Halogenated polymer and method for producing same

Abstract

The present invention addresses the problem of providing a halogenated polymer having excellent heat resistance and whiteness compared to known halogen-containing polymers. According to the technical scheme for solving the technical problem, the invention provides the halogenated polymer which contains bromide ions and is represented by the following general formula (1), and the content of the bromide ions is 1-2000ppm. # imgabs0 # (in the formula, R represents a C1-C6 alkylene group,-S-or-SO2-, and n represents a real number)

Description

Technical Field

[0001] The present invention relates to a halogenated polymer having high heat resistance which is used as a flame retardant or the like and a method for producing the same. Background Art

[0002] Flame retardants are widely known as additives that impart flame retardancy to resins by mixing with them. For example, compounds having multiple halogen atoms have been used as halogen flame retardants since ancient times. It should be noted that some low-molecular-weight halogen flame retardants (such as polybrominated biphenyls) are subject to restrictions under the RoHS Directive due to their harmfulness. Therefore, the recent development of halogen flame retardants has tended to shift to high-molecular-weight types.

[0003] As a high molecular weight brominated flame retardant, for example, a polymer having tetrabromobisphenol A as a monomer is known. As such a polymer, a polymer obtained by reacting tetrabromobisphenol A with 1,2-dihalogenated ethane in the presence of a base is known (Patent Documents 1 to 4).

[0004] Regarding the heat resistance of the high molecular weight brominated flame retardant, it is described that the decomposition temperature is about 180°C, but in order to improve the flame retardancy, a brominated flame retardant with a higher decomposition temperature is required. As a brominated flame retardant with a higher decomposition temperature, a halogen-containing polymer is reported in Patent Document 5.

[0005] Prior art literature Patent Literature Patent Document 1: Japanese Patent Application Laid-Open No. 51-117737 Patent Document 2: Japanese Patent Publication No. 56-8809 Patent Document 3: Japanese Patent Application Laid-Open No. 53-128656 Patent Document 4: Japanese Patent Publication No. 62-1973 Patent Document 5: Japanese Patent Application Publication No. 2019-77857 Summary of the invention

[0006] Technical problem to be solved by the invention The halogen-containing polymer of Patent Document 5 tends to be yellow or gray. When such a halogen-containing polymer is added to a resin as a flame retardant, there is a technical problem of color residue from the flame retardant. For example, resins used in white household appliances are required to be white, so the flame retardant added for flame retardancy is also required to be white.

[0007] An object of the present invention is to provide a halogenated polymer having excellent heat resistance and whiteness compared with the above-mentioned halogen-containing polymers.

[0008] Technical solutions for solving technical problems The present inventors have conducted intensive studies and have found that the following invention can solve the above-mentioned technical problems, thereby completing the present invention.

[0009] That is, the present invention has the following [1] to [7]. [1] A halogenated polymer comprising bromide ions and represented by the following general formula (1), wherein the bromide ion content is 1 to 2000 ppm.

[0011] [Chemistry 1]

[0012] (In the formula, R represents a C1-C6 alkylene group, -S- or -SO2-, and n represents a real number.) [2] The halogenated polymer according to [1], wherein the weight loss temperature of 3% by weight is 370° C. or higher at a heating rate of 10° C. / min. [3] The halogenated polymer according to [1] or [2], wherein the color difference D between the halogenated polymer and white (R:G:B=255:255:255) calculated based on the following formula (Euclidean distance) using a colorimeter is 33 or less.

[0014] [Chemistry 2] [4] The halogenated polymer according to any one of [1] to [3], wherein the average primary particle size (D50) is 1 to 50 μm. [5] The method for producing a halogenated polymer described in [1] above is characterized in that a mixture containing a compound represented by the following general formula (2), a compound represented by the following general formula (3), a base, a radical scavenger and a solvent is heated in the range of 110 to 150° C. while stirring.

[0017] [Chemistry 3]

[0018] (In the formula, R represents a C1-C6 alkylene group, -S- or -SO2-.) [Chemistry 4]

[0019] (In the formula, X and Y represent halogen atoms.) [6] The production method according to [5], wherein the radical scavenger is used in an amount of 0.001 to 10 parts by mass based on 100 parts by mass of the compound represented by the general formula (2). [7] The production method according to [5] or [6], wherein the radical scavenger is at least one selected from the group consisting of a phenolic radical scavenger, a quinone radical scavenger, a phosphite radical scavenger, an amine radical scavenger and a sulfur radical scavenger.

[0021] Effects of the Invention The halogenated polymer of the present invention has excellent heat resistance and whiteness. Therefore, the halogenated polymer of the present invention has the following effects: the operating temperature range in the processing operation of kneading or molding into resin is expanded, and the use of the halogenated polymer as a flame retardant for resins that attach importance to aesthetic appearance is expanded. DETAILED DESCRIPTION

[0022] Hereinafter, the present invention will be described in more detail.

[0023] One embodiment of the present invention relates to a halogenated polymer which contains bromide ions and is represented by the following general formula (1), wherein the content of the bromide ions is 1 to 2000 ppm.

[0024] [Chemistry 5]

[0025] (In the formula, R represents a C1-C6 alkylene group, -S- or -SO2-, and n represents a real number.) The terminal groups of the halogenated polymer of the present invention are usually 2-halogenated ethyl and / or phenolic hydroxyl groups derived from the raw material monomers, and these terminal groups can be blocked by low-reactive compounds. There is no particular limitation on the type of compound used in the blocking, and examples thereof include 4-bromophenol, 1,3,5-tribromophenol, pentabromophenol, benzyl chloride, halogenated methane or halogenated benzene. The halogenated polymer of the present invention includes a halogenated polymer whose terminal groups are blocked by the above-mentioned compounds.

[0026] The C1-C6 alkylene group represented by R is not particularly limited, and examples thereof include a methylene group, an ethylene group, a 2,2-propylene group, a 2,2-butylene group, a hexadienyl group, and a 1,1-cyclohexylene group.

[0027] R is preferably a 2,2-propylene group in terms of excellent heat resistance.

[0028] In the general formula (1), n ​​represents the average value of the number of repetitions of the repeating units of the halogenated polymer. In the present invention, n represents a real number.

[0029] This n is preferably a real number of 4 to 50, more preferably a real number of 5 to 30, and even more preferably a real number of 6 to 20, from the viewpoint of excellent heat resistance.

[0030] For example, when R is a 2,2-propylene group, the terminal structures are a 2-chloroethyl group and a phenolic hydroxyl group, and n is 11, the theoretical average molecular weight of the halogenated polymer of the present invention is 6368.

[0031] The halogenated polymer of the present invention is characterized in that it contains bromide ions as a component, and the content of the bromide ions is 1 to 2000 ppm based on the mass of the halogenated polymer (including the mass of the bromide ions).

[0032] The bromide ions are dispersed in the halogenated polymer in the form of bromide salts. Examples of the bromide salts include bromide salts formed from bromide ions and cations derived from a base generally used in the production of halogenated polymers, and more specifically, include lithium bromide, sodium bromide, potassium bromide, and the like.

[0033] The halogenated polymer of the present invention achieves the effects of improved heat resistance and improved whiteness by satisfying the constituent requirements. This is presumably because the content of bromide ions affects the heat resistance and whiteness.

[0034] The bromide ion content is preferably 1 to 1800 ppm, more preferably 10 to 1500 ppm, and even more preferably 20 to 1200 ppm based on the mass of the halogenated polymer (including the mass of the bromide ions), in order to improve the heat resistance and whiteness of the halogenated polymer and reduce the average primary particle size (D50).

[0035] The bromide ion content is not particularly limited, and can be measured, for example, by solvent extraction and ion chromatography. The measurement method is described in detail in the Examples.

[0036] The halogenated polymer of the present invention preferably has a high weight loss temperature in terms of excellent heat resistance. More specifically, in terms of excellent heat resistance, the 3 wt % weight loss temperature of the halogenated polymer of the present invention is preferably 370° C. or higher, more preferably 370° C. to 400° C. at a heating rate of 10° C. / min.

[0037] The 3 wt % weight loss temperature can be measured using a generally known thermal analysis device. The thermal analysis device is not particularly limited, and for example, a thermogravimetric-differential thermal (TG-DTA) simultaneous measurement device can be used.

[0038] It should be noted that in the present invention, the measurement of the thermogravimetric reduction temperature is carried out using ThermoPlus TG8120 manufactured by Rigaku Corporation, using an aluminum container, using a sample of about 10 mg, and carried out under the conditions of an air atmosphere and 10 °C / minute. Regarding the measurement, it is carried out based on the device manual and JIS K 7120-1987.

[0039] Especially in resins formed and processed at high temperatures, it is required that the flame retardant has excellent heat resistance at higher temperatures. The halogenated polymer of the present invention shows excellent heat resistance as described above. Therefore, as a flame retardant for resins formed and processed at temperatures around 250 to 300 °C, it can be expected to contribute to the improvement of quality stability and productivity.

[0040] For a flame retardant such as the halogenated polymer of the present invention, it is required that its primary particle size is small. The reason is considered to be that the smaller the primary particle size, the higher the dispersibility of the flame retardant in the resin. Along with this, the probability of the reaction between the combustible gas and oxygen generated during the combustion of the resin and the above-mentioned flame retardant is increased (that is, the probability of the appearance of the flame retardant effect is increased) (source: Introduction to Flame Retardancy - Protect Your Life and Property from Fire (Japanese: 難燃学入門―火災からあなたの命と財産を守る), supervised by Daisuke Kitano, Chemical Industry Daily).

[0041] The halogenated polymer of the present invention shows the characteristic of having a very small primary particle size (average primary particle size (D50)) compared with known halogen-containing polymers. As a result, it achieves a significantly different effect of excellent dispersibility in the resin. In addition, in terms of being able to impart significantly high flame retardancy to the resin, it can be expected that the halogenated polymer of the present invention achieves an extremely significant effect that is not possessed by known halogen-containing polymers based on the action of the above-mentioned excellent dispersibility.

[0042] It should be noted that regarding the halogenated polymer of the present invention, it is speculated that there is a correlation between its bromide ion content and its average primary particle size (D50).

[0043] That is, for the halogenated polymer of the present invention, it is speculated that due to its low bromide ion content, the generation of polymer primary particles with a distorted shape can be suppressed. As a result, its average primary particle size (D50) can be reduced. On the contrary, regarding the halogenated polymer of the present invention, it is speculated that due to its ability to reduce its average primary particle size (D50), the residual bromide ions inside the above-mentioned halogenated polymer can be suppressed. As a result, its bromide ion content can be reduced.

[0044] Regarding the halogenated polymer of the present invention, there is no particular limitation. In terms of excellent dispersibility in the resin, its average primary particle size (D50) is preferably 1 to 50 μm, more preferably 2 to 30 μm, and still more preferably 3 to 15 μm.

[0045] There is no particular limitation on the method for measuring the average primary particle size (D50), and examples thereof include laser diffraction scattering method, imaging method, sedimentation method, resistance method, electron microscopy method, specific surface area method, or sieving method. Among them, laser diffraction scattering method or imaging method is preferred, and laser diffraction scattering method is more preferred. Among them, the measurement method using laser diffraction scattering method is further described in detail in the examples.

[0046] The halogenated polymer of the present invention has a standard polystyrene-equivalent weight average molecular weight determined by gel permeation chromatography of preferably 4,000 or more, more preferably 8,000 or more, and even more preferably 11,000 or more, in order to obtain higher heat resistance.

[0047] Regarding the halogenated polymer of the present invention, from the viewpoint of obtaining higher heat resistance, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of standard polystyrene measured by gel permeation chromatography is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and even more preferably 1.0 to 2.0.

[0048] The method and conditions for measuring the weight average molecular weight of the halogenated polymer of the present invention by gel permeation chromatography are in accordance with ISO 16014-3:2012 (JIS K 7252-3:2016). The above method and conditions are described in more detail in the Examples.

[0049] The halogenated polymer of the present invention preferably has a bromine content of 53 to 60% by weight, more preferably 54 to 60% by weight, from the viewpoint that high flame retardancy can be expected.

[0050] The bromine content (wt%) of the halogenated polymer of the present invention is not particularly limited and can be quantified by combustion-ion chromatography. It should be noted that the specific analysis method and analysis conditions of combustion-ion chromatography are described in IEC 62321-3-2.

[0051] The halogenated polymer of the present invention is not particularly limited, and can be produced, for example, by heating a mixture containing a compound represented by the following general formula (2), a compound represented by the following general formula (3), a base, a radical scavenger, and a solvent at a temperature within a range of 110 to 150° C. while stirring.

[0052] [Chemistry 6]

[0053] (In the formula, R represents a C1-C6 alkylene group, -S- or -SO2-.) [Chemistry 7]

[0054] (Wherein, X and Y represent halogen atoms.) The compound represented by the general formula (2) is not particularly limited, and examples thereof include tetrabromobisphenol A, tetrabromobisphenol F, and bis(4'-hydroxy-3',5'-dibromophenyl)sulfone. Among them, tetrabromobisphenol A is preferred from the viewpoint of obtaining a halogenated polymer having excellent heat resistance.

[0055] In the production method of the present invention, the halogen atom represented by X and Y is not particularly limited, and examples thereof include chlorine, bromine, and iodine. Among them, chlorine is preferred from the viewpoint of obtaining a halogenated polymer having excellent heat resistance.

[0056] The compound represented by the general formula (3) is not particularly limited, and examples thereof include dichloroethane, dibromoethane, diiodoethane, 1-bromo-2-chloroethane, 1-chloro-2-iodoethane, and 1-bromo-2-iodoethane. Among them, dichloroethane and dibromoethane are preferred, and dichloroethane is more preferred, from the perspective of obtaining a halogenated polymer having excellent whiteness.

[0057] In the production method of the present invention, the base is not particularly limited, and examples thereof include lithium hydroxide, potassium hydroxide, sodium hydroxide, cesium hydroxide, lithium bicarbonate, potassium bicarbonate, sodium bicarbonate, cesium bicarbonate, lithium carbonate, potassium carbonate, sodium carbonate, cesium carbonate, calcium hydroxide, strontium hydroxide, or barium hydroxide, etc. Among them, sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate is preferred, and potassium carbonate is more preferred, from the perspective of obtaining a halogenated polymer having excellent heat resistance.

[0058] In the production method of the present invention, the solvent is not particularly limited as long as it does not react with the substrate, and examples thereof include aprotic polar solvents.

[0059] The aprotic polar solvent is not particularly limited, and examples thereof include tetrahydrofuran, dioxane, pyridine, N-methylpyrrolidone, propylene carbonate, dimethylacetamide, dimethylformamide, and dimethyl sulfoxide, etc. Among them, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, and dimethyl sulfoxide are preferred from the perspective of obtaining a halogenated polymer having excellent heat resistance.

[0060] In the production method of the present invention, the reaction temperature is characterized by being in the range of 110 to 150°C, and preferably in the range of 120 to 145°C in order to obtain a halogenated polymer having excellent whiteness.

[0061] The production method of the present invention may be carried out under reduced pressure, normal pressure or increased pressure, but is preferably carried out under normal pressure or increased pressure from the viewpoint of obtaining a halogenated polymer having excellent heat resistance.

[0062] The atmosphere of the production method of the present invention is not particularly limited, and examples thereof include an air atmosphere, a nitrogen atmosphere, and an argon atmosphere.

[0063] Regarding the production method of the present invention, a phase transfer catalyst can be used in combination. As the above-mentioned phase transfer catalyst, there is no particular limitation, and examples thereof include quaternary ammonium salts, phosphonium salts and crown ethers. More specifically, examples thereof include: tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium iodide, benzyltributylammonium chloride, benzyltributylammonium bromide, decyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, methyltrioctylammonium chloride, benzyldimethyltetradecylammonium chloride, ethylhexadecyldimethylammonium bromide, tetrabutylphosphonium bromide, tetraethylphosphonium hexafluorophosphate , tributyldodecylphosphonium bromide, tributylhexadecylphosphonium bromide, tetraethylphosphonium bromide, hexadecyltributylphosphonium bromide, benzyltriphenylphosphonium chloride, 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, benzo-12-crown-4-ether, benzo-15-crown-5-ether, dibenzo-18-crown-6-ether, dicyclohexyl-18-crown-6-ether, dibenzo-24-crown-8-ether, dicyclohexyl-24-crown-8-ether, 1-aza-15-crown-5-ether, or 1-aza-18-crown-6-ether, etc.

[0064] The production method of the present invention may be carried out in a continuous manner or in a batch manner.

[0065] Regarding the manufacturing method of the present invention, from the perspective of obtaining a halogenated polymer with better whiteness, it is preferred to carry out polymerization in a non-aqueous system. The method for carrying out polymerization in a non-aqueous system is not particularly limited, and examples thereof include: a method using a dehydrating solvent, a method using a dehydrating agent to carry out dehydration in a polymerization reaction system, a method not using a raw material that is the cause of generating water in the reaction, etc. As the above-mentioned dehydrating agent, it is not particularly limited, and examples thereof include molecular sieves and zeolites.

[0066] Regarding the non-aqueous system, specifically, the water concentration in the polymerization reaction system is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 200 ppm or less.

[0067] The radical scavenger is not particularly limited, and examples thereof include at least one radical scavenger selected from the group consisting of phenol radical scavengers, quinone radical scavengers, phosphite radical scavengers, amine radical scavengers, and sulfur radical scavengers. More specifically, for example, 4-methoxyphenol, 6-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butylphenol, 2-tert-butyl-4-methoxyphenol, 4-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol (also known as dibutylhydroxytoluene), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 3,6-dihydroxybenzonorbornane, 2,2'-methylenebis(6-cyclohexyl-p-cresol), hydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 1,4-benzoquinone, 2-tert-butyl-1,4-benzoquinone, 4-tert-butylcatechol, pentaerythritol Alcohol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], diphenylamine, N,N-diethylhydroxylamine, nitrosophenylhydroxylamine ammonium salt, 2,2,6,6-tetramethylpiperidin-1-oxyl, 2-benzimidazolethiol, phenothiazine, 3,3'-didodecyl thiodipropionate, 3,3'-dioctadecyl thiodipropionate, triethyl phosphite, trihexyl phosphite, tris(1,1,1-hexafluoro-2-propyl) phosphite, triphenyl phosphite, tris(2-methylphenyl) phosphite, tris(4-methylphenyl) phosphite, tris(4-nonylphenyl) phosphite, pentaerythritol bis(2,4-di-tert-butylphenyl phosphite) or tris(2,4-di-tert-butylphenyl) phosphite, etc.

[0068] In the production method of the present invention, the mixing ratio of the compound represented by the general formula (2) and the compound represented by the general formula (3) is preferably 0.8 to 2.0 mol parts, more preferably 1.0 to 1.8 mol parts, and even more preferably 1.2 to 1.5 mol parts per 1 mol part of the compound represented by the general formula (2).

[0069] In the production method of the present invention, the amount of the base used is preferably 0.8 to 2.5 mol parts, more preferably 0.9 to 2.0 mol parts, and even more preferably 1.0 to 1.8 mol parts per 1 mol part of the compound represented by the general formula (3).

[0070] In the production method of the present invention, the amount of the radical scavenger used is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 8 parts by mass, and even more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the compound represented by the general formula (2).

[0071] In the production method of the present invention, the amount of the solvent used is preferably 200 to 2000 parts by mass, more preferably 250 to 900 parts by mass, and even more preferably 300 to 700 parts by mass, based on 100 parts by mass of the compound represented by the general formula (2).

[0072] The halogenated polymer of the present invention can impart flame retardancy to a resin by being blended into the resin.

[0073] The resin is not particularly limited, and examples thereof include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyurethane, acrylonitrile-butadiene-styrene resin, acrylic resin, phenolic resin, epoxy resin, melamine resin, urea resin, polyester resin, alkyd resin, polyurea, polyimide, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polytetrafluoroethylene, polysulfone, polyethersulfone, polyetheretherketone or polyamideimide.

[0074] The blending amount of the halogenated polymer of the present invention to the resin is preferably 5 to 30 parts by mass, more preferably 10 to 28 parts by mass, and even more preferably 12 to 25 parts by mass, based on 100 parts by mass of the resin.

[0075] The halogenated polymer of the present invention can impart flame retardancy to fibers by impregnating the fibers.

[0076] The fiber is not particularly limited, and examples thereof include polyethylene, polypropylene, polyvinyl chloride, acrylic fiber, modacrylic fiber, acrylate, acetate, rayon, melamine, polyurethane, polyimide, polyamide, polyacetal, polyester, polylactic acid, polyarylate, polyphenylene sulfide, and polyether ester.

[0077] Example Hereinafter, the present invention will be described in further detail based on Examples, but the present invention is not limited to these Examples.

[0078] [Measurement of weight loss temperature] As an index of the thermal stability of the halogenated polymer, the weight loss temperature was measured under the following conditions.

[0079] Analysis device: ThermoPlus TG8120 manufactured by Rigaku Corporation Measurement conditions: 10 mg of a sample was heated at a rate of 10° C. / min in air.

[0080] [Measurement of weight average molecular weight] The molecular weight (weight average molecular weight) of the halogenated polymer was measured under the following conditions.

[0081] Analytical method: Gel permeation chromatography Analysis device: HLC-8320GPC manufactured by Tosoh Corporation Eluent: Tetrahydrofuran Measuring temperature: 40℃ Detector: UV detector Molecular weight standard: polystyrene [Determination of bromide ion content] 0.2 g of the halogenated polymer was mixed with 10 g of ultrapure water, and bromide ions were extracted by osmosis for 1 hour. Then, the mixture was centrifuged (2800 ppm, 30 minutes) to separate the water layer. The obtained water layer was passed through a pretreatment cartridge (TOYOPAC IC-SP M manufactured by Tosoh Corporation), and the halogen ion concentration was measured by ion chromatography to calculate the bromide ion content. The bromide ion concentration was calculated by the absolute calibration curve method.

[0082] Measuring device: IC-2010 manufactured by Tosoh Corporation Analytical column: TSKgel SuperIC-Anion HS Guard column: TSKguardcolumn SuperIC-A HS Eluent: 7.5mmol / L sodium bicarbonate aqueous solution + 0.8mmol / L sodium carbonate aqueous solution Flow rate: 1.5mL / min Column temperature: 40°C Injection volume: 30μL Suppress gel: TSKgel suppress IC-A Detection: Conductivity [Measurement of average primary particle size (D50)] The average primary particle size of the halogenated polymer after ultrasonic dispersion in the following solvent was measured under the following conditions.

[0083] Analysis method: Laser diffraction / scattering particle size distribution measurement Measuring device: MICROTRAC MT3300EXII manufactured by MicrotracBEL Measurement conditions: wet Solvent: Water [Measurement of chromaticity and evaluation of color difference D from white] Using 2.0 g of the halogenated polymer, the chromaticity RGB of the halogenated polymer based on the RGB color model was measured using the following colorimeter.

[0084] Analysis method: Colorimeter method Measuring device (colorimeter): Pico mobile color picker manufactured by SOFTWARE TOOL CO., LTD. (RGB R=Red, G=Green, B=Blue).

[0085] The color difference D between the chromaticity RGB obtained by the measurement and white (R:G:B=255:255:255) is calculated. The color difference D is calculated based on the following Euclidean distance.

[0086] [Chemistry 8]

[0087] The smaller the value of the color difference D is, the smaller the chromaticity difference from white (R:G:B=255:255:255) is, which means that the color of the measured sample is closer to white.

[0088] Example 1. In a 300 mL glass eggplant flask, add 20.0 g (37 mmol) of tetrabromobisphenol A, 4.7 g (48 mmol) of dichloroethane, 6.4 (46 mmol) of potassium carbonate, 0.4 g (1.8 mmol) of dimethylformamide, and heat to 140°C while stirring and mixing. After stirring at 140°C for 2 hours, cool to room temperature. Add water to the reaction solution to precipitate solids. Filter the precipitated solids, wash with water, and then dry them. A white solid halogenated polymer was obtained with a yield of 94%.

[0089] The obtained halogenated polymer was subjected to [measurement of weight loss temperature], [measurement of weight average molecular weight], [measurement of bromide ion content], [measurement of average primary particle size (D50)], and [measurement of chromaticity and evaluation of color difference D from white].

[0090] The weight average molecular weight was 12000. The bromide ion content was 220 ppm. The average particle size was 8 μm. The color difference D from white was 29. The results are shown in Table 1.

[0091] Example 2. A halogenated polymer as a white solid was obtained at a yield of 93% in the same manner as in Example 1 except that 0.2 g (1.3 mmol) of 4-tert-butylphenol (PTBP) was used instead of 0.4 g (1.8 mmol) of BHT. The evaluation results of the obtained halogenated polymer are shown in Table 1.

[0092] Example 3. In Example 1, the same operation as in Example 1 was performed except that 0.02 g (0.01 mmol) of tris(2,4-di-tert-butylphenyl)phosphite (TDBPP) was used instead of 0.4 g (1.8 mmol) of BHT to obtain a halogenated polymer in the form of a white solid at a yield of 95%. The evaluation results of the obtained halogenated polymer are shown in Table 1.

[0093] Example 4. A white solid halogenated polymer was obtained in a yield of 96% by performing the same operation as in Example 1 except that 0.02 g (0.18 mmol) of hydroquinone (HQ) was used instead of 0.4 g (1.8 mmol) of BHT.

[0094] Example 5. A halogenated polymer as a white solid was obtained at a yield of 96% in the same manner as in Example 1 except that 0.02 g (0.16 mmol) of 4-methoxyphenol (4OMeP) was used instead of 0.4 g (1.8 mmol) of BHT. The evaluation results of the obtained halogenated polymer are shown in Table 1.

[0095] Example 6. A halogenated polymer as a white solid was obtained at a yield of 96% in the same manner as in Example 1 except that 0.02 g (0.16 mmol) of 4-tert-butylphenol (PTBP) was used instead of 0.4 g (1.8 mmol) of BHT. The evaluation results of the obtained halogenated polymer are shown in Table 1.

[0096] Example 7. A halogenated polymer as a white solid was obtained at a yield of 97% by performing the same operation as in Example 1 except that 0.02 g (0.12 mmol) of 4-tert-butylcatechol (4tBuC) was used instead of 0.4 g (1.8 mmol) of BHT. The evaluation results of the obtained halogenated polymer are shown in Table 2.

[0097] Example 8. A halogenated polymer as a white solid was obtained at a yield of 97% in the same manner as in Example 1 except that 0.02 g (0.12 mmol) of tert-butylhydroquinone (TBHQ) was used instead of 0.4 g (1.8 mmol) of BHT.

[0098] Example 9. In Example 1, the same operation as in Example 1 was performed except that 0.02 g (0.11 mmol) of 6-tert-butyl-4,6-dimethylphenol (6tBu4,6DMP) was used instead of 0.4 g (1.8 mmol) of BHT to obtain a halogenated polymer in the form of a white solid at a yield of 97%. The evaluation results of the obtained halogenated polymer are shown in Table 2.

[0099] Example 10. The same operation as in Example 1 was carried out except that 0.02 g (0.10 mmol) of 2,6-di-tert-butylphenol (2,6DtBuP) was used instead of 0.4 g (1.8 mmol) of BHT to obtain a halogenated polymer in the form of a white solid at a yield of 97%. The evaluation results of the obtained halogenated polymer are shown in Table 2.

[0100] Example 11. In Example 1, the same operation as in Example 1 was performed except that 0.02 g (0.11 mmol) of 2-tert-butyl-4-methoxyphenol (2tBu4OMeP) was used instead of 0.4 g (1.8 mmol) of BHT to obtain a halogenated polymer in the form of a white solid at a yield of 96%. The evaluation results of the obtained halogenated polymer are shown in Table 2.

[0101] Example 12. A halogenated polymer as a white solid was obtained in a yield of 97% by performing the same operation as in Example 1 except that 0.02 g (0.09 mmol) of 2,5-di-tert-butylhydroquinone (2,5DtBuHQ) was used instead of 0.4 g (1.8 mmol) of BHT. Table 2 shows the evaluation results of the obtained halogenated polymer.

[0102] Example 13. A halogenated polymer as a white solid was obtained at a yield of 96% by performing the same operation as in Example 1 except that 0.02 g (0.11 mmol) of 3,6-dihydroxybenzonorbornane (3,6DHN) was used instead of 0.4 g (1.8 mmol) of BHT. The evaluation results of the obtained halogenated polymer are shown in Table 3.

[0103] Example 14. In Example 1, except that 0.02 g (0.05 mmol) of 2,2'-methylenebis(6-cyclohexyl-p-cresol) (2,2'MB(6CHPC)) was used instead of 0.4 g (1.8 mmol) of BHT, the same operation as in Example 1 was carried out to obtain a halogenated polymer in the form of a white solid at a yield of 96%. The evaluation results of the obtained halogenated polymer are shown in Table 3.

[0104] Example 15. In Example 1, except that 0.02 g (0.04 mmol) of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (PETP) was used instead of 0.4 g (1.8 mmol) of BHT, the same operation as in Example 1 was carried out to obtain a halogenated polymer in the form of a white solid with a yield of 96%. The evaluation results of the obtained halogenated polymer are shown in Table 3.

[0105] Example 16. A white solid halogenated polymer was obtained in a yield of 96% by performing the same operation as in Example 1 except that 0.02 g (0.19 mmol) of 1,4-benzoquinone (1,4BQ) was used instead of 0.4 g (1.8 mmol) of BHT.

[0106] Example 17. In Example 1, the same operation as in Example 1 was performed except that 0.02 g (0.12 mmol) of 2-tert-butyl-1,4-benzoquinone (2tBu1,4BQ) was used instead of 0.4 g (1.8 mmol) of BHT to obtain a halogenated polymer in the form of a white solid at a yield of 97%. The evaluation results of the obtained halogenated polymer are shown in Table 3.

[0107] Example 18. A halogenated polymer as a white solid was obtained in a yield of 96% by performing the same operation as in Example 1 except that 0.01 g (0.06 mmol) of triethyl phosphite (TEP) was used instead of 0.4 g (1.8 mmol) of BHT.

[0108] Example 19. A white solid halogenated polymer was obtained in a yield of 96% by performing the same operation as in Example 1 except that 0.01 g (0.03 mmol) of trihexyl phosphite (THP) was used instead of 0.4 g (1.8 mmol) of BHT.

[0109] Example 20. In Example 1, except that 0.01 g (0.02 mmol) of tris(1,1,1-hexafluoro-2-propyl)phosphite (THFPP) was used instead of 0.4 g (1.8 mmol) of BHT, the same operation as in Example 1 was carried out to obtain a halogenated polymer in the form of a white solid at a yield of 97%. The evaluation results of the obtained halogenated polymer are shown in Table 4.

[0110] Example 21. A white solid halogenated polymer was obtained in a yield of 96% by performing the same operation as in Example 1 except that 0.01 g (0.03 mmol) of triphenyl phosphite (TPPI) was used instead of 0.4 g (1.8 mmol) of BHT.

[0111] Example 22. In Example 1, the same operation as in Example 1 was performed except that 0.002 g (0.006 mmol) of tris(2-methylphenyl)phosphite (T2MPP) was used instead of 0.4 g (1.8 mmol) of BHT to obtain a halogenated polymer in the form of a white solid at a yield of 97%. The evaluation results of the obtained halogenated polymer are shown in Table 4.

[0112] Example 23. In Example 1, the same operation as in Example 1 was performed except that 0.002 g (0.006 mmol) of tris(4-methylphenyl)phosphite (T4MPP) was used instead of 0.4 g (1.8 mmol) of BHT to obtain a halogenated polymer in the form of a white solid at a yield of 96%. The evaluation results of the obtained halogenated polymer are shown in Table 4.

[0113] Example 24. In Example 1, the same operation as in Example 1 was performed except that 0.002 g (0.003 mmol) of tris(4-nonylphenyl)phosphite (T4NPP) was used instead of 0.4 g (1.8 mmol) of BHT to obtain a halogenated polymer in the form of a white solid at a yield of 95%. The evaluation results of the obtained halogenated polymer are shown in Table 4.

[0114] Example 25. In Example 1, except that 0.002 g (0.003 mmol) of pentaerythritol bis(2,4-di-tert-butylphenyl phosphite) (PEBPP) was used instead of 0.4 g (1.8 mmol) of BHT, the same operation as in Example 1 was carried out to obtain a halogenated polymer in the form of a white solid at a yield of 96%. The evaluation results of the obtained halogenated polymer are shown in Table 5.

[0115] Example 26. A white solid halogenated polymer was obtained in a yield of 96% by performing the same operation as in Example 1 except that 0.02 g (0.12 mmol) of diphenylamine (DPA) was used instead of 0.4 g (1.8 mmol) of BHT.

[0116] Example 27. A halogenated polymer as a white solid was obtained at a yield of 96% in the same manner as in Example 1 except that 0.02 g (0.22 mmol) of N,N-diethylhydroxylamine (DEHA) was used instead of 0.4 g (1.8 mmol) of BHT. The evaluation results of the obtained halogenated polymer are shown in Table 5.

[0117] Example 28. In Example 1, except that 0.02 g (0.13 mmol) of 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) was used instead of 0.4 g (1.8 mmol) of BHT, the same operation as in Example 1 was carried out to obtain a halogenated polymer in the form of a white solid at a yield of 96%. The evaluation results of the obtained halogenated polymer are shown in Table 5.

[0118] Example 29. A halogenated polymer as a white solid was obtained at a yield of 96% in the same manner as in Example 1 except that 0.02 g (0.13 mmol) of nitrosophenylhydroxylamine ammonium salt (ANPHA) was used instead of 0.4 g (1.8 mmol) of BHT. The evaluation results of the obtained halogenated polymer are shown in Table 5.

[0119] Example 30. A halogenated polymer as a white solid was obtained in a yield of 96% by performing the same operation as in Example 1 except that 0.02 g (0.13 mmol) of 2-benzimidazolethiol (2BIT) was used instead of 0.4 g (1.8 mmol) of BHT. Table 5 shows the evaluation results of the obtained halogenated polymer.

[0120] Example 31. A white solid halogenated polymer was obtained in a yield of 96% by performing the same operation as in Example 1 except that 0.02 g (0.10 mmol) of phenothiazine (PT) was used instead of 0.4 g (1.8 mmol) of BHT.

[0121] Example 32. In Example 1, the same operation as in Example 1 was performed except that 0.02 g (0.04 mmol) of 3,3'-didodecyl thiodipropionate (3,3'TDPDD) was used instead of 0.4 g (1.8 mmol) of BHT to obtain a halogenated polymer in the form of a white solid at a yield of 96%. The evaluation results of the obtained halogenated polymer are shown in Table 6.

[0122] Example 33. In Example 1, except that 0.02 g (0.03 mmol) of 3,3'-dioctadecyl thiodipropionate (3,3'TDPDOD) was used instead of 0.4 g (1.8 mmol) of BHT, the same operation as in Example 1 was carried out to obtain a halogenated polymer in the form of a white solid at a yield of 96%. The evaluation results of the obtained halogenated polymer are shown in Table 6.

[0123] Comparative Example 1. In Example 1, except that BHT was not added, the same operation as in Example 1 was carried out to obtain a brown solid halogenated polymer with a yield of 92%. Table 7 shows the evaluation results of the obtained halogenated polymer.

[0124] Comparative Example 2. In Example 1, the same operation as in Example 1 was carried out except that 0.2 g (1.49 mmol) of tert-butylbenzene (TBB) was used instead of 0.4 g (1.8 mmol) of BHT to obtain a brown solid halogenated polymer at a yield of 95%.

[0125] Comparative Example 3. A brown solid halogenated polymer was obtained in a yield of 95% by performing the same operation as in Example 1 except that 0.4 g (1.2 mmol) of triphenyl phosphate (TPPA) was used instead of 0.4 g (1.8 mmol) of BHT.

[0126] [Table 1]

[0127] [Table 2]

[0128] [Table 3]

[0129] [Table 4]

[0130] [Table 5]

[0131] [Table 6]

[0132] [Table 7]

[0133] As described above, the halogenated polymer of the present invention has higher heat resistance and higher whiteness than known halogen-containing polymers.

[0134] While the invention has been described in detail and with reference to specific embodiments, it will be apparent to one skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

[0135] It should be noted that all the contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2022-130888 filed on August 19, 2022 are cited herein and are introduced as a disclosure of the specification of the present invention.

Claims

1. A halogenated polymer, characterized in that A halogenated polymer containing bromide ions and represented by the following general formula (1), wherein the content of the bromide ions is 1 to 2000 ppm. , In the formula (1), R represents a C1-C6 alkylene group, -S- or -SO2-, and n represents a real number.

2. The halogenated polymer according to claim 1, wherein At a temperature increase rate of 10° C. / min, the weight loss temperature of 3% by weight is 370° C. or higher.

3. The halogenated polymer according to claim 1, wherein The color difference D between the halogenated polymer and white (R:G:B=255:255:255) calculated based on the following formula (Euclidean distance) using a colorimeter is 33 or less, 。 4. The halogenated polymer according to claim 1, wherein The average primary particle size D50 is 1 to 50 μm.

5. The method for producing a halogenated polymer according to claim 1, characterized in that: A mixture containing a compound represented by the following general formula (2), a compound represented by the following general formula (3), a base, a radical scavenger, and a solvent is heated at a temperature within a range of 110° C. to 150° C. while stirring. , In formula (2), R represents a C1-C6 alkylene group, -S- or -SO2-; , In formula (3), X and Y represent halogen atoms.

6. The manufacturing method according to claim 5, wherein: The amount of the radical scavenger used is 0.001 to 10 parts by mass based on 100 parts by mass of the compound represented by the general formula (2).

7. The manufacturing method according to claim 5, wherein: The free radical scavenger is at least one selected from the group consisting of a phenol-based free radical scavenger, a quinone-based free radical scavenger, a phosphite-based free radical scavenger, an amine-based free radical scavenger, and a sulfur-based free radical scavenger.

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