JPS6135207B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a hydroxystyrene polymer containing methyl phosphate or an ester group thereof, and a method for producing the same, and more specifically relates to a hydroxystyrene polymer containing methyl phosphate or its ester group, and more particularly, (In the formula, R is hydrogen, an alkyl group having 1 to 3 carbon atoms, and Y is oxygen or sulfur) is 10 to 100 mol%, general formula (B) (In the formula, R ¹ is an alkyl group having 1 to 3 carbon atoms) is 0 to 15 mol%, general formula (C) is 0 to 50 mol% and general formula D is essentially the remaining mole% as the main structural unit, and each of the above structural units is randomly connected with the main chain〓〓〓〓
The present invention relates to a hydroxystyrene polymer containing methyl phosphate or its ester group having a polymerization degree of 10 to 100 and a method for producing the same. 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. Research has been conducted to introduce phosphorus into cellulose and polyvinyl alcohol to impart ion exchange ability and flame retardant effects, but there are no known reports of successful production of soluble phenolic polymers containing phosphorus. do not have. And for example, J.Chem.Soc.
, (1967) 2620 (DIPackham), there has been some success in introducing arsenic into polyparahydroxystyrene, but it is considered impossible to introduce phosphate groups. 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, the present invention was achieved. The phosphorus-containing hydroxystyrene polymer 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 itself as a suitable curing agent. By curing it, it can be made into molded products with excellent heat resistance and flame resistance. A feature of the present invention is to provide a novel phosphorus-containing hydroxystyrene polymer containing methyl phosphate or its ester, which is produced by reacting the methylol group in the methylolated hydroxystyrene polymer with phosphoric acid or its esters. be. Here, for the sake of simplicity, what is referred to as phosphoric acid or its ester is used in the sense that it includes monothiophosphoric acid ester, as is clear from the general formula shown above. Therefore, two of the remaining four bonds of the pentavalent phosphorus atom bonded via the oxygen of the methylol group in the polymer are bonded to an oxygen atom or a sulfur atom through a double bond. , the remaining two bonds may be bonded to hydrogen or an alkyl group having 1 to 3 carbon atoms via an oxygen atom, and one bond may be directly bonded to chlorine. Although some of the phosphorus-containing hydroxystyrene polymers of the present invention are gelatinized by crosslinking, most of them are soluble. That is, according to the present invention, a soluble product or a gelatinized product by crosslinking can be obtained as desired, and the introduction rate of phosphorus can also be controlled as desired. In the reaction of the present invention, polymer chain cleavage or crosslinking hardly occurs, so depending on the selection of starting materials, molecular weights ranging from oligomers to 20,000 can be obtained.
It can be manufactured arbitrarily up to a certain degree. The structure of the hydroxystyrene unit of the methylolated hydroxystyrene polymer serving as the backbone of the polymer of the present invention may be ortho, meta or para-hydroxystyrene, or a mixture thereof in any proportion. The methylol group is present in the ortho and/or para position relative to the phenolic hydroxyl group. In the present invention, the hydroxystyrene polymer refers to a hydroxystyrene homopolymer and a hydroxystyrene polymer produced by producing an acetoxystyrene polymer instead of hydroxystyrene and hydrolyzing it. . One of the established methods for producing the methylolated hydroxystyrene polymer, which is the starting material for the polymer synthesis of the present invention, is to methylolize the hydroxystyrene polymer with formaldehyde. The molecular weight of this hydroxystyrene polymer can be adjusted from approximately 1000 to 1000 by appropriately selecting polymerization conditions.
The molecular weight can be arbitrarily controlled within a range of about 2,000,000, but in order to obtain the polymer of the present invention, the molecular weight is about
Use 1000 to 12000. The methylolization reaction can be carried out by reacting a hydroxystyrene polymer with formaldehyde, such as an aqueous formalin solution or alcohol solution, paraformaldehyde, or oxymethylene glycols of various degrees of polymerization. At this time, an alkaline aqueous solution, alcohols such as methanol, ethanol, propanol, butanol, or polar solvents such as tetrahydrofuran and dioxane are used as the solvent. During the reaction, the molar ratio of formaldehyde per 1 mole of hydroxystyrene units in the hydroxystyrene polymer is generally used in the range of 1/10 to 50 moles, and the actual amount used depends on the desired introduction rate of methylol groups. It is adjusted accordingly. Reaction temperature is 0℃
~200℃ range, preferably room temperature to 150℃
The range is adopted. Reaction time is 72 in most cases
〓〓〓〓
It is enough within the hour. Although the reaction proceeds at a sufficient rate even without a catalyst, an acid, alkali, or a tertiary amine compound can be used as a catalyst to further accelerate the reaction. Hydrochloric acid, sodium hydroxide, potassium hydroxide, ammonia, pyridine,
Trimethylamine, triethylamine, etc. are suitable for use as catalysts. At the end of the reaction, the methylolated hydroxystyrene polymer is dissolved in most cases, so the solvent is removed or it is precipitated using a non-solvent such as water, benzene, n-heptane, etc., and then separated. It is obtained as a white to brown solid. The above is an example of the method for producing the starting material for the polymer synthesis of the present invention, and is not within the scope of the present invention. Therefore, the present invention is not limited to the method for synthesizing the methylolated hydroxystyrene polymer that is the raw material. It is not binding. Next, a method for introducing phosphorus into a methylolated hydroxystyrene polymer will be described. First, phosphoric acid is applied to the methylol groups of the methylolated hydroxystyrene polymer, and the phosphoric acid is bonded to the methylol groups through a dehydration reaction. That is, Here, the term phosphoric acid is used to include not only orthophosphoric acid but also polyphosphoric acid and phosphorus pentoxide. As a solvent for this reaction, a cyclic ether such as tetrahydrofuran or dioxane, or an aprotic polar solvent such as pyridine or dimethylformamide is used. In order to accelerate the dehydration effect during the reaction, it is necessary to coexist phosphorus pentoxide, or polyphosphoric acid is used. Further, during this reaction, urea or ammonia may be used as an additive to improve solubility and prevent side reactions such as gelation. In carrying out this reaction, the amount of the above-mentioned phosphorus compound to be charged is 1/5 to 20 mole in terms of orthophosphoric acid per mole of methylol group in the methylolated hydroxystyrene polymer as the raw material. The amount used is adjusted within the above range depending on the desired phosphorus introduction rate. The reaction temperature is 0~
The temperature range is 200°C, preferably 50 to 200°C. A reaction time of 48 hours or less is sufficient in most cases. Depending on the case, if the reaction product precipitates from the reaction solution at the end of the reaction,
If dissolved, the reaction product is obtained as a white or brown solid by removing the solvent or adding a non-solvent to precipitate the reaction product, or by salting out or dialysis and freeze-drying. . In this case, if the product is dried too much, an intermolecular dehydration reaction may occur in the phosphoric acid methyl ester moiety, and the product may gel due to crosslinking. The product obtained in this reaction has the general formula (A) shown above, where R is hydrogen and Y is oxygen,
It has a structure that does not contain the structural unit of general formula (B). Next, a method for synthesizing the product of the present invention using phosphoric chloride or monothiophosphoric acid ester will be described. The parts involved in the reaction in this method can be expressed in the following general formula. (In the formula, Y is oxygen or sulfur, and R ¹ is an alkyl group having 1 to 3 carbon atoms.) That is, a phosphoric acid or monothiophosphoric acid ester group is bonded to the hydroxyl group of methylol by a dehydrochlorination reaction. Also in this reaction, a cyclic ether such as tetrahydrofuran or dioxane, or an aprotic polar solvent such as dimethylformamide or dimethyl sulfoxide is used as a solvent. As the phosphoric acid chloride or monothiophosphoric acid ester used in this reaction, dimethyl chlorophosphate, dimethyl chloromonothiophosphate, diethyl chlorophosphate, diethyl chloromonothiophosphate, dipropyl chlorophosphate, and dipropyl chloromonothiophosphate are used. During the reaction, the amount of phosphoric acid chloride or diester monothiophosphoric acid charged per mole of methylolated hydroxystyrene units in the methylolated hydroxystyrene polymer ranges from 1/2 to 40 moles, preferably from 1 to 10 moles. The actual amount to be charged is adjusted within the above range depending on the desired phosphorus introduction rate. The temperature for carrying out this reaction is from 0°C to 200°C, preferably from room temperature to 100°C. A reaction time of 48 hours or less is sufficient in most cases.
〓〓〓〓
Although a tertiary amine can be added to the reaction system as a catalyst, the reaction proceeds at a sufficient rate even without a catalyst. If the reaction product precipitates from the reaction solution at the end of the reaction, separate it, and if it is dissolved, remove the solvent or add a non-solvent such as benzene, n-heptane, water, etc. Separate the reaction product by means such as precipitation and separation.
to recover. The isolated product of this reaction is a white to amber solid material. Since this reaction does not involve a dehydration reaction, the presence of phosphorus pentoxide is not required. As is clear from the examples below, most of the structural units containing a phosphoric acid ester group in the product obtained in this reaction have a structure represented by the general formula (A) when a chlorophosphoric acid diester is used. However, when chlorinated monothiophosphoric acid diester is used, dealcoholization occurs in addition to dehydrochlorination, and the general formula (A)
and has a structure represented by general formula (B). If necessary, the structural unit represented by general formula (B) can be easily replaced with the type represented by general formula (A) by solvolysis. Solvolysis is performed using methanol, ethanol or propanol as a solvolysis agent from 0 to 200%.
℃, preferably at a temperature of 0 to 100℃. During the reaction, it is of course possible to use cyclic ethers such as tetrahydrofuran and dioxane, and aprotic polar solvents such as dimethyl sulfoxide and dimethyl formamide, but solvolytic agents such as methanol, ethanol, and propanol can also be used as solvents. It works so there is no need to add any other solvent. Generally, a reaction time of 48 hours or less is sufficient, and although it depends on the reaction temperature, a reaction time of 24 hours or less is usually employed. In this reaction using phosphoric acid chloride or monothiophosphoric acid ester, not only the hydroxyl group of methylol but also the phenolic hydroxyl group reacts to some extent as a side reaction. If it is desired to obtain a product in which R is hydrogen in this reaction using phosphoric chloride or monothiophosphoric acid ester, the product obtained above may be hydrolyzed. Hydrolysis of the above polymer is carried out using an acid catalyst. In this case, it is not preferable to use an alkali catalyst because it tends to cause elimination of the phosphoric acid group, that is, dissociation of the phenol and the phosphoric ester moieties, so an acid catalyst is used. Water or dioxane as a solvent
Mixed solvents such as water, tetrahydrofuran-water, methanol-water are used. As the acid catalyst used in this reaction, hydrochloric acid, acetic acid, etc. are preferably used. The amount of acid catalyst used is not limited to the amount of catalyst.
A large amount of acid, such as a water mixed solvent, can also be used. The temperature of the hydrolysis reaction is generally in the range of 0 to 150℃, and usually
It is carried out at temperatures within the range of 50-100°C. A reaction time of 48 hours or less is sufficient, and although it depends on the reaction temperature, a reaction time of 24 hours or less is usually employed. Separation and recovery of the product from the reaction system can be performed in the same manner as described above. A method for synthesizing the target product of the present invention using phosphoric acid or monothiophosphoric acid triester will be described below. This reaction is a transesterification reaction, and the formula is as follows. (In the formula, Y is oxygen or sulfur, and R ¹ is an alkyl group having 1 to 3 carbon atoms.) During the reaction, cyclic ethers such as tetrahydrofuran and dioxane, and aprotic solvents such as dimethylformamide and dimethyl sulfoxide are used as solvents. Polar solvents are used. As the phosphorus compound used in this reaction, pentavalent phosphoric acid or monothiophosphoric acid triesters are used, such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, trimethyl monothiophosphate, and triethyl monothiophosphate. During the reaction, the amount of the above-mentioned phosphorus compound charged per mole of methylolated hydroxystyrene units in the methylolated hydroxystyrene polymer is 1/2 to 40 moles, and preferably 1 to 10 moles. The actual amount to be charged is selected from within the above range depending on the desired phosphorus introduction rate. The temperature at which this reaction is carried out is in the range of 0 to 200°C, preferably in the range of room temperature to 150°C. A reaction time of 72 hours or less is sufficient in most cases. Since this reaction is not a dehydration reaction, the presence of phosphorus pentoxide is not required. Further, in this reaction, the phenolic hydroxyl group does not react and remains unchanged. At the end of the reaction, the reaction products are almost always dissolved and the solvent is usually removed or a non-solvent, e.g.
The mixture is separated as a precipitate by adding diluted salt, n-heptane, water, etc. to precipitate it, or by salting out with a saline solution or the like. The separated polymer is obtained as a white to brown solid material. There are no particular restrictions on the substitution position of the phenolic hydroxyl group in the methylolated hydroxystyrene polymer that is the starting material. The methylol group is preferably substituted at the ortho and/or para position relative to the phenolic hydroxyl group. The molecular weight of the product of the present invention is determined mostly by the molecular weight of the methylolated hydroxystyrene polymer used as a raw material, and cleavage of the polymer chain hardly occurs during the phosphorus introduction reaction. As mentioned above, if conditions are selected to avoid intermolecular crosslinking, crosslinking will not substantially occur, and the degree of polymerization will not substantially change during this reaction. Some representative examples of the target products of the present invention include methylolated polyparahydroxystyrene having phosphate groups, methylolated polyparahydroxystyrene having diethyl phosphate groups,
Examples include methylolated polyparahydroxystyrene having a diethylmonothiophosphate group and an ethylchloromonothiophosphate group, and methylolated polyparahydroxystyrene having a dimethylphosphate 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; method of dissolving the polymer of the present invention in a solvent and then removing the solvent; method of polymerizing the monomer in the presence of the polymer of the present invention or adding the polymer of the present invention during the polymerization process of the monomer; Any method such as mixing with a synthetic resin in the form of chips or powder can be used, and any suitable molding method can be used such as injection molding, extrusion molding, compression molding, rotational molding, etc. obtain. 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. Example 1 A device with a stirrer, thermometer, dropping roll, and reflux condenser
In a 300 ml four-necked flask, add methylolated polyparahydroxystyrene (0.96 methylol groups per hydroxystyrene unit, molecular weight 6860).
3.0 g, 100 ml of pyridine, 3.2 ml of orthophosphoric acid, and 8.4 g of phosphorus pentoxide were added and uniformly dissolved to form an orange, almost transparent solution. While stirring this solution
The temperature was raised to 100°C, and the temperature was maintained at 100-110°C for 10 hours with stirring. After the reaction is complete, filter the brownish-orange, almost transparent solution and concentrate it to 1/2 of its volume to 200ml.
of ethanol and 500 ml of benzene to obtain 5.2 g of a yellowish white solid. 50 of this
The mixture was dissolved in a mixed solvent of 1 ml of water and 50 ml of ethanol, 15 g of common salt was added, stirred at room temperature for 1 hour, and filtered to obtain 3.2 g of a flesh-colored solid. As a result of elemental analysis, this polymer had a P content of 10.3%, and as a result of IR analysis, it was confirmed that it was phosphoric acid methyl esterified polyparahydroxystyrene. The following characteristic absorption was observed by IR analysis. The infrared absorption curve is shown in FIG. 1110cm ^-1 ν(P)―O―CH ₂ ― Around 1015cm ^-1 νP―O―(CH ₂ )― and νP―
The introduction rate of O-(H) phosphate groups was 0.70 per methylol group. Example 2 100 ml of dimethylformamide was used in place of the solvent pyridine in Example 1, and the reaction temperature was the same as in Example 1.
The reaction was carried out in the same manner as in Example 1 except that the temperature was 150°C instead of 100-110°C, and 3.6g of a skin-colored solid was obtained. As a result of elemental analysis, this polymer had a P content of 12.1%, and as a result of IR analysis, it was phosphoric acid methyl esterified polyparahydroxystyrene. The introduction rate of phosphate groups was 0.88 per methylol group. The IR curve of the product is shown in FIG. Example 3 In a 300 ml container similar to that used in Example 1, 3.0 g of methylolated polyparahydroxystyrene (having 0.32 methylol groups per hydroxystyrene unit, molecular weight 5942) and dimethylformamide were added.
100ml, orthophosphoric acid 3.2ml, phosphorus pentoxide 8.4g and urea
When 3.6 g was added and uniformly dissolved, it became an orange, slightly opaque solution. This solution was heated to 150° C. with stirring, and reacted at this temperature for 3 hours with stirring. After the reaction is completed, the slightly yellow color obtained is
The opaque solution was filtered, further concentrated to 1/2 volume, and poured into 500 ml of n-heptane to obtain 7.8 g of a white-yellow solid. 50ml of this
Extract with methanol and add 20g to the methanol soluble part.
By adding 10 ml of brine containing 100 ml of common salt and stirring, 2.5 g of a white, auburn solid was obtained. As a result of elemental analysis, this polymer has a P content of 4.5% and an IR
As a result of analysis, it was confirmed that it was polyparahydroxystyrene esterified with methyl phosphate. The introduction rate of phosphate groups was 0.67 per methylol group. The IR curve of the product is shown in FIG. Example 4 In the same container used in Example 1, methylolated polyparahydroxystyrene (0.96 methylol groups per hydroxystyrene unit and a molecular weight
6860) and 100 ml of paradioxane were added and uniformly dissolved to form a brownish-brown transparent solution. Add diethyl chlorphosphate to this solution.

[Formula] 10.4g was added dropwise at room temperature with stirring using a dropping funnel. After the dropwise addition was completed, several drops of triethylamine were added and the temperature was raised to 90°C, resulting in a light brown transparent solution. this
The reaction was stirred at 90°C for 5 hours. After the reaction was completed, the dark brown-red transparent solution was poured into 700 ml of water to obtain 3.5 g of a pale amber powder polymer. As a result of elemental analysis, this polymer had a P content of 7.2% and a Cl content of 0.04%. As a result of IR analysis, this product was confirmed to be methylolated polyparahydroxystyrene having diethyl phosphate groups. As a result of IR analysis, the following characteristic absorption was observed. 1115cm ^-1 and 1103cm ^-1 ν―CH ₂ -O― (P) 1040cm ^-1 νP―O― (CH ₂ ) 980cm ^-1 νP―O - aromatic Of the above absorptions, the absorption at 980cm ^-1 is due to side reactions. This indicates that the phenolic hydroxyl group is also slightly reacted. The introduction rate of diethyl phosphate groups is approximately 0.51 per hydroxystyrene unit (approximately 0.53 per methylol group).
). The IR curve of the product is shown in FIG. Example 5 In a container similar to that used in Example 1, methylolated polyparahydroxystyrene (having 0.32 methylol groups per hydroxystyrene unit, molecular weight
5942) and 100 ml of paradioxane were added and uniformly dissolved, resulting in a brownish transparent solution.
Add diethyl chloromonothiophosphate to this solution.

[Formula] 11.3g was added drop by drop from the dropping funnel at room temperature while stirring. After the dropwise addition was completed, the temperature was raised to 90°C, and the solution turned into a light brown transparent solution.
This was reacted at 90°C for 5 hours with stirring. After the reaction was completed, this solution was poured into n-heptane to obtain 3.8 g of a brown powdered polymer. As a result of elemental analysis, this polymer has a P content of 4.5% and a Cl
The content rate was 2.45%, and the S content rate was 5.41%. As a result of IR analysis, it was confirmed that it was methylolated polyparahydroxystyrene having about half each diethyl monothiophosphate group and half ethylchloromonothiophosphate group. As a result of IR analysis, the following characteristic absorption was observed. 1103cm ^-1 ν-CH ₂ -O-(P) 1020cm ^-1 νP-O-(CH ₂ ) 977cm ^-1 νP-O-Aromatic Among the above absorptions, the absorption at 977cm ^-1 is due to the phenolic hydroxyl group due to a side reaction. It also shows that there is some reaction. The introduction rate of diethyl monothiophosphate group and ethylchloromonothiophosphate group was about 0.12 each per hydroxystyrene unit, and a total of about 0.24 (0.74 per methylol group). Product IR
The curve is shown in FIG. Example 6 In a flask similar to that used in Example 1, 3.0 g of methylolated polyparahydroxystyrene (having 0.32 methylol groups per hydroxystyrene unit, molecular weight 5942) and 100 ml of paradioxane were placed and dissolved uniformly. It became a brownish transparent solution.
10.2 ml of phosphoric acid triethyl ester was added to this solution, the temperature was raised to 90°C, and the reaction was allowed to stir at this temperature for 12 hours, resulting in a yellow-brown transparent solution. This solution was concentrated to 1/2 and then poured into a large amount of benzene to obtain 3.2 g of a brown solid. This weight〓〓〓〓
As a result of elemental analysis of the coalescence, the P content was 4.8%. As a result of IR analysis, the product was confirmed to be methylolated polyparahydroxystyrene having diethyl phosphate groups. The introduction rate of diethyl phosphate groups was 0.81 per methylol group. In this transesterification reaction, the phenolic hydroxyl group was hardly transesterified, and the hydroxyl group of the methylol group was selectively transesterified. Example 7 10 of the phosphoric acid methyl esterified polyparahydroxystyrene obtained in Example 1 (P content 10.3%, introduction rate of phosphoric acid groups 0.70 per methylol group)
Add 85 parts of polystyrene (dencastyrol) and 5 parts of antimony trioxide to the mixture, mix well, and
It was extruded into pellets at 180°C. The molding material thus obtained was injection molded at a temperature of 250° C. and a residence time of 10 minutes. Obtained flame retardant test piece (6.5 x 3 x 15
When the limiting oxygen index (LOI) was measured for the sample (mm), it was 32.9. Example 8 Methylolated polyparahydroxystyrene having diethyl phosphate groups obtained in Example 4 (P content 7.2%, Cl content 0.04%, introduction rate of diethyl phosphate groups was approximately 0.51 per hydroxystyrene unit)
8.5 parts of polystyrene (Dencastyrol) and 5 parts of antimony trioxide were added to 10 parts of the mixture, mixed well, and then extruded at 180°C to form pellets.
The molding material thus obtained was injection molded at a temperature of 220-230°C and a residence time of 15 minutes. The limiting oxygen index (LOI) of the obtained flame retardant test piece (6.5 x 3 x 15 mm) was measured and found to be 33.5. Example 9 Methylolated polyparahydroxystyrene (P content
4.5%, Cl content 2.45%, S content 5.41%), 100 parts of Epicote 828 and 400 parts of acetone.
It was uniformly dissolved at 80°C. Furthermore, after adding 1 part of BF ₃ /imidazole as a curing accelerator, the solvent was removed. This mixture was cast at 100℃ and 50℃ at 170℃.
Flame retardant test piece (6.5×
3 x 15 mm). When the limiting oxygen index (LOI) of this test piece was measured, it was 39.6, 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 (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 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 become phosphoric acid and do not become toxic gases, but bromides generate bromine (toxic gas), which is corrosive (pollution) and has a bad odor. Phosphorus compounds have slightly better compatibility with phenolic resins, and are also somewhat less likely to cause coloring.
Adhesion is also good. When a phosphorus compound and a halogen compound coexist, the total amount of the phosphorus compound and 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, it is possible to reduce the total amount of the phosphorus compound and the halogen compound added. The flame retardant effect can be expected.

[Brief explanation of the drawing]

Figure 1 is the product of Example 1, Figure 2 is the product of Example 2, Figure 3 is the product of Example 3, Figure 4 is the product of Example 4, and Figure 5 is the product of Example 5. This is an external absorption curve. 〓〓〓〓

Claims (1)

[Claims] 1 General formula (A) (In the formula, R is hydrogen, an alkyl group having 1 to 3 carbon atoms, and Y is oxygen or sulfur) is 10 to 100
Mol%, general formula (B) (In the formula, R ¹ is an alkyl group having 1 to 3 carbon atoms) is 0 to 15 mol%, general formula (C) is 0 to 50 mol% and general formula (D) A hydroxystyrene polymer containing methyl phosphate or its ester group with a degree of polymerization of 10 to 100 and having a structure in which substantially the remaining mole % is the main structural unit, and each of the above structural units is randomly linked through the main chain. . 2 R is hydrogen, Y is oxygen, general formula (B)
The polymer according to claim 1, in which the structural unit represented by is not present. 3. The polymer according to claim 1, wherein R is an alkyl group having 1 to 3 carbon atoms, Y is oxygen, and there is no structural unit represented by general formula (B). 4. A polymer according to claim 1, wherein R is the same as R ¹ and Y is sulfur. 5 Methylolated hydroxystyrene polymer with polymerization degree of 10 to 100 and general formula (In the formula, E is chlorine, hydroxyl group, or has 1 to 3 carbon atoms.)
an alkoxyl group, Y is oxygen or sulfur, and R is hydrogen or an alkyl group having 1 to 3 carbon atoms), optionally in the coexistence of P ₂ O ₅ General formula (A) consisting of reacting at a reaction temperature between 0°C and 200°C in the presence of a cyclic ether or an aprotic polar solvent. (in the formula, R and Y are the same as above) is 10 to
100 mol%, general formula (B) (In the formula, R ¹ is an alkyl group having 1 to 3 carbon atoms) is 0 to 15 mol%, general formula (C) is 0 to 50 mol% and general formula (D) A hydroxystyrene polymer containing methyl phosphate or its ester group with a degree of polymerization of 10 to 100 and having a structure in which the remaining mol% is substantially the main structural unit, and each of the above structural units is randomly bonded through the main chain. manufacturing method. 6. The manufacturing method according to claim 5, wherein E is a hydroxyl group, Y is oxygen, and R is hydrogen, P ₂ O ₅ is used, and there is no structural unit represented by the general formula (B). 7 E is chlorine, Y is oxygen, and R has 1 to 3 carbon atoms
The method according to claim 5, wherein the alkyl group is P ₂ O ₅ and the structural unit represented by the general formula (B) is not present. 8 E is chlorine, Y is sulfur, and R has 1 to 3 carbon atoms
Claim ₅ which is _an alkyl group of
The manufacturing method described in section. 9 E is an alkoxyl group having 1 to 3 carbon atoms, Y is oxygen, and R is an alkyl group having 1 to 3 carbon atoms,
The manufacturing method according to claim 5, in which P ₂ O ₅ is not used and the structural unit represented by general formula (B) is not present.