JPH11255826A - Narrow distribution poly(1-(alkoxyalkoxy)-4-ethenylbenzene) and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide narrow distribution poly[1-(1-alkoxyalkoxy)4- ethenylbenzenes] useful as chemically intensifying-type resist materials and a simple and efficient process for preparing nallow distribution poly[1-(1- alkoxyalkoxy)-4-ethenylbenzens] with the use of industrially readily available alkyl vinyl ethers. SOLUTION: Nallow distrubution poly[1-(1-alkoxyalkoxy)-4ethenylbenzens] are prepared by alkoxyalkoxylating p-hydroxystyrene by the reaction with an alkyl vinyl ether in the presence of an acid and then, anionically polymerizing the resulting product with the use of an organoalkali metal compound or an alkali metal as the polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to narrowly dispersible poly {1- (1-alkoxyalkoxy) -4-ethenylbenzene} and a method for producing the same. For more information, narrowly dispersible poly-1-useful as a chemically amplified positive resist material
1- (1-alkoxyalkoxy) -4-in which the hydroxyl group of p-hydroxystyrene is 1-alkoxyalkoxylated using (1-alkoxyalkoxy) -4-ethenylbenzene} and an industrially available alkyl vinyl ether. The present invention relates to a method for producing narrowly dispersible poly {1- (1-alkoxyalkoxy) -4-ethenylbenzene} using ethenylbenzene as a raw material.

[0002]

2. Description of the Related Art In order to further increase the density of integrated circuits, various studies have been made on chemically amplified resist materials in recent years. Among the above-mentioned resists, those having a functional group easily removable by an acid and having significantly different solubility in an aqueous alkali solution before and after the removal are awarded. Further, many functions are required for the resist material to achieve high resolution and high developability such as dry etching resistance and transparency at 248 nm in the plasma etching process. From such a viewpoint, a styrene derivative is known as a preferable one, and poly {1- (1-alkoxyalkoxy) -4-ethenylbenzene} is chemically amplified having high sensitivity, high resolution, and high dry etching resistance. It is useful as a positive resist material. It is also useful as a raw material for producing a p-hydroxystyrene polymer by removing a part or all of a 1-alkoxyalkoxy group in a polymer.

[0003] Poly {1- (1-alkoxyalkoxy) -4-
The following two methods are known as methods for producing ethenylbenzene. Reaction of p-bromophenol with an alkyl vinyl ether yields p-bromo- (1-alkoxyethoxy) benzene, which is then converted to metallic magnesium and then used as a catalyst for dichloro {1,2-bis (diphenylphosphino) ethane}. Grignard reaction with vinyl bromide in the presence of nickel to give p- (1-alkoxyethoxy) styrene, to which 2,2'-azobisisobutyronitrile is added as an initiator and produced by radical polymerization (Japanese Unexamined Patent Publication No. 6-1
94842, JP-A-5-249682).

[0004] 2,2'-Azobisisobutyronitrile is added as an initiator to p-tert-butoxystyrene and subjected to radical polymerization to obtain poly (p-tert-butoxystyrene). A method of producing a poly (p-hydroxystyrene) by removing a butoxy group and reacting the poly (p-hydroxystyrene) with an alkyl vinyl ether (Japanese Patent Application Laid-Open No.
319155).

However, in these methods, a polymer having a narrow dispersibility was not obtained, and it was insufficient as a chemically amplified resist material requiring a high resolution.
In addition, among these methods, p-bromophenol is used as a raw material, and after the hydroxyl group of phenol is alkoxyethoxylated, a Grignard reaction is carried out, and radical polymerization is carried out. Since a catalyst having an expensive phosphine ligand is used in the Grignard reaction, the recovery and reuse are indispensable, and the production process is further complicated. In addition, a large amount of by-product magnesium bromide is also a problem, and it cannot be an industrial method for producing poly (1- (1-alkoxyalkoxy) -4-ethenylbenzene).

The above method is a method in which poly (p-hydroxystyrene) is once obtained and then alkoxyalkoxylation is performed. However, since the reaction is a reaction between an alkyl vinyl ether and a polymer, it is difficult to carry out a sufficient alkoxyalkoxylation reaction. Difficult, the reaction product is a copolymer of p- (1-alkoxyalkoxy) styrene and p-hydroxystyrene, and a homopolymer of 1- (1-alkoxyalkoxy) -4-ethenylbenzene is obtained. Not been.

Japanese Patent Application Laid-Open No. 5-1115 discloses dihydropyran and
p-Vinylphenol is reacted with pyridinium-p-toluenesulfonate in the presence of pyridinium-p-toluenesulfonate. ). The above-mentioned tetrahydropyranylation reaction proceeds catalytically, and there is no by-product of alkali metal halide.

However, dihydropyran used as a raw material is, for example, furfuryl alcohol obtained by high-pressure hydrogenation of furfurylaldehyde, and further high-pressure hydrogenation to obtain tetrahydrofurfuryl alcohol.
Thereafter, it is obtained by a dehydrogenation rearrangement reaction of tetrahydrofurfuryl alcohol with alumina or the like (J. Am. Chem.
Soc. 1946. 68. 1646). As described above, since the production of dihydropyran requires multiple steps and complicated steps, the method of synthesizing poly (p-tetrahydropyranylstyrene) using dihydropyran cannot be said to be practical, and The types of commercially available dihydropyrans are also limited.

The performance required as a resist material varies variously depending on external factors such as the film thickness, substrate, solvent or photoacid generator used. In order to appropriately meet these requirements, it is essential that a series of compounds having various properties can be easily produced using industrially available raw materials. However, the above-mentioned dihydropyrans are easily available and have very few anion-polymerizable analogs, and it is difficult to improve the properties. On the other hand, alkyl vinyl ethers can be easily obtained by the addition reaction of alcohols to acetylenes.

[0010]

Accordingly, the present inventors have keenly developed a method for producing a series of narrowly dispersible polystyrene derivatives useful as a base polymer of a chemically amplified resist material in a simple and high yield. As a result of the investigation, p-hydroxystyrene was reacted with alkyl vinyl ethers to carry out alkoxyalkoxylation, and then anionically polymerized with a certain initiator to obtain a narrow-dispersion poly (1- (1-alkoxyalkoxy)) having an arbitrary molecular weight. The present inventors have found that 4--4-ethenylbenzene can be easily produced at a high yield, and have reached the present invention. The narrow-dispersion poly ｛1- obtained
The properties of (1-alkoxyalkoxy) -4-ethenylbenzene can be changed by changing the type of the alkyl vinyl ether used.

[0011]

That is, the present invention provides: [Claim 1] Chemical formula (1)

[0012]

Embedded image (In the formula, R ¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ² is hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ³ is a carbon atom having 1 to ³ carbon atoms. To 20 unsubstituted or alkoxy-substituted alkyl groups, cycloalkyl groups having 5 to 10 carbon atoms, or 6 carbon atoms
To 20 unsubstituted or alkoxy-substituted aryl groups. ) Having a weight average molecular weight of 1,000 to 100,000 and a ratio of the weight average molecular weight to the number average molecular weight of 1.0 to 1.6. -(1-alkoxyalkoxy) -4-ethenylbenzene}, [Claim 2] Chemical formula (2)

[0013]

Embedded image (In the formula, R ¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ² is hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ³ is a carbon atom having 1 to ³ carbon atoms. To 20 unsubstituted or alkoxy-substituted alkyl groups, cycloalkyl groups having 5 to 10 carbon atoms, or 6 carbon atoms
To 20 unsubstituted or alkoxy-substituted aryl groups. (1) Anion polymerization of 1- (1-alkoxyalkoxy) -4-ethenylbenzene represented by the formula (1) using an organic alkali metal compound or an alkali metal as a polymerization initiator. -Alkoxyalkoxy) -4-ethenylbenzene {Claim 3] 1- (1-alkoxyalkoxy) -4
-Ethenylbenzene is converted to alkyl vinyl ethers and p-
The method according to claim 2, which is 1- (1-alkoxyalkoxy) -4-ethenylbenzene obtained by reacting hydroxystyrene with an acid, and wherein the alkyl vinyl ether is ethyl. The method according to claim 3, which is a vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, or cyclohexyl vinyl ether.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The narrow-dispersion poly {1- (1-alkoxyalkoxy) -4-ethenylbenzene} of the present invention has a weight average molecular weight of 1,000 to 10,000.
0, preferably 2000 to 50000, more preferably 3000 to 30000, and the ratio of the weight average molecular weight to the number average molecular weight is 1.6 or less, preferably 1.0 to 1.5.

In the method of the present invention, 1- (1-alkoxyalkoxy) -4-ethenylbenzene represented by the chemical formula (2) is obtained by reacting p-hydroxystyrene with an alkyl vinyl ether in the presence of an acid. Can be manufactured.

Alkyl vinyl ethers include, for example,
Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-
Butyl vinyl ether, sec-butyl vinyl ether, te
rt-butyl vinyl ether, iso-octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether,
Cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, tert-pentyl vinyl ether, octadecyl vinyl ether, cesyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl-2- (2-ethoxyethoxy) ethyl ether, ethylene glycol butyl vinyl ether or tert-amyl vinyl ether Alkoxy-substituted or unsubstituted alkyl vinyl ethers. Among them, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether, sec-
Butyl vinyl ether, tert-butyl vinyl ether,
Cyclohexyl vinyl ether or tert-amyl vinyl ether is preferred. More preferably ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether, even more preferably ethyl vinyl ether, n-propyl vinyl ether, n-butyl Vinyl ether, tert-butyl vinyl ether, or cyclohexyl vinyl ether. The amount of these alkyl vinyl ethers to be used is generally 10 mol or less, preferably 0.1 mol, per 1 mol of p-hydroxystyrene.
To 5 moles, more preferably 0.5 to 3 moles.

In some cases, p-hydroxystyrene and alkyl vinyl ethers used as raw materials contain an alkaline compound such as potassium hydroxide, a polymerization inhibitor, and the like as a stabilizer, and these are subjected to purification operations such as distillation. There is no particular problem if used as it is without performing. However, since the amount of acid used as a catalyst increases when potassium hydroxide is mixed, for example, a purification operation is performed in advance to remove these stabilizers, or a raw material containing no stabilizer is used. More preferred.

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 organic such as p-toluenesulfonic acid, trifluoroacetic acid, propionic acid, malonic acid, oxalic acid, chlorosulfonic acid / pyridine salt, trifluoroacetic acid / pyridine salt, sulfuric acid / pyridine salt or p-toluenesulfonic acid / pyridine salt Acids, of which hydrogen chloride gas, hydrochloric acid,
Trifluoroacetic acid, trifluoroacetic acid / pyridine salt, p-
Preference is given to toluenesulfonic acid / pyridine salts or sulfuric acid / pyridine salts. These acids can be used alone or in combination of two or more. The use amount of these acids is usually 2 mol or less, preferably 0.00001 to 0.2 mol, more preferably 0.001 to 0.05 mol, per mol of p-hydroxystyrene. Range.

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. As a solvent to be used, any solvent can be used as long as it does not inhibit the reaction. Specifically, for example, water; n-hexane, n-pentane,
Aliphatic or alicyclic hydrocarbons such as n-heptane and cyclohexane; 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, 1,4-dioxane,
Ethers such as ethylene glycol dimethyl ether and ethylene glycol diethyl ether; ketones such as acetone, ethyl methyl ketone, 2-heptanone, cyclohexanone and acetophenone; nitriles such as acetonitrile and propionitrile; and ethyl acetate and ethyl propionate Esters and the like. These may be used alone or in combination of two or more. Further, 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 method of carrying out the reaction in the method of the present invention is not particularly limited, and a method in which p-hydroxystyrene, alkyl vinyl ethers, an acid and a solvent to be used are effectively mixed and contacted is used. Any method may be used as long as it is a batch type, a semi-batch type, or a continuous flow type.

The temperature and time for the reaction vary depending on the kind and amount of the starting material alkylvinyl ethers 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 generally within 20 hours, preferably 0.02 hours.
The range is 1 to 10 hours. 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.

According to the reaction in the method of the present invention, 1- (1-alkoxyalkoxy) -4- represented by the chemical formula (2)
Ethenylbenzene is obtained. Then, the obtained 1-
(1-Alkoxyalkoxy) -4-ethenylbenzene is anionically polymerized using an organic alkali metal compound or an alkali metal as a polymerization initiator.

1- (1-Alkoxyalkoxy) -4-ethenylbenzene is obtained from the reaction solution obtained by the above reaction
It can be used after isolation by treating it by a conventional method such as extraction, distillation, and / or crystallization, or it can be used in a usual manner such as extraction, neutralization, filtration, or ion exchange resin treatment from the reaction solution. After removing the acid by the operation, it can be directly used for anionic polymerization without isolation. Also, it is preferable that 1- (1-alkoxyalkoxy) -4-ethenylbenzene is stored by adding an alkali component such as potassium hydroxide or sodium carbonate as a stabilizer, but this alkali component is removed. It can be used for anionic polymerization without any treatment.

As the polymerization initiator used for the anionic polymerization, it is possible to use an organic alkali metal compound or an alkali metal which is usually used as a polymerization initiator for the anionic polymerization. Preferred examples of the organic alkali metal compound include n-butyllithium. , Sec-butyllithium, tert-butyllithium, α-methylstyrene dimer potassium, α-methylstyrene tetramer sodium, sodium-naphthalene, lithium-naphthalene, potassium-
Naphthalene, cumyl potassium or cumyl cesium, and preferred alkali metals are lithium,
Sodium, potassium or cesium. In addition, even if it is 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, it is not isolated after separately preparing these organic alkali metal compounds. May be used as is. The amount of the organic alkali metal compound or alkali metal to be used is not uniform depending on the kind thereof and the molecular weight of the intended poly {1- (1-alkoxyalkoxy) -4-ethenylbenzene}.
0.5 mol or less, preferably 0.00 mol, per mol of (1-alkoxyalkoxy) -4-ethenylbenzene.
It is in the range of 001 to 0.1 mol, more preferably in the range of 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 includes, for example, aliphatic or alicyclic hydrocarbons such as n-hexane, n-pentane, n-heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and ethylbenzene; And ethers such as diethyl ether, 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 carrying out the anionic polymerization in the method of the present invention is not particularly limited, and 1- (1-alkoxyalkoxy) -4-ethenylbenzene, an organic alkali metal compound or an alkali metal, and Any method may be used as long as the solvent or the like is effectively mixed and brought into contact, and may be any of a batch system, a semi-batch system, and a continuous flow system.

The temperature and time during the anionic polymerization are as follows:
(1-Alkoxyalkoxy) -4-ethenylbenzene, an organic alkali metal compound or alkali metal, and the type and amount of a solvent used when used are not uniform. However, the polymerization temperature is usually in the range of 100 ° C to 150 ° C below zero, preferably 80 ° C to 8 ° C below zero.
It is in the range of 0 ° 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 comprises:
This is performed in an atmosphere of an inert gas such as argon or nitrogen.

In addition, in the anionic polymerization in the method of the present invention, additives such as crown ethers and polyglycols which have been used in the anionic polymerization so far are added in order to increase the polymerization rate and the polymerization yield. It can also be used.

When the desired degree of polymerization is reached, the polymerization reaction is stopped by adding a polymerization terminator, thereby selectively polymerizing through the vinyl group of 1- (1-alkoxyalkoxy) -4-ethenylbenzene. Thus, a narrowly dispersible poly {1- (1-alkoxyalkoxy) -4-ethenylbenzene} having a repeating unit represented by the chemical formula (1) 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 acetic acid and propionic acid. Organic carboxylic acids and the like can be mentioned. Further, after polymerization, after treatment with carbon dioxide or a cyclic ether compound such as, for example, ethylene oxide or propylene oxide, a functional group such as a carboxyl group or a hydroxyl group is introduced into the polymer side chain by further treating with a polymerization terminator. be able to. If necessary, known terminal modifiers, terminal branching agents, coupling agents and the like can be used.

Next, when the obtained poly {1- (1-alkoxyalkoxy) -4-ethenylbenzene} is used as a polymerization solvent for anionic polymerization, an organic solvent having low solubility such as hydrocarbon is used. Because it precipitates as a solid, it can be isolated by ordinary separation operations such as filtration and decantation, and when using a highly soluble organic solvent such as tetrahydrofuran, it is uniformly dissolved and extracted, After performing a normal purification operation such as stripping and ion exchange, or without performing any purification operation, precipitated using a suitable solvent such as methanol, for example,
Washing and drying methods, desolvation, and methods using drying operations such as steam stripping drying or heat drying,
It can be isolated and purified by a usual method. By the above operation, narrowly dispersible poly {1- (1-alkoxyalkoxy) -4-ethenylbenzene} is obtained.

[0031]

The present invention will be described in more detail with reference to the following examples.
However, these are not intended to be limiting, but merely
Should be. Example 1 Synthesis of 1- (1-ethoxyethoxy) -4-ethenylbenzene A stirrer, a thermometer, a dropping funnel with an inner volume of 30 ml, and the like.
And 200 ml capacity with cooling tube
Fill the flask with 10.0 grams of p-hydroxystyrene (83.2
P-toluenesulfonic acid / pyridine salt as acid
10 milligrams (0.04 mmol) and chloride as solvent
80.0 ml of styrene was charged. Do not stir this liquid.
The internal temperature is reduced to 10 by a water bath equipped with a cooling device.
℃, ethyl vinyl ether from the dropping funnel
6.13 grams (85.0 mmol) of methylene chloride in 20 milliliters
The solution dissolved in the bottle started dropping. Drops over 10 minutes
After lowering, the reaction was allowed to proceed for 6 hours in an air atmosphere.
After the reaction, add 1.0 g of calcium hydride
And stirring was continued at 25 ° C for another 2 hours to remove acid and acid in the solution.
And water were removed. The organic solution obtained in this way is
Analysis of components by high performance liquid chromatography
At this time, the desired product, 1- (1-ethoxyethoxy) -4-ethe
15.7 grams (81.7 mmol) of nilbenzene and
0.10 grams of p-hydroxystyrene (0.83 mmol
) And therefore the conversion of p-hydroxystyrene
Conversion rate is 99.0%, based on p-hydroxystyrene charged.
The yield of-(1-ethoxyethoxy) -4-ethenylbenzene is
98.2%. The hydrogenated calcium thus obtained is
Calcium hydride was present in the solution
The methylene chloride was distilled off as it was, and the resulting 1-
2.0mmH of (1-ethoxyethoxy) -4-ethenylbenzene
g, distilled at 70 ° C. for purification. The yield is 14.1 grams
Was. 1- (1-ethoxyethoxy) -4-ethe
Nilbenzene is as shown below¹H-NMR analysis,¹³C-NMR
Identification by analysis and elemental analysis.¹ H-NMR (90 MHz, based on tetramethylsilane, ppm): 1.20
(3H, O-CH_Two-CH ₃ ), 1.50 (3H, O-CH (CH ₃ ) -O), 3.66
(2H, O-CH ₂ -CH_Three), 5.12 (1H,CH ₂ = CH-), 5.36 (1H,CH ₂
= CH-), 5.43 (1H, O-CH(CH_Three) -O), 6.50 (1H, CH_Two=CH
-), 6.92 (2H, Ph), 7.40 (2H, Ph)¹³ C-NMR (22.5 MHz, based on tetramethylsilane, ppm): 2
1.8 (O-CH_Two-CH ₃ ), 23.4 (O-CH (CH ₃ ) -O), 62.1 (O-C
H ₂ -CH_Three), 99.8 (O-CH(CH_Three) -O), 111.7 (CH ₂ = CH-),
 117.9 (Ph), 127.3 (Ph), 135.5 (CH_Two=CH-), 143.8
(Ph), 156.8 (Ph) Elemental analysis: Calculated value (C₁₂H₁₆O_Two); C: 74.47%, H: 8.39%,
Measurement: C: 74.79%, H: 8.54%

Poly {1- (1-ethoxyethoxy) -4-ethe
Synthesis of Nylbenzene II In a 100 ml Schlenk flask, place an argon atmosphere.
Under an atmosphere, a stir bar is inserted, and then tetrahydrogen is used as a solvent.
Lofuran 50 ml, n-butyl phenyl as polymerization initiator
0.34 ml of a 1.6 N solution of n-hexane (0.54
Mmol). Dry this solution while stirring.
After heating to -78 ° C in a chair / methanol bath,
1- (1-ethoxyethoxy) -4-ethenylbenzene 1
0.0 grams (52.0 mmol) were added. This solution is
Occasionally dark red. After the polymerization for 3 hours,
5.0 ml of ethanol was added to stop the polymerization.
This polymerization solution was poured into 1.0 liter of methanol,
The body was precipitated, filtered and separated, and further dried under reduced pressure to 9.68
Grams of a white polymer were obtained. 1- (1-Ethoxye)
The weight yield based on (toxi) -4-ethenylbenzene was 96.
8%. The obtained white polymer is¹H-NMR analysis,¹³C-
From the results of NMR analysis and elemental analysis, the target structure
Poly (1- (1-ethoxyethoxy) -4-ethenylbenze)
It turned out to be｝.¹ H-NMR (90 MHz, based on tetramethylsilane, ppm): 0.5 to
2.0 (9H,-CH ₂ -CH-/-CH_Two-CH-/ O-CH_Two-CH ₃ / O-CH (CH ₃ )-
O), 3.3-4.0 (2H, O-CH ₂ -CH_Three), 5.0-5.4 (1H, O-CH
(CH_Three) -O), 6.2 to 7.1 (4H, Ph)¹³ C-NMR (22.5 MHz, based on tetramethylsilane, ppm): 2
1.2 (O-CH_Two-CH ₃ ), 24.1 (O-CH (CH ₃ ) -O), 42.2 (-CH
_Two -CH-), 60 (-CH_Two-CH-), 62.1 (O-CH ₂ -CH_Three), 99.8 (O
-CH(CH_Three) -O), 116 (Ph), 128 (Ph), 141 (Ph), 1
54 (Ph) Elemental analysis: Calculated value (C₁₂H₁₆O_Two); C: 74.47%, H: 8.39%,
Measurement value: C: 75.01%, H: 8.83% Also, as a result of GPC analysis using polystyrene as a standard, weight
The average molecular weight (Mw) is 19600, and the molecular weight dispersity
(Mw / Mn) was 1.04.

Comparative Example 1 In Example 1, except that the p-toluenesulfonic acid / pyridine salt used as the acid was not used, the reaction was carried out in the same manner as in Example 1. Similarly, calcium hydride was added and hydrogen was added. A solution treated with calcium iodide was obtained. When the analysis was carried out in the same manner as in Example 1, the production of the desired 1- (1-ethoxyethoxy) -4-ethenylbenzene was not observed.

Example 2 1- (1-tert-butoxyethoxy) -4-ethenylbenzene
Synthesis In the same reactor as in Example 1, p-hydroxystyrene 1
0.0 g (83.2 mmol), trifluoro vinegar as acid
10 mg (0.05 mmol) of acid / pyridine salt and dissolved
80.0 ml of methylene chloride was charged as a medium. This
Keep the internal temperature at 25 ° C with a water bath while stirring the liquid
Tert-butyl vinyl acetate from the dropping funnel
Ter 8.51 g (85.0 mmol) in methylene chloride 20 mm
The solution dissolved in liter began to drop. Over 10 minutes
After dropping, let it react for 1 hour under air atmosphere
Was. After the reaction is completed, this reaction solution is separated into 300 ml
Transfer to a funnel and add
Extract once with 100 ml of deionized water.
Washing twice with a torr removes the acid content. Also used for extraction
The mixed alkaline water and water are mixed, and the reaction solvent
Perform back extraction with styrene and mix with the first organic layer.
Was. The organic solution thus obtained is dried over anhydrous sodium sulfate.
After drying with high-performance liquid chromatography,
As a result of analysis, the target product, 1- (1-tert-butoxy
16.5 g of ethoxy) -4-ethenylbenzene (74.9 mm
Mol), and 0.09 g of raw material p-hydroxystyrene
(0.75 mmol) and therefore p-hydroxy
The conversion of styrene is 99.1%, and the p-hydroxystyrene
1- (1-tert-butoxyethoxy) -4-etheni
The yield of benzene was 90.0%. This obtained al
After distilling methylene chloride from the potash-treated liquid,
1- (1-tert-butoxyethoxy) -4-ethenylben
Zen at 2.0 mmHg, 85 ° C in the presence of sodium hydride
Distilled and purified. The yield was 13.2 grams. Raw
1- (1-tert-butoxyethoxy) -4-ethenylben
Zen¹H-NMR analysis, ¹³C-NMR analysis and elemental analysis
Identified.

Poly {1- (1-tert-butoxyethoxy) -4-
Synthesis of ethenylbenzene II A 200 mL Schlenk flask was charged with a stir bar under an argon atmosphere, and then 50 mL of tetrahydrofuran and 50 mL of hexane as a solvent, and 2.5 mL of 0.4N tetrahydrofuran solution of sodium naphthalene (1.0 mL) as a polymerization initiator. Mmol). The solution was brought to −20 ° C. in a dry ice / carbon tetrachloride bath with stirring, and then distilled and purified.
10.0 g (45.4 mmol) of -tert-butoxyethoxy) -4-ethenylbenzene were added. After the polymerization was continued for 3 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 further dried under reduced pressure to obtain 9.75 g of a white polymer. 1- (1-
The weight yield based on (tert-butoxyethoxy) -4-ethenylbenzene was 97.5%. According to ¹ H-NMR analysis, ¹³ C-NMR analysis and elemental analysis, the obtained polymer was confirmed to be poly {1- (1-tert-butoxyethoxy) -4-ethenylbenzene} having the desired structure. confirmed. Also, as a result of GPC analysis using polystyrene as a standard, the weight average molecular weight (Mw) was 1
The molecular weight distribution (Mw / Mn) was 1.10.

Example 3 Synthesis of 1- (1-cyclohexyloxyethoxy) -4-ethenylbenzene In Example 1, 10.73 g (85.0 mmol) of cyclohexyl vinyl ether was used instead of ethyl vinyl ether, and methylene chloride was used as a solvent. instead,
The reaction was carried out in the same manner as in Example 1 except that 80.0 ml of diethyl ether was used, and the acid and water were removed by adding calcium hydride in the same manner to obtain a calcium hydride-treated liquid. When component analysis was performed by high performance liquid chromatography, the target product, 1- (1-
1 cyclohexyloxyethoxy) -4-ethenylbenzene
7.8 g (72.3 mmol) and 0.60 g (4.99 mmol) of p-hydroxystyrene as a raw material were contained. Therefore, the conversion of p-hydroxystyrene was 94.0%, and 1- (1- The yield of cyclohexyloxyethoxy) -4-ethenylbenzene was 86.9%.
Met. Diethyl ether was distilled off from the obtained calcium hydride-treated liquid, and the resulting 1- (1-
Cyclohexyloxyethoxy) -4-ethenylbenzene was purified by distillation at 123 ° C. and 2.0 mmHg in the presence of sodium hydride. The yield was 14.1 grams. The generated 1- (1-cyclohexyloxyethoxy) -4-ethenylbenzene was identified by ¹ H-NMR analysis, ¹³ C-NMR analysis and elemental analysis.

Synthesis of poly {1- (1-cyclohexyloxyethoxy) -4-ethenylbenzene} In a polymerization apparatus similar to that in Example 1, 80 ml of benzene was used as a solvent, and 0.3 ml of separately prepared anthracene potassium was used as a polymerization initiator. 2.0 ml (0.6 mmol) of N tetrahydrofuran solution was charged. The solution was brought to 35 ° C. in a water bath with stirring, and 10.0 g (40.6 mmol) of 1- (1-cyclohexyloxyethoxy) -4-ethenylbenzene was added. After polymerization was continued for 6 hours, 5.0 ml of methanol was added to terminate the polymerization. The polymerization solution was poured into 2.0 liters of methanol, and the polymer was precipitated, filtered and separated, and dried under reduced pressure to obtain 9.28 g of a white polymer. The weight yield based on the charged 1- (1-cyclohexyloxyethoxy) -4-ethenylbenzene was 92.8%. The obtained polymer is ¹ H-NM
By R analysis, ¹³ C-NMR analysis and elemental analysis, it was confirmed that the target poly {1- (1-cyclohexyloxyethoxy) -4-ethenylbenzene} was obtained. In addition, the result of GPC analysis using polystyrene as a standard, the weight average molecular weight (Mw)
Was 16500, and the molecular weight dispersity (Mw / Mn) was 1.12.

Example 4 Synthesis of 1- (1-n-propoxyethoxy) -4-ethenylbenzene In Example 1, n-vinyl ether was used instead of ethyl vinyl ether.
7.32 g (85.0 mmol) of propyl vinyl ether
Except for using, all were reacted for 4 hours in the same manner as in Example 1. After completion of the reaction, the reaction mixture was added to ICN alumina N-activity I (IC
N Biomedical Co., Ltd.) was added, and the reaction solution was filtered under reduced pressure with a filter further covered with activated alumina on a 4.7 cm glass filter, and washed twice with 10 ml of methylene chloride. The filtrates were combined to obtain about 120 ml of an activated alumina treatment liquid. When the reaction results were calculated in the same manner as in Example 1, the conversion of p-hydroxystyrene was 99.4%,
The yield of 1- (1-n-propoxyethoxy) -4-ethenylbenzene relative to -hydroxystyrene was 97.2%. After the methylene chloride was distilled off from the obtained activated alumina treatment liquid, the resulting 1- (1-n-propoxyethoxy) -4- was formed.
Ethenylbenzene in the presence of sodium hydride, 2.0mmH
g, distilled at 76 ° C. for purification. The yield was 12.8 grams. The generated 1- (1-n-propoxyethoxy) -4-
Ethenylbenzene was identified by ¹ H-NMR analysis, ¹³ C-NMR analysis and elemental analysis.

Poly {1- (1-n-propoxyethoxy) -4-
Synthesis of ethenylbenzene II The same polymerization apparatus as in Example 1 was charged with 80 ml of tetrahydrofuran as a solvent and 2.0 ml (1.0 mmol) of a 0.5N tetrahydrofuran solution of α-methylstyrene dimer potassium separately prepared as a polymerization initiator. The solution was stirred and cooled to -25 ° C. by a methanol bath equipped with a throw-in type cooler, and then 10.0 g of 1- (1-n-propoxyethoxy) -4-ethenylbenzene (4 g) was added.
8.5 mmol) was added. After the polymerization was continued for 3 hours, 5.0 ml of methanol was added to stop the polymerization. Pour this polymerization solution into 2.0 liters of methanol,
The polymer is precipitated, filtered and separated, and further dried under reduced pressure.
9.57 grams of a white polymer was obtained. The weight yield based on the charged 1- (1-n-propoxyethoxy) -4-ethenylbenzene was 95.7%. The obtained polymer was analyzed by ¹ H-NMR, ¹³ C
-The target poly 1-
(1-n-propoxyethoxy) -4-ethenylbenzene} was confirmed. Also, use polystyrene as standard
As a result of GPC analysis, the weight average molecular weight (Mw) was 9,800,
The molecular weight dispersity (Mw / Mn) was 1.04.

Example 5 A reaction was carried out for 6 hours in the same manner as in Example 1 except that tetrahydrofuran was used instead of methylene chloride used as a solvent, and all operations were performed in a nitrogen atmosphere. After the reaction, add ICN alumina N
-Addition of 10.0 g of activity I (manufactured by ICN Biomedical Co., Ltd.) and filtration of the reaction solution under reduced pressure through a filter further covered with activated alumina on a glass filter of 4.7 cm, and adding 10 ml of tetrahydrofuran.
After washing twice, these filtrates were combined to obtain about 120 ml of an activated alumina treatment liquid. When the reaction results were calculated in the same manner as in Example 1, the conversion of p-hydroxystyrene was 9
The yield of 1- (1-ethoxyethoxy) -4-ethenylbenzene relative to the charged p-hydroxystyrene was 9.4%, and was 97.2%. 100 ml of this alumina treatment liquid was directly charged into a 200 ml Schlenk flask, a stirrer was inserted, and after sufficient argon substitution, the temperature was lowered to −78 ° C. with a dry ice / methanol bath while stirring.
0.6 ml (1.8 mmol) of a 0.3N tetrahydrofuran solution of cumyl cesium separately prepared as a polymerization initiator
Was added. After polymerization for 6 hours, methanol
5.0 milliliters were added to stop the polymerization. The polymer solution was poured into 2.0 liters of methanol, and the polymer was precipitated, filtered and separated, and dried under reduced pressure to obtain 5.58 g of poly {1- (1-ethoxyethoxy) -4-ethenylbenzene}.
I got The weight yield with respect to the raw material p-hydroxystyrene was 34.9% without considering the loss in the middle. As a result of GPC analysis using polystyrene as a standard, the weight average molecular weight (Mw) was 15,300, and the molecular weight dispersity (Mw / Mn)
Was 1.15.

Example 6 Synthesis of poly {1- (1-ethoxyethoxy) -4-ethenylbenzene} A 3-liter three-necked flask equipped with a stirring blade and an internal thermometer was placed in an argon atmosphere under the atmosphere of tetrahydrofuran as a solvent. 1 liter, 30 ml of a 1.08N cyclohexane solution of sec-butyl lithium as a polymerization initiator (32.4
Mmol). The solution was stirred and cooled to -25 ° C. by a methanol bath equipped with a throw-in type cooling device, and then 300 g of 1- (1-ethoxyethoxy) -4-ethenylbenzene obtained by the same operation as in Example 1. (1.56 mol) was added. After the polymerization was continued for 3 hours, 50 ml of methanol was added to stop the polymerization. The polymerization solution was poured into 10 liters of methanol to precipitate the polymer, which was separated by filtration and further dried under reduced pressure to obtain 281 g of poly {1- (1-ethoxyethoxy) -4-ethenylbenzene}. . The weight yield based on the charged 1- (1-ethoxyethoxy) -4-ethenylbenzene was 93.7%.
As a result of GPC analysis using polystyrene as a standard, the weight average molecular weight (Mw) was 9,300 and the molecular weight dispersity (Mw / Mn) was 1.07.

Example 7 The polymerization apparatus used in Example 1 was charged with metal sodium (0.1%).
One gram (4.3 mmol) was evaporated under vacuum, creating a sodium mirror in the flask. Argon gas was injected, and 50 ml of tetrahydrofuran and a stirrer were charged as a solvent under an argon atmosphere. When the temperature was lowered to −78 ° C. with a dry ice / methanol bath while stirring, 0.90 g (4.68 mmol) of 1- (1-ethoxyethoxy) -4-ethenylbenzene obtained by the same operation as in Example 1 was added. And stirred for 30 minutes. The sodium mirror in the flask dissolved and the solution turned dark red. After 30 minutes, 20.0 g (0.10 mol) of 1- (1-ethoxyethoxy) -4-ethenylbenzene obtained by the same operation as in Example 1 again.
After stirring for further 6 hours, 5.0 ml of methanol was added to terminate the polymerization. The polymerization solution was poured into 2.0 liters of methanol, and the polymer was precipitated, filtered and separated, and dried under reduced pressure to obtain 18.4 g of poly-1-
(1-ethoxyethoxy) -4-ethenylbenzene was obtained. The weight yield based on 1- (1-ethoxyethoxy) -4-ethenylbenzene used was 92.1%. As a result of GPC analysis using polystyrene as a standard, the weight average molecular weight (Mw) was 4,200 and the molecular weight dispersity (Mw / Mn) was 1.36.

[0043]

According to the method of the present invention, 1- (1-alkoxyalkoxy) -4-ethenylbenzene obtained by reacting an alkyl vinyl ether with p-hydroxystyrene in the presence of an acid is converted to an organic compound. Anionic polymerization of an alkali metal compound or an alkali metal as a polymerization initiator allows narrow-dispersion poly (1- (1-alkoxyalkoxy) -4) useful as a base polymer of a chemically amplified resist material.
-Ethenylbenzene can be easily produced in high yield.

 ──────────────────────────────────────────────────の Continued on the front page (72) Keiichi Ikeda 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemical Co., Ltd. (72) Inventor Retsu 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture

Claims (4)

[Claims] [Claim 1] Chemical formula (1) (In the formula, R ¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ² is hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ³ is a carbon atom having 1 to ³ carbon atoms. To 20 unsubstituted or alkoxy-substituted alkyl groups, cycloalkyl groups having 5 to 10 carbon atoms, or 6 carbon atoms
To 20 unsubstituted or alkoxy-substituted aryl groups. ) Having a weight average molecular weight of 1,000 to 100,000 and a ratio of the weight average molecular weight to the number average molecular weight of 1.0 to 1.6. -(1-alkoxyalkoxy) -4-ethenylbenzene}. 2. Chemical formula (2) (In the formula, R ¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R ² is hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ³ is a carbon atom having 1 to ³ carbon atoms. To 20 unsubstituted or alkoxy-substituted alkyl groups, cycloalkyl groups having 5 to 10 carbon atoms, or 6 carbon atoms
To 20 unsubstituted or alkoxy-substituted aryl groups. (1) Anion polymerization of 1- (1-alkoxyalkoxy) -4-ethenylbenzene represented by the formula (1) using an organic alkali metal compound or an alkali metal as a polymerization initiator. -Alkoxyalkoxy) -4-ethenylbenzene}. 3. 1- (1-alkoxyalkoxy) -4
-Ethenylbenzene is converted to alkyl vinyl ethers and p-
The method according to claim 2, which is 1- (1-alkoxyalkoxy) -4-ethenylbenzene obtained by reacting hydroxystyrene with an acid. 4. The method according to claim 3, wherein the alkyl vinyl ether is ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, or cyclohexyl vinyl ether.