JP3237235B2 - Styrene polymer 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 polymer of styrenes and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, applications of a polymer having a reactive group as a functional polymer in fields such as electronic materials and medical instruments have been studied. For example, a polymer having a reactive group such as a carboxyethylene group is expected to be applied as a photosensitive material. As a method for producing a polymer having such a reactive group, a polymer reaction for introducing a reactive group into a polymer is generally performed, but there is a problem that it is difficult to reliably introduce a reactive group.

As a method for solving such a problem, there is a method of polymerizing a monomer having a reactive group. In this method, the reactive group inhibits the polymerization reaction or the reactive group causes a side reaction, There was a problem that it was difficult to obtain the desired polymer.

[0004]

In order to solve the problems in the prior art, the present inventors have made intensive studies and found that anionic polymerization of a compound in which a carboxyethylene group was substituted with an oxazolinylethylene group was carried out. It has been found that polymerization proceeds to obtain a target polymer, and then a polymer having a carboxyethylene group can be obtained by removing an oxazolinylethylene group. Further, it has been found that the obtained polymer is synthesized by anionic polymerization, so that the molecular weight can be easily controlled and the molecular weight distribution is narrow. The present invention has been completed based on the above findings.

[0005]

Thus, according to the present invention, the general formula 8

Embedded image (Wherein, R is a hydrogen atom or a lower alkyl group, m = 2-
2500) and general formula 9

Embedded image (Where n represents 0 or 2 to 4500) as a repeating structural unit, and has a number average molecular weight of 500 to 500.
(4-oxazolinylethylene) styrene-based polymer is provided.

According to the present invention, the general formula 10

Embedded image (Wherein, R is a hydrogen atom or a lower alkyl group, x = 2-
2500) and general formula 11

Embedded image (In the formula, y represents 2 to 4500) as a repeating structural unit, and a (4-carboxyethylene) styrene-based polymer having a number average molecular weight of 500 to 500,000 is provided.

Further, according to the present invention, there is provided a compound represented by the general formula (12) obtained by hydrolyzing a (4-oxazolinylethylene) styrene-based polymer in the presence of an acid.

Embedded image (Wherein, R is a hydrogen atom or a lower alkyl group, x = 2-
2500) and general formula 13

Embedded image (In the formula, y = 0 or represents 2 to 4500) as a repeating structural unit, and has a number average molecular weight of 500 to 500.
000 is provided, and a method for producing a (4-carboxyethylene) styrene-based polymer is provided.

Next, according to the present invention, general formula 14

Embedded image (Wherein, R represents a hydrogen atom or a lower alkyl group), wherein (4-oxazolinylethylene) styrenes are provided.

The (4-oxazolinylethylene) styrenes used as monomers in the present invention are novel compounds and are represented by the general formula (14). In the formula, R is a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group, a propyl group, or an isopropyl group. Among them, a hydrogen atom or a methyl group is preferable.

The (4-oxazolinylethylene) styrenes are represented by the general formula 15 with 4-formylstyrene.

Embedded image (Wherein R represents the same as described above) by dehydration-condensation with an oxazolinyl compound represented by the following formula (for example, described in Journal of Organic Chemistry, 27, 4418, p. 1962). the method of). The dehydration condensation is performed in an organic solvent in the presence of a catalyst such as sulfuric acid, phosphoric acid, sodium hydrogen sulfate, zinc chloride, acetic anhydride, phthalic anhydride, and iodine.

The proportion of each component used is usually 1 to 10 oxazolinyls per mole of 4-formylstyrene.
Mol, preferably 1 to 5 mol, and the catalyst is 0.01 to
1 mol, preferably 0.02 to 0.5 mol.

[0012] The reaction temperature is usually 50 to 150 ° C. The reaction time is usually 5 to 100 hours.

The (4-oxazolinylethylene) of the present invention
The styrene-based polymer is obtained by anionic polymerization in the presence of an anionic initiator using the aforementioned (4-oxazolinylethylene) styrenes and styrene as monomers,
It has the above general formula 8 and general formula 9 as a repeating structural unit. The number average molecular weight (Mn) of the (4-oxazolinylethylene) styrene polymer is measured by vapor pressure osmometry (VPO) or measured by gel permeation chromatography (GPC) in terms of standard polystyrene. And usually 500 to 500
000, preferably 1,000 to 400,000, more preferably 1,000 to 300,000. Also, GPC
The molecular weight distribution (Mw / Mn), which is the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn), calculated in terms of standard polystyrene, is 1.35 or less.

Such a (4-oxazolinylethylene) styrene-based polymer is a (4-oxazolinylethylene) styrene homopolymer when n is 0 in the general formula 9, and when n is 2 to 4500. Represents a block copolymer having a segment (segment A) of poly (4-oxazolinylethylene) styrene and a segment (segment B) of polystyrene. The structure of the block copolymer is
It is represented by the general formulas (AB) _l and (AB) _m -A (where _l and _m represent an integer of 1 or more).

Hereinafter, a production method in the case where the (4-oxazolinylethylene) styrene polymer is a (4-oxazolinylethylene) styrene homopolymer will be described first. The (4-oxazolinylethylene) styrene homopolymer can be obtained by anionic polymerization of (4-oxazolinylethylene) styrene in the presence of an anionic polymerization initiator. As such an anionic polymerization initiator, usually,
It is not particularly limited as long as it is used, for example,
Examples thereof include an alkali metal, an alkali metal alkyl compound, an alkali metal aromatic compound complex, an alkali metal amide, an organic magnesium compound, an alkali metal ketyl, and an ate complex. Specifically, alkali metals such as cesium, rubidium, potassium, sodium, and lithium; n
Alkali metal alkyl compounds such as -butyllithium, sec-butyllithium and t-butyllithium; alkali metal aromatic compound complexes such as sodium naphthalene, potassium naphthalene, lithium naphthalene and cumyl potassium; alkali metal amides such as potassium amide and lithium diethylamide; Organic magnesium compounds such as Grignard reagents and alkyl magnesium; alkali metal ketyls such as sodium benzophenone ketyl; LiA
Art complexes such as 1H ₄ and NaAlH ₂ (O—CH ₂ CH ₂ OCH ₃ ) ₂ are exemplified.

Among such anionic polymerization initiators, alkali metal alkyl compounds or alkali metal aromatic compound complexes are awarded.

The anionic polymerization initiator is used in an amount of 0.0005 to 1 mol of (4-oxazolinylethylene) styrene.
It is used in an amount of 0.5 mol, preferably in the range of 0.005 to 0.05 mol.

When the anionic polymerization initiator is an alkali metal alkyl compound or an alkali metal aromatic compound complex, it can be used in combination with a compound such as 1,1-diphenylethylene, tetraphenylbutadiene or α-methylstyrene. Such a compound is used in an amount of usually 1 to 10 mol, preferably 1 to 5 mol, per 1 mol of the alkali metal alkyl compound or the alkali metal aromatic compound complex.

In the polymerization, a solvent is usually used.
The solvent is not particularly limited as long as it is inert to polymerization, and examples thereof include aliphatic compounds, aromatic compounds, and ether compounds. Specifically, pentane, hexane,
Aliphatic compounds such as heptane and cyclohexane; aromatic compounds such as benzene, toluene and xylene; ether compounds such as ethyl ether, tetrahydrofuran and dimethoxyethane. These can be used alone or in combination.

The solvent is (4-oxazolinylethylene)
The styrene is used in an amount of usually 1 to 30% by weight, preferably 5 to 20% by weight.

The polymerization is usually carried out under high vacuum or under reduced pressure in an inert gas. The polymerization time is not particularly limited, but is usually 5 minutes or more. The polymerization temperature is usually -120 to 50C, preferably -100 to 30C,
More preferably, it is -100 to -30C.

Next, the (4-oxazolinylethylene) styrene polymer is poly (4-oxazolinylethylene)
The production method in the case of a block copolymer of styrenes and polystyrene will be described. Such a block polymer can be obtained, for example, by subjecting styrene to anionic polymerization to obtain living polystyrene, and subsequently adding (4-oxazolinylethylene) styrenes thereto to continue polymerization. In the copolymerization, the initiator, solvent, reaction conditions, and the like used are the same as described above. The proportion of poly (4-oxazolinylethylene) styrenes in the block copolymer can be set arbitrarily, but is usually 5 to 95% by weight,
Preferably it is 10 to 90% by weight.

By hydrolyzing the (4-oxazolinylethylene) styrene polymer thus obtained, the oxazolinyl group is eliminated, and the compounds represented by the general formulas 12 and 13 are obtained.
(4-carboxyethylene) styrene-based polymer having the following as a repeating structural unit. The number average molecular weight (Mn) of the (4-carboxyethylene) styrene-based polymer can be measured by vapor pressure osmometry (VPO) or gel permeation chromatography (G
PC), and is a value measured in terms of standard polystyrene by PC).
~ 400,000, more preferably 1000 ~ 3000
00. The molecular weight distribution (Mw / Mn), which is the ratio between the weight average molecular weight (Mw) obtained by conversion into standard polystyrene by GPC and the number average molecular weight (Mn), is as follows:
1.35 or less.

When a homopolymer of (4-oxazolinylethylene) styrene is used as the (4-oxazolinylethylene) styrene polymer, the general formula 13 A homopolymer of (4-carboxyethylene) styrenes having y of 0 is obtained, and when a block copolymer of poly (4-oxazolinylethylene) s and polystyrene is used, y in general formula 13 is A block copolymer of poly (4-carboxyethylene) styrenes having 2 to 4500 and polystyrene is obtained.

The hydrolysis is carried out by a conventional method.
After heating the (4-carboxyethylene) styrene-based polymer in the presence of an acid, a method of heating the polymer in the presence of a base may be used. Usually, an inorganic acid or an organic acid is used as the acid. Specific examples include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; and organic acids such as formic acid, acetic acid, and propionic acid. Examples of the base include sodium hydroxide and potassium hydroxide.

The hydrolysis is generally performed in the presence of a solvent. The solvent is not particularly limited as long as it is inert to the hydrolysis reaction, and examples thereof include water, an aliphatic compound, an aromatic compound, and an ether compound. In particular,
Aliphatic compounds such as pentane, hexane, heptane and cyclohexane; aromatic compounds such as benzene, toluene and xylene; ether compounds such as ethyl ether, tetrahydrofuran and dimethoxyethane. These can be used alone or in combination.

[0027] The reaction temperature is usually 50 to 100 ° C.
The reaction time is usually 10 to 100 hours.

The (4-carboxyethylene) styrene-based polymer thus obtained has a reactive carboxyethylene group, so that it can be expected to be used for photosensitive materials, optical materials, and electronic materials.

[0029]

According to the present invention, a polymer having a carboxyethylene group can be obtained by using the novel compound.

[0030]

The present invention will be described more specifically with reference to the following examples. In the examples, parts and% are based on weight unless otherwise specified. Example 1 4,4-Dimethyl-2- (4-vinylstyryl) -2-
Synthesis of oxazoline 15.1 g (115 mmol) of 4-formylstyrene, 2-methyloxazoline
9 g (221 mmol) and 1.1 g of paratoluenesulfonic acid are dissolved in 70 ml of toluene,
After refluxing for 35 hours in a Dean-Stark apparatus, the mixture was cooled and ether was added. Then, the mixture was washed with sodium hydrogen sulfite and an aqueous solution of sodium hydroxide, and dried with magnesium sulfate. The obtained crude product was purified by silica gel column chromatography and recrystallized from hexane to give 4,4-dimethyl-2- (4-vinylstyryl)-
13.7 grams of 2-oxazoline (53.0% yield)
Obtained.

The physical properties of 4,4-dimethyl-2- (4-vinylstyryl) -2-oxazoline are shown below. 90 MHz ¹ H NMR (CDCl ₃ ) δ: 1.34
(S, 6H), 4.03 (s, 2H), 5.28, 5.
78 (2d, 2H, J = 11, 18 Hz), 6.58
(D, 1H, J = 16 Hz), 6.71 (dd, 1
H), 7.24 to 7.41 (m, 5H)

23 MHz ¹³ C NMR (CDCl ₃ )
δ: 28.2, 67.2, 78.7, 114.6, 11
5.3, 126.5, 127.5, 134.7, 13
8.6, 139.0, 161.7

IR (KBr) cm ^-1 : 1657,160
4,1355,1308,1202,1008,97
7,899,826

Elemental analysis: Calculated C79.26, H7.54, N6.16 Observed C78.64, H7.63, N6.01 Melting point: 35.0-36.0 ° C

Example 2 Synthesis of 4,4-dimethyl-2- (α-methyl-4-vinylstyryl) -2-oxazoline was as follows: 10.4 g (78.4 mmol) of 4-formylstyrene, 4-ethyloxazoline 19.6 grams (15
(4 mmol) and 1.7 g of p-toluenesulfonic acid were dissolved in 150 ml of toluene, and the mixture was refluxed for 20 hours with a Dean-Stark apparatus. (Α-methyl-4-vinylstyryl) -2-oxazoline is 13.7
Grams (53.4% yield) were obtained.

4,4-dimethyl-2- (α-methyl-4
The physical properties of (vinylstyryl) -2-oxazoline are shown below. 90 MHz ¹ H NMR (CDCl ₃ ) δ: 1.35
(S, 6H), 2.21 (s, 3H), 4.03 (s,
2H), 5.27, 5.77 (2d, 2H, J = 11,
18Hz), 6.73 (dd, 1H), 7.24-7.
49 (m, 5H)

23 MHz ¹³ C NMR (CDCl ₃ )
δ: 15.2, 28.3, 67.4, 78.9, 11
4.3, 125.6, 126.1, 129.7, 13
4.4, 135.9, 136.3, 136.9, 16
4.1 IR (KBr) cm ^-1 : 1629, 1608, 138
5,1278,1207,1185,1087,100
6,962,906,847

Elemental analysis: Calculated values C 79.63, H 7.94, N 5.80 Found C 79.49, H 7.82, N 5.72 Melting point: 48.7-49.7 ° C.

Example 3 Poly [4,4-dimethyl-2- (4-vinylstyryl)
-2-Oxazoline] The following polymerization reaction was carried out under a vacuum in a glass polymerization reaction tube equipped with a break seal. 6 ml of a tetrahydrofuran solution containing 2.48 mmol of 4,4-dimethyl-2- (4-vinylstyryl) -2-oxazoline is added to 5 ml of a tetrahydrofuran solution containing 0.031 mmol of cumyl potassium and 0.08 mmol of diphenylethylene. After reacting at −78 ° C. for 12 hours, the polymerization tube was opened, and a small amount of methanol was added to terminate the polymerization. Then, the reaction solution was poured into a large amount of hexane to precipitate the polymer. The obtained crude polymer was purified with tetrahydrofuran and hexane, and lyophilized with benzene to obtain 0.47 g of poly [4,4-dimethyl-2- (4-vinylstyryl) -2-oxazoline] (yield). 84
%). The number average molecular weight (Mn) determined by vapor pressure osmometry (VPO) was 13,900. The molecular weight distribution (Mw / Mn), which is the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene, measured by gel permeation chromatography (GPC) is 1.30. Met.

The physical properties of poly [4,4-dimethyl-2- (4-vinylstyryl) -2-oxazoline] are shown below. 90 MHz ¹ H NMR (CDCl ₃ ) δ: 0.2-3.
0 (m, 9H), 4.0 (s, 2H), 5.0 to 7.6
(M, 6H)

IR (KBr) cm ^-1 : 1657, 160
4,1363,1310,1202,1004,975

Example 4 Synthesis of poly [4,4-dimethyl-2- (α-methyl-4-vinylstyryl) -2-oxazoline] A glass polymerization reactor equipped with a break seal, and the following polymerization was carried out under vacuum. The reaction was performed. 4,5-Dimethyl-2- (α-methyl-4-vinylstyryl) -2-in 5 ml of tetrahydrofuran solution containing 0.065 mmol of cumyl potassium and 0.15 mmol of diphenylethylene.
After adding 6 ml of a tetrahydrofuran solution containing 2.68 mmol of oxazoline and reacting at -78 ° C. for 12 hours, the polymerization tube was opened and a small amount of methanol was added to terminate the polymerization. Then, the reaction solution was poured into a large amount of hexane to precipitate the polymer. The obtained crude polymer was purified with tetrahydrofuran and hexane and freeze-dried with benzene to obtain poly [4,4-dimethyl-2- (α-
Methyl-4-vinylstyryl) -2-oxazoline] in 0.65 grams (100% yield). The number average molecular weight (Mn) determined by the vapor pressure osmometry (VPO) was 11,000. In addition, the molecular weight distribution (Mw
/ Mn) was 1.05.

The physical properties of poly [4,4-dimethyl-2- (α-methyl-4-vinylstyryl) -2-oxazoline] are shown below. 90 MHz ¹ H NMR (CDCl ₃ ) δ: 0.6 to 2.
0 (m, 3H), 1.3 (s, 6H), 2.1 (s, 3
H), 4.0 (s, 2H), 6.2 to 7.3 (m, 5
H)

23 MHz ¹³ C NMR (CDCl ₃ )
δ: 15.3, 78.5, 39.0 to 42.0, 67.
5,125.0,127.6,128.3,134.
1,134.8, 144.5, 164.4 IR (KBr) cm ^-1 : 1641, 1609, 136
3,1192,1089,1008,979

Example 5 Synthesis of Block Copolymer Having Poly [4,4-dimethyl-2- (α-methyl-4-vinylstyryl) -2-oxazoline] Segment and Polystyrene Segment Made of glass with a break seal The following polymerization reaction was performed in a polymerization reaction tube and under vacuum. Potassium naphthalene 0.13
10 ml of a tetrahydrofuran solution containing 7.06 mmol of styrene was added to a milliliter of tetrahydrofuran solution containing 1 mmol at −78 ° C.
The reaction was carried out for a time to obtain living polystyrene. to this,
2.45 mmol of 4,4-dimethyl-2- (α-methyl-4-vinylstyryl) -2-oxazoline were added,
After reacting at 78 ° C. for 1 hour, the polymerization tube was opened and a small amount of methanol was added to terminate the polymerization. Next, the reaction solution was poured into a large amount of methanol to precipitate the polymer. The obtained crude polymer was purified with tetrahydrofuran and methanol and freeze-dried with benzene, whereby 1.32 g (100% yield) of a brook copolymer was obtained. The number average molecular weight (Mn) determined by vapor pressure osmometry (VPO) was 21,100. The molecular weight distribution (Mw / Mn) was 1.05. The GPC curve of the block copolymer moved from polystyrene to the high molecular weight side while maintaining a narrow molecular weight distribution. When the ratio of the polymer segments in the block copolymer was determined by ¹ HNMR, poly [4,4-dimethyl-2- (α-methyl-4-vinylstyryl) -2-oxazoline] segment: polystyrene segment = 0.35: 1,
The value almost coincided with the charged value, and a block copolymer as designed was obtained.

The physical properties of the block copolymer having a poly [4,4-dimethyl-2- (α-methyl-4-vinylstyryl) -2-oxazoline] segment and a polystyrene segment are shown below. Total 90 MHz ¹ H NMR (CDCl ₃ ) δ: 0.8-2.
4 (m, 6H), 4.0 (s, 2H), 6.0 to 7.4
(M, 5H)

Example 6 Synthesis of poly [3- (4-vinylphenyl) -2-methyl-propenoic acid] Poly [4,4-dimethyl-2 synthesized according to Example 4.
-(Α-methyl-4-vinylstyryl) -2-oxazoline] (number average molecular weight 8400, molecular weight distribution 1.0
5) (0.30 g) was dissolved in tetrahydrofuran (2 ml), 3N-HCl (17.8 ml) was added thereto, and the mixture was refluxed for 10 hours. 30 ml of a water: methanol (1: 1) solution of 15% sodium hydroxide was added, and the mixture was refluxed for 11 hours. The reaction solution was concentrated under reduced pressure, and poured into dilute hydrochloric acid to precipitate a polymer. Then, the mixture was filtered, washed with water, and dried under reduced pressure.
(4-vinylphenyl) -2-methyl-propenoic acid] was obtained in 0.24 grams (100% yield). Then
Poly [3- (4-vinylphenyl) -2-methyl-propenoic acid] was subjected to methyl esterification using diazomethane, and the number average molecular weight (Mn) was determined by gel permeation chromatography (GPC). Met. The molecular weight distribution (Mw / Mn), which is the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene, measured by gel permeation chromatography (GPC) is 1.05. Met.

Poly [3- (4-vinylphenyl) -2-
Methyl-propenoic acid] have the following physical properties. 90 MHz ¹ H NMR (CDCl ₃ ) δ: 0.6 to 2.
6 (m, 3H), 2.1 (s, 3H), 6.2 to 8.0
(M, 5H) 0.6-IR (KBr) cm ^-1 : 3700-2700,168
6,1637,1418,1268,1211,112
9,995

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08F 212: 34) C08F 212: 34) (C08F 297/02 (C08F 297/02 212: 08) 212: 08) (56) Reference Document JP-A-49-107710 (JP, A) JP-A-62-205106 (JP, A) JP-A-62-280249 (JP, A) JP-A-4-263263 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08F 12/00-12/36 C08F 112/00-112/36 C08F 212/00-212/36 C07D 263/12 C08F 8/12 C08F 297/02 CA (STN )

Claims (6)

(57) [Claims] 1. A compound of the general formula 1 (Wherein, R is a hydrogen atom or a lower alkyl group, m = 2-
2500) and general formula 2 (Where n represents 0 or 2 to 4500) as a repeating structural unit, and has a number average molecular weight of 500 to 500.
(4-oxazolinylethylene) styrene-based polymer characterized by being 000. 2. The (4-oxazolinylethylene) styrene polymer according to claim 1, wherein n = 0. 3. The (4-oxazolinylethylene) styrene polymer according to claim 1, wherein n = 2-4500. 4. A compound of the general formula 3 (Wherein, R is a hydrogen atom or a lower alkyl group, x = 2-
2500) and the general formula 4 (In the formula, y represents 2 to 4500) as a repeating structural unit, and has a number average molecular weight of 500 to 500,000. 5. A compound of the general formula 5 obtained by hydrolyzing the (4-oxazolinylethylene) styrene polymer according to claim 1. (Wherein, R is a hydrogen atom or a lower alkyl group, x = 2-
2500) and the general formula 6 (In the formula, y = 0 or represents 2 to 4500) as a repeating structural unit, and has a number average molecular weight of 500 to 500.
A method for producing a (4-carboxyethylene) styrene-based polymer, wherein 6. A compound of the general formula 7 (Wherein, R represents a hydrogen atom or a lower alkyl group). (4-Oxazolinylethylene) styrenes.