CN110607060A - Thermoplastic resin composition, preparation method and application thereof - Google Patents

Abstract

The invention discloses a thermoplastic resin composition which comprises, by weight, 30-80 parts of polycarbonate, 5-50 parts of polyester, 2-25 parts of an impact modifier and 0.5-20 parts of boehmite, wherein the boehmite has an average particle size of 0.01 ~ 10 micrometers and an Fe element content of not more than 100 ppm.

Description

Thermoplastic resin composition, preparation method and application thereof

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a thermoplastic resin composition, a preparation method and an application thereof.

Background

The rapid development of the automobile industry in China drives the rapid growth of the application market of the lightweight plastic of automobiles, the lightweight of automobiles and energy conservation and emission reduction become important problems to be solved urgently in the automobile industry in China in the future, and meanwhile, higher innovation requirements are provided for the innovative application of the lightweight plastic technology of automobiles. The automobile exterior trim which takes high strength, high toughness, excellent weather resistance and impact resistance as application characteristics is one of main fields of automobile light weight. The automobile exterior trimming part includes: front and rear bumpers, engine hoods, radiator grilles, fenders, door handles outside the vehicle, rear deflectors, vehicle body trim strips and the like. Polyester (polyethylene terephthalate PET, polybutylene terephthalate PBT and the like)/Polycarbonate (PC) alloy, in particular to elastomer toughened PC/PBT alloy and PC/PET alloy which are ideal materials for manufacturing automobile exterior trimming parts by replacing steel with plastics, are suitable for manufacturing automobile parts such as bumpers, door handles, luggage supports, body plates, door modules, side guard plates, mud guards, anti-collision steel beams and the like, and have a wide application prospect.

Taking PC/PBT alloy as an example, the PC and the PBT are blended and modified, so that the defects of poor heat resistance, low impact resistance and low notch impact strength of the PBT can be overcome, and the defects of chemical resistance, molding processability and wear resistance of the PC can be overcome. The reason for this is that PC is an amorphous material, the toughness of thin products is good, PBT is a semi-crystalline material, and the resistance to corrosion of chemicals is improved due to the crystal region contained in the PBT alloy, so that the PC/PBT alloy has excellent chemical resistance, mechanical property, processability, heat resistance and the like due to the fact that the PC/PBT alloy has strong and weak points. However, both PC and PBT are high-gloss materials, and when applied to automotive interior, reflection and glare may be formed on a windshield, causing drivers to feel fatigue and reducing driving safety. Thus, the development of low gloss polycarbonate/polyester alloys has allowed for improved driving safety and reduced environmental damage from spray applications.

To reduce the gloss of materials, the art developers reduce the gloss of PC/PBT and PC/PET by surface embossing and adding matting agents, which can be divided into inorganic matting agents, non-reactive matting agents and reactive matting agents.

1. The rough appearance of the microstructure is etched on the surface of the mold through surface embossing, and the excellent matte effect is achieved through excellent replication of the material to the skin texture of the mold. However, the technical level is closely related to the technical capability of the mold manufacturer, and at the same time, extremely complicated etching procedures are required, the process and material costs are greatly increased, and when the frequency of use of the mold is too high, the surface skin is easily worn out and failed, and the good sensory effect of low gloss cannot be maintained for a long time.

2. CN201410760333 discloses a low-gloss toughened modified PTT polyester which comprises 5% of ~% of nano-silica and 1% of ~% of crosslinked butadiene-acrylonitrile polymer or crosslinked styrene-acrylonitrile polymer, 70% of PTT, 70% of modified wollastonite, 8% of modified wollastonite, ~% of toughening agent 6315% of toughening agent ~% of the PTT, 0.5% of matting agent ~%, wherein the matting agent is crosslinked butadiene-acrylonitrile polymer or crosslinked styrene-acrylonitrile polymer, the composition of the low-gloss toughened modified PTT polyester is prepared by compounding 70% of PTT, 70% of modified wollastonite, 8% of modified wollastonite, 6% of toughening agent 6315% of the PTT, 0.5% of matting agent ~%, wherein the matting agent is crosslinked butadiene-acrylonitrile polymer or crosslinked styrene-acrylonitrile polymer, the composition is prepared by using organic non-reactive matting agent and inorganic wollastonite to achieve the effect of reducing gloss, CN 61532-61532% of high-flame-resistant functional PET/wollastonite, 358% of crosslinked acrylonitrile-acrylonitrile copolymer, and 358% of crosslinked styrene-acrylonitrile copolymer, and 3% of crosslinked acrylonitrile-acrylonitrile copolymer.

3. The addition of non-reactive matting agents, named for inorganic matting agents and reactive matting agents, respectively, i.e. organic non-reactive matting agents, such as various rubber micropowder or core shell rubbers of different particle size, crosslinked polymers including the most classical matting agent crosslinked san (bmat) or crosslinked polyethylene, high molecular weight polymers such as PTFE, high molecular weight polyethylene, acrylic polymers, etc., various organic additives such as acrylates, silicone, lignin, PMMA and POE, etc. CN201610301230 discloses a low gloss PC/PBT alloy material whose gloss is reduced by the addition of 4 parts of crosslinked styrene-acrylonitrile polymer CN201410558762 discloses a matte master batch based on polytrimethylene terephthalate containing 10% of matting agent ~% of crosslinked butadiene-acrylonitrile polymer or crosslinked styrene-acrylonitrile polymer CN 2017107969 discloses a matte PC/PBT alloy material whose gloss is reduced by the use of crosslinked acrylonitrile-styrene, CN 201acrylonitrile microsphere CN 201556304 or crosslinked styrene-acrylonitrile copolymer CN 201201365519, CN 201365535% of crosslinked styrene-acrylonitrile alloy, CN 20136857-PC-3636 3, and PC-PC.

4. For example, CN03820623 discloses a thermoplastic molding composition comprising a blend of 35% ~% acrylate-styrene-acrylonitrile interpolymer resin and 1% ~% gloss reducing agent, wherein the gloss reducing agent is the reaction product of (i) an epoxidized graft rubber having a structure comprising a graft base comprising a rubber and a graft phase comprising a major amount of epoxy functionality and being at least one vinyl monomer not containing epoxy functionality and at least one vinyl monomer having epoxy functionality and (ii) two or more terminal primary amine groups per molecule, and (ii) a thermoplastic molding composition comprising a polycarbonate alloy having a gloss reducing effect by adding thereto a reactive gloss reducing agent, i.e., a component comprising reactive functional groups, which reacts with the gloss reducing agent in situ to reduce the gloss of the polycarbonate/polyester alloy material, wherein CN 03820620623 discloses a low gloss flame retardant alloy having a gloss property of 200355% gloss reducing agent, wherein the gloss reducing agent comprises at least one more epoxy functional groups than the flame retardant resin, wherein CN 038180% of the gloss reducing agent is added to the gloss of the polycarbonate/polyester alloy material by adding thereto a low gloss reducing agent comprising no epoxy functional groups, preferably no epoxy functional groups, wherein CN 038180% gloss reducing agent comprises no epoxy functional groups, no more than the gloss reducing agent added CN 038180, wherein CN 03355% polycarbonate ABS 5630% gloss reducing agent comprises No. 10, No. CN 035, No. 7, No. 5, No. 2, No. 5, No. 2, No. 3, No. more epoxy functional groups, No. 2, No. 3, No. 5, No. 3, No. 5% gloss reducing the gloss reducing agent, No. 3, No. 5, No. 3, No. 5.

Numerous researchers have made many attempts to provide good low gloss characteristics for polycarbonate/polyester alloy materials. From the prior technical means of modified extinction, the inorganic extinction agent is relatively less applied to alloy materials such as PC/PBT, PC/PET and the like; the non-reactive matting agent is often poor in compatibility with PC/PBT or PC/PET alloy, a two-phase incompatible structure is formed after the addition of the non-reactive matting agent, and meanwhile, most of the organic matting agents are toughening agents, so that the mechanical property and the heat resistance of the material are greatly influenced when the addition amount is high. For the reactive matting agent, if the desired matting effect is to be achieved, more reactive matting agent needs to be added, and phase separation of two phases or a great reduction in mechanical properties may be caused. In the case of inorganic matting agents, most patents suggest that a large amount of inorganic filler is required to achieve a desired degree of matting, and when the amount of the filler is excessive, the interface between the filler and the resin increases, and the interface bonding strength is low, which tends to deteriorate the overall mechanical properties. In view of the foregoing, there are limitations to the three current modified matte technologies, and there is still a need for more advanced technologies to further reduce the gloss of polycarbonate/polyester systems.

Disclosure of Invention

The invention aims to provide a thermoplastic resin composition and a preparation method thereof, which have good matt effect.

It is another object of the present invention to provide the use of boehmite for improving the matte properties of a thermoplastic resin composition.

The invention is realized by the following technical scheme:

a thermoplastic resin composition comprises the following components in parts by weight:

30-80 parts of polycarbonate;

5-50 parts of polyester;

2-25 parts of an impact modifier;

0.5-20 parts of boehmite;

the boehmite has the average grain diameter of 0.01 ~ 10 microns and the Fe element content of no more than 100 ppm.

By controlling the content of Fe element, the long cubic boehmite can be obtained in a controlled manner, on one hand, the boehmite can contribute to forming a rough karst cliff morphology on the surface during resin injection molding, and the morphology has an excellent effect on reduction of glossiness; on the other hand, the control of the content of the Fe element prevents the Fe element from generating obvious degradation effect on the PC polyester alloy, and ensures that the mechanical property is maintained to the maximum extent.

Boehmite, also called boehmite and boehmite, has a chemical formula of gamma-AlOOH and belongs to an orthorhombic system. The gamma-AlOOH is composed of a plurality of AlOs₆The structure is characterized by comprising an octahedron, wherein Al is arranged in the center of the octahedron, O is arranged at the vertex of the octahedron, double chains are formed by the octahedron through coplanarity, and a three-dimensional framework structure is formed by the octahedron and the vertex. γ -AlOOH is a layered structure, but as a whole the O atoms are not cubic close-packed, but the O atoms within the layer are cubic close-packed. The aluminum ions are in oxygen octahedron to form a double-layer structure, and the layers are connected by hydrogen bonds to form a Z-shaped long-chain structure. Boehmite with various shapes such as wrinkled sheet, needle, chain, boat, cube, diamond sheet and the like and greatly different grain sizes can be obtained by different preparation methods.

Boehmite is generally used as a filler added to the resin matrix, and functions similarly to talc and calcium carbonate.

The cube is a solid shape like a cuboid or a cube with 8 vertices and 6 faces, in particular an elongated cube, i.e. with four faces, at least three times longer than it is wide.

The general synthesized boehmite in the market is mostly in a sheet shape or a corrugated shape, has the average particle size distribution of 0.01 ~ 300 microns, and is widely distributed, the content of Fe element exceeds 550ppm, and the content of aluminum element is 38% to ~ 64%.

The conventional matting agents are mostly spherical, the light reflection surfaces are mostly planar or hemispherical, and after light is incident and reflected, even if scattering occurs, part of the light is still normally reflected into human eyes, so that the glossiness cannot be remarkably reduced.

The particle size and Fe content of the boehmite are limited to obtain the cuboid-shaped boehmite, the boehmite is not smooth on each surface of a cuboid except for integrally keeping the cuboid form, a rough karst cliff appearance is presented, the appearance has an excellent effect on reduction of glossiness, the karst cliff appearance is like a rectangular wave with extremely narrow peaks and troughs, and most of light rays are blocked by steep cliff walls when being incident on the surface, so that extremely few light rays are normally reflected, and the boehmite with the characteristic can be used as an optimal matting agent for taking polycarbonate and polyester as a resin matrix.

"polycarbonate" as used herein refers to a polymer having repeating carbonate structural units of the general formula (1):

(1)

wherein at least 60 percent of the total number of R groups contain aromatic moieties and the balance thereof are aliphatic, alicyclic, or aromatic moieties. In one embodiment, each R is C_6-30Aromatic groups, that is to say which comprise at least one aromatic moiety, R may be derived from an aromatic dihydroxy compound of the general formula HO-R-OH, in particular of the general formula (2):

HO-A¹-Y¹-A²-OH (2)

wherein A is¹And A²Each is a monocyclic divalent aromatic radical, and Y¹To separate A¹And A²A single bond or a bridging group having one or more atoms. In one embodiment, A may be separated by different atoms or groups¹And A². Each R may be derived from a bisphenol of formula (3):

(3)

wherein both arylene groups may also be substituted by other halogen, alkoxy or alkyl groups, in particular unsubstituted arylene groups, X is a bridging group connecting the two hydroxy-substituted aryl groups, wherein the bridging group is connected to each C₆Hydroxy substituents of arylene radicals at C₆The arylene groups are located ortho, meta or para, especially para, to each other. In one embodiment, the bridging group X may be a single bond, -O-, -S-, -S (O) -, -S (O)₂-, -C (O) -or C_1-18An organic group. Said C is_1-18The organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can also contain heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. Can place C_1-18Organic group such that each C attached thereto₆Arylene radicals bound to C_1-18The organic bridging group may be on the same alkylene carbon or different carbons. In one embodiment, X is isopropyl, two methyl groups are placed on either side of the C atom in the middle of X, and the C atom is attached to a hydroxy-substituted arylene group at each para position.

Polycarbonates include homopolycarbonates, i.e., copolymers in which R is structurally the same in all units in formula 1, and copolymers which may include different R moieties in the carbonate, i.e., copolycarbonates, or copolymers comprising carbonate units with other types of polymer units, such as other ester units or siloxane units.

A particular type of copolymer is poly (ester-carbonate), also known as polyester-polycarbonate. Such copolymers comprise, in addition to the recurring carbonate units of formula (1), recurring units of formula (4):

(4)

wherein J is a divalent radical derived from a dihydroxy compound (including reactive derivatives thereof), and may be, for example, C_2-20Alkylene radical, C_6-20Cycloalkylene radical, C_6-20Arylene or polyoxyalkylene, in which the alkylene radical contains 2 ~ 6 carbon atoms, especially 2,3 or 4 carbon atoms, and T is a divalent radical derived from a dicarboxylic acid (including reactive thereof) derivative, and may be, for example, C_2-20Alkylene radical, C_6-20Cycloalkylene radical, C_6-20An arylene group. Copolyesters containing combinations of different T and/or J groups may be used. The polyester units may be branched or linear.

In one embodiment, J is C having a branched, to branched, or cyclic (including polycyclic) structure_2-30Alkylene, for example ethylene, n-propylene, i-propylene, 1, 4-butylene, 1, 6-cyclohexylene or 1, 4-methylenecyclohexane. In another embodiment, J is derived from a bisphenol of formula (3), such as bisphenol A. In another embodiment, J is derived from an aromatic dihydroxy compound, such as resorcinol.

Aromatic dicarboxylic acids that can be used to prepare the polyester units include isophthalic or terephthalic acid, 1, 2-bis (p-carboxyphenyl) ethane, 4,4 '-dicarboxydiphenyl ether, 4, 4' -bisbenzoic acid, or a combination comprising at least one of the foregoing acids, as well as fused ring containing acids such as 1,4-, 1,5-, or 2, 6-naphthalenedicarboxylic acid, specific dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, or a combination comprising at least one of the foregoing acids, specific dicarboxylic acids include a combination of isophthalic and terephthalic acids, wherein the weight ratio of isophthalic to terephthalic acid is 80:20 ~ 1: 99.

Specific ester units include ethylene terephthalate, n-propylene terephthalate, n-butylene terephthalate, 1, 4-cyclohexanedimethanol terephthalate, and ester units derived from isophthalic acid, terephthalic acid, and resorcinol the molar ratio between ester units and carbonate units in the copolymer can vary over a wide range, such as 0.5: 99.5 ~ 99.5.5: 0.5 specific poly (ester-carbonates) are those comprising bisphenol a carbonate units and isophthalate-terephthalate-bisphenol a ester units, also commonly referred to as poly (carbonate-esters), poly (phthalate-carbonates), and the like.

The boehmite has the average grain diameter of 3 ~ 5 microns and the Fe element content of not more than 50 ppm.

The boehmite is one or a mixture of more of the shapes of a wrinkled sheet, a needle, a chain, a boat, a cube, a rhombus sheet, a sphere, a bagel and the like; preferably, the boehmite is cubic.

Aromatic dicarboxylic acids that may be used to prepare the polyester units include isophthalic or terephthalic acid, 1, 2-bis (p-carboxyphenyl) ethane, 4,4 '-dicarboxydiphenyl ether, 4, 4' -bisbenzoic acid, or a combination comprising at least one of the foregoing acids, and fused ring containing acids, such as 1,4-, 1,5-, or 2, 6-naphthalenedicarboxylic acid, may also be present. Specific dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1, 4-cyclohexane dicarboxylic acid, or a combination comprising at least one of the foregoing acids.

Specifically, the polyester is selected from at least one of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexanedimethylene terephthalate, polycyclohexanedimethylene-ethylene terephthalate, polytrimethylene terephthalate and derivatives thereof

0-20 parts of compatilizer;

the compatilizer is selected from terpolymer of ethylene-acrylic ester-glycidyl methacrylate, wherein the weight percentage of ethylene in the chain segment is 20% ~ 80%.

The impact modifier is selected from methyl methacrylate-butadiene-styrene (MBS) impact modifiers with a core-shell structure, wherein the butadiene accounts for 30 percent ~ 70 percent of the weight of the chain segment, and the rubber is not limited to butadiene and can be alkyl acrylate.

The impact modifiers comprise elastomers, i.e., rubbers, which may include elastomer-modified graft copolymers comprising (1) an elastomeric (i.e., rubber) polymer matrix and having a glass transition temperature of less than about 10^oC, more specifically less than about-10^oC, or more specifically about-40 to-80^oC, and (2) a rigid polymeric base layer grafted to the elastomeric polymeric matrix. It is known that elastomer-modified graft copolymers can be prepared as follows: the graft copolymer is obtained by first providing an elastomeric polymer and then polymerizing the constituent monomers of the rigid phase in the presence of the elastomer. The grafts may be attached to the elastomer core as graft branches or as shells. The shell may merely physically encapsulate the core, or the shell portion may be substantially completely grafted to the core.

Suitable materials for use as the elastomeric phase include, for example, conjugated diene rubbers; copolymers of less than 50wt% of a conjugated diene with a copolymerizable monomer, olefin rubbers such as ethylene-propylene copolymers (EPR), or ethylene-propylene diene monomer rubbers (EPDM); ethylene-acrylate rubbers; silicone rubber; elasticity C_1-8Alkyl (meth) acrylates; c_1-8Elastomeric copolymers of alkyl (meth) acrylates with butadiene and/or styrene; or combinations comprising at least one of the foregoing elastomers.

Suitable conjugated diene monomers for preparing the elastomeric phase are conjugated diene monomers of formula (6):

(6)

wherein each X is independently hydrogen, C₁-C₅Alkyl groups, and the like. Examples of conjugated diene monomers which may be used are butadiene, isoprene, 1, 3-heptadiene, methyl-1, 3-pentadiene, 2, 3-dimethyl-1, 3-butadiene, 2-ethyl-1, 3-pentadiene; 1, 3-and 2, 4-hexadienes, and the like, as well as mixtures comprising at least one of the foregoing conjugated diene monomers. Specific conjugated diene homopolymers include isoprene and polybutadiene.

Copolymers of conjugated diene rubbers may also be used, such as those prepared by aqueous free radical polymerization of a conjugated diene and one or more monomers copolymerizable therewith. Suitable monomers for the copolymerization of the conjugated diene include monovinylaromatic monomers containing a condensed aromatic ring structure such as vinylnaphthalene, vinylanthracene, etc., or monomers of formula (7).

(7)

Wherein X in formula (6) is independently hydrogen or C₁-C₁₂Alkyl radical, C₃-C₁₂Cycloalkyl radical, C₆-C₁₂Aryl radical, C₇-C₁₂Aralkyl radical, C₇-C₁₂Alkylaryl group, C₁-C₁₂Alkoxy radical, C₃-C₁₂Cycloalkoxy, C₆-C₁₂Aryloxy, chloro, bromo, or hydroxy, R is hydrogen, C₁-C₅Alkyl, bromo, or chloro, and the like. Examples of suitable monovinylaromatic monomers that may be used include styrene, 3-methylstyrene, 3, 5-diethylstyrene, 4-n-propylstyrene, α -methylstyrene, α -methylvinyltoluene, α -chlorostyrene, α -bromostyrene, dichlorostyrene, dibromostyrene, tetra-chlorostyrene, and the like, and combinations comprising at least one of the foregoing monovinylaromatic monomers. Styrene and/or alpha-methylstyrene may be used as monomers copolymerizable with the conjugated diene monomer.

Other monomers copolymerizable with the conjugated diene are monovinylic monomers such as itaconic acid, acrylamide, N-substituted acrylamide or methacrylamide, maleic anhydride, maleimide, N-alkyl-, aryl-, or haloaryl-substituted maleimide, glycidyl (meth) acrylates and monomers of formula (8):

(8)

wherein R is hydrogen, C₁-C₅Alkyl, bromo or chloro, X is cyano, C₁-C₁₂Alkoxycarbonyl group, C₁-C₁₂Aryloxycarbonyl, hydroxycarbonylAnd the like. Examples of monomers of formula (8) include acrylonitrile, ethacrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile, beta-chloroacrylonitrile, alpha-bromoacrylonitrile, acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like, as well as combinations comprising at least one of the foregoing monomers. Monomers such as n-butyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate are often used as monomers copolymerizable with the conjugated diene monomer. Mixtures of the foregoing monovinyl monomers and monovinylaromatic monomers may also be used.

Suitable (meth) acrylate monomers for the elastomeric phase include crosslinked, particulate emulsion homopolymers or copolymers of: (meth) acrylic acid C_1-8Alkyl esters, in particular acrylic acid C_4-6Alkyl esters, such as n-butyl acrylate, t-butyl acrylate, n-propyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, and the like, as well as combinations comprising at least one of the foregoing monomers. (meth) acrylic acid C_1-8The alkyl ester monomer may optionally be polymerized in admixture with up to 80% of a comonomer of formula (5), (6) or (7) as detailed above. Exemplary comonomers include, but are not limited to, butadiene, isoprene, styrene, methyl methacrylate, phenyl methacrylate, phenylethyl methacrylate, N-cyclohexylacrylamide, vinyl methyl ether, or acrylonitrile, and mixtures comprising at least one of the foregoing comonomers. Optionally, up to 10% of a polyfunctional crosslinking comonomer may be present, such as divinylbenzene, alkylenediol di (meth) acrylates, such as glycol bisacrylate, alkylenetriol tri (meth) acrylates, polyester di (meth) acrylates, bisacrylamides, triallyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate, diallyl maleate, diallyl fumarate, diallyl adipate, triallyl esters of citric acid, triallyl esters of phosphoric acid, and the like, as well as combinations comprising at least one of the foregoing crosslinking agents.

Can be prepared by polymerizing in one or more elastomersGraft polymerizing a mixture comprising a monovinylaromatic monomer and optionally one or more comonomers in the presence of a substrate to form a rigid phase in the elastomer-modified graft copolymer. Monovinylaromatic monomers of formula (6) as described in detail above, including styrene, alpha-methylstyrene, halostyrenes such as dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, p-hydroxystyrene, methoxystyrene, and the like, or a combination comprising at least one of the foregoing monovinylaromatic monomers, can be used in the rigid graft phase. Suitable comonomers include, for example, the monovinylic monomers and/or monomers of the formula (7) described in detail above. In one embodiment, R is hydrogen or C₁-C₂Alkyl, and X is cyano or C₁-C₁₂An alkoxycarbonyl group. Specific examples of suitable comonomers for use in the rigid phase include acrylonitrile, ethacrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and the like, and combinations comprising at least one of the foregoing comonomers.

The rigid phase may generally include up to 100 weight percent monovinyl aromatic monomer, specifically about 20 ~ about 100 weight percent, more specifically about 40 ~ about 80 weight percent monovinyl aromatic monomer, the remainder being comonomer.

Typically, such impact modifiers comprise about 30 ~ about 80 wt.% elastomer-modified graft copolymer, and about 20 ~ about 70 wt.% rigid polymer (copolymer), based on the total weight of the impact modifier in another embodiment, such impact modifiers comprise more specifically about 45 ~ about 65 wt.% rubber-modified graft copolymer, and more specifically about 35 ~ about 55 wt.% rigid polymer (copolymer), based on the total weight of the impact modifier, the average particle size of the elastomeric rubber is 0.01 ~ 5.0.0 micrometers, more preferably 0.05 ~ 4.0.0 micrometers.

If desired, impact modifiers of the aforementioned type may be prepared by emulsion polymerization processes which avoid the use of basic species, such as C_6-30Alkali metal salts of fatty acids, such as sodium stearate, lithium stearate, sodium oleate, potassium oleate, and the like, alkali metal carbonates, amines such as dodecyl dimethylamine, dodecylamine, and the like, and ammonium salts of amines, and other materials containing degradation catalysts, such as acids. Such materials are commonly used as polymerization aids, for example, surfactants in emulsion polymerization, and may catalyze transesterification and/or degradation of polycarbonates. In contrast, ionic sulfate, sulfonate, or phosphate surfactants may be used in the preparation of impact modifiers, particularly the elastomeric substrate portion of the impact modifiers. Suitable surfactants include, for example, C_1-22Alkyl or C_7-25Alkylaryl sulfonate, C_1-22Alkyl or C_7-25Alkylaryl sulfates, C_1-22Alkyl or C_7-25Alkylaryl phosphates, substituted silicates, and combinations comprising at least one of the foregoing surfactants. A specific surfactant is C_6-16And in particular C₈-C₁₂An alkyl sulfonate. This emulsion polymerization process is described and disclosed in, for example, Rohm&Haas and General Electric Company, among others. In practice, any of the above-described impact modifiers may be used so long as it is free of the alkali metal salts of fatty acids, alkali metal carbonates, and other basic materials.

A specific impact modifier of this type is a methyl methacrylate-butadiene-styrene (MBS) impact modifier wherein the butadiene substrate is prepared using the above-described sulfonate, sulfate, or phosphate salts as surfactants, in a proportion of 2% ~ 25% of the total formulation.

The molecular weight of the polycarbonate is 10000-80000 daltons.

0-10 parts of auxiliary agent is also included; the auxiliary agent is at least one selected from antioxidant, lubricant, heat stabilizer, light stabilizer and colorant.

Antioxidants include primary antioxidants or stabilizers (such as hindered phenols and/or secondary arylamines) and optional secondary antioxidants (such as phosphates and/or thioesters). Suitable antioxidants include, for example, organophosphates such as tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite or the like, alkylated monophenols or polyphenols; alkylation reaction products of polyhydric phenols with dienes such as tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane and the like; butylated reaction products of p-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ether; alkylidene bisphenols; a benzyl compound; esters of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with mono-or polyhydric alcohols; esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono-or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as distearylthiopropionate, dilaurylthiopropionate, ditridecylthiopropionate, octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) ] propionate and the like; amides of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid and the like; or combinations comprising at least one of the foregoing antioxidants.

Suitable heat stabilizers include, for example, organophosphites such as triphenyl phosphite, tris (2, 6-dimethylphenyl) phosphite, tris (mixed mono-and dinonylphenyl) phosphite, and the like; phosphonates such as dimethylbenzene phosphonate or the like; phosphate esters such as trimethyl phosphate and the like; or combinations comprising at least one of the foregoing heat stabilizers.

The lubricant is at least one selected from stearate lubricant, fatty acid lubricant and stearate lubricant; the stearate lubricant is at least one selected from calcium stearate, magnesium stearate and zinc stearate; the fatty acid lubricant is at least one selected from fatty acid, fatty acid derivative and fatty acid ester; the stearate lubricant is at least one selected from pentaerythritol stearate; preferably, the lubricant is at least one selected from fatty acid lubricants and stearate lubricants.

Suitable light stabilizers include, for example, benzotriazoles such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -benzotriazole, and 2-hydroxy-4-n-octyloxybenzophenone, and the like, as well as triazine based ultraviolet light absorbers or combinations comprising at least one of the foregoing light stabilizers.

Such as pigment and/or dye additives. Suitable pigments include, for example, inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxide, iron oxide, and the like; sulfides such as zinc sulfide and the like; an aluminate salt; sodium-sulfur silicate sulfate, chromate, and the like; carbon black; zinc ferrite; ultramarine blue; pigment brown 24; pigment red 101; pigment yellow 119; organic pigments such as azo, diazo, quinacridone, perylene, napthalenetetracarboxylic acid, flavanthrone, isoindolinone, tetrachloroisoindolinone, anthraquinone, anthanthrone, dioxazine, phthalocyanine, and azo lakes; pigment blue 60, pigment Red 122, pigment Red 149, pigment Red 177, pigment Red 179, pigment Red 202, pigment Red 29, pigment blue 15, pigment Green 7, pigment yellow 147 and pigment yellow 150, or a combination comprising at least one of the foregoing pigments. Preferred colorants include carbon black, iron oxide red or titanium dioxide. Suitable dyes may be organic materials and include, for example, coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile red lamp; a lanthanide complex; hydrocarbon and substituted hydrocarbon dyes; a polycyclic aromatic hydrocarbon dye; scintillation dyes, such as oxazole or oxadiazole dyes; aryl or heteroaryl substituted poly (C2-8) olefin dyes; a carbocyanine dye; indanthrone dyes; a phthalocyanine dye; an oxazine dye; a quinolone dye; a naphthalene tetracarboxylic acid dye; a porphyrin dye; bis (styryl) biphenyl dyes; an acridine dye; anthraquinone dyes; a cyanine dye; a methine dye; an arylmethane dye; an azo dye; indigoid dyes, thioindigoid dyes; a diazo dye; nitro dyes; quinone imine dyes; an aminoketone dye; a tetrazolium dye; a thiazole dye; a perylene dye; a perylene ketone dye; di-benzoxazolyl thiophene; a triarylmethane dye; a thioxanthene dye; naphthalimide dyes; a lactone dye; fluorophores such as anti-stokes shift dyes that absorb in the near infrared wavelength and emit in the visible wavelength, and the like; luminescent dyes, such as 7-amino-4-methylcoumarin; 3- (2' -benzothiazolyl) -7-diethylaminocoumarin; 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole; 2, 5-bis- (4-biphenyl) -oxazole; 2, 2' -dimethyl-p-quaterphenyl; 2,2, -dimethyl-p-terphenyl; 3,5,3 ', 5' -tetra-tert-butyl-p-pentabiphenyl; 2, 5-diphenylfuran; 2, 5-diphenyloxazole; 4, 4' -diphenylstilbene; 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran; 1,1 '-diethyl-2, 2' -carbocyanine iodide; 3,3 ' -diethyl-4, 4 ', 5,5 ' -dibenzothiatricarbocyanin iodide; 7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2; 7-dimethylamino-4-methylquinolone-2; 2- (4- (4-dimethylaminophenyl)) -1, 3-butadienyl) -3-ethylbenzothiazole perchlorate; 3-diethylamino-7-diethyliminophenoxazole perchlorate; 2- (1-naphthyl) -5-phenyloxazole; 2, 2' -p-phenylene-bis (5-phenyloxazole); rhodamine 700; rhodamine 800; pyrene; 1, 2-triphenylene; (ii) a rubrene; coronene, or the like, or combinations comprising at least one of the foregoing dyes.

The preparation method of the thermoplastic resin composition comprises the following steps of uniformly mixing the polycarbonate, the polyester, the impact modifier, the boehmite and the auxiliary agent, and then putting the mixture into a screw extruder for extrusion granulation (200 ~ 300 ℃ and the rotation speed of 200 ~ 700 r/min) to obtain the thermoplastic resin composition.

The application of boehmite for improving matte performance of thermoplastic resin composition comprises the following components in parts by weight:

30-80 parts of polycarbonate;

5-50 parts of polyester;

2-25 parts of an impact modifier;

0.5-20 parts of boehmite;

the boehmite has the average grain diameter of 0.01 ~ 10 microns and the Fe element content of no more than 100 ppm.

The invention has the following beneficial effects:

according to the invention, boehmite is added into the resin which is mainly composed of polycarbonate, polyester and impact modifier, and the particle size, the content of characteristic elements and the particle shape of the boehmite are screened and optimized, so that the thermoplastic resin composition with a good matte effect is obtained.

Drawings

FIG. 1: a cubic boehmite photograph showing that the cube is a solid shape similar to a cuboid or a cube, having 8 vertexes and 6 faces;

FIG. 2: a schematic illustration of a boehmite surface having a karst morphology;

FIG. 3: lamellar boehmite photographs.

Detailed Description

The present invention is described in more detail by the following examples, but the present invention is not limited by the following examples.

The raw materials used in the invention are as follows:

polypropylene: PP 7033N, exxonmobil chemical;

polycarbonate (C): bisphenol a polycarbonate, 20000 daltons, produced by the japanese emperor;

polyester, namely polybutylene terephthalate, the melting point of which is 224 ℃, the intrinsic viscosity of which is 0.8 ~ 1.0.0 dl/g, and the production of the instrumented chemical fiber;

impact modifier: methacrylate-butadiene-styrene with a butadiene content of 60%, produced chemically with LG;

a compatilizer: ethylene-acrylate-glycidyl methacrylate, with an ethylene content of 48%;

boehmite A: the grain size is cubic, the average grain size is 1.0 micron, the content of Fe element is 80ppm, and the surface presents a rough karst cliff appearance;

boehmite B: the grain size is cubic, the average grain size is 2.0 microns, the content of Fe element is 50ppm, and the surface presents a rough karst cliff appearance;

boehmite C: the grain size is cubic, the average grain size is 5.0 microns, the content of Fe element is 30ppm, and the surface presents a rough karst cliff appearance;

boehmite D: the material is boat-shaped, the average grain diameter is 6.4 microns, the content of Fe element is 94ppm, and the surface presents a rough karst cliff appearance;

boehmite E: the particles are flaky, the average particle size is 7.2 microns, the content of Fe element is 75ppm, and the surface presents a rough karst cliff appearance;

boehmite F: cubic, the average grain diameter is 12 microns, the Fe element content is 150ppm, and the surface is smooth;

boehmite G: the average grain diameter of the cube is 8 microns, the content of Fe element is 210ppm, and the surface is smooth;

lubricant: pentaerythritol stearate;

antioxidant: a hindered phenol antioxidant;

the thermoplastic resin compositions of examples and comparative examples were prepared by uniformly mixing polycarbonate, styrenic impact toughener, vinyl aromatic monomer and ethylenically unsaturated nitrile monomer copolymer (or other thermoplastic resin), boehmite, and aid, and then feeding into a screw extruder for extrusion granulation (200 ~ 300 ℃ C., rotation speed 200 ~ 700r/min, 700 r/min) to obtain thermoplastic resin compositions.

The performance test method comprises the following steps:

(1) gloss: using a male-shocking injection molding machine to injection mold various standard sample strips and sample plates; surface Gloss of popular K31 fine grain board was tested according to ASTM D523 using a Garden Gloss Meter at C and reported in Gloss Units (GU), where the Gloss of a standard black glass sheet was 100 GU.

(2) Mechanical properties: and (5) using a male-shocking injection molding machine to injection mold various standard sample strips and templates.

Tensile strength: testing according to ISO527 standard, wherein the tensile speed is 50 mm/min; flexural modulus: testing according to ISO178 standard, with speed of 2mm/min and span of 64 mm; notched Izod impact strength: testing according to ISO180/1eA standard;

the products prepared in examples and comparative examples were subjected to performance tests, and the results are shown in tables 1 and 2.

Table 1: examples the proportions (parts by weight) of the respective components of the thermoplastic resin compositions and the results of the respective property tests

	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7
								Polycarbonate resin	60	60	60	70	60	60	40
Polyester	40	40	40	30	40	40	40
								Compatilizer	5	5	5	5	5	5	5
Impact modifier	5	5	5	5	5	10	20
								Boehmite A	5			5	15	2	5
Boehmite B		5
								Boehmite C			5
Lubricant agent	0.2	0.2	0.2	0.2	0.2	0.2	0.2
								Antioxidant agent	0.2	0.2	0.2	0.2	0.2	0.2	0.2
gloss/GU	6.2	4.3	3.5	8.1	3.0	9.2	5.4
								Tensile strength/MPa	63	64	65	68	70	58	54
Flexural modulus/MPa	2480	2500	2510	2550	2680	2410	2350
								Izod notched impact Strength/kJ/m2	51	53	56	60	32	55	61

As can be seen from examples 1 to 3, boehmite C is preferred, which has the best matting effect.

Table 3: comparative example thermoplastic resin composition component ratios (parts by weight) and results of various property tests

	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5
						Polypropylene	100
Polycarbonate resin		60	60	60	60
						Polyester		40	40	40	40
Compatilizer		5	5	5	5
						Impact modifier		5	5	5	5
Boehmite A	10
						Boehmite D		5
Boehmite E			5
						Boehmite F				5
Boehmite G					5
						Lubricant agent	0.2	0.2	0.2	0.2	0.2
Antioxidant agent	0.2	0.2	0.2	0.2	0.2
						gloss/GU	8.8	10.5	11.2	3.0	3.2
Tensile strength/MPa	29.5	65	67	41	36
						Flexural modulus/MPa	1470	2620	2670	1800	1600
Izod notched impact Strength/kJ/m2	19.7	45	40	29	25

As can be seen from comparative example 1, the matting properties of boehmite in a polypropylene matrix are generally reduced to 8.8 when the addition amount reaches 10 parts.

As can be seen from comparative example 2/3, the matting properties were poor for boehmite of other shapes.

It can be seen from comparative example 4/5 that when the content of iron element and the particle size of boehmite are out of the range of the present invention, the compatibility with the resin matrix is poor, which results in poor mechanical properties, and the low gloss is also due to compatibility and cracking factor of iron element to polycarbonate.

Claims (10)

1. A thermoplastic resin composition is characterized by comprising the following components in parts by weight:

30-80 parts of polycarbonate;

5-50 parts of polyester;

2-25 parts of an impact modifier;

0.5-20 parts of boehmite;

the boehmite has the average grain diameter of 0.01 ~ 10 microns and the Fe element content of no more than 100 ppm.

2. The thermoplastic resin composition of claim 1, wherein said boehmite has an average particle size of 3 ~ 5 μm and an Fe element content of not more than 50 ppm.

3. The thermoplastic resin composition of claim 1, wherein said boehmite has a cubic shape.

4. The thermoplastic resin composition according to claim 1, wherein said polyester is at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexanedimethylene terephthalate, polycyclohexanedimethylene-ethylene terephthalate, and polytrimethylene terephthalate, and derivatives thereof.

5. The thermoplastic resin composition of claim 1, wherein said impact modifier is selected from the group consisting of core-shell methylmethacrylate-butadiene-styrene impact modifiers, wherein butadiene comprises 30% ~ 70% by weight of the segments.

6. The thermoplastic resin composition of claim 1, further comprising 0-20 parts by weight of a compatibilizer selected from the group consisting of ethylene-acrylate-glycidyl methacrylate terpolymers wherein ethylene comprises 20% ~ 80% by weight of the segments.

7. The thermoplastic resin composition of claim 1, wherein said polycarbonate has a molecular weight of 10000-80000 daltons.

8. The thermoplastic resin composition according to claim 1, further comprising 0 to 10 parts by weight of an auxiliary; the auxiliary agent is at least one selected from antioxidant, lubricant, heat stabilizer, light stabilizer and colorant.

9. The method of claim 8, wherein the polycarbonate, the polyester, the impact modifier, the boehmite, and the assistant are uniformly mixed in a predetermined ratio, and the mixture is extruded and pelletized (200 ~ 300 ℃ C., 200 ~ 700 r/min) in a screw extruder to obtain the thermoplastic resin composition.

10. The application of boehmite for improving the matte property of a thermoplastic resin composition is characterized by comprising the following components in parts by weight:

30-80 parts of polycarbonate;

5-50 parts of polyester;

2-25 parts of an impact modifier;

0.5-20 parts of boehmite;

the boehmite has the average grain diameter of 0.01 ~ 10 microns and the Fe element content of no more than 100 ppm.