KR101799637B1 - Graft copoymer and polycarbonate and san blend resin composition comprising the same - Google Patents
Graft copoymer and polycarbonate and san blend resin composition comprising the same Download PDFInfo
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- KR101799637B1 KR101799637B1 KR1020150095442A KR20150095442A KR101799637B1 KR 101799637 B1 KR101799637 B1 KR 101799637B1 KR 1020150095442 A KR1020150095442 A KR 1020150095442A KR 20150095442 A KR20150095442 A KR 20150095442A KR 101799637 B1 KR101799637 B1 KR 101799637B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2300/22—Thermoplastic resins
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Abstract
The present invention relates to a graft copolymer for an impact modifier having a core-shell-shell (CSS) structure in which compatibility and mixing properties of a polycarbonate with a SAN blend resin are improved, and a graft copolymer for the impact modifier, And a SAN blend thermoplastic resin composition having improved impact strength.
Description
The present invention relates to a multi-layered graft copolymer for an impact modifier and a polycarbonate and SAN blend thermoplastic resin composition containing the same, wherein the polycarbonate and the SAN blend resin are improved in compatibility and mixing properties.
Polycarbonate (PC) resin is an engineering thermoplastic resin with toughness and stiffness that is excellent in impact resistance, electrical characteristics and heat resistance. The above-mentioned polycarbonate resin is widely used as an internal and external material throughout the industry such as automobiles and the manufacture of electric / electronic molded articles.
However, the polycarbonate has a disadvantage of low workability due to its high melt viscosity. Accordingly, attempts have been made to blend a polycarbonate resin with various resins to produce a thermoplastic resin composition having good impact strength and flow characteristics (processability).
As a representative example thereof, a blend resin composition in which a polycarbonate resin and an acrylonitrile-butadiene-styrene resin (ABS) resin or an acrylonitrile (SAN) resin are mixed has been developed. However, the polycarbonate and the SAN resin composition have disadvantages of causing a brittle material. On the other hand, in the case of the polycarbonate-ABS blend thermoplastic resin composition in which the ABS-based impact modifier is mixed, excellent balance of impact strength, heat resistance, molding processability, and the like are obtained in addition to excellent properties of the polycarbonate itself. Automobile interior materials and so on.
On the other hand, thermoplastics, which are currently applied to almost all electronic products, are easily combustible and are not resistant to fire. Therefore, the thermoplastic resin can easily burn by the ignition source, and can further spread the fire. In view of this, many countries have recently regulated the use of only thermoplastic polymers that meet the flame retardant specifications.
Accordingly, a method of imparting flame retardant properties to a thermoplastic resin by adding a flame retardant has been proposed. As the flame retardant, a halogen-based flame retardant or a phosphorus-based flame retardant is used. The halogen-based flame retardant is superior in terms of cost and performance, and is widely used for housing materials for electric appliances and office equipment. However, since the halogen hydrogen gas generated during processing has a fatal effect on the human body, It is reported that it is difficult to maintain the environment and it is not soluble in water and bioaccumulation is high.
On the other hand, in the case of the phosphorus-based flame retardant, when used in a thermoplastic resin composition of polycarbonate and an ABS blend, it is reported that the flame retardancy is improved but the physical properties such as workability, impact strength and gloss characteristics are lowered.
Recently, a method of using a methyl methacrylate-butadiene-styrene (MBS) impact modifier instead of an ABS-based impact modifier in a polycarbonate-ABS blend thermoplastic resin composition has been proposed .
However, in the case of the MBS impact modifier, compatibility with polycarbonate including the phosphorus-based flame retardant and SAN blend thermoplastic resin composition is not sufficient, so that the effect of improving workability and impact strength is insufficient.
Accordingly, development of a graft copolymer for an impact modifier having improved compatibility and miscibility between a polycarbonate and a SAN blend thermoplastic resin composition has been demanded.
SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art, and it is an object of the present invention to provide a multi-layered graft copolymer for an impact modifier having improved compatibility and mixing of polycarbonate with SAN resin.
It is another object of the present invention to provide a polycarbonate and SAN blend thermoplastic resin composition having improved processability and impact strength by including the graft copolymer for impact modifier.
In order to solve the above problems,
In one embodiment of the present invention
A conjugated diene-based rubber polymer core (A); And
Layered graft shell (B) coated on the surface of the conjugated diene-based rubber polymer core,
The multi-layered graft shell (B)
(i) a first grafted shell comprising an alkyl acrylate-based monomer; And
(ii) a second graft shell coated on the surface of the first graft shell, the second graft shell comprising a (meth) acrylic acid alkyl ester monomer and a (meth) acrylate comonomer including an alicyclic ring or an aromatic ring; Wherein the weight average molecular weight of the graft copolymer is in the range of 100 to 200,000.
In the present invention,
60 to 65% by weight of a polycarbonate resin,
10 to 15% by weight of SAN resin;
10 to 15% by weight phosphorylated flame retardant; And
5 to 12% by weight of a graft copolymer for an impact modifier of the present invention; and polycarbonate and SAN blend thermoplastic resin composition.
As described above, according to the present invention, it is possible to produce a graft copolymer for an impact modifier having improved compatibility and mixing properties between a polycarbonate and a SAN resin, and further, a polycarbonate having improved processability and impact strength SAN blended thermoplastic resin composition can be prepared.
Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention. Herein, terms and words used in the present specification and claims should not be construed to be limited to ordinary or dictionary meanings, and the inventor may appropriately define the concept of the term to describe its own invention in the best way. It should be construed as meaning and concept consistent with the technical idea of the present invention.
The term "polycarbonate " as used herein, on the other hand, refers to a polymer comprising the same or different carbonate units, or a copolymer comprising the same or different carbonate units, as well as one or more units other than carbonates (I. E., Copolycarbonate); &Quot; Cycloaliphatic " means a radical having one or more valencies including an array of three or more carbon atoms, which is not cyclic or aromatic; &Quot; An aromatic " means a radical having one or more valencies including one or more aromatic groups; &Quot; Alkyl " means a monovalent hydrocarbon radical of a straight or branched chain; The term " about " used in connection with an amount is intended to encompass the stated value and the contextually referred meaning (including, for example, the error range associated with the measurement of a particular content); The term " optional " or " optionally " means that the subsequently described event or circumstance occurs or does not occur, or that thereafter the relevant material is present or absent, Includes situations where a situation occurs or a substance is present, and when a work or situation does not occur or when a substance is not present.
The methyl methacrylate-butadiene-styrene (MBS) graft copolymer used as a conventional impact modifier has a core-shell structure composed of a rubber polymer core and a graft shell surrounding the core surface have. At this time, it is known that the metal methacrylate and the styrene monomer constituting the graft shell are poorly mixed with the polycarbonate resin. Therefore, when such an MBS-based graft copolymer is used in a polycarbonate and SAN blend thermoplastic resin composition, it is difficult to obtain a high level of compatibility, so that the effect of improving the workability and impact strength of the thermoplastic resin composition is insufficient There are disadvantages.
Therefore, the inventors of the present invention have been studying commercially available graft copolymers for impact modifiers, and found that a second graft made of a (meth) acrylate comonomer having an alicyclic ring or an aromatic ring on the surface of an MBS impact modifier It has been confirmed that the dispersibility and the impact strength of the impact modifier can be improved when the shell is additionally introduced into the multi-layered shell structure, and based on this, a graft copolymer for an impact modifier, It was completed.
Specifically, in one embodiment of the present invention
The present invention provides a graft copolymer for an impact modifier having improved compatibility between a polycarbonate and a SAN resin.
In addition, the present invention provides a polycarbonate and SAN blend thermoplastic resin composition improved in workability and impact strength by including the graft copolymer for impact modifier.
Hereinafter, the present invention will be described in detail.
Manufacture of Graft Copolymers for Impact Adjuster with Core-Shell-Shell Structure
First, in an embodiment of the present invention
A conjugated diene-based rubber polymer core (A); And
Layered graft shell (B) coated on the surface of the conjugated diene-based rubber polymer core,
The multi-layered graft shell (B)
(i) a first grafted shell comprising an alkyl acrylate-based monomer; And
(ii) a second graft shell coated on the surface of the first graft shell, the second graft shell comprising a (meth) acrylic acid alkyl ester monomer and a (meth) acrylate comonomer including an alicyclic ring or an aromatic ring; ≪ / RTI >
(A) Conjugated diene series Manufacture of rubber polymer cores
In the graft copolymer of the present invention, the conjugated diene rubber polymer core is characterized by being obtained by emulsion polymerization of a conjugated diene compound in the presence of a carboxylic acid-based emulsifier.
For example, the conjugated diene rubber polymer core may be prepared by polymerizing a conjugated diene compound, an emulsifier, a polymerization initiator, an electrolyte, ion-exchanged water, etc. in a batch or multi-step at 40 to 85 ° C for 12 to 18 hours .
The conjugated diene compound may be used alone or in combination with other compounds such as 1,3-butadiene, isoprene, chloroprene, and piperylene. As the other compounds, aromatic vinyl compounds such as styrene and? -Methylstyrene, and vinyl cyan compounds such as acrylonitrile, methacrylonitrile, and ethacrylonitrile may be used. The total amount of the conjugated diene compound And 20 parts by weight or less.
Examples of the carboxylic acid emulsifier include fatty acid soaps such as sodium oleate, potassium oleate, sodium stearate, and potassium stearate, and rosin acid soaps may be mixed together It is preferable for improving workability and impact strength.
The use of such a carboxyl-based emulsifier makes it possible to agglomerate with an acid after the graft copolymerization and to minimize the amount of multivalent cations of salt polyphosphates.
The carboxylic acid emulsifier may be used in an amount of 1.5 to 2.5 parts by weight, specifically 1.7 to 2.3 parts by weight based on 100 parts by weight of the conjugated diene compound constituting the core. If the carboxylic acid emulsifier is used in an amount of less than 1.5 parts by weight, excessive amounts of solidification products are generated during the polymerization and are unproductive. When the amount of the carboxylic acid emulsifier is excessively used in excess of 2.5 parts by weight, A large amount of carboxylic acid is generated to accelerate the hydrolysis of the polycarbonate resin, and there is a disadvantage that gas is generated in the appearance of the molded article during injection molding.
Examples of the polymerization initiator include peroxides such as t-butyl hydroperoxide (TBHP), cumene hydroperoxide and diisopropylbenzene hydroperoxide, and peroxide such as sodium formaldehyde sulfoxylate, ethylenediamine tetra sodium acetate, Iron-based catalysts such as iron, sodium pyrophosphate and dextrose may be used. The polymerization initiator may be used in an amount of 0.05 to 0.5 parts by weight, specifically 0.1 to 0.4 parts by weight, based on 100 parts by weight of the conjugated diene compound. If the polymerization initiator is used in an amount of less than 0.05 parts by weight, the polymerization conversion decreases and the reaction time becomes longer. If the polymerization initiator is used in excess of 0.5 parts by weight, the impact strength is lowered.
The electrolyte may include Na 2 SO 4 , KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7 , Na 4 P 2 O 7 , K 3 PO 4 , Na 3 PO 4 , K 2 HPO 4 or Na 2 HPO 4 may be used singly or in combination of two or more kinds. Specifically, Na 2 SO 4 may be used. The electrolyte may be used in an amount of 0.2 to 2 parts by weight based on 100 parts by weight of the conjugated diene compound constituting the core. If the electrolyte is used in a small amount less than 0.2 part by weight, a core having a desired particle diameter can not be produced. If the amount is more than 2 parts by weight, polymerization stability is difficult to be secured.
It is preferable that pure water having a metal ion concentration of 2 ppm or less through the ion exchanger is used as the ion exchange water. The amount of the ion exchange water used may be within the range of 65 to 135 parts by weight based on 100 parts by weight of the conjugated diene compound. If the amount of the ion-exchanged water to be used is less than the above range, it is difficult to adjust the reaction heat during the polymerization reaction. If the amount exceeds the above range, excessive use of the ion-exchanged water results in a low slurry content.
The polymerization temperature for the production of the core may be controlled according to the gel content and the degree of swelling of the diene-based rubbery polymer latex, and the selection and administration time of the polymerization initiator should also be considered. For example, within the temperature range of 40 to 85 占 폚.
Specifically, the conjugated diene rubber polymer core of the present invention preferably has an average particle diameter of from 180 to 220 nm after emulsion polymerization. If the particle diameter of the rubber polymer core is less than 180 nm, the impact strength at the target level is not exhibited. If the particle diameter exceeds 220 nm, the impact strength is improved as the particle diameter of the rubber polymer core increases, There is a disadvantage that the reactor is solidified due to a problem.
(B) Multilayer Graft Shell manufacture
Specifically, the graft copolymer of the present invention comprises
65 to 80% by weight of a conjugated diene-based rubber polymer core;
0.5 to 10% by weight of a first graft shell coated on the surface of the conjugated diene-based rubber polymer core; And
And 10 to 34.5 wt% of a second graft shell coated on the surface of the first graft shell.
The latex constituting the core within the content range of the core and the multi-layer graft shell as described above sufficiently increases the graft rate and improves the dispersibility in the resin and the impact strength when the resin is used for the polycarbonate resin, It is also possible to prevent the agglomeration during drying.
If the content of the core is less than 65% by weight, compatibility with the polycarbonate resin may be poor, and the impact strength may be lowered, and sufficient elasticity may not be obtained, so that the impact strength may be lowered. When the content of the core exceeds 80% by weight, shell formation is not easy, and compatibility with the polycarbonate resin is poor, resulting in poor workability and impact strength.
The core polymerization step for producing the core component of the graft polymer for the impact modifier proceeds through a temporary charging method, and the core polymerization step can be carried out for 10 to 30 hours.
On the other hand, the shell serves to impart compatibility between the graft copolymer and the thermoplastic resin, and enables the rubber polymer core to exert its impact strength well. At this time, it is important to coat the shell well so that the rubber polymer core can be dispersed well, but when the shell is coated too thick, the rubber content is relatively low and the impact strength is lowered. For example, when the content of the second grafted shell is less than 10% by weight, compatibility with the polycarbonate resin is poor, resulting in poor workability and impact strength. When the content of the second grafted shell is more than 34.5% by weight, .
Specifically, in the graft copolymer of the present invention, the multi-layered graft shell (B) comprises a first graft shell including an alkyl acrylate monomer, and a second graft shell coated on the first graft shell surface (Meth) acrylic acid alkyl ester monomer and a (meth) acrylate comonomer including an alicyclic ring or an aromatic ring.
The alkyl acrylate monomer constituting the first graft shell is a material capable of improving workability and impact strength, and preferably has a glass transition temperature (Tg) lower than 0 ° C. Typical examples thereof include ethyl acrylate, n-propyl acrylate, or n-butyl acrylate.
The alkyl acrylate-based monomer constituting the first graft shell improves the dispersibility of the MBS-based graft polymer by lowering the softening temperature.
Further, in the graft copolymer of the present invention, the (meth) acrylic acid alkyl ester monomer, which is one of the components constituting the second graft shell, improves the compatibility with the polycarbonate resin and the compatibility thereof, As a material capable of improving the strength, examples thereof include a single substance selected from the group consisting of methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, lauryl methacrylate and stearyl methacrylate, And mixtures of two or more.
Further, in the graft copolymer of the present invention, the (meth) acrylate-based comonomer including the alicyclic ring and / or the aromatic ring, which is one of the components constituting the second graft shell, (meth) acrylic acid alkyl ester monomer by the repulsive effect of the poly (alkyl methacrylate) monomer, examples of which include cyclopentyl methacrylate, cyclohexyl methacrylate, Benzyl methacrylate, cyclohexyl acrylate, 2-phenoxyethyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, 4-t-butylcyclohexyl methacrylate, 3-cyclohexylpropyl methacrylate , Phenyl methacrylate, 4-t-butyl phenyl methacrylate, 4-methoxyphenyl methacrylate, 1-phenylethyl methacrylate, Methacrylate, 2-petil methacrylate, may be mentioned 2-phenoxyethyl methacrylate and 2-naphthyl meth danilmul mixture or two or more kinds selected from the group consisting of a methacrylate.
In the graft copolymer of the present invention, the (meth) acrylic acid alkyl ester monomer constituting the second graft shell is, for compatibility with the polycarbonate resin, 10 weight% based on the total content of the graft copolymer % To 34.5% by weight. If it is contained in an amount of 10 wt% or less, there is a problem that dispersibility and mechanical properties, that is, workability are lowered due to insufficient compatibility with a thermoplastic resin. When the content is more than 34.5 wt%, the rubber content is lowered, There is a problem.
The (meth) acrylate comonomer including the alicyclic ring or aromatic ring may be contained in an amount of 0.5 to 10% by weight based on the total amount of the graft copolymer. If it is used in an amount of more than 10% by weight, the polymerization stability is lowered and the compatibility with the polycarbonate resin is lowered to deteriorate the physical properties. If the amount is less than 0.5% by weight, the effect of addition of the comonomer is insufficient.
Specifically, the weight ratio of the (meth) acrylic acid alkyl ester monomer constituting the second graft shell: the (meth) acrylate comonomer including the alicyclic ring or the aromatic ring is 80:20 to 90:10, specifically 85 : 15 is preferable.
In addition, in the graft copolymer of the present invention, the second graft shell may further include an ethylenically unsaturated aromatic monomer as a comonomer, considering the compatibility with the resin. At this time, the ethylenically unsaturated aromatic monomer has low compatibility with the resin, and when used in excess, degrades the physical properties such as the impact strength is lowered, but improves the coloring property and gloss by improving the refractive index.
The ethylenically unsaturated aromatic monomer may be a single or a mixture of two or more selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, vinyltoluene and 3,4-dichlorostyrene.
In addition, the ethylenically unsaturated aromatic monomer may be contained in an amount of 0 to 5% by weight based on the total content of the graft copolymer. If the content of the ethylenically unsaturated aromatic monomer is more than 5% by weight, the 1/4 "thick impact strength is significantly reduced.
MBS-based graft shells having such physical properties can realize an effect of improving compatibility with polycarbonate resin.
The emulsifier, the polymerization initiator, and the ion exchange water used in the production of the shell may be selected from various types well known in the emulsion polymerization technique and may be different from those used in the polymerization of the rubber polymer core, Is preferably used.
The emulsifier may be used in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the conjugated diene compound and 0.01 to 0.52 parts by weight of the polymerization initiator.
The ion-exchanged water may be used within a range of 20 to 30 parts by weight based on 100 parts by weight of the latex and the compound constituting the shell constituting the shell. If the amount of the ion-exchanged water used is smaller than the above range, it is difficult to adjust the heat of reaction during the polymerization reaction. If the amount exceeds the above range, excessive use of the ion-exchanged water causes slurry content to be low. The ion exchange water is not used at the time of forming the first graft shell, but can be used only at the time of forming the second graft shell.
In the polymerization reaction for forming the first and second shells of the present invention, an activation liquid can be used for redox initiation. (Ethylenediaminetetraacetic acid (EDTA), sodium formaldehyde sulfoxylate (SFS), and ferrosulfate (FES)), which are conventionally used in the copolymer polymerization reaction, unless otherwise specified, , Or a compound commonly used for polymerization activation.
The polymerization conditions for preparing the shell may vary depending on the kind of the initiator, for example, at a temperature of 45 to 80 ° C for 1 to 4 hours. Specifically, the graft polymerization for forming the first shell is preferably carried out at a temperature in the range of about 40 to 65 ° C, more preferably 45 to 55 ° C. The emulsion graft polymerization for forming the second graft shell may be performed at a temperature of 50 to 80 캜.
Further, in the graft copolymer of the present invention, the method for introducing the compound for forming the first and second shells can be performed in parallel with the temporary input method and the continuous input method, thereby improving the workability and the impact strength .
Specifically, the first graft shell proceeds through a temporary input method, and the second graft shell proceeds through a continuous input method. The continuous charging time of the second graft shell can be 1 to 3 hours. More specifically, the monomers can be temporarily injected to proceed the polymerization reaction for forming the first graft shell, or the second shell polymerization reaction can proceed continuously without proceeding. That is, the polymerization reaction proceeds so that a polymer having a low Tg is located inside the graft shell and a polymer having a high Tg is excluded from the graft shell. As a result, the graft copolymer and the graft copolymer The thermoplastic resin can be produced.
According to the method of the present invention, 100 parts by weight of the graft copolymer, which is the same as the sum of the charged monomer compounds, can be obtained.
Thereafter, the obtained graft copolymer was stirred with an antioxidant to separate salts of polymer and water by adding salt, heat and acid, followed by dehydration and drying to prepare powder
The thus-obtained core-shell-shell type graft copolymer can be dried by an acid or salt flocculation process or spray drying process.
Furthermore, silicone oil may be further added to improve the impact strength after completion of the graft copolymer polymerization of the present invention.
In this case, the silicone oil may include polymethylhydrosiloxane, and may include about 0.1 to 0.3 parts by weight based on the total weight of the graft copolymer. In the case of silicone oil, it can be added to the polymerized MBS latex, which can be added in the coagulation step and can be added to the powder after the coagulation. Silicone oil itself migrates to the core of MBS particles and acts to increase rubber efficiency.
The average particle size of the graft polymer for the impact modifier of the core-shell-shell structure of the present invention produced by this method is preferably 190 to 230 nm.
The glass transition temperature of the graft copolymer of the core-shell-shell structure of the present invention is preferably -30 캜 or lower.
Polycarbonate and SAN Blend Thermoplastic resin composition
In the present invention,
60 to 65% by weight of a polycarbonate resin;
10 to 15% by weight of SAN resin;
10 to 15% by weight phosphorylated flame retardant; And
5 to 12% by weight of the graft copolymer of the present invention; and SAN blend thermoplastic resin composition.
Specifically, the polycarbonate and SAN blend thermoplastic resin composition of the present invention contained 63% by weight of a polycarbonate resin; SAN resin 14 wt%; 14% by weight phosphorylated flame retardant; And 9% by weight of the graft copolymer of the present invention; and a SAN blend thermoplastic resin composition comprising the polycarbonate and the SAN blend.
The SAN resin may comprise about 0.1 to about 10 weight percent oligomer. The oligomer may be generally defined as a resin having a molecular weight of about 15,000 g / mole or less, more typically an oligomer is defined as a resin having a molecular weight of about 10,000 g / mole or less. A preferred SAN resin has a relative weight average molecular weight of from about 40,000 to about 110,000 g / mole, more preferably from 50,000 to about 90,000 g / mole, more preferably from about 40,000 to about 90,000 g / mole, as measured by gel permeation chromatography for narrow dispersion polystyrene standards Is from about 60,000 to about 85,000 g / mole SAN resin. The SAN resin typically comprises 10 to 40 wt.% Acrylonitrile, preferably 15 to 35 wt.%, More preferably 20 to 30 wt.%, With the remainder being composed of styrene.
The SAN resin may comprise about 10 to 15% by weight based on the total weight of the resin composition. If it is used in an amount exceeding 15% by weight, impact resistance and heat resistance may be deteriorated. If the amount is less than 10% by weight, moldability and workability may be deteriorated.
Examples of the phosphorus-based flame retardant include phosphate-based compounds such as triphenyl phosphate, tricresyl phosphate, tri (2,6-dimethylphenyl) phosphate and tri (2,4,6-trimethylphenyl) phosphate; Diphosphate-based compounds such as tetraphenylresorcinol diphosphate, tetracycylresocynol diphosphate, tetra (2,6-dimethylphenyl) resorcinol diphosphate, and tetraphenyl bisphenol A diphosphate; At least one selected from the group consisting of a polyphosphate-based compound having at least three phosphate groups, a phosphonate-based compound and a phosphinate-based compound, and comprises about 10 to 15% by weight, based on the total weight of the resin composition . If it is used in an amount of more than 15% by weight, it may deteriorate impact resistance and processability. If it is contained in an amount of less than 10% by weight, the flame retardancy is deteriorated.
In addition, the graft copolymer of the present invention may comprise about 5 to 12% by weight based on the total weight of the resin composition. If it is used in an amount exceeding 12% by weight, there is a problem in that the processability is lowered, and when it is less than 5% by weight, impact strength is lowered.
In addition, the polycarbonate and SAN blend thermoplastic resin composition of the present invention may further contain an antioxidant, a filler, and a pigment capable of coloring, which can complement the thermoplastic resin composition at the time of processing, if necessary.
When the graft polymer for an impact modifier produced by the method of the present invention as described above is used as an impact modifier for a thermoplastic resin, a polycarbonate / SAN resin thermoplastic composition having improved processability and impact properties can be produced.
Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples and experimental examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.
Example
(Example 1)
Graft Copolymer production
(a) Production of conjugated diene rubber polymer core
To a 120 L high-pressure polymerization vessel equipped with a stirrer, 75 parts by weight of ion exchange water, 0.04 parts by weight of EDTA, 0.01 parts by weight of FES, 0.1 parts by weight of SFS, 100 parts by weight of 1,3-butadiene, 0.5 parts by weight of potassium oleate as an emulsifier, 1.5 parts by weight of rosin soap, 0.9 parts by weight of Na 2 SO 4 and 0.1 part by weight of diisopropylbenzene hydroperoxide were added in one portion and then polymerized at 65 ° C for 23 hours to prepare a conjugated diene rubber polymer core having an average particle diameter of 200 nm Respectively.
(b) Production of the first graft shell
2 parts by weight of a 1.5% KOH aqueous solution, 0.003 parts by weight of EDTA as an activator, 0.0002 parts by weight of FES and 0.01 part by weight of SFS were added to a four-necked flask reactor in which a stirrer, a thermometer, a nitrogen inlet and a circulating condenser were formed. Respectively.
Subsequently, 75% by weight of the conjugated diene rubber polymer core prepared in the step (a) was charged into a closed polymerization reactor, and nitrogen was charged. Then, 0.1 part by weight of potassium oleate was added as an emulsifier, Similarly, 3.5 parts by weight of ethyl acrylate and 0.02 part by weight of t-butyl hydroperoxide were collectively administered, and the mixture was polymerized at 50 ° C for 71 hours to prepare a second graft shell immediately.
(c) Production of second grafted shell
In a separate mixing vessel, 0.3 part by weight of potassium oleate, 20 parts by weight of ion-exchanged water, 15.5 parts by weight of methyl methacrylate, 3 parts by weight of cyclohexyl methacrylate and 3 parts by weight of styrene were mixed To prepare a monomer emulsion. 0.1 part by weight of the monomer emulsion and t-butyl hydroperoxide prepared above and 0.015 part by weight of EDTA and 0.01 part by weight of FES were added to the conjugated diene-based rubber polymer core coated with the first graft sieve prepared in the step (b) , And 0.08 parts by weight of SFS were continuously added for 2 hours to conduct the reaction.
The polymerization conversion of the obtained graft copolymer was 98% and the particle diameter was 210 nm.
(d) Preparation of Graft Copolymer Powder Step
0.5 parts by weight of an antioxidant (Irganox-245) was added to 100 parts by weight of the rubbery graft copolymer prepared in the step (e), and the mixture was agitated with an aqueous sulfuric acid solution while stirring. Followed by dehydration and drying to obtain a graft copolymer powder.
Thermoplastic resin manufacturing
63 parts by weight of polycarbonate (1300-22 of LG-DOW Co.), 14 parts by weight of SAN (LG 92 HR), 14 parts by weight of flame retardant (Daihachi PX 200) 9 parts by weight of the impact modifier of the present invention, 0.5 parts by weight of PTFE (XFLON-G) as a processing additive, 0.3 parts by weight of a phenol antioxidant (BASF IR1076, manufactured by Leistritz, And extruded at 200 rpm at a rate of 60 Kg / hr and at a temperature of 250 DEG C to obtain a pellet. The pellet was extruded at a temperature of 250 DEG C using an EC100? 30 extruder manufactured by ENGEL, The properties of the specimens were evaluated and are shown in Table 1 below.
(Example 2)
Except that 3 parts by weight of phenyl methacrylate was added instead of cyclohexyl methacrylate in the preparation of the second graft shell and 0.001 part by weight of FES was contained as an active liquid. And a thermoplastic resin composition were prepared.
Then, the thermoplastic resin composition was used to prepare specimens, and physical properties of the specimens were evaluated and shown in Table 1 below.
(Example 3)
Except that 2.5 parts by weight of butyl acrylate was added instead of ethyl acrylate in the preparation of the first graft shell and 16.5 parts by weight of methyl methacrylate was added in preparing the second graft shell. To prepare a graft copolymer and a thermoplastic resin composition.
Then, the thermoplastic resin composition was used to prepare specimens, and physical properties of the specimens were evaluated and shown in Table 1 below.
delete
Evaluation of Izod Impact Strength: A sheet prepared by making the composition as a sheet was cut to prepare specimens having a thickness of 0.5 mm and 10 cm x 14 cm (ASTM D-256 standard), aged at 25 ° C for 2 hours, and then rotated with a circular saw blade The rpm was measured at 50% cracking of the specimen when it was applied to the saw blade at a speed of 15 mm / sec. The obtained results are summarized in Table 1 below.
* Surface protrusion characteristics: The number of protrusions which can be visually confirmed by the coloring property measurement sample (7 em x 4 cm) obtained after the injection was confirmed. The smaller the number of projections, the better the workability.
* Gloss (45 ° angle): measured according to ASTM E97 at 45 degrees. The higher the value, the better the dispersibility.
(Comparative Examples 1 to 8)
A graft copolymer and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that the monomer was added in a content ratio as shown in Table 2 below.
Then, the thermoplastic resin composition was used to prepare specimens, and the properties of the specimens were evaluated and shown in Table 2 below.
Graft copolymer
Methacrylate
(Kgf m / m)
As shown in Tables 1 and 2, in the case of a thermoplastic resin containing 70% by weight of a polycarbonate resin and not containing a graft copolymer for an impact modifier in the production of a thermoplastic resin as in Comparative Example 1, .
Also, as in Comparative Example 2, it was confirmed that impact strength and gloss were lowered when an ABS-based impact modifier (LG Chem DP270) was added in place of the MBS impact modifier in the production of the thermoplastic resin.
In addition, when the content of the monomer component and the amount of the emulsifier were out of the predetermined critical range in the preparation of the graft copolymer as in Comparative Examples 3 to 5, it was confirmed that the obtained thermoplastic resin had a high impact strength and a large number of surface projections.
In the case of Comparative Examples 6 and 7, when the particle size size of the graft copolymer was reduced by changing the method of shortening the reaction time and decreasing the TSC, the impact strength and the number of surface projections were high, .
Finally, as in Comparative Example 8, it was confirmed that the impact strength was reduced by about 10% when the silicone oil was not added during the production of the graft copolymer.
On the other hand, when the graft copolymer for an impact modifier comprising the multi-layered grafted shells as in Examples 1 to 4 of the present invention was included, it was confirmed that the impact strength and workability were all improved as compared with Comparative Examples 1 to 8 there was.
Claims (15)
Layered graft shell (B) coated on the surface of the conjugated diene-based rubber polymer core,
The multi-layered graft shell (B)
(i) a first grafted shell comprising an alkyl acrylate-based monomer; And
(ii) a second graft shell coated on the surface of the first graft shell, the second graft shell comprising a (meth) acrylic acid alkyl ester monomer and a (meth) acrylate comonomer including an alicyclic ring or an aromatic ring; .
In the graft copolymer,
The (meth) acrylic acid alkyl ester monomer is contained in an amount of 10% by weight to 34.5% by weight based on the total amount of the graft copolymer,
The (meth) acrylate comonomer comprising the alicyclic ring or the aromatic ring is contained in an amount of 0.5 to 10% by weight based on the total content of the graft copolymer,
Wherein the weight ratio of the (meth) acrylic acid alkyl ester monomer constituting the second graft shell to the (meth) acrylate comonomer including the alicyclic ring or the aromatic ring is 80:20 to 90:10. Copolymer.
Wherein the conjugated diene rubber polymer core has a particle diameter of 190 nm to 230 nm.
The graft copolymer
65 to 80% by weight of a conjugated diene-based rubber polymer core;
0.5 to 10% by weight of a first graft shell coated on the surface of the conjugated diene-based rubber polymer core; And
And 10 to 34.5% by weight of a second graft shell coated on the surface of the first graft shell.
Wherein the alkyl acrylate monomer is a single substance selected from the group consisting of ethyl acrylate, n-propyl acrylate, and n-butyl acrylate, or a mixture of two or more thereof.
The (meth) acrylic acid alkyl ester monomer is a single or a mixture of two or more selected from the group consisting of methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, lauryl methacrylate and stearyl methacrylate Wherein the graft copolymer is a graft copolymer.
The (meth) acrylate-based comonomer including the alicyclic ring or the aromatic ring may be cyclopentylmethacrylate, cyclohexylmethacrylate, benzylmethacrylate, cyclohexyl acrylate, 2-phenoxyethyl acrylate, 3 , 4-t-butylcyclohexyl methacrylate, 3-cyclohexylpropyl methacrylate, phenyl methacrylate, 4-t-butylphenyl methacrylate, 4-t-butylcyclohexyl methacrylate, 2-phenylethyl methacrylate, 2-phenethylethyl methacrylate, 2-phenoxyethyl methacrylate, and 2-naphthyl methacrylate. Or a mixture of two or more kinds of the graft copolymers.
Wherein said second grafted shell further comprises an ethylenically unsaturated aromatic monomer as a comonomer.
Wherein the ethylenically unsaturated aromatic monomer is a single substance selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, vinyltoluene, and 3,4-dichlorostyrene or a mixture of two or more thereof.
Wherein the ethylenically unsaturated aromatic monomer is contained in an amount of 0 to 5 wt% based on the total content of the graft copolymer.
Wherein the graft polymer has an average particle diameter of 190 to 230 nm.
Wherein the graft polymer has a glass transition temperature of -30 占 폚 or lower.
10 to 15% by weight of SAN resin;
10 to 15% by weight phosphorylated flame retardant; And
And 5 to 12% by weight of the graft copolymer according to claim 1; and a SAN blend thermoplastic resin composition comprising polycarbonate and SAN blend.
The polycarbonate and SAN blend thermoplastic resin composition
Polycarbonate resin 63 wt%
SAN resin 14 wt%;
14% by weight phosphorylated flame retardant; And
9 wt% of the graft copolymer according to claim 1; and
Polycarbonate and SAN blend thermoplastic resin composition.
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| EP3947485A4 (en) * | 2019-04-04 | 2023-01-18 | Trinseo Europe GmbH | Hydrophobic high heat optical acrylic copolymers |
| KR20210132484A (en) | 2020-04-27 | 2021-11-04 | 주식회사 엘지화학 | Method for preparing graft copoymer, graft copolymer prepared by the method and resin composition comprising the copolymer |
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