US20020026023A1 - Method for producing poly(p-t-butoxystyrene) - Google Patents

Method for producing poly(p-t-butoxystyrene) Download PDF

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US20020026023A1
US20020026023A1 US09/935,046 US93504601A US2002026023A1 US 20020026023 A1 US20020026023 A1 US 20020026023A1 US 93504601 A US93504601 A US 93504601A US 2002026023 A1 US2002026023 A1 US 2002026023A1
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Prior art keywords
butoxystyrene
hydrocarbon type
water
type reaction
reaction solvent
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US6423821B1 (en
Inventor
Takanori Okahashi
Hiroharu Takeshima
Seigo Ito
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/06—Treatment of polymer solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms

Definitions

  • the present invention relates to a method for producing poly(p-t-butoxystyrene) by a polymerization of p-t-butoxystyrene in a hydrocarbon type reaction solvent in the presence of a polymerization initiator, in which, after termination of the polymerization reaction, separation of the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) and the water layer is improved.
  • Poly(p-t-butoxystyrene) has been used as a resin component in a photoresist composition, and produced by a polymerization of p-t-butoxystyrene in a hydrocarbon type reaction solvent in the presence of a polymerization initiator, the polymerization reaction being terminated by dropwise adding or pouring the reaction solution to water.
  • a method for removing the decomposed products and the like comprising a wash with water or an acidic water containing an organic acid such as oxalic acid, acetic acid or paratoluenesulfonic acid or inorganic acid such as hydrochloric acid or sulfuric acid.
  • an organic acid such as oxalic acid, acetic acid or paratoluenesulfonic acid or inorganic acid such as hydrochloric acid or sulfuric acid.
  • the method requires a separation of the hydrocarbon type reaction solvent layer and the water layer, and the separation takes a long time due to inferior separation efficiency.
  • the method since water is taken in the hydrocarbon type reaction solvent layer, the method causes problems, such as that an operation for removing water, for example concentration, is required in the latter step, and that poly(p-t-butoxystyrene) having the intended quality cannot be obtained due to the contamination of the decomposed products and the like dissolving in the water.
  • the inventors of the present invention have conducted extensive and intensive studies for solving the above problems. As a result, they have found that the separation efficiency improves by a specific amount of a polar solvent existing at the separation, after termination of the polymerization reaction, of the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) and the water layer. The present invention was thus completed.
  • the present invention provides a method for producing poly(p-t-butoxystyrene), which comprises polymerizing p-t-butoxystyrene in a hydrocarbon type reaction solvent in the presence of a polymerization initiator, and, after termination of the polymerization reaction, conducting a separation of the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) and the water layer in the presence of 1-50 parts by weight of a polar solvent per 100 parts by weight of the hydrocarbon type reaction solvent layer.
  • a polar solvent exists at the separation of the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) and the water layer.
  • Examples of the polar solvent include lower aliphatic alcohols such as methanol and ethanol, ethers such as ethyleneglycoldimethylether and ethyleneglycoldiethylether, and ketones such as 2-methyl-3-pentanon and 2-methyl-4-pentanon.
  • lower aliphatic alcohols are preferred and methanol is particularly preferred.
  • amount of the polar solvent is 1-50 parts by weight per 100 parts by weight of the hydrocarbon type reaction solvent layer.
  • the amount is 2-20 parts by weight per 100 parts by weight of the hydrocarbon type reaction solvent layer.
  • the amount of the polar solvent is within the above range, generation of an emulsion is suppressed at the surface between the water layer and the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) after termination of the polymerization reaction. Particularly, generation of an emulsion is efficiently suppressed at separation of the hydrocarbon type reaction solvent layer after washed with water or acidic water.
  • the polar solvent may exist in water or acidic water to which the polymerization reaction mixture is poured to terminate the polymerization reaction. However,it is more preferred that the polymerization reaction mixture poured in water or acidic water is separated to obtain a hydrocarbon type reaction solvent layer, and then the hydrocarbon type reaction solvent layer is washed In the existence of a polar solvent.
  • hydrocarbon type reaction solvent examples include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, cyclohexane and methylcyclohexane, ethers such as tetrahydrofuran, 1,4-dioxane and ethyleneglycoldimethylether, and mixtures of two or more of them.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • aliphatic hydrocarbons such as hexane, heptane, cyclohexane and methylcyclohexane
  • ethers such as tetrahydrofuran, 1,4-dioxane and ethyleneglycoldimethylether
  • Examples of the polymerization initiator include alkyl lithium such as n-butyl lithium and sec-butyl lithium, and organic metal compounds such as lithium naphthalene.
  • the polymerization initiator is used preferably in an amount of about 10 ⁇ 5 ⁇ 10 ⁇ 3 mol, per 1 g of p-t-butoxystyrene.
  • the polymerization reaction is usually conducted in an atmosphere of an inert gas such as argon or nitrogen, at a temperature of ⁇ 50-0° C., for 10 minutes-20 hours.
  • the polymerization reaction is usually terminated by dropwise adding or pouring the polymerization reaction mixture in water or an alcohol.
  • the separation efficiency, after termination of the polymerization reaction, of the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) and the water or acidic water layer conspicuously improves.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A method for producing poly(p-t-butoxystyrene), which comprise polymerizing p-t-butoxystyrene in a hydrocarbon type reaction solvent in the presence of a polymerization initiator, and, after termination of the polymerization reaction, conducting a separation of the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) and the water layer in the presence of 1-50 parts by weight of a polar solvent per 100 parts by weight of the hydrocarbon type reaction solvent layer, wherein the separation efficiency, after termination of the polymerization reaction, of the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) and the water or acidic water layer conspicuously improves.

Description

    BACKGROUND OF THE INVENTION
  • The present invention relates to a method for producing poly(p-t-butoxystyrene) by a polymerization of p-t-butoxystyrene in a hydrocarbon type reaction solvent in the presence of a polymerization initiator, in which, after termination of the polymerization reaction, separation of the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) and the water layer is improved. [0001]
  • Poly(p-t-butoxystyrene) has been used as a resin component in a photoresist composition, and produced by a polymerization of p-t-butoxystyrene in a hydrocarbon type reaction solvent in the presence of a polymerization initiator, the polymerization reaction being terminated by dropwise adding or pouring the reaction solution to water. [0002]
  • In the production, decomposed products of the polymerization initiator and the like need to be removed. A method for removing the decomposed products and the like is proposed which comprising a wash with water or an acidic water containing an organic acid such as oxalic acid, acetic acid or paratoluenesulfonic acid or inorganic acid such as hydrochloric acid or sulfuric acid. However, the method requires a separation of the hydrocarbon type reaction solvent layer and the water layer, and the separation takes a long time due to inferior separation efficiency. Further, since water is taken in the hydrocarbon type reaction solvent layer, the method causes problems, such as that an operation for removing water, for example concentration, is required in the latter step, and that poly(p-t-butoxystyrene) having the intended quality cannot be obtained due to the contamination of the decomposed products and the like dissolving in the water. [0003]
  • The inventors of the present invention have conducted extensive and intensive studies for solving the above problems. As a result, they have found that the separation efficiency improves by a specific amount of a polar solvent existing at the separation, after termination of the polymerization reaction, of the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) and the water layer. The present invention was thus completed. [0004]
    • SUMMARY OF THE INVENTION
  • The present invention provides a method for producing poly(p-t-butoxystyrene), which comprises polymerizing p-t-butoxystyrene in a hydrocarbon type reaction solvent in the presence of a polymerization initiator, and, after termination of the polymerization reaction, conducting a separation of the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) and the water layer in the presence of 1-50 parts by weight of a polar solvent per 100 parts by weight of the hydrocarbon type reaction solvent layer. [0005]
    • EMBODIMENT OF THE INVENTION
  • In the present invention, a polar solvent exists at the separation of the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) and the water layer. [0006]
  • Examples of the polar solvent include lower aliphatic alcohols such as methanol and ethanol, ethers such as ethyleneglycoldimethylether and ethyleneglycoldiethylether, and ketones such as 2-methyl-3-pentanon and 2-methyl-4-pentanon. Among them, lower aliphatic alcohols are preferred and methanol is particularly preferred. [0007]
  • In the present invention, amount of the polar solvent is 1-50 parts by weight per 100 parts by weight of the hydrocarbon type reaction solvent layer. Preferably, the amount is 2-20 parts by weight per 100 parts by weight of the hydrocarbon type reaction solvent layer. [0008]
  • If the amount of the polar solvent exceeds 50 parts by weight, yield of the poly(p-t-butoxystyrene) lowers On the other hand, if the amount of the polar solvent is less than 1 part by weight, the separation efficiency does not improve. [0009]
  • When the amount of the polar solvent is within the above range, generation of an emulsion is suppressed at the surface between the water layer and the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) after termination of the polymerization reaction. Particularly, generation of an emulsion is efficiently suppressed at separation of the hydrocarbon type reaction solvent layer after washed with water or acidic water. [0010]
  • The polar solvent may exist in water or acidic water to which the polymerization reaction mixture is poured to terminate the polymerization reaction. However,it is more preferred that the polymerization reaction mixture poured in water or acidic water is separated to obtain a hydrocarbon type reaction solvent layer, and then the hydrocarbon type reaction solvent layer is washed In the existence of a polar solvent. [0011]
  • Examples of the hydrocarbon type reaction solvent include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, cyclohexane and methylcyclohexane, ethers such as tetrahydrofuran, 1,4-dioxane and ethyleneglycoldimethylether, and mixtures of two or more of them. [0012]
  • Examples of the polymerization initiator include alkyl lithium such as n-butyl lithium and sec-butyl lithium, and organic metal compounds such as lithium naphthalene. The polymerization initiator is used preferably in an amount of about 10[0013] −5−10−3 mol, per 1 g of p-t-butoxystyrene.
  • The polymerization reaction is usually conducted in an atmosphere of an inert gas such as argon or nitrogen, at a temperature of −50-0° C., for 10 minutes-20 hours. The polymerization reaction is usually terminated by dropwise adding or pouring the polymerization reaction mixture in water or an alcohol.[0014]
  • The following examples further illustrate the present invention, but do not limit the scope thereof. [0015]
    • EXAMPLE 1
  • Under an nitrogen atmosphere, 790 ml of hexane and 6.2 mmol of sec-butyllithium are charged in a flask, and cooled to −20° C. Then, a mixed solvent of 118 g of p-t-butoxystyrene and 8 ml of ethyleneglycoldimethylether was added dropwise thereto to conduct the polymerization reaction. After about 650 g of the resultant reaction mass was dropwise added to water, a separation was conducted. After the separation, 33 g of methanol and water were added to the solvent layer thus obtained, and stirred. Then, a separation was conducted to obtain a solvent layer. No generation of emulsion was observed and water content in the solvent layer was 0.1%. [0016]
    • Compartive Example 1
  • Under an nitrogen atmosphere, 330 ml of hexane and 2.7 mmol of sec-butyllithium are charged in a flask, and cooled to −20° C. Then, a mixed solvent of 49 g of p-t-butoxystyrene and 3 ml of ethyleneglycoldimethylether was added dropwise thereto to conduct the polymerization reaction. After 270 g of the resultant reaction mass was dropwise added to water, a separation was conducted. After the separation, water was added to the solvent layer thus obtained, and stirred. Then, a separation was conducted but whole of the solvent layer became emulsion and water content in the solvent layer was 3.2%. [0017]
    • EXAMPLE 2
  • To 100 parts by weight of the solvent layer obtained in Compartive example 1, 5 parts by weight of 2-methyl-4-pentanone was added, and stirred. Then, a separation was conducted. No generation of emulsion was observed and water content in the solvent layer thus obtained was 0.2%. [0018]
  • According to the method of the present invention, the separation efficiency, after termination of the polymerization reaction, of the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) and the water or acidic water layer conspicuously improves. [0019]

Claims (1)

What is claimed is:
1. A method for producing poly(p-t-butoxystyrene), which comprises
polymerizing p-t-butoxystyrene in a hydrocarbon type reaction solvent in the presence of a polymerization initiator, and, after termination of the polymerization reaction, conducting a separation of the hydrocarbon type reaction solvent layer containing poly(p-t-butoxystyrene) and the water layer in the presence of 1-50 parts by weight of a polar solvent per 100 parts by weight of the hydrocarbon type reaction solvent layer.
US09/935,046 2000-08-25 2001-08-23 Method for producing poly(p-t-butoxystyrene) Expired - Fee Related US6423821B1 (en)

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JP2000255117A JP2002069120A (en) 2000-08-25 2000-08-25 METHOD FOR PRODUCING POLY(p-t-BUTOXYSTYRENE)
JP2000-255117 2000-08-25

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TW553955B (en) * 1999-09-06 2003-09-21 Sumitomo Chemical Co A method for producing poly(p-t-butoxystyrene)
US8084866B2 (en) * 2003-12-10 2011-12-27 Micron Technology, Inc. Microelectronic devices and methods for filling vias in microelectronic devices
JP6539517B2 (en) * 2015-06-24 2019-07-03 日本エラストマー株式会社 Method for producing purified polymer

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JPS6336602A (en) 1986-07-31 1988-02-17 Nippon Telegr & Teleph Corp <Ntt> Snow melting device for antenna
JPH03277608A (en) 1990-03-27 1991-12-09 Nippon Soda Co Ltd Production of p-alkenylphenol polymer
JP2746053B2 (en) 1993-04-12 1998-04-28 信越化学工業株式会社 Method for producing poly (p-tert-butoxystyrene)
US6218485B1 (en) * 1995-09-19 2001-04-17 Nippon Soda Co., Ltd. Process for producing narrow polydispersity alkenylphenol polymer
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