WO2011021392A1 - 変性ポリシロキサン化合物の製造方法 - Google Patents
変性ポリシロキサン化合物の製造方法 Download PDFInfo
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- WO2011021392A1 WO2011021392A1 PCT/JP2010/005123 JP2010005123W WO2011021392A1 WO 2011021392 A1 WO2011021392 A1 WO 2011021392A1 JP 2010005123 W JP2010005123 W JP 2010005123W WO 2011021392 A1 WO2011021392 A1 WO 2011021392A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
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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
- C08F212/00—Copolymers 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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
Definitions
- the present invention relates to a method for producing a modified polysiloxane compound, and more specifically, a method for producing a modified polysiloxane compound having a phenol skeleton introduced by block copolymerization using p-alkenylphenol units and organosiloxane units as essential constituent units.
- This application claims priority to Japanese Patent Application No. 2009-192151 filed on August 21, 2009, the contents of which are incorporated herein by reference.
- Organopolysiloxane compounds are widely used in various fields because of their excellent interface properties such as thermal stability, water repellency, defoaming properties, and releasability.
- the use as a film-forming agent has been expanded by taking advantage of its unique interface characteristics, but a modifier for imparting the temperature characteristics and interface characteristics of organopolysiloxane compounds to various resins. As an application, it is being actively deployed.
- dimethylpolysiloxane, methylphenylpolysiloxane, fatty acid-modified polysiloxane, polyether-modified polysiloxane, and the like have been used to improve the performance of synthetic resins such as paints and molded articles.
- these materials have insufficient compatibility with the resin or have insufficient heat resistance, so the range of use has been limited.
- thermosetting resins and thermoplastic resins such as mechanical properties, moisture resistance, surface properties, etc.
- thermoplastic resins such as mechanical properties, moisture resistance, surface properties, etc.
- a separation membrane or a biocompatible polymer material a polysiloxane compound having a controlled structure and having an arbitrary number of functional groups in the molecule is craved.
- the method using a low-molecular-weight dimethylsiloxane compound having a group has a drawback in that the compatibility with other resins is not sufficient, resulting in a decrease in molding processability and mechanical strength.
- the method using a reaction product of a polysiloxane having a functional group at the terminal and another resin easily causes undesirable phenomena such as abnormal thickening and gelation during the modification reaction, and unreacted components remain. As a result, there has been a problem that the compatibility is lowered.
- Patent Document 4 requires the use of an acidic substance in order to remove a saturated aliphatic protecting group, but depending on the type of acid used and the reaction conditions, the molecular weight may change due to decomposition or condensation, There is concern about coloring.
- Patent Document 4 a specific example in which a protecting group is eliminated by blowing hydrogen chloride gas is described, but the proper use conditions and the proper use amount of hydrogen chloride are unknown.
- An object of the present invention is to provide conditions and amounts of hydrogen chloride that do not change molecular weight or cause coloration due to decomposition or condensation.
- the present inventors have made hydrogen chloride react with a saturated aliphatic protective group in an approximately equivalent amount in a non-aqueous system in order to remove the saturated aliphatic protective group.
- the present invention was completed.
- the present invention provides a compound of formula (I) X (Y) n (I) [Wherein X is the formula (II)
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a linear or branched alkyl group having 1 to 6 carbon atoms.
- Y is the formula (III)
- R 3 and R 4 each represent a linear or branched alkyl group, cycloalkyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms. In the formula, R 3 and R 4 May be the same or different from each other.), And n is 1 or 2.
- a modified polysiloxane compound having a weight ratio of X and Y of 1/99 ⁇ X / Y ⁇ 90/10 and a number average molecular weight of 1,000 to 100,000 is present in a non-aqueous solvent.
- a polymer block having a repeating unit represented by the above definition, Y and n are as defined above, preferably a molecular weight distribution.
- the present invention relates to a method for producing a modified polysiloxane compound having a ratio of 1.05 to 1.5.
- the modified polysiloxane compound represented by the formula (I) is represented by the formula (VII) in the presence of an anionic polymerization initiator.
- R 5 represents a hydrogen atom or a methyl group
- R 6 represents a linear or branched alkyl group having 1 to 6 carbon atoms
- a compound (VII) It is related with the manufacturing method of the modified
- modified polysiloxane compound The modified polysiloxane compound used in the present invention is represented by the following formula (I). X (Y) n (I) [Wherein X is the formula (II)
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a linear or branched alkyl group having 1 to 6 carbon atoms.
- Y is the formula (III)
- the modified polysiloxane compound has a weight ratio of X to Y of 1/99 ⁇ X / Y ⁇ 90/10 and a number average molecular weight of 1,000 to 100,000.
- X is a polymer block having a repeating unit derived from one or more p-alkenylphenol derivatives, or a repeating unit derived from a p-alkenylphenol derivative and one or more conjugated dienes and / or one Or the block which consists of a random copolymer or a block copolymer which consists of a repeating unit of 2 or more types of vinyl compounds, and what is shown by following formula (VI) is also contained.
- R 1 and R 2 have the same meaning as described above, and a and b are arbitrary natural numbers depending on the degree of polymerization.
- Y in the above formula (I) of the present invention is a polymer block having an organosiloxane represented by the above formula (III) as a repeating unit.
- the compound represented by the formula (I) is represented by XY or YXY.
- the modified polysiloxane compound represented by X (Y) n of the present invention is not particularly limited in its production method, and a known method can be adopted. For example, it can be produced by the following method (patent) No. 3471010).
- Formula (VII) in the presence of an anionic polymerization initiator is not particularly limited in its production method, and a known method can be adopted. For example, it can be produced by the following method (patent) No. 3471010).
- R 5 represents a hydrogen atom or a methyl group
- R 6 represents a linear or branched alkyl group having 1 to 6 carbon atoms
- Polymerization Method for X Part A compound represented by the formula (VII) or a compound copolymerizable therewith can be converted into an alkali metal and / or organic in an organic solvent under vacuum or in an inert gas atmosphere such as nitrogen or argon.
- Anionic polymerization is performed at a temperature of ⁇ 100 ° C. to 150 ° C. using an alkali metal compound as a polymerization initiator.
- a polymer having a controlled molecular weight and a narrow molecular weight distribution can be obtained.
- Examples of the compound represented by the formula (VII) used in the present invention include pn-butoxystyrene, p-sec-butoxystyrene, p-tert-butoxystyrene, p-tert-butoxy- ⁇ -methylstyrene, and the like. In particular, p-tert-butoxystyrene and p-tert-butoxy- ⁇ -methylstyrene are preferable.
- the compound copolymerizable with the formula (VII) used in the present invention is preferably a conjugated diene or a vinyl compound.
- conjugated diene or vinyl compound examples include 1,3-butadiene, isoprene, 2,3-dimethyl- Conjugated dienes such as 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene; styrene, p-methylstyrene, ⁇ -methylstyrene, p-tert-butylstyrene, vinylnaphthalene, divinylbenzene, 1, Vinyl aromatic compounds such as 1-diphenylethylene; (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate; 2-vinylpyridine, 4-vinylpyridine Vinyl pyridines such as; acrylonitrile and the like, and they are used as one kind or a mixture of two or more kinds. That.
- Examples of the alkali metal used as the anion polymerization initiator include lithium, sodium, and potassium, and examples of the organic alkali metal compound include alkylated products, allylated products, and arylated products of the alkali metals.
- Specific examples of organic alkali metal compounds include ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, ethyl sodium, butadienyl dilithium, butadienyl disodium, lithium biphenyl, lithium naphthalene, lithium fluorene.
- organic solvent aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as cyclohexane and cyclopentane; aromatic hydrocarbons such as benzene and toluene; diethyl ether, dioxane, tetrahydrofuran and the like
- organic solvents such as ethers usually used in anionic polymerization are used as one or two or more mixed solvents.
- the form of the copolymer obtained by the anionic polymerization is such that a random copolymer is formed by adding a mixture of the compound represented by the formula (IV) and the monomer to the reaction system and polymerizing the mixture. Is then polymerized in advance, and then a mixture of both is added to continue the polymerization to obtain a partial block copolymer, and the compound represented by the formula (IV) and the monomer are sequentially added to the reaction system. A complete block copolymer is synthesized by polymerization.
- a cyclic siloxane compound is added to the reaction system, and the anionic polymerization reaction is continued under the same conditions as exemplified above.
- a block copolymer (hereinafter referred to as a precursor) composed of a chain composed of the compound represented by the formula (VII) alone or a compound copolymerizable therewith and a polysiloxane chain is produced.
- the cyclic siloxane compound used here is a compound represented by the following formula (VIII).
- R 7 and R 8 are each a linear or branched alkyl group, cycloalkyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, and c is a positive integer of 3 to 7) R 7 and R 8 may be the same or different from each other.
- Specific examples of the compound represented by the formula (VIII) include, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexaethylcyclotrisiloxane, and octaethylcyclohexane.
- Examples thereof include tetrasiloxane and hexaphenylcyclotrisiloxane, and these can be used as one kind or a mixture of two or more kinds.
- polymerization conditions such as reaction temperature and reaction solvent can be appropriately changed within a set range.
- the modified polysiloxane compound of the present invention is a compound other than the above-described method, for example, a compound that can be copolymerized with the compound represented by (VII) after the homopolymerization of the compound represented by (VII).
- an organosiloxane compound having a functional group capable of reacting with the growth terminal of the polymer is added to the reaction system, and a coupling reaction is performed under the same conditions as exemplified above, whereby the above formula ( A copolymer comprising a chain of the compound represented by VII) or a chain of a compound copolymerizable with the compound represented by (VII) and a polysiloxane chain is produced.
- the organosiloxane compound used here is not particularly limited as long as it has a functional group capable of coupling reaction with the growth terminal of the polymer. Specific examples include the following formulas (IX) and (X And the like are used.
- R 9 and R 10 are each a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and X 1 and X 2 are halogen atoms.
- R 9 , R 10 , X 1 and d represent the same meaning as described above, and R 11 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or Represents an aralkyl group.
- Specific examples of the compound represented by the formula (IX) or (X) include, for example, commercially available ⁇ , ⁇ -bis (chloromethyl) polydimethylsiloxane, 1- (3-chloropropyl) -1,1,3. , 3,3-pentamethyldisiloxane, ⁇ , ⁇ -bis (3-glycidoxypropyl) polydimethylsiloxane, ⁇ , ⁇ -dichloropolydimethylsiloxane, and the like.
- conditions such as reaction temperature and reaction solvent can be appropriately changed within a set range.
- the reaction for removing the hydroxyl-protecting group present in the repeating unit of the formula (II) from the modified polysiloxane compound represented by the formula (I) to form a p-alkenylphenol skeleton is a non-aqueous solvent, for example, aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as cyclohexane and cyclopentane; aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether, dioxane and tetrahydrofuran; Chlorinated solvents such as carbon chloride; alcohols such as methanol, ethanol and 2-propanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate, butyl acetate, ethyl
- the polymerization reaction crude liquid produced by the above method may be used as it is.
- a non-aqueous solution containing hydrogen chloride can be prepared by blowing hydrogen chloride gas into a dehydrated solvent and dissolving it. Or you may purchase a commercial item. When dissolved, the concentration can be defined by neutralization titration.
- the amount of hydrogen chloride used is 0.9 to 1.3 equivalents, preferably 0.95 to 1.1 equivalents of hydrogen chloride per equivalent of repeating unit represented by formula (II). .
- the reaction temperature is 0 to 100 ° C., preferably room temperature to 70 ° C.
- Ethers such as tetrahydrofuran and a dioxane
- the solvent of the solution containing hydrogen chloride include aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as cyclohexane and cyclopentane; aromatic hydrocarbons such as benzene and toluene.
- Ethers such as diethyl ether, dioxane and tetrahydrofuran; chlorinated solvents such as carbon tetrachloride; alcohols such as methanol, ethanol and 2-propanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate and butyl acetate , Esters such as ethyl propionate and propylene glycol monomethyl ether acetate; organic acids such as formic acid, acetic acid, propionic acid, and butyric acid may be used alone or in combination of two or more.
- Preferred are ethers such as tetrahydrofuran and dioxane.
- the modified polysiloxane compound deprotected by the above production method has a number average molecular weight of 2,000 to 20,000, more preferably 4,000 to 12,000.
- the molecular weight distribution is 1.05 to 1.5, preferably 1.1 to 1.3.
- composition of the deprotected modified polysiloxane compound is not limited as long as the respective characteristics of p-hydroxystyrene and dimethylsiloxane are not impaired.
- a copolymer considering the balance between the amount of hydroxyl groups, alkali solubility, etc. and the heat resistance, weather resistance, flame retardancy, dielectric properties, electrical insulation, water repellency, releasability, etc. of the dimethylsiloxane part
- the composition ratio at which a characteristic performance is exhibited is 10/90 to 90/10, preferably 30/70 to 70/30, in terms of p-hydroxystyrene / dimethylsiloxane (mole% ratio of each unit).
- PTBST means p-tert butoxystyrene
- Mn number average molecular weight
- PTBST / dimethylsiloxane 50/50, mol%.
- Example 1 To 20 g of a 35 wt% concentration THF solution of the precursor polymer (PTBST-dimethylsiloxane) obtained in the Reference Example, 8.1 g of a 4M hydrogen chloride-dioxane solution was added. The amount of hydrogen chloride added corresponds to 1.1 equivalents relative to PTBST in the precursor polymer. The mixture was heated to 50 ° C. and sampled every hour. Confirmation of debutylation reaction progress was carried out by IR spectrum measurement, and the end point of the reaction was judged by disappearance of the 899 cm ⁇ 1 peak derived from PTBST aromatic ring CH out-of-plane bending vibration. As a result, since the peak at 899 cm ⁇ 1 disappeared 6 hours after the start of the reaction, it was confirmed that the reaction was completed.
- Example 1 The same operation as in Example 1 was conducted except that the amount of the 4M hydrogen chloride-dioxane solution added was 3.8 g. The amount of hydrogen chloride added corresponds to 0.5 equivalent with respect to PTBST in the precursor polymer. As a result, since the 899 cm ⁇ 1 peak derived from PTBST aromatic ring C—H out-of-plane bending vibration did not disappear even 48 hours after the start of the reaction, it was confirmed that the reaction was not completed with 0.5 equivalent.
- Example 2 The same procedure as in Example 1 was conducted except that the amount of the 4M hydrogen chloride-dioxane solution added was 7.3 g in 10 g of a 35 wt% THF solution of the precursor polymer. The amount of hydrogen chloride added corresponds to 2 equivalents relative to PTBST in the precursor polymer. As a result, it was confirmed that the debutylation reaction was completed since the 899 cm ⁇ 1 peak derived from the PTBST aromatic ring C—H out-of-plane bending vibration disappeared 2 hours after the start of the reaction. It became clear that the shape of the curve was degraded and the polymer was decomposed.
- Example 3 The same procedure as in Example 1 was performed, except that the amount of sulfuric acid added was changed to 6.0 g in 40 g of a 35 wt% THF solution of the precursor polymer.
- the amount of sulfuric acid added corresponds to 1.1 equivalents relative to PTBST in the precursor polymer.
- sulfuric acid when sulfuric acid was used, it turned brown immediately after the start of the reaction. Further, since the 899 cm ⁇ 1 peak derived from PTBST aromatic ring CH out-of-plane bending vibration disappeared in 1 hour, it was confirmed that the debutylation reaction was completed, but the shape of the GPC elution curve is It was found that the polymer was degraded and the polymer was decomposed.
- Example 4 The same operation as in Example 2 was conducted except that the amount of the 4M hydrogen chloride-dioxane solution added was 7.3 g. The amount of hydrogen chloride added corresponds to 2 equivalents relative to PTBST in the precursor polymer. As a result, the peak of 899 cm ⁇ 1 derived from PTBST aromatic ring CH out-of-plane bending vibration disappeared after 24 hours at room temperature and 1 hour at 50 ° C. It was confirmed that the GPC elution curve had deteriorated in shape and the polymer was decomposed.
- Example 3 After adding 87 g of n-butyllithium (15.36 wt% hexane solution) to a mixed solution of 1320 g of toluene and 707 g of THF while stirring at ⁇ 40 ° C. over 30 minutes, the reaction was continued for another 30 minutes. Then, 1190 g of a THF solution containing 0.22 mol of hexamethylcyclotrisiloxane was added to this reaction solution over 1 hour, and the reaction temperature was kept at 40 ° C., followed by stirring for 4 hours and further stirring at room temperature overnight. Subsequently, 25 g of trimethylsilyl chloride was added to the reaction solution to stop the reaction to obtain a precursor polymer.
- n-butyllithium 15.36 wt% hexane solution
- the p-hydroxystyrene-dimethylsiloxane copolymer obtained by debutylation was measured by GPC.
- the number average molecular weight (Mn) was 5800, the molecular weight distribution was 1.17, and the butyl group was eliminated. A decrease in molecular weight was confirmed, and the shape of the GPC elution curve was almost the same as that before the reaction, indicating that no polymer degradation occurred.
- a modified polysiloxane compound in which a phenol skeleton having a narrow molecular weight distribution and a molecular weight and a structure are introduced is synthesized without causing a molecular weight change or coloring due to decomposition or condensation. Can do. Therefore, the modified polysiloxane compound is used as a resist material having a submicron resolution necessary for the production of VLSI, as a modifier for various thermosetting resins and thermoplastic resins, and as a separation membrane. It is expected to be used in a wide range of fields as biocompatible materials.
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Abstract
Description
本願は、2009年8月21日に出願された日本国特許出願第2009-192151号に対し優先権を主張し、その内容をここに援用する。
本発明は、分解や縮合により、分子量が変化したり、着色などを起こさない塩化水素の使用条件及び使用量を提供することが目的である。
X(Y)n (I)
[式中、Xは式(II)
X’(Y)n (IV)
〔式中、X’は式(V)
本発明において使用する変性ポリシロキサン化合物は、以下の式(I)で表される。
X(Y)n (I)
[式中、Xは式(II)
上記変性ポリシロキサン化合物は、XとYとの重量比が1/99≦X/Y≦90/10、数平均分子量が、1,000~100,000である。
式(I)で表される化合物は、X-Y又はY-X-Yで表される。
本発明のX(Y)nで表される変性ポリシロキサン化合物は、その製法に特に制限はなく、公知の方法を採用することができるが、例えば、以下の方法で製造することができる(特許3471010号公報参照)。
アニオン重合開始剤の存在下、式(VII)
式(VII)で表される化合物、又はそれと共重合可能な化合物とを、真空下又は窒素、アルゴン等の不活性ガス雰囲気下、有機溶媒中において、アルカリ金属及び/又は有機アルカリ金属化合物を重合開始剤とし、-100℃~150℃の温度でアニオン重合を行う。当該方法により、分子量が制御され、かつ分子量分布の狭い重合体を得ることができる。
本発明に用いる前記式(VII)と共重合可能な化合物は、好ましくは、共役ジエン又はビニル化合物であり、共役ジエン又はビニル化合物としては、1,3-ブタジエン、イソプレン、2,3-ジメチル-1,3-ブタジエン、1,3-ペンタジエン、1,3-ヘキサジエン等の共役ジエン類;スチレン、p-メチルスチレン、α-メチルスチレン、p-tert-ブチルスチレン、ビニルナフタリン、ジビニルベンゼン、1,1-ジフェニルエチレン等のビニル芳香族化合物;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル等の(メタ)アクリル酸エステル類;2-ビニルピリジン、4-ビニルピリジン等のビニルピリジン類;アクリルニトリル等が挙げられ、それらは一種又は二種以上の混合物として使用される。
前記X部分の重合反応後、反応系に環状シロキサン化合物を加え、前記例示したと同様の条件下においてアニオン重合反応を継続する。
最終的に、前記式(VII)で示される化合物単独又はそれと共重合可能な化合物とからなる連鎖と、ポリシロキサン連鎖とからなるブロック共重合体(以下、前駆体と記す)が製造される。
ここで用いられる前記環状シロキサン化合物としては、下記式(VIII)で示される化合物である。
前記式(VIII)で示される化合物の具体例としては、例えば、ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン、ヘキサエチルシクロトリシロキサン、オクタエチルシクロテトラシロキサン、ヘキサフェニルシクロトリシロキサン等であり、これらは一種又は二種以上の混合物として使用することができる。
この逐次的に行なれるアニオン重合反応において、反応温度、反応溶媒等の重合条件は、設定した範囲内で適宜変更して行うことができる。
この逐次的に行われる重合反応及びカップリング反応において、反応温度、反応溶媒等の条件は、設定した範囲内で適宜変更して行うことができる。
上記式(I)で表される変性ポリシロキサン化合物から式(II)の繰り返し単位に存在する水酸基の保護基を脱離させ、p-アルケニルフェノール骨格を生成せしめる反応は、非水系溶媒、例えば、n-ヘキサン、n-ヘプタン等の脂肪族炭化水素類;シクロヘキサン、シクロペンタン等の脂環族炭化水素;ベンゼン、トルエン等の芳香族炭化水素類;ジエチルエーテル、ジオキサン、テトラヒドロフラン等のエーテル類;四塩化炭素等の塩素系溶媒;メタノール、エタノール、2-プロパノール等のアルコール類;アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類;酢酸エチル、酢酸ブチル、プロピオン酸エチル、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル等のエステル類;ギ酸、酢酸、プロピオン酸、酪酸等の有機酸類の溶媒存在下、塩化水素を含有する非水系溶液を加えることにより行うことができ、分子量、構造が制御され、かつ分子量分布の狭いフェノール骨格を導入した変性ポリシロキサン化合物が製造される。
塩化水素の使用量は、式(II)で表される繰り返し単位1当量に対して塩化水素として0.9~1.3当量、好ましくは、0.95~1.1当量となるように加える。反応温度は、0~100℃、好ましくは室温~70℃である。
また、塩化水素を含有する溶液の溶媒としては、n-ヘキサン、n-ヘプタン等の脂肪族炭化水素類;シクロヘキサン、シクロペンタン等の脂環族炭化水素;ベンゼン、トルエン等の芳香族炭化水素類;ジエチルエーテル、ジオキサン、テトラヒドロフラン等のエーテル類;四塩化炭素等の塩素系溶媒;メタノール、エタノール、2-プロパノール等のアルコール類;アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類;酢酸エチル、酢酸ブチル、プロピオン酸エチル、プロピレングリコールモノメチルエーテルアセテート等のエステル類;ギ酸、酢酸、プロピオン酸、酪酸等の有機酸類の一種単独又は二種以上の混合溶媒を使用することができる。好ましくはテトラヒドロフラン、ジオキサン等のエーテル類である。
なお、以下の例中において、「PTBST」は、p-tertブトキシスチレンを意味する。
前駆体ポリマー(PTBST-ジメチルシロキサン)の調製
n-ブチルリチウム(15.36重量%濃度ヘキサン溶液)87gを、トルエン1320gとTHF707gの混合溶液に、-40℃で攪拌しながらPTBST707gを30分かけて添加し、さらに30分反応を継続した後、この反応溶液にヘキサメチルシクロトリシロキサン0.22モルを含むTHF溶液1190gを1時間かけて添加し、更に反応温度を40℃に保ち4時間攪拌後、さらに室温で一晩攪拌した。続いて、反応液にトリメチルシリルクロリド25gを加えて反応を停止し前駆体ポリマーを得た。前駆体ポリマーのPTBST-ジメチルシロキサンは数平均分子量(Mn)=6200、分子量分布=1.14、組成比:PTBST/ジメチルシロキサン=50/50、モル%であった。この重合粗液を水洗し有機層を濃縮した後、35重量%濃度のTHF溶液に調製した。
参考例において得られた前駆体ポリマー(PTBST-ジメチルシロキサン)の35重量%濃度のTHF溶液20gに、4M塩化水素-ジオキサン溶液8.1gを添加した。塩化水素の添加量は前駆体ポリマー中のPTBSTに対し1.1当量に相当する。この混合液を50℃に加温し、1時間毎にサンプリングした。脱ブチル化の反応進行確認はIRスペクトル測定で行い、反応終点はPTBST芳香環C-H面外変角振動に由来する899cm-1のピークの消失で判定した。
結果、反応開始後6時間で899cm-1のピークは消失したため、反応が終了したことを確認した。
4M塩化水素-ジオキサン溶液の添加量を3.8gとする以外は、実施例1と同様に行った。この塩化水素の添加量は前駆体ポリマー中のPTBSTに対し0.5当量に相当する。
結果、反応開始後48時間でもPTBST芳香環C-H面外変角振動に由来する899cm-1のピークは消失していないため、0.5当量では反応が終了しないことを確認した。
前駆体ポリマーの35重量%濃度のTHF溶液10gに、4M塩化水素-ジオキサン溶液の添加量を7.3gとする以外は、実施例1と同様に行った。この塩化水素の添加量は前駆体ポリマー中のPTBSTに対し2当量に相当する。
結果、反応開始後2時間でPTBST芳香環C-H面外変角振動に由来する899cm-1のピークは消失していることから、脱ブチル化反応は終了することを確認したが、GPC溶出曲線の形状が劣化しており、ポリマーが分解してしまうことが明らかとなった。
前駆体ポリマーの35重量%濃度のTHF溶液40gに、硫酸の添加量を6.0gとする以外は、実施例1と同様に行った。この硫酸の添加量は前駆体ポリマー中のPTBSTに対し1.1当量に相当する。
結果、硫酸を使用すると反応開始後すぐに褐色になった。また1時間でPTBST芳香環C-H面外変角振動に由来する899cm-1のピークは消失していることから、脱ブチル化反応は終了することを確認したが、GPC溶出曲線の形状が劣化しており、ポリマーが分解してしまうことが明らかとなった。
前駆体ポリマー(PTBST-ジメチルシロキサン、数平均分子量(Mn)=6200、分子量分布=1.14、組成比:PTBST/ジメチルシロキサン=50/50モル%)の35重量%濃度のジオキサン溶液10gに、4M塩化水素-ジオキサン溶液4.0gを添加した。塩化水素の添加量は前駆体ポリマー中のPTBSTに対し1.1当量に相当する。この混合液をそれぞれ室温、40℃、50℃、60℃、70℃で反応させ、1時間毎にサンプリングした。脱ブチル化の反応進行確認はIRスペクトル測定で行い、反応終点はPTBST芳香環C-H面外変角振動に由来する899cm-1のピークの消失で判定した。
結果、反応開始後、室温では48時間、40℃では6時間、50℃では3時間、60℃では2時間、70℃では2時間で899cm-1のピークの消失していることから、ジオキサン溶液に溶媒置換して、さらに温度を変えても脱ブチル化反応は終了することを確認した。
4M塩化水素-ジオキサン溶液の添加量を7.3gとする以外は、実施例2と同様に行った。この塩化水素の添加量は前駆体ポリマー中のPTBSTに対し2当量に相当する。
結果、反応開始後、室温では24時間、50℃では1時間でPTBST芳香環C-H面外変角振動に由来する899cm-1のピークの消失していることから、脱ブチル化反応は終了することを確認したが、GPC溶出曲線が形状劣化しており、ポリマーが分解してしまうことが明らかとなった。
n-ブチルリチウム(15.36重量%濃度ヘキサン溶液)87gを、トルエン1320gとTHF707gの混合溶液に、-40℃で攪拌しながらPTBST707gを30分かけて添加し、さらに30分反応を継続した後、この反応溶液にヘキサメチルシクロトリシロキサン0.22モルを含むTHF溶液1190gを1時間かけて添加し、更に反応温度を40℃に保ち4時間攪拌後、さらに室温で一晩攪拌した。続いて、反応液にトリメチルシリルクロリド25gを加えて反応を停止し前駆体ポリマーを得た。前駆体ポリマーのPTBST-ジメチルシロキサンは数平均分子量(Mn)=6200、分子量分布=1.14、組成比:PTBST/ジメチルシロキサン=50/50、モル%であった。
結果、反応開始後2時間で899cm-1のピークの消失していることから、重合反応粗液を用いても反応は終了することを確認した。
この脱ブチル化して得られたp-ヒドロキシスチレン-ジメチルシロキサン共重合体をGPC測定したところ、数平均分子量(Mn)=5800、分子量分布=1.17であり、ブチル基が脱離した分の分子量低下が確認され、また、GPC溶出曲線の形状は反応前とほぼ同一であり、ポリマーの分解は起こっていないことが示された。
従って、該変性ポリシロキサン化合物は、超LSIの製造に必要なサブミクロンの解像能力を有するレジスト材料として、また、種々の熱硬化性樹脂や熱可塑性樹脂の改質剤として、さらには分離膜や生体適合性材料として広範な分野での利用が期待される。
Claims (3)
- 式(I)
X(Y)n (I)
[式中、Xは式(II)
X’(Y)n (IV)
〔式中、X’は式(V)
- 分子量分布が1.05~1.5である請求項1記載の変性ポリシロキサン化合物の製造方法。
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59199705A (ja) * | 1983-04-28 | 1984-11-12 | Toyo Soda Mfg Co Ltd | フエノ−ル残基を有する狭分散高分子の製造方法 |
JPH0247109A (ja) * | 1988-08-08 | 1990-02-16 | Hoechst Celanese Corp | ポリ(アセトキシスチレン)の酸触媒エステル交換によるポリ(ビニルフェノール)の製造方法 |
JPH04279608A (ja) * | 1990-06-29 | 1992-10-05 | Hoechst Celanese Corp | フォトレジスト用低光学密度ポリマー及びコポリマーの製造方法 |
JPH05170920A (ja) * | 1991-12-20 | 1993-07-09 | Nippon Soda Co Ltd | 変性ポリシロキサン化合物の製造方法 |
JPH06298862A (ja) * | 1993-01-07 | 1994-10-25 | Basf Ag | p−ヒドロキシスチレン重合体の製造方法 |
JP2000026536A (ja) * | 1998-07-14 | 2000-01-25 | Nippon Soda Co Ltd | アルケニルフェノール系重合体の製造方法 |
WO2001018084A1 (fr) * | 1999-09-08 | 2001-03-15 | Nippon Soda Co., Ltd. | Copolymere alcenylphenolique de type a-b-a |
WO2001018083A1 (fr) * | 1999-09-03 | 2001-03-15 | Nippon Soda Co., Ltd. | Copolymere d'alkylphenol et son procede de production |
JP3471010B2 (ja) * | 1991-05-31 | 2003-11-25 | 日本曹達株式会社 | 変性ポリシロキサン化合物及びその製造方法 |
JP2009235132A (ja) * | 2008-03-25 | 2009-10-15 | Fujifilm Corp | アルケニルフェノール系重合体の製造方法、この製造方法によって製造されたアルケニルフェノール系重合体、このアルケニルフェノール系重合体を含有するポジ型レジスト組成物及びこのポジ型レジスト組成物を用いたパターン形成方法 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6173725A (ja) | 1984-09-20 | 1986-04-15 | Denki Kagaku Kogyo Kk | エポキシ樹脂組成物 |
JPS62174222A (ja) | 1986-01-28 | 1987-07-31 | Hitachi Chem Co Ltd | 電子部品封止用エポキシ樹脂成形材料 |
JPS62212417A (ja) | 1986-03-13 | 1987-09-18 | Shin Etsu Chem Co Ltd | エポキシ樹脂組成物 |
US4775730A (en) * | 1987-03-23 | 1988-10-04 | Hoechst Celanese Corporation | Copolymers of p-acetoxystyrene with any of certain polyunsaturated compounds |
US4877843A (en) * | 1987-09-11 | 1989-10-31 | Hoechst Celanese Corporation | Selective hydrolysis of copolymers of para-acetoxy styrene and allyl esters of ethylenically unsaturated acids |
US4857601A (en) * | 1987-09-11 | 1989-08-15 | Hoechst Celanese Corp. | Selective hydrolysis of copolymers of para-acetoxy styrene and dialkyl muconates or alkyl sorbates |
US5274175A (en) * | 1988-07-19 | 1993-12-28 | Hoechst Celanese Corporation | Process for the preparation of 4-acetoxyphenylmethyl carbinol |
US6051659A (en) * | 1992-08-20 | 2000-04-18 | International Business Machines Corporation | Highly sensitive positive photoresist composition |
US5239015A (en) | 1990-06-29 | 1993-08-24 | Hoechst Celanese Corporation | Process for making low optical density polymers and copolymers for photoresists and optical applications |
JP3060153B2 (ja) * | 1994-09-30 | 2000-07-10 | 信越化学工業株式会社 | 部分tert−ブトキシ化ポリ(p−ヒドロキシスチレン)の製造方法 |
ATE296321T1 (de) * | 2001-01-26 | 2005-06-15 | Nippon Soda Co | Verfahren zur herstellung von teilgeschützten poly(hydroxystryolen) |
-
2010
- 2010-08-19 EP EP10809738.7A patent/EP2468799B1/en not_active Not-in-force
- 2010-08-19 JP JP2011527588A patent/JP5503654B2/ja not_active Expired - Fee Related
- 2010-08-19 CN CN201080036410.1A patent/CN102471491B/zh not_active Expired - Fee Related
- 2010-08-19 US US13/389,169 patent/US8420744B2/en not_active Expired - Fee Related
- 2010-08-19 ES ES10809738.7T patent/ES2478069T3/es active Active
- 2010-08-19 KR KR1020127003609A patent/KR101375894B1/ko not_active IP Right Cessation
- 2010-08-19 WO PCT/JP2010/005123 patent/WO2011021392A1/ja active Application Filing
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59199705A (ja) * | 1983-04-28 | 1984-11-12 | Toyo Soda Mfg Co Ltd | フエノ−ル残基を有する狭分散高分子の製造方法 |
JPH0247109A (ja) * | 1988-08-08 | 1990-02-16 | Hoechst Celanese Corp | ポリ(アセトキシスチレン)の酸触媒エステル交換によるポリ(ビニルフェノール)の製造方法 |
JPH04279608A (ja) * | 1990-06-29 | 1992-10-05 | Hoechst Celanese Corp | フォトレジスト用低光学密度ポリマー及びコポリマーの製造方法 |
JP3471010B2 (ja) * | 1991-05-31 | 2003-11-25 | 日本曹達株式会社 | 変性ポリシロキサン化合物及びその製造方法 |
JPH05170920A (ja) * | 1991-12-20 | 1993-07-09 | Nippon Soda Co Ltd | 変性ポリシロキサン化合物の製造方法 |
JPH06298862A (ja) * | 1993-01-07 | 1994-10-25 | Basf Ag | p−ヒドロキシスチレン重合体の製造方法 |
JP2000026536A (ja) * | 1998-07-14 | 2000-01-25 | Nippon Soda Co Ltd | アルケニルフェノール系重合体の製造方法 |
WO2001018083A1 (fr) * | 1999-09-03 | 2001-03-15 | Nippon Soda Co., Ltd. | Copolymere d'alkylphenol et son procede de production |
WO2001018084A1 (fr) * | 1999-09-08 | 2001-03-15 | Nippon Soda Co., Ltd. | Copolymere alcenylphenolique de type a-b-a |
JP2009235132A (ja) * | 2008-03-25 | 2009-10-15 | Fujifilm Corp | アルケニルフェノール系重合体の製造方法、この製造方法によって製造されたアルケニルフェノール系重合体、このアルケニルフェノール系重合体を含有するポジ型レジスト組成物及びこのポジ型レジスト組成物を用いたパターン形成方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2468799A4 * |
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US8420744B2 (en) | 2013-04-16 |
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