JPS6135205B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a hydroxystyrene polymer containing a phosphonic acid ester group. (In the formula, a is 0 or 1, 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, R ² is a straight or branched alkyl group having 1 to 4 carbon atoms, a phenyl group or hydrogen, X is chlorine, bromine or iodine, m' is 1 or 2, m'' is 0 or 1 and m'+m'' is 1 or 2
A hydroxystyrene-based polymer containing a phosphonium group containing a structural unit represented by General formula consisting of (Here, a ^{, t} , It is something.

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 a result, we have arrived at the present invention.

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 method for producing a novel phosphorus-containing hydroxystyrene polymer in which a pentavalent phosphonic acid ester group is introduced directly into the phenol nucleus or via a methylene group, and the phosphorus-containing hydroxystyrene polymer can be It is possible to produce a phosphorus-containing hydroxystyrene polymer or a cross-linked phosphorus-containing hydroxystyrene polymer, and if desired, it is possible to provide a product having properties intermediate between the two. You can also do it.

Furthermore, the molecular weight of the phosphonium group-containing hydroxystyrene polymer used as a starting material in the present invention,
Halogen content, phosphonium group content, substituents〓〓〓〓
Since it is possible to select the position etc. of
The phosphonate group-containing hydroxystyrene polymer obtained by the method of the present invention can be produced with any molecular weight, halogen content, phosphonate group content, and substitution position as desired.

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

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

Since the hydroxystyrene polymer containing phosphonium groups, which is a raw material for producing the hydroxystyrene polymer containing phosphonic acid ester groups of the present invention, is also a new substance, this synthesis method will be explained first.

One currently established method for synthesizing hydroxystyrenic polymers containing phosphonium groups is to start from known halogenated or halogenomethylated hydroxystyrenic polymers.

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 therefore the present invention is not defined by the above steps, but halogenation,
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 °C to 100 °C,
A reaction time of 48 hours or less 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 mole per mole of hydroxystyrene unit in the hydroxystyrene polymer, and the desired ratio is generally used. It is adjusted according to the 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 ₅ , 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, from the thus obtained halogenated or halogenomethylated hydroxystyrene polymer,
The synthesis process of a phosphonium group-containing hydroxystyrene polymer, which itself is a new substance, will be explained in detail. That is, the following reaction is carried out by reacting a trivalent phosphite to the halogen moiety of a halogenated or halogenomethylated hydroxystyrene polymer (for the sake of understanding, only the parts involved in the reaction are shown). ).

(In the formula ^{, a} , t,
Ethers such as tetrahydrofuran and dioxane, or aprotic polar solvents such as pyridine, acetone, dimethylformamide, dimethyl sulfoxide, and hexamethylphosphoric triamide are used.

Preferred examples of phosphorus compounds used in this reaction include trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, triphenyl phosphite, dimethyl methylphosphonate, diethyl methylphosphonite, diethyl ethylphosphonite,
Diphenyl phenylphosphonite, methyl dimethylphosphonite, ethyl diethylphosphonite, phenyl diphenylphosphonite, 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 the starting material is 1/10 to 40 mole, preferably 1 to 10 mole, and the desired amount 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 influenced by the type of phosphorus compound used; for example, when trimethyl phosphite is used, a lower temperature can be used than when triphenyl phosphite is used.

In most cases, a reaction time of 48 hours or less is sufficient, and a reaction time of 24 hours or less can usually be employed. Although it depends on the type of phosphorus compound used and the reaction temperature used, a reaction of several hours is sufficient to achieve the purpose.

When a halogenated hydroxystyrene polymer in which a halogen is directly bonded to the aromatic nucleus of a hydroxystyrene unit is used at the end of the reaction, the reaction product is almost always obtained as a solution. Non-solvents such as benzene, n-heptane,
In some cases, it is common to precipitate with water or the like and then separate.On the other hand, the starting material is a halogenomethylated hydroxystyrene system in which a halogen is bonded to the aromatic nucleus of a hydroxystyrene unit via a methylene group. When a polymer is used, the reaction product is obtained in suspension in most cases at the end of the reaction, so the product is usually separated separately.

It is theoretically possible to use the above reaction mixture directly as a raw material for the next step without isolating the hydroxystyrene polymer containing phosphonium groups.

〓〓〓〓
The above phosphonium group introduction reaction easily proceeds under mild conditions and does not require the use of a catalyst.

The method for producing a hydroxystyrene polymer containing a phosphonic acid ester group, which is the object of the present invention, from a hydroxystyrene polymer containing a phosphonium group is to release a halogenated hydrocarbon by heating, and at the same time release a halogenated hydrocarbon from a tetravalent phosphonium group. conversion into a functional phosphonic acid ester group. For ease of understanding, only the parts involved in the reaction are shown in the following general formula.

( ^{In the} formula, a, t, Aprotic polar solvents such as formamide, dimethyl sulfoxide, and hexamethyl phosphoric triamide are used.

The reaction temperature ranges from room temperature to 300°C, preferably
Performed in the range of 50℃ to 200℃, usually 90 to 200℃
Temperatures between .

The longer the reaction time, the better, but usually within 72 hours is enough to achieve the purpose, and generally a reaction time of 24 hours or less will be employed, depending on the reaction temperature and type of phosphonium group used.

Upon completion of the reaction, if the starting material has a phosphonium group directly bonded to the aromatic nucleus of the hydroxystyrene unit in the hydroxystyrenic polymer, the reaction product is generally soluble in the solvent used and is therefore It is common practice to remove or separate by precipitation using a non-solvent such as benzene, n-heptane, or in some cases water.

As described earlier, in the present invention, it is not necessary to isolate and use the hydroxystyrene polymer containing phosphonium groups, and the reaction mixture can be used as a raw material for the next step, and in this case, halogenated Alternatively, it is possible to synthesize a hydroxystyrene polymer containing a phosphonium group from a halogenomethylated hydroxystyrene polymer at a high reaction temperature of about 300°C. When synthesizing hydroxystyrene-based polymers containing phosphonium groups at such high reaction temperatures,
As soon as the phosphonium group is generated, it undergoes the reaction of the present invention and is converted into a phosphonic acid ester group.
At first glance, it seems as if the desired product of the present invention, a hydroxystyrene polymer containing a phosphonic acid ester group, can be obtained in one step from a halogenated or halogenomethylated hydroxystyrene polymer without passing through a hydroxystyrene polymer containing a phosphonium group. Although it tends to be interpreted as if it were obtained, considering the reaction mechanism, it is reasonable to think that it goes through a hydroxystyrene polymer containing a phosphonium group,
The method of the present invention also includes the above method.

As is clear from the above explanation, the target product of the method of the present invention, a hydroxystyrene polymer containing phosphonate groups, may also contain other structural units, such as halogenated or halogenomethylated hydroxystyrene units. What can be included in the polymer chain〓〓〓〓
Of course. Further, the halogen or halogenomethyl group in the halogenated or halogenomethylated hydroxystyrene polymer used is usually introduced at the ortho and/or para position relative to the hydroxyl group of the hydroxystyrene unit.

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 during the phosphorus introduction reaction and the conversion reaction to the phosphonic acid ester type, the polymer chain is Cleavage and crosslinking are usually not observed. Therefore, the molecular weight of the product is about 100, which is obtained from the oligomer of about 1000 and the polymer of acetoxystyrene.
It is possible to easily produce a phosphonic acid ester group-containing hydroxystyrenic polymer having any desired molecular weight depending on the purpose of its use.

Some typical examples of the polymers obtained in the present invention include polyparahydroxystyrene having a dimethyl phosphonate group, polymetahydroxystyrene having a dimethyl phosphonate group, and polymethahydroxystyrene having a dimethyl phosphonate group. Examples include parahydroxystyrene, polyparahydroxystyrene having an ethyl methylene ethylphosphonate group, and polyparahydroxystyrene having a diphenyl phosphonate group.

Methods for using the polymer of the present invention as a flame retardant include mixing the polymer of the present invention and other synthetic resins in a kneader or extruder under heating; A method of dissolving the monomer in a solvent of the present invention and then removing the solvent, a method of polymerizing the monomer in the presence of the polymer of the present invention, or a method of adding the polymer of the present invention during the polymerization process of the monomer,
Any method can be used, such as a method of mixing the polymer of the present invention and another synthetic resin in the form of chips or powder, and molding methods include injection molding, extrusion molding, compression molding, rotational molding, etc. Any suitable means may be employed.

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

Example 1 A device with a stirrer, thermometer, dropping funnel, and reflux condenser
Brominated polyparahydroxystyrene (per hydroxystyrene unit) in a 300 ml four-necked flask
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. While stirring this solution at room temperature, 7.5 ml of P(OCH ₃ ) ₃ (trimethyl phosphite) was added drop by drop through the dropping funnel. After the addition was completed, the solution became a brown transparent solution. This solution was heated to 90 °C, and at this temperature 14
The reaction was stirred for hours. After the reaction was completed, the orange transparent solution thus obtained was poured into a large amount of n-heptane to obtain 4.3 g of a pale green solid. As a result of elemental analysis, this polymer has a P content of 2.5% and a Br content of 12.5%, and as a result of infrared absorption (IR) analysis, it is polyparahydroxystyrene having dimethyl phosphonate groups and unreacted bromine groups. acknowledged.

The characteristic absorptions observed in the IR analysis are shown below.

1200cm ^-1 νCH ₃ -O-(P) 1040cm ^-1 νP-O-(CH ₃ ) Around 1000cm ^-1 P-aromatic nucleus From the above results, the introduction rate of dimethyl phosphonate group is 0.12 per hydroxystyrene unit. , the residual bromine is not ionic but covalent, and is calculated to be 0.24 per hydroxystyrene unit. In other words, 0.24 unreacted bromines remain in the phenol nucleus, and the dimethyl phosphonate group directly attaches to the phenol nucleus.
It is thought that 0.12 bromines were introduced and the other 0.76 bromines (per hydroxystyrene unit) were debrominated during the reaction process. Product IR
The absorption curve is shown in FIG.

Example 2 Into the same flask used in Example 1 were placed 5.8 g of iodinated polymethahydroxystyrene (having a molecular weight of 6970 with 1.32 iodine per hydroxystyrene unit, i.e. 58.3% iodine content) and 200 ml of dimethylformamide. When it was uniformly dissolved, 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 produced.
I got it. As a result of elemental analysis, this polymer has a P content of
The I content was 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.

The thus obtained polymetahydroxystyrene with trimethoxyphosphonium iodide groups 3.0
Dissolve g in a mixed solvent of 100 ml of dimethylformamide and 100 ml of dimethyl sulfoxide, and heat at 150℃.
The mixture was stirred and reacted for 10 hours. After the reaction was completed, the brown-orange 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. The IR curve of the product is shown in FIG.

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 pale yellow 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%,
The Cl content was 7.2%, and as a result of IR analysis, it was confirmed to be polyparahydroxystyrene having trimethoxyphosphonium methyl chloride groups.

2.1 g of the thus obtained polyparahydroxystyrene having trimethoxyphosphonium methyl chloride groups was suspended in a mixed solvent of 50 ml of dimethyl sulfoxide and 50 ml of paradioxane, 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 1.7 g of a pale yellow solid. As a result of elemental analysis, this polymer has 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. The IR absorption curve of the product is shown in FIG.

Example 4 In a flask similar to that used in Example 1, 4.0 g of bromomethylated polyparahydroxystyrene (having 0.89 bromomethyl groups per hydroxystyrene unit, i.e. 35.1% Br content) and 200 ml of dimethyl sulfoxide were placed. When the mixture was stirred, an amber colored suspension solution was obtained. In this solution, P(OC ₂ H ₅ ) ₂ .
9 g of C ₂ H ₅ (diethyl ethylphosphonite) was added, the temperature was raised to 150° C., and the reaction was stirred at this temperature for 16 hours. After the reaction was completed, the brownish-orange suspension solution thus obtained was filtered and thoroughly washed with dioxane and methanol to obtain a brownish-orange solid.
I got g. As a result of elemental analysis, this polymer had a P content of 9.3%, Br content of 2.1%, and S content of 1.6%, and as a result of IR analysis, it was confirmed to be polyparahydroxystyrene having an ethyl methylene ethylphosphonate group. It was done. The IR absorption curve is shown in Figure 4.

Example 5 In a flask similar to that used in Example 1, brominated polyparahydroxystyrene (1.53 bromes per hydroxystyrene unit, or Br content of 50.5
%, molecular weight 3850) and 10 ml of dimethylformamide are added and uniformly dissolved to form a brown transparent solution. While stirring this solution at room temperature,
18.6 g of (OC ₆ H ₅ ) ₃ (triphenyl phosphite) was added. This solution was heated to 90°C and reacted with stirring for 5 hours, then 100 ml of dimethyl sulfoxide was further added, the temperature was raised to 150°C, and reacted with stirring at this temperature for 10 hours. After the reaction was completed, the brown-orange transparent solution was poured into n-heptane and filtered to obtain 6.2 g of an orange powdery solid. As a result of elemental analysis, this polymer has a P content of 8.1% and a Br content of 8.2%.
As a result of IR analysis, it was confirmed that it was polyparahydroxystyrene having a diphenyl phosphonate group.

Reference Example 1 50 parts of Epicote 828 and 400 parts of acetone were added to 100 parts of polyparahydroxystyrene having dimethyl phosphonate groups and bromine groups (P content 2.5%, Br content 12.5%) obtained in Example 1. was added and dissolved uniformly at 80℃, and then BF ₃ was added as a curing accelerator.
After adding 0.5 parts of piperidine, the solvent was removed.
This mixture was cast at 100℃ and cured at 170℃ for 2 hours.
A flame retardant test piece (6.5 x 3 x 15
mm) was produced. When the limiting oxygen index (LOI) (specified in JISK-7201) of this test piece was measured using Toyo Rika Kogyo's ON-1 type oxygen index furnace, it was 41.2, indicating excellent flame retardancy. It was hot.

Reference Example 2 Polymetahydroxystyrene having dimethyl phosphonate group obtained in Example 2 (P content 10.6
%, I content 2.1%, S content 1.1%), add 100 parts of polystyrene (Dencastyrol),
The mixture was thoroughly mixed and then extruded at 180°C to form pellets. The molding material thus obtained is heated to a temperature of 200 to 220.
By injection molding at °C with a residence time of 15 minutes.
A flame retardant test piece was prepared. When the LOI of this test piece was measured in the same manner as in Example 6, it was 39.5, indicating excellent flame retardancy.

Reference Example 3 Polymetahydroxystyrene having dimethyl phosphonate group obtained in Example 2 (P content 10.6
%, I content 2.1%, S content 1.1%) 70 per 100 parts
Epicote 828 of the Department, Epicote 1001 of the 30th Department,
Add 1 part of _BF3 /piperidine and 3 parts of calcium stearate and knead for 20 minutes with a hot roll at 100℃.
Next, this was heated to 170°C for 30 minutes in a hot air circulation system.
The mixture was heated for a minute, cooled, and then crushed. This was made into a 40 mm tablet using a tablet machine, and this was compression molded to prepare a flame retardant test piece. The LOI of this test piece was measured in the same manner as in Example 6, and was found to be 42.3, indicating excellent flame retardancy.

As described above, the phosphorus-containing hydroxystyrene polymer of the present invention exhibits excellent flame retardancy. For reference, when the flame retardant mechanism of the polymer of the present invention 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 generated during 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 generated by thermal decomposition of phosphorus compounds (for example, NH ₃ , CO ₂ , H ₂ O combined with phosphorus)
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 reaction between cellulose and air is 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 less reactive Br. ^* or R ^* produces,
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) and are corrosive (pollution-related). And this is not good even if it smells bad. Phosphorus compounds have slightly better compatibility with phenolic resins, are slightly less likely to be colored, and have better adhesive properties.

The coexistence of phosphorus compounds and halogen compounds can reduce the total amount of phosphorus compounds and halogen compounds added (synergistic effect).Also, since the melting and decomposition temperatures of phosphorus compounds and halogen compounds are different, difficulties may arise in the combined temperature range of each. A burning effect can be expected.

[Brief explanation of the drawing]

1 shows the infrared absorption curves of the products of Example 1, FIG. 2 shows the products of Example 2, FIG. 3 shows the products of Example 3, and FIG. 4 shows the products of Example 4. 〓〓〓〓

Claims (1)

[Claims] 1 [Formula] (wherein a is 0 or 1, t is 1, 2 or 3, R ¹ is a carbon number of 1 to 4
a straight-chain or branched alkyl group or phenyl group, ^R2 is a straight-chain or branched alkyl group having 1 to 4 carbon atoms, phenyl group or hydrogen, and X is chlorine, bromine or iodine); General formula consisting of heating a hydroxystyrenic polymer containing to a reaction temperature between room temperature and 300 °C (In the formula, a, t, R ¹ and R ² are the same as above.) A method for producing a hydroxystyrene polymer containing a phosphonic acid ester group. 2. The manufacturing method according to claim 1, wherein the reaction temperature is between 50 and 200°C. 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 - (CH ₂ ) _a X (where a is 0 or 1 and X
is chlorine, bromine or iodine) and the general formula P(OR ¹ )tR ² _3-t (where t is 1, 2 or 3, R ¹ is Carbon number 1~
4 is a straight or branched alkyl group or a phenyl group, and ^R2 is a straight or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, or hydrogen) at room temperature. ~300
The reaction is carried out at a reaction temperature between ℃ and the general formula A hydroxystyrene polymer containing ^a phosphonium group represented by the formula (a, ^t , The general formula consists of heating to a reaction temperature between (In the formula, a, t, R ¹ and R ² are the same as above.) A method for producing a hydroxystyrene polymer containing a phosphonic acid ester group. 〓〓〓〓