JP2001353720A - Method of treating resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treating method for a resin composition, in which the same consisting of a thermoplastic resin and a halogen base fire retardant is separated into the thermoplastic resin and a halogenated metallic compound and these are recovered. SOLUTION: A specific metallic compound, a processing agent having a capacity for hydrogenating halogen and a specific polymer are added to the resin composition consisting of a thermoplastic resin and a halogen base fire retardant. The mixture is allowed to react with each other in the conditions of <=450 deg.C. Thereby, halogen is made to a halogenated metallic compound. The thermoplastic resin and the halogenated metallic compound are separated from the resin composition and recovered.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition comprising a thermoplastic resin and a halogen-based flame retardant, which is used for treating a specific metal compound, a treating agent capable of hydrogenating halogen, and a method for converting a thermoplastic resin and halogen to hydrogen. In the presence of a polymer having a group having an affinity and / or a reactivity with both of a treating agent capable of forming a halogen, a halogen is converted into a metal halide compound at a temperature of 450 ° C. or less, and the resin composition is converted into a halogenated compound. The present invention relates to a method for separating and recovering a plastic resin and a metal halide compound.

[0002]

2. Description of the Related Art Flame retardant prescriptions are applied to resin materials used for housings of home appliances and building materials. For example, in many cases, a bromine-based flame retardant is kneaded in a television housing or a personal computer housing material in order to impart effective flame retardancy. These housings and housing materials contain 12 to 1 bromine.
In many cases, it is contained at 5% by weight. Further, in order to make the flame retardancy more effective, a metal compound is kneaded as a flame retardant auxiliary. These flame retardants and flame retardant auxiliaries have the effect of cutting off the contact between oxygen and the resin by heating, whereby halogen and a metal or a metal compound combine to form a metal halide compound and evaporate. Therefore, when the flame-retarded resin composition is burned or incinerated,
Metal halide compounds derived from these flame retardants and flame retardant aids are released, and at 800 ° C. or lower, brominated dioxins and benzofurans may be generated.

The following methods have been disclosed as methods for recovering halogens and metals or metal compounds from these halogen-containing resins. For example, JP-A-11-
293259 discloses a method for removing halogen from a halogen-containing thermoplastic resin. However, in this method, halogen is used as a metal salt using an alkaline earth metal, but this metal salt remains in the reaction residue,
Recovery of this metal salt is difficult. Further, the resin is thermally decomposed using a phosphorus-based or nitrogen-based catalyst to convert the resin into oil, and the oil is recovered. .

JP-A-10-328641 discloses a method for dechlorinating vinyl chloride using a thermoplastic resin. However, there is no disclosure or suggestion about a method for separating and recovering a halogen atom from a resin composition in the form of a metal halide compound. Japanese Patent Application Laid-Open No. Hei 10-237214 discloses a method in which waste plastic mixed with chlorine-containing plastic is heated, and a metal compound is generated by reacting a metal with hydrogen chloride generated here to perform vaporization and recovery. I have. However, this method is a method in which a metal chloride functions as a catalyst for thermally decomposing a resin and gasifies or oilifies the resin, and does not describe decomposition efficiency and the like.

JP-A-6-144801 discloses a method in which bromine and antimony contained in a thermosetting epoxy resin as an LSI encapsulant are heated to generate a gas, and the gas is hydrolyzed with an alkali to obtain a bromine. And a method of recovering antimony. However, there is no disclosure or suggestion regarding a thermoplastic resin. JP-A-6-1
No. 36458 discloses a technique in which zinc oxide is reduced to zinc and then reacted with vinyl chloride as a chlorine source to form zinc chloride, thereby reducing the boiling point. It is a method of collecting.

As described above, various methods for treating halogen have been studied. Halogen is separated, recovered, and separated from a resin composition comprising a thermoplastic resin and a halogenated compound at a temperature of 450 ° C. or less. A method for effectively obtaining a thermoplastic resin with a high recycling rate has not been developed.

[0007]

SUMMARY OF THE INVENTION The present invention provides a method for treating a resin composition comprising a thermoplastic resin and a halogenated compound without gasification or oilification of the resin by combustion or thermal decomposition.
It is an object of the present invention to provide a method for removing and recovering halogens such as bromine and metal oxides in a short time and at a high yield, and recovering and treating the treated resin as a solid fuel or a resin composition with high efficiency.

[0008]

Means for Solving the Problems The inventors of the present invention have proposed a method of hydrogenating a halogenated metal compound which reacts with a halogenated compound such as bromine to become a metal halide having a boiling point or sublimation point of 450 ° C. or less at atmospheric pressure. By using a polymer having a group having affinity and / or reactivity for both a thermoplastic resin and a treating agent capable of hydrogenating a halogen. The present inventors have found that compounds can be separated and recovered in a high yield in a short time, and have accomplished the present invention.

That is, the present invention provides: Metal compound capable of forming a metal halide compound having a boiling point or sublimation point of 450 ° C. or less at atmospheric pressure by combining a resin composition comprising a thermoplastic resin and a halogenated compound with a halogen atom, and the ability to hydrogenate halogen. Extrusion at 100 to 450 ° C. in the presence of a polymer having a group having affinity and / or reactivity for both a thermoplastic resin and a processing agent having the ability to hydrogenate halogen. A method for separating and recovering a thermoplastic resin and a metal halide compound from a resin composition, wherein the halogenated compound is a metal halide compound,

[0010] 2. Kneading at 100 to 450 ° C. with a radical generator added to a polymer having a group having affinity and / or reactivity for both a thermoplastic resin and a treating agent capable of hydrogenating halogen. Extrusion, wherein said halogenated compound is a metal halide compound.
2. The method for separating and recovering a thermoplastic resin and a metal halide compound from a fat composition according to 2. 3. The method for separating and recovering a thermoplastic resin and a metal halide compound from a resin composition according to the above 2, wherein the radical generator is an organic peroxide or an azo compound.

4. The resin composition according to any one of the above 1 to 3, wherein the resin composition contains a treating agent capable of hydrogenating halogen with a weight ratio of treating agent capable of hydrogenating halogen / resin composition of 0.7 or less. 4. The method for separating and recovering a thermoplastic resin and a metal halide compound from a resin composition according to any one of the above, The treating agent capable of hydrogenating halogen is carbon /
An organic compound in which the element ratio of hydrogen is 0.25 to 1.0,
Alternatively, characterized in that it is a polymer, a method for separating and recovering a thermoplastic resin and a metal halide compound from the resin composition according to any one of the above 1 to 4,

6. The treating agent having the ability to hydrogenate halogen is a polyolefin, and the thermoplastic resin and the metal halide compound are separated and recovered from the resin composition according to any one of 1 to 5 above. Method, 7. The method according to any one of the above items 1 to 6, wherein the effective treatment surface area is 5 m ^{2 to} 1000 m ² , and the degree of reduced pressure is 13.3 kPa or less, using a device having a rotary stirring function. A method for separating and recovering a thermoplastic resin and a metal halide compound from a resin composition,

8. The value of the specific energy applied to the resin composition before the temperature of the resin composition reaches 300 ° C. is 10 MJ /
characterized in that it is a m ³ ~300MJ / m ^3, the 1
A method for separating and recovering a thermoplastic resin and a metal halide compound from a resin composition according to any one of claims 1 to 7,

9. Wherein the separated and recovered metal halide compound is treated with an aqueous alkali solution, and the metal of the metal halide compound is converted into a metal oxide.
9. The method for separating and recovering a thermoplastic resin and a metal halide compound from a resin composition according to any one of the above, 10. the metal oxide obtained by the method according to 9 above; Obtained by the method according to any one of the above 1 to 9,
And the separated and recovered thermoplastic resin.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The thermoplastic resin in the present invention may be any resin that can be plasticized by heating. Specific examples include vinyl chloride, polyvinylidene chloride, styrene-based resin, and modified PPE resin (eg, GE Plastic brand name NORYL and Asahi Kasei Kogyo brand name XYRON),
Polymethyl methacrylate (PMMA), polyvinyl acetate (PVA), polyacetal (POM), polybutylene terephthalate (PBT), polyamide (PA), polyacrylonitrile and the like. The styrene-based resin as used herein refers to a polymer having a styrene monomer unit of 50% by weight or more, such as GPPS, syndiotactic polystyrene,
High impact polystyrene (HIPS), styrene
Acrylonitrile / butadiene graft copolymer (AB
S resin), styrene-acrylonitrile copolymer (SA
N), styrene-methyl methacrylate copolymer (M
S), styrene-methacrylic acid copolymer (SMAA),
Styrene / maleic anhydride copolymer (SMAH), styrene / butyl methacrylate copolymer and the like.

The halogenated compound in the present invention may be any compound which is added to impart flame retardancy to the resin composition and is a compound containing halogen. Specifically, brominated polystyrene, chlorinated polystyrene, brominated polystyrene, or styrene-based resin, decabromodiphenyl ether, tetrabisphenol A, or an oligomer thereof, polybrominated modified epoxy compound, hexabromobenzene, brominated polyethylene, decapolyethylene Bromobiphenyl, 1,2,3,4,5 pentabromotoluene, 1,2,3,4,5 pentabromoethylbenzene, bis (1,3,5 tribromophenoxy) ethylene 1,2,3,4,5 Pentabromophenol, 1,
Examples include 3,5 tribromophenol, polybrominated styrene monomers and oligomers, and polybrominated cycloalkanes.

The metal compound having a boiling point or sublimation point of 450 ° C. or less at atmospheric pressure in combination with a halogen atom in the present invention includes zirconium oxide (zirconia), zinc oxide (zinc white), stannous oxide, There are stannic oxide, tetraphenylstibine, bismuth oxide (pyrite), diantimony trioxide (pyroxene), cerium oxide (ceria), titanium oxide (titania), oxoantimony (III) chloride, and the like.

These react quickly with the halogenated compound in the presence of the resin component to vaporize and evaporate. This reactivity greatly depends on the temperature at which the metal oxide reacts with the hydrocarbon resin to reduce the metal. The prior art describes that the generated hydrogen halide reacts with the metal to form a metal halide compound. However, the reaction does not proceed efficiently even when the above-described metal is reacted with the hydrogen halide. This is presumably because when the metal and the halogenated compound react, a part of the metal compound is transferred to the metal halide compound, but most of the metal halide compound remains in the resin component as a halogenated organometallic compound. When aluminum powder was reacted with a styrene resin composition having a bromine concentration of 16% by weight at 350 ° C., the bromine removal rate was 3%.
It stays at around 0%. In order to quickly and effectively convert a halogen into a metal halide as described above, it is preferable to react with the halogenated compound in an atmosphere in which the metal compound is reduced to a metal. That is, the metal compound and the halogenated compound are effectively generated in the resin. The reaction temperature at this time is an important factor when removing the halogen and metal compound components, and at the same time, an important factor in determining the performance of the metal compound as a flame retardant aid. This temperature depends on the boiling point and the sublimation temperature of the metal halide compound generated in the above reaction.

The treating agent capable of hydrogenating halogen in the present invention is preferably an organic compound or a polymer. The organic compound refers to a compound mainly composed of carbon and hydrogen atoms, and is not particularly limited, but includes alkane hydrocarbons including mineral oil,
Those having a high boiling point, such as heavy oil, are preferred. The above-mentioned polymer mainly refers to a thermoplastic resin.

The treating agent capable of hydrogenating halogen in the present invention refers to an organic compound having a secondary or tertiary hydrogen in the molecule, a thermoplastic resin, or a mixture thereof. Specific examples include PP wax, PE wax, beeswax, paraffin wax, 9,10-dihydroanthracene, mineral oil, tetralin, petroleum resin,
Refers to polyolefin resins and the like. Here, examples of the polyolefin resin include low-density polyethylene, high-density polyethylene, polyethylene / polypropylene copolymer, and polypropylene. Preferably, it is a polyolefin resin having tertiary hydrogen having a high hydrogenation ability, particularly preferably polypropylene. The polypropylene may be a virgin polypropylene that is distributed as a normal product or a polypropylene that is discharged from waste products such as home appliances and automobiles. Of course, a mixture of these may be used.

The polymer having a group having affinity and / or reactivity for both the thermoplastic resin and the treating agent capable of hydrogenating halogen in the present invention will be described. Having an affinity means having the structural unit having the same or the same chemical structure as the above-mentioned polymer in the present invention, the thermoplastic resin in the present invention, and a treating agent capable of hydrogenating halogen. These structural units are represented by nuclear magnetic resonance (NMR)
Method) and an infrared absorption method (IR method).

As a preferred example having affinity, a polymer having a structural unit having a chemical structure similar to or the same as that of the thermoplastic resin and the treating agent capable of hydrogenating halogen in the present invention, The composition obtained by kneading and extruding a plastic resin and a treating agent having an ability to hydrogenate halogen is observed when its structure is observed by, for example, a scanning electron microscope (SEM), when it is in a uniform phase, or The case where the dispersed phase is the continuous phase and the case where the average particle diameter in terms of circle of the dispersed phase is 30 μm or less can be mentioned.

Examples of such combinations having affinity include a styrene-conjugated diene copolymer, polyethylene,
Polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer or other homo- or copolymer containing α-olefin containing ethylene as a constituent unit, homo- or copolymer containing aromatic vinyl as a constituent unit such as polystyrene , A combination of PPE, a homo- or copolymer containing aromatic vinyl such as polystyrene in the constituent unit and a combination of PPE, a combination of polycarbonate and polymethyl methacrylate, a combination of ABS resin and MS, a combination of polyethylene terephthalate and polybutylene terephthalate As described above, there is a combination of polymers having an ester bond in the main chain.

Other than the combinations exemplified here, a composition having a similar or identical chemical structure to the above-mentioned polymer in the present invention, the thermoplastic resin in the present invention, and the treating agent capable of hydrogenating halogen. Any combination may be used as long as it has a unit.

Examples of the combination of groups having reactivity include a combination of an amino group with an acid anhydride group, an epoxy group, a carboxylic acid group, an isocyanate group, and the like.
Of course, any combination of groups may be used as long as a chemical reaction occurs. As a method for confirming these chemical reactions, a conventionally known method, specifically, a nuclear magnetic resonance method (NMR)
Method), infrared absorption method (IR method) and the like. Further, a polymer having a group reactive with both the thermoplastic resin in the present invention and a treating agent capable of hydrogenating halogen has the ability to hydrogenate the thermoplastic resin and halogen in the present invention. When the composition of the composition after kneading and extruding the treatment agent is observed by, for example, a scanning electron microscope (SEM), when the composition is in a uniform phase,
Alternatively, when the dispersed phase is a continuous phase and the average particle diameter of the dispersed phase in terms of circle is 30 μm or less, it can be determined that a chemical reaction has occurred.

The term "metal halide compound" as used herein means a halogen compound formed from the above metal compound.
X ₄ , ZnX ₂ , SnX ₂ , SnX ₄ , SbX ₃ , SbX ₅ ,
BiX ₃ , CeX ₃ , TiX _{4 and the} like. Here, X is a halogen element. The kneading extrusion in the present invention means that two or more components of a resin or a resin composition are continuously kneaded by a machine such as an extruder, a kneader, and a Banbury.
Separating and recovering the thermoplastic resin and the metal halide compound from the resin composition in the present invention means removing the halogen from the resin component by vaporizing and recovering the metal halide compound produced by the reaction.

The radical generator in the present invention may be any compound as long as it is a compound which generates a radical by causing a chemical reaction by the application of external energy such as heat or light. . Preferably, it is a compound that undergoes thermal decomposition to generate a radical. Specific examples of these radical generators include 2,2-di (t-butylperoxy) butane, 2,2-di (t-butylperoxy) octane, 1,1-di-t-butylperoxy- Organic peroxides of 3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, benzoyl peroxide Examples thereof include oxides and azo compounds such as azobisisobutyronitrile. Other compounds may be used as long as they generate a radical by causing a chemical reaction when energy from the outside such as heat or light is applied.

These radical generators may be used alone, two or more radical generators may be used in combination, or any of them may be used. Further, the radical generator is present in a resin composition comprising a thermoplastic resin and a halogenated compound and a composition comprising a metal compound having a boiling point or a sublimation point of 450 ° C. or less at atmospheric pressure in combination with a halogen atom. The method may be either before kneading / extrusion, during kneading / extrusion, or a method in which a part is present before kneading / extrusion and the remainder is present during kneading / extrusion.

The apparatus having a rotary stirring function in the present invention refers to an apparatus whose surface is constantly renewed in order to knead a melt and vaporize and recover a halogen and a metal halide. Specifically, extruders, kneaders, reactors with rotating blades,
A continuous degassing device in which a filler is present may be used. In addition,
An effective surface area is defined as an index indicating the deaeration efficiency as follows. The effective treatment surface area indicates the degree of renewal of the volatile surface for removing volatile bromine compounds and antimony compounds, and is defined as follows.
Here, a method for introducing an effective surface area will be described with a specific example of a kneader as a device having a rotary stirring function.

As shown in FIG. 1, consider a cross section of the barrel of the kneader viewed perpendicularly to the screw direction. At this time, when the screw rotates, the resin pool (FIG. 4) rotates, and the depopulated resin is stretched to form a thin film (FIG. 5) on the inner surface of the barrel. Hydrogen bromide and antimony compounds are volatilized from the thin film-like resin film. Film surface area dS _f of the screw unit construction element length per dL at this time is represented by the following formula.

DS _f = (1/2) · D · [(4π−2
β) -i (θ + α)] dL where D represents the internal diameter of the cylinder, π is the pi,
β is the side opening angle (flank angle), α is the vertex angle of the screw element, and i is the number per section of the resin pool. When removing volatile components from the resin component, it depends on how much the film surface area can be obtained during processing. This index is defined as the processing surface area. Accordingly, the processing surface area of the kneader is represented by the following equation.

S _f = {dSf = (１ ／) · D} [(4
π-2β) -i (θ + α)] dL However, integration range shown here L ₀ is kneader barrel length from L = 0 to L = L _0. Since the angle θ related to the resin pool is presumed to have little dependence on L when the screw element configuration is a desk type, the above method can be simplified. Effective treatment surface area S _e during the treatment from The thus obtained treated surface area S _f
Derive. This surface area indicates how much the surface has been degassed when the resin is treated in the kneader, and is defined as follows.

S _e = S _f · τ / t _f where τ is the residence time of the kneader, t _f is the time until this treated surface is newly regenerated, and 1 / t _f is the treated surface per unit time. Indicates the number of updates to The value of this t _f is derived by the following equation. t _f = (1/2) · (D / v) [(4π−2β) / i−
(Θ + α)] where v represents the speed of the screw in the barrel,
(Inner diameter of barrel) × (number of screw rotations).

Although the above is an example of a kneader, the present invention is not limited to a kneader as long as the reactor is of a type in which the surface is constantly renewed as defined above. For example, the reactor may be filled with a filler. The effective processing surface area at this time is represented by S _e = a · N · F. Here, a is the surface area per packing, N is the number of packings present in the reactor, and F is the surface renewal coefficient.

In the present invention, the specific energy is an index indicating how much energy per unit volume the mixture of the treating agent and the resin receives by shearing when the treating agent and the resin are mixed with each other. It shows the mixing index of the agent. That is, the higher the value, the better the kneading. This definition is expressed by the following equation. e _v = η · (dγ / dt) · τ where (dγ / dt) is the average shear rate, η is the viscosity of the resin compound, and τ is the residence time. As this equation shows,
If the viscosity is low, this value becomes small, and the kneading of the resin and the treating agent is not performed well.

In the present invention, the treatment with an aqueous alkali solution means neutralizing and hydrolyzing the vaporized and recovered gas with an aqueous alkali solution having a pH of 7 or more, such as a sodium hydroxide solution, a potassium hydroxide aqueous solution, or a hydroxide solution. It refers to calcium suspension, sodium bicarbonate aqueous solution, sodium carbonate aqueous solution, ammonia aqueous solution and the like.

A halogen-containing thermoplastic resin or a thermoplastic resin composition containing a halogenated compound has a temperature of 280 ° C.
Then, it reacts with the metal compound to become a metal halide compound and evaporates. Factors affecting this effect are greatly related to the reduction temperature of the metal compound with the hydrocarbon compound and the boiling point and sublimation point at normal pressure of the generated metal halide compound. The reduction temperature is 450 ° C. or less, preferably 400 ° C.
C. or lower, more preferably 300 ° C. or lower. Also,
The boiling point or sublimation point of the resulting metal halide compound under normal pressure is 400 ° C or lower, preferably 350 ° C or lower, more preferably 300 ° C or lower.

If the reduction temperature exceeds 450 ° C., the formation of the metal halide compound does not occur unless the temperature is considerably high. The effect of the boiling point or sublimation point under normal pressure of the generated metal halide compound is not only that the dehalogenation effect is lowered when the temperature exceeds 400 ° C. The metal halide compound remains undesirably. For example, diantimony trioxide (reduction temperature with polystyrene is 280 to 300 ° C.)
Is a brominated compound at a temperature of 280 in the presence of a thermoplastic resin.
At ~ 300 ° C, antimony tribromide is generated and begins to evaporate. The temperature condition at this time is 100 to 450 ° C, preferably 150 to 380 ° C, and more preferably 200 to 450 ° C.
320 ° C. If the temperature condition at this time is lower than 100 ° C., the reaction does not proceed. If the temperature condition is 450 ° C. or higher, the decomposition reaction of the resin itself proceeds in addition to the reaction between the halogen and the metal compound, which is not preferable because the amount of recovered resin decreases.

In order to further accelerate the effect of producing the metal halide compound and enhance the dehalogenation effect, it is preferable to add a treating agent having a hydrogenation ability. The carbon / hydrogen element ratio in the treating agent having the ability to hydrogenate halogen in the present invention refers to the constituent hydrogen number and carbon number ratio of the compound used as the hydrogenating agent. (2n + 2). Here, n indicates the number of carbon atoms. The treating agent is not particularly limited, but the element number ratio of carbon / hydrogen is 0.25 to 1.0, preferably 0.255.
-0.8, more preferably 0.3-0.7. If the element number ratio of carbon / hydrogen exceeds 1.0, halogen is not hydrogenated and the treating agent is carbonized, which is not preferable.

As the treating agent having the hydrogenation ability, a polyolefin resin, particularly, a polypropylene having tertiary hydrogen is preferable. The ratio of the treating agent capable of hydrogenating the halogen to the resin mixture is a weight ratio, and is preferably 0.7 or less. If the weight ratio exceeds 0.7, the metal is reduced by the reducing ability of the treating agent, and this component cannot be degassed and recovered, which is not preferable. In the present invention, the value of the specific energy applied to the resin composition in order for the temperature of the resin composition to reach 300 ° C. means that the resin composition to be treated and the treating agent are charged from the raw material inlet of the preheating kneading extruder. Indicates the energy per unit volume of the kneaded material that has been incurred by shearing until the temperature of the melt reaches 300 ° C.

A halogen-containing thermoplastic resin and a metal compound,
Or to efficiently react the thermoplastic resin composition containing a halogenated compound, the metal compound and the hydrotreating agent,
It is necessary that the preheating and kneading be sufficiently uniform before the reaction. The value of the specific energy indicating the kneading condition at this time is 10 MJ / m.
^{3 to} 300 MJ / m ³ , preferably 20 MJ / m ^{3 to} 20
0 MJ / m ³ , more preferably 50 MJ / m ^{3 to} 150
MJ / m ³ . If it is less than 10 MJ / m ³ , the resin, the treating agent and the metal compound cannot be kneaded well, and 300 MJ / m ³
If the temperature exceeds the limit, shear heat generation becomes remarkable, and the treatment agent and the resin and the metal compound react before being uniformly kneaded, which is not preferable.

Further, when a treating agent is kneaded with a resin, a certain degree of viscosity is required. The viscosity at this time is governed by the temperature, and when the resin temperature is 300 ° C. or higher, the viscosity decreases. Therefore, the treating agent, the resin and the metal compound are not well kneaded. Therefore, the value of the specific energy before the resin temperature reaches 300 ° C. is an important factor for effectively proceeding this reaction system. This confirmation, after pre-kneading the treatment agent and the resin and the metal compound in the extruder, once open the extruder barrel, measure the resin temperature with a thermocouple thermometer, extract the melted portion below 300 ℃, This was quenched in liquid nitrogen, cut with a microtome, and the state of dispersion was confirmed with a transmission electron microscope. Uniform dispersion here means
This refers to a state in which the treating agent and the resin component to be treated are dispersed at approximately 100 μm or less.

The thus uniformly mixed resin melt is sent to an apparatus having a rotary stirring function, where the reaction and deaeration are performed. Here, the reaction proceeds at a stretch, and a metal halide compound and hydrogen halide are generated. It is preferable to remove both of them promptly. An index indicating this efficiency, that is, the effective treatment surface area is 5 to 1000 m ² , preferably 20 to 500 m ² , and more preferably 100 to 3 m ² .
It is a 00m ^2. If it is less than 5 m ² , the generated metal halide compound reacts with the resin component. For example, in the case of antimony tribromide, an alkyl stibine is formed, and the purity of the recovered antimony decreases, which is not preferable. If it exceeds 1000 m ² , this removal step becomes unstable, which is not preferable.

The degree of decompression in the present invention refers to FIG.
Means the pressure inside the kneader. When the pressure in the removal system is reduced, halogen and metal halide can be removed more effectively. This degree of pressure reduction is 13.3 kPa or less,
Preferably, 6.7 kPa, more preferably 1.3 kPa
Pa. If the degree of decompression exceeds 13.3 kPa, the degassing efficiency will be poor, and it will not be possible to remove halogens and metal compounds in a short time. In addition to the reduced pressure, an inert gas such as nitrogen or argon gas can be introduced into the removal system to increase the efficiency of vaporization and recovery. Since the resin treated in this manner becomes waxy and contains almost no halogen or metal compound, it may be solidified after cooling and used as a solid fuel or a raw material for oilification.

The metal halide is hydrolyzed by passing the recovered gas through an alkaline aqueous solution or spraying and washing the alkaline aqueous solution. For example, in the case of antimony tribromide, it becomes diantimony trioxide and easily precipitates because of its high specific gravity. At this time, since bromine is present as sodium bromide in the aqueous solution, the crystals can be recovered by removing the precipitate and then evaporating to dryness.
The reaction in the present invention employs a method of vaporizing and recovering halogens and metals, and thus the recovered metals and halogens have high purity and can be reused as industrial raw materials.

The metal oxide in the present invention refers to a metal oxide obtained by hydrolyzing a produced metal halide compound and then drying it. For example, antimony trioxide, diantimony pentoxide, Zinc, bismuth oxide, etc. The recovered thermoplastic resin in the present invention refers to a resin component that has been dehalogenated by the method in the present invention. Hereinafter, the present invention will be described with reference to examples.

(1) Analysis of Halogen and Metal Halogen was analyzed by burning in a combustion flask under pure oxygen, absorbing this gas into water previously placed in the flask, and mixing acetic acid and sodium acetate. Liquid (buffer)
After adjusting the pH with a bromine ion meter (Towa Denpa Co., Ltd.)
IN55S). The metal (antimony) was measured by a plasma ion method (ICP method) or an atomic absorption spectrometry.

(2) a halogenated compound-containing resin composition,
Treatment agent, metal compound Commercially available HIPS (trade name A & M Polystyrene H8
117) / decabromodiphenyl ether (manufactured by Tosoh Corporation) or zinc white (manufactured by Wako Pure Chemical Industries, Ltd.) was previously kneaded with an extruder at a weight ratio of 80.25 / 5 to prepare a model resin composition. The treating agent is polypropylene (manufactured by Nippon Polyolefin Co., Ltd., trade name J-ALOMER PM)
600A, melt index 20g / 10min) to 90
200 parts by weight of perhexa 25B or perbutyl P (both manufactured by NOF Corporation) as a radical generator
0 ppm was added.

(3) Measurement of Viscosity The viscosity was measured by a capillary viscometer, and after the Baclay correction was performed, the viscosity was determined.

(4) Implementation Process Before the reaction between the model resin composition and the treatment agent, a pre-kneading extruder is installed before the kneader in order to knead well.
At this time, the tip pressure of the pre-kneading extruder is maintained at 12 MPa. The kneaded treating agent and the model resin composition are sent to a kneader through an orifice tube, and deaeration is performed.
The L / D of the pre-kneading extruder is 10.25, the screw diameter is 24.5 mm, the clearance between the screw and the barrel of the preheating kneading extruder is 0.5 mm, and the screw rotation speed is 50 to 200 rpm. The resin temperature at the outlet of the preheating kneading extruder was 280 to 310 ° C. The completely homogeneously kneaded model resin composition and the treating agent are sent to a kneader. The pressure in the kneader system was 1.3 kPa to 13 kPa.

The processing time was set so as to be paid out within 5 minutes. The generated gas is sucked by a corrosion-resistant ceramic vacuum pump and introduced into the washing tower through an exhaust line. An aqueous solution of sodium hydroxide is sprayed from the upper stage of the washing tower to react with the gas, and antimony tribromide or zinc bromide and hydrogen bromide are excluded. PH of the recovered washing liquid at this time
Was adjusted to be 7 to 12. The recovered washing liquid is sent to a continuous filtration device in a white suspension state, and is separated into diantimony trioxide or zinc white and an aqueous sodium bromide solution.
The diantimony trioxide or zinc white is dried. In the case of antimony, its purity was 99.8%. The separated aqueous solution was evaporated to obtain NaBr with a purity of 99%.

[0052]

Examples 1 and 2 and Comparative Examples 1 and 2
Comparative Examples 2 and Comparative Examples 1 and 2 show the effect of adding a polymer having a group having affinity and / or reactivity to both a thermoplastic resin and a treating agent capable of hydrogenating halogen. . In each of Examples and Comparative Examples, decabromodiphenyl ether and a metal compound were added to high impact polystyrene (HIPS) using a ZSK-25 extruder manufactured by Warner Co., Ltd.
A resin composition premixed at 30 ° C. was used. To this resin composition was added 9 polypropylene (PP) as a hydrotreating agent.
0 parts by weight, and a styrene-hydrogenated butadiene block copolymer as a polymer having a group having affinity and / or reactivity for both a thermoplastic resin and a treating agent capable of hydrogenating halogen were added. . As a styrene-hydrogenated butadiene block copolymer, Tuftec H1043 manufactured by Asahi Kasei Corporation was used. The reaction conditions are as follows: effective treatment surface area is 300 m ² , specific energy is 15
0 MJ / m ³ .

[0053]

[Table 1]

[0054]

According to the present invention, resin waste is treated without gasification or oilification of the resin by combustion or thermal decomposition, and halogen or metal oxide such as bromine is removed therefrom for a short time.
It is possible to provide a method in which the resin that has been removed and recovered in a high yield and that has been treated can be efficiently recovered and reused as a solid fuel.

[Brief description of the drawings]

FIG. 1 shows a cross section of a kneader.

FIG. 2 is an implementation process used in the study of the present invention.

[Explanation of symbols]

1: Indicates the apex angle α of the screw element. 2: Indicates the side opening angle β. 3: Indicates the angle θ related to the resin pool. 4: Indicates a resin pool. 5: The barrel surface of the kneader involved in degassing is shown. 6: A feeder for feeding the resin to be treated into the preheating kneading extruder. 7: Preheating kneading extruder is shown. 8: Shows an orifice tube. 9: Degassing line is shown. 10: Indicates a kneader. 11: Indicates a vacuum pump. 12: Dispensing gear pump is shown. 13: Indicates a payout port. 14: Shows a washing tower (gas absorption tower). 15: Shows the entrance of the alkaline aqueous solution. 16: A sprayer of an alkaline aqueous solution is shown. 17: Exhaust line is shown. 18: Shows a filtration device. 19: Shows a device for discharging the filtrate. 20: Shows the outlet of the filtrate.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 11/00 F term (Reference) 4D002 AA24 AC10 BA02 CA01 CA06 DA02 DA03 DA05 DA07 DA12 DA16 EA07 FA02 FA04 FA05 FA06 FA10 4F301 AB01 AD02 BA12 BA21 BC13 BC26 BC36 BC40 BE44 BF29 BF31 CA04 CA09 CA11 CA32 CA41 CA68 CA72 4G048 AA06 AB01 AB02 AB08 AD03 AE02

Claims (11)

[Claims] 1. A resin composition comprising a thermoplastic resin and a halogenated compound is bonded to a halogen atom to form a resin composition under atmospheric pressure.
A metal compound that produces a metal halide compound having a boiling point or sublimation point of 50 ° C. or less, a treating agent capable of hydrogenating halogen, and both a thermoplastic resin and a treating agent capable of hydrogenating halogen. 100 to 4 in the presence of a polymer having a group having affinity and / or reactivity.
A method of kneading and extruding at 50 ° C. to convert the halogenated compound into a metal halide compound and to separate and recover a thermoplastic resin and a metal halide compound from the resin composition. 2. A polymer having a group having an affinity and / or a reactivity with both a thermoplastic resin and a treating agent capable of hydrogenating halogen, and a radical generator is added to the polymer. 2. The method of claim 1, wherein the halogenated compound is a metal halide compound.
4. The method for separating and recovering a thermoplastic resin and a metal halide compound from a fat composition according to the above. 3. The method for separating and recovering a thermoplastic resin and a metal halide compound from a resin composition according to claim 2, wherein the radical generator is an organic peroxide or an azo compound. 4. A resin composition comprising a treating agent capable of hydrogenating halogen with a weight ratio of treating agent capable of hydrogenating halogen / resin composition of 0.7 or less. A method for separating and recovering a thermoplastic resin and a metal halide compound from a resin composition according to any one of claims 1 to 3. 5. The treatment agent having the ability to hydrogenate halogen is an organic compound or a polymer having a carbon / hydrogen element ratio of 0.25 to 1.0. 5. The method for separating and recovering a thermoplastic resin and a metal halide compound from a resin composition according to any one of 1 to 4. 6. The resin composition according to claim 1, wherein the treating agent having the ability to hydrogenate halogen is a polyolefin. A method for separating and recovering compounds. 7. Using a device having a rotary stirring function, the effective treatment surface area is 5 m ^{2 to} 1000 m ² , and the degree of pressure reduction is 13.
The method for separating and recovering a thermoplastic resin and a metal halide compound from a resin composition according to any one of claims 1 to 6, wherein the method is carried out under a condition of 3 kPa or less. 8. The value of the specific energy applied to the resin composition until the temperature of the resin composition reaches 300 ° C. is 10 MJ / m.
2. The method according to claim 1, wherein the amount is ^{3 to} 300 MJ / m ^3.
8. The method for separating and recovering a thermoplastic resin and a metal halide compound from a resin composition according to any one of items 7 to 7. 9. The method according to claim 1, wherein the separated and recovered metal halide compound is treated with an aqueous alkali solution to convert the metal of the metal halide compound into a metal oxide.
The method for separating and recovering a thermoplastic resin and a metal halide compound from a resin composition according to any one of the above. 10. The metal oxide obtained by the method of claim 9. 11. The separated and recovered thermoplastic resin obtained by the method according to claim 1.