CN117264398A - Polycarbonate composition with low shrinkage and preparation method and application thereof - Google Patents
Polycarbonate composition with low shrinkage and preparation method and application thereof Download PDFInfo
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- CN117264398A CN117264398A CN202311089625.5A CN202311089625A CN117264398A CN 117264398 A CN117264398 A CN 117264398A CN 202311089625 A CN202311089625 A CN 202311089625A CN 117264398 A CN117264398 A CN 117264398A
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- 239000000203 mixture Substances 0.000 title claims abstract description 81
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 79
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 86
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 14
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 14
- 239000012745 toughening agent Substances 0.000 claims abstract description 14
- 241000276425 Xiphophorus maculatus Species 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 15
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 229920001038 ethylene copolymer Polymers 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000003466 welding Methods 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000463 material Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000009472 formulation Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 8
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical group C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000005476 size effect Effects 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 229920003314 Elvaloy® Polymers 0.000 description 1
- 101000631616 Homo sapiens Translocation protein SEC62 Proteins 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 102100029007 Translocation protein SEC62 Human genes 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a polycarbonate composition with low shrinkage, a preparation method and application thereof. The polycarbonate composition with low shrinkage comprises the following components in parts by weight: 55 to 99.9 portions of polycarbonate resin, 0.5 to 10 portions of toughening agent, 0.1 to 2 portions of spherical filler and 5 to 30 portions of composite flaky filler. The polycarbonate composition has low shrinkage, excellent rigidity and toughness, high strength of welding lines of products and good appearance, and can meet the quality requirements of various processing technologies and post-assembly.
Description
Technical Field
The invention relates to the field of engineering plastics, in particular to a polycarbonate composition with low shrinkage rate, and a preparation method and application thereof.
Background
A polycarbonate material comprising polycarbonate as a main component. Polycarbonates are amorphous polymers which, after melting and cooling, become transparent glass-like and have excellent optical and mechanical properties. The polycarbonate material has higher melting point, low temperature resistance, small water absorption, better impact resistance, insulativity and ageing resistance, and can resist inorganic and organic dilute acid and the like.
With the trend of replacing steel with plastic, the application field of plastic is becoming wider and wider, so that the requirement of plastic parts on dimensional accuracy is becoming more stringent. Precision injection molding has become an important method for plastic molding, and is characterized by high precision of injection molding, including dimensional precision and repetition precision. In order to meet the requirements of precision injection molding, polycarbonate materials with low shrinkage (< 0.3%) have been developed. In addition, polycarbonate materials are required to have excellent rigidity and toughness for application scenes of important parts in computers, video recorders, electronic display screens and color televisions, as well as housings, covers, frames, and the like of mechanical devices.
Chinese patent named aromatic polycarbonate resin composition reduces the shrinkage rate of the material by adding hollow microspheres into the aromatic polycarbonate resin, but the shrinkage rate can only reach 0.4-0.6%, which is still a higher level; in addition, as the strength of the hollow microsphere with one dimension at the joint line is lower, the screw column of the product of the material is easy to crack, and the welding line is low in strength, so that the related application scene is difficult to meet.
Therefore, the problems that the shrinkage rate of the existing polycarbonate material is still high, the polycarbonate material cannot have good rigidity and toughness at the same time, and the welding line strength of a finished product is low are solved.
Disclosure of Invention
The primary object of the present invention is to overcome the problems that the shrinkage rate of the existing polycarbonate material is still high, the polycarbonate material cannot have good rigidity and toughness at the same time, and the weld line strength of the product is low, and to provide a polycarbonate composition with low shrinkage rate. The polycarbonate composition has low shrinkage, excellent rigidity and toughness, high strength of welding lines of products and good appearance, and can meet the quality requirements of various processing technologies and post-assembly.
It is a further object of the present invention to provide a process for the preparation of the above polycarbonate composition.
It is a further object of the present invention to provide the use of the above polycarbonate composition for the preparation of a display screen, housing or cover.
The above object of the present invention is achieved by the following technical solutions:
a polycarbonate composition with low shrinkage comprises the following components in parts by weight:
the composite platy filler is prepared by compounding a first platy filler and a second platy filler according to the mass ratio of (0.33-3), wherein the average grain diameter of the first platy filler is 5-7 mu m, and the average grain diameter of the second platy filler is 0.5-2 mu m. The average particle diameter of the first sheet filler may be 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, etc.; the average particle diameter of the second sheet filler may be 0.5 μm, 1 μm, 1.5 μm, 2 μm, or the like. And specific point values between the above point values, are limited in space and for brevity, the present invention is not intended to exhaustively enumerate the specific point values included in the range.
The inventors of the present invention have found through many studies that a polycarbonate composition having a low shrinkage and excellent rigidity and toughness is obtained by adding a spherical filler and a composite sheet filler compounded from a specific average particle diameter and mass ratio to a polycarbonate resin. The reason for this is: on one hand, the contact area of the matrix resin and the flaky filler can be improved through the size effect to form good riveting, so that the shrinkage of the polycarbonate composition is reduced to a certain extent, and on the basis, the spherical filler is added, the rolling effect of the spherical filler can disturb the orientation of the flaky filler, so that the size effect is further amplified, the polycarbonate composition flows more smoothly during injection molding, the shrinkage is further reduced (less than 0.3%), and further the polycarbonate composition product has good size stability; on the other hand, the size effect brought by the two flaky fillers with different average particle diameters can generate a synergistic effect with the spherical filler, so that the dispersibility of the filler is good, the balance of the rigidity and the toughness of the polycarbonate composition is realized, and the polycarbonate composition has excellent rigidity and toughness. In addition, the combination of the composite sheet filler and the spherical filler can also ensure that the welding line of the polycarbonate composition product has high strength (high clamping force of the metal screw column) and good appearance.
The polycarbonate composition has low shrinkage, excellent rigidity and toughness, high strength of welding lines of products and good appearance, and can meet the quality requirements of various processing technologies and post-assembly.
Preferably, the polycarbonate composition comprises the following components in parts by weight:
polycarbonate resins, toughening agents and spherical fillers commonly used in the art can be used in the present invention.
Optionally, the polycarbonate resin is at least one of an aromatic polycarbonate resin or an aliphatic polycarbonate resin.
Alternatively, the weight average molecular weight of the polycarbonate resin is 22000 to 30000.
The weight average molecular weight of the polycarbonate resin of the present invention can be measured by gel chromatography.
Preferably, the weight average molecular weight of the polycarbonate resin is 24500 to 30000.
Under the condition of the weight average molecular weight, the obtained polycarbonate composition has higher clamping force of the metal screw column under the conditions of good rigidity and toughness and low shrinkage, so that the welding line of the product has higher strength and better appearance.
Preferably, the toughening agent is an ethylene copolymer toughening agent, including but not limited to EMA, EBA, EVA and the like.
More preferably, the toughening agent is an ethylene butyl acrylate copolymer (EBA).
The ethylene-butyl acrylate copolymer is selected as a toughening agent, so that the obtained polycarbonate composition has better toughness, lower shrinkage and higher clamping force of the metal screw column.
Preferably, the mass ratio of the spherical filler to the composite flaky filler is 1 (15-50).
Alternatively, the average particle diameter of the spherical filler is 0.2 to 45. Mu.m, preferably 0.22 to 7.5. Mu.m.
The average particle size of the spherical filler may be 0.2 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 9.5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm and specific point values between the above point values, the invention is not intended to be exhaustive of the specific point values included in the range for reasons of space and for conciseness.
Optionally, the spherical filler is at least one of glass bead, titanium pigment or calcium carbonate.
Preferably, the first platy filler is at least one of talcum powder, platy kaolin, montmorillonite, mica or flake glass powder, and the second platy filler is at least one of talcum powder, platy kaolin, montmorillonite, mica or flake glass powder.
The first and second sheet fillers may have the same or different compositions.
More preferably, the first platy filler is talcum powder and the second platy filler is talcum powder.
Preferably, the polycarbonate composition further comprises 1 to 30 parts, more preferably 8 to 14 parts of a flame retardant.
Preferably, the polycarbonate composition further comprises 0.01 to 5 parts, more preferably 0.3 to 1 part of an anti-dripping agent.
In order to meet more application scenes, when the flame retardant and the anti-dripping agent are added, the polycarbonate composition provided by the invention has good initial thin-wall flame retardance (1.0 mm V-0) under the conditions of low shrinkage, excellent rigidity and toughness and high welding line strength of a product, and still has good thin-wall flame retardance (1.0 mm V-0) after double-85 wet heat aging treatment. Wherein, for the initial flame retardancy, the flammability test is carried out according to the procedure of "flammability test of plastic material, UL 94-2022". Flame retardant rating is derived based on the burn rate, the time to extinguish, the ability to resist low falls, and whether or not low falls are burning. Sample for testing: 125mm length and 13mm width, the thickness of the invention is selected to be 1.0mm when tested, and the flame retardant rating of the materials can be classified as (UL 94-HB) according to the UL94 protocol: v0, V1, V2, 5VA and 5VB. For flame retardance after humid heat aging, first, a sample was subjected to humid heat aging treatment in a constant temperature and humidity box at a set temperature of 85 ℃ and humidity of 85% for 500 hours, and then, flammability test was performed according to the procedure of "flammability test of plastic materials, UL 94-2022".
The flame retardant is not particularly limited in the present invention. Optionally, the flame retardant is at least one of bisphenol a bis (diphenyl phosphate), triphenyl phosphate, or resorcinol-bis (biphosphate).
The anti-dripping agent of the present invention is not particularly limited. Optionally, the anti-drip agent is at least one of PTFE, PTFE/SAN blend, PTFE/PE blend, or PTFE/ABS blend. Preferably, the polycarbonate composition further comprises 0.1 to 2 parts of other auxiliary agents.
More preferably, the other auxiliary agent is at least one of an antioxidant or a lubricant.
Optionally, the antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], phosphite ester or n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Optionally, the lubricant is at least one of a polyol ester, a polyethylene wax, or a montan wax.
The preparation method of the polycarbonate composition comprises the following steps:
and mixing the components, carrying out melt extrusion and granulation to obtain the polycarbonate composition.
Preferably, the preparation method comprises the following steps: stirring and mixing the components in a high-speed mixer, then carrying out melt extrusion in a double-screw extruder, and granulating to obtain the polycarbonate composition.
More preferably, the stirring speed is 50-200 rpm; the length-diameter ratio of the double-screw extruder is 36-60:1, the temperature of the screw cylinder is 230-290 ℃, and the rotating speed of the screw is 200-800 revolutions/min.
The use of the polycarbonate compositions described above for the preparation of display screens, housings or covers is also within the scope of the invention.
Alternatively, the screen is displayed as a computer county food, video recorder display screen, or color television display screen.
Optionally, the housing is a mechanical device housing.
Optionally, the cover is a mechanical device cover.
Compared with the prior art, the invention has the beneficial effects that:
the polycarbonate composition has low shrinkage, excellent rigidity and toughness, high strength of welding lines of products and good appearance, and can meet the quality requirements of various processing technologies and post-assembly.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples for the purpose of illustration and not limitation, and various modifications may be made within the scope of the present invention as defined by the appended claims.
The reagents selected for the examples and comparative examples of the present invention are described below:
polycarbonate # 1: PC 1300-10NP, korean LG, weight average molecular weight 24500;
polycarbonate # 2: PC 1300-03NP, korean LG, weight average molecular weight 30000;
polycarbonate # 3: PC 1300-22NP, korean LG, weight average molecular weight 22000;
flame retardant: bisphenol a bis (diphenyl phosphate), commercially available;
anti-drip agent: PTFE/SAN blends, commercially available;
other auxiliaries: antioxidant 1076, commercially available;
toughening agent 1#: elvaloy-AC1125, DOW, EMA (ethylene-methyl acrylate copolymer);
toughening agent # 2: elvaloy PTW, dupont, EBA (ethylene-butyl acrylate copolymer);
toughening agent 3#: evaflex EVA460, duPont Mitsui, EVA (ethylene-vinyl acetate copolymer);
toughening agent 4#: ABS POW HR181, jinhu, high-glue powder;
spherical filler # 1: titanium dioxide, kemu R-103, with average particle size of 0.22 microns;
spherical filler # 2: titanium dioxide, TR50 2000 mesh, guangdong source epitaxy powder limited, average particle size 6.5 microns;
spherical filler 3#: titanium dioxide, TR50 mesh, guangdong source epitaxial powder Co., ltd., average particle size of 45 μm;
spherical filler # 4: calcium carbonate, filmlink 520, IMERYS, average particle size 2.7 microns;
first platy Filler 1#: talcum powder, BHS-1250A, liaoning sea city, xufeng; average grain diameter is 6.5-7 microns;
first platy Filler 2#: talcum powder, TYT-777, north sea company of Liaoning, with an average particle size of 5 μm;
second platy filler 1#: talcum powder, HTPULTra5L, liaoning Ai Hai and average grain size of 0.5 micron;
second platy filler # 2: talc, HTP1, IMIFABI, average particle size 1.9 microns;
the filler related to the invention can directly obtain spherical filler and flaky filler with corresponding particle sizes through the market, or can obtain the spherical filler and flaky filler with corresponding particle sizes through the prior art after the market.
Composite sheet filler 1-8 #: homemade, its composition is shown in table 1; the preparation process is as follows: mixing the first and second platy fillers to obtain the final product.
Table 1 formulation of composite sheet filler (parts by weight)
The components (e.g., adjuvants) selected for each of the parallel examples and comparative examples are the same commercially available products, unless otherwise specified.
The polycarbonate compositions provided in the examples and comparative examples of the present invention were subjected to performance measurements according to the following test methods:
flexural modulus: the flexural modulus of 3.0mm was measured according to astm d790-2018, and 5 samples were subjected to an average measurement after conditioning for 48 hours or more at room temperature of 25 ℃ and humidity of 50%.
Bending toughness: the deflection is characterized by the deflection, which is the linear displacement of the rod member axis in the direction vertical to the axis or the linear displacement of the middle surface of the plate shell in the direction vertical to the middle surface when being stressed. Performing a 3.2mm bending test according to the standard of ASTMD790-2018, placing the test piece in an environment with the room temperature of 25 ℃ and the humidity of 50%, adjusting for more than 48 hours, and then performing test piece 5 linear displacements, and averaging to obtain a final result; the larger the numerical value is, the larger the deflection is, and the better the bending toughness is; the smaller the value, the smaller the deflection, and the worse the bending toughness.
Shrinkage ratio: the injection molding temperature is fixed at 265 ℃, the injection molding pressure is 50%, the injection molding speed is 50%, the cross shrinkage rate plate with the thickness of 2.0mm is injected, the plate is placed in an environment with the room temperature of 25 ℃ and the humidity of 50% for more than 48 hours after injection molding, and then the shrinkage rate is obtained by measuring and recording the result through a secondary element.
Binding force of metal screw column: the magnitude (N) of the clamping force required for fastening (locking) the screw to the sliding tooth or breaking is measured according to the GB/T3098.9-2020 standard, and is judged by the value of the maximum clamping force (N) of the screw column, the lower the value is, the poor combination is, and the higher the value is, the better combination is.
The polycarbonate compositions of the examples and comparative examples of the present invention were prepared as follows: the components are weighed according to the proportion, added into a high-speed mixer for stirring and blending to obtain premix, then extruded in a double-screw extruder, and melted and granulated to obtain the polycarbonate composition. Wherein the stirring speed is 150 revolutions per minute; the length-diameter ratio of the double-screw extruder is 40:1, the temperature of a screw cylinder is 230-290 ℃, and the rotating speed of a screw is 600 revolutions per minute.
Examples 1 to 19
Examples 1-19 provide a series of polycarbonate compositions having the formulations shown in tables 2, 3 and 4.
Table 2 formulations (parts by weight) of examples 1 to 6
Table 3 formulations (parts by weight) of examples 7 to 14
Table 4 formulations (parts by weight) of examples 15 to 19
Comparative example 1
This comparative example provides a polycarbonate composition whose formulation differs from that of example 1 in that the composite sheet filler # 1 is replaced with a composite sheet filler # 7.
Comparative example 2
This comparative example provides a polycarbonate composition whose formulation differs from that of example 1 in that composite platy filler 1# is replaced with composite platy filler 8#.
Comparative example 3
This comparative example provides a polycarbonate composition whose formulation differs from that of example 1 in that the composite platy filler consists entirely of the first platy filler 1 #.
Comparative example 4
This comparative example provides a polycarbonate composition whose formulation differs from that of example 1 in that the composite platy filler consists entirely of the second platy filler 1 #.
Comparative example 5
This comparative example provides a polycarbonate composition whose formulation differs from that of example 1 in that the composite sheet filler # 1 is replaced with the same weight part of the spherical filler # 1, i.e., the composite sheet filler # 1 is not added, and the addition amount of the spherical filler # 1 is 16 weight parts.
Comparative example 6
This comparative example provides a polycarbonate composition whose formulation differs from that of example 1 in that the spherical filler # 1 is replaced with the same parts by weight of the composite sheet filler # 1, i.e., the spherical filler # 1 is not added, and the amount of the composite sheet filler # 1 added is 16 parts by weight.
The properties of the polycarbonate compositions of the examples and comparative examples were determined according to the test methods mentioned above, and the test results are shown in Table 5.
TABLE 5 results of Performance test of polycarbonate compositions of examples and comparative examples
As can be seen from Table 5, the polycarbonate compositions of examples 1 to 19 have flexural moduli of 2900MPa or more, bending toughness of 15mm or more, shrinkage rate of less than 0.3%, and metal screw column clamping force of 3800N or more, indicating that the polycarbonate composition of the invention has excellent rigidity and toughness, low shrinkage rate, high weld line strength of the product, good appearance, and can meet the quality requirements of various processing techniques and post-assembly.
The mass ratio of the composite platy filler added in comparative example 1 and that of the composite platy filler added in comparative example 2 is not proper, wherein the shrinkage rate of the polycarbonate composition in comparative example 1 is 0.3 percent, and the clamping force of a metal screw column is too small; the clamping force of the metal screw column of comparative example 2 is too small. The composite flaky filler selected in the comparative example 3 is composed of the first flaky filler, the shrinkage rate of the polycarbonate composition is too high, the toughness is smaller, and the clamping force of the metal screw column is too small; the composite flaky filler selected in comparative example 4 is composed of the second flaky filler, the shrinkage rate of the polycarbonate composition is too high, and the clamping force of the metal screw column is too small; comparative example 5 without the addition of a composite platy filler, the polycarbonate composition had too low rigidity and too high shrinkage; comparative example 6 was not added with the spherical filler, the toughness of the polycarbonate composition was too low, the shrinkage was too high, and the clamping force of the metal screw column was too small.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. A polycarbonate composition with low shrinkage, which is characterized by comprising the following components in parts by weight:
55 to 99.9 parts of polycarbonate resin,
0.5 to 10 parts of toughening agent,
0.1 to 2 parts of spherical filler,
5-30 parts of composite flaky filler;
the composite platy filler is prepared by compounding a first platy filler and a second platy filler according to the mass ratio of (0.33-3), wherein the average grain diameter of the first platy filler is 5-7 mu m, and the average grain diameter of the second platy filler is 0.5-2 mu m.
2. The polycarbonate composition according to claim 1, wherein the polycarbonate composition comprises the following components in parts by weight:
65-95 parts of polycarbonate resin,
0.8 to 3.5 portions of toughening agent,
0.5 to 1.2 parts of spherical filler,
8-25 parts of composite flaky filler.
3. The polycarbonate composition of claim 1, wherein the weight average molecular weight of the polycarbonate resin is 22000 to 34000.
4. The polycarbonate composition of claim 1, wherein the toughening agent is an ethylene copolymer toughening agent.
5. The polycarbonate composition according to claim 1, wherein the mass ratio of the spherical filler to the composite platy filler is 1 (15 to 50).
6. The polycarbonate composition according to claim 1, wherein the average particle diameter of the spherical filler is 0.2 to 45. Mu.m.
7. The polycarbonate composition of claim 1, wherein the spherical filler is at least one of glass beads, titanium dioxide, or calcium carbonate; the first sheet filler is talcum powder, and the second sheet filler is talcum powder.
8. The polycarbonate composition of claim 1, wherein the polycarbonate composition further comprises 1 to 30 parts of a flame retardant and 0.01 to 5 parts of an anti-drip agent.
9. The method for producing a polycarbonate composition according to any one of claims 1 to 8, comprising the steps of:
and mixing the components, carrying out melt extrusion and granulation to obtain the polycarbonate composition.
10. Use of a polycarbonate composition according to any of claims 1 to 8 for the preparation of a display screen, a housing or a cover.
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