CN113831715B - Polycarbonate composite material and preparation method and application thereof - Google Patents
Polycarbonate composite material and preparation method and application thereof Download PDFInfo
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- CN113831715B CN113831715B CN202111145621.5A CN202111145621A CN113831715B CN 113831715 B CN113831715 B CN 113831715B CN 202111145621 A CN202111145621 A CN 202111145621A CN 113831715 B CN113831715 B CN 113831715B
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 62
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title description 6
- 229920001896 polybutyrate Polymers 0.000 claims abstract description 28
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 18
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims description 21
- 238000005809 transesterification reaction Methods 0.000 claims description 16
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical group O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 3
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 claims description 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 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 claims description 2
- 230000032683 aging Effects 0.000 abstract description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 230000001590 oxidative effect Effects 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 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 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- -1 bisphenol A) Chemical compound 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000004431 polycarbonate resin Substances 0.000 description 4
- 229920005668 polycarbonate resin Polymers 0.000 description 4
- 230000035882 stress Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 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
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- UDKBLXVYLPCIAZ-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-3,6-di(propan-2-yl)phenyl]phenol Chemical compound C=1C=C(O)C=CC=1C=1C(C(C)C)=CC=C(C(C)C)C=1C1=CC=C(O)C=C1 UDKBLXVYLPCIAZ-UHFFFAOYSA-N 0.000 description 1
- BRGDDIPTNDBIGV-UHFFFAOYSA-N C(CCCO)O.C(CCC(=O)O)(=O)O.C(C1=CC=C(C(=O)O)C=C1)(=O)O Chemical compound C(CCCO)O.C(CCC(=O)O)(=O)O.C(C1=CC=C(C(=O)O)C=C1)(=O)O BRGDDIPTNDBIGV-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920009537 polybutylene succinate adipate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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 provides a polycarbonate composite material, which comprises the following components in parts by weight: 80 parts of polycarbonate; 5-10 parts of ethylene-vinyl acetate copolymer; 10-20 parts of PBAT. On one hand, the flowability and the thermo-oxidative aging resistance are improved by adding a certain amount of PBAT into a PC/EVA system; on the other hand, EVA also improves compatibility between PC/PBAT.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polycarbonate composite material and a preparation method and application thereof.
Background
As known in the technical field, the polycarbonate PC product has the characteristics of good transparency, high impact resistance, high heat resistance, good dimensional stability, good flame retardant property and the like, and is widely applied to the fields of automobiles, IT, electronic appliances, household appliances and the like; the defects are that the melt viscosity is high, the residual internal stress is high, the notch sensitivity is easy to crack, and the like. The poly (terephthalic acid) -butanedioic acid-1, 4 butanediol copolyester (PBAT) belongs to thermoplastic biodegradable plastics, has the characteristics of PBA and PBT, and has better ductility and elongation at break because the macromolecule has soft aliphatic chains and rigid aromatic groups; in addition, the material also has excellent biodegradability, and is one of the best degradable materials which are very active in the research of biodegradable plastics and are applied to the market at present.
Since polycarbonate has excellent transparency and high toughness, but it is prone to stress cracking, modification is required to improve stress cracking resistance. First, the modification is carried out by adding PBAT in the prior art, but on the one hand, transesterification reaction between PC and PBAT is easily carried out during melt blending to lower the performance in all aspects, so that a sufficient amount of transesterification inhibitor needs to be added. On the other hand, the compatibility between the two resins of PC and PBAT is not satisfactory, which makes practical use difficult. Second, there are reports of toughening modification of polycarbonate with EVA, but addition of EVA tends to cause poor thermo-oxidative aging resistance, and insufficient melt flow stability.
Disclosure of Invention
The invention aims to provide a polycarbonate composite material which has the advantages of good fluidity, good compatibility, good thermo-oxidative aging resistance and the like.
Another object of the present invention is to provide a method for producing the polycarbonate composite material.
The invention is realized by the following technical scheme:
the polycarbonate composite material comprises the following components in parts by weight:
80 parts of polycarbonate;
5-10 parts of ethylene-vinyl acetate copolymer;
10-20 parts of PBAT;
in the PBAT chain segment repeating unit, the weight content of the butylene terephthalate unit is 40-60wt%, and the weight content of the butylene adipate unit is 40-60wt%.
The polycarbonate resin of the present invention may be obtained by reacting a dihydroxy compound or its and a small amount of a polyhydroxy compound with phosgene or a carbonic diester. The present invention is not particularly limited to a production method of the polycarbonate resin, and a polycarbonate resin produced by a heretofore known phosgene method (interfacial polymerization method) or a melt method (transesterification method) may be used. The dihydroxy compound may be exemplified by 2, 2-bis (4-hydroxyphenyl) propane (i.e., bisphenol A), tetramethyl bisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4-dihydroxydiphenyl, etc., with bisphenol A being preferred. Compounds in which at least one tetraalkyl phosphine sulfonate is bound to the aforementioned dihydroxy compound may also be used. The polycarbonate resin may also be a copolymer of a segment whose main composition is an aromatic monomer, for example, a copolymer with a polymer or oligomer containing a siloxane structure.
The average molecular weight of the polycarbonate is 15000-40000; preferably, the average molecular weight of the polycarbonate is 17000-20000.
Preferably, in the ethylene-vinyl acetate copolymer, the vinyl acetate content is 12-25wt%, and the melt index is 8-20 g/10min (190 ℃,2.16 kg); more preferably, the ethylene-vinyl acetate copolymer has a vinyl acetate content of 16 to 20wt%.
Preferably, the weight content of the polybutylene terephthalate unit in the PBAT chain segment repeating unit is 45-55wt%, and the weight content of the polybutylene adipate unit is 45-55wt%.
The intrinsic viscosity of PBAT is not limited in the present invention, and it has been found through experiments that the object of the present invention can be achieved when the intrinsic viscosity of PBAT is 1-3.5dL/g (test condition 25 ℃).
The source of PBAT may be homemade or commercially available. The preparation method of PBAT in the examples is provided below: firstly, 1, 4-butanediol, adipic acid, terephthalic acid and tetrabutyl titanate serving as a catalyst are firstly added into a reaction container according to the metering, the temperature is raised to 160-180 ℃ for 4-5 hours, and nitrogen is introduced in the process until no water is distilled out. And step two, raising the temperature to 220-240 ℃ and maintaining the vacuum degree to 20-30Pa. Stopping the reaction when the viscosity reaches the set value to obtain the designed PBAT.
Intrinsic viscosity test: mixing phenol and tetrachloroethane with a ratio of 1:1 as a solvent, preparing a PBAT or PBSA solution with a mass concentration of 2.5g/L, standing for 24 hours, and measuring at 25 ℃ by using a Ubbelohde viscometer.
Whether one or more of a transesterification inhibitor, a hydrolysis inhibitor, an antioxidant and a lubricant are added or not can be selected according to actual needs.
The amount of the transesterification inhibitor added is generally in the range of 0 to 0.1 part, and the transesterification inhibitor is at least one selected from sodium dihydrogen phosphate, octadecyl phosphate and triphenyl phosphate. The addition amount of the hydrolysis-resistant agent can be added according to actual needs, the addition amount ranges from 0 part to 3 parts, and the hydrolysis-resistant agent is at least one selected from phenyl glycidyl ether, bisphenol A diglycidyl ether, carbodiimide and 2-oxazoline.
The preparation method of the polycarbonate composite material comprises the following steps: the components are uniformly mixed according to the proportion, extruded and granulated by a double-screw extruder, the temperature range of the screw is 220-260 ℃, and the rotating speed range is 300-600rpm, so as to obtain the polycarbonate composite material.
The polycarbonate composite material is applied to electronic and electric appliance films.
The invention has the following beneficial effects:
1. EVA has a lower melt viscosity relative to polycarbonate, but because of its characteristics, it has little effect on the flowability of polycarbonate, resulting in the disadvantage that blending unevenness at the time of melt extrusion is liable to occur. By adding PBAT, the melt flow stability of the composite material is improved; the EVA improves the compatibility between the polycarbonate and the PBAT, and improves the thermo-oxidative aging resistance; meanwhile, the polycarbonate composite material has the advantage of low addition amount (0-0.1 part) of the transesterification inhibitor, and even can be added without adding the transesterification inhibitor.
2. In the technical scheme of the invention, the addition of the hydrolysis resistance agent can further improve the thermo-oxidative aging resistance.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The raw materials used in the examples and comparative examples of the present invention are as follows:
polycarbonate a: average molecular weight 1.5 ten thousand, light-emitting FN1500;
polycarbonate B: the average molecular weight is 1.7 ten thousand, mitsubishi H-3000F;
polycarbonate C: the average molecular weight is 2 ten thousand, mitsubishi H-2000F;
polycarbonate D: the average molecular weight is 3.5 ten thousand, mitsubishi E-1000F.
EVA-A: ethylene content of 12.5wt% and melt index of 10.5g/10min (190 ℃,2.16 kg);
EVA-B: ethylene content of 24wt% and melt index of 17 g/10min (190 ℃,2.16 kg);
EVA-C: ethylene content of 16wt% and melt index of 12 g/10min (190 ℃,2.16 kg);
EVA-D: ethylene content of 20wt% and melt index of 9.8 g/10min (190 ℃,2.16 kg);
EVA-E: ethylene content of 10wt% and melt index of 14 g/10min (190 ℃,2.16 kg);
EVA-F: ethylene content of 30wt% and melt index of 11g/10min (190 ℃,2.16, kg);
PBAT-a: the weight content of the butylene terephthalate unit is 45wt%, the weight content of the butylene adipate unit is 55wt%, the intrinsic viscosity is 1.8dL/g, the temperature is 25 ℃, and the butylene terephthalate unit is purchased from KMI with the brand KM801T;
PBAT-B: the weight content of the butylene terephthalate unit is 55wt%, the weight content of the butylene adipate unit is 45wt%, the intrinsic viscosity is 2.0dL/g, and the butylene adipate unit is available from AFC ecosystems under the brand name ANBIO BG1000;
PBAT-C: the weight content of the butylene terephthalate unit is 40 percent, the weight content of the butylene adipate unit is 60 percent, the intrinsic viscosity is 1.9dL/g, and the self-made product is prepared at 25 ℃;
PBAT-D: the weight content of the butylene terephthalate unit is 60wt%, the weight content of the butylene adipate unit is 40wt%, the intrinsic viscosity is 2.1dL/g, and the self-made product is at 25 ℃;
PBAT-E: the weight content of the butylene terephthalate unit is 35wt%, the weight content of the butylene adipate unit is 65wt%, the intrinsic viscosity is 2.0dL/g, and the butylene adipate unit is self-made at 25 ℃;
PBAT-F: the weight content of the butylene terephthalate unit is 65wt%, the weight content of the butylene adipate unit is 35wt%, the intrinsic viscosity is 1.85dL/g, and the butylene adipate unit is self-made at 25 ℃;
octadecyl phosphate: C18P, alcissi, transesterification inhibitors.
Bisphenol a diglycidyl ether: kesai, maritime, hydrolysis inhibitor.
Examples and comparative examples polycarbonate composite preparation method: uniformly mixing polycarbonate, ethylene-vinyl acetate copolymer, PBAT, ester interchange inhibitor and hydrolysis inhibitor according to the proportion, extruding and granulating by a double-screw extruder, wherein the temperature range of a screw is 120-140 ℃ in a first region, 160-180 ℃ in a second region, 220-240 ℃ in a third region, 240-260 ℃ in a fourth region, 240-260 ℃ in a fifth region, 4, 220-240 ℃ in a sixth region, 220-240 ℃ in a seventh region, 220-240 ℃ in an eighth region, 200-220 ℃ in a ninth region, 240-260 ℃ in a tenth region and the rotating speed range of 350rpm, and obtaining the polycarbonate composite material.
The testing method comprises the following steps:
(1) Thermal oxidative aging resistance: the retention of impact strength of the unbaked and baked bars was measured according to ISO-179-1-2010 standard after baking at 70℃for 300 hours.
(2) Melt flow: according to the melt index of the test material under the conditions of 260 ℃ and 2.16kg according to ISO 1133-1-2011, the melt index is a key index for measuring the flowability of the material.
In the following examples and comparative examples, the heat aging resistance was mainly examined.
Table 1: examples 1-6 polycarbonate composite materials component contents (parts by weight) and test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Polycarbonate A | 80 | |||||
| Polycarbonate B | 80 | |||||
| Polycarbonate C | 80 | 80 | 80 | |||
| Polycarbonate D | 80 | |||||
| EVA-A | 5 | 5 | 5 | 5 | 10 | 8 |
| PBAT-A | 10 | 10 | 10 | 10 | 20 | 15 |
| Transesterification inhibitors | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 |
| Thermal oxidative aging resistance (impact Strength retention%) | 55.7 | 75.7 | 81.5 | 82.1 | 84.9 | 89.1 |
| Melt flow index, g/10min | 32.7 | 26.1 | 12.1 | 4.5 | 17.7 | 14.2 |
As is clear from examples 1 to 4, when the average molecular weight of PC increases, the thermal oxidative aging resistance increases, but after the average molecular weight reaches 2 ten thousand, the thermal oxidative aging resistance increases smoothly, but the melt flow index decreases too much, so that the average molecular weight is preferably 1.7 ten thousand to 2 ten thousand.
Table 2: examples 7-11 polycarbonate composite materials component contents (parts by weight) and test results
| Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | |
| Polycarbonate C | 80 | 80 | 80 | 80 | 80 |
| EVA-B | 5 | ||||
| EVA-C | 5 | ||||
| EVA-D | 5 | ||||
| EVA-E | 5 | ||||
| EVA-F | 5 | ||||
| PBAT-A | 10 | 10 | 10 | 10 | 10 |
| Transesterification inhibitors | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 |
| Thermal oxidative aging resistance (impact strength retention) | 83.7 | 87.7 | 89.5 | 72.1 | 75.1 |
| Melt flow index, g/10min | 14.7 | 10.2 | 11.9 | 10.1 | 16.6 |
As is evident from the comparison of examples 3/7-11, EVA has the best resistance to thermo-oxidation at the preferred ethylene content.
Table 3: examples 12-15 polycarbonate composite materials component contents (parts by weight) and test results
| Example 12 | Example 13 | Example 14 | Example 15 | |
| Polycarbonate C | 80 | 80 | 80 | 80 |
| EVA-A | 5 | 5 | 5 | 5 |
| PBAT-B | 10 | 10 | ||
| PBAT-C | 10 | |||
| PBAT-D | 10 | |||
| Transesterification inhibitors | 0.03 | 0.03 | 0.03 | 0.01 |
| Hydrolysis-resistant agent | 0.1 | 0.1 | 0.1 | |
| Thermal oxidative aging resistance (impact strength retention) | 87.2 | 66.4 | 69.6 | 87.0 |
| Melt flow index, g/10min | 10.9 | 13.6 | 9.8 | 11.3 |
As can be seen from the comparison of examples 3/12/13/14, the PBAT segment repeat units significantly affect the thermal oxidative aging resistance, melt flow properties of the polycarbonate composite, with preferred PBAT thermal aging resistance being better.
Table 4: comparative example polycarbonate composite Material component content (parts by weight) and test results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Polycarbonate C | 80 | 80 | 80 | 80 | 80 | 80 |
| EVA-A | 5 | 5 | 10 | 5 | ||
| PBAT-A | 5 | 25 | 10 | 10 | ||
| PBAT-E | 10 | |||||
| PBAT-F | 10 | |||||
| Transesterification inhibitors | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.08 |
| Hydrolysis-resistant agent | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.2 |
| Thermal oxidative aging resistance (impact strength retention) | 47.3 | 48.3 | 51.5 | 39.1 | 31.9 | 32.7 |
| Melt flow index, g/10min | 13.3 | 8.2 | 28.1 but unstable | 38.2 but unstable | 18.4 but unstable | 16.2 but unstable |
As is clear from comparative example 1/2, PBAT resins not falling within the scope of the present invention are insufficient in improvement of polycarbonate/EVA compatibility.
As is clear from comparative examples 3/4, too low a PBAT content is insufficient in improving the compatibility of polycarbonate/EVA; too high a PBAT content would instead reduce the resistance to thermo-oxidative aging, and in practice the melt is prone to delamination despite the high melt flow index value.
As is clear from comparative example 5/6, if EVA is not added, it is difficult to improve the thermo-oxidative aging resistance even if the contents of the transesterification inhibitor and the hydrolysis inhibitor are increased.
Claims (10)
1. The polycarbonate composite material is characterized by comprising the following components in parts by weight:
80 parts of polycarbonate;
5-10 parts of ethylene-vinyl acetate copolymer;
10-20 parts of PBAT;
in the PBAT chain segment repeating unit, the weight content of the butylene terephthalate unit is 40-60wt%, and the weight content of the butylene adipate unit is 40-60wt%;
the average molecular weight of the polycarbonate is 15000-40000;
in the ethylene-vinyl acetate copolymer, the vinyl acetate content is 12-25wt%.
2. The polycarbonate composite material according to claim 1, wherein the average molecular weight of the polycarbonate is 17000 to 20000.
3. The polycarbonate composite of claim 1, wherein the ethylene-vinyl acetate copolymer has a melt index of 8 to 20 g/10min at 190 ℃ and a vinyl acetate content of 16 to 20 wt.% at 2.16 kg.
4. The polycarbonate composite material of claim 1, wherein the weight content of butylene terephthalate units and the weight content of butylene adipate units in the PBAT segment repeat units are 45-55wt%.
5. The polycarbonate composite material of claim 1, wherein the intrinsic viscosity of the PBAT is 1-3.5dL/g, under test conditions of 25 ℃.
6. The polycarbonate composite material according to claim 1, further comprising one or more of a transesterification inhibitor, a hydrolysis inhibitor, an antioxidant, and a lubricant in an amount of 0 to 5 parts by weight.
7. The polycarbonate composite material according to claim 6, wherein the transesterification inhibitor is at least one selected from the group consisting of sodium dihydrogen phosphate, octadecyl phosphate and triphenyl phosphate.
8. The polycarbonate composite material according to claim 6, wherein the hydrolysis inhibitor is at least one selected from the group consisting of phenyl glycidyl ether, bisphenol a diglycidyl ether, carbodiimide and 2-oxazoline.
9. The method for preparing a polycarbonate composite material according to any one of claims 1 to 8, comprising the steps of: the components are uniformly mixed according to the proportion, extruded and granulated by a double-screw extruder, the temperature range of the screw is 220-260 ℃, and the rotating speed range is 300-600rpm, so as to obtain the polycarbonate composite material.
10. Use of a polycarbonate composite material according to any of claims 1-8, for an electronic and electrical film.
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