (In the formula, R ¹ and n are the same as above.)