JPS6135206B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel hydroxystyrene polymer containing pentavalent phosphorus and a method for producing the same, and more particularly, it relates to a novel hydroxystyrene polymer containing pentavalent phosphorus and a method for producing the same. (In the formula, Y is oxygen or sulfur, t is 0 or 1,
R ¹ is an alkyl group having 1 to 3 carbon atoms, a phenyl group, or hydrogen) is 20 to 100 mol%, general formula (B) is 0 to 10 mol% and general formula (C) (In the formula, M is hydrogen or an alkali metal) is a phosphoric acid group having a polymerization degree of 10 to 100 and having a structure in which substantially the remaining mol% is the main structural unit, and the above structural units are randomly bonded in the main chain. , a hydroxystyrene polymer containing a monothiophosphoric acid group or an ester group thereof, and three methods for producing the polymer. 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 considered impossible to introduce phosphate groups. was. The present inventors have continued research on the development of hydroxystyrene-based polymers for a long period of time, and as part of that research, they have made earnest efforts to develop phosphorus-containing hydroxystyrene-based polymers as part of research on the use of hydroxystyrene-based 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. The feature of the present invention is to provide a novel polymer in which a pentavalent phosphorus atom is bonded directly or via a methylene group to the oxygen of the hydroxyl group of the phenol nucleus in a hydroxystyrene polymer, and the remaining phosphorus atoms are Two of the four bonds are bonded to an oxygen atom or a sulfur atom via a double bond, and the other two bonds are bonded via oxygen to an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a phenyl group. Combined with hydrogen. Book〓〓〓〓
According to the invention, it is possible to easily obtain a hydroxystyrene polymer containing pentavalent phosphorus which is soluble or gelled by crosslinking as desired, and furthermore, it is possible to control the rate of phosphorus introduction within a wide range. . Furthermore, in the reaction of the present invention, polymer chain cleavage or cross-linking hardly occurs, so depending on the selection of starting materials, it is possible to easily obtain target products with molecular weights ranging from oligomers to about 20,000. can. The present invention also provides a facile method for producing new polymers with the above characteristics. The unit structure of the hydroxystyrene polymer serving as the backbone of the polymer of the present invention may be ortho-, meta- or para-hydroxystyrene, or a mixture of these in any proportion. In the present invention, hydroxystyrene polymer refers to a hydroxystyrene homopolymer and a hydroxystyrene polymer produced by producing an acetoxystyrene polymer instead of hydroxystyrene and hydrolyzing it. do. The method for synthesizing the hydroxystyrene polymer, which is the starting material for the first method of producing the pentavalent phosphorus-containing hydroxystyrene polymer of the present invention, is known, and the method for producing the alkali metal salt described above is also known. . The phosphorus-containing hydroxystyrene polymer of the present invention is prepared from the hydroxystyrene polymer or its alkali metal salt by the general formula (In the formula, t is 0 or 1, Y is oxygen or sulfur,
is chlorine or bromine and R ² is an alkyl group having 1 to 3 carbon atoms or a phenyl group). It is. For ease of understanding, only the parts involved in the reaction are shown. (In the formula, M ^, t, ^Y , It can be easily obtained by further hydrolysis. To explain in detail, first of all, the hydroxystyrene polymer or its alkali metal salt is When the compound shown in is applied, a deMX reaction occurs and the oxygen of the hydroxyl group of the phenol nucleus in the hydroxystyrene polymer is

[Formula] A polymer to which groups are bonded is obtained. At this time, the solvent usually used is an alkaline aqueous solution, an ether such as tetrahydrofuran or dioxane, or an aprotic polar solvent such as dimethyl sulfoxide or dimethyl formamide. When an alkaline aqueous solution is used as a solvent, some hydrolysis of the ester part of the phosphoric acid ester occurs, but this rate is lower than that of the deMX reaction, so it usually does not pose any problem, but if you want to avoid hydrolysis as much as possible It is generally preferred to use aprotic polar solvents. Phosphorus compounds used in this reaction include dimethyl chlorophosphate, dimethyl bromophosphate, dimethyl chlorothiophosphate, dimethyl bromothiophosphate, diethyl chlorophosphate, diethyl bromophosphate, diethyl chlorothiophosphate, diethyl bromothiophosphate, dipropyl chlorophosphate, dipropyl chlorothiophosphate, and chlorothiophosphate. Dimethyl methyl phosphate, diethyl chloromethyl phosphate, dipropyl chloromethyl phosphate, etc. are used. Note that if chlorophosphoric acid, chlorothiophosphoric acid, chloromethylphosphoric acid, or chloromethylthiophosphoric acid is used instead of diester, crosslinking tends to occur during the reaction, which is not preferable. 〓〓〓〓
In the reaction, 1/2 to 10 moles, preferably 1 to 2 moles of the above phosphorus compound are used per mole of hydroxystyrene units in the hydroxystyrene polymer. Of course, the actual amount of the phosphorus compound used is adjusted depending on the desired introduction rate of substituents. The reaction temperature for carrying out this reaction is in the range of 0 to 200°C, and preferably in the range of room temperature to 100°C. The reaction proceeds rapidly, in most cases being fully complete within 48 hours, and generally depending on the reaction temperature.
A reaction time of up to 24 hours is sufficient. As mentioned above, although the reaction rate is sufficiently fast, a catalytic amount of a tertiary amine such as pyridine, trimethylamine, or triethylamine can also be added as a reaction catalyst. At the end of the reaction, if the reaction product precipitates from the reaction solution, it is separated, and if it is dissolved, the solvent is removed or the product is precipitated using a non-solvent, such as water, and separated. is common. The separated polymer is a white to brown solid material.
When a polymer in which R ² is replaced by hydrogen is desired, it is necessary to hydrolyze the polymer produced as described above. 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.
As the solvent, water or a mixed solvent such as dioxane-water, tetrahydrofuran-water, methanol-water is 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 catalytic amount, and a large amount of acid such as an acetic acid-water mixed solvent can also be used. The temperature of the hydrolysis reaction is generally in the range of 0 to 150°C, and is usually carried out at a temperature in the range of 50 to 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. The second method for producing the target polymer of the present invention is by hydrolysis or solvolysis of a hydroxystyrene polymer containing dichloro or dibromophosphate groups. Since the combination is also a new substance, we will explain this synthesis method first. The dichloro- or dibromophosphate group-containing hydroxystyrene polymer is synthesized from the hydroxystyrene polymer used in the first method or its alkali metal salt by a reaction represented by the following formula. For ease of understanding, only the parts involved in the reaction are shown. (In the formula, _M and A hydroxystyrene polymer containing phosphate groups is obtained. At this time, ethers such as tetrahydrofuran and dioxane, aprotic polar solvents such as acetone, dimethyl sulfoxide, and dimethyl formamide are used as solvents, and the phosphorus oxyhalide used in this reaction is phosphorus oxychloride or oxybromide. I can give you phosphorus. When carrying out the reaction of the present invention, the above-mentioned phosphorus oxyhalide is used at a ratio of 1/2 to 20 moles per mole of hydroxystyrene units in the hydroxystyrene polymer, preferably in the range of 1 to 5 moles. . The actual amount of phosphorus oxyhalide used is adjusted depending on the desired introduction rate of substituents, but in general, if the amount of phosphorus oxyhalide used is small, phosphorus oxyhalide acts as a crosslinking agent and The solubility of hydroxystyrene polymers having dichloro or dibromophosphate groups tends to decrease, and if a soluble target product is desired, use 1 mole or more of phosphorus oxyhalide per mole of hydroxystyrene unit. is desirable. The temperature for this reaction is 0 to 200℃
is usually selected, preferably from room temperature to 100
A range of degrees Celsius is used. In most cases, the reaction time is
A reaction time of 48 hours or less is sufficient, and although it depends on the reaction temperature used, a reaction time of less than 12 hours is generally sufficient to achieve the purpose. However, even if a long reaction time is used, no adverse effects such as the occurrence of side reactions are observed. In order to accelerate the reaction, a catalytic amount of tertiary amine, such as pyridine,
Although trimethylamine, triethylamine, etc. can be added to the reaction system as a catalyst, this reaction proceeds at a sufficient speed even without a catalyst. At the end of the reaction, if the reaction product precipitates from the reaction solution, separate it, and if it dissolves, remove the solvent or add it to a non-solvent, such as water, benzene, n-heptane. Usually, it is precipitated and separated using, for example, In addition, when the product is precipitated using water, it is inevitable that the product undergoes partial hydrolysis, so if it is desired to avoid hydrolysis, it is preferable to use a non-solvent other than water. Hydroxystyrenic polymers containing isolated dichloro or dibromophosphate groups are obtained as white to brown solid materials. The hydroxystyrene polymer containing a phosphate group or a phosphate ester group, which is the target product of the present invention, can be obtained by hydrating or adding a hydroxystyrene polymer containing a dichloro or dibromophosphate group obtained in this way. It can be produced by solvent decomposition. At this time, water, acidic or alkaline aqueous solutions, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and dioxane, and aprotic polar solvents such as dimethyl sulfoxide and dimethyl formamide are used as solvents, and as a hydrolysis or solvolysis agent. For example, water, alcohols such as methanol, ethanol, and propanol, phenol, and sodium salts of phenols are used. In the reaction, the hydrolyzing agent or solvolyzing agent is used in an amount of 2 moles or more per mole of dichloro or dibromophosphate group contained in the polymer, and the reaction temperature is generally in the range of 0 to 200°C, preferably A range of 0 to 100°C is used. The reaction time is generally within 48 hours, and usually within 24 hours, depending on the reaction temperature. The method for separating and recovering the product is the same as that described in the first production method. In addition, when using a hydroxystyrene polymer that does not contain dibromophosphate groups, unless complete hydration or solvolysis is performed, the product will contain bromine instead of chlorine, causing no actual damage in terms of use. This is completely unacceptable, but does not meet the definition of the object of the present invention. The third method for producing the target polymer of the present invention is
This is a method in which phosphorous acid or a phosphorous acid diesterized hydroxystyrene polymer is treated with an oxidizing agent. Since the starting material of this method, phosphorous acid or phosphorous acid diesterized hydroxystyrene polymer itself, is a new material, the synthesis method thereof will be explained below. First, a hydroxystyrene polymer or its alkali metal salt is reacted with phosphorus trihalide to produce a dihalogenophosphorous hydroxystyrene polymer, which is then mixed with water, an alcohol having 1 to 3 carbon atoms, a phenol, or its alkali metal salt. The starting material, phosphorous acid or phosphorous acid diesterized hydroxystyrene polymer, can be obtained by hydrolysis or solvolysis using . More specifically, the method for producing a trivalent phosphorus-containing hydroxystyrene polymer from a hydroxystyrene polymer or its alkali metal salt using phosphorus trihalide is as follows. For ease of understanding, only the parts involved in the reaction are shown. (In the formula, M is the same as above, and X' is chlorine, bromine or iodine.) Specifically, phosphorus trihalide _PX'3 is allowed to act on a hydroxystyrene polymer or its alkali metal salt. A trivalent phosphorus-containing hydroxystyrene polymer is produced by causing a deMX′ reaction.
In this case, as a solvent, ethers such as tetrahydrofuran and dioxane, dimethylformamide, hexamethylphosphoric triamide,
An aprotic polar solvent such as acetone is used. The phosphorus compound used in the reaction is phosphorus trichloride, phosphorus tribromide, or phosphorus triiodide, and the amount used is the above-mentioned phosphorus trihalide per mole of hydroxystyrene unit in the hydroxystyrene polymer. It is used in a proportion of 1/2 to 20 moles, preferably 1 to 5 moles. Of course, the actual amount of phosphorus trihalide used will be adjusted depending on the desired introduction rate of substituents, but in general, if the amount of phosphorus trihalide used is small, the amount of phosphorus trihalide will be reduced. The solubility of the product trivalent phosphorus-containing hydroxystyrene polymer acting as a crosslinking agent tends to decrease, and if it is desired to produce a soluble target product, the 1 phosphorus halide
It is desirable to use mol or more. The temperature for carrying out this reaction is usually selected to be in the range of 0 to 200°C, preferably in the range of room temperature to 100°C. In most cases, a reaction time of 48 hours or less is sufficient, and although it depends on the reaction temperature used, generally a reaction time of 12 hours or less is sufficient to achieve the purpose. However, even if a long reaction time is used, no adverse effects such as the occurrence of side reactions are observed. During this reaction, a catalytic amount of tertiary amine such as pyridine, trimethylamine, triethylamine, etc. can be added to the reaction system as a catalyst to promote the reaction, but the reaction proceeds at a sufficient rate even without a catalyst. At the end of the reaction, if the reaction product precipitates from the reaction solution, separate it, and if it is dissolved, remove the solvent or add a non-solvent, such as water, benzene, n-heptane. Usually, it is precipitated and separated using, for example, Next, in order to produce a hydroxystyrene polymer containing a -P(OR ¹ ) ₂ group (wherein R ¹ is hydrogen, an alkyl group having 1 to 3 carbon atoms, or a phenyl group), the above -PX' ₂ group Hydrolyze or solvolyze the hydroxystyrene polymer containing. Hydrolysis or solvolysis agents include water, methanol, ethanol,
n-propanol, i-propanol or phenol or an alkali metal salt thereof is used. When using phenol, the reaction is faster when an alkali metal salt is used. As the reaction solvent, water, an acidic or alkaline aqueous solution, a lower alcohol, or an aprotic polar solvent such as tetrahydrofuran, dioxane, dimethylformamide, or hexamethylphosphoric triamide can be used. As is clear from the above, since water, alcohol, etc. act not only as decomposing agents but also as reaction solvents, there is generally no need to add a reaction solvent separately in this case. In this reaction, the hydrolyzing agent or solvolytic agent is

[Formula] Hydroxystyrene containing group in polymers

[Formula] 2 or more moles per mole of the group are usually used. Reaction temperature is 0~200℃
and preferably a range of 0 to 100°C. The reaction generally proceeds quickly;
The reaction is usually complete within 48 hours, and more usually reaction within 24 hours is sufficient. At the end of the reaction, if the reaction product is suspended in the reaction solution, separate it, or if it is dissolved, remove the solvent or precipitate it with a non-solvent and separate it. is common. Furthermore, prior to this hydration or solvolysis,

It is optional whether or not to isolate the hydroxystyrene polymer containing the group [Formula], but generally the decomposition reaction is carried out without isolation. When an oxidizing agent is applied to the thus obtained phosphorous acid diesterized hydroxystyrene polymer, the phosphoric acid or phosphoric acid diesterized hydroxystyrene polymer, which is the object of the present invention, can be easily oxidized. A union is obtained. For ease of understanding, only the parts involved in the reaction are shown. 〓〓〓〓
(In the formula, R ¹ is the same as above.) As the oxidizing agent, a nitric acid aqueous solution or a hydrogen peroxide solution is used. The amount of oxidizing agent to be used is theoretically 1 gram atom of oxygen per mole of phosphorous acid or phosphorous diester group in the raw material phosphorous acid or phosphorous diester-containing hydroxystyrene polymer, but in practice An excess of oxidizing agent is used.
Moreover, at this time, water is employed as the reaction solvent.
The reaction temperature ranges from 0 to 150°C, preferably from room temperature to 100°C, and the reaction time is usually 48°C.
Within hours will be accepted. After completion of the oxidation reaction, if the product is insoluble, it is separated as is; if it is dissolved, it is separated by removing the solvent or precipitating it with a nonsolvent. The product is a pale yellow to brown colored polymer. In the third method described above, not only phosphorus trichloride but also phosphorus tribromide and phosphorus triiodide can be used in the production of raw materials during the subsequent hydrolysis or solvolysis and during the subsequent oxidation step. This is because the halogen initially introduced disappears almost completely. As the hydroxystyrene polymer which is the starting material or basic material of the present invention, a hydroxystyrene polymer or an alkali metal salt thereof is used. Although there are no particular restrictions on the substitution position of the hydroxyl group in hydroxystyrene, rose-substituted ones are preferred, followed by meta-substituted ones, and although it is possible to use ortho-substituted ones, no particular benefit is recognized by doing so. . The molecular weight of the product of the present invention is mostly determined by the molecular weight of the hydroxystyrene polymer or its alkali metal salt or alkaline earth metal salt used, and during the phosphorus introduction reaction, the conditions that avoid the above-mentioned crosslinking reaction are applied. If selected, large variations in the degree of polymerization usually do not occur. Therefore, the molecular weight of the product is
The molecular weight can be changed from an oligomer of about 1,000 to one having a molecular weight of about 20,000 depending on the purpose. Some typical examples of the polymers obtained in the present invention are diethyl phosphorylated polyparahydroxystyrene, diethyl monothiophosphorylated polyparahydroxystyrene, diethyl phosphorylated methylated polyparahydroxystyrene, and phosphomethylated polyparahydroxystyrene. Examples include polyparahydroxystyrene, dimethyl phosphorylated polyparahydroxystyrene, and the like. 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 other synthetic resins in the form of chips or powder, and molding methods include injection molding, extrusion molding, compression molding, and rotary molding. Any suitable means may be adopted. 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 scope of the present invention. Example 1 In a 300 ml four-necked flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser, etc., 6 g of polyparahydroxystyrene (molecular weight 5530) prepared by thermal polymerization of parahydroxystyrene was added to 100 ml of paradioxane. When the solution was added and dissolved uniformly, it became a brownish transparent solution. Add diethyl chlorphosphate to this solution.

[Formula] 26g was added dropwise from the dropping funnel at room temperature with stirring. After the dripping is finished,
When the temperature was increased to 90°C, it became a dark brown transparent solution. This was allowed to react under stirring for 5 hours while maintaining the same temperature. After the reaction is complete, the solvent is removed from this dark brown permeable solution to produce a brown solid.
6.86g was obtained. As a result of elemental analysis, this polymer was found to be P
The content is 11% and the Cl content is 0.46%, and as a result of infrared absorption (IR) analysis and nuclear magnetic resonance (NMR) analysis,
It was confirmed that it was diethyl phosphate polyparahydroxystyrene. As a result of IR analysis, absorption of νP-O-(C ₂ H ₅ ) at 1020 cm ^-1 and absorption of νP-O- aromatic nucleus at 970 cm ^-1 was observed, and as a result of NMR analysis, absorption of νP-O-(C 2 H 5 ) in 10% heavy methanol at 34°C was observed. δ=1.3ppm (P-O-CH ₂
CH ₃ ) and δ=4.02 ppm (P—O— CH ₂ CH ₃ ) peaks were observed. The introduction rate of diethyl phosphate groups into the product was 0.83 per hydroxystyrene unit of the polymer. The IR and NMR graphs of the product are shown in Figures 1 and 2, respectively. still,
The chlorine contained in the produced polymer is thought to be due to the substitution of a portion of the ethoxy groups in the phosphoric acid ester groups with chlorine. Example 2 Diethyl chlorothiophosphate was used instead of diethyl chlorophosphate in Example 1.

Monothiophosphoric acid esterification of polyparahydroxystyrene was carried out in the same manner as in Example 1 except that 25 g of the formula was used. When the reaction was carried out at a temperature of 95°C for 5 hours, a dark brown transparent solution was obtained. By pouring this solution into a large amount of water, a auburn powdery solid is formed.
6.5g was obtained. As a result of elemental analysis, this polymer has a P content of 4.5%, a Cl content of 4.68%, and a S content of 5.01%, and as a result of IR and NMR analysis, it was confirmed to be diethyl monothiophosphate polyparahydroxystyrene. It was done. As a result of IR analysis, ν-CH ₂ -O- at 1100cm ^-1
(P), 1015cm ^-1 νP-O-(CH ₂ ), 973cm
^-1 to νP-O-aromatic nucleus and 660cm ^-1 to νP=
Absorption of S was observed, and as a result of NMR analysis, 10
δ=1.32ppm at 34℃ in % heavy methanol
(P-O-CH ₂ CH ₃ ) and δ=4.2ppm (P-O-
A peak of CH ₂ CH ₃ ) was observed. Product IR and
NMR graphs are shown in Figures 3 and 4, respectively. Example 3 Diethyl chloromethyl phosphate instead of diethyl chlorophosphate in Example 1

Polyparahydroxystyrene was methylated with diethyl phosphate using the formula. That is, in the same flask as used in Example 1, 6 g of polyparahydroxystyrene (molecular weight 5500) obtained by thermal polymerization and dimethylformamide were placed.
When I added 100ml of the solution and dissolved it uniformly, it became a brown transparent solution. To this solution were added 28 g of diethyl chloromethyl phosphate, 6.5 g of anhydrous potassium carbonate, and 0.01 g of potassium iodide. After the addition was complete, the temperature was raised to 90°C, resulting in a dark brown transparent solution. This was reacted at that temperature for 5 hours with stirring, and after the reaction was completed,
By pouring this solution into a large amount of water, 7.01 g of an amber colored powder solid was obtained. As a result of elemental analysis, this polymer has a P content of 9.5% and a Cl content of 0.41%.
As a result of IR and NMR analysis, it was confirmed to be diethyl phosphate methylated polyparahydroxystyrene. As a result of IR analysis, νP— ^O— (CH ₂
-) and absorption of νP-CH ₂ was observed at 690 cm ^-1 , and NMR results showed that in 10% heavy methanol,
δ=1.3ppm (P-O-CH ₂ -
CH ₃ ) δ = 3.65 ppm (P - CH ₂ -) and δ =
A peak of 4.1 ppm (P—O— CH ₂ —CH ₃ ) was observed. The introduction rate of methyl diethyl phosphate groups was 0.68 per hydroxystyrene unit. of the product
IR and NMR graphs are shown in Figures 5 and 6, respectively. Example 4 4.4 g of diethyl phosphate methylated polyparahydroxystyrene obtained in Example 3 was suspended in a mixed solvent of 20 ml of methanol and 80 ml of water, 1 ml of acetic acid was added, and the mixture was stirred at 80°C for 5 hours. reacted to. After the reaction was completed, 3.2 g of a pale amber solid was obtained by removing the solvent from the amber suspension. As a result of elemental analysis, this polymer has a P content of 8.4%, and as a result of IR and NMR analysis, it is a polymer in which the methyl diethyl phosphate groups in the raw material are almost completely hydrolyzed to methyl phosphate groups. was confirmed.
Note that the rate of introduction of methyl phosphate groups into the product depends on the polymerization rate.
The number was 0.44 per hydroxystyrene unit in the body. Example 5 Diphenyl chlorophosphate [bp 222°C (16 mmHg),
bp160-162℃ (0.15mmHg), ^n23D _1.6068 ]

[Formula] The reaction was carried out in the same manner as in Example 1 except that 40 g of paradioxane and 300 ml of paradioxane were used. 13.1 g of a brown solid was obtained as a product. As a result of elemental analysis, this polymer has a P content of 7.8% and a Cl content of 0.41%.
It was %. Further, as a result of IR and NMR analysis, it was confirmed to be diphenylphosphate polyparahydroxystyrene. The introduction rate of diphenyl phosphate groups into the polymer was 0.73 per hydroxystyrene unit in the polymer. Example 6 Polyparahydroxystyrene (molecular weight
When 6 g of 5530) and 100 ml of paradioxane were added and uniformly dissolved, a brownish transparent solution was obtained. To this solution, 23 g of phosphorus oxychloride (POCl ₃ ) was added drop by drop from a dropping roll at room temperature while stirring.
After the dropwise addition was completed, the temperature was raised to 85°C, and a dark brown transparent solution was formed. The reaction was carried out under stirring for 5 hours while maintaining the temperature at 85°C. After the reaction was completed, the resulting dark brown, slightly opaque solution was poured into a large amount of n-pentane to obtain 10.6 g of a brown solid. The elemental analysis result of this polymer shows that the P content is 12.4.
%, and the Cl content was 12.6%. Furthermore, based on the results of infrared absorption (IR) analysis, nuclear magnetic resonance (NMR) analysis, and the above elemental analysis, this product is a dichlorophosphate with 0.90 dichlorophosphate groups per hydroxystyrene unit in the polymer. It was confirmed that it was group-containing polyparahydroxystyrene. 4.5 g of the polymer thus obtained was placed in the same flask as used above, and 10 ml of paradioxane was added to uniformly dissolve it, resulting in a brown transparent solution. 10 ml of methanol and a few drops of pyridine were added to this solution, and the mixture was stirred and reacted at 60°C for 10 hours, yielding a dark brown transparent solution. After the reaction was completed, this solution was poured into a large amount of water to obtain 4.0 g of a brownish powdery solid. Elemental analysis of this polymer revealed that the P content was 10.1% and the Cl content was 10.1%.
It was found to be 1.2%, and this and IR and NMR
From the analysis results, it was confirmed that the dichlorophosphated polyparahydroxystyrene was solvolyzed dimethylphosphated polyparahydroxystyrene. The introduction rate of dimethyl phosphate groups was 0.60 per hydroxystyrene unit. The IR curve of the product is shown in FIG. Example 7 In a 300 ml four-necked flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser, etc., 6 g of polyparahydroxystyrene (molecular weight 5530) obtained by thermal polymerization of parahydroxystyrene and 100 ml of paradioxane. When the solution was added and dissolved uniformly, a brownish-brown transparent solution was obtained. When 20.6 g of phosphorus trichloride was added to this solution under stirring at room temperature, white smoke was immediately generated and the solution turned into a yellow-orange transparent solution. After dropping, lower the temperature to 85℃
The mixture was raised to a temperature of 100.degree. C. and allowed to react under stirring for 3 hours, resulting in a yellowish white opaque solution. The reaction was terminated at this point, and 100 ml of methanol was added to this solution and the reaction was stirred, turning into a yellow transparent solution. After further reaction at 80°C for 5 hours, the mixture turned into a dark yellow, slightly opaque solution. When this solution was poured into a large amount of n-hexane, 7.7 g of an orange solid was obtained. As a result of elemental analysis, this polymer has a P content of 7.9% and a Cl content of 7.9%.
0.46%, and as a result of IR and NMR analysis, it was confirmed that it was dimethylphosphite polyparahydroxystyrene. The introduction rate of dimethyl phosphorous acid groups was 0.4 per hydroxystyrene unit. 3.1 g of this polymer was placed in the same flask as used above, and 100 ml of acetone was added to uniformly dissolve it, resulting in a yellow transparent solution. 30% on this
When 20 ml of hydrogen peroxide solution was added thereto and the mixture was stirred and reacted at 56°C for 4 hours, a brown, slightly opaque solution was obtained.
After the reaction was completed, the solvent was removed from this solution, the solution was redissolved in 50 ml of acetone, and the solution was poured into a large amount of water to obtain 30 g of a brownish red solid. As a result of elemental analysis, this polymer has a P content of
7.3%, and the result of IR and NMR analysis is dimethyl〓〓〓〓
It was confirmed that it was phosphated polyparahydroxystyrene, and the introduction rate of dimethyl phosphate groups was found to be 0.38 per hydroxystyrene unit. Example 8 Diethyl phosphate polyparahydroxystyrene obtained in Example 1 (P content 11%, Cl
Add 85 parts of polystyrene (dencastyrol) and 5 parts of antimony trioxide to 10 parts of hydroxystyrene (containing 0.46%, introduction rate of diethyl phosphate group: 0.83 per hydroxystyrene unit), mix well, and heat at 180°C.
It was extruded into pellets. The molding material thus obtained was injection molded at a temperature of 220-230°C and a residence time of 15 minutes. Obtained flame retardant test piece (6.5 x 3 x 15
mm), the limiting oxygen index (LOI) (JISK-
7201) was measured.
33.7, indicating excellent flame retardancy. Example 9 Diethylmonothiophosphate polyparahydroxystyrene obtained in Example 2 (P content
4.5%, Cl content 4.68%, S content 5.01%), 100 parts of polystyrene (dencastyrol) and 5 parts of antimony trioxide were added, mixed well, and extruded at 180°C to form pellets. Thereafter, the limiting oxygen index (LOI) was measured in the same manner as in Example 8 and found to be 40.3, indicating excellent flame retardancy. Example 10 Methylated polyparahydroxystyrene obtained in Example 4 (P content: 8.4%, introduction rate of methyl phosphate group: 0.44 per hydroxystyrene unit)
) 100 parts to 50 parts Epicote 828 and acetone 400
of the mixture was added and uniformly dissolved at 80°C. Furthermore, after adding 1 part of BF ₃ and morpholine as a curing accelerator,
Solvent was removed. This mixture was cast at 120℃,
A flame retardant test piece (6.5 x 3 x 15 mm) was prepared by curing at 170°C for 5 hours. The limiting oxygen index (LOI) was measured for this test piece.
41.2, indicating excellent flame retardancy. Example 11 Dimethyl phosphate polyparahydroxystyrene obtained in Example 6 (P content 10.1%, Cl
The content is 1.2%, the introduction rate of dimethyl phosphate groups is 0.60 per hydroxystyrene unit) 10 parts,
When 85 parts of polystyrene (dencastyrol) and 5 parts of antimony trioxide were added and the limiting oxygen index (LOI) was measured in the same manner as in Example 8, it was 32.1, 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 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 reaction between cellulose and air flame 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 reactions. Br ^* or R ^* is produced and the chain reaction is stopped. (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 contain bromine.
It generates poisonous gas (poisonous gas) and is corrosive (pollution), which is bad 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. 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, the combined temperature range of each can be reduced. It can be expected to have a flame retardant effect.

[Brief explanation of the drawing]

Figure 1 is the IR curve of the product of Example 1, Figure 2 is its NMR curve, and Figure 3 is the product of Example 2.
4 is the NMR curve, FIG. 5 is the IR curve of the product of Example 3, FIG. 6 is the NMR curve, and FIG. 7 is the IR curve of the product of Example 6. 〓〓〓〓

Claims (1)

[Claims] 1 General formula (A) (In the formula, Y is oxygen or sulfur, t is 0 or 1,
R ¹ is an alkyl group having 1 to 3 carbon atoms, a phenyl group, or hydrogen) is 20 to 100 mol%, general formula (B) is 0 to 10 mol% and general formula (C) Phosphoric acid with a degree of polymerization of 10 to 100 and having a structure in which (M in the formula is hydrogen or an alkali metal) constitutes substantially the remaining mol% as the main structural unit, and each of the above structural units is randomly bonded in the main chain. A hydroxystyrenic polymer containing a monothiophosphoric acid group or an ester group thereof. 2 t is 1 and the content of the structural unit represented by the general formula (B) is 0 mol %, Claim 1
Polymers described in Section. 3 t is 0 and the content of the structural unit represented by the general formula (B) is 0 mol %, Claim 1
Polymers described in Section. 4. The polymer according to claim 1, wherein t is 0 and Y is oxygen. 5 Hydroxystyrene polymer with a degree of polymerization of 10 to 100 or its alkali metal salt and general formula (In the formula, t is 0 or 1, Y is oxygen or sulfur,
X is chlorine or bromine and ^R2 is an alkyl group having 1 to 3 carbon atoms or a phenyl group) with a halogenated phosphoric acid diester or halogenated monothiophosphoric acid diester in the presence or absence of a tertiary amine catalyst. , a general formula (A) consisting of reacting at a reaction temperature between 0 and 200°C and then hydrolyzing using an acid catalyst if necessary.
(in the formula, t and Y are the same as above, R ¹ is an alkyl group having 1 to 3 carbon atoms, a phenyl group, or hydrogen) is 20 to 100 mol% and the general formula (C) Phosphoric acid with a degree of polymerization of 10 to 100 and having a structure in which (M in the formula is hydrogen or an alkali metal) constitutes substantially the remaining mol% as the main structural unit, and each of the above structural units is randomly bonded in the main chain. A method for producing a hydroxystyrenic polymer containing a monothiophosphoric acid group, a monothiophosphoric acid group, or an ester group thereof. 6. The manufacturing method according to claim 5, wherein the reaction temperature is from room temperature to 100°C, and the reaction is carried out in the presence of an alkaline aqueous solution or an aprotic polar solvent. 7. The manufacturing method according to claim 6, wherein R ¹ is R ² and no hydrolysis operation is performed. 8. The manufacturing method according to claim 6, wherein R ¹ is hydrogen and a hydrolysis operation is performed. 9 halogenated phosphoric acid diester or halogenated monothiophosphoric acid diester per mole of hydroxylene unit in the hydroxystyrene polymer.
The manufacturing method according to claim 7 or 8, in which 2 to 10 mol is used. 10 A dichloro or dibromophosphate group-containing hydroxystyrene polymer with a degree of polymerization of 10 to 100 is hydrolyzed with water, an alcohol having 1 to 3 carbon atoms, a phenol or an alkali metal salt thereof, or a solvolysis agent between 0 and 200°C. General formula (A)′ which is hydrolyzed or solvolyzed at a reaction temperature of (In the formula, R ¹ is an alkyl group having 1 to 3 carbon atoms, a phenyl group, or hydrogen) is 20 to 100 mol%, general formula (B) is 0 to 10 mol% and general formula (C) Phosphoric acid with a degree of polymerization of 10 to 100 and having a structure in which (M in the formula is hydrogen or an alkali metal) constitutes substantially the remaining mol% as the main structural unit, and each of the above structural units is randomly bonded in the main chain. A method for producing a hydroxystyrene polymer containing a group or an ester group thereof. 11. Claim 10: The hydrolysis or solvolysis reaction is carried out using the hydrolysis or solvolysis agent itself, an acidic or alkaline aqueous solution, or an aprotic polar solvent as a solvent, and at a reaction temperature of 0 to 100°C. The manufacturing method described in section. 12. The production method according to claim 11, in which 2 or more moles of the hydrating or solvolytic agent are used per mole of dichloro or dibromophosphate group in the hydroxystyrene polymer containing dichloro or dibromophosphate group. 13 Phosphous acid or phosphorous acid diesterized hydroxystyrene polymer with a degree of polymerization of 10 to 100 is oxidized using a nitric acid aqueous solution or a hydrogen peroxide solution as an oxidizing agent.
General formula (A)′ consisting of oxidation at a reaction temperature between 150°C 〓〓〓〓
(in the formula, R ¹ is an alkyl group having 1 to 3 carbon atoms, a phenyl group, or hydrogen) is 20 to 100 mol% and the general formula (C) Phosphoric acid with a degree of polymerization of 10 to 100 and having a structure in which (M in the formula is hydrogen or an alkali metal) constitutes substantially the remaining mol% as the main structural unit, and each of the above structural units is randomly bonded in the main chain. A method for producing a hydroxystyrene polymer containing a group or an ester group thereof. 14. The manufacturing method according to claim 13, wherein the oxidation temperature is from room temperature to 100°C, water is used as a reaction solvent, and an excess of the oxidizing agent is used.