WO2016082521A1 - Flame-retardant polycarbonate reinforced high-modulus molding composition and preparation method therefor - Google Patents

Abstract

Provided are a flame-retardant polycarbonate reinforced high-modulus molding composition and a preparation method therefor. The flame-retardant polycarbonate reinforced high-modulus molding composition of the present invention comprises a polycarbonate or/and a polyester carbonate, a glass fibre, an impact modifier, a flame retardant, a polyalkylacrylate and an additive, and is characterized in that the polycarbonate and/or polyester carbonate is 40-90 parts by weight, the glass fibre is 5-50 parts by weight, the impact modifier is 1-20 parts by weight, the flame retardant comprises 1-20 parts by weight of a phosphorus-containing flame retardant and 0.1-5 parts by weight of a fluorohydrocarbon resin, the polyalkylacrylate is 1-20 parts by weight, and the additive comprises at least 0.1 parts by weight of an antioxidant. In the present invention, a phosphorus-based flame retardant is used in combination with a cocoon-type or flat glass fibre and a polyalkylacrylate with a high molecular weight, and the flame-retardant polycarbonate reinforced molding material having an excellent appearance and mechanical properties can be obtained.

Description

Flame-retardant polycarbonate reinforced high modulus molding composition and preparation method thereof Technical field

The invention relates to a flame-retardant polycarbonate reinforced high modulus molding composition and a preparation method thereof, and belongs to the technical field of flame-retardant thermoplastic molding materials.

Background technique

Polycarbonate has high impact resistance, good heat resistance and excellent processability. Therefore, they are widely used in the fields of automobile parts, household appliances, electronic appliances and the like. Materials used in 3C appliances, household appliances and office automation equipment have flame retardant requirements. With the demand for thinner and lighter, the material strength is required to be higher and higher. The glass fiber reinforced material can improve the strength of the material, but because it is in a solid state in the processing window of the molding material of the reinforced glass fiber material, the strength of the weld line of the material is lowered. Due to the orientation of the reinforced glass fiber material in the melt, the various surfaces of the material have a variety of anisotropy from the surface to make a significant deformation of the surface of the thin wall material. This phenomenon is more obvious at the weld line of multi-point injection molding, so that the material The ultra-thinness is limited.

Korean Patent Application KR 20090052447A discloses a glass fiber reinforced polycarbonate composition comprising 50 to 90% polycarbonate, 10 to 40% glass fiber, 1 to 10% thermoplastic elastomer, 1 to 10% Core-shell structural material. In this case, the surface of the material is apparent on the anisotropy, and the joint at the weld line is weak and easy to be deformed, and the surface appearance of the material is poor, which does not meet the design requirements of many products.

Summary of the invention

The object of the present invention is to provide a flame-retardant polycarbonate-reinforced high-modulus molding composition and a preparation method thereof, in combination with the above-mentioned problems, using a phosphorus-based flame retardant in combination with a crucible or a flat Flat glass fibers and high molecular weight polyalkyl acrylates provide polycarbonate flame retardant reinforced molding materials with good appearance and mechanical properties.

The above objectives are achieved by the following technical solutions:

A flame retardant polycarbonate reinforced high modulus molding composition comprising polycarbonate or/and polyester carbonate, glass fiber, impact modifier, flame retardant, polyalkyl acrylate, additive, It is characterized in that the polycarbonate and/or polyester carbonate is 40 to 90 parts by weight, the glass fiber is 5 to 50 parts by weight, and the impact modifier is 1 to 20 parts by weight. The flame retardant comprises 1-20 parts by weight of a phosphorus-containing flame retardant, 0.1-5 parts by weight of a fluorohydrocarbon resin, and the polyalkyl acrylate is 1-20 parts by weight, and the additive comprises At least 0.1 parts by weight of an antioxidant.

The flame-retardant polycarbonate reinforced high modulus molding composition, the glass fiber is a bismuth type glass fiber or a flat glass fiber, the length of the glass fiber is 2 to 5 mm, and the longitudinal mode ratio of the section is 2 to 10. .

The flame retardant polycarbonate reinforced high modulus molding composition, the impact modifier is a graft polymer, and the graft base is diene rubber, acrylate rubber, silicone rubber or ethylene/ Propylene/diene rubber.

The flame retardant polycarbonate reinforced high modulus molding composition, the phosphorus-containing flame retardant, having the structural formula of one or more compounds of Formula 1:

Formula 1:

among them

R ¹ , R ² , R ³ , R ⁴ independently of each other represent an optionally C ₁ -C ₈ alkyl group, or a C ₅ -C ₆ cycloalkyl group, a C ₆ -C ₂₀ aryl group or a C ₇ -C ₁₂ aralkyl group a group, each of which may be optionally substituted by a C ₁ -C ₄ alkyl group;

n independently of each other represents 0 or 1;

N is a positive integer from 0 to 30;

And X represents a mono- or polynuclear aromatic group having 6 to 30 carbon atoms.

The flame retardant polycarbonate reinforced high modulus molding composition further comprising a stabilizer, a pigment, a release agent, a flow promoter, an inorganic reinforcing material, a small particle, and/or an antistatic agent. At least one of the additives.

The method for preparing the above flame-retardant polycarbonate reinforced high modulus molding composition is characterized in that: after mixing the components at a high speed, the mixture is melt extruded by a screw extrusion, and then granulated by a granulator. The resulting pellets were dried in an oven at 80 ° C for 4 hours and then injection molded.

The flame retardant polycarbonate reinforced high modulus molding composition is prepared by extruding at a temperature of from 230 to 300 °C.

Beneficial effects:

The present invention uses a phosphorus-based flame retardant in combination with a ruthenium type or flat glass fiber and a high molecular weight polyalkyl acrylate to obtain a polycarbonate flame-retardant reinforced molding material having good appearance and mechanical properties. The molding compositions of the present invention can be used in any type of molded body, such as: notebook computers, televisions and coffee machines in household appliances, printers and displays for office equipment, shredder components, and other components requiring flame retardancy. The molding composition of the present invention can be molded by a suitable apparatus such as a hot press, an internal mixer, a single screw extruder, a twin screw extruder, Injection molding machine, etc. It can also be formed into small particles and then molded into the final part two or more times.

detailed description

A halogen-free flame-retardant polycarbonate/polyester-based resin composition comprising: polycarbonate or/and polyester carbonate (A), glass fiber (B), impact modifier (C), a flame retardant (D), a polyalkyl acrylate (E) additive, characterized in that the polycarbonate and/or polyester carbonate is 40 to 90 parts by weight, and the glass fiber is 5 to 50. The anti-shock modifier is 1 to 20 parts by weight, and the flame retardant comprises 1 to 20 parts by weight of the phosphorus-containing flame retardant (D) and 1 to 20 parts by weight of the polyalkyl acrylate. (E), 0.1 to 5 parts by weight of the fluorocarbon resin (F), and optionally at least 0.1 part of an additive such as an antioxidant.

The polycarbonates and/or polyestercarbonates of component A have been found to be produced by methods known in the literature and are available from a number of commercial sources. It may be an aromatic polycarbonate obtained by reacting various dihydroxy aryl compounds with phosgene, or a transesterification reaction of a dihydroxy aryl compound with diphenyl carbonate, and an aromatic polycarbonate and a polycarbonate thereof. Copolymer.

Polycarbonate raw material dihydroxy aryl compound is based on formula (V) bisphenol

among them:

A represents a single bond, C ₁ -C ₅ alkylene, C ₂ -C ₅ alkyl, C ₅ -C ₆ cycloalkyl, -S-, -SO ₂ -, -O-, -CO-, or a C ₆ -C ₁₂ arylene group, which group may optionally be condensed with other aromatic rings containing a hetero atom;

B independently of each other represents a C ₁ -C ₈ alkylene group, a C ₆ -C ₁₀ aryl group, preferably a phenyl group, a C ₇ -C ₁₂ cycloalkyl group;

X independently of each other represents 0, 1, or 2;

P represents 1 or 0.

Suitable dihydric phenols may be bis(4-hydroxyphenyl)methane, 1,1'-bis(4-hydroxyphenyl)ethane, 2,2'-bis(4-hydroxyphenyl)propane ("double Phenol A"), 2,2'-bis(4-hydroxyphenyl)butane, 2,2'-bis(4-hydroxy-3-methylphenyl)propane, 2,2'-bis (4- Hydroxy-3-methoxyphenyl)propane, 2,2'-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2'-bis(4-hydroxy-3-cyclohexyl) Phenyl)propane, 1,1'-bis(4-hydroxyphenyl)cyclopentane, 1,1`-bis(4-hydroxyphenyl)cyclohexane, 1,1`-bis(4-hydroxybenzene) Cyclododecane, 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl) a ketone, 2,6-dihydroxynaphthalene, and the like. Preference is given to bis(4-hydroxyphenyl)methane, 2,2'-bis(4-hydroxyphenyl)propane ("bisphenol A"), 2,2'-bis(4-hydroxy-3-methylphenyl) ) Propane. Bisphenol A is particularly preferred.

Polyester carbonate is also suitable for use in the present invention, and may be a copolyester-carbonate resin of an aromatic polycarbonate resin component. It can be produced from the carbonate precursor, at least one dihydric phenol, and at least one dicarboxylic acid or dicarboxylic acid equivalent. It is preferably produced from an aromatic dicarboxylic acid, particularly preferably one or more of terephthalic acid and isophthalic acid.

These polycarbonate resins and polyester carbonates can be obtained by known methods such as transesterification, interfacial polymerization, solution polymerization, and bulk polymerization.

The polycarbonates and/or polyestercarbonates of component A have been found to be linear, also branched, preferably branched polycarbonates and/or polyestercarbonates.

The component A of the present invention may be a polycarbonate or a polyester carbonate, or may be A variety of polycarbonates or polyestercarbonates of varying viscosities are also available in a variety of different polycarbonates and polyestercarbonates.

The component B glass fiber according to the present invention is: bismuth type glass fiber or flat glass fiber, and has a length of 2 to 5 mm, and an average diameter of the cross section is 10 to 50 μm, preferably 14 to 40 μm, more preferably 20 to 35 μm. The longitudinal mode ratio of the cross section is from 2 to 10, preferably from 2 to 6, more preferably from 3 to 5. The aforementioned longitudinal mode ratio is an average value. The flatter glass fiber can greatly improve the anisotropy of the material, while also improving the flame retardant performance of the large cap. The surface of the glass fiber can be either surface treated or untreated. The surface treatment may be an epoxy silane treatment or a titanate treatment, but is not limited thereto.

The glass composition of the B glass fiber found here is suitable for various glasses such as A glass, C glass and E glass, but E glass is preferred.

The component C impact modifier of the present invention may be a graft polymer, a compound having a core-shell structure, and a blend of the above compounds.

The above graft polymer is obtained by polymerizing two or more monomers of the following monomers: 1,3-butadiene, acrylonitrile, styrene, isoprene, α-methylstyrene, horse Anhydride, N-phenylmaleimide, methyl methacrylate, ethyl methacrylate, butyl methacrylate, preferably 1,3-butadiene, acrylonitrile, styrene, isoprene Copolymer.

The graft polymer is partially crosslinked and has a gel content of more than 20% by weight, preferably more than 30% by weight, particularly preferably more than 40% by weight.

The graft polymer may be a bulk polymerization method or a copolymer obtained by a known polymerization method such as an emulsion method, an emulsion-suspension method, or a suspension method. Can pass Obtained by continuous method, semi-continuous method or batch method.

The graft polymer has a glass transition temperature of less than 10 ° C, preferably a glass transition temperature of less than 0 ° C, and particularly preferably a graft polymer having a glass transition temperature of less than -20 ° C.

The component C impact modifier of the present invention may be a copolymer having a core-shell structure having a core of an elastomer and a fine particle form of at least one thermoplastic shell. The size of the particles is generally from 50 to 1000 nm, preferably from 100 to 500 nm.

The core of the above core-shell copolymer may be: isoprene, butadiene, alkyl acrylate, alkyl methacrylate homopolymer, silicone rubber elastomer, isoprene and/or a copolymer of butadiene and vinyl. The vinyl group may be styrene, acrylonitrile, methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, octyl methacrylate. The core of the core-shell copolymer may also contain a small amount of functional group monomers such as maleic anhydride, glycidic acid methacrylate, acrylic acid, and the like. It preferably contains butadiene rubber, isoprene rubber, acrylate rubber and silicone rubber and their methacrylic acid glycidic acid copolymer.

The core of the copolymer may be crosslinked in whole or in part.

The core copolymer has a glass transition temperature of less than 10 ° C, preferably a glass transition temperature of less than 0 ° C, and particularly preferably a copolymer having a glass transition temperature of less than -20 ° C.

The shell is one or two or more compounds of styrene olefin, alkyl styrene, alkyl acrylate, alkyl methacrylate, or a copolymer thereof with a vinyl group. The vinyl group may be styrene, acrylonitrile or vinyl acetate. The shell of the core-shell copolymer may also contain a small amount of functional group monomers such as maleic anhydride, glycidic acid methacrylate, acrylic acid, and the like. It preferably contains a styrene-acrylonitrile copolymer, methyl methacrylate.

The component D of the present discovery comprises at least one organophosphorus compound of (I):

among them

R ¹ , R ² , R ³ , R ⁴ independently of each other represent an optionally C ₁ -C ₈ alkyl group, or a C ₅ -C ₆ cycloalkyl group, a C ₆ -C ₂₀ aryl group or a C ₇ -C ₁₂ aralkyl group Any group optionally substituted by C ₁ -C ₄ alkyl, preferably phenyl, tolyl, xylyl, C ₁ -C ₄ alkyl, cyclohexane, particularly preferably phenyl;

n independently of each other represents 0 or 1, preferably 1;

N is a positive integer of 0 to 30, preferably a positive integer of 0 to 10, and particularly preferably a positive integer of 0 to 5;

X represents a mono- or polynuclear aromatic group having 6 to 30 carbon atoms, which may be p-phenyl, m-phenyl, bisphenol A, hydroquinone or the like, preferably m-phenyl or bisphenol A.

Corresponding (I) suitable phosphide include: triphenyl phosphate, trimethyl present phosphate, tributyl phosphate, tris(2,4-dimethylphenyl) phosphate, isophthalic dimer O-(diphenyl phosphate), bisphenol A bis-(diphenyl phosphate), diphenyl pentaerythritol diphosphate, and the like. Preference is given to triphenyl phosphate, meta-benzene di-bis-(diphenyl phosphate), bisphenol A bis-(diphenyl phosphate). Bisphenol A bis-(diphenyl phosphate) is particularly preferred.

Component E was found to be a polyalkyl acrylate, which may be a polyalkyl methacrylate or a polyalkyl methacrylate. The alkyl group in this compound is a C ₁ -C ₄ alkyl compound. This compound is preferably polymethyl methacrylate. This methyl methacrylate can be obtained by polymerizing methyl methacrylate. This methyl methacrylate can be obtained by radical polymerization or by other polymerization methods. These problems are aggravated by the addition of glass fibers and flame retardants which cause a decrease in the strength of the weld lines of the polymer and the addition of this compound at the glass fibers at the weld lines.

The component fluorine-substituted polyolefin of the present invention has been found to be a high molecular weight compound and has a glass transition temperature of more than -30 ° C, preferably more than 100 ° C, which has an effect of suppressing combustion of carbon and dripping. The fluorine-substituted polyolefin may be: CF ₂ =CF ₂ , CHF=CF ₂ , CH ₂ =CF ₂ , CH ₂ =CHF, CF ₃ CF=CF ₂ , CF ₃ CF=CHF, CF ₃ CF=CH ₂ ,CF A homopolymer or copolymer of ₃ CH=CH ₂ , CHF ₂ CF=CF ₂ or the like. Preference is given to CF ₂ =CF ₂ , CHF=CF ₂ , CH ₂ =CF ₂ polymer, particular preference being given to polytetrafluoroethylene. The fluorine-substituted polyolefin of the present invention may also be a copolymer of a fluorine-containing olefin and a plurality of ethylene.

The fluoroolefin polymer particles of the present invention may further comprise a layer of a second polymer on the periphery which facilitates dispersion of the fluoroolefin in the resin. This second polymer may be a mixture of one or a plurality of different monomers. The second polymer may be acrylonitrile, styrene, α-styrene, methyl acrylate, methyl methacrylate or butyl methacrylate. Preferred is a styrene-acrylonitrile copolymer, methyl methacrylate.

The compositions of the present invention may also optionally contain one or more additives such as heat stabilizers, light stabilizers, pigments, mold release agents, lubricants, flow promoters, inorganic reinforcing materials, carbon fibers, small particles and/or anti-resistances. An additive for an electrostatic agent. The molding compositions of the present invention may comprise one or more additional flame retardants, optionally with synergistic effects, such as inorganic magnesium hydroxide or aluminum, Cerium oxide, zinc borate, tin oxide, and silicon oxide.

The molding compositions of the present invention can be used in any type of molded body, such as: notebook computers, televisions and coffee machines in household appliances, printers and displays for office equipment, shredder components, and other components requiring flame retardancy.

The molding composition of the present invention can be molded by a suitable apparatus, for example, a hot press, an internal mixer, a single-screw extruder, a twin-screw extruder, an injection molding machine, etc., or can be first formed into small particles and then twice. Or molded into the final part multiple times.

Example

The present invention is specifically described by the following examples, and the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

After the resin and various auxiliaries are mixed at a high speed, they are melt-extruded by double (or single) screw extrusion, and then granulated by a granulator to obtain the composition. The extrusion temperature is 230 to 300 °C. The resulting pellets were dried in an oven at 80 ° C for 4 hours and then tested for physical properties by injection molding.

Use the following ingredients:

Component A: PC Korea Lotte Chemical Co., Ltd., grade 1100;

B: B1 round glass fiber, Chongqing International ECS301HP;

B2 flat glass fiber, Nitto Spin 3PA830;

C: Epoxy-functionalized acrylic core-shell copolymer, manufactured by Rhom & Haas, grade

EXL2314;

D: BDP, produced by Akzo Nobel Chemicals, USA, under the designation

BDP;

E: PMMA is Chi Mei CM207;

F: PTFE PTFE, produced by DuPont, USA, under the designation

30N. Further, styrene and acrylonitrile were copolymerized in the presence of an aqueous PTFE dispersion to obtain SAN-coated PTFE containing 50% of a styrene-acrylonitrile copolymer.

The physical properties of the examples and comparative examples were tested under the following conditions.

(I) Test the tensile strength of the material according to ISO 527.

(II) Weld line strength retention rate: melt line tensile strength/no melt finger tensile strength.

(III) The flexural modulus of the material was tested according to ASTM D178.

(III) Surface quality: The appearance surface of the molded article was comprehensively evaluated by visual and electron microscopic observation, and the results were classified into a grade 1 (good) to a grade 6 (bad) grade.

(IV) Variant: Samples with an injection length of 120 mm, a width of 60 mm, and a thickness of 1.6 mm have melt marks on the center. Fix the three corners of the sample and the highest height of the test sample minus the thickness.

(V) Test the vertical flame retardancy of the material according to the UL-94 standard and test using a 1/16 inch thick flame retardant spline.

Table 1

The above description is only a specific embodiment of the invention and should not be considered as the only embodiment. It is apparent to those skilled in the art that various modifications and changes in form and detail may be made without departing from the spirit and scope of the invention. Changes are still within the scope of the claims of the present invention.

Claims (7)

1. A flame retardant polycarbonate reinforced high modulus molding composition comprising: polycarbonate or/and polyester carbonate, glass fiber, impact modifier, flame retardant, polyalkylacrylic acid The ester and the additive are characterized in that the polycarbonate and/or polyester carbonate is 40 to 90 parts by weight, the glass fiber is 5 to 50 parts by weight, and the impact modifier is 1 ～20 parts by weight, the flame retardant comprises 1-20 parts by weight of a phosphorus-containing flame retardant, 0.1-5 parts by weight of a fluorocarbon resin, and the polyalkyl acrylate is 1-20 parts by weight, The additive includes at least 0.1 parts by weight of an antioxidant.
2. The flame-retardant polycarbonate reinforced high modulus molding composition according to claim 1, wherein the glass fiber is a bismuth type glass fiber or a flat glass fiber, and the glass fiber has a length of 2 to 5 mm. The longitudinal mode ratio of the section is 2 to 10.
3. The flame retardant polycarbonate reinforced high modulus molding composition according to claim 1, wherein said impact modifier is a graft polymer, and the graft base is diene rubber or acrylic acid. Ester rubber, silicone rubber or ethylene/propylene/diene rubber.
4. The flame retardant polycarbonate reinforced high modulus molding composition according to claim 1, wherein said phosphorus-containing flame retardant has a structural formula of one or more compounds of formula 1:

   Formula 1:

   

   among them:

   R ¹ , R ² , R ³ , R ⁴ independently of each other represent an optionally C ₁ -C ₈ alkyl group, or a C ₅ -C ₆ cycloalkyl group, a C ₆ -C ₂₀ aryl group or a C ₇ -C ₁₂ aralkyl group a group, each of which may be optionally substituted by a C ₁ -C ₄ alkyl group;

   n independently of each other represents 0 or 1;

   N is a positive integer from 0 to 30;

   And X represents a mono- or polynuclear aromatic group having 6 to 30 carbon atoms.
5. The flame retardant polycarbonate reinforced high modulus molding composition according to claim 1, wherein said additive further comprises a stabilizer, a pigment, a mold release agent, a flow promoter, an inorganic reinforcing material, and a small At least one of an additive of particles and/or an antistatic agent.
6. The invention relates to a method for preparing a flame-retardant polycarbonate reinforced high modulus molding composition, which is characterized in that: the components are mixed by high speed, melt extruded by screw extrusion, and then formed. The pellets were pelletized, and the resulting pellets were dried in an oven at 80 ° C for 4 hours and then injection molded.
7. A method of producing a flame-retardant polycarbonate-reinforced high modulus molding composition according to claim 6, wherein said extrusion temperature is from 230 to 300 °C.