CN114591614A - Polycarbonate composition and preparation method thereof - Google Patents
Polycarbonate composition and preparation method thereof Download PDFInfo
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- CN114591614A CN114591614A CN202011418931.5A CN202011418931A CN114591614A CN 114591614 A CN114591614 A CN 114591614A CN 202011418931 A CN202011418931 A CN 202011418931A CN 114591614 A CN114591614 A CN 114591614A
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- toughening agent
- polycarbonate composition
- carboxylic acid
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- polycarbonate
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 35
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title description 4
- 239000012745 toughening agent Substances 0.000 claims abstract description 49
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 24
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 21
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 21
- 239000000945 filler Substances 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 229920002943 EPDM rubber Polymers 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 2
- 229920001038 ethylene copolymer Polymers 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010455 vermiculite Substances 0.000 claims description 2
- 229910052902 vermiculite Inorganic materials 0.000 claims description 2
- 235000019354 vermiculite Nutrition 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 229940068965 polysorbates Drugs 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 238000010382 chemical cross-linking Methods 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 230000032798 delamination Effects 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003921 oil Substances 0.000 description 8
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 7
- 229960000583 acetic acid Drugs 0.000 description 6
- 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
- 239000012362 glacial acetic acid Substances 0.000 description 6
- 239000003999 initiator Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229950008882 polysorbate Drugs 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000004427 Tarflon Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Images
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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- 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 discloses a polycarbonate composition, wherein a toughening agent containing carboxylic acid group branched chain grafting, a filler containing hydroxyl on the surface and a metal oxide are used as modifiers, chemical crosslinking and physical crosslinking can be formed in a polycarbonate resin matrix, and the internal stress of the composition is remarkably reduced by dynamically dissipating the internal stress in PC application, so that the solvent resistance of the polycarbonate composition is improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polycarbonate composition and a preparation method thereof.
Background
Polycarbonate is a thermoplastic engineering plastic with excellent rigidity and toughness balance, and is the most widely applied engineering plastic at present. However, due to the existence of benzene rings in the polycarbonate molecular chain, the molecular chain has high rigidity, high melt viscosity and large residual stress in application, so that the solvent resistance of the polycarbonate is poor, and the application range of the polycarbonate is limited to a great extent.
In the prior art, the technical proposal for improving the solvent resistance of PC is mostly to introduce a third component with crystallinity (such as PA or PBT) or to add a large amount of flexible toughening agent. In the scheme of the alloy, two alloy components can generate ester exchange reaction, the ester exchange reaction is difficult to control, and the product performance stability is poor. The processability of the flexible toughener approach can deteriorate.
Disclosure of Invention
The invention aims to provide a polycarbonate composition with good solvent resistance.
Another object of the present invention is to provide a method for producing the polycarbonate composition.
The invention is realized by the following technical scheme:
the polycarbonate composition comprises the following components in parts by weight:
100 parts of polycarbonate resin;
0.1-4 parts of metal oxide;
0.1-6 parts of filler with hydroxyl on the surface;
3-15 parts of a toughening agent containing carboxylic acid group branched chain grafting;
the proportion of the carboxylic acid group-containing branched chain is 0.1-10wt% based on the weight percentage of the carboxylic acid group-containing branched chain grafted toughening agent.
As an example, the carboxylic acid group-containing branched chain is selected from at least one of polyitaconic acid, polysorbate and polyglycidyl acrylate.
The main chain of the toughening agent can be at least one selected from methyl methacrylate-butadiene-styrene graft copolymer (MBS), silicon toughening agent with a core-shell structure of methyl methacrylate shell, octene-ethylene copolymer grafted maleic anhydride (POE-MAH) and Ethylene Propylene Diene Monomer (EPDM). These toughener backbones all contain double bonds prior to grafting the carboxylic acid group-containing branches.
Preferably, the proportion of carboxylic acid group containing branches is from 1.5 to 5wt%, based on the weight percentage of the toughening agent containing carboxylic acid group containing branches.
The metal oxide is at least one selected from zinc oxide, magnesium oxide, iron oxide and aluminum oxide.
The present invention does not require any particular particle size of the metal oxide, and the average particle size of the metal oxide may be in the range of 100nm to 2000 nm.
The type and parameters of the polycarbonate in the present invention are not particularly limited. However, experiments show that the solvent resistance of the polycarbonate resin is improved more obviously when the weight average molecular weight of the polycarbonate resin is 20000-35000.
The filler with the surface containing hydroxyl is selected from at least one of talcum powder, kaolin, wollastonite, vermiculite, mica and halloysite.
The present invention does not particularly require the particle size of the filler having hydroxyl groups on the surface, and the average particle size of the filler having hydroxyl groups on the surface is in the range of 100nm to 2000 nm.
The preparation method of the polycarbonate composition comprises the following steps: weighing polycarbonate resin, a toughening agent containing carboxylic acid group branched chain grafting, metal oxide and a filler containing hydroxyl on the surface according to the formula dosage, and sequentially adding the raw materials into a mixer to blend uniformly to obtain a premix; putting the premix into a double-screw extruder, wherein the length-diameter ratio of a screw of the double-screw extruder is 40-48: 1, the temperature of a screw cylinder is 240-290 ℃, and the rotating speed of the screw is 300-500 rpm; the premixes are melt-mixed in the twin-screw extruder and extruded for granulation to prepare the polycarbonate composition.
The carboxylic acid group-containing branched chain grafted toughening agent adopted by the invention can be prepared by the following process: according to the weight percentage of the carboxylic acid group-containing branched chain in the toughening agent containing the carboxylic acid group branched chain grafting, the toughening agent containing double bonds in a molecular chain, a carboxylic acid monomer and an initiator are mixed by a mixing roll, the temperature range is 120-180 ℃, and the mixing time is 5 min. Based on the total weight of the double bond-containing toughening agent, the carboxylic acid monomer and the initiator, the initiator content is 0.01-0.1 wt%; the carboxylic acid monomer is at least one of itaconic acid, sorbic acid and glycidyl acrylate; the initiator is at least one selected from benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
Initiating in situ polymerization between carboxylic acid monomers by an initiator to form carboxylic acid group-containing branches, and grafting reaction between the carboxylic acid group-containing branches and a double bond-containing toughening agent. After the carboxylic acid group-containing branched chain is grafted to the double-bond-containing toughening agent, the infrared spectrum is 3200cm-1Characteristic peaks are shown.
The invention has the following beneficial effects:
because the toughening agent has a carboxyl structure in the structure, the toughening agent is easy to react with metal oxide to produce carboxylate, the metal salt can be uniformly dispersed in the composition through the dispersion effect of the double screws, and the metal salt and hydroxyl on the surface of the filler can generate physical action to form an ionic bond structure of copolymer salt, so that the filler can be uniformly dispersed in matrix resin; meanwhile, the carboxylate can also have physical action with the end group on the polycarbonate, so that the interaction of two phases is improved, and the dispersion uniformity of the carboxylate in a matrix is improved. The ionic bond structure of the copolymer salt dispersed in the PC composition can form hydrogen bonds or generate coupling action with terminal hydroxyl groups and polar groups in a PC molecular chain, the acting force is reversible, the internal stress in a system can be effectively absorbed, and meanwhile, the filler in the composition can serve as a physical crosslinking point and a stress concentration point in the system, so that the stress in the system can be effectively dissipated, and the solvent resistance of the system can be greatly improved.
Drawings
FIG. 1: spline fixture diagram in the glacial acetic acid resistant internal stress test.
Detailed Description
The present invention is described in more detail by the following examples, but the present invention is not limited by the following examples.
The raw materials used in the invention are as follows:
polycarbonate resin a: the weight-average molecular weight is 20000, and the brand number is 1300-22 NP;
polycarbonate resin B: weight average molecular weight 24000, number 1300-10 NP;
polycarbonate resin C: weight average molecular weight 35000, number 1300-03 NP;
polycarbonate resin D: weight average molecular weight 18000, trade name POLYCARBONATE RESIN TARFLON IR1700 WW.
Toughening agent A1: grafting MBS by polyitaconic acid, wherein the weight content of the polyitaconic acid is 0.1 wt%;
toughening agent A2: grafting MBS by polyitaconic acid, wherein the weight content of the polyitaconic acid is 0.5 wt%;
toughening agent A3: grafting MBS by polyitaconic acid, wherein the weight content of the polyitaconic acid is 1.5 wt%;
toughening agent A4: grafting MBS by polyitaconic acid, wherein the weight content of the polyitaconic acid is 5.0 wt%;
toughening agent A5: grafting MBS with polyitaconic acid, wherein the weight content of the polyitaconic acid is 9.5 wt%;
a toughening agent B: the weight content of the polysorbate grafted POE-MAH is 4.5 wt%;
a toughening agent C: the polyitaconic acid grafted shell is a silicon-based toughening agent with a core-shell structure of methyl methacrylate, and the weight content of the polyitaconic acid is 3.6 wt%;
a toughening agent D: grafting EPDM by using polyglycidyl acrylate, wherein the weight content of the polyglycidyl acrylate is 2.5 wt%;
a toughening agent E: MBS, EM500;
a toughening agent F: POE-MAH, FUSABONDN493;
a toughening agent G: the shell is a silicon toughener with a core-shell structure of methyl methacrylate, S-2501;
a toughening agent H: EPDM, NORDEL IP 4770R.
Zinc oxide: the average particle size is 200 nm;
magnesium oxide: the average particle size is 800 nm.
Talc powder: the average particle size is 300 nm;
kaolin: the average particle size was 500 nm.
The performance test method comprises the following steps:
(1) solvent resistance: the surface of the sample strip was observed by holding the sample strip with a curvature of 1.5% by the jig of FIG. 1, using the sample strip prepared in ISO-527-2012 as a standard.
(2) Glacial acetic acid internal stress resistance: the surface condition of the sample strip was observed by holding the sample strip with a curvature of 1.5% by the jig of FIG. 1 in the specification prepared in accordance with ISO-527-.
The solvent resistance and internal stress of the material are graded according to the condition of the surface of the sample bar and are corresponding to the following table
| Rating | - | + | ++ | +++ |
| Solvent resistance performance | Fracture of | Large and dense cracks | Fine and dense cracks | Fine and short cracks or no cracks |
| Manifestation of internal stress | Large and dense cracks | Fine and dense cracks | Fine and sparse cracks | Without cracks |
Table 1: EXAMPLES 1-7 polycarbonate compositions the proportions (parts by weight) of the ingredients and the results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 6 | Comparative example 7 | |
| Polycarbonate resin A | 100 | 100 | 100 | |||
| Polycarbonate resin B | 100 | |||||
| Polycarbonate resin C | 100 | |||||
| Polycarbonate resin D | 100 | |||||
| Toughening agent A3 | 8 | 8 | 8 | 8 | 3 | 15 |
| Zinc oxide | 1.5 | 1.5 | 1.5 | 1.5 | 0.5 | 4 |
| Talcum powder | 2 | 2 | 2 | 2 | 0.5 | 6 |
| Anti-rust oil | ++ | ++ | ++ | + | ++ | + |
| Mold washing resistant water | +++ | ++ | +++ | +++ | +++ | +++ |
| Mold release resistant agent | +++ | ++ | +++ | ++ | +++ | +++ |
| Thimble-resistant oil | +++ | ++ | +++ | ++ | +++ | +++ |
| Glacial acetic acid resistance (internal stress) | ++ | ++ | ++ | + | ++ | ++ |
| Workability | No peeling and delamination | No peeling and delamination | No peeling and delamination | No peeling and delamination | No peeling and delamination | No peeling and delamination |
As is clear from examples 1 to 4, the polycarbonate resin preferably has a weight average molecular weight of 20000-35000.
Table 2: examples 8 to 14 polycarbonate compositions with respective component ratios (parts by weight) and test results
| Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | |
| Polycarbonate resin C | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Toughening ofAgent A1 | 8 | ||||||
| Toughening agent A2 | 8 | ||||||
| Toughening agent A4 | 8 | ||||||
| Toughening agent A5 | 8 | ||||||
| Flexibilizer B | 8 | ||||||
| Flexibilizer C | 8 | ||||||
| Toughening agent D | 8 | ||||||
| Zinc oxide | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Talcum powder | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Anti-rust oil | ++ | ++ | +++ | ++ | ++ | ++ | ++ |
| Mold washing resistant water | +++ | +++ | +++ | ++ | +++ | +++ | +++ |
| Mold release resistant agent | ++ | +++ | +++ | +++ | +++ | +++ | +++ |
| Thimble-resistant oil | ++ | ++ | +++ | ++ | +++ | +++ | +++ |
| Glacial acetic acid resistance (internal stress) | + | + | ++ | ++ | ++ | ++ | ++ |
| Workability | No peeling and delamination | No peeling and delamination | No peeling and delamination | No peeling and delamination | No peeling and delamination | No peeling and delamination | No peeling and delamination |
From example 1/8/9/10/11, it is preferred that the proportion of carboxylic acid group-containing branches is from 1.5 to 5% by weight.
Table 3: EXAMPLES 15 TO 17 polycarbonate compositions the proportions (parts by weight) of the respective components and the results
| Example 15 | Example 16 | Example 17 | |
| Polycarbonate resin C | 100 | 100 | 100 |
| Toughening agent A3 | 10 | 4 | 1 |
| Flexibilizer B | 7 | 13 | |
| Zinc oxide | 0.5 | 4 | |
| Magnesium oxide | 1.7 | 2.5 | |
| Talcum powder | 2 | ||
| Kaolin clay | 5 | 5 | 2 |
| Anti-rust oil | ++ | ++ | ++ |
| Mold washing resistant water | +++ | +++ | +++ |
| Mold release resistant agent | +++ | +++ | +++ |
| Thimble-resistant oil | +++ | +++ | +++ |
| Glacial acetic acid resistance (internal stress) | ++ | ++ | ++ |
| Workability | No peeling and delamination | No peeling and delamination | No peeling and delamination |
Table 4: comparative polycarbonate composition the proportions (parts by weight) of the components and the results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Polycarbonate resin C | 100 | 100 | 100 | 100 | 100 | 100 |
| Flexibilizer A3 | 8 | 8 | ||||
| Flexibilizer H | 8 | |||||
| Toughening agent G | 8 | |||||
| Toughening agent F | 8 | |||||
| Toughening agent E | 8 | |||||
| Zinc oxide | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | |
| Talcum powder | 2 | 2 | 2 | 2 | 2 | |
| Anti-rust oil | + | + | + | + | + | + |
| Mold washing resistant water | + | + | + | + | + | + |
| Mold release resistant agent | ++ | + | ++ | - | ++ | ++ |
| Thimble-resistant oil | ++ | - | ++ | - | ++ | ++ |
| Glacial acetic acid resistance (internal stress) | - | - | - | - | - | - |
| Workability | No peeling and delamination | No peeling and delamination | No peeling and delamination | No peeling and delamination | No peeling and delamination | No peeling and delamination |
Comparative example 1/2 shows that the combination of carboxylic acid group-containing branched toughener/surface hydroxyl-containing filler/metal oxide is required to significantly improve solvent resistance in the system of the present invention.
From comparative example 3/4/5/6, it is clear that some conventional toughening agents, which are commonly used in polycarbonate, do not improve solvent resistance.
Claims (10)
1. The polycarbonate composition is characterized by comprising the following components in parts by weight:
100 parts of polycarbonate resin;
0.1-4 parts of metal oxide;
0.1-6 parts of filler with hydroxyl on the surface;
3-15 parts of a toughening agent containing carboxylic acid group branched chain grafting;
the proportion of the carboxylic acid group-containing branched chain is 0.1-10wt% based on the weight percentage of the carboxylic acid group-containing branched chain grafted toughening agent.
2. The polycarbonate composition of claim 1, wherein the carboxylic acid group-containing branches are selected from at least one of polyitaconic acid, polysorbates, and polyglycidyl acrylates.
3. The polycarbonate composition of claim 1, wherein the toughening agent backbone is selected from at least one of a methyl methacrylate-butadiene-styrene graft copolymer, a silicon-based toughening agent with a core-shell structure in which the shell is methyl methacrylate, an octene-ethylene copolymer grafted maleic anhydride, and an ethylene-propylene-diene monomer.
4. The polycarbonate composition of claim 1, wherein the carboxylic acid group-containing branches comprise from 1.5wt% to 5wt% based on the weight percent of the toughening agent grafted with carboxylic acid group-containing branches.
5. The polycarbonate composition of claim 1, wherein the metal oxide is at least one selected from the group consisting of zinc oxide, magnesium oxide, iron oxide, and aluminum oxide.
6. The polycarbonate composition of claim 5, wherein the metal oxide has an average particle size in the range of 100nm to 2000 nm.
7. The polycarbonate composition of claim 1, wherein the polycarbonate resin has a weight average molecular weight of 20000-35000.
8. The polycarbonate composition of claim 1, wherein the filler having hydroxyl groups on the surface is at least one member selected from the group consisting of talc, kaolin, wollastonite, vermiculite, mica, and halloysite.
9. The polycarbonate composition of claim 8, wherein the filler having hydroxyl groups on the surface has an average particle size in the range of 100nm to 2000 nm.
10. The method of any one of claims 1-9, comprising the steps of: weighing polycarbonate resin, a carboxylic acid group-containing branched chain grafted toughening agent, metal oxide and a filler with hydroxyl on the surface according to the formula amount, and sequentially adding the raw materials into a mixer to blend uniformly to obtain a premix; putting the premix into a double-screw extruder, wherein the length-diameter ratio of a screw of the double-screw extruder is 40-48: 1, the temperature of a screw cylinder is 240-290 ℃, and the rotating speed of the screw is 300-500 rpm; the pre-mixture is melted and mixed in the double screw extruder and extruded for granulation, so as to prepare the polycarbonate composition.
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