JPH10259203A - Poly(1-(2-tetrahydrofuranyloxy)-4-(1-methylethenyl) benzene) with narrow distribution and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer having a narrow molecular weight distribution, capable of allowing an molecular weight to be readily regulated, and capable of being utilized as a resist material by regulating a weight average molecular weight, and the ratio of the weight average molecular weight to the number average molecular weight so as to be within a specified range. SOLUTION: The objective polymer is obtained by regulating a weight average molecular weight so as to be 2,000-100,000, and the ratio of the weight average molecular weight to a number average molecular weight so as to be <=1.5. The polymer can be obtained by polymerizing (A) 1-(2- tetrahydrofuranyloxy)-4-(1-methylethenyl)benzene obtained by reacting (i) 4-(1- methylethenyl)phenol with (ii) dihydrofurans in the presence of (iii) an acid, in the presence of (B) a polymerization initiator comprising an organic alkali metal compound. For example, the component B is, preferably, a compound of formula I (R<1> and R<2> are each a 1-10C alkyl or a 7-11C aralkyl; R<3> is H or a 1-10C alkyl; M is an alkali metal such as Li and K), etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polydispersible poly (1- (2-tetrahydrofuranyloxy) -4- (1)
-Methylethenyl) benzene) and its production process. Specifically, narrowly dispersed poly {1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene} useful as a chemically amplified positive resist material, and 4- (4- (1-methylethenyl) benzene), which is industrially easily available 1-methylethenyl)
The present invention relates to a method for producing narrowly dispersible poly {1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene} using phenol as a raw material.

[0002]

2. Description of the Related Art A related poly {1- (2-tetrahydrofuranyloxy) -4-ethenylbenzene} is a chemically amplified positive resist material having high sensitivity, high resolution, and high dry etch resistance. It is known that it is useful as a raw material for producing a p-hydroxystyrene polymer by removing a part or all of a 2-tetrahydrofuranyloxy group in a polymer (Journal of Appl.
lied Polymer Science, Vol. 42, 877-883 (1991) and Polym. Mater. Sci. Eng., Vol. 61, 417-421 (198
9)). It is also known that a tetrahydrofuranyloxy group has a higher acid-decomposability than a tetrahydropyranyloxy group, and is useful as a resist material.

As a method for producing this poly {1- (2-tetrahydrofuranyloxy) -4-ethenylbenzene}, p-hydroxybenzaldehyde and 2,3-dihydrofuran are reacted in the presence of an acid to form p-hydroxybenzaldehyde. Dihydrofuranyloxybenzaldehyde was obtained and then subjected to Wittig reaction with (bromomethyl) triphenylphosphonium bromide in the presence of potassium tert-butoxy to give 1
A method is described in which-(2-tetrahydrofuranyloxy) -4-ethenylbenzene is obtained and is produced by radical polymerization of azoisobutyronitrile using azoisobutyronitrile as a polymerization initiator.

However, in this method, a narrowly dispersible polymer was not obtained, and therefore, it was insufficient as a chemically amplified positive resist material requiring a high resolution. Further, in the lithography process, when the resist is removed with a release agent, there is a disadvantage that the dissolution rate is too high.

Further, this production method is a method in which p-hydroxybenzaldehyde is used as a raw material, a phenol hydroxyl group is tetrahydrofuranyloxylated, then a Wittig reaction is carried out, and radical polymerization is carried out, but the reaction is complicated in multiple stages. Not only that, in the Wittig reaction, an expensive phosphonium salt is converted into phosphine oxide, so that a large amount of by-products are generated, which makes the handling more difficult, and the industrial poly {1- (2-)
It cannot be a method for producing (tetrahydrofuranyloxy) -4-ethenylbenzene}. On the other hand, 4- (1-methylethenyl) phenol (common name p-hydroxy-α
-Methylstyrene) is easily obtained by the thermal decomposition of 2,2-bis (4'-oxyphenyl) propane (common name bisphenol A) (JP-B-56-52886).
Such).

[0006]

The inventors of the present invention have conducted intensive studies on a novel polymer having a narrow molecular weight distribution, capable of adjusting the molecular weight arbitrarily, and which can be suitably used as a resist material. -(1-methylethenyl) phenol is tetrahydrofuranyloxylated by reaction with dihydrofuran, and then anionically polymerized to give a polydisperse compound having a desired molecular weight and a narrow dispersibility.
-(2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene} can be easily produced at a high yield, and this polymer has a suitable dissolution rate in a release agent. Heading, the present invention has been reached.

[0007]

That is, the present invention relates to a narrow-dispersion poly # 1 having a weight average molecular weight of 2,000 to 100,000 and a ratio of the weight average molecular weight to the number average molecular weight of 1.5 or less. -(2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene}.

The present invention also relates to 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) obtained by reacting 4- (1-methylethenyl) phenol with dihydrofurans in the presence of an acid. A) narrowly dispersible poly {1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl), wherein benzene is anionically polymerized using an organic alkali metal compound as a polymerization initiator;
A method for producing benzene, and the reaction of 4- (1-methylethenyl) phenol with dihydrofurans in the presence of an acid to obtain 1- (2-tetrahydrofuranyloxy) -4- (1- Methylethenyl) benzene,
Chemical formula (1)

[0009]

Embedded image (Wherein, R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 11 carbon atoms; R ³ is hydrogen or an alkyl group having 1 to 10 carbon atoms; Represents an alkali metal selected from lithium, sodium, potassium or cesium.), A chemical formula (2)

[0010]

Embedded image (Wherein, R ⁴ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ⁵ is an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 11 carbon atoms, and R ⁶ is a hydrogen atom or a carbon atom. An alkyl group, an alkoxy group or an alkoxyalkoxy group of the formulas 1 to 10, M represents an alkali metal selected from lithium, sodium, potassium or cesium, and l represents an integer of 1 to 200), chemical formula (3)

[0011]

Embedded image (Wherein R ⁷ is an alkyl group having 1 to 3 carbon atoms;
⁸ is hydrogen or an alkyl group having 1 to 10 carbon atoms,
An alkoxy group or an alkoxyalkoxy group, M is an alkali metal selected from lithium, sodium, potassium or cesium, and m and n each represent an integer of 1 to 100. ) Or chemical formula (4)

[0012]

Embedded image wherein Ar is naphthalene, anthracene, indene,
An organic group selected from cyclopentadiene or fluorene, and M represents an alkali metal selected from lithium, sodium, potassium or cesium. The method for producing narrowly dispersible poly {1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene}, characterized by anionic polymerization using an organic alkali metal compound represented by the formula (1) as a polymerization initiator: is there.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The narrow-dispersion poly {1- (2-tetrahydrofuranyloxy) -4- (1)
-Methylethenyl) benzene} has the chemical formula (5)

[0014]

Embedded image And has a weight average molecular weight of 2,000 to 100,000, preferably 5,000 to 80,000, and more preferably 6,000 to 50,000. And the ratio between the weight average molecular weight and the number average molecular weight is 1.5 or less,
Preferably it is in the range of 1.0 to 1.2.

In the method of the present invention, first, 4- (1
-Methylethenyl) phenol is reacted with dihydrofurans in the presence of an acid to give 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene. 4- (1-methylethenyl) phenol is 2,2
It can be easily obtained by thermal decomposition of -bis (4'-oxyphenyl) propane (JP-B-56-52886).

The dihydrofurans are 2,3-dihydrofuran or 2,5-dihydrofuran, and may have an alkyl or alkoxy substituent on the furan ring as long as the reaction is not hindered. Preferably, it is 2,3-dihydrofuran. The amount of these dihydrofurans to be used is generally 10 mol or less, preferably 0.1 to 5 mol, more preferably 0.5 to 5 mol, per 1 mol of 4- (1-methylethenyl) phenol. 3
Range of moles.

As the acid, for example, hydrogen halide such as hydrogen chloride gas, mineral acid such as sulfuric acid, phosphoric acid, hydrochloric acid or hydrobromic acid, solid acid such as heteropoly acid or Nafion, or p-toluenesulfonic acid , Trifluoroacetic acid, acetic acid, propionic acid, malonic acid, oxalic acid, chlorosulfonic acid / pyridine salt, sulfuric acid / pyridine salt or p
And organic acids such as toluenesulfonic acid / pyridine salt. Of these, hydrogen chloride gas, hydrochloric acid, trifluoroacetic acid, p-toluenesulfonic acid / pyridine salt, and sulfuric acid / pyridine salt are preferable. These acids alone,
Alternatively, two or more kinds can be used simultaneously or sequentially. The use amount of these acids is usually 2 mol or less per 1 mol of 4- (1-methylethenyl) phenol,
Preferably, it is in the range of 0.00001 to 0.2 mol, more preferably in the range of 0.0001 to 0.05 mol.

In some cases, the reaction in the method of the present invention can be carried out without using a solvent, but is usually carried out in the presence of a solvent. Any solvent can be used as long as it does not inhibit the reaction. Specific examples thereof include water; and aliphatic solvents such as n-hexane, n-pentane, n-heptane, and cyclohexane. Or alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, ethylbenzene and cumene; aliphatic or aromatic halogen compounds such as dichloromethane, chloroform, chlorobenzene and dichlorobenzene; diethyl ether, diphenyl ether, tetrahydrofuran, ,
Ethers such as 4-dioxane, ethylene glycol dimethyl ether and ethylene glycol diethyl ether; ketones such as acetone, ethyl methyl ketone and acetophenone; nitriles such as acetonitrile and propionitrile; and esters such as ethyl acetate and ethyl propionate And the like. These can be used alone or 2
A mixture of more than one species may be used. In addition, it is preferable that the reaction liquid be a homogeneous phase by using these solvents, but a plurality of non-uniform phases may be formed.

The mode of carrying out the reaction in the method of the present invention is as follows:
The method is not particularly limited, and any method may be used as long as 4- (1-methylethenyl) phenol, dihydrofurans, acid, and a solvent when used are effectively mixed and contacted. , Semi-batch type or continuous flow type.

The temperature and time during the reaction vary depending on the types and amounts of the starting materials such as dihydrofurans and acids, and the solvent used, and are not uniform. However, the reaction temperature is usually in the range of 10 ° C to 100 ° C below zero, preferably in the range of 0 ° C to 60 ° C. The reaction time is usually within 20 hours, preferably 0.01 to 10 hours.
Time range. The reaction can be carried out under reduced pressure, normal pressure or increased pressure as the case may be. The reaction in the method of the present invention can be performed under an inert gas atmosphere or in the presence of molecular oxygen such as air. 1- (2-tetrahydrofuranyloxy) by the reaction in the method of the present invention
-4- (1-Methylethenyl) benzene is obtained.

Next, the obtained 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene is subjected to anionic polymerization using an organic alkali metal compound as a polymerization initiator.

1- (2-tetrahydrofuranyloxy)
-4- (1-Methylethenyl) benzene can be used after being isolated from the reaction solution obtained by the above reaction by extraction, distillation, and / or treatment by a conventional method such as crystallization, Alternatively, the acid can be removed from the reaction solution by a usual operation such as extraction, neutralization, filtration, or treatment with an ion exchange resin, and then used directly for anionic polymerization without isolation. In addition, 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene is preferably stored by adding an alkali component such as potassium hydroxide or sodium carbonate as a stabilizer. The alkali component can be used for anionic polymerization without removal.

In the anionic polymerization in the method of the present invention,
An organic alkali metal compound is used as a polymerization initiator. Preferred organic alkali metal compounds include organic alkali metal compounds represented by chemical formula (1), chemical formula (2), chemical formula (3) or chemical formula (4). More preferably, sec-butyllithium, α −
Methyl styrene dimer potassium, α-methyl styrene tetramer sodium, cumyl potassium, cumyl cesium, sodium naphthalene or sodium anthracene.

In addition, a combination of components capable of generating these organic alkali metal compounds under polymerization conditions, such as a combination of cumene and an alkali metal,
Alternatively, these organic alkali metal compounds may be separately used and then used without isolation. The amount of these organic alkali metal compounds used depends on their type and the intended poly {1- (2-tetrahydrofuranyloxy)-
Although it is not uniform depending on the molecular weight of 4- (1-methylethenyl) benzene}, it is usually 0.5 mol or less per 1 mol of 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene, Preferably 0.000
The range is from 0.01 to 0.1 mol, and more preferably from 0.0001 to 0.05 mol.

The anionic polymerization in the method of the present invention is preferably carried out in an organic solvent. The organic solvent used in this case is, for example, n-hexane, n-pentane, n
-Aliphatic or alicyclic hydrocarbons such as heptane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, ethylbenzene and cumene; and diethyl ether;
Examples thereof include ethers such as diphenyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether. These may be used alone or in combination of two or more. When these solvents are used in the reaction of the present invention, it is preferable to use the same solvent in the anionic polymerization in order to omit operations such as solvent recovery. The method of performing anionic polymerization in the method of the present invention is not particularly limited, and 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene, an organic alkali metal compound, and a solvent when used. Any method can be used as long as they are effectively mixed and brought into contact with each other, and any of a batch system, a semi-batch system, and a continuous flow system may be used.

The temperature and time for the anionic polymerization are as follows:
-(2-Tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene, an organic alkali metal compound, and the type and amount of a solvent used when used are not uniform. However, the polymerization temperature is usually below 100 ° C.
To 150 ° C, preferably below 80 ° C
To 80 ° C. The polymerization time is usually within 100 hours, preferably in the range of 0.01 to 20 hours. The polymerization can be carried out under reduced pressure, normal pressure or increased pressure as the case may be.

The anionic polymerization in the method of the present invention is carried out in an atmosphere of an inert gas such as argon or nitrogen. Further, in the anionic polymerization in the method of the present invention, additives such as crown ethers and polyglycols which have been used so far in the anionic polymerization are further used to increase the polymerization rate and the polymerization yield. Can also. By the above operation, 1- (2-tetrahydrofuranyloxy)
Polymerizes selectively through the vinyl group of -4- (1-methylethenyl) benzene.

When the desired degree of polymerization is reached, a polymerization terminator is added to stop the polymerization, so that the weight average molecular weight becomes 2
000 to 100,000 and a ratio of the weight average molecular weight to the number average molecular weight of 1.5 or less.
(2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene} is obtained. As the polymerization terminator, an ordinary anionic polymerization terminator can be used, for example, water; alcohols such as methanol and ethanol;
Alkyl halides such as methyl bromide and methyl iodide; and organic carboxylic acids such as acetic acid and propionic acid. Further, after polymerization, carbon dioxide, or after treatment with, for example, a cyclic ether compound such as ethylene oxide or propylene oxide, and then further treatment with the above-mentioned polymerization terminator, the functional group such as a polymer chain terminal hecarboxyl group or a hydroxyl group. Can be introduced.

The obtained narrow-dispersion poly {1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene} is precipitated using a suitable solvent such as methanol, washed and dried. It can be isolated and purified by a conventional method.

[0030]

The following examples further illustrate the present invention, but are not to be construed as limiting, but merely as illustrative. Example 1 10.0 g (74.6 mmol) of 4- (1-methylethenyl) phenol was placed in a 200 ml 4-neck flask equipped with a stirrer, a thermometer, a dropping funnel of 30 ml in volume and a condenser. Then, 5.0 ml (5.0 mmol) of a 1N solution of hydrogen chloride in diethyl ether as an acid and 100.0 ml of diethyl ether as a solvent were charged. When this solution was stirred and the internal temperature was cooled to 0 ° C with ice, 15.77 g (225.0 g) of 2,3-dihydrofuran was dropped from the dropping funnel.
(Mmol). After dripping over 20 minutes,
The reaction was allowed to proceed for 8 hours in an air atmosphere. After the completion of the reaction, this reaction solution was transferred to a 300 ml separating funnel, extracted and washed three times with 100 ml of a 0.2 N sodium hydroxide aqueous solution, and further washed twice with 100 ml of ion-exchanged water to remove acid components. Removed. The alkaline water and water used for the extraction were mixed, back-extracted with diethyl ether as a reaction solvent, and mixed with the first organic layer. After the thus obtained organic solution was dried over anhydrous sodium sulfate and subjected to component analysis by high performance liquid chromatography, the target product, 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) was obtained. 9.) 9.39 grams (46.0 mmol) of benzene;
And 2.97 g (22.1 mmol) of raw material 4- (1-methylethenyl) phenol, the conversion of 4- (1-methylethenyl) phenol was 70.3%, and the charged 4- ( The yield of 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene relative to 1-methylethenyl) phenol is 6
1.7%. Diethyl ether was distilled off from the resulting alkali-treated organic solution, and the resulting 1
1.-(2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene in the presence of calcium hydride.
It was purified by distillation at 0 mmHg and 80 ° C. The yield is 7.
It weighed 6 grams. The generated 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene was identified by ¹ H-NMR, ¹³ C-NMR, IR and elemental analysis.

A 100 ml Schlenk flask was charged with a stir bar under an argon atmosphere, and then 50 ml of tetrahydrofuran as a solvent and 0.3 ml of a 1.08 N cyclohexane solution of sec-butyllithium as a polymerization initiator (0.3 ml). Mmol). The solution was cooled to −78 ° C. with a dry ice / methanol bath with stirring, and then distilled and purified.
5.0 g (24.5 mmol) of -tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene were added. The solution immediately turned dark red. After the polymerization was continued for 5 hours, 5.0 ml of methanol was added to stop the polymerization. This polymerization solution was poured into 1.0 liter of methanol to precipitate the polymer, which was separated by filtration and further dried under reduced pressure to obtain 4.61 g of a white polymer. The weight yield based on the charged 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene was 92.2%. From the results of ¹ H-NMR analysis, IR analysis, and elemental analysis, the obtained white polymer was obtained from the target poly {1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene}.
Met. As a result of GPC analysis using polystyrene as a standard, the weight average molecular weight (Mw) was 16,000,
And the molecular weight dispersity (Mw / Mn) was 1.06.

Comparative Example 1 In Example 1, except that a 1N / diethyl ether solution of hydrogen chloride used as an acid was not used, the reaction was carried out in the same manner as in Example 1. A treated organic solution was obtained. Analysis was performed in the same manner as in Example 1. As a result, formation of the desired 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene was not observed.

Example 2 A reaction was carried out in the same manner as in Example 1 except that the scale of the reaction carried out in Example 1 was all increased by a factor of ten, treated with alkali, distilled and purified to obtain 1- (2- 82.4 grams of tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene were obtained. A stirring bar was inserted into a 200-mL Schlenk flask under an argon atmosphere, and then 40 mL of tetrahydrofuran and 40 mL of hexane as a solvent, and 2.3 mL (0.9 mmol) of a 0.4N tetrahydrofuran solution of sodium naphthalene as a polymerization initiator were used. ). The solution was brought to −20 ° C. with a dry ice / carbon tetrachloride bath while stirring, and then 20.0 g of a part of 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene distilled and purified ( 97.9 mmol) was added. After polymerization for 3 hours as it was, 5.0 ml of methanol was added to terminate the polymerization. The polymerization solution was poured into 2.0 liters of methanol to precipitate a polymer, which was filtered and separated, and further dried under reduced pressure to obtain a polymer.
7.26 grams of poly {1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene} were obtained. The weight yield based on 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene charged was 86.3%. Also, as a result of GPC analysis using polystyrene as a standard, the weight average molecular weight (Mw)
Is 19000 and the molecular weight dispersity (Mw / M
n) was 1.08.

Example 3 In the polymerization vessel used in Example 2, 100 ml of benzene was used as a solvent, and a 0.2 N tetrahydrofuran solution of cumyl potassium, which was separately prepared as a polymerization initiator, was 3.0.
Milliliters (0.6 mmol) were charged. The solution was heated to 35 ° C. in a water bath with stirring, and then 20.0 g (97 parts) of a part of 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene distilled and purified in Example 2 was used. .9 mmol) was added. After polymerization was continued for 6 hours, methanol (5.0 ml) was added to terminate the polymerization. The polymerization solution was poured into 2.0 liters of methanol to precipitate the polymer, which was filtered and separated, and dried under reduced pressure to obtain 14.18 g of poly {1- (2-tetrahydrofuranyloxy) -4.
-(1-methylethenyl) benzene) was obtained. 1- (2-tetrahydrofuranyloxy) -4- (1-
The weight yield based on methylethenyl) benzene was 70.
9%. GPC with polystyrene as standard
As a result of the analysis, the weight average molecular weight (Mw) was 23,000, and the molecular weight dispersity (Mw / Mn) was 1.09.

Example 4 In the polymerization vessel used in Example 2, 100 ml of benzene was used as a solvent, and α was separately prepared as a polymerization initiator.
2.7 ml (0.8 mmol) of a 0.3 N solution of potassium methylstyrene dimer in tetrahydrofuran, and 1,4,7,10,13,1 as an additive
0.62 g (2.4 mmol) of 6-hexaoxacyclooctadecane (18-crown-6) was charged.
The solution was brought to −20 ° C. with a dry ice / carbon tetrachloride bath while stirring, and then distilled and purified in Example 2 to give 1- (2-tetrahydrofuranyloxy) -4- (1).
-Methylethenyl) benzene in part 20.0 grams (9
7.9 mmol) was added. After the polymerization was continued for 4 hours, 5.0 ml of methanol was added to stop the polymerization. The polymerization solution was poured into 2.0 liters of methanol to precipitate the polymer, which was filtered and separated, and dried under reduced pressure to obtain 16.66 g of poly {1- (2-tetrahydrofuranyloxy) -4- (1 -Methylethenyl) benzene was obtained. The weight yield based on the charged 1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene was 83.3%. As a result of GPC analysis using polystyrene as a standard, the weight average molecular weight (Mw) was 22000, and the molecular weight dispersity (Mw)
(w / Mn) was 1.08.

[0036]

According to the method of the present invention, 1- (2-tetrahydrofuranyloxy) -4- obtained by reacting 4- (1-methylethenyl) phenol with dihydrofurans in the presence of an acid. Anionic polymerization of (1-methylethenyl) benzene using an organic alkali metal compound as a polymerization initiator allows narrow-dispersion poly {1- (2-tetrahydrofuranyloxy) useful for a chemically amplified positive photoresist material or the like. 4- (1-methylethenyl) benzene} can be produced simply and in high yield.

Continued on the front page (72) Inventor Retsu 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Mitsui Toatsu Chemicals Co., Ltd.

Claims (5)

[Claims] (1) a weight average molecular weight of 2,000 to 100;
A narrow-dispersion poly {1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene} having a ratio of the weight average molecular weight to the number average molecular weight of 1.5 or less. 2. 1- (2-Tetrahydrofuranyloxy) -4- (1) obtained by reacting 4- (1-methylethenyl) phenol with dihydrofurans in the presence of an acid.
Production of narrowly dispersible poly {1- (2-tetrahydrofuranyloxy) -4- (1-methylethenyl) benzene}, characterized by subjecting -methylethenyl) benzene to anionic polymerization using an organic alkali metal compound as a polymerization initiator. Method. 3. The organic alkali metal compound represented by the chemical formula (1): (Wherein, R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 11 carbon atoms; R ³ is hydrogen or an alkyl group having 1 to 10 carbon atoms; Represents an alkali metal selected from lithium, sodium, potassium or cesium.), A chemical formula (2): (Wherein, R ⁴ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ⁵ is an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 11 carbon atoms, and R ⁶ is a hydrogen atom or a carbon atom. An alkyl group, an alkoxy group or an alkoxyalkoxy group of the formulas 1 to 10, M represents an alkali metal selected from lithium, sodium, potassium or cesium, l represents an integer of 1 to 200), and a chemical formula (3) (Wherein R ⁷ is an alkyl group having 1 to 3 carbon atoms;
⁸ is hydrogen or an alkyl group having 1 to 10 carbon atoms,
An alkoxy group or an alkoxyalkoxy group, M is an alkali metal selected from lithium, sodium, potassium or cesium, and m and n each represent an integer of 1 to 100. ) Or a chemical formula (4): M-Ar (4) (where Ar is naphthalene, anthracene, indene,
An organic group selected from cyclopentadiene or fluorene, and M represents an alkali metal selected from lithium, sodium, potassium or cesium. 3. The method according to claim 2, wherein 4. The method according to claim 2, wherein the organic alkali metal compound is sec-butyllithium, α-methylstyrene dimerge potassium, α-methylstyrene tetramerge sodium, cumyl potassium, cumyl cesium, sodium naphthalene or sodium anthracene. 5. The method according to claim 2, wherein the dihydrofurans are 2,3-dihydrofurans.