WO2022095365A1 - 一种玻纤增强的聚碳酸酯组合物及其制备方法和应用 - Google Patents

一种玻纤增强的聚碳酸酯组合物及其制备方法和应用 Download PDF

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WO2022095365A1
WO2022095365A1 PCT/CN2021/090757 CN2021090757W WO2022095365A1 WO 2022095365 A1 WO2022095365 A1 WO 2022095365A1 CN 2021090757 W CN2021090757 W CN 2021090757W WO 2022095365 A1 WO2022095365 A1 WO 2022095365A1
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glass fiber
fiber reinforced
reinforced polycarbonate
parts
polycarbonate composition
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French (fr)
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李明昆
岑茵
黄险波
艾军伟
彭民乐
吴俊�
刘贤文
丁超
叶南飚
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金发科技股份有限公司
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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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
    • 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
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • 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
    • C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
    • C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • 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
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients

Definitions

  • the invention belongs to the field of engineering plastics, and in particular relates to a glass fiber reinforced polycarbonate composition and a preparation method and application thereof.
  • PCABS is a traditional high-performance alloy with beneficial characteristics such as high surface gloss, good toughness, and good processing fluidity. It is used in various fields, especially in the fields of electronic appliances, transportation, and building materials. With the development of the industry, the requirements for materials are also getting higher and higher.
  • the modified polycarbonate and its alloys are reinforced by glass fibers, giving the material higher strength, rigidity, high temperature resistance and insulation properties. development trend.
  • the matte technology of materials can improve the use of materials.
  • the visual comfort is improved, for example, on the housing of household appliances, the frame and the back shell of the PAD, etc., from the perspective of improving the visual comfort, the enhancement of the hand feel, and the convenience of post-processing, the appropriate matte effect should be considered.
  • Glass fiber reinforced polycarbonate material is one of the key considerations for design optimization, so the development of glass fiber reinforced polycarbonate with matte effect has broad application prospects in different industries.
  • the surface of the material can also have a certain roughness through the pattern design of the injection mold, so as to achieve a matte effect.
  • the purpose of the present invention is to overcome the defects or deficiencies in the prior art that glass fiber reinforced polycarbonate is difficult to take into account of matteness, bending toughness and dependence on processing conditions, and provides a glass fiber reinforced polycarbonate composition.
  • the invention can greatly improve the bending toughness of the glass fiber reinforced polycarbonate through the synergistic effect of the acrylic shell silicone rubber and the polyurethane, and can achieve a satisfactory matte effect in both injection molding and extrusion processes.
  • Another object of the present invention is to provide a method for preparing the above-mentioned glass fiber reinforced polycarbonate composition.
  • Another object of the present invention is to provide the application of the above glass fiber reinforced polycarbonate composition in the preparation of electrical or electronic carrying products.
  • a glass fiber reinforced polycarbonate composition comprising the following components in parts by weight:
  • the diameter of the glass fiber is 8-15 ⁇ m
  • the rubber D50 of the acrylic shell silicone rubber is not less than 350nm.
  • Glass fiber can achieve reinforcement, acrylic shell silicone rubber has good compatibility with polycarbonate (PC), and polyurethane (PU) has shape memory function; the invention adds acrylic shell to glass fiber reinforced polycarbonate Silicone-like rubber and polyurethane can ensure that the glass fiber reinforced polycarbonate has higher bending toughness and better matte effect.
  • PC polycarbonate
  • PU polyurethane
  • the acrylic shell silicone rubber and the PC phase in the glass fiber reinforced polycarbonate phase have a better compatibility tendency, and the addition of acrylic shell silicone rubber with a certain particle size will partially reduce the glass fiber reinforced polycarbonate.
  • Gloss to achieve a weak matte effect;
  • the addition of polyurethane can adjust the compatibility between polycarbonate and other components, the addition of glass fibers with a certain diameter can appropriately increase the surface roughness of the composition, polyurethane and glass
  • the addition of fiber makes the micro-shrinkage of the rubber particles in the composition more obvious, making the glass fiber, acrylic shell silicone rubber and polyurethane have a better synergistic effect on the reduction of gloss, giving glass fiber reinforced polycarbonate Has a more dominant matte finish.
  • the addition of glass fiber can strengthen the system and improve the toughness of the material; while the addition of acrylic shell silicone rubber improves the toughness of the system, but the flexural modulus decreases slightly; polyurethane has good fluidity, and its addition
  • the toughness and flexural modulus of the system will be improved, and the glass fiber reinforced polycarbonate composition provided by the present invention has better bending toughness and higher bending through the synergistic cooperation of glass fiber, acrylic shell silicone rubber and polyurethane. modulus.
  • the flexural modulus of the glass fiber reinforced polycarbonate composition provided by the invention is greater than 7000MPa, and the bending is continuous, the injection glossiness is less than 15, and the extrusion glossiness is less than 20, which can meet the requirements of different processing techniques (extrusion, injection molding, etc.). Matte effect required.
  • the glass fiber reinforced polycarbonate comprises the following components in parts by weight:
  • Polycarbonate, ABS, glass fibers, tougheners, antioxidants, and lubricants conventionally used in the art to prepare polycarbonate compositions can be used in the present invention.
  • the weight average molecular weight of the polycarbonate is 32,000-60,000, and the content of terminal hydroxyl groups is less than 100 ppm.
  • the content of terminal hydroxyl groups is measured by the following method: take a specific content of the test sample to prepare a 1% concentration (mass concentration) clear solution, rinse with neutral ethanol, add quantitative phenolphthalein indicator, and titrate with 0.5mol/L hydrochloric acid solution The content of terminal hydroxyl group is obtained according to the consumption of hydrochloric acid.
  • ABS is acrylonitrile-butadiene-styrene copolymer, which is generally prepared by bulk polymerization, emulsion polymerization, and bulk-suspension polymerization, and all of which can be used in the present invention.
  • the content of acrylonitrile in the ABS is not less than 17% (for example, 17-40%), and the rubber content is not less than 12% (for example, 12-45%).
  • the glass fiber is an impregnated chopped glass fiber, with a diameter of 5-20 ⁇ m and a length of 1-10 mm.
  • the soaking treatment can avoid the bonding between strands during the winding process of the glass fiber strands, and protect the glass fibers from abrasion during the manufacturing process of the glass fibers. Improve the compatibility and interfacial adhesion between glass fiber and resin, and can eliminate the static electricity on the surface of glass fiber, ensure the smooth production and further processing of glass fiber, and keep glass fiber reinforced products with ideal physical and chemical properties, mechanical properties , electrical properties and aging resistance and so on. In general, commercially available chopped glass fibers are soaked.
  • the silica gel content of the acrylic shell silicone rubber is greater than 10%.
  • the diameter of the glass fiber is 10-13 ⁇ m.
  • the rubber D50 of the acrylic shell silicone rubber is 800-1000 nm.
  • the acrylic shell silicone rubber is one or both of S-2130 or S-2100.
  • the Tg temperature of the polyurethane is lower than -30°C, the refractive index is 1.52, the oil absorption value is 50-150, and the D50 is 3-40 ⁇ m.
  • the Tg temperature of polyurethane is measured by the following method: take a specific weight of the polyurethane test sample and put it in a differential calorimeter, set the heating rate to 10 °C/min, and the heating range to -60 to 200 °C. Cycle to read the Tg temperature from the analytical curve.
  • the refractive index of the polyurethane was directly measured by an Abbe refractometer with a thickness of 2.0 mm.
  • the oil absorption value of polyurethane is measured by the following method: gradually add dioctyl phthalate in the polyurethane of a fixed weight, fully stir until no reagent is precipitated, and the oil absorption value of the polyurethane can be obtained according to the quality of the added reagent.
  • the D50 of the polyurethane is 5-8 ⁇ m.
  • the toughening agent is a rubber-containing graft polymer.
  • Toughening agents are generally prepared by emulsion polymerization.
  • component A is grafted onto component B.
  • the dosage of component A and component B is 5-95% of component A and 5-95% of component B based on the weight of the toughening agent; preferably 10-70% of component A and 30-90% of component B; especially It is preferably 20-60% of component A and 40-80% of component B.
  • component A consists of the following: vinyl aromatic compounds (eg styrene, alpha-methyl styrene), vinyl aromatic compounds substituted on the ring (eg p-methyl styrene, p-chlorostyrene) and methyl styrene
  • vinyl aromatic compounds eg styrene, alpha-methyl styrene
  • vinyl aromatic compounds substituted on the ring eg p-methyl styrene, p-chlorostyrene
  • methyl styrene At least one monomer of (C1-C8)-alkyl methacrylate (such as methyl methacrylate, ethyl methacrylate) (the amount of which is 65-85% by weight of component A, preferably 70-80%) %), as well as vinyl cyanide (such as unsaturated nitriles such as acrylonitrile and methacrylonitrile), (C1-C8)-alkyl (meth)
  • Component B provides the elastomeric graft base.
  • the graft base preferably has a glass transition temperature of ⁇ 0°C, more preferably ⁇ 20°C, particularly preferably ⁇ 60°C.
  • component B can be one or more of the following substances: diene rubber, diene-vinyl block copolymer rubber, EP(D)M rubber, polyurethane rubber, silicone rubber, chloroprene Ethylene rubber, ethylene/vinyl acetate rubber, etc.
  • the toughening agent is one or both of HR-181 or M722.
  • the antioxidants are hindered phenolic antioxidants (such as 1010, 176, etc.), phosphite antioxidants (such as 168, 626, 9228, etc.) or hindered amine antioxidants (such as 1098, etc.) ) one or more of them.
  • hindered phenolic antioxidants such as 1010, 176, etc.
  • phosphite antioxidants such as 168, 626, 9228, etc.
  • hindered amine antioxidants such as 1098, etc.
  • the lubricant is one or more of PETS, GTS, GMS, silicone oil or white oil.
  • the glass fiber reinforced polycarbonate composition of the present invention may also include some other functional additives to achieve more diverse properties.
  • flame retardants such as BDP, RDP, phenoxyphosphazene, etc., 1 to 20% by weight
  • antistatic agents such as conductive carbon black, conductive graphite, polyamide polyether block copolymer, ionic liquid, etc., 1 to 30% by weight
  • antibacterial agents such as silver ion antibacterial agents with a certain carrier, etc., 0.01 to 5% by weight
  • fillers such as calcium carbonate, talc, wollastonite, titanium dioxide, barium sulfate, etc. , the weight percentage is 0.1-90%
  • toner such as carbon black, zinc sulfide and other inorganic pigments, anthraquinone and other organic dyes, the weight percentage is 0.001-20%).
  • the glass fiber reinforced polycarbonate composition has good flexural toughness, a flexural modulus greater than 7000 MPa, an injection glossiness of less than 15, and an extrusion glossiness of less than 20.
  • the glass fiber reinforced polycarbonate provided by the present invention can be obtained by extrusion or injection molding.
  • the preparation method of the above-mentioned glass fiber reinforced polycarbonate comprises the following steps: mixing polycarbonate, ABS, glass fiber, acrylic shell silicone rubber, polyurethane, toughening agent, antioxidant and lubricant, extruding, making granules to obtain the glass fiber reinforced polycarbonate composition.
  • polycarbonate, ABS, glass fiber, acrylic shell silicone rubber, toughening agent, antioxidant and lubricant are mixed through a high mixer and then added from the main feeding port, and the polyurethane component is separately fed through the side.
  • the material is added in the mouth, extruded, and pelletized to obtain the glass fiber reinforced polycarbonate composition.
  • the heat resistance of the polyurethane component is poor, and adding it through the side feed port can better ensure the performance of the polyurethane.
  • the process of preparing the glass fiber reinforced polycarbonate composition by the injection molding process is as follows:
  • the preparation method of the above glass fiber reinforced polycarbonate composition comprises the following steps: mixing polycarbonate, ABS, glass fiber, acrylic shell silicone rubber, polyurethane, toughening agent, antioxidant and lubricant, injection molding, That is, the glass fiber reinforced polycarbonate composition is obtained.
  • the preparation method of the invention has the advantages of simple process, strong applicability and easy popularization and application.
  • the application of the glass fiber reinforced polycarbonate composition in the preparation of electronic and electrical enclosure products is preferably, the application of the glass fiber reinforced polycarbonate composition in the preparation of electronic and electrical enclosure products.
  • the present invention has the following beneficial effects:
  • the glass fiber reinforced polycarbonate provided by the invention improves the gloss by adding acrylic shell silicone rubber and polyurethane, gives the glass fiber reinforced polycarbonate a better matte effect, and can meet the requirements of various processes for gloss; In addition, the glass fiber reinforced polycarbonate can also maintain high flexural toughness.
  • the preparation method of the invention has the advantages of simple process, strong applicability and easy popularization and application.
  • PC resin S-2000F, Shanghai Mitsubishi, the weight average molecular weight is 48000, and the content of terminal hydroxyl groups is 10ppm;
  • PC resin E-1000F, Shanghai Mitsubishi, with a weight average molecular weight of 50,000 and a hydroxyl end content of 25ppm;
  • ABS resin PA747S, Chi Mei, the content of acrylonitrile is 27%, and the rubber content is 35%;
  • ABS resin 277, Shanghai Gaoqiao, with acrylonitrile content of 42% and rubber content of 10%;
  • Glass fiber 436T (chopped glass fiber), boulder group, diameter 13 ⁇ m, length 5 ⁇ 8mm;
  • Glass fiber EDR-17-984 (long cut glass fiber), boulder group, diameter 14 ⁇ m, length greater than 20mm;
  • Glass fiber 433 (chopped glass fiber), boulder group, 7 ⁇ m in diameter, 11-13mm in length;
  • Acrylic shell silicone rubber S-2130, Japan Mitsubishi Rayon, the content of silica gel is 30%, and the rubber particle size D50 is 800nm;
  • Acrylic shell silicone rubber S-2100, Mitsubishi Rayon, Japan, the content of silica gel is 10%, and the rubber particle size D50 is 850nm;
  • Acrylic shell silicone rubber Sx-006, Mitsubishi Rayon, Japan, the content of silica gel is 10%, and the rubber particle size D50 is 100nm;
  • Polyurethane PC-8 innovative chemical industry, Tg is -48°C, refractive index is 1.52, oil absorption value is 80, D50 is 5 ⁇ m;
  • Polyurethane PC-5 innovative chemical industry, Tg is -35°C, refractive index is 1.52, oil absorption value is 52, D50 is 38 ⁇ m;
  • Tg is -35°C
  • refractive index is 1.52
  • oil absorption value is 40
  • D50 is 38 ⁇ m
  • Antioxidants 1076 and 168, BASF;
  • Toughening agent HR-181, Chi Mei, Taiwan.
  • processing aids fillers, wollatstoll, IMEREYS company.
  • the glass fiber reinforced polycarbonates of the respective examples and comparative examples were prepared by the following method.
  • Extrusion process Polycarbonate, ABS, glass fiber, acrylic shell silicone rubber, toughener, antioxidant, lubricant and other processing aids (if any) are mixed through a high mixer and then mixed from the main feed The polyurethane component is separately added through the side feeding port, extruded, and pelletized to obtain the glass fiber reinforced polycarbonate composition.
  • Injection molding process Mix polycarbonate, ABS, glass fiber, acrylic shell silicone rubber, polyurethane, toughening agent, antioxidant, lubricant and other processing aids (if any), and then inject the glass fiber. Reinforced polycarbonate composition.
  • Flexural modulus According to the ASTM D790-2017 standard, a 3.0mm-thick bending spline test is performed, and the injection temperature is 280°C; the higher the flexural modulus, the better the material rigidity;
  • Bending toughness when the extrusion temperature is 300°C, the diameter is 2mm, the length of the strip is 10cm, and the two ends are bent 90 degrees to see if it breaks;
  • Injection gloss According to the ASTM-D523-2014 standard, test the injection molding plate with a thickness of 3.0mm and a diameter of not less than 60mm. The injection temperature is 300°C. Use a gloss meter to test the gloss at 60°. The smaller the gloss, the better the matte effect. Well, when the injection gloss is less than 20° and the extrusion gloss is less than 25°, the comprehensive matte effect is the best.
  • Extrusion gloss The sheet with a film thickness of 3.0mm is formed at an extrusion temperature of 260°C. After cooling at room temperature for 48 hours, the gloss at 60° is tested with a gloss meter according to the ASTM-D523-2014 standard. The smaller, the better the matte finish.
  • This example provides a series of glass fiber reinforced polycarbonate compositions whose components are shown in Table 1.
  • This example provides a series of glass fiber reinforced polycarbonate compositions whose components are shown in Table 2.
  • This comparative example provides a series of glass fiber reinforced polycarbonate compositions whose components are shown in Table 3.
  • Comparative Example 5 developed serious cosmetic defects after extrusion/injection molding.
  • the glass fiber reinforced polycarbonate provided by each embodiment of the present invention has good bending toughness and excellent matte performance.
  • the introduction of glass fiber in addition to the enhancement of the material, due to the difference in the surface tension between the glass fiber and the resin, the injection gloss of the material will decrease with the increase of the glass fiber content, while the bending mold
  • the increase of the amount of glass fiber it can cooperate with the matteness and toughness of acrylic silicone rubber and polyurethane within a certain range to achieve higher flexural toughness; with the increase of glass fiber content, the flexural modulus also increases.
  • the addition of acrylic shell silicone rubber can make the gloss show a satisfactory matte effect, but the flexural modulus will decrease slightly; When the addition amount of acrylic shell silicone rubber continues to increase, the bending toughness is better guaranteed, and the injection molding matte effect becomes more and more obvious, and the extrusion matte effect maintains a satisfactory level; when the addition amount of acrylic shell silicone rubber continues to increase, the matte finish
  • the effect is also slightly reduced due to the weakening of the synergistic effect of acrylic shell silicone rubber and polyurethane; however, when the addition amount of acrylic shell silicone rubber is large, there will be hidden defects in appearance; if the addition amount of acrylic shell silicone rubber is too large (such as Comparative example 4), will cause serious delamination appearance defects of the material, and the rubber particles in the acrylic shell silicone rubber will precipitate to the surface of the composition resulting in phase separation, and make the matte effect relative to no addition (Comparative example 1) Only slightly improved.
  • the addition of polyurethane can improve toughness and gloss effect.
  • the matte effect is getting better and better, especially the extrusion matte is improved, and the bending toughness is also enhanced; but the addition amount of polyurethane is relatively
  • the matte effect is also slightly reduced due to the weakening of the synergistic effect of acrylic shell silicone rubber and polyurethane, and the reduction of the thermal stability of the system will lead to a decrease in bending toughness; if the amount of polyurethane added is too large (such as Comparative Example 5 ), it will seriously reduce the thermal stability of the system, resulting in a decrease in bending toughness and a fracture phenomenon; when the addition of acrylic shell silicone rubber is 5-10, and the addition of polyurethane is 5-10, it has better performance comprehensive performance.
  • Comparative Example 1 since the glass fiber reinforced polycarbonate composition was not modified, and the traditional polycarbonate composition (PCABS material) was high gloss, a matte surface texture could not be achieved.
  • the addition of the toughening agent cannot achieve a matte effect, but it brings the risk of processing defects and phase separation; in Comparative Example 3, because only acrylic shell silicone rubber was added, the matte effect could not be achieved through the addition amount; in Comparative Example 2, only the addition of Polyurethane, although it can reduce the gloss, does not meet the requirements of uniform matte, and adding polyurethane alone will cause the polycarbonate resin matrix to not have enough toughness, resulting in application limitations;
  • Comparative Example 6 is due to the addition of acrylic shell silicone rubber rubber particles The diameter (D50) is too small, and the fluidity is further improved, which will easily lead to unstable extrusion; when subjected to external force, the thickness of the resin layer between the rubber particles is not enough to effectively prevent the crack from expanding, so the bending toughness is not good, and the phenomenon of fracture occurs; At the same time,
  • Comparative Example 7 Because the diameter of the added glass fiber is too large, the effective surface roughness under the same amount of addition is difficult to exert the limiting effect on the rubber particles on the surface of the composition, and the distribution of the excessive glass fiber diameter in the matrix resin causes stress The transfer point is greatly reduced, so the flexural modulus decreases, the flexural toughness is broken, and the gloss cannot be effectively improved.

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Abstract

本发明涉及一种玻纤增强的聚碳酸酯组合物及其制备方法和应用。该组合物包括聚碳酸酯、ABS、玻璃纤维，丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂等。本发明提供的玻纤增强的聚碳酸酯组合物通过添加丙烯酸壳类硅橡胶和聚氨酯来改善光泽，赋予玻纤增强的聚碳酸酯组合物较好的哑光效果，可满足多种工艺对光泽度的需求；同时保持较高的弯折韧性。

Description

一种玻纤增强的聚碳酸酯组合物及其制备方法和应用 技术领域
本发明属于工程塑料领域，具体涉及一种玻纤增强的聚碳酸酯组合物及其制备方法和应用。
背景技术
PCABS是一种传统的高性能合金，具有表面光泽度高，韧性好，加工流动性好等有益特点，应用于各个领域当中，特别是电子电器，交通运输，建筑材料等领域工程塑料技术领域。随着行业的发展，对材料的要求也越来越高。通过玻璃纤维来增强改性聚碳酸酯及其合金，赋予材料更高的强度，刚性以及耐高温和绝缘性，是一种应用广泛的改性产品，符合各行各业的轻量化和薄壁化的发展趋势。除了对材料要求高刚性，高模量等高性能化发展要求之外，还需要赋予材料一定的视觉感官度，尤其在电器和电子携带产品外壳设计中，材料的哑光技术可以提高材料在使用过程中对视觉的舒适感提高，例如家用电器外壳上，PAD的边框和后壳等，从视觉的舒适性的提高，手感的增强，以及后处理的便利等角度考虑，适当的哑光效果的玻纤增强聚碳酸酯材料是设计优化的考虑关键因素之一，因此开发具有哑光效果的玻纤增强聚碳酸酯在不同行业中均具有广泛的应用前景。
目前常用哑光技术有以下几种：
1)添加无机材料，如纳米二氧化硅，通过利用填料表面和基体树脂之间的不相容性和不易浸润性，在加工的过程中填料会迁移，形成凹凸不平的的表面，从而产生哑光效果；CN201410177444.2就公开通过添加ACS和纳米二氧化硅来实现哑光效果的PCABS。
2)加入含量较高的橡胶，尤其是粒径较大或者具有一定交联度的橡胶，在加工过程中橡胶和树脂基体会发生分相，通过橡胶发生的微收缩导致材料表面形成粗糙的效果而产生哑光效果；
3)加入环氧类物质，通过环氧基团的引入，降低了ABS和PC树脂之间的相容性，从而降低材料表面的光泽度，从而产生哑光效果；CN201810442932.X就公开了通过添加环氧化物和云母粉来实现哑光效果的PCABS。
4)也可通过注塑模具的纹路设计，使材料表面具有一定的粗糙度，从而实现哑光效果。
以上的哑光技术均具有一定的局限性，如填料的加入会导致基体连续相的不一致，容易引起力学性能和外观等其它性能，尤其是加工过程中熔接线隐患；橡胶和环氧的大量加入会大幅度影响树脂的流动性，以及降低材料的刚性，因此在一定程度上限制了材料的应用，尤其是薄壁化的行业发展趋势下，较低的流动性将产生较大的弊端；依靠模具设计对材料的加工条件依赖性强，适用性不广。
因此，开发一种兼具哑光，弯折韧性，且易于加工的玻纤增强聚碳酸酯具有重要的研究意义和经济价值。
发明内容
本发明的目的在于克服现有技术中玻纤增强聚碳酸酯难以兼顾哑光、弯折韧性及依赖加工条件的缺陷或不足，提供一种玻纤增强聚碳酸酯组合物。本发明通过丙烯酸壳类硅橡胶和聚氨酯的协同增效作用，可以大幅度提高玻纤增强聚碳酸酯的弯折韧性，并在注塑和挤出的工艺上均可实现满意的哑光效果。
本发明的另一目的在于提供上述玻纤增强的聚碳酸酯组合物的制备方法。
本发明的另一目的在于提供上述玻纤增强的聚碳酸酯组合物在制备电器或电子携带产品中的应用。
为实现上述发明目的，本发明采用如下技术方案：
一种玻纤增强的聚碳酸酯组合物，包括如下重量份数的组分：
Figure PCTCN2021090757-appb-000001
所述玻璃纤维的直径为8～15μm；
所述丙烯酸壳类硅橡胶的橡胶D50不小于350nm。
玻璃纤维可实现增强作用，丙烯酸壳类硅橡胶与聚碳酸酯(PC)具有较好的相容性，聚氨酯(PU)具有形状记忆功能；本发明向玻纤增强的聚碳酸酯中添加丙烯酸壳类硅橡胶和聚氨酯，可以保证玻纤增强的聚碳酸酯的具有较高的弯折韧性和较好的哑光效果。
其中，丙烯酸壳类硅橡胶与玻纤增强的聚碳酸酯相中PC相有更好的相容性倾向，一定粒径大小丙烯酸壳类硅橡胶的加入会部分降低玻纤增强的聚碳酸酯的光泽度，实现微弱的哑光效果；聚氨酯的加入可以调节聚碳酸酯和其它组分之间的相容性，一定直径的玻璃纤维的加入可适当地增加组合物表面的粗糙度，聚氨酯和玻璃纤维的加入让组合物中的橡胶粒子微收缩作用更为明显，使得玻璃纤维、丙烯酸壳类硅橡胶和聚氨酯在光泽的降低上具有较好的协同增效作用，赋予玻纤增强的聚碳酸酯具有更加具有优势的哑光效果。
另外，玻璃纤维的加入可对体系进行增强，提高材料的韧性；而丙烯酸壳类硅橡胶的加入，体系的韧性得到改善，但弯曲模量会稍微下降；聚氨酯具有较好的流动性，其加入将提升体系的韧性和弯曲模量，通过玻璃纤维、丙烯酸壳类硅橡胶和聚氨酯的协同配合，本发明提供的玻纤增强的聚碳酸酯组合物具有较好的弯折韧性和较高的弯曲模量。
本发明提供的玻纤增强聚碳酸酯组合物的弯曲模量大于7000MPa，且弯折不断，注塑光泽度小于15，挤出光泽度小于20，可满足不同加工工艺(挤出、注塑等)的哑光效果需求。
优选地，所述玻纤增强的聚碳酸酯包括如下重量份数的组分：
聚碳酸酯60～75份，
ABS25～40份，
玻璃纤维25～40份，
丙烯酸壳类硅橡胶 5～8份，
聚氨酯5～12份，
增韧剂          1～15份，
抗氧剂          0.01～2份，
润滑剂          0.1～3份。
本领域常规用来制备聚碳酸酯组合物的聚碳酸酯、ABS、玻璃纤维、增韧剂、 抗氧剂和润滑剂均可用于本发明中。
优选地，所述聚碳酸酯的重均分子量为32000～60000，端羟基含量小于100ppm。
端羟基的含量通过如下方法测得：取特定含量的测试样配制1％浓度(质量浓度)的澄清溶液，用中性乙醇冲洗，并加入定量的酚酞指示剂，用0.5mol/L盐酸溶液滴定量至红色消失，根据盐酸消耗量即得到端羟基含量。
ABS为丙烯腈-丁二烯-苯乙烯共聚物，现有一般通过本体聚合法、乳液聚合法、本体-悬浮聚合法制备得到，其均可用于本发明中。
优选地，所述ABS中丙烯腈的含量不低于17％(例如17～40％)，橡胶含量不低于12％(例如12～45％)。
优选地，所述玻璃纤维为经过浸润处理的短切玻璃纤维，直径为5～20μm，长度为1～10mm。
浸润处理可以避免在玻纤原丝在缠绕过程中股间的粘结，并保护在玻纤的制造过程中保护玻纤不受磨损，赋予玻纤具有集束性，短切性和分散性，可以增进玻纤和树脂之间的相容性和界面粘结力，并可以消除玻纤表面的静电，保证玻纤能顺利生产和进一步加工，保持玻纤增强产品具备理想的物理化学性能，机械性能，电性能以及耐老化性能等等。一般情况下商购的短切玻璃纤维均经过浸润处理。
优选地，所述丙烯酸壳类硅橡胶的硅胶含量大于10％。
优选地，所述玻璃纤维的直径为10～13μm。
优选地，所述丙烯酸壳类硅橡胶的橡胶D50为800～1000nm。
优选地，所述丙烯酸壳类硅橡胶为S-2130或S-2100中的一种或两种。
优选地，所述聚氨酯的Tg温度低于-30℃，折射率为1.52，且吸油值在50～150，D50为3～40μm。
聚氨酯的Tg温度通过如下方法测得：取特定重量的聚氨酯测试样放入示差热量分析仪器中，设定升温速率为10℃/min，升温范围为-60～200℃，氮气氛围并进行两个循环，从分析曲线中读取Tg温度。
聚氨酯的折射率通过厚度为2.0mm的测试样板阿贝折射仪直接测得。
聚氨酯的吸油值通过如下方法测得：在固定重量的聚氨酯中逐步加入邻苯二 甲酸二辛酯，充分搅拌直至无试剂析出，根据添加试剂的质量即可得到聚氨酯的吸油值。
更为优选地，所述聚氨酯的D50为5～8μm。
优选地，所述增韧剂为含橡胶的接枝聚合物。
增韧剂一般通过乳液聚合制备得到。
具体地，由组分A接枝至组分B上。A组分和组分B的用量按增韧剂重量计，为组分A 5～95％，组分B 5～95％；优选为组分A10～70％，组分B30～90％；特别优选为组分A20～60％，组分B40～80％。
其中组分A组成如下：乙烯基芳族化合物(例如苯乙烯、α-甲基苯乙烯)、在环上取代的乙烯基芳族化合物(例如对甲基苯乙烯、对氯苯乙烯)和甲基丙烯酸(C1～C8)-烷基酯(例如甲基丙烯酸甲酯、甲基丙烯酸乙酯)的至少一种单体(其用量为组分A重量的65～85％，优选为70～80％)，以及乙烯基氰(例如不饱和腈，如丙烯腈和甲基丙烯腈)、(甲基)丙烯酸(C1～C8)-烷基酯(例如甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸叔丁酯)和不饱和羧酸的衍生物(例如酐和酰亚胺、马来酸酐和N-苯基马来酰亚胺)的至少一种单体(其用量为组分A重量的15～35％，优选为20～30％)。
组分B提供弹性体接枝基础。该接枝基础优选具有<0℃，更优选<-20℃，特别优选<-60℃的玻璃化转变温度。
具体地，组分B可为如下物质中的一种或几种：二烯橡胶、二烯-乙烯基嵌段共聚物橡胶、EP(D)M橡胶、聚氨酯橡胶、硅酮橡胶、氯丁二烯橡胶、乙烯/乙酸乙烯酯橡胶等。
具体地，所述增韧剂为HR-181或M722中的一种或两种。
优选地，所述抗氧剂为受阻酚类抗氧剂(例如1010、176等)、亚磷酸酯类抗氧剂(例如168、626、9228等)或受阻胺类抗氧剂(例如1098等)中的一种或几种。
优选地，所述润滑剂为PETS、GTS、GMS、硅油或白油中的一种或几种。
本发明的玻纤增强的聚碳酸酯组合物还可以包括一些其它的功能助剂以实现更多样化的性能。
例如阻燃剂(如BDP、RDP、苯氧磷腈等，重量百分数为1～20％)；抗静电 剂(如导电炭黑、导电石墨、聚酰胺聚醚嵌段共聚物、离子液体等，重量百分数为1～30％)；抗菌剂(如具有一定载体的银离子抗菌剂等，重量百分数为0.01～5％)；填料(如碳酸钙、滑石粉、硅灰石、二氧化钛、硫酸钡等，重量百分数为0.1～90％)；色粉(如炭黑、硫化锌等无机类颜料，蒽醌等有机类染料，重量百分数为0.001～20％)。
优选地，所述玻纤增强的聚碳酸酯组合物的弯折韧性好，弯折模量大于7000MPa；注塑光泽度小于15；挤出光泽度小于20。
本发明提供的玻纤增强的聚碳酸酯既可挤出得到，也可注塑得到。
利用挤出工艺制备得到玻纤增强的聚碳酸酯的过程如下：
上述玻纤增强的聚碳酸酯的制备方法，包括如下步骤：将聚碳酸酯、ABS、玻璃纤维、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂混合，挤出，造粒，即得所述玻纤增强的聚碳酸酯组合物。
具体地，将聚碳酸酯、ABS、玻璃纤维、丙烯酸壳类硅橡胶、增韧剂、抗氧剂和润滑剂混合通过高混机混合后从主喂料口加入，聚氨酯组分单独通过侧喂料口加入，挤出，造粒，即得所述玻纤增强的聚碳酸酯组合物。
相较于聚碳酸酯，聚氨酯组分的耐热性较差，通过侧喂料口加入可以更好地保证聚氨酯的性能。
利用注塑工艺制备得到玻纤增强的聚碳酸酯组合物的过程如下：
上述玻纤增强的聚碳酸酯组合物的制备方法，包括如下步骤：将聚碳酸酯、ABS、玻璃纤维、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂混合，注塑，即得所述玻纤增强的聚碳酸酯组合物。
本发明的制备方法工艺简单，适用性强，易于推广应用。
上述玻纤增强的聚碳酸酯在制备工程塑料中的应用也在本发明的保护范围内。
优选地，玻纤增强的聚碳酸酯组合物在制备电子电器外壳制品中的应用。
与现有技术相比，本发明具有如下有益效果：
本发明提供的玻纤增强的聚碳酸酯通过添加丙烯酸壳类硅橡胶和聚氨酯来改善光泽，赋予玻纤增强的聚碳酸酯较好的哑光效果，可满足多种工艺对光泽度的需求；另外，还可使得玻纤增强的聚碳酸酯保持较高弯折韧性。
本发明的制备方法工艺简单，适用性强，易于推广应用。
具体实施方式
下面结合实施例进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。下例实施例中未注明具体条件的实验方法，通常按照本领域常规条件或按照制造厂商建议的条件；所使用的原料、试剂等，如无特殊说明，均为可从常规市场等商业途径得到的原料和试剂。本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
本发明各实施例及对比例选用的部分试剂说明如下：
PC树脂：S-2000F，上海三菱，重均分子量为48000，端羟基含量为10ppm；
PC树脂：E-1000F，上海三菱，重均分子量为50000，端羟基含量为25ppm；
ABS树脂：PA747S，奇美，丙烯腈的含量为27％，橡胶含量为35％；
ABS树脂：277，上海高桥，丙烯腈含量为42％，橡胶含量为10％；
玻璃纤维：436T(短切玻璃纤维)，巨石基团，直径为13μm，长度为5～8mm；
玻璃纤维：EDR-17-984(长切玻璃纤维)，巨石基团，直径为14μm，长度大于20mm；
玻璃纤维：433(短切玻璃纤维)，巨石基团，直径为7μm，长度为11～13mm；
丙烯酸壳类硅橡胶：S-2130，日本三菱丽阳，硅胶含量为30％，橡胶粒径D50为800nm；
丙烯酸壳类硅橡胶：S-2100，日本三菱丽阳，硅胶含量为10％，橡胶粒径D50为850nm；
丙烯酸壳类硅橡胶：Sx-006，日本三菱丽阳，硅胶含量为10％，橡胶粒径D50为100nm；
聚氨酯：PC-8创新化工，Tg为-48℃，折射率为1.52，吸油值为80，D50为5μm；
聚氨酯：PC-5创新化工，Tg为-35℃，折射率为1.52，吸油值为52，D50为38μm；
聚氨酯：PC-3创新化工，Tg为-35℃，折射率为1.52，吸油值为40，D50为38μm；
抗氧剂：1076和168，BASF；
润滑剂：PETS，发基；
增韧剂：HR-181，台湾奇美。
其它加工助剂：填料，wollatstoll，IMEREYS公司。
各实施例和对比例的玻纤增强的聚碳酸酯通过如下方法制备得到。
挤出工艺：将聚碳酸酯、ABS、玻璃纤维、丙烯酸壳类硅橡胶、增韧剂、抗氧剂、润滑剂和其它加工助剂(如有)混合通过高混机混合后从主喂料口加入，聚氨酯组分单独通过侧喂料口加入，挤出，造粒，即得所述玻纤增强的聚碳酸酯组合物。
注塑工艺：将聚碳酸酯、ABS、玻璃纤维、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂、润滑剂和其它加工助剂(如有)混合，注塑，即得所述玻纤增强的聚碳酸酯组合物。
本发明各实施例及对比例的玻纤增强聚碳酸酯的各项性能的测试方法如下：
弯曲模量：根据ASTM D790-2017标准下进行厚度为3.0mm弯曲样条测试，其中注塑温度为280℃；其中弯曲模量越高，材料刚性越好；
弯折韧性：在挤出温度为300℃的直径为2mm，截取长度为10cm的料条，两端弯折90度看是否断裂；
注塑光泽度：根据ASTM-D523-2014标准下测试3.0mm厚度直径不小于60mm的注塑板，注塑温度为300℃，用光泽度仪测试60°光泽度大小，光泽度越小，哑光效果越好，当注塑光泽度小于20°，挤出光泽度小于25°的情况下，综合哑光效果最佳。
挤出光泽度：在挤出温度为260℃下成型膜厚为3.0mm的板材，经过室温冷却48h后，按照ASTM-D523-2014标准下用光泽度仪测试60°光泽度大小，光泽度越小，哑光效果越好。
实施例1～13
本实施例提供一系列的玻纤增强的聚碳酸酯组合物，其组分如表1。
表1 实施例1～13提供的玻纤增强的聚碳酸酯组合物的组分(份)
Figure PCTCN2021090757-appb-000002
Figure PCTCN2021090757-appb-000003
实施例14～20
本实施例提供一系列的玻纤增强的聚碳酸酯组合物，其组分如表2。
表2 实施例14～20提供的玻纤增强聚碳酸酯组合物的组分(份)
Figure PCTCN2021090757-appb-000004
Figure PCTCN2021090757-appb-000005
对比例1～7
本对比例提供一系列的玻纤增强的聚碳酸酯组合物，其组分如表3。
表3 对比例1～7提供的玻纤增强的聚碳酸酯组合物的组分(份)
Figure PCTCN2021090757-appb-000006
Figure PCTCN2021090757-appb-000007
按上述提及的测试方法对各实施例和对比例的玻纤增强的聚碳酸酯组合物的性能进行测定，测试结果如表4。
其中，对比例5由于聚氨酯的添加量过大，无法挤出/注塑成型，故无法进行性能测试。对比例4挤出/注塑成型后出现了严重的外观缺陷。
表4 各实施例和对比例的玻纤增强聚碳酸酯组合物的性能测试结果
Figure PCTCN2021090757-appb-000008
从表4可知，本发明各实施例提供的玻纤增强的聚碳酸酯具有较好的弯折韧性及优异的哑光性能。
其中，玻纤的引入，除可实现材料的增强外，由于玻纤与树脂之间的的表面 张力存在一定的差异，材料的注塑光泽度会随着玻纤含量的增加而降低，同时弯曲模量增高，在一定范围内和丙烯酸酯类硅橡胶以及聚氨酯的哑光和韧性协同，实现较高的弯折韧性；随着玻纤含量的增加，弯曲模量也增加。
丙烯酸壳类硅橡胶的加入可使得光泽度能呈现较为满意的哑光效果，但弯曲模量会稍微下降；具体地，在一定范围内(实施例1、6～9)，丙烯酸壳类硅橡胶的添加量增大时，弯折韧性得到较好的保障，而且注塑哑光效果越来越明显，挤出哑光效果维持满意水平；丙烯酸壳类硅橡胶的添加量继续增大时，哑光效果由于丙烯酸壳类硅橡胶和聚氨酯的协同作用减弱也略有降低；但丙烯酸壳类硅橡胶的添加量较大时，外观会出现缺陷隐患；如丙烯酸壳类硅橡胶的添加量过大(如对比例4)，会引起材料的严重分层外观缺陷，并且丙烯酸壳类硅橡胶中的橡胶粒子将析出至组合物的表面导致相分离，且使得哑光效果相对于不添加(对比例1)仅略有提升。
聚氨酯的加入可改善韧性和光泽效果。在一定范围内(实施例1、10～13)，聚氨酯的添加量增大时，哑光效果越来越好，尤其是挤出哑光改善，弯折韧性也增强；但聚氨酯的添加量较大时，哑光效果由于丙烯酸壳类硅橡胶和聚氨酯的协同作用减弱也略有降低，且体系的热稳定性降低将导致弯折韧性的下降；如聚氨酯的添加量过大(如对比例5)，会严重降低体系的热稳定性导致弯折韧性的下降，进而出现折断现象；当丙烯酸壳类硅橡胶的添加量为5～10，聚氨酯的添加量为5～10时，具有更佳的综合性能。而对比例1由于未对玻纤增强的聚碳酸酯组合物进行改性处理，和传统的聚碳酸酯组合物(PCABS材料)都为高光泽，无法实现哑光的表面质感，通过单一的增韧剂的加入不能实现哑光效果，却带来加工缺陷和相分离的风险；对比例3由于仅添加丙烯酸壳类硅橡胶，无法通过添加量实现哑光效果的呈现；对比例2由于仅添加聚氨酯，虽然可以降低光泽度但是不满足均匀的哑光要求，同时单独加入聚氨酯会导致聚碳酸酯树脂基体不具备足够的韧性导致应用局限；对比例6由于添加的丙烯酸壳类硅橡胶的橡胶粒径(D50)过小，流动性得到进一步提升易引起挤出不稳定；在受到外力作用时，橡胶粒间的树脂层厚度不足以有效阻止裂纹扩展，因此弯折韧性不佳，出现折断现象；同时玻纤增强的聚碳酸酯组合物无法形成足够的表面质量的橡胶粒子来达到一定的漫反射效果，对光泽的改善效果不佳。对比例7由于添加的玻璃纤维的 直径过大，在同等添加量下有效的表面粗糙度对组合物表面的橡胶粒子的限制作用难以发挥，同时玻纤直径过大在基体树脂中的分布造成应力传递点大大降低，故弯曲模量下降，弯曲韧性差出现折断，光泽度也无法得到有效提升。
本领域的普通技术人员将会意识到，这里的实施例是为了帮助读者理解本发明的原理，应被理解为本发明的保护范围并不局限于这样的特别陈述和实施例。本领域的普通技术人员可以根据本发明公开的这些技术启示做出各种不脱离本发明实质的其它各种具体变形和组合，这些变形和组合仍然在本发明的保护范围内。

Claims (10)

  1. 一种玻纤增强的聚碳酸酯组合物，其特征在于，包括如下重量份数的组分：
    聚碳酸酯 10～90份，
    ABS 10～90份，
    玻璃纤维 1～50份，
    丙烯酸壳类硅橡胶 0.5～20份，
    聚氨酯 0.5～20份，
    增韧剂 0.1～20份，
    抗氧剂 0.001～5份，
    润滑剂 0.001～5份，
    所述玻璃纤维的直径为8～15μm；
    所述丙烯酸壳类硅橡胶的橡胶D50不小于350nm。
  2. 根据权利要求1所述玻纤增强的聚碳酸酯组合物，其特征在于，包括如下重量份数的组分：
    聚碳酸酯 60～75份，
    ABS 25～40份，
    玻璃纤维 25～40份，
    丙烯酸壳类硅橡胶 5～8份，
    聚氨酯 5～12份，
    增韧剂 1～15份，
    抗氧剂 0.01～2份，
    润滑剂 0.1～3份。
  3. 根据权利要求1所述玻纤增强的聚碳酸酯组合物，其特征在于，所述聚碳酸酯的重均分子量为32000～60000，端羟基含量不大于100ppm。
  4. 根据权利要求1所述玻纤增强的聚碳酸酯组合物，其特征在于，丙烯酸壳类硅橡胶的硅胶含量不小于10％。
  5. 根据权利要求1所述玻纤增强的聚碳酸酯组合物，其特征在于，所述丙烯酸壳类硅橡胶的橡胶D50为800～1000nm。
  6. 根据权利要求1所述玻纤增强的聚碳酸酯组合物，其特征在于，所述聚氨酯的Tg温度小于-30℃，折射率为1.52，且吸油值在50～150，D50为3～40μm。
  7. 根据权利要求1所述玻纤增强的聚碳酸酯组合物，其特征在于，所述增韧剂为含橡胶的接枝聚合物；所述抗氧剂为受阻酚系抗氧化剂、亚磷酸酯类抗氧剂或受阻胺类抗氧剂中的一种或几种；所述润滑剂为PETS、GTS、GMS、硅油或白油中的一种或几种。
  8. 根据权利要求1所述玻纤增强的聚碳酸酯组合物，其特征在于，所述玻纤增强聚碳酸酯组合物的弯折模量大于7000MPa，并保持弯折不断；注塑光泽度小于15；挤出光泽度小于20。
  9. 权利要求1～8任一所述玻纤增强的聚碳酸酯组合物的制备方法，其特征在于，包括如下步骤：将聚碳酸酯、ABS、玻璃纤维、丙烯酸壳类硅橡胶、增韧剂、抗氧剂和润滑剂挤出，造粒，即得所述玻纤增强的聚碳酸酯组合物；或将聚碳酸酯、ABS、玻璃纤维、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂混合，注塑，即得所述玻纤增强的聚碳酸酯组合物。
  10. 权利要求1～8任一所述玻纤增强的聚碳酸酯组合物在制备电器或电子携带产品中的应用。
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