JP3537575B2 - Terminal reactive polymer compound 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 polymer compound having various reactive functional groups at one terminal and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, methyl methacrylate (MM)
The anionic polymerization of an α, β-unsaturated carbonyl compound represented by A) is important for obtaining a polymer compound having a regulated molecular weight or terminal, and has been widely studied.
For example, in anionic polymerization of MMA, alkali metal alkyls such as butyllithium and naphthalene are generally widely used and molecular designs have been made. However, MMA
In the case of using an oxonium anion such as an alkali metal alcoholate as an initiator, the reactivity is extremely low, and at present it is impossible to polymerize without various measures such as using a complexing agent such as a crown ether. .

[0003] In recent years, poly (2-hydroxyethyl methacrylate) (PolyHEMA), which is expected as a hydrogel or a blood-compatible material, is a homologue of an α, β-unsaturated carbonyl compound, but its production is mainly carried out by radicals. 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 not possible to introduce a polymerizable vinyl group or the like into the initiator fragment to perform the terminal function of the resulting polymer.

A radical chain transfer polymerization method has been used for introducing an unsaturated group or an amino group to a terminal. Okano et al. Used Polyl having a primary amino group at one end by radical polymerization using aminoethanethiol hydrochloride as a chain transfer agent.
y (HEMA) has been successfully synthesized (Polymer
Journal, 10 (5), 477 (1978)).
For example, methacrylic anhydride or the like is condensed with this amino group to introduce a polymerizable unsaturated group into the terminal. 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 molecular weight distribution is theoretically 2, and it is presently very difficult to obtain a polymer compound having a uniform molecular weight.

In the course of studying the anionic polymerization characteristics of a monomer in which the hydroxyl group of HEMA is protected with a trialkylsilyl group (ProHEMA) in detail, the monomer itself acts as a complexing agent. It was found that the polymer was easily polymerized with an alkali metal alcoholate. Thereby, the introduction of the terminal group into PolyHEMA, which has been conventionally performed only by radical polymerization, can be performed more widely. Further, anionic polymerization becomes possible without using an alkali metal alkyl which is extremely reactive and difficult to handle as anionic polymerization.

[0006]

SUMMARY OF THE INVENTION The present inventor has previously described α,
Alkali metal alcoholates which have been considered to have little polymerizability to β-unsaturated carbonyl compounds
It is useful for EMA polymerization, its molecular weight and molecular weight distribution are regulated, and it succeeded in quantitatively introducing a functional group into the terminal. According to the present invention, for example, a so-called HEMA macromonomer in which an unsaturated group is introduced into a terminal of PolyHEMA having a uniform molecular weight, which has been difficult until now, can be easily produced. This is extremely useful for molecular design in creating biomaterials,
Not only unsaturated groups but also various functional groups can be introduced into PolyHEMA whose molecular weight is controlled, and it is extremely useful as a material. Furthermore, the poly (ProHEMA) having an organosilicon group synthesized in the present invention itself can introduce various functional groups into its terminals, and thus is useful as a resist material for oxygen-resistant plasma etching.

[0007]

Means for Solving the Problems The gist of the present invention is to provide a compound represented by the following structural formula (A) having a functional group at a terminal quantitatively.
oly (ProHEMA)

[0008]

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

[0010]

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(Wherein R ¹ and n are the same as described 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 the following 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 an unsaturated group 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. These initiators can be used in an amount of 0.0001 to 100 times, and more preferably 0.0001 to 1 ba times the mol of the monomer. The conversion of the alcohol to the alkali metal alcoholate is prepared by adding the corresponding alkali metal hydride, alkali metal alkyl, alkali metal amide and the like to the alcohol in an equivalent amount.

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

The temperature at which the polymerization reaction is carried out in the present invention is not particularly limited, but is preferably from -150 ° C to 150 ° C, more preferably from -30 ° C to 80 ° C.
The reaction time is not particularly limited, but may be from 5 seconds to 100
The time is preferred, more preferably 1 minute to 30 minutes. The atmosphere of the polymerization reaction is argon,
This is performed 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, or the like.

The method of hydrolyzing the thus obtained compound (A) to convert it to the compound (B) mainly uses an oxidized water decomposition reaction. As the acid used, besides hydrochloric acid, sulfuric acid, etc., nitric acid, acetic acid, phosphoric acid, trifluoroacetic acid, methanesulfonic acid, toluenesulfonic acid and the like can be used. Further, tetrafluoroammonium fluoride or the like can be used. It reacts in very small quantities because it reacts catalytically. Specifically, the molar ratio is 0.000001 to 1 with respect to the siloxy unit in the polymer.
It can be used at 0-fold, and more preferably 0.0001 to 0.1-fold. A solvent can be used for the hydrolysis reaction, and after the above-mentioned polymerization, the acid can be added to the same solvent to carry out the hydrolysis reaction. All of the above-mentioned polymerization solvents can be used in the hydrolysis reaction. There is no particular limitation on the temperature at which the hydrolysis reaction is carried out,
0 ° C to 150 ° C is preferable, and more preferably -30 ° C.
° C to 80 ° C. Although the reaction time is not particularly limited, it 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 at the terminal derived from the initiator fragment. 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 preparing comb polymers having lyHEMA components and hydrogels having branches. In addition, functional groups such as acetal, cyano group, ester group, siloxy group, etc. can be converted into polymer compounds having aldehyde, amino group, carboxyl group, silanol group, etc. at their terminals by acid treatment or reduction, etc. Useful as oligomers.

[0021]

The present invention will be further described with reference to the following examples, which do not limit the scope of the present invention. Example 1 The atmosphere in the reaction vessel was replaced with argon, and at room temperature, 15 ml of tetrahydrofuran, 0.06 ml of ethanol, and 3.0 ml of a potassium naphthalene THF solution (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 g).
%). The number average molecular weight and molecular weight distribution of the polymer determined by GPC were 8,800 and 1.59, respectively.
FIG. 1 shows the ¹³ C NMR spectrum of (t-butyldimethylsiloxy) ethyl methacrylate of the obtained polymer. In FIG. 1, it was confirmed that a signal derived from the initiator ethoxy group appeared.

Example 2 The inside of the reaction vessel was replaced with argon, and 0 ° C., 15 ml of tetrahydrofuran, 0.06 ml of ethanol, and 3.0 ml of a potassium naphthalene THF solution (0.333 mol / l) were used.
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 methanol to obtain a polymer. The yield of the obtained polymer was 4.41 g (89.4).
%). The number average molecular weight and molecular weight distribution of the polymer determined by GPC were 7,300 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) 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 resulting polymer was 4.45 g (88.7%). The number average molecular weight and the molecular weight distribution of the polymer determined by GPC were 8600, 1.
54. FIG. 2 shows ¹ HNMR of the obtained polymer, poly (t-butyldimethylsiloxy) ethyl methacrylate. A signal derived from a vinylbenzyl proton appeared around 6 to 8 ppm in FIG. 2, and the introduction rate of the vinylbenzyl group was 94% based on 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, 15 ml of tetrahydrofuran and 0.0 of 3.3-diethoxypropanol were added.
8 ml, 3.0 ml of THF solution of potassium naphthalene
(0.333 mol / l) 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 resulting polymer was 4.5.
9 g (91.2%). The number average molecular weight and molecular weight distribution of the polymer determined by GPC were 750 and 750, respectively.
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 acetal group introduction rate was 98% based on the methyl group signal 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. Produces potassium alcoholate. 5.4 ml of 2- (t-butyldimethylsiloxy) ethyl methacrylate was added to this solution.
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 molecular weight distribution of the polymer determined by GPC were 7,400 and 1.46, respectively. ¹ H NMR
A signal derived from the t-butyl group appeared around 2 ppm, and the introduction rate of the ester group was 99% based on the signal of the methyl group of this signal repeating unit.

Example 6 The atmosphere in the reaction vessel was replaced with argon, and at room temperature, tetrahydrofuran (15 ml), acetonitrile (0.06 ml), and a potassium naphthalene THF solution (3.0 ml, 0.333 mol) were added.
/ L) and 0.25 ml of ethylene oxide 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 7,700 and 1.48, respectively. A signal derived from cyanomethylene appeared at around 13 ppm in ¹³ C NMR, confirming that the terminal had a cyano group.

Example 7 In a reaction solution, 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 resulting precipitate was separated by filtration and dried under reduced pressure to obtain a polymer. The yield of the obtained polymer was 0.43.
g (81.1%). In addition, ¹ HNM of polymer
R is shown in FIG. FIG. 4 shows the 0 ppm observed in FIG.
The signal of the nearby silylmethyl group had completely disappeared, confirming the deprotection.

Example 8 1.0 g of the polymer obtained in Example 3 was added to 1 part of 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 resulting precipitate was separated by filtration and dried under reduced pressure to obtain a polymer. The yield of the resulting polymer was 0.45 g (83.8).
%). The ¹ H NMR of this polymer is shown in FIG. FIG.
In FIG. 2, the signal of the silylmethyl group observed at around 0 ppm completely disappears while the signal of the vinylbenzyl group at 6 to 8 ppm shown in FIG. 2 remains. 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 of the reaction solution.
Dissolve in 0.0 ml of THF and add 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 completely disappeared at around 4.6 ppm in FIG.
A signal derived from the aldehyde group appeared around 6 ppm. Furthermore, it was confirmed that the signal of the silylmethyl group observed at around 0 ppm in FIG. 3 completely disappeared and deprotection was performed.

Example 10 In a reaction solution, 1.0 g of the polymer obtained in Example 5 was added to 1
Dissolve in 0.0 ml of THF and add 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 disappeared completely at around 1.2 ppm in ¹ HNMR. Further, it was confirmed that the signal of the silylmethyl group observed at around 0 ppm in ¹ HNMR completely disappeared and deprotection was performed.

Example 11 1.0 g of the polymer obtained in Example 6 was added to 1 part of the reaction solution.
Dissolve in 0.0 ml of THF, add 0.10 g of lithium aluminum hydride and stir for 2 hours. 1 mol /
Hydrochloric acid was added to pH 7 and 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 completely disappeared at around 13 ppm,
A signal derived from primary aminomethylene appeared at around ppm. Further, it was confirmed that the signal of the silylmethyl group observed at around 0 ppm in ¹³ CNMR in FIG. 7 completely disappeared and deprotection was performed.

[0032]

According to the present invention, poly (2-hydroxyethyl methacrylate) having various functional groups at its terminals is expected as a hydrogel or biomedical material, but the conventional method is not suitable for molecular weight distribution and introduction of specific functional groups. There were various problems such as being limited. The synthesis 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, polymers having a siloxy group in the side chain are expected to be used as lithography materials having etching resistance.

[Brief description of the 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-diethoxypropylalkoxide as an initiator

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

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

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

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

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-250011 (JP, A) JP-A-61-190511 (JP, A) JP-A-8-239425 (JP, A) JP-A-60-1985 52845 (JP, A) JP-A-7-309903 (JP, A) JP-A-2-166102 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 130/08 C08F 4 / 46 C08F 8/12

Claims (4)

(57) [Claims] 1. A polymer compound having a functional group at one end represented by the following structural formula (A). Embedded image (In the formula, R ¹ represents a straight-chain or side-chain alkyl group, aryl group, or aralkyl group having 1 to 15 carbon atoms. In addition, an acetal group, a cyano group, an aldehyde group, a carboxyl group, an amino group, an ester R ² , R ³ , and R ⁴ may have any of a bond, an amide bond, a siloxy group, a silanol group , and a silylamino group. Represents an aralkyl group, which may be the same or different, and n represents an integer of 5 to 10,000.) 2. A polymer compound having a functional group at one end represented by the following structural formula (B). Embedded image (In the formula, R ¹ and n are the same as described above.) 3. A polymerization initiator comprising an alkali metal alcoholate represented by the following structural formula (C): (In the formula, R ¹ is the same as described above. M represents an alkali metal such as lithium, sodium, or potassium.) An α, β-unsaturated carbonyl compound represented by the following structural formula (D) Polymerized, (In the formula, R ² , R ³ and R ⁴ are the same as described above.) A 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 described above.) 4. A polymerization initiator comprising an alkali metal alcoholate represented by the following structural formula (C): (Wherein R ¹ and M are the same as described 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 described above.) 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 described above.)