JP4686757B2 - ABS resin and process for producing the same - Google Patents

Description

  The present invention relates to an ABS resin having a carbonate group on an aromatic side chain and having a drip suppression effect during thermal decomposition or combustion.

ABS resin has excellent properties such as processability, dimensional stability, electrical properties, mechanical properties, and chemical stability, so it can be used in a wide range of fields such as transportation equipment, electrical and electronic equipment, housing equipment, and general merchandise. Has been used. However, the use of ABS resins is limited because they are flammable, and there are many application fields that require flame retardance in order to minimize damage during fires. And the method of making it flame retardant by the synergistic effect by adding antimony trioxide and the like has been employed (see, for example, Patent Document 1). However, the toxicity of halogen-based gases generated during combustion has become a problem, and the development of a flame-retardant method that does not generate these halogen-based gases has been desired.
Further, as non-halogen flame retardants added to ABS-based resins, phosphate esters are known (for example, see Non-Patent Document 1), but the performance is still insufficient, and phosphate esters are also included. The inherent hydrolyzability is also regarded as a problem in relation to the stability of resin physical properties. Furthermore, it is said that the environmental impact of phosphorus compounds is usually less than that of halogen compounds, but it is not always clear.

  On the other hand, in order to prevent the spread of damage due to the spread of fire at the time of fire, flame-retardant standards such as UL-94, JIS Z 2391, etc., are evaluated as the burning rate and dripping while dripping softened material (drip ) Has been incorporated into the regulations. For this reason, in addition to an additive that makes the polymer itself difficult to burn, an additive that suppresses the drip that causes fire spread to others is also added. As an additive for suppressing this drip, a fluororesin is often used (for example, see Patent Document 2), but it is known that a fluororesin generates a toxic gas at a high temperature.

Japanese Patent Laid-Open No. 10-147692 JP-A-6-9887 Journal of Japan Society for Technology Information, 2000, p320 “High-functionality / reforming technology for olefin and styrene resins”

  This invention is made | formed in view of the above-mentioned actual condition in a prior art. That is, an object of the present invention is to provide a flame-retardant ABS-based resin that does not generate harmful substances that adversely affect the environment and the human body, lowers the burning rate and suppresses drip, and a simple manufacturing method thereof. It is to provide.

  As a result of intensive studies to solve the above-mentioned problems, the inventors have given a specific functional group on the aromatic ring in the ABS resin, thereby reducing the burning rate during combustion. The present inventors have found that a flame-retardant ABS-based resin capable of effectively suppressing drip can be obtained, and based on this fact, the present invention has been completed.

That is, the present invention provides the following (1) to (5).
(1) An ABS resin characterized in that a part or all of the aromatic rings are substituted with an organic carbonate group.
(2) A siloxane or silsesquioxane in which a part or all of the aromatic ring is substituted with an organic carbonate group and the carbon-carbon unsaturated bond of the conjugated diene polymer has a Si-H bond is added. It is an ABS resin characterized by being.
(3) An ABS resin in which the organic carbonate group of the substituent directly bonded to the aromatic ring is an aryloxycarbonyloxy group or an alkoxycarbonyloxy group.
(4) A method for producing an ABS resin, comprising reacting a conjugated diene polymer, a vinyl cyanide compound, and a vinyl compound containing an aromatic vinyl compound having an aromatic ring substituted with an organic carbonate group. .
(5) A vinyl compound comprising a conjugated diene polymer bonded with a siloxane or silsesquioxane having a Si-H bond, a vinyl cyanide compound, and an aromatic vinyl compound in which an aromatic ring is substituted with an organic carbonate group. It is the manufacturing method of ABS resin characterized by making these react.
(6) An ABS resin characterized by reacting a conjugated diene polymer with a vinyl compound containing a vinyl cyanide compound, an aromatic vinyl compound, and an aromatic vinyl compound in which an aromatic ring is substituted with an organic carbonate group. It is a manufacturing method.
(7) Conjugated diene polymers bonded with siloxanes or silsesquioxanes having Si-H bonds, vinyl cyanide compounds, aromatic vinyl compounds, and aromatic vinyl compounds in which aromatic rings are substituted with organic carbonate groups A process for producing an ABS resin characterized by reacting with a vinyl compound containing.

  According to the present invention, since the burning speed is slow at the time of combustion and excellent drip resistance, a good flame retardant ABS-based resin that can be used in a wide range of fields as a highly safe synthetic resin is easily provided. The

  In the ABS resin of the present invention, not only the ternary copolymer of acrylonitrile, butadiene and styrene, which are basic components, but also part or all of the acrylonitrile component is replaced with another vinyl cyanide compound such as methyl methacrylate. Resins, resins in which the butadiene component is replaced with other conjugated diene polymers, resins in which part or all of the styrene component is replaced with other aromatic vinyl compounds such as vinyl naphthalenes or vinyl biphenyls, and acrylates In addition, resins added with vinyl compounds such as acrylamides and vinyl esters, resins added with unsaturated compounds such as α-methylstyrene and N-phenylmaleimide, and mixed resins obtained by mixing these, A part or all of the aromatic rings contained in the organic carbonate group Which is substituted, and further conjugated diene polymer carbon - those, appended siloxanes or silsesquioxanes having a Si-H bond to carbon unsaturated bond.

  As a method for producing the above-mentioned ABS resin, for example, a conjugated diene polymer or a conjugated diene polymer obtained by adding a siloxane or silsesquioxane having a Si-H bond to its carbon-carbon unsaturated bond is cyanidated according to a conventional method. It can be obtained by subjecting a vinyl halide compound and an aromatic vinyl compound having an aromatic ring substituted with an organic carbonate group to a polymerization reaction, particularly a graft polymerization reaction. The ABS resin thus obtained is a flame-retardant thermoplastic resin that has a low combustion rate during combustion, does not generate harmful chemical substances, and has improved drip resistance.

  The ABS-based resin of the present invention can be used alone, but an additive can be added as appropriate to this. Moreover, it can also be used by mixing with other resin.

  As the conjugated diene polymer used for the production of the ABS resin, any polymer can be used as long as it contains conjugated dienes in the monomer, and includes homopolymers, copolymers, and the like. , Polyisoprene, butadiene-isoprene copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene rubber, ethylene-propylene-butadiene copolymer, and the like. Among them, polybutadiene is preferable.

  Next, a conjugated diene polymer or a conjugated diene polymer obtained by adding a siloxane or a silsesquioxane having a Si-H bond to the carbon-carbon unsaturated bond is converted into a vinyl cyanide compound and an aromatic ring as the next step. An ABS resin is produced by using the above for a graft polymerization reaction with an aromatic vinyl compound substituted with an organic carbonate group such as an aryloxycarbonyloxy group or an alkoxycarbonyloxy group.

The vinyl cyanide compound is not particularly limited, and examples thereof include acrylonitrile, methacrylonitrile, vinylidene cyanide and the like. A vinyl cyanide compound can also be used individually by 1 type or in mixture of 2 or more types.
The aromatic vinyl compound is not limited at all, but typical examples thereof include styrenes such as styrene and 4-methylstyrene, vinyl naphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene, Examples include vinyl biphenyls such as 4-phenylstyrene.

  The aromatic vinyl compound in which the aromatic ring is substituted with an organic carbonate group is not limited as long as the carbonate group is directly bonded to the aromatic ring, but a typical one has an aromatic ring. An organic carbonate group such as an aryloxycarbonyloxy group or an alkoxycarbonyloxy group is directly bonded to an aromatic ring other than a vinyl group. For example, 4-phenoxycarbonyloxystyrene, 3-phenoxycarbonyloxy Aryloxycarbonyloxystyrenes such as styrene, (aryloxycarbonyloxy) (vinyl) naphthalenes such as 1-aryloxycarbonyloxy-4-vinylnaphthalene, 2-aryloxycarbonyloxy-6-vinylnaphthalene, 4- ( Aryloxycarboni (Aryloxycarbonyloxy) (vinyl) biphenyls such as oxyphenyl) styrene, alkoxycarbonyloxystyrenes such as 4-alkoxycarbonyloxystyrene, 3-alkoxycarbonyloxystyrene, 1-alkoxycarbonyloxy-4-vinylnaphthalene, (Alkoxycarbonyloxy) (vinyl) naphthalene such as 2-alkoxycarbonyloxy-6-vinylnaphthalene, (alkoxycarbonyloxy) (vinyl) biphenyl such as 4- (alkoxycarbonyloxyphenyl) styrene, and the like.

  The aryl is not particularly limited, and is preferably a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a naphthyl group, and particularly preferably a phenyl group. The alkoxy is not particularly limited but is preferably a methoxy, ethoxy, propoxy group or the like, and particularly preferably methoxy. These aromatic vinyl compounds can be used individually by 1 type or in mixture of 2 or more types. Further, these aryl groups or alkyl groups may be further substituted with an alkoxy group, an allyloxy group, an aryl group, an alkyl group, or the like.

  The ratio of the conjugated diene polymer to the vinyl cyanide compound and the aromatic vinyl compound substituted with an organic carbonate group on part or all of the aromatic ring is not particularly limited, but preferably 1 part of the conjugated diene polymer. 1 to 50 parts by weight of the vinyl cyanide compound, 0 to 20 parts of the aromatic vinyl compound, and 1/10 to 50 of the aromatic vinyl compound substituted on the aromatic ring with an organic carbonate group. Parts, more preferably, 1 part by weight of conjugated diene polymer is substituted by 1/20 to 5 parts by weight of vinyl cyanide compound, 0 to 10 parts of aromatic vinyl compound, and the aromatic ring is substituted with an organic carbonate group. Graft polymerization is carried out using 1/2 to 20 parts of the aromatic vinyl compound.

  Furthermore, other vinyl compounds capable of further copolymerization can be added to the vinyl cyanide compound or the aromatic vinyl compound having a part or all of the aromatic rings substituted with an organic carbonate group. There are no particular restrictions on such vinyl compounds, but examples include vinyl acrylates such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate, various acrylamides, vinyl acetate, and the like. Examples thereof include aromatic compounds such as esters, α-methylstyrene, and N-phenylmaleimide.

  Graft polymerization can be performed by a known method, and bulk polymerization, emulsion polymerization, emulsion suspension polymerization, emulsion bulk polymerization, and the like can be used as appropriate, and bulk polymerization is preferred. In this graft polymerization, a generally known radical initiator can be used. Examples thereof include dicumyl peroxide, benzoyl peroxide, ditertiary butyl peroxide, 2,2'-azobis (isobutyronitrile) and the like. The amount used is arbitrary, but it is preferably in the range of 1/20000 to 1/20, preferably about 1/2000 to 1/100 by weight with respect to the conjugated diene polymer. Although there is no restriction | limiting in particular in the reaction temperature of graft polymerization, If reaction rate is considered, the range of 50-200 degreeC is preferable, and the range of 70-150 degreeC is especially preferable. The reaction time is not particularly limited, but a reaction time of about 1 to 2 days is desirable. After finishing the graft polymerization reaction, the solvent and unreacted low-boiling substances are removed under reduced pressure to obtain an ABS resin having a carbonate group on the aromatic side chain.

  On the other hand, a conjugated diene polymer obtained by bonding a siloxane or silsesquioxane having a Si-H bond to a conjugated diene polymer is organically applied on the vinyl cyanide compound, which is the next stage, and a part or all of the aromatic rings. It can also be used for graft polymerization reaction with an aromatic vinyl compound substituted with a carbonate group to produce an ABS resin.

  In the case of using a conjugated diene polymer bonded with a siloxane or silsesquioxane having a Si-H bond, as a siloxane or silsesquioxane having a Si-H bond to be bonded to the conjugated diene polymer. Can be used as long as they have at least one Si-H bond in the molecule. Examples thereof include pentamethyldisiloxane, tetramethyldisiloxane, heptamethyltrisiloxane, octamethyltetrasiloxane, Methyltris (dimethylsiloxy) silane, tetramethylcyclotetrasiloxane, pentamethylcyclopentasiloxane, octakis (dimethylsiloxy) octasilsesquioxane, octakis (hydridosilsesquioxane), hydridosilsesquioxane, H-terminal poly Methyl siloxane, methyl H siloxane-dimethyl siloxane copolymer, polymethyl H siloxane, polyethyl H siloxane, polyphenyl (dimethyl H siloxy) siloxane H-terminated, methyl H siloxane-phenyl methyl siloxane copolymer, methyl H siloxane-octyl methyl siloxane copolymer, H siloxane Q resin etc. are mentioned.

  The amount of these siloxanes or silsesquioxanes having a Si-H bond is not particularly limited, but is preferably 1 to 0.00 with respect to the total amount of carbon-carbon double bonds in the conjugated diene polymer. 001 molar equivalent, more preferably 0.7 to 0.01 equivalent.

  In order to bond the conjugated diene polymer and the siloxane or silsesquioxane having a Si-H bond, a hydrosilylation reaction of an olefinic double bond is performed. The hydrosilylation reaction is preferably carried out in the presence of a catalyst, and a known transition metal catalyst or radical initiator catalyst is used. Transition metal complexes include iron pentacarbonyl, ruthenium trichloride, dicobalt octacarbonyl, tristriphenylphosphine rhodium chloride, iridium trichloride, bistriphenylphosphine ethylene nickel, bistriphenylphosphine nickel dichloride, tetrakistriphenylphosphine palladium, bistriphenyl. Examples thereof include phosphine palladium dichloride, tristriphenylphosphine platinum, ethylene platinum dichloride dimer, chloroplatinic acid, platinum divinyltetramethyldisiloxane complex, and the like. Examples of the radical initiator catalyst include benzoyl peroxide, ditertiary butyl peroxide, 2,2'-azobis (isobutyronitrile) and the like. The catalyst to be used is preferably one containing platinum, particularly a platinum divinyltetramethyldisiloxane complex. Although there is no restriction | limiting in particular in the usage-amount of these catalysts, Preferably 0.5-0.00001 equivalent of the total amount of the olefinic double bond to react, More preferably, 0.1-0.001 equivalent is used.

  Any solvent can be used as the solvent used in the hydrosilylation reaction except for those containing active hydrogen or aliphatic double bonds that may react with the raw material. For example, toluene, xylene, Examples include xane, heptane, cyclohexane, and tetrahydrofuran. The amount of the solvent used may be 0.1 to 1000 times, preferably 1 to 200 times the total weight of the reaction raw materials.

  Although there is no restriction | limiting in particular in the reaction temperature of hydrosilylation, Preferably it is -20-200 degreeC, More preferably, it carries out at 0-150 degreeC. The reaction time is not particularly limited, but a long time is required when the reaction temperature is lowered, but a reaction time of 1 minute to 10 days is used depending on the reaction temperature.

  The reaction product solution in which siloxanes or silsesquioxanes having Si—H bonds are bonded to the conjugated diene polymer thus obtained is directly or after being concentrated to an appropriate degree or dried. In the same manner as the conjugated diene polymer used in the above, it is used for the graft polymerization reaction with the vinyl cyanide compound, which is the next step, and the aromatic vinyl compound substituted with an aromatic carbonate group on part or all of the aromatic ring. Manufactured resin.

  Next, 1) an ABS resin obtained by reacting a conjugated diene polymer with a vinyl cyanide compound and a vinyl compound containing an aromatic vinyl compound substituted on the aromatic ring with an organic carbonate group, and 2) a conjugated diene system. ABS resin obtained by reacting a polymer with a vinyl cyanide compound, an aromatic vinyl compound, and a vinyl compound containing an aromatic vinyl compound substituted on the aromatic ring with an organic carbonate group, and 3) having a Si-H bond ABS system obtained by reacting a conjugated diene polymer to which siloxanes or silsesquioxanes are bonded with a vinyl cyanide compound and a vinyl compound containing an aromatic vinyl compound substituted on the aromatic ring with an organic carbonate group. And conjugated dienes to which siloxanes or silsesquioxanes having a Si-H bond are bonded After molding according to a conventional method, an ABS resin obtained by reacting a polymer with a vinyl cyanide compound, an aromatic vinyl compound, and a vinyl compound containing an aromatic vinyl compound substituted on the aromatic ring with an organic carbonate group, By evaluating the flame retardancy by the HB method based on UL-94, it can be seen that the combustion speed is suppressed and that drip is hardly generated during combustion.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by this Example.

0.75 g of polybutadiene (manufactured by Aldrich, 38,369-4, 1,2-adduct 20%), 7.86 g of (4-ethenylphenyl) phenyl carbonate, 1.5 ml of acrylonitrile, 2 mg of dicumyl peroxide, 4 ml of toluene It put in the stainless steel pressure vessel, and heated in a 100-140 degreeC hot water bath for 2 days. Thereafter, the reaction product was taken out, and the solvent was removed under a vacuum of 0.1 mmHg to obtain an ABS resin as a target product.
Next, as a result of evaluating the flame retardancy and drip property of the ABS resin test piece, which was filled in an injection mold and thermoformed, by the HB method in accordance with UL-94, no drip was observed during combustion, and combustion The speed was 11 mm / min.

0.75 g of polybutadiene (manufactured by Aldrich, 38,369-4, 1,2-added 20%), 0.8 g of octakis (hydridosilsesquioxane), 75 ml of toluene and a xylene solution of platinum divinyltetramethyldisiloxane complex (Guerest) (SIP6831.0) 20 μL was placed in a 500 ml round bottom flask and stirred for 4 days at room temperature with a magnetic stirrer to cause reaction. Then, it concentrated to 13 ml under room temperature pressure reduction.
Next, the concentrated solution was transferred to a stainless steel pressure vessel and heated overnight in a 100-140 ° C. hot water bath with 7.86 g of (4-ethenylphenyl) phenyl carbonate, 1.5 ml of acrylonitrile and 2 mg of dicumyl peroxide. Reacted. Thereafter, the reaction product was taken out, and the solvent was removed under a vacuum of 0.1 mmHg to obtain an ABS resin as a target product.

  Next, as a result of evaluating the flame retardancy and drip property of the ABS resin test piece, which was filled in an injection mold and thermoformed, by the HB method in accordance with UL-94, no drip was observed during combustion, and combustion The speed was 9 mm / min.

Comparative Example 1

  Overnight in a 110 ° C water bath with 1 g of polybutadiene (Aldrich, 38,369-4, 1,2-added 20%), 2 ml of toluene, 5 ml of styrene, 2 ml of acrylonitrile, 2 mg of dicumyl peroxide in a stainless steel pressure vessel. Heated to react. Thereafter, the reaction product was taken out, and the solvent was removed under a vacuum of 0.1 mmHg to obtain an ABS resin.

  Next, as a result of evaluating the flame retardancy and drip property of the ABS resin test piece, which was filled in an indentation mold and thermoformed, by the HB method according to UL-94, drip was recognized during combustion, and the burning rate Was 30 mm / min.

Comparative Example 2

  A commercially available ABS resin (manufactured by Kanto Chemical Co., Ltd., 31080-1A) is filled into a mold, and a heat-molded ABS resin test piece is evaluated for flame retardancy and drip by the HB method according to UL-94. As a result, drip was observed during combustion, and the combustion rate was 25 mm / min.

  From the above examples, the ABS resin having the carbonate group of the present invention on the aromatic side chain has a lower burning rate than the ABS resin having no carbonate group on the aromatic side chain, and at the time of combustion. It was confirmed that drip was suppressed.

The ABS resin of the present invention is an ABS resin having a carbonate group on an aromatic side chain, and is a flame retardant thermoplastic resin having a low combustion rate and capable of suppressing the occurrence of drip, which is a problem during combustion. In addition, fire spread can be suppressed in the event of a fire. In addition, since no flame retardant or drip suppressant, which may be a source of environmental pollution, is added, it has a low environmental impact during production, use, and disposal, and can therefore be used in a wide range of fields.

Claims (7)

An ABS resin characterized in that some or all of the aromatic rings are substituted with organic carbonate groups , wherein the conjugated diene polymer, the vinyl cyanide compound, and the aromatic rings are substituted with organic carbonate groups. Or a conjugated diene polymer, a vinyl cyanide compound, an aromatic vinyl compound, and an aromatic vinyl compound in which an aromatic ring is substituted with an organic carbonate group. An ABS resin produced by reacting a vinyl compound with the resin . That some or all of the aromatic rings are substituted with an organic carbonate group, and that the carbon-carbon unsaturated bond of the conjugated diene polymer is a siloxane or silsesquioxane having an Si-H bond added thereto. ABS resin characterized by being a conjugated diene polymer bonded with siloxanes or silsesquioxanes having a Si-H bond, a vinyl cyanide compound, and an aromatic ring substituted with an organic carbonate group A conjugated diene polymer obtained by reacting a vinyl compound containing a vinyl compound or a siloxane or silsesquioxane having a Si-H bond, a vinyl cyanide compound, an aromatic vinyl compound, and an aromatic ring. Is reacted with a vinyl compound containing an aromatic vinyl compound substituted with an organic carbonate group. Characterized in that it is manufactured Ri, ABS resins.   The ABS resin according to claim 1 or 2, wherein the organic carbonate group is an aryloxycarbonyloxy group or an alkoxycarbonyloxy group.   A method for producing an ABS resin, comprising reacting a conjugated diene polymer, a vinyl cyanide compound, and a vinyl compound containing an aromatic vinyl compound having an aromatic ring substituted with an organic carbonate group.   Reaction of a conjugated diene polymer bonded with a siloxane or silsesquioxane having a Si-H bond with a vinyl compound including a vinyl cyanide compound and an aromatic vinyl compound in which an aromatic ring is substituted with an organic carbonate group. A method for producing an ABS resin, characterized by comprising:   A process for producing an ABS resin comprising reacting a conjugated diene polymer with a vinyl compound containing a vinyl cyanide compound, an aromatic vinyl compound, and an aromatic vinyl compound in which an aromatic ring is substituted with an organic carbonate group .   A conjugated diene-based polymer bonded with a siloxane or silsesquioxane having a Si-H bond, and a vinyl cyanide compound, an aromatic vinyl compound, and an aromatic vinyl compound in which an aromatic ring is substituted with an organic carbonate group. A method for producing an ABS resin, characterized by reacting with a vinyl compound.