JPS6134444B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a hydroxystyrene polymer containing a phosphonium group. (In the formula, a is 0 or 1, m is 1 or 2, and X is chlorine, bromine, or iodine) in the polymer chain. P(OR ¹ ) _t R ² _3-t (in the formula, t is 1, 2 or 3, R ¹ is a straight or branched alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ₂ is a carbon Using a trivalent phosphite represented by a linear or branched alkyl group, phenyl group, or hydrogen of numbers 1 to 4 as a starting material, the general formula [In the formula, a, ^{t ,} The present invention relates to a method for producing a hydroxystyrene polymer containing a phosphonium group.

Generally, polymer compounds containing phosphorus are flame retardants,
It is a useful substance used as ion exchange agents, plasticizers, metal collectors, polymer catalysts, surfactants, antistatic agents, fiber treatment agents, rust inhibitors, etc.

In the past, research has been conducted on introducing phosphorus into cellulose and polyvinyl alcohol to impart ion exchange ability and flame retardant effects, but there are no known reports of the successful production of soluble phenolic polymers containing phosphorus. Not yet. And for example, J.Chem.
Soc., (1964) 2620 (DIPackham), there has been some success in introducing arsenic into polyparahydroxystyrene, but it is thought that it is impossible to introduce phosphate groups. Ta.

The present inventors have continued research on the development of hydroxystyrene polymers for a long period of time, and as part of that research, they have made earnest efforts to develop phosphorus-containing hydroxystyrene polymers as part of research on the use of hydroxystyrene polymers. As a result, the present invention was achieved.

The phosphorus-containing hydroxystyrene polymer, which is the object of the method of the present invention, exhibits excellent effects as a reactive polymeric flame retardant when added in a predetermined amount to other thermoplastic or thermosetting resins, and can also be used as a reactive polymer flame retardant by itself. Heat resistant by curing with an appropriate hardening agent,
It can also be made into a molded product with excellent flame resistance.

A feature of the present invention is to provide a production method for producing a novel phosphorus-containing hydroxystyrene polymer in which a tetravalent phosphonium group is introduced directly or via a methylene group into the phenol nucleus. A phosphorus-containing hydroxystyrene polymer can be produced, or a crosslinked phosphorus-containing hydroxystyrene polymer can be produced, or a product having properties intermediate between the two can be produced. Further, by appropriately selecting reaction conditions, it is possible to arbitrarily control the introduction rate of phosphonium groups to a desired ratio. Furthermore, since it is possible to appropriately select the molecular weight, halogen content, position of substituents, etc. of the halogenated or halogenomethylated hydroxystyrene polymer used as a starting material in the present invention, the phosphorus-containing hydroxyl The styrenic polymer can have any molecular weight, halogen content, substitution position, and phosphonium group introduction rate as desired.

The unit structure of the hydroxystyrene-based polymer serving as the backbone of the polymer obtained in the present invention may be ortho-, meta-, or para-hydroxystyrene, or may be a mixture of these in any proportion.

In the present invention, hydroxystyrene polymer refers to a homopolymer of hydroxystyrene and a hydroxystyrene polymer produced by producing an acetoxystyrene polymer instead of hydroxystyrene and hydrolyzing it. do.

Halogens introduced into hydroxystyrene polymers through halogenation or halogenomethylation reactions include chlorine, bromine, and iodine. Any known method can be used to introduce these substituents. For example, when halogenating the above polymer, a simple halogen or other halogenating agent is introduced in the presence or absence of an appropriate solvent. The halogenomethylation reaction can be carried out using, for example,
This can be achieved with hydrogen halides and aldehydes or by the use of halogenated methyl ethers. Halogenation, halogenomethylation steps are not subject to the present invention and are therefore not defined by the above steps of the invention;
Of course, a polymer obtained by first synthesizing halogenomethylated hydroxystyrene and then polymerizing it can also be used. The rate of introduction of halogen or halogenomethyl groups into the polymer is generally 2 or less per hydroxystyrene unit, but can be arbitrarily controlled by selecting reaction conditions.

The above reaction will be explained in more detail below for reference.

The halogenation reaction uses chlorine, bromine, or iodine (hereinafter referred to as halogen) alone or a halogenating agent such as thionyl halide or hypohalite, and the solvent is a halogenated hydrocarbon such as chloroform, carbon tetrachloride, or disulfide. It is carried out using organic solvents such as carbon, acetic acid, and alcohols. During the reaction, the charging ratio of halogen or halogenating agent per mole of hydroxystyrene units in the hydroxystyrene polymer is generally in the range of 1/10 to 40 moles, and may be adjusted as appropriate depending on the desired introduction rate of halogen. Ru. Reaction temperature is -30℃~+150℃
C., preferably in the range of 0.degree. C. to 100.degree. C., and a reaction time of less than 48 hours is sufficient in most cases.
Further, as a post-treatment, it is preferable to perform either a ketone solvent treatment, an alkali and acid treatment, or a combination of both.

The halogenomethylation reaction can be carried out by reacting the hydroxystyrene polymer with, for example, hydrogen halide and formaldehyde or with halogenomethyl ether. As the solvent, alcohols such as methanol and ethanol, or polar solvents such as tetrahydrofuran and dioxane are used. During the reaction, the charging ratio of hydrogen halide and halogenomethylating agent such as formaldehyde or halogenomethyl ether is generally used in the range of 1/5 to 40 moles per mole of hydroxystyrene units in the hydroxystyrene polymer.
It is adjusted according to the desired halogenomethyl group introduction rate. The reaction temperature is from 0°C to 150°C, preferably from room temperature to 100°C, and the reaction time is sufficient within 48 hours in most cases. Further, Lewis acid catalysts such as AlCl ₃ , SbCl ₃ , FeCl ₃ , SnCl ₄ and ZnCl ₂ are usually used in the reaction. During the above-mentioned halogenation, crosslinking of the polymer does not occur and the halogenated product is generally soluble, but in this halogenomethylation reaction, the polymer crosslinks as a side reaction, so the halogenated product Normally, it forms a three-dimensional network-like structure, and there is a tendency for it to become insolubilized. When the halogenomethylation reaction is completed, the reaction product is obtained as a suspension or precipitate in most cases, so it is usually collected separately.

Next, the step of introducing phosphorus into the halogenated or halogenomethylated hydroxystyrene polymer, which is the starting material of the method of the present invention, will be explained in detail. That is, the following reaction is carried out by allowing a trivalent phosphite to act on the halogen moiety of a halogenated or halogenomethylated hydroxystyrene polymer. : (In the formula, a, t, R ¹ , R ² , X, m, m' and
m″ is the same as above.) Ethers such as diethyl ether, tetrahydrofuran, dioxane, etc. can be used as a solvent during the reaction.
Alternatively, an aprotic polar solvent such as pyridine, acetone, dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, etc. can be used.

Preferred examples of phosphorus compounds used in this reaction include trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, triphenyl phosphite, dimethyl methylphosphonate, and methyl phosphorous. diethyl phosphonite, diethyl ethyl phosphonite,
Diphenyl phenylphosphonite, methyl dimethylphosphinate, ethyl diethylphosphinate, phenyl diphenylphosphinate, and the like can be mentioned.

During the reaction, the amount of the above-mentioned phosphorus compound charged per mole of halogen moiety in the halogenated or halogenomethylated hydroxystyrene polymer as a starting material is 1/10 to 40 mole, preferably 1 to 10 mole, and the amount as desired It is adjusted as appropriate depending on the phosphorus introduction rate.

The reaction temperature ranges from 0°C to 200°C, preferably from room temperature to 100°C. The reaction temperature is affected by the type of phosphorus compound used; for example, when using trimethyl phosphite, it is preferable to use a lower temperature than when using triphenyl phosphite, and when the reaction temperature is high, the When a tetravalent phosphorus substituent is converted to a pentavalent phosphorus substituent, a side reaction that releases a halogenated hydrocarbon is likely to occur.

In most cases, a reaction time of 48 hours or less is sufficient, and it is usually preferable to use a reaction time of 24 hours or less.Although it varies depending on the type of phosphorus compound used, a reaction of several hours is enough to achieve a sufficient reaction time. In many cases, the reaction can be completed, and unnecessarily prolonging the reaction time, depending on the reaction temperature used, tends to promote the above-mentioned side reactions.

At the end of the reaction, when a halogenated hydroxystyrene polymer in which a halogen is directly bonded to the aromatic nucleus of a hydroxystyrene unit is used as a starting material, the reaction product is obtained as a solution in most cases. For non-solvents such as benzene,
Generally, the product is precipitated using n-heptane, water in some cases, and then separated, and the product is obtained as a white to brown solid substance. On the other hand, when a halogenomethylated hydroxystyrene polymer in which a halogen is bonded to the aromatic nucleus of a hydroxystyrene unit via a methylene group is used as a starting material, most of the reaction products are In this case, since the product is obtained in suspension, the product is usually separated separately.

As described above, this reaction easily proceeds under mild conditions and does not require the use of a catalyst.

The reaction product of the present invention is of course a useful compound in itself, as shown in the Examples mentioned above and later, but it is also noteworthy as an intermediate that can react with various reagents to give excellent products. For example, the product of the present invention can be easily converted into a hydroxystyrenic polymer having a stable phosphonic acid ester group by heating. Although this heating temperature varies depending on the type of phosphonium group, it is generally achieved by heating at a temperature between room temperature and 300°C, and the higher the reaction temperature, the faster the reaction. As the solvent used in the reaction, the same solvent as used in the present invention can be used, and therefore, isolation of the product of the present invention is not necessarily necessary when it is desired to carry out this conversion reaction. I don't.

As is clear from the above explanation, the phosphonium group-containing hydroxystyrene polymer, which is the object of the method of the present invention, also contains other constituent units such as unreacted halogenated or halogenomethylated hydroxystyrene units in the polymer chain. Of course, it may be included. In addition, the halogen or halogenomethyl group in the halogenated or halogenomethylated hydroxystyrene polymer that is the starting material is ortho and/or to the hydroxyl group of the hydroxystyrene unit.
Or, it is usual to use one introduced at the para position.

The molecular weight of the product of the present invention is determined mostly by the molecular weight of the halogenated or halogenomethylated hydroxystyrene polymer used, and cleavage and crosslinking of polymer chains are usually not observed during phosphorus introduction. Therefore, the molecular weight of the product can be obtained from oligomers of about 1000 to polymers of acetoxystyrene.
Phosphorus-containing hydroxystyrenic polymers can be readily produced having any desired molecular weight depending on the intended use, which can vary over a wide range up to polymers as high as 1 million or more.

Some typical examples of the polymers obtained in the present invention include polyparahydroxystyrene having triphenoxyphosphonium bromide groups, polymetahydroxystyrene having trimethoxyphosphonium iodide groups, trimethoxyphosphonium methyl Polyparahydroxystyrene with chloride groups, polyparahydroxystyrene with triethoxyphosphonium bromide groups, polyparahydroxystyrene with diethoxymethylphosphonium bromide groups, polyparahydroxystyrene with methoxymethylethylphosphonium bromide groups, trimethoxy Examples include polyparahydroxystyrene having a phosphonium bromide group.

Methods for using the polymer of the present invention as a flame retardant include a method of mixing the polymer of the present invention and other synthetic resins in a kneader or extruder under heating; Methods of dissolving in a common solvent and then removing the solvent, methods of polymerizing monomers in the presence of the polymer of the present invention or adding the polymer of the present invention during the polymerization process of the monomers, polymers of the present invention and others Any suitable method such as mixing with the synthetic resin in chip or powder form can be used, and any suitable molding method can be used such as injection molding, extrusion molding, compression molding, rotational molding, etc. can be done.

EXAMPLES The present invention will be described in more detail with reference to Examples below, but these are merely illustrative and should not be construed as limiting the scope of the present invention.

Example 1 A device with a stirrer, thermometer, dropping funnel, and reflux condenser
In a 300 ml four-necked flask, add prominated polyparahydroxystyrene (per unit of hydroxystyrene).
1.12 bromine, i.e. bromine content 42.9%, molecular weight 9654) 4.2g and paradioxane 100ml
When the solution was added and dissolved uniformly, it became a brownish-brown transparent solution. P(OC ₆ H ₅ ) ₃ (triphenyl phosphite) was added to this solution from the dropping funnel while stirring at room temperature.
When 18.6 g was added drop by drop, it became a brown transparent solution after the addition was completed. This solution was heated to 90° C., and stirred and reacted at this temperature for 14 hours. After the reaction is complete, add 200 ml of methanol to the yellow-orange transparent solution obtained in this way.
When I added it, it became cloudy. Thereafter, the solvent was completely removed to obtain 4.8 g of a brownish-orange solid. As a result of elemental analysis, this polymer has a P content of 2.3% and a Br content of 2.7%,
Infrared absorption (IR) analysis revealed that it was polyparahydroxystyrene having triphenoxyphosphonium bromide groups and diphenyl phosphonate groups.
The characteristic absorption observed in the IR analysis is shown below, and the IR absorption curve is shown in Figure 1.

1452cm ^-1 P ⁺ - aromatic nucleus 1172cm ^-1 aromatic nucleus - O - (P) 1120cm ^-1 P ⁺ - aromatic nucleus 950cm ^-1 P - O - aromatic nucleus Example 2 Iodine in the same flask used in Example 1 5.8 g of polymethahydroxystyrene (molecular weight 6970 with 1.32 iodine per hydroxystyrene unit, i.e. iodine content 58.3%) and dimethylformamide
When 200 ml of the solution was added and dissolved uniformly, it became a brown transparent solution. While stirring this solution at room temperature,
Add 7.5ml of (OCH ₃ ) ₃ (trimethyl phosphite),
The reaction was stirred at a reaction temperature of 100° C. for 5 hours to obtain a brown transparent solution. By pouring this solution into a large amount of n-heptane, 6.1 g of an orange powdery solid was obtained. As a result of elemental analysis, this polymer has a P content of 8.87.
%, and the I content was 20.4%, and as a result of IR analysis, it was confirmed that it was polymetahydroxystyrene having trimethoxyphosphonium iodide groups.
CH ₃ -O- (P) 1200cm ^-1 :P-O- (CH ₃ )
1030cm ^-1 .

The IR absorption curve is shown in Figure 2.

Reference Example 1 3.0 g of the thus obtained polymetahydroxystyrene having trimethoxyphosphonium iodide groups
was dissolved in a mixed solvent of 100 ml of dimethylformamide and 100 ml of dimethyl sulfoxide, and stirred and reacted at 150°C for 1 hour. After the reaction was completed, the brown transparent solution was poured into n-heptane to obtain 2.0 g of an orange powdery solid. As a result of elemental analysis, this polymer has a P content of 10.6% and an I content of 2.1%.
%, and the S content was 1.1%, and as a result of IR analysis, it was confirmed that it was polymetahydroxystyrene having dimethyl phosphonate groups. Incidentally, the sulfur in the product is considered to be due to the solvent used.

Example 3 In the same flask used in Example 1, chloromethylated polyparahydroxystyrene (0.63 chloromethyl groups per hydroxystyrene unit, i.e.
When 3.0 g (Cl content 14.9%) and 100 ml of paradioxane were added and stirred, a whitish-orange suspension solution was obtained. Add P(OCH ₃ ) ₃ trimethyl phosphite to this solution.
7.5 ml was added, the temperature was raised to 90°C, and the reaction was stirred at this temperature for 14 hours. After the reaction was completed, the obtained amber colored suspension solution was filtered and thoroughly washed with dioxane to obtain 3.7 g of a light amber colored solid. As a result of elemental analysis, this polymer has a P content of 8.7% and a Cl
The content was 7.2%, and as a result of IR analysis, it was confirmed to be polyparahydroxystyrene having trimethoxyphosphonium methyl chloride groups. The IR absorption curve is shown in Figure 3.

Reference Example 2 Polyparahydrocystyrene having trimexyphosphonium methyl chloride groups thus obtained
2.1 g was suspended in a mixed solvent of 50 ml of dimethyl sulfoxide and 50 ml of paraoxane, heated to 100° C., and reacted with stirring for 20 hours. After the reaction was completed, a deep amber colored suspension solution was obtained, which was filtered and thoroughly washed with dioxane and methanol to obtain a pale yellow solid.
Obtained 1.7g. As a result of elemental analysis, this polymer had a P content of 9.4%, a Cl content of 0.9%, and an S content of 0.7%, and as a result of IR analysis, it was confirmed that it was polyparahydroxystyrene having dimethyl methylenephosphonate groups. It was done.

Example 4 P instead of triphenyl phosphite in Example 1
The reaction was carried out in the same manner as in Example 1 except that 10 ml of (OC ₂ H ₅ ) ₃ (triethyl phosphite) was used. The product is a yellowish-orange solid.
Obtained 3.3g. As a result of elemental analysis, this polymer was found to be polyparahydroxystyrene having triethoxyphosphonium bromide groups and diethyl phosphonate groups. IR analysis is C ₂ H ₅ -O-(P) 1170cm ^-1 ;
It showed an absorption of P—O—(C ₂ H ₅ ) 1053 cm ⁻¹ . IR
The absorption curve is shown in FIG.

Example 5 P in place of triphenyl phosphite in Example 1
(OC ₂ H ₅ ) ₂ CH ₃ (diethyl methylphosphonite 50
The reaction was carried out in the same manner as in Example 1, except that 13.6 g (boiling point 47° C., n ²⁵ _D 1.4168) in mmHg was used. 4.1g light yellow solid as product
I got it. As a result of elemental analysis, this polymer has a P content of
The Br content was 4.7% and the Br content was 4.6%, and as a result of IR analysis, it was polyparahydroxystyrene having diethoxymethylphosphonium bromide groups and methylethyl phosphonate groups. The infrared absorption curve is shown in FIG.

Example 6 P instead of triphenyl phosphite in Example 1
(OCH ₃ ) CH ₃・C ₂ H ₅ (Methyl ethyl phosphinate Boiling point 87.5-88.5°C at 7 mmHg, n ²⁰ _D
1.4485, d ²⁰ 1.0043) The reaction was carried out in the same manner as in Example 1 except that 10 ml was used. 4.4 g of a yellow solid was obtained as a product. As a result of elemental analysis, this polymer had a P content of 5.1% and a Br content of 5.1%, and as a result of IR analysis, it was polyparahydroxystyrene having a methoxymethylethylphosphonium bromide group and a methylethyl phosphonate group. . The infrared absorption curve is shown in FIG.

Example 7 In the same flask used in Example 1, brominated polyparahydroxystyrene (1.53 bromes per hydroxystyrene unit, or bromine content of 50.5
%, molecular weight 3850) and 100 ml of tetrahydrofuran were added and uniformly dissolved to obtain a brown transparent solution. To this solution, 7.5 ml of trimethyl P(OCH ₃ ) ₃ phosphite was added through a dropping funnel while stirring at room temperature, resulting in a brown transparent solution. After the dropwise addition was completed, this solution was heated to 60° C. and reacted with stirring for 5 hours, resulting in a brown-orange transparent solution. By pouring this transparent solution into a large amount of a mixed solvent of petroleum ether and ethyl acetate (volume ratio 50:50), 5.3 g of a yellow-orange solid was obtained. As a result of elemental analysis, this polymer has a P content of 7.2%, an ionic Br content of 14.7%,
15.1% covalent Br, and as a result of IR analysis, it is a prominated polyparahydroxystyrene with trimethoxyphosphonium bromide groups (approximately 0.7 trimethoxyphosphonium bromide groups per hydroxystyrene unit) was recognized. The IR absorption curve is shown in Figure 7.

Reference Example 3 Polyparahydroxystyrene (P content: 2.3
%, Br content 2.7%) 70 parts to 30 parts Epicote 828
and 200 parts of acetone at 50℃, and further p-
0.3 part of dimethylaminobenzaldehyde was added and the solvent was removed. This mixture was cast at 80℃,
A flame retardant test piece was prepared by curing at 145°C for 2 hours. The LOI of this was 30.3, and the average burning time was around 18 seconds.

The evaluation of flame retardancy is based on the "Limiting Oxygen Index (LOI)" (specified in JISK-7201).
or "average number of seconds of combustion" (measured based on the method of UL-94).

Reference Example 4 Add 100 parts of polystyrene (Denka Styrol) to 20 parts of polymetahydroxystyrene (P content: 8.87%, I content: 20.4%) having trimethoxyphosphonium iodide groups obtained in Example 2, and mix well. Then, it was extruded at 180°C and pelletized.
The molding material thus obtained was injection molded at a temperature of 220-230°C and a residence time of 15 minutes. The average burning time of the obtained test pieces was around 13 seconds.

Reference Example 5 30 parts to 70 parts of brominated polyparahydroxystyrene having trimethoxyphosphonium bromide groups obtained in Example 7 (P content 7.2%, ionic Br 14.7%, covalent Br 15.1%) Epicote 828
and 200 parts of acetone were dissolved at 50° C., 0.3 parts of BF ₃ /piperidine was added as a curing accelerator, and the solvent was removed. This mixture was cast at 90 to 100°C and cured at 170°C for 2 hours to prepare a flame retardant test piece. The LOI of this was 35.8, and the average burning time was around 8 seconds.

As described above, the phosphorus-containing hydroxystyrene polymer of the present invention exhibits excellent flame retardancy. For reference, when the flame retardant mechanism of phosphorus-containing polymers is compared with that of conventionally known halogenated polymers, it is believed that there are roughly the following differences.

(1) Flame retardant mechanism of phosphorus compounds Phosphorus compounds perform flame retardant effects in both the solid phase (melt) and gas phase (nonflammable gas).

First, the phosphorus compound melts into a glassy state due to the heat of combustion, and this forms a film that covers the surface of the flammable object, blocking oxygen and stopping the continuation of combustion.

Next, nonflammable gases (e.g., NH ₃ , CO ₂ , H ₂ O combined with phosphorus) generated by thermal decomposition of phosphorus compounds are
and the volatiles of the compound itself) dilute the combustible gases generated from the combustible material.

It also liberates phosphoric acid as a high-temperature product, which promotes the dehydration and carbonization of combustible materials.

(2) Flame retardant effect of halides (bromides) Bromine performs flame retardant effect in the gas phase. The effect is that the non-flammable bromine gas dilutes the combustible gases from the combustible material being generated and stops the combustion reaction.

The important reactions in the flame between cellulose and air are HO ^* + CO → CO ₂ + H ^* (A) H ^* + O ₂ → HO ^* + O ^* (B), and reactions (A) and (B) complement each other. A chain reaction begins. To stop this, it is necessary to lower the concentrations of H ^* and HO ^* . Bromine has this ability, for example, HO ^* +HBr→HOH+Br ^* (C) Br ^* +RH→HBr→R ^* (D) (C) and (D) are inhibition and regeneration reactions, respectively, which lead to the inhibition of reactivity. less Br ^* or R ^* is produced,
The chain reaction stops.

(3) Comparison of phosphorus compounds and bromides As mentioned in (1) and (2), phosphorus compounds act as flame retardants in both the solid and gas phases, but bromides only act in the gas phase. In addition, phosphorus compounds eventually turn into phosphoric acid and do not become toxic gases, but bromides generate bromine (toxic gas), which is corrosive (pollution-related) and has a bad odor. Phosphorus compounds have slightly better compatibility with phenolic resins, are slightly less likely to be colored, and have better adhesive properties.

By using a phosphorus compound and a halogen compound together, the total amount of the phosphorus compound and the halogen compound added can be reduced (synergistic effect), and since the melting and decomposition temperatures of the phosphorus compound and the halogen compound are different, the combined temperature of each can be reduced. It can be expected to have a flame retardant effect in the area.

[Brief explanation of the drawing]

Figure 1 shows Example 1, Figure 2 shows Example 2, Figure 3 shows Example 3, Figure 4 shows Example 4, Figure 5 shows Example 5, and Figure 6 shows Example 2. 6 and 7 are the infrared absorption curves of the product of Example 7.

Claims (1)

[Scope of Claims] _A halogenated _or halogenomethylated hydroxystyrene polymer containing 1 P(OR ¹ ) _t R ² _3-t (In the formula, R ₁ is a straight chain or branched alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ₂ is a straight chain or branched chain having 1 to 4 carbon atoms. alkyl group, phenyl group or hydrogen, and t is 1, 2 or 3) at a reaction temperature between 0°C and 200°C. A method for producing a hydroxystyrene polymer containing a phosphonium group represented by the formula (wherein a, t, R ₁ , R ₂ and X are the same as above). 2. The production method according to claim 1, wherein the reaction temperature is between room temperature and 100°C, and the reaction is carried out in the presence of ethers and/or an aprotic polar solvent. 3. The manufacturing method according to claim 1 or 2, wherein a is 0. 4. The manufacturing method according to claim 1 or 2, wherein a is 1. 5 1/10 per equivalent of halogen in halogenated or halogenomethylated hydroxystyrene polymer
5. The production method according to claim 1, wherein the reaction is carried out using 40 moles of the trivalent phosphite. 6 The solvent is a chain or cyclic ether, ketone,
The manufacturing method according to any one of claims 1 to 5, which is pyridine, dimethyl sulfoxide, hexamethyl phosphoric triamide, or dimethyl formamide. 7 1 to 1 equivalent of halogen in the halogenated or halogenomethylated hydroxystyrene polymer
7. The production method according to any one of claims 1 to 6, wherein the reaction is carried out using 10 moles of the trivalent phosphite.