JPH0518844B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a soluble hydroxystyrene polymer, which is a novel compound, in which part or all of the phenolic hydroxyl groups of the hydroxystyrene polymer are substituted with an ester group-containing alkyl ether group, and a method for producing the same. More specifically, the present invention relates to the general formula () [wherein X is Cl, Br or I; p is 0-
is an integer of 2; Y is

[expression] or

[Formula]; R is a linear or branched alkyl group having 1 to 20 carbon atoms (when the number of carbon atoms is 3 or more)] 10 to 100 mol% of repeating units represented by the general formula () 0 to 90 mol% of repeating units represented by the formula [wherein X and p are the same as above], and repeating of at least one other vinyl monomer selected from styrene and α-methylstyrene Unit is 0
~50 mol%, has a structure in which each of the above repeating units are randomly connected with the main chain, has an average degree of aggregation of 5 to 500, and is represented by the general formula () and the general formula (). It relates to a soluble ester group-containing alkyl etherified hydroxystyrene polymer in which the average number of X per phenol nucleus in the unit is 0 or greater than 0 and less than 2, and the hydroxystyrene polymer is Etherification of the above-mentioned soluble ester group-containing alkyl by reacting it with a monoglycidyl carboxylic acid ester or monoglycidyl sulfonic acid ester compound in the presence or absence of a solvent, with or without using an acidic compound or a basic compound as a catalyst. This invention relates to a method for producing hydroxystyrene polymers. Conventionally, polyparahydroxystyrene is reacted with epichlorohydrin to form the general formula It is known that soluble glycidyl etherified polyparahydroxystyrene can be obtained as shown in (Journal of the Society of Organic Synthetic Chemistry, Vol. 26, p. 1102).
1968)). Alternatively, a halohydrin ether is first produced by reacting a hydroxystyrene polymer with epihalohydrin, and the halohydrin ether is subjected to a ring-closing reaction to obtain a glycidyl etherified hydroxystyrene polymer. It is also known (Japanese Patent Application Laid-Open No. 52-123488). However, in any of the above cases, an etherification reaction product using a monoglycidyl ester has not been obtained. Also,
It is also known that a reaction between a hydroxystyrene polymer and an epi-bis type epoxy resin, such as in a thermosetting resin composition of a hydroxystyrene polymer and an epi-bis type epoxy resin (Japanese Patent Publication No. 1973-
29800), but the reaction product (cured product) obtained in this case is a solvent-insoluble crosslinked product because the epoxy resin is a bis type. Therefore, soluble ester group-containing alkyl ethers containing the repeating unit represented by the above general formula () as an essential component, such as those obtained by reacting a monoglycidyl ester compound with a hydroxystyrene polymer. Hydroxystyrene-based polymers have not yet been obtained or known. By the way, hydroxystyrene-based polymers have many various uses as functional polymers, but the present inventors have investigated the adhesion or compatibility of hydroxystyrene-based polymers with inorganic materials or other organic materials, Furthermore, as a result of various studies in order to improve physical properties such as water resistance, by reacting a hydroxystyrene polymer and a monoglycidyl ester compound, a product represented by the above general formula (), which has never been proposed, was obtained. An ester group-containing alkyl etherified hydroxystyrene polymer containing a repeating unit as an essential constituent can be obtained, and this ester group-containing alkyl etherified hydroxystyrene polymer is soluble, moldable, and processable. This is thought to be due to its ester group-containing alkyl ether group, but it also has excellent adhesion to inorganic materials,
It has excellent compatibility with other organic materials, and is also excellent in moisture resistance, aging resistance, flexibility, etc., and is used as a raw material for useful products such as chelating agents, polymer matrix agents, and photosensitive resins. It has also been found that it is useful as a metal surface treatment agent itself or its raw material. Furthermore, the present inventors have also obtained the following knowledge regarding the usefulness of this ester group-containing alkyl etherified hydroxystyrene polymer as a metal surface treatment agent. In other words, this ester group-containing alkyl etherified hydroxystyrene polymer is useful as a metal surface treatment agent as it is, but this polymer can easily introduce a methylol group into its phenol nucleus with formaldehyde. This polymer into which methylol groups have been introduced has even better performance as a metal surface treatment agent. This ester group-containing alkyl etherified hydroxystyrene polymer or its methylolated product can be used, among other metal surface treatments, for cold-rolled steel sheets, high-strength steel sheets, carbon steel, zinc, aluminum, galvanized steel, tin-plated steel, or steel-mesh steel. It is useful as a post-treatment agent after treatment with phosphates (for example, zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, etc.) or chromic acid. When this ester group-containing alkyl etherified hydroxystyrene polymer or its methylolated product is used as a metal surface treatment agent, it improves the rust prevention, heat resistance, durability, processability, lubricity, and even coating properties of the treated metal surface. Adhesion, adhesion, etc. are improved. Therefore, the gist of the present invention is, first of all, that the general formula () [wherein X is Cl, Br or I; p is 0-
is an integer of 2; Y is

[expression] or

[Formula]; R is a linear or branched alkyl group having 1 to 20 carbon atoms (when the number of carbon atoms is 3 or more)] 10 to 100 mol% of repeating units represented by the general formula () 0 to 90 mol% of repeating units represented by the formula [wherein X and p are the same as above], and repeating of at least one other vinyl monomer selected from styrene and α-methylstyrene Unit is 0
~50 mol%, has a structure in which each of the above repeating units are randomly connected with the main chain, has an average degree of polymerization of 5 to 500, and is represented by the general formula () and the general formula (). It exists in a soluble ester group-containing alkyl etherified hydroxystyrene polymer in which the average number of X per phenol nucleus in the unit is 0 or greater than 0 and less than 2. And, secondly, the general formula () [wherein X is Cl, Br or I; p is 0-
is an integer of 2], the repeating unit is 50~
100 mol%, and 0 to 50 mol% of repeating units of at least one other vinyl monomer selected from styrene and α-methylstyrene, and each of the above repeating units is randomly arranged in the main chain. Soluble, which has a bonded structure, has an average degree of polymerization of 5 to 500, and has an average number of X per phenol nucleus in the repeating unit represented by the general formula () of 0 or greater than 0 and less than 2. A hydroxystyrene polymer of the general formula () is prepared in the presence or absence of an organic solvent, with or without using an acidic compound or a basic compound as a catalyst. [In the formula, Y is

[expression] or

[Formula]; R is a linear or branched alkyl group having 1 to 20 carbon atoms (when the number of carbon atoms is 3 or more)]. The present invention relates to a method for producing the above-mentioned soluble ester group-containing alkyl etherified hydroxystyrene polymer. The hydroxystyrene polymer used as a starting material in the method of the present invention for producing the ester group-containing alkyl etherified hydroxystyrene polymer according to the present invention has the general formula () [wherein X is Cl, Br or I; p is 0-
is an integer of 2], the repeating unit is 50~
It is mainly composed of 100 mol% and 0 to 50 mol% of repeating units of other vinyl monomers, and has a structure in which each of the above repeating units is randomly connected with the main chain, and has an average degree of polymerization of 5 to 500. A soluble hydroxystyrene polymer in which the average number of X per phenol nucleus in the repeating unit represented by the general formula () is 0 or more than 1 and less than 2 is suitable. The hydroxystyrene polymer may be a homopolymer of hydroxystyrene (ortho, meta, para, or a mixture thereof) or a copolymer of hydroxystyrene and another vinyl monomer. Hydroxystyrene as a polymerization unit may be any isomer, but the para or meta isomer is preferable. Furthermore, it is more preferable that these polymers contain as little water as possible, such as those that are heated and dried. Examples of other vinyl monomers in the copolymer include styrene or α-
Examples include methylstyrene. Furthermore,
The hydroxystyrene polymer used in the method of the present invention may be produced by any method, and its origin does not matter. For example, polyparahydroxystyrene, which is a parahydroxystyrene homopolymer, is easily prepared by cationic polymerization, radical polymerization, polymerization with an organic acid, or thermal polymerization of parahydroxystyrene. Polymerization using an organic acid yields a polymer with a weight average molecular weight of 1,000 to several hundreds of thousands, cationic polymerization yields a polymer with a weight average molecular weight of tens to hundreds of thousands, and thermal polymerization yields a polymer with a weight average molecular weight of 1000 to 100,000. , and by hydrolyzing after radical polymerization of paraacetoxystyrene,
About 10,000 polyparahydroxystyrene can be obtained. Halogenated hydroxystyrene polymers are
For example, as disclosed in Japanese Patent Publication No. 56-39762, it can be easily obtained by halogenating a hydroxystyrene polymer with halogen or hydrogen halide. The hydroxystyrene polymer used in the method of the present invention has an average degree of polymerization of 5 to 500.
A moderate amount is appropriate. As the monoglycidyl carboxylic acid ester or monoglycidyl sulfonic acid ester compound used in the method of the present invention, those represented by the following general formula () are suitable. [In the formula, Y is

[expression] or

[Formula]; R is a linear or branched alkyl group having 1 to 20 carbon atoms (when the number of carbon atoms is 3 or more)] As the monoglycidyl carboxylic acid ester having an alkyl group, glycidyl acetate ester

[Formula] Glycidyl laurate ester

[Formula] Glycidyl myristate ester

[Formula] Glycidyl palmitate ester

[Formula] Glycidyl stearate

[Formula], etc., and tertiary fatty acid monoglycidyl esters such as Cardiura E (trade name of Ciel Co., Ltd.), Phthalkyd (trade name of Hitachi Chemical Co., Ltd.), and Betucosol (trade name of Dainippon Ink Chemical Co., Ltd.). Examples of the monoglycidyl sulfonic acid ester having an alkyl group include glycidylpropane sulfonic acid ester. The monoglycidyl ester compound used may be a single compound or a mixture. As the organic solvent used in the method of the present invention, cyclic ethers such as tetrahydrofuran and dioxane, aprotic polar organic solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, and hexamethylphosphorotriamide are preferably used. In the case of acidic compounds, the catalyst used in the method of the present invention includes formic acid, acetic acid, propionic acid, n-butyric acid,
Aliphatic saturated monocarboxylic acids such as iso-butyric acid, n-valeric acid, iso-valeric acid, methylethyl acetate, trimethylacetic acid, caproic acid, heptonic acid, caprylic acid, pelargonic acid, capric acid, oxalic acid, malonic acid, Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, and pimelic acid; aliphatic unsaturated monocarboxylic acids such as acrylic acid, vinyl acetic acid, crotonic acid, and methacrylic acid; and aliphatic unsaturated acids such as maleic acid and fumaric acid. Organic carboxylic acids such as saturated dicarboxylic acids, aromatic carbonic acids such as benzoic acid, toluic acid, phthalic acid, and salicylic acid, or p
-Organic sulfonic acids such as toluenesulfonic acid are used. In addition, when using a basic compound as a catalyst, an alkali metal hydroxide or alkaline earth hydroxide such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, or N,N -dimethylaniline,
Organic amine compounds such as pyridine, picoline, imidazole, 2-methylimidazole, and triphenylamine are used. In the method of the present invention, the alkyl etherification reaction of a hydroxystyrene polymer with a monoglycidyl ester compound is performed at a reaction temperature of 0°C to 350°C, preferably 70°C to 250°C, and a reaction time of 5 minutes to 50 hours, preferably It is appropriate to do this for 30 minutes to 5 hours. The molar ratio of the monoglycidyl ester compound to be charged is within the range of 0.1 to 10 mol, preferably 0.1 to 0.8 mol, per phenol nucleus of the raw material hydroxystyrene polymer. The concentration of styrenic polymer is less than 80% by weight, preferably 50%
If a catalyst is used within the following range, the ratio of the catalyst used is based on the raw material hydroxystyrene polymer.
0.1 to 40 parts by weight per 100 parts by weight, preferably 0.1 to 40 parts by weight
Suitably, the amount is within the range of 10 parts by weight. This alkyl etherification reaction in the method of the present invention is preferably carried out in a liquid phase by melting or dissolving the starting materials, hydroxystyrene polymer and monoglycidyl ester compound, in a solvent.
If the reaction is carried out with the starting material in a solid state, the yield of the target product, a soluble alkyl etherified hydroxystyrene polymer containing an ester group, will be significantly reduced. When this alkyl etherification reaction is carried out in the absence of a solvent, after the reaction is completed, unreacted monoglycidyl ester compounds are removed using, for example, an evaporator as necessary, and then the alkyl etherification reaction product is can be used as is for various purposes. In addition, when the reaction is carried out in the presence of a solvent, after the reaction is completed, the alkyl etherification reaction product is mixed with a non-solvent such as water (which always becomes a non-solvent), petroleum ether, hexane, etc.
The target alkyl etherified hydroxystyrene polymer may be isolated by reprecipitation using benzene or the like (which becomes a non-solvent or a solvent depending on the degree of alkyl etherification), or
Further, after the reaction is completed, the solvent and, if necessary, the unreacted monoglycidyl ester compound are removed using, for example, an evaporator, and then the alkyl etherification reaction product can be used as it is for various purposes. The present invention will be further explained below with reference to Examples, but these are merely illustrative. Example 1 Polyparahydroxystyrene with a weight average molecular weight of 5200 (manufactured by Maruzen Oil Co., Ltd., trade name Resin M, melting temperature
175°C, insoluble in ethyl ether) 12.0 g and 8.3 g of 2,4,4-trimethylpentane-2-carboxylic acid (C ₉ ) glycidyl ester of the following formula, which is a monoglycidyl ester of tertiary fatty acid. The mixture was placed in a 100 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser, stirred and dissolved uniformly at 200°C on an oil bath, and reacted with stirring at 200°C for 1 hour. As a result, 20.3g of reaction product was obtained.
Regarding this reaction product, the following IR and ¹³ C−
From the results of NMR analysis, it was confirmed that it was an ester group-containing alkyl etherified polyparahydroxystyrene having a structure of the following formula (expressed as an average composition). Furthermore, ¹³ C-NMR analysis confirmed that 33% of the phenolic hydroxyl groups reacted with the monoglycidyl ester and were converted into acyl ether. This ester group-containing alkyl etherified polyparahydroxystyrene was soluble in ethyl ether at a melting temperature of 99°C, and easily soluble in methanol, tetrahydrofuran, and the like. Furthermore, when the molecular weight was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, the weight average molecular weight had increased to 7,700. In order to clarify the attribution by ^13C -NMR analysis,
The molecular model of the product obtained in this example is shown below. (In the formula, Z is -H or , a and b are each 0 or 1, and m is an integer. However, when both Z's are H, at least one b is not 0. The numbers assigned to carbons indicate carbon numbers δ _1-19 assigned by ¹³ C-NMR analysis. ) IR results; KBr pellet method 2960cm ^-1 νasCH (-CH ₃ ) 2870cm ^-1 νaCH (-CH ₃ ) 1730cm ^-1 1710cm ^-1 νC-O (ester) 1460cm ^-1 δasCH ₃ 1380cm ^-1 δsCH ₃ 1240cm ^-1 Skeleton (

[Formula]), δOH (secondary C -OH), νasC-O(

[Formula]) 1105cm ^-1 νC-O (secondary C-OH) 1040cm ^-1 νaC-O (

[Formula]) 940cm ^-1 δCH (

[Formula]) was recognized as a new or stronger absorption. ^13C -NMR results: δ ₁ = 16.7ppm δ ₂ = 21.1ppm (δ ₃ = 27.3; δ ₄ = 29-28; δ ₅ = 30.4ppm) at 27°C in 30% heavy acetone (0 point is TMS carbon) is superimposed on heavy acetone and was measured in heavy THF. δ ₆ = 37.0ppm δ ₇ = 39~41ppm δ ₈ = 49.8ppm δ ₉ = 50.9ppm δ 10 = 61.5ppm δ ₁₁ = 67.0ppm δ ₁₂ = 73.1ppm ^** δ ₁₃ = _{115.3ppm δ 14 =} 129.0ppm δ ₁₅ = 137.0ppm δ ₁₆ = 152.5ppm δ ₁₇ = 156.0ppm δ ₁₈ = 157.5ppm ^* δ ₁₉ = 177.2ppm *Absorption based on carbon with aliphatic alcoholic hydroxyl group** etherified oxygen of phenolic OH There was an absorption of ¹³ C based on the carbon of the phenol nucleus. The IR spectrum of the product is shown in Figure 1, and ^{the 13} C-NMR spectrum is shown in Figure 2. Reference Example 1 The ester group-containing alkyl etherified polyparahydroxystyrene obtained in Example 1 was divided into two parts, one of which was dissolved in a 10% aqueous sodium hydroxide solution, and reacted with formalin at 60°C for 5 hours. However, the total amount of formamine reacts quantitatively,
An ester group-containing alkyl etherified polyparahydroxystyrene having a methylol group was obtained, in which 0.20 methylol groups per phenol nucleus were introduced at the ortho position to the hydroxyl group of the phenol nucleus. The above-mentioned ester group-containing alkyl etherified polyparahydroxystyrene itself (the other divided into two) and the ester group-containing alkyl etherified polyparahydroxystyrene having a methylol group into which a methylol group was introduced were subjected to metal surface treatment as follows. It was used as a drug and evaluated. As a result, it was confirmed that these are very excellent metal surface treatment agents. After pre-treating the cold-rolled steel sheet with a strong alkaline cleaning solution, rinsing it with hot water, and performing a parkerizing treatment with an aqueous zinc phosphate solution at 65°C, the ester group-containing alkyl etherified polyparahydroxystyrene itself or its After post-treatment at 60°C with a 5% alkaline aqueous solution (polymer concentration approximately 10% by weight) of the methylol group-introduced product, the product was thoroughly rinsed and dried at 150°C for 10 minutes, followed by thermosetting. The acrylic painting was done. Each plate obtained was subjected to a salt spray test using the ASTM-B117-61 method for 504 hours for plates using ester group-containing alkyl etherified polyparahydroxystyrene itself, and for plates using its methylol group-introduced product. Even after 672 hours, each plate showed good performance with no corrosion observed. Example 2 Polyparahydroxystyrene with a weight average molecular weight of 2900 (melting temperature 150°C, insoluble in ethyl ether)
12.0g and Cardiura E10, a tertiary aliphatic monoglycidyl ester (trade name from Ciel, epoxy equivalent 240-250, melting point -60℃ or less, boiling point 275℃)
8.6g and 0.03g of imidazole as a catalyst were placed in a 100ml three-necked flafco equipped with a stirrer, thermometer, and reflux condenser, stirred and dissolved uniformly at 150℃ on an oil bath, and then stirred at 150℃ for 5 hours. I let it happen. As a result, 20.6 g of reaction product was obtained. It was confirmed from the results of IR and NMR analysis that this reaction product was polyparahydroxystyrene in which 34% of the phenolic hydroxyl groups were alkyl etherified.
Furthermore, this reaction product had a melting temperature of 77°C and was soluble in ethyl ether and readily soluble in tetrahydrofuran (THF), and when its molecular weight was measured by GPC, it was found that the weight average molecular weight had increased to 4120. ¹³ C-NMR results δ ₁₂ = 72.9 ppm δ ₁₈ = 157.5 ppm Example 3 Using 12.0 g of polymetahydroxystyrene with a weight average molecular weight of 7300, 8.6 g of Cardiura E10, and 0.02 g of maleic acid, the reaction temperature was 200°C. The reaction was carried out in the same manner as in Example 2 except that the reaction was carried out for 2 hours. The obtained reaction product was confirmed to be polymethahydroxystyrene in which 35% of the phenolic hydroxyl groups were alkyl etherified from the results of IR and NMR analysis, and the weight average molecular weight was 10350 as a result of GPC analysis. It was increasing. Moreover, this reaction product was easily soluble in THF. ¹³ C-NMR results δ ₁₂ = 73.2 ppm δ ₁₈ = 157.7 ppm Example 4 17.9 g of radical copolymer of para-hydroxystyrene and styrene (para-hydroxystyrene content: 67 mol%) and glycidyl laurate ester
The reaction was carried out in the same manner as in Example 2, except that 9.8 g of the sample was used and the reaction was carried out at a reaction temperature of 180° C. for 3 hours. It was confirmed from the results of IR and NMR analysis that the obtained reaction product was a copolymer of parahydroxystyrene and styrene in which 32% of the phenolic hydroxyl groups were alkyl etherified. Moreover, this reaction product was easily soluble in THF. ¹³ C-NMR results δ ₁₂ = 73.4 ppm δ ₁₈ = 157.5 ppm Example 5 Using 12.0 g of pora-parahydroxystyrene with a weight average molecular weight of 5200 and 6.3 g of glycidylpropanesulfonic acid ester (molecular weight 180), the reaction temperature was 170
The reaction was carried out in the same manner as in Example 2 except that the reaction was carried out at .degree. C. for 5 hours. The obtained reaction product is
From the results of IR and NMR analysis, it was confirmed that 30% of the phenolic hydroxyl groups were alkyl etherified polyparahydroxystyrene. Also,
This reaction product was easily soluble in THF. ¹³ C-NMR results δ ₁₂ = 72.7 ppm δ ₁₈ = 157.6 ppm Example 6 12.0 g of polyparahydroxystyrene with a weight average molecular weight of 5200 and glycidyl acetate (molecular weight
116) 8.2g and 0.03g of 2-methylimidazole
It was dissolved in 50 g of dioxane, reacted at a reaction temperature of 100° C. for 7 hours, and then poured into a large amount of water to obtain 20.0 g of a white polymer. The results of IR and NMR analyzes confirmed that this white polymer was polyparahydroxystyrene in which 70% of the phenolic hydroxyl groups were alkyl etherified, and was easily soluble in THF. ¹³ C-NMR results δ ₁₂ = 72.7 ppm δ ₁₈ = 157.4 ppm Example 7 24.2 g of brominated polyparahydroxystyrene with a weight average molecular weight of 8300 (1.52 bromine atoms are introduced per phenol nucleus) and glycidyl acetic acid Dissolve 4.1 g of ester (molecular weight 116) and 0.03 g of 2-methylimidazole in 70 g of dioxane,
After reacting at a reaction temperature of 100° C. for 7 hours, the mixture was poured into a large amount of water to obtain 28.0 g of a pale yellow-white polymer. From the results of IR and NMR analyses, it was confirmed that this pale yellow-white polymer was brominated polyparahydroxystyrene in which 35% of the phenolic hydroxyl groups were alkyl etherified. Moreover, this pale yellowish-white polymer was easily soluble in THF. ¹³ C-NMR results δ ₁₂ = 73.7ppm δ ₁₈ = 157.9ppm

[Brief explanation of the drawing]

Figure 1 is the IR spectrum of the product obtained in Example 1, and Figure 2 is its ¹³ C-NMR.
It is a spectrum.

Claims (1)

[Claims] 1 General formula () [wherein X is Cl, Br or I; p is 0-
is an integer of 2; Y is [Formula] or [Formula]; R is a linear or branched alkyl group having 1 to 20 carbon atoms (when the number of carbon atoms is 3 or more); 10 to 100 mol% of repeating units, general formula () 0 to 90 mol% of repeating units represented by the formula [wherein X and p are the same as above], and repeating of at least one other vinyl monomer selected from styrene and α-methylstyrene Unit is 0
~50 mol%, has a structure in which each of the above repeating units are randomly connected with the main chain, has an average degree of aggregation of 5 to 500, and is represented by the general formula () and the general formula (). A soluble ester group-containing alkyl etherified hydroxystyrene polymer in which the average number of X per phenol nucleus in the unit is 0 or greater than 0 and less than 2. 2 General formula () [wherein X is Cl, Br or I; p is 0-
is an integer of 2], the repeating unit is 50~
100 mol%, and 0 to 50 mol% of repeating units of at least one other vinyl monomer selected from styrene and α-methylstyrene, and each of the above repeating units is randomly arranged in the main chain. Soluble, which has a bonded structure, has an average degree of polymerization of 5 to 500, and has an average number of X per phenol nucleus in the repeating unit represented by the general formula () of 0 or greater than 0 and less than 2. A hydroxystyrene polymer of the general formula () is prepared in the presence or absence of an organic solvent, with or without using an acidic compound or a basic compound as a catalyst. [Wherein, Y is [Formula] or [Formula]; R is a linear or branched alkyl group having 1 to 20 carbon atoms (when the number of carbon atoms is 3 or more)]
General formula () characterized by reacting with a monoglycidyl ester compound represented by 10 to 100 mol% of repeating units represented by [wherein X, p, Y and R are the same as above],
General formula () 0 to 90 mol% of repeating units represented by the formula [wherein X and p are the same as above], and repeating of at least one other vinyl monomer selected from styrene and α-methylstyrene Unit is 0
~50 mol%, has a structure in which each of the above repeating units are randomly connected with the main chain, has an average degree of polymerization of 5 to 500, and is represented by the general formula () and the general formula (). A method for producing a soluble ester group-containing alkyl etherified hydroxystyrene polymer in which the average number of X per phenol nucleus in the unit is 0 or greater than 0 and less than 2. 3. The manufacturing method according to claim 2, wherein the organic solvent is an aprotic organic solvent. 4. The manufacturing method according to claim 2, which does not use an organic solvent. 5. The production method according to claim 2, wherein the acidic compound used as a catalyst is an organic carboxylic acid or an organic sulfonic acid. 6. Claim 2, wherein the basic compound used as a catalyst is an alkali metal or alkaline earth metal hydroxide, or an organic amine compound.
Manufacturing method described in section.