Powder comprising halogen-containing polymer and method for producing the same

Abstract

To provide a halogen-containing polymer which has excellent handling properties and exhibits excellent impact resistance when blended into a resin.SOLUTION: A powder comprises a halogen-containing polymer represented by the general formula (1) in the figure (where R represents a C1-6 alkylene group,-S-, or -SO2-, and n represents a real number), the halogen-containing polymer having a bulk density of 0.18 to 0.80 g / cm3.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a powder composed of a halogen-containing polymer used for a flame retardant or the like, and a method for producing the same.

Background Art

[0002] A flame retardant is well known as an additive that imparts flame retardancy to a resin by mixing with the resin. For example, a compound having a plurality of halogen atoms has been used as a halogen-based flame retardant for a long time. Note that some low molecular weight halogen-based flame retardants (for example, polybrominated biphenyls) are subject to regulation under the PoPs Convention due to their harmful properties. Therefore, in recent years, high molecular weight halogen-based flame retardants with high biosafety have been developed.

[0003] As a high molecular weight bromine-based flame retardant, for example, a halogen-containing polymer having high heat resistance in which tetrabromobisphenol A is linked with an ethylene group is known (Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The powder composed of a conventionally known halogen-containing polymer has a problem of insufficient impact resistance when blended with a resin. Further, the powder composed of the halogen-containing polymer has high dispersibility, which causes problems in handling properties such as deteriorating the working environment during weighing or making it difficult to uniformly disperse in the resin during resin processing.

[0006] The present invention has been made in view of the above background art, and an object thereof is to provide a powder composed of a halogen-containing polymer that has excellent handleability and exhibits excellent impact resistance when compounded with a resin.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventors have found that a halogen-containing polymer with improved powder properties can solve the above problems, and have completed the present invention.

[0008] That is, the present invention relates to a powder composed of a halogen-containing polymer shown below.

[0009] [1] A halogen-containing polymer represented by the following general formula (1)

[0010]

Chemical formula

[0011] (In the formula, R represents an alkylene group having 1 to 6 carbon atoms, -S-, or -SO2-, and n represents a real number.) The powder composed of a halogen-containing polymer, characterized in that the bulk density is 0.18 to 0.80 g / cm 3 .

[0012] [2] The powder according to [1], characterized in that in the general formula (1), R is an alkylene group having 1 to 6 carbon atoms.

[0013] [3] The powder according to [1] or [2], characterized in that in the general formula (1), R is a 2,2-propylene group.

[0014] [4] The powder according to any one of [1] to [3], characterized in that the shape of the primary particles measured using a particle shape image analyzer has an aspect ratio of 1.0 to 1.9.

[0015] [5] The powder according to any one of [1] to [3], characterized in that the volume ratio of particles having a particle size of 1.0 to 20 μm measured using an optical particle size measuring instrument such as a laser diffraction / scattering type particle size distribution measuring instrument is 80% or more.

[0016] [6] The powder comprising a halogen-containing polymer according to any one of [1] to [3], characterized in that in the particle size distribution measured using an optical particle size measuring instrument such as a laser diffraction / scattering type particle size distribution measuring instrument, the particle size (d50) at which the cumulative frequency is 50% is 2 to 50 μm.

[0017] [7] The powder according to any one of [1] to [3], characterized in that the volume ratio of particles having a particle size of 20 μm or more measured using an optical particle size measuring instrument such as a laser diffraction / scattering type particle size distribution measuring instrument is 15% or less.

[0018] [8] The powder according to any one of [1] to [3], characterized in that the volume ratio of particles having a particle size of 1 μm or less measured using an optical particle size measuring instrument such as a laser diffraction / scattering type particle size distribution measuring instrument is 15% or less.

[0019] [9] The powder according to any one of [1] to [3], characterized in that in the particle size distribution measured using an optical particle size measuring instrument such as a laser diffraction / scattering type particle size distribution measuring instrument, the particle size (d90) at which the cumulative frequency is 90% is 25 μm or less.

[0020]

[10] A step of synthesizing a halogen-containing polymer using a compound represented by the following general formula (2), a compound represented by the following general formula (3), a base, and a solvent, and a step of processing the obtained halogen-containing polymer to a bulk density of 0.18 to 0.80 g / cm 3 The method for producing the powder according to any one of [1] to [3], comprising the step of performing the processing.

[0021] [Chemical formula]

[0022] (In the formula, R represents an alkylene group having 1 to 6 carbon atoms, -S-, or -SO2-.)

[0023] [Chemical formula]

[0024] (In the formula, X and Y represent halogen atoms.) [Advantages of the Invention]

[0025] The powder composed of the halogen-containing polymer of the present invention has the effect of ensuring excellent mechanical properties when compounded with a resin, as compared with the powder composed of a conventionally known halogen-containing polymer. Further, the powder composed of the halogen-containing polymer of the present invention has low dispersibility and has the effect of improving handleability during resin processing. [Modes for Carrying Out the Invention]

[0026] Hereinafter, the present invention will be described in more detail. In this specification, the numerical range indicated by using "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. Further, unless specifically specified, the units of the numerical values described before and after "~" are the same.

[0027] One aspect of the present invention is the following general formula (1)

[0028] [Chemical formula]

[0029] (In the formula, R represents an alkylene group having 1 to 6 carbon atoms, -S-, or -SO2-, and n represents a real number.) A powder composed of a halogen-containing polymer represented by the formula, having a bulk density of 0.18 to 0.80 g / cm 3relating to powder, characterized by being

[0030] Here, the bulk density is the static density measured in a state where the powder is allowed to fall naturally. For example, in a predetermined 100 cm 3 cylindrical container, an appropriate amount of powder is dropped from the upper opening end of the container for loose filling, the filled mass is measured and the volume is read, and the mass of the powder per volume is calculated to obtain it.

[0031] The powder composed of the halogen-containing polymer of the present invention has a bulk density of 0.18 to 0.80 g / cm 3 and is characterized by this. In terms of excellent mechanical properties of the resin containing the powder composed of the halogen-containing polymer and good handling properties during resin processing, the bulk density is 0.20 to 0.70 g / cm 3 within the range is more preferable, and 0.22 to 0.60 g / cm 3 is even more preferable.

[0032] As an index representing the shape of the primary particles of the powder, there is the aspect ratio of the powder. Regarding the aspect ratio, particles were observed with a particle image analyzer PITA-04 (manufactured by Seishin Enterprise Co., Ltd.), and for each particle, the major axis and the minor axis were measured and calculated.

[0033] The powder composed of the halogen-containing polymer of the present invention is preferably such that the shape aspect ratio in the primary particles is 1.0 to 1.9, and more preferably 1.0 to 1.6, in terms of excellent mechanical properties of the resin to be compounded and good handling properties during resin processing.

[0034] In the general formula (1), the alkylene group having 1 to 6 carbon atoms 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 hexadiene group, or a 1,1-cyclohexylene group.

[0035] Regarding R, it is preferably a 2,2-propylene group in terms of excellent heat resistance.

[0036] In general formula (1), n represents the average value of the number of repetitions of the repeating unit of the halogen-containing polymer, and in the present invention, n represents a real number.

[0037] Regarding this n, in terms of excellent heat resistance, it 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.

[0038] For example, when R is a 2,2-propylene group, the terminal structure is a 2-chloroethyl group and a phenolic hydroxyl group, and n is 11, the theoretical average molecular weight of the halogen-containing polymer of the present invention is 6,368.

[0039] The terminal groups of the halogen-containing polymer constituting the powder of the halogen-containing polymer of the present invention are usually a 2-haloethyl group and / or a phenolic hydroxyl group derived from the raw material monomer, but these terminal groups may be blocked with a low-reactive compound. The compound used for the blocking is not particularly limited in type. For example, 4-bromophenol, 1,3,5-tribromophenol, pentabromophenol, benzyl chloride, methyl halide, or halogenated benzene can be mentioned. Regarding the halogen-containing polymer constituting the powder of the halogen-containing polymer of the present invention, those whose terminal groups are blocked by the above compounds are included.

[0040] Regarding the halogen-containing polymer that constitutes the powder composed of the halogen-containing polymer of the present invention, in terms of expecting high flame retardancy, its bromine content is preferably 50 to 60% by mass, and more preferably 52 to 60% by mass. The powder composed of the halogen-containing polymer of the present invention has a particle size (hereinafter referred to as d50) at which the cumulative frequency is 50% in the particle size distribution measured using an optical particle size measuring instrument such as a laser diffraction / scattering type particle size distribution measuring instrument, preferably 2 to 50 μm, more preferably 2 to 16 μm, still more preferably 3 to 14 μm, and even more preferably 3 to 12 μm. When d50 is within the above range, when kneaded with a resin, it is easy to disperse uniformly, the flame retardancy can be improved, and furthermore, the decrease in the mechanical properties of the resin can be suppressed.

[0041] The powder composed of the halogen-containing polymer of the present invention relates to a powder, characterized in that the volume ratio of particles having a particle size of 1.0 to 20 μm measured using an optical particle size measuring instrument such as a laser diffraction / scattering type particle size distribution measuring instrument is 80% or more. Here, the particle size is indicated by the value of the diameter of a sphere equivalent to the volume of the measured particle.

[0042] The powder composed of the halogen-containing polymer of the present invention is excellent in the mechanical properties of the blended resin. In terms of this, the volume ratio of particles having a particle size of 1.0 to 20 μm measured using an optical particle size measuring instrument such as a laser diffraction / scattering type particle size distribution measuring instrument is preferably 80% or more, preferably 85% or more, and more preferably 90% or more.

[0043] The powder composed of the halogen-containing polymer of the present invention preferably has a volume ratio of particles having a particle size of 20 μm or more measured using an optical particle size measuring instrument such as a laser diffraction / scattering type particle size distribution measuring instrument of 15% or less, more preferably 10% or less, still more preferably 5% or less, and preferably 0%, that is, preferably not containing. The powder composed of the halogen-containing polymer of the present invention preferably has a volume ratio of particles having a particle size of 1 μm or less, measured using an optical particle size measuring instrument such as a laser diffraction / scattering type particle size distribution measuring instrument, of 15% or less, more preferably 10% or less, and even more preferably 5% or less.

[0044] The powder composed of the halogen-containing polymer of the present invention is not particularly limited, but the particle diameter (hereinafter referred to as d90) at which the cumulative frequency is 90%, measured using an optical particle size measuring instrument such as a laser diffraction / scattering type particle size distribution measuring instrument, is preferably 25 μm or less, more preferably 20 μm or less, and even more preferably 15 μm. When d90 is within the above range, when kneaded with a resin, it is easy to disperse, the flame retardancy can be improved, and furthermore, the decrease in the mechanical properties of the resin can be suppressed.

[0045] The method for producing the powder composed of the halogen-containing polymer of the present invention is not particularly limited, but a step of synthesizing a halogen-containing polymer using a compound represented by the following general formula (2), a compound represented by the following general formula (3), a base, and a solvent, and the obtained halogen-containing polymer is processed to a bulk density of 0.18 to 0.80 g / cm 3 including a step of performing processing.

[0046] As an example, 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 trap agent, and a solvent is heated in the range of 110 to 150 °C with stirring to synthesize a halogen-containing polymer, and the obtained halogen-containing polymer is processed into a powder with a bulk density of 0.18 to 0.80 g / cm 3 There is a method of performing powder processing.

[0047]

Chemical formula

[0048] (In the formula, R represents an alkylene group having 1 to 6 carbon atoms, -S-, or -SO2-.)

[0049]

Chem.

[0050] (In the formula, X and Y each represent a halogen atom.) The compound represented by the general formula (2) is not particularly limited, and examples thereof include tetrabromobisphenol A, tetrabromobisphenol F, or bis(4'-hydroxy-3',5'-dibromophenyl) sulfone. Among these, tetrabromobisphenol A is preferred in that a halogen-containing polymer having excellent heat resistance can be obtained.

[0051] The compound represented by the general formula (3) is not particularly limited, and examples thereof include ethane dichloride, ethane dibromide, ethane diiodide, 1-bromo-2-chloroethane, 1-chloro-2-iodoethane, or 1-bromo-2-iodoethane.

[0052] In the production of the halogen-containing polymer of the present invention, the base is not particularly limited, and examples thereof include lithium hydroxide, potassium hydroxide, sodium hydroxide, cesium hydroxide, lithium hydrogen carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, cesium hydrogen carbonate, lithium carbonate, potassium carbonate, sodium carbonate, cesium carbonate, calcium hydroxide, strontium hydroxide, or barium hydroxide. Among these, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate is preferred, and potassium carbonate is more preferred, in that a halogenated polymer having excellent heat resistance can be obtained.

[0053] In the production of the powder composed of the halogen-containing polymer of the present invention, the solvent may be any one that does not react with the substrate, and is not particularly limited, and examples thereof include aprotic polar solvents.

[0054] Examples of the aprotic polar solvent are not particularly limited, and include, for example, tetrahydrofuran, dioxane, pyridine, N-methylpyrrolidone, propylene carbonate, dimethylacetamide, dimethylformamide, or dimethyl sulfoxide. Among these, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, or dimethyl sulfoxide is preferable in that a halogen-containing polymer excellent in heat resistance can be obtained.

[0055] In the production of the powder composed of the halogen-containing polymer of the present invention, the reaction temperature is preferably in the range of 110°C to 150°C, and more preferably in the range between 120°C and 145°C.

[0056] The above radical scavenger is not particularly limited. For example, at least one radical scavenger selected from the group consisting of phenolic radical scavengers, quinone radical scavengers, phosphite radical scavengers, amine radical scavengers, and sulfur radical scavengers can be mentioned. 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 (alias, dibutylhydroxytoluene), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 3,6-dihydroxybenzobornane, 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 tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], diphenylamine, N,N-diethylhydroxylamine, ammonium nitrosophenylhydroxylamine, 2,2,6,6-tetramethylpiperidine-1-oxyl, 2-benzimidazolethiol, phenothiazine, didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-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. can be mentioned.

[0057] In the production of the powder composed of the halogen-containing polymer 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 mole parts of the compound represented by the general formula (3) with respect to 1 mole part of the compound represented by the general formula (2), more preferably 1.0 to 1.8 mole parts, and even more preferably 1.2 to 1.5 mole parts.

[0058] In the production of the powder composed of the halogen-containing polymer of the present invention, the amount of the base used is preferably 0.8 to 2.5 mole parts with respect to 1 mole part of the compound represented by the general formula (2), more preferably 0.9 to 2.0 mole parts, and even more preferably 1.0 to 1.8 mole parts.

[0059] In the production of the powder composed of the halogen-containing polymer of the present invention, the amount of the radical trap 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 with respect to 100 parts by mass of the compound represented by the general formula (2).

[0060] In the production of the powder composed of the halogen-containing polymer of the present invention, the amount of the solvent used is preferably 200 to 2,000 parts by mass, more preferably 250 to 900 parts by mass, and even more preferably 250 to 500 parts by mass with respect to 100 parts by mass of the compound represented by the general formula (2).

[0061] Examples of the step of synthesizing the halogen-containing polymer include a first step of synthesizing a compound represented by the following general formula (4) 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, and a solvent in the range of 110 to 150 °C while stirring, and a second step of synthesizing a halogen-containing polymer by heating a mixture containing the obtained compound represented by the following general formula (4), a compound represented by the following general formula (2), a base, and a solvent in the range of 110 to 150 °C while stirring.

[0062]

Chem.

[0063] (In the formula, R represents an alkylene group having 1 to 6 carbon atoms, -S-, or -SO2-.)

[0064]

Chem.

[0065] (In the formula, X and Y represent halogen atoms.)

[0066]

Chem.

[0067] (In the formula, Z represents a halogen atom.) The compound represented by the general formula (2) is not particularly limited, and examples thereof include tetrabromobisphenol A, tetrabromobisphenol F, or bis(4'-hydroxy-3',5'-dibromophenyl)sulfone. Among these, tetrabromobisphenol A is preferable in terms of obtaining a halogen-containing polymer having excellent heat resistance.

[0068] The compound represented by the general formula (3) is not particularly limited, and examples thereof include ethane dichloride, ethane dibromide, ethane diiodide, 1-bromo-2-chloroethane, 1-chloro-2-iodoethane, or 1-bromo-2-iodoethane, etc.

[0069] In the production of the halogen-containing polymer of the present invention, the base is not particularly limited, and examples thereof include lithium hydroxide, potassium hydroxide, sodium hydroxide, cesium hydroxide, lithium hydrogen carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, cesium hydrogen carbonate, lithium carbonate, potassium carbonate, sodium carbonate, cesium carbonate, calcium hydroxide, strontium hydroxide, or barium hydroxide. Among these, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate is preferable, and potassium carbonate is more preferable in terms of obtaining a halogenated polymer having excellent heat resistance.

[0070] In the above general formula (4), Z represents a halogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, or an iodine atom. Among these, a chlorine atom is preferable in terms of excellent whiteness of the halogen-containing polymer.

[0071] When the step of synthesizing the halogen-containing polymer is divided into the first step and the second step, the bases and solvents used in each step may be the same or different.

[0072] In the production of the halogen-containing polymer of the present invention, the base is not particularly limited, and examples thereof include lithium hydroxide, potassium hydroxide, sodium hydroxide, cesium hydroxide, lithium hydrogen carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, cesium hydrogen carbonate, lithium carbonate, potassium carbonate, sodium carbonate, cesium carbonate, calcium hydroxide, strontium hydroxide, or barium hydroxide. Among these, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate is preferable, and potassium carbonate is more preferable in terms of obtaining a halogenated polymer having excellent heat resistance.

[0073] In the production of the powder composed of the halogen-containing polymer of the present invention, the solvent may be any one that does not react with the substrate and is not particularly limited. Examples thereof include aprotic polar solvents.

[0074] The aprotic polar solvents are not particularly limited, and examples thereof include tetrahydrofuran, dioxane, pyridine, N-methylpyrrolidone, propylene carbonate, dimethylacetamide, dimethylformamide, or dimethyl sulfoxide. Among these, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, or dimethyl sulfoxide is preferable in terms of obtaining a halogen-containing polymer with excellent heat resistance.

[0075] When the step of synthesizing the halogen-containing polymer is divided into the first step and the second step, the reaction temperatures of each reaction may be the same or different. Each reaction temperature is preferably in the range of 110°C to 150°C, and more preferably in the range between 120°C and 145°C.

[0076] When the step of synthesizing the halogen-containing polymer is divided into the first step and the second step, in the first step, the mixing ratio of the compound represented by the general formula (2) and the compound represented by the general formula (3) is preferably 5.0 to 20.0 molar parts of the compound represented by the general formula (3) with respect to 1 molar part of the compound represented by the general formula (2), more preferably 8.0 to 17.0 molar parts, and even more preferably 10.0 to 15.0 molar parts. In the second step, the mixing ratio of the compound represented by the general formula (4) and the compound represented by the general formula (3) is preferably 0.5 to 2.0 molar parts of the compound represented by the general formula (2) with respect to 1 molar part of the compound represented by the general formula (4), more preferably 0.8 to 1.6 molar parts, and even more preferably 0.9 to 1.3 molar parts.

[0077] When the step of synthesizing the halogen-containing polymer is divided into the first step and the second step, in the first step, the amount of the base used is preferably 1.5 to 4.0 mole parts, more preferably 1.9 to 3.5 mole parts, and even more preferably 2.0 to 3.0 mole parts with respect to 1 mole part of the compound represented by the general formula (2). In the second step, the amount of the base used is preferably 1.0 to 3.0 mole parts, more preferably 1.5 to 2.5 mole parts, and even more preferably 1.8 to 2.2 mole parts with respect to 1 mole part of the compound represented by the general formula (4).

[0078] When the step of synthesizing the halogen-containing polymer is divided into the first step and the second step, in the first step, the amount of the solvent used is preferably 200 to 2,000 parts by mass, more preferably 300 to 900 parts by mass, and even more preferably 400 to 700 parts by mass with respect to 100 parts by mass of the compound represented by the general formula (2). In the second step, the amount of the solvent used is preferably 200 to 2,000 parts by mass, more preferably 300 to 900 parts by mass, and even more preferably 400 to 700 parts by mass with respect to 100 parts by mass of the compound represented by the general formula (4).

[0079] Here, the bulk density of the halogen-containing polymer after the step of synthesizing the halogen-containing polymer is 0.05 to 0.20 g / cm 3 is.

[0080] Examples of the method for powder processing include granulation processing, particle size homogenization processing, or spheroidization processing.

[0081] The apparatus for powder processing is not particularly limited, and examples thereof include a roll press, a quick mill, a high-speed stirring type powder spheroidization apparatus, a flash jet dryer, or a crush seal (manufactured by Seishin Enterprise Co., Ltd.).

[0082] In this embodiment, it is preferable to perform powder processing by combining one or more of a high-speed stirring type spheronizer, a flash jet dryer, and a crush seal (manufactured by Seishin Enterprise Co., Ltd.).

[0083] The high-speed stirring type powder spheronizer can pulverize the material by colliding the powder with the inclination and high-speed rotation of the rotor inside the apparatus, and can perform chamfering and granulation by the collision between the rotor, the wall surface, or the powders themselves.

[0084] As the pulverization conditions for obtaining the powder composed of the halogen-containing polymer of the present invention using the high-speed stirring type powder spheronizer, the rotation speed is preferably carried out under the condition of 1500 to 8000 rpm.

[0085] The flash jet dryer can instantaneously dry and pulverize the cake - slurry - like hydrous powder in a high-temperature and high-speed air stream.

[0086] As the drying and pulverization conditions for obtaining the powder composed of the halogen-containing polymer of the present invention using the flash jet dryer, the hot air temperature is preferably 120 to 240 °C, and the processing speed is preferably 20 to 80 kg / hr.

[0087] The crush seal can classify the supplied raw material into coarse powder and fine powder by using the rotation speed of the classification rotor and the air volume adjustment in combination.

[0088] As the dry classification conditions for obtaining the powder composed of the halogen-containing polymer of the present invention using the crush seal, the rotation speed of the classification rotor is preferably 3000 to 9000 °C, and the processing speed is preferably 0.1 to 100 kg / hr.

[0089] The powder composed of the halogen-containing polymer of the present invention can impart flame retardancy to the resin by being blended with the resin.

[0090] The resin is not particularly limited. For example, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyvinyl 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, etc. may be mentioned.

[0091] The mixing amount of the halogen-containing polymer of the present invention with respect to the above 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 with respect to 100 parts by mass of the above resin.

[0092] The powder composed of the halogen-containing polymer of the present invention can impart flame retardancy to the fiber by impregnating the fiber.

[0093] The fiber is not particularly limited. For example, polyethylene, polypropylene, polyvinyl chloride, acrylic, modacrylic, acrylate, acetate, rayon, melamine, polyurethane, polyimide, polyamide, polyacetal, polyester, polylactic acid, polyarylate, polyphenylene sulfide, or polyether ester, etc. may be mentioned.

Examples

[0094] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples at all. <Measurement of weight average molecular weight> Regarding the polymer samples synthesized in the examples and the like, a molecular weight measurement column (TSKgel (registered trademark) SuperH1000 + 2000 + 3000 + 5000, manufactured by Tosoh Corporation) was connected to a gel permeation chromatography apparatus (HLC-8320GPC, manufactured by Tosoh Corporation), and measurement was performed under the detection conditions of a flow rate of 0.6 mL / min, a temperature of 40 °C, and UV (254 nm) using a tetrahydrofuran eluent. Furthermore, using standard polystyrene, the weight average molecular weight of the sample in terms of standard polystyrene was measured. Regarding other matters, it was carried out in accordance with JIS-K-7252 series. <Measurement of bulk density> Regarding the polymer samples synthesized in the examples and the like, using a multi-tester MT-1000 (manufactured by Seishin Enterprise Co., Ltd.), a cylindrical container with a diameter of 5 cm and a volume of 100 cm 3 was used to measure the resulting bulk density. <Measurement of aspect ratio> Regarding the polymer samples synthesized in the examples and the like, using particle image analysis PITA-04 (manufactured by Seishin Enterprise Co., Ltd., measurement range: 2 to 500 μm, solvent used: purified water, objective lens 4 times magnification, particles with a circle equivalent of 5 μm or less are not measured), the major axis and minor axis of each were measured, and the aspect ratio was calculated. <Measurement of particle size distribution> Regarding the polymer samples synthesized in the examples and the like, measurement was performed using a laser micron sizer LMS-3000 (manufactured by Seishin Enterprise Co., Ltd.). <Evaluation of dispersibility> From a drop point 50 cm above the table, 5 g of the polymer synthesized in the examples and the like was allowed to fall naturally onto the table. The dispersibility was evaluated based on whether the fallen polymer was contained within a circle with a diameter of 50 cm centered on the point on the table directly below the drop point. 〇: All of the fallen polymer was contained within the circle, and the dispersibility was low. ×: A part of the fallen polymer was not contained within the circle, and the dispersibility was high. <Synthesis of halogen-containing polymer> Example 1 Into a 5 L glass cylindrical separable flask equipped with a stirrer and a reflux condenser, 800.0 g (1.471 mol) of tetrabromobisphenol A, 254.1 g (1.839 mol) of potassium carbonate, 4.00 g (26.6 mmol) of 4-tert-butylphenol, 4.01 g (6.19 mmol) of tris(2,4-di-tert-butylphenyl) phosphite, and 2100 g of dimethylformamide were charged, and the temperature was raised to 130 °C while stirring and mixing. At this temperature, 187.8 g (1.898 mol) of dichloroethane was added, and after stirring at 130 °C for 4 hours, it was allowed to cool to room temperature. Methanol was added to the reaction solution to precipitate a solid. The precipitated solid was filtered, washed with water, and then dried at 130 °C using a shelf dryer. This was charged into a high-speed stirring type powder spheronizer (manufactured by Seishin Enterprise Co., Ltd.), and spheronization treatment was performed by stirring at 4500 rpm for 30 minutes. A white solid halogen-containing polymer (A) was obtained with a yield of 94%.

[0095] The weight average molecular weight of the obtained halogen-containing polymer (A) was 11,000. The bulk density was 0.32 g / cm 3 It was. The aspect ratio was 1.3. The volume ratio of particles having a particle size of 1.0 to 20 μm was 87.1%. The d50 was 4.3 μm. The sedimentation rate, the volume ratio of particles having a particle size of 20 μm or more and 1.0 μm or less, and the d90 are shown in Table 1 in the analysis results.

[0096] Example 2 (According to the method of Example 8 described in JP-A-2019-77857), a halogen-containing polymer was synthesized, and drying treatment was performed at 150 °C using a flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.). A white solid halogen-containing polymer (B) was obtained with a yield of 95%. The analysis results of the obtained halogenated polymer (B) are shown in Table 1.

[0097] Example 3 In Example 1, drying with a shelf dryer and treatment with a high-speed stirring type powder spheronizer were carried out in the same manner as in Example 1 except that drying treatment was carried out at 150 °C using a flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.). As a result, a white solid halogen-containing polymer (C) was obtained with a yield of 94%. The analysis results of the obtained halogenated polymer (C) are shown in Table 1.

[0098] Example 4 In Example 3, after drying, the same operations as in Example 3 were carried out except that classification treatment was additionally carried out at a rotor rotation speed of 7000 rpm and a throughput of 300 g / hr using a high-efficiency precision air classifier (manufactured by Seishin Enterprise Co., Ltd.). As a result, a white solid halogen-containing polymer (D) was obtained with a yield of 45%. The analysis results of the obtained halogenated polymer (D) are shown in Table 1.

[0099] Example 5 In Example 1, 203.7 g (2.059 mol) of dichloroethane was used instead of 187.8 g (1.898 mol) of dichloroethane. After drying, it was put into a high-speed stirring type powder spheronizer (manufactured by Seishin Enterprise Co., Ltd.), and the same experimental operations as in Example 1 were carried out except that spheronization treatment was additionally carried out by stirring at 4500 rpm for 30 minutes. As a result, a white solid halogen-containing polymer (E) was obtained with a yield of 88%. The analysis results of the obtained halogenated polymer (E) are shown in Table 1.

[0100] Comparative Example 1 A halogen-containing polymer was synthesized according to the method of Example 8 described in JP-A-2019-77857. The analysis results of the obtained halogen-containing polymer (F) are shown in Table 1.

[0101]

Table 1

[0102] <Evaluation of Flame Retardancy and Mechanical Properties of Resin Containing Powder Composed of Halogen-Containing Polymer> The materials used for the evaluation of the compounded resin are shown below.

[0103] Polypropylene resin: BC3AD manufactured by Nippon Polypro Flame retardant aid: AT-3CN (antimony trioxide) manufactured by Suzuhiro Chemical Inorganic filler: 5000PJ (talc) manufactured by Matsumura Sangyo Examples 6 to 10, Comparative Example 2 First, polypropylene resin and talc were charged into the hopper of a twin-screw extruder (ZSK-26, manufactured by Coperion) at the compounding ratios shown in Table 2. On the other hand, a halogen-containing polymer and antimony trioxide were charged into the side hopper of the twin-screw extruder at the compounding ratios shown in Table 2, mixed at a maximum temperature of 235°C, discharged as strands, and pelletized.

[0104] Using the pellets obtained above, they were molded with an injection molding machine (J55AD manufactured by Japan Steel Works, Ltd.) to obtain test pieces for the Izod impact strength test. The Izod impact strength (hereinafter referred to as IZOD) was measured in accordance with JIS K 7110. An Izod tester JISL-D (manufactured by Toyo Seiki Seisakusho, Ltd.) was used as the testing machine. The results are shown in Table 2.

[0105] Regarding handleability, when measuring and charging into the twin-screw extruder, those in which the powder was difficult to scatter, the working environment did not deteriorate, and feeding was easy during kneading were rated as ○. Those in which the powder was easy to scatter, the working environment deteriorated, and feeding was difficult during kneading were rated as △.

[0106] [Table 2]

[0107] From the results in Table 2, it can be seen that the halogen-containing polymer of the present invention exhibits excellent impact resistance and handleability when compounded with the resin as compared with the conventional halogen-containing polymer.

Claims

1. The following general formula (1) 【Chemistry 1】 (In the formula, R represents an alkylene group having 1 to 6 carbon atoms, -S-, or -SO ２ - and n indicates a real number.) A halogen-containing polymer having a bulk density of 0.18 to 0.80 g / cm ３ 1. A powder made of a halogen-containing polymer, comprising:

2. 2. The powder made of a halogen-containing polymer according to claim 1, wherein in general formula (1), R is an alkylene group having 1 to 6 carbon atoms.

3. 2. The powder comprising the halogen-containing polymer according to claim 1, wherein in general formula (1), R is a 2,2-propylene group.

4. 4. A powder comprising the halogen-containing polymer according to claim 1, characterized in that the shape of the primary particles has an aspect ratio of 1.0 to 1.9 as measured using a particle shape image analyzer.

5. 4. A powder comprising the halogen-containing polymer according to claim 1, characterized in that a volume ratio of particles having a particle size of 1.0 to 20 μm as measured using an optical particle size analyzer such as a laser diffraction / scattering type particle size distribution analyzer is 80% or more.

6. 4. A powder comprising the halogen-containing polymer according to claim 1, characterized in that in a particle size distribution measured using an optical particle size analyzer such as a laser diffraction / scattering type particle size distribution analyzer, a particle size (d50) at which a cumulative frequency of 50% is reached is 2 to 50 μm.

7. 4. A powder comprising the halogen-containing polymer according to claim 1, characterized in that a volume ratio of particles having a particle size of 20 μm or more as measured using an optical particle size analyzer such as a laser diffraction / scattering type particle size distribution analyzer is 15% or less.

8. 4. A powder comprising the halogen-containing polymer according to claim 1, characterized in that a volume ratio of particles having a particle size of 1 μm or less as measured using an optical particle size analyzer such as a laser diffraction / scattering type particle size distribution analyzer is 15% or less.

9. 4. A powder comprising the halogen-containing polymer according to claim 1, characterized in that the particle size (d90) at which the cumulative frequency is 90% is 25 μm or less, as measured using an optical particle size analyzer such as a laser diffraction / scattering particle size distribution analyzer.

10. A step of synthesizing a halogen-containing polymer using a compound represented by the following general formula (2), a compound represented by the following general formula (3), a base, and a solvent, and then subjecting the obtained halogen-containing polymer to a polymerization reaction with a bulk density of 0.18 to 0.80 g / cm ３ and processing the powder. 【Chemistry 2】 (In the formula, R represents an alkylene group having 1 to 6 carbon atoms, -S-, or -SO ２ - indicates.) 【Chemistry 3】 (In the formula, X and Y represent halogen atoms.)

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