CN105482425B - Polycarbonate composite material - Google Patents
Polycarbonate composite material Download PDFInfo
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- CN105482425B CN105482425B CN201510988089.1A CN201510988089A CN105482425B CN 105482425 B CN105482425 B CN 105482425B CN 201510988089 A CN201510988089 A CN 201510988089A CN 105482425 B CN105482425 B CN 105482425B
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- composite material
- polycarbonate composite
- polycarbonate
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- iron
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- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 55
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 54
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- 238000005452 bending Methods 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 14
- 241001274660 Modulus Species 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 239000012745 toughening agent Substances 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 239000003063 flame retardant Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004609 Impact Modifier Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 3
- 239000006081 fluorescent whitening agent Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 238000005227 gel permeation chromatography Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000012764 mineral filler Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000013618 particulate matter Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims 2
- 238000009833 condensation Methods 0.000 claims 2
- 229960002089 ferrous chloride Drugs 0.000 claims 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 abstract description 10
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 abstract description 10
- 238000000465 moulding Methods 0.000 abstract description 10
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 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 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 101100272412 Arabidopsis thaliana BIA1 gene Proteins 0.000 description 1
- 101100388296 Arabidopsis thaliana DTX51 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- HPTULVAFZQXKIS-UHFFFAOYSA-N NC1=C(C=CC=C1)C=CC1=CC=CC=C1.N1=NN=CC=C1 Chemical class NC1=C(C=CC=C1)C=CC1=CC=CC=C1.N1=NN=CC=C1 HPTULVAFZQXKIS-UHFFFAOYSA-N 0.000 description 1
- 206010044565 Tremor Diseases 0.000 description 1
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 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 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 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
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- -1 whisker Chemical compound 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
Abstract
The invention discloses a polycarbonate composite material, which is prepared from the following components in terms of parts by weight: 30 to 80 parts of polycarbonate, 5 to 40 parts of ABS (Acrylonitrile-butadiene-styrene) and 5 to 80 parts of fillers, wherein on the basis of the total weight of the polycarbonate composite material, the weight content of iron element is 0.1 to 50 ppm. Discovered in surprise, an elementary ferrous substance or an iron-containing compound with a lower content of soluble iron is added into the composite material, and the addition of other iron-containing compounds into the composite material is reduced or avoided, so that the prepared polycarbonate composite material has the advantages of improved bending modulus, improved impact strength, excellent molding use stability and excellent color stability.
Description
Technical field
The invention belongs to polymer modification field, and in particular to a kind of strong with the bending moduluses for improving and impact
Degree, and the stable polycarbonate composite material of long-term behaviour.
Background technology
Polycarbonate has excellent thermostability and compared with high-impact, is widely used in electrical/electronic product, vapour
The exterior material such as car part field.In recent years, the thin-walled property of products formed resin combination being molded with is developed, to into
The raising of the various physical property of type product requires to improve constantly.
More preferable rigidity can be obtained by adding filler in Merlon, but ductility can be substantially reduced.In order to
Improve the impact strength of material, have at present technology be by adding anti-impact modifier improving the impact strength of compositionss, but
It is the heat distortion temperature and mobile performance that can affect product, also has the choosing that technology is size by filler or surface treatment
Select to improve impact strength, but the amplitude for improving is less, DeGrain.
The present invention surprisingly it has been found that, in the polycarbonate composite material containing filler, by adding relatively low soluble iron
The iron containing compoundses of content and reduction avoid the addition of other iron containing compoundses from being combined can obtained Merlon
Material has the bending moduluses and impact strength for improving, and with excellent molding stability in use and colour stability.
The content of the invention
It is an object of the invention to provide a kind of polycarbonate composite material, by adding in polycarbonate composite material
Micro ferrum element, can make obtained polycarbonate composite material have the bending moduluses and impact strength for improving, and have
Excellent molding stability in use and colour stability.
The present invention is achieved by the following technical solutions：
A kind of polycarbonate composite material, including following component：
The Merlon of 30-80 weight portions；
The ABS of 5-40 weight portions；
The filler of 5-80 weight portions；
Wherein, the gross weight based on polycarbonate composite material, the weight content of ferrum element is 0.1ppm-50ppm.
The present invention has the iron content simple substance or iron containing compoundses of relatively low soluble iron content by addition in the composite,
And reduce or bring in avoiding composite and other compounds containing extraneous metal injure, particularly active alkali metal
Trace exist, by composite ferrum element content control in the range of 0.1ppm-50ppm, not only can avoid to filling out
The pretreatment of feed powder body, and can also stabilising system neutral and alkali ion, while in process because there is 0.1ppm-
The ferrum element of 50ppm, can reduce screw rod or bringing into for other metals causes to darken and performance damage, makes obtained poly- carbon
Acid esters composite has the bending moduluses and impact strength being obviously improved, and with excellent molding stability in use and color
Stability.
Preferably, the gross weight based on polycarbonate composite material, the weight content of ferrum element is 5ppm-40ppm, more excellent
Elect 10ppm-30ppm as.
Wherein, the ferrum element derives from iron content simple substance or iron containing compoundses, and the iron containing compoundses are selected from iron chloride, chlorine
Change one or more in the complex of ferrous, ferric nitrate, iron sulfate, ferrous sulfate or ferrum.
The Merlon is selected from the homo-polycarbonate or Copolycarbonate for including repetitive structure carbonate unit.
Described Merlon can have the weight average molecular weight of about 15000-40000, and weight average molecular weight can be by this
Method well known to field goes to determine.Using the Merlon in this weight average molecular weight range as modified component, can take into account and add
Work mobility and mechanical performance, if weight average molecular weight is less than 15000, modified compositionss can lose toughness, it is impossible to
Meet the use requirement of product, if weight average molecular weight is higher than 40000, in processing difficulties, percent defective and energy consumption can be increased.
It is 2.0-4.0 that the Merlon is provided simultaneously with PDI coefficients, and PDI coefficients are polydispersity index, based on the poly- carbon of BPA
Acid esters standard gel chromatography determination.PDI values represent the homogeneity of polymer molecular chain more than or equal to 1, PDI values.
It is 3g/ according to 300 DEG C of polycarbonate melt flow rates measured under 1.2kg loads of ASTM D1238
10min-30g/10min；The general forming temperature of compositionss is 300 DEG C, under this processing temperature, if Merlon
Flow rate is too low, then viscosity is excessive, the poor compatibility with other each components in compositionss, ultimately results in the shakiness of properties of product
Qualitative raising, if the flow rate of Merlon is more than 30g/10min, shows that molecule segment endgroup content is higher, activity
Height, the mechanical performance and colour stability of product are easily subject to heat and the invasion of oxygen to cause failure in process.
The ABS refers to acrylonitrile-butadiene-phenylethene grafted copolymer, is to prepare by methods known in the art
, can be prepared by emulsion method or solwution method, specifically, first by conjugated diene, such as butadiene or other
Copolymerizable monomer, such as styrene polymerization prepare graft copolymer to provide main polymer chain, after main polymer chain is formed,
By at least one grafted monomers, and specific two kinds are polymerized to obtain graft copolymerization in the case where there is main polymer chain
Thing.
ABS can be obtained by emulsion method or mass polymerization.
Acrylonitrile Butadiene―Styrene copolymer has the particle mean size of 500nm to 2000nm, the preferably particle mean size with 750nm-1250nm,
The more preferably particle mean size of 900nm to 1100nm.If particle mean size is more than 2000nm, ABS dispersibility in the base can be big
Big to reduce, if particle mean size is less than 500nm, synthesis technique requirement is harsher, and yield is relatively low, it is impossible to meet industrialized wanting
Ask.
The glass transition temperature of Acrylonitrile Butadiene―Styrene copolymer is more than 25 DEG C, preferably greater than 70 DEG C, more preferably greater than 100 DEG C.Vitrification
Temperature is too low, and rubber content is too high to affect the compatibility, and the too high then ABS polarity of glass transition temperature is high, and surface energy is big, increases
Scattered difficulty.
Described filler is mineral filler, is specifically as follows Pulvis Talci, wollastonite, Kaolin, clay, whisker, kieselguhr etc.
It is 20um to 90um Deng, its volumetric surface product value.
Described filler can not carry out any surface treatment, or coating processing, such as alkyl surface bag
Cover, epoxy-surface process, amide surface process, hydroxy silicon oil, alkyl silane, methoxy silane, sulfonic group etc. is processed.
According to different purposes needs, the polycarbonate composite material of the present invention can further include 0-20 weight portions
Antioxidant, light stabilizer, impact modifier, fire retardant, fluorescent whitening agent, lubricant, plasticizer, toughener, antistatic
Agent, releasing agent, pigment etc..
The antioxidant in suffocated amine antioxidant, Hinered phenols antioxidant or phosphite ester kind antioxidant one
Plant or several, can specifically include the mixture of the one or two kinds of and the above in 1010,168,1076,445,1098；
The toughener is EVA type toughener, EMA type toughener, ASA type toughener, AES type toughener, SAS type toughness reinforcings
Agent, esters of acrylic acid toughener, one or more mixture in organosilicon toughener.
The light stabilizer is hindered amines or the mixing of one or more in UV absorbent, can specifically be enumerated
Go out the mixture of UV-944, UV-234, the one or two kinds of in 770DF, 328,531,3896 and the above；
The impact modifier is PTW, the one kind in styrene-ethylene/butylene-styrene block copolymer SEBS or
Two kinds of mixture；
The fire retardant is phosphorus flame retardant, be specifically as follows double (diphenyl phosphoester) BDP of bisphenol-A, red phosphorus,
The mixture of one or two kinds of and the above in OP1240, OP1230;
The fluorescent whitening agent is double triazine amino-stilbenes, a kind of or mixture of the two in titanium dioxide;
The lubricant be Pulvis Talci, ethylene bis stearamide EBS, erucyl amide, zinc stearate, the one kind in silicone oil or
Two kinds of person and the mixture of the above；
The plasticizer be the one or two kinds of in glycerol, citric acid, butyl citrate, epoxy soybean oil etc. and more than
Mixture;
The antistatic additive is permanent antistatic agent, can specifically include PELESTAT-230, PELESTAT-
6500th, the mixture of the one or two kinds of and the above in SUNNICO ASA-2500；
The releasing agent is the mixture of silicone oil, paraffin, white mineral oil, the one or two kinds of in vaseline and the above；
The pigment be white carbon black, black race, titanium dioxide, zinc sulfide, phthalocyanine blue, the one or two kinds of in fluorescent orange and more than
Mixture.
The access approaches of ferrum element of the present invention, can be by directly adding in the polycarbonate composite material course of processing
Plus iron content simple substance or iron containing compoundses, iron content simple substance or iron containing compoundses addition so that in composite ferrum element content
It is suitable to reach 0.1ppm-50ppm.
Polycarbonate composite material of the present invention is 12.6mm*3.2mm in batten size, and length is more than 100mm, temperature
It is more than 5700MPa for 23 DEG C of bending moduluses.
Polycarbonate composite material of the present invention is 12.6mm*3.2m*67mm in batten size, using the pendulum of 2.75J
Hammer, temperature are that 23 DEG C of notch impact strength is more than 70 J/m.
The polycarbonate composite material of the present invention is due to excellent bending moduluses and impact strength, can be applicable to thin-walled
Product, needs higher rigid field with enhanced characteristic, such as notebook computer casing, household appliances shell etc..
The present invention compared with prior art, has the advantages that：
Experiment surprisingly it has been found that, the present invention is by the addition in polycarbonate composite material with relatively low soluble iron content
Iron content simple substance or iron containing compoundses and reduction or avoid the addition of other iron containing compoundses, by ferrum element in composite
Content control in the range of 0.1-50ppm, can make obtained polycarbonate composite material have improve bending moduluses and
Impact strength, and with excellent molding stability in use and colour stability.
Specific embodiment
The present invention is further illustrated below by specific embodiment, and following examples are the present invention preferably embodiment party
Formula, but embodiments of the present invention are not limited by following embodiments.
PC：Homopolymer, weight average molecular weight are that 22000, PDI coefficients are 2.0, and melt flow rate (MFR) is that 10g/10min is Japanese
Go out light；
ABS1：SAN is grafted butadiene, and particle mean size is 1000nm, 110 DEG C of glass transition temperature；
ABS2：SAN is grafted butadiene, and particle mean size is 750nm, 80 DEG C of glass transition temperature；
ABS3：SAN is grafted butadiene, and particle mean size is 1500nm, 60 DEG C of glass transition temperature；
Fire retardant：Double (diphenyl phosphoester) BDP, Adeka of bisphenol-A；
Iron content simple substance, iron containing compoundses：It is commercial；
Filler 1：Pulvis Talci, without cladding Imery, volumetric surface product is 29um；
Filler 2：Pulvis Talci, alkyl surface cladding Imery, volumetric surface product is 32um；
Filler 3；Pulvis Talci, epoxy-surface process Imery, and volumetric surface product is 40um；
Filler 4；Pulvis Talci, amide surface process Imery, and volumetric surface product is 25um；
Other auxiliary agents：Toughener：HR-181
Antioxidant 1076, ciba
Irgasfos 168, ciba
Releasing agent PETS, Long Sha
Light stabilizer 3896, cyanogen are special
Embodiment 1-12 and comparative example 1-2：The preparation of polycarbonate composite material
By 1 formula of table, Merlon, ABS resin and iron containing compoundses, filler, fire retardant are carried out in high mixer
Blending, obtains the resin matrix of pretreatment；After the resin matrix of pretreatment and other auxiliary agents are proportionally weighed, by high mixed
Machine or mixer complete blending, and extrusion temperature is 240 DEG C, cross water cooling, and pelletize obtains the Merlon of cylindrical particle and is combined
Material.Each component it is as shown in table 1 with when the performance test results.
Each method of evaluating performance：
（1）Bending moduluses：
By polycarbonate composite material injection mo(u)lding under 260 DEG C of injection temperature, mold temperature is 100 DEG C, batten chi
It is very little for 12.6mm*3.2mm and length more than 100mm test sample, using the omnipotent of Shimadzu Corporation
Testing machine Autogragf, determines the bending moduluses at 23 DEG C, and sensor pressure sensitivity bar speed is 1mm/min.
（2）Impact strength
By polycarbonate composite material injection mo(u)lding under 260 DEG C of injection temperature, mold temperature is 100 DEG C, batten chi
It is very little for 12.6mm*3.2m*67mm, using the pendulum of 2.75J, determine the notch impact strength at 23 DEG C.
（3）Molding stability in use
The 80 tons of injection (mo(u)lding) machines manufactured using Nissei Plastic Industrial Co., Ltd, are detained 20 at 300 DEG C of barrel temperature
Minute, polycarbonate composite material is then injected, the weight average molecular weight before and after injection is determined, and molding is evaluated using steady
It is qualitative.The absolute value of the difference of " weight average molecular weight after injection " and " weight average molecular weight before injection " is more little more preferred.Here, it is poor
Absolute value when being less than 2000, be evaluated as " good (G) ", poor absolute value is more than 2000, less than 5000 when, be evaluated as " in
Deng (M) ", when poor absolute value is more than 5000, it is evaluated as " bad (NG) ".
（4）The content assaying method of ferrum element
The granule 2g of accurate weighing polycarbonate composite material in analytical balance, pours 100ml into and clears up in bottle, Ran Houjia
Enter 97% concentrated sulphuric acid 5ml, heat 10 minutes in 300 DEG C of iron plate heating instruments of preset temperature, then add 68% nitric acid
5ml, then heating 20 minutes is kept, make particulate matter after decomposing completely, be cooled to room temperature, in the hydrogen peroxide of addition 20ml with acidity extremely
After pH value is 7, liquid is imported in ICP detecting instruments by sample feeding pipe and determines ferrum element by deionized water dilution aforesaid liquid
Concentration.
（5）Colour stability
The polycarbonate composite material is molded, 2 millimeters of thickness, 40 millimeters of width, 100 millimeters of length is produced
, at 80 DEG C, injection molding plates carry out chromatism test after 23 DEG C of humidity of room temperature are 50% regulation 48h, together for plate, wherein mold temperature set
When according to（3）Injecting condition, produce 2 millimeters of thickness, 40 millimeters of width, the plate of 100 millimeters of length, wherein mold temperature sets
It is scheduled on 80 DEG C.Injection molding plates carry out chromatism test after 23 DEG C of humidity of room temperature are 50% regulation 48h, by calculating two test boards
Difference (Δ E).This difference is less, and tone variations are also less.
（6）Anti-flammability：Standard UL94
The proportioning of 1 embodiment 1-12 of table and comparative example 1-2 each component（Weight portion）And the performance test results
Iron content be can be seen that in polycarbonate composite material in 0.1-50ppm scopes from embodiment 1-12 of table 1
Interior, the bending moduluses of polycarbonate composite material are more than 5700MPa, and notch impact strength is more than 70 J/m；While these poly- carbon
Acid esters composite has excellent molding stability in use and colour stability.In comparative example 1-2, when Merlon composite wood
When in material, iron content is less than 0.1ppm or is more than 50ppm, the bending moduluses of polycarbonate composite material, notch shock are strong
Degree, molding stability in use, colour stability and anti-flammability are significantly worse than embodiment.It can thus be seen that poly- by control
The content of ferrum element in carbonic ester composite, the polycarbonate composite material for preparing have the bending moduluses being obviously improved
And impact strength, and with excellent molding stability in use and colour stability, excellent combination property.
Claims (13)
1. a kind of polycarbonate composite material, it is characterised in that including following component：
The Merlon of 30-80 weight portions；
The ABS of 5-40 weight portions；
The filler of 5-80 weight portions；
Wherein, the gross weight based on polycarbonate composite material, the weight content of ferrum element is 0.1ppm-50ppm.
2. polycarbonate composite material according to claim 1, it is characterised in that the weight content of the ferrum element is adopted
Following method is determined：The granule 2g of accurate weighing polycarbonate composite material in analytical balance, pours 100ml into and clears up in bottle,
97% concentrated sulphuric acid 5ml is subsequently adding, is heated 10 minutes in 300 DEG C of iron plate heating instruments of preset temperature, is then added 68%
Nitric acid 5ml, then keep heating 20 minutes, make particulate matter after decomposing completely, be cooled to room temperature, add the hydrogen peroxide neutralization of 20ml
After acidity is 7 to pH value, liquid is imported in ICP detecting instruments by sample feeding pipe and is determined by deionized water dilution aforesaid liquid
The concentration of ferrum element.
3. polycarbonate composite material according to claim 1, it is characterised in that based on the total of polycarbonate composite material
Weight, the weight content of ferrum element is 5ppm-40ppm.
4. polycarbonate composite material according to claim 3, it is characterised in that based on the total of polycarbonate composite material
Weight, the weight content of ferrum element is 10ppm-30ppm.
5. polycarbonate composite material according to claim 1, it is characterised in that the Merlon is homo-polycarbonate
Or Copolycarbonate, the weight average molecular weight of the Merlon is 15000-40000, and PDI coefficients are based on BPA polycarbonate standard
Gel chromatography is 2.0-4.0, and melt flow rate (MFR) is measured as under 1.2kg loads for 300 DEG C according to ASTM D1238
3g/10min-30g/10min。
6. polycarbonate composite material according to claim 1, it is characterised in that the ABS is emulsion method or solution
Prepared by method, particle mean size is 500nm to 2000nm, and glass transition temperature is more than 25 DEG C.
7. polycarbonate composite material according to claim 6, it is characterised in that the ABS particle mean sizes are 750nm-
1250nm, glass transition temperature are more than 70 DEG C.
8. polycarbonate composite material according to claim 7, it is characterised in that the ABS particle mean sizes are 900nm-
1100nm, glass transition temperature are more than 100 DEG C.
9. polycarbonate composite material according to claim 1, it is characterised in that described filler is mineral filler, volume
Surface area is 20um to 90um.
10. polycarbonate composite material according to claim 1, it is characterised in that the ferrum element derives from iron content list
Matter or iron containing compoundses, the iron containing compoundses are selected from iron chloride, ferrous chloride, ferric nitrate, iron sulfate, ferrous sulfate or ferrum
One or more in complex.
11. polycarbonate composite materials according to claim 1, it is characterised in that the polycarbonate composite material is also
Antioxidant, light stabilizer, impact modifier, fire retardant, fluorescent whitening agent, lubricant, plasticizer including 0-20 weight portions,
One or more in toughener, antistatic additive, releasing agent, pigment.
12. polycarbonate composite materials according to any one of claim 1-11, it is characterised in that the Merlon is multiple
Condensation material is 12.6mm*3.2mm in batten size, and more than 100mm, temperature is that 23 DEG C of bending moduluses are more than 5700MPa to length.
13. polycarbonate composite materials according to any one of claim 1-11, it is characterised in that the Merlon is multiple
Condensation material is 12.6mm*3.2m*67mm in batten size, and using the pendulum of 2.75J, temperature is that 23 DEG C of notch impact strength is big
In 70 J/m.
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| CN201510988089.1A CN105482425B (en) | 2015-12-25 | 2015-12-25 | Polycarbonate composite material |
| PCT/CN2016/102705 WO2017107634A1 (en) | 2015-12-25 | 2016-10-20 | Polycarbonate composite material |
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| CN107793722A (en) * | 2016-11-22 | 2018-03-13 | 金发科技股份有限公司 | A kind of polycarbonate compositions and preparation method thereof |
| CN107793721A (en) * | 2016-11-22 | 2018-03-13 | 金发科技股份有限公司 | A kind of polycarbonate compositions and preparation method thereof |
| CN109852023A (en) * | 2018-12-17 | 2019-06-07 | 上海凯雄新材料科技有限公司 | A kind of fire retardation PC-ABS alloy building template |
| JP7076664B1 (en) * | 2020-12-18 | 2022-05-27 | 三菱瓦斯化学株式会社 | Multilayers and molded products |
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| DE10103237A1 (en) * | 2001-01-25 | 2002-08-01 | Bayer Ag | Polycarbonate compositions with reduced iron content |
| JP2002348459A (en) * | 2001-05-29 | 2002-12-04 | Mitsubishi Engineering Plastics Corp | Flame-retardant polycarbonate resin composition |
| US7358293B2 (en) * | 2005-05-02 | 2008-04-15 | General Electric Company | Thermoplastic polycarbonate compositions with improved optical surface quality, articles made therefrom and method of manufacture |
| CN102206414B (en) * | 2011-05-25 | 2013-02-20 | 广东高怡新工程塑料有限公司 | Calorific electromagnetic shielding plastic-based composite material and preparation method thereof |
| JP5634981B2 (en) * | 2011-12-29 | 2014-12-03 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing polycarbonate resin composition |
| CN103013143B (en) * | 2012-12-13 | 2013-09-04 | 肖菁 | High-elasticity modulus fiber composite asphalt |
| JP6398242B2 (en) * | 2013-03-21 | 2018-10-03 | 三菱ケミカル株式会社 | Resin composition and film using the same |
| CN103146111A (en) * | 2013-04-04 | 2013-06-12 | 青岛文晟汽车零部件有限公司 | ABS (Acrylonitrile butadiene styrene) alloy material for instrument panels of automobiles |
| WO2014186548A1 (en) * | 2013-05-16 | 2014-11-20 | Sabic Innovative Plastics Ip B.V. | Branched polycarbonate compositions having conversion material chemistry and articles thereof |
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