CN115975367A - Polycarbonate composition with good processing stability and preparation method and application thereof - Google Patents
Polycarbonate composition with good processing stability and preparation method and application thereof Download PDFInfo
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- CN115975367A CN115975367A CN202310164206.7A CN202310164206A CN115975367A CN 115975367 A CN115975367 A CN 115975367A CN 202310164206 A CN202310164206 A CN 202310164206A CN 115975367 A CN115975367 A CN 115975367A
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- polycarbonate
- polycarbonate composition
- polyethylene terephthalate
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 105
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 105
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 238000012545 processing Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 50
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 50
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 44
- 239000006084 composite stabilizer Substances 0.000 claims abstract description 21
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims abstract description 5
- 125000004185 ester group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 11
- 239000006078 metal deactivator Substances 0.000 claims description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 238000005809 transesterification reaction Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- WRMXOVHLRUVREB-UHFFFAOYSA-N phosphono phosphate;tributylazanium Chemical compound OP(O)(=O)OP([O-])([O-])=O.CCCC[NH+](CCCC)CCCC.CCCC[NH+](CCCC)CCCC WRMXOVHLRUVREB-UHFFFAOYSA-N 0.000 claims description 5
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- KKZSDWROKQKKPM-UHFFFAOYSA-N 1-n',12-n'-bis(2-hydroxybenzoyl)dodecanedihydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)CCCCCCCCCCC(=O)NNC(=O)C1=CC=CC=C1O KKZSDWROKQKKPM-UHFFFAOYSA-N 0.000 claims description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 abstract description 6
- 239000012745 toughening agent Substances 0.000 abstract description 6
- 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 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 30
- 239000000463 material Substances 0.000 description 22
- 238000009472 formulation Methods 0.000 description 12
- 238000001746 injection moulding Methods 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000007790 solid phase Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 9
- 150000002148 esters Chemical group 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 108090000765 processed proteins & peptides Proteins 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 2
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 235000019820 disodium diphosphate Nutrition 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 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 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 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
- 238000011056 performance test Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- 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
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention relates to a polycarbonate composition with good processing stability, a preparation method and application thereof. The polycarbonate composition comprises the following components in parts by weight: 50-100 parts of polycarbonate, 5-30 parts of polyethylene terephthalate, 1-18 parts of toughening agent, 10-25 parts of filler, 9-15 parts of flame retardant, 0.01-5 parts of anti-dripping agent and 0.01-2 parts of composite stabilizer. The composite stabilizer is prepared from a metal passivator and an ester exchange inhibitor in a mass ratio of 1: (0.33-4) compounding; the viscosity of the polyethylene terephthalate is more than or equal to 0.85. The polycarbonate composition can maintain the shrinkage rate within the range of 0.3-0.45%, and has excellent rigidity and good processing stability.
Description
Technical Field
The invention relates to the field of engineering plastics, in particular to a polycarbonate composition with good processing stability, and a preparation method and application thereof.
Background
Polycarbonate (PC) resins are widely used in the production of products in the fields of electronics, electrical, transportation, medical equipment, construction, lighting, etc., and are also likely to cause serious environmental pollution after being discarded.
Polyethylene terephthalate (PET) resins are widely used to produce PET bottles, PET films, and the like. As the living standard of human beings increases, these PET bottles and PET films are used in large quantities and discarded after use, and therefore, studies on recycling thereof are also required.
PC/PET resin is one of the most commonly used resins in the field of engineering plastics. In some application scenarios of precision injection molding, for example: in a household appliance shell scene, the shrinkage rate of PC/PET resin is required to be kept between 0.3 and 0.45 percent so as to ensure the requirements of demolding and assembling, and meanwhile, the PC/PET resin has excellent rigidity; in addition, because some household appliance housings are large (such as a television rear housing of more than 60 inches), some large injection molding machines (1600 tons or more) can be selected, and the residence time of materials in a screw cylinder is long, the materials are required to have good processing stability, and the conventional PC/PET resin materials are difficult to meet the requirements. The chinese patent entitled flame retardant modified polycarbonate/polyethylene terephthalate provides a PC/PET resin material, but it does not address the problems of shrinkage, rigidity, processing stability, etc.
Therefore, the problems of the prior PC/PET resin such as improper shrinkage rate range, poor rigidity and poor processing stability need to be solved.
Disclosure of Invention
The primary object of the present invention is to overcome the problems of the conventional PC/PET resin, such as inadequate shrinkage range, poor rigidity and poor processing stability. A polycarbonate composition having good processing stability is provided. The polycarbonate composition can maintain the shrinkage rate within the range of 0.3 to 0.45%, and has excellent rigidity and good processing stability.
It is a further object of the present invention to provide a process for the preparation of the above polycarbonate composition.
The invention further aims to provide application of the polycarbonate composition in preparation of household appliances.
The above object of the present invention is achieved by the following technical solutions:
a polycarbonate composition with good processing stability comprises the following components in parts by weight:
the composite stabilizer is prepared from a metal passivator and an ester exchange inhibitor in a mass ratio of 1: (0.33-4) compounding; the viscosity of the polyethylene terephthalate is more than or equal to 0.85dL/g.
The material obtained by mixing the polycarbonate and the polyethylene terephthalate has certain rigidity, the filling material is added, the shrinkage rate of the polycarbonate composition can be reduced to a certain extent, on the basis, the viscosity of the polyethylene terephthalate is further regulated and controlled, and the composite stabilizer is added, so that the shrinkage rate of the obtained polycarbonate composition can be kept within 0.3-0.45%, and the polycarbonate composition has excellent rigidity and good processing stability. The reason is that: the ester exchange inhibitor can further stabilize a polycarbonate composition system, the presence of the metal deactivator can slow down catalytic reaction caused by metal impurities remained in the polyethylene terephthalate, and the polycarbonate composition has good compatibility and stability due to the cooperation of the metal deactivator and the metal deactivator, so that the rigidity and the processing stability of the polycarbonate composition are improved, and the shrinkage rate is reduced; the viscosity of the polyethylene terephthalate is further regulated, so that the ester exchange reaction of ester groups of the PC and PET resins can be reduced, the polycarbonate composition system is kept stable, the processing stability is further improved, the polyethylene terephthalate has lower crystallinity, and the stable shrinkage of the polycarbonate composition is kept within the range of 0.3-0.45% due to the matching of the two aspects. Since the transesterification inhibitor and the polyethylene terephthalate of a specific viscosity act on the terminal groups of the matrix resin, and the metal deactivator acts on the metal impurities of the polyethylene terephthalate, the technique of the present invention is applicable not only to virgin polycarbonate and virgin polyethylene terephthalate, but also to recycled polycarbonate and recycled polyethylene terephthalate.
That is, the shrinkage of the polycarbonate composition of the present invention can be maintained in the range of 0.3 to 0.45%, which has excellent rigidity and good processing stability.
The viscosity of the polyethylene terephthalate according to the invention can be determined in accordance with GB/T10247-2008.
Preferably, the polycarbonate composition comprises the following components in parts by weight:
preferably, the polycarbonate is virgin polycarbonate and/or recycled polycarbonate.
It should be understood that the recycled polycarbonate means a recycled material obtained by sorting and collecting waste polycarbonate according to a physical recycling treatment means which is conventional in the art.
More preferably, the recycled polycarbonate has a BPA content of 45 to 100ppm and a terminal hydroxyl group content of 300 to 1100ppm.
The recovered polycarbonate with the BPA content and the terminal hydroxyl group content is selected, so that the obtained polycarbonate composition has better processing stability and higher flexural modulus.
The BPA content of the recycled polycarbonate of the invention can be measured according to GB/T32889-2016, and the terminal hydroxyl group content can be measured according to HG/T2709-1995.
More preferably, the virgin polycarbonate is prepared by a phosgene process.
Preferably, the polyethylene terephthalate has a viscosity of 0.9 to 1.1dL/g.
The viscosity in the viscosity range is selected, so that the obtained polycarbonate composition has better processing stability and higher flexural modulus.
Preferably, the polyethylene terephthalate is virgin polyethylene terephthalate or recycled polyethylene terephthalate.
The recycled polyethylene terephthalate generally has a viscosity of 0.6 to 0.75, and the viscosity can be adjusted to the viscosity required in the present invention by the conventional techniques, for example, solid-phase thickening. Solid phase tackifying, also called solid phase polycondensation, is a polycondensation reaction that is carried out in the solid state. The solid phase tackifying process of the recovered polyethylene terephthalate comprises the following steps: the recovered polyethylene terephthalate is put into a rotary drum system (comprising a heating system) and heated to a temperature (generally lower than the temperature of 10-40 ℃ below the melting point) which is lower than the glass transition temperature of the recovered polyethylene terephthalate, so as to carry out polycondensation reaction, vacuum is formed in the rotary drum through a vacuum system, by-products formed by the reaction are pumped away, the polycondensation reaction is continued, the viscosity of the material is increased along with the increase of the tackifying time, the tackifying time is generally controlled to be 5-10 hours, and the viscosity of the recovered polyethylene terephthalate can reach 0.85-1.1 dL/g (the viscosity can be monitored on line through an Ubbelohde viscometer).
Fillers, toughening agents, flame retardants, metal deactivators, anti-drip agents, and transesterification inhibitors commonly used in the art may be used in the present invention.
Preferably, the filler is a filler having a sheet structure.
The filler with a sheet structure is selected, so that the obtained polycarbonate composition has better processing stability.
More preferably, the filler is at least one of talc, wollastonite, kaolin, or glass powder.
Preferably, the toughening agent is at least one of a silicon rubber-acrylic copolymer, high rubber powder or a methyl methacrylate-butadiene-styrene toughening agent.
Preferably, the flame retardant is at least one of bisphenol a bis (diphenyl phosphate), triphenyl phosphate, or resorcinol-bis (bis-diphosphate).
Preferably, the metal deactivator is at least one of 1, 2-bis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine or dodecanedioic acid bis [2- (2-hydroxybenzoyl) hydrazide ].
More preferably, the metal deactivator is 1, 2-bis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine.
The metal passivator selects 1, 2-bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ], and the obtained polycarbonate composition has better processing stability and higher flexural modulus.
Preferably, the transesterification inhibitor is anhydrous sodium dihydrogen phosphate (AMSP), sodium dihydrogen pyrophosphate (SAPP) or sodium dihydrogen phosphate (MSP).
More preferably, the transesterification inhibitor is sodium dihydrogen pyrophosphate.
The ester exchange inhibitor is sodium dihydrogen pyrophosphate, and the obtained polycarbonate composition has better processing stability and higher flexural modulus.
Optionally, the anti-drip agent is polytetrafluoroethylene.
Preferably, the polycarbonate composition also comprises 0.1 to 1 part of other auxiliary agents.
More preferably, the other auxiliary agent is at least one of an antioxidant or a lubricant.
Optionally, the antioxidant is at least one of 1076, 1010 or 168.
Optionally, the lubricant is at least one of pentaerythritol stearate or E-wax.
The preparation method of the polycarbonate composition comprises the following steps: mixing the components, melting, extruding and granulating to obtain the polycarbonate composite material.
More preferably, the rotating speed of stirring and mixing is 100-150 r/min; the length-diameter ratio of the double-screw extruder is 40-48, the temperature of a screw barrel is 240-280 ℃, and the rotating speed of the screw is 400-600 revolutions/mim.
The application of the polycarbonate composition in the preparation of household appliances is also within the protection scope of the invention.
Preferably, the household appliance is a television housing or a sound housing.
Compared with the prior art, the invention has the beneficial effects that:
the polycarbonate composition of the present invention can maintain the shrinkage rate within the range of 0.3 to 0.45%, and has excellent rigidity and good processing stability.
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
Some reagents selected in the examples and comparative examples of the present invention are described below:
polycarbonate (recovered) 1#: PC-TJ17CR01ST (sky torch, source is bucket), physical recovery, melt mean 5g/10min, terminal hydroxy content is 300PPM, BPA content is 45PPM;
polycarbonate (recovered) 2#: PC ASL-06 (Oselal, source is bucket), physically recovering, melting finger 10g/10min, terminal hydroxyl content of 650PPM, BPA content of 55PPM;
polycarbonate (recovered) 3#: PC 1800 (Oselar, source is car light), physically recovering, wherein the melt index is 20g/10min, the content of terminal hydroxyl is 1100PPM, and the content of BPA is 100PPM;
polycarbonate (recovered) 4#: PC-TJ17CR01BT (ceiling, plate material) is physically recovered, the melt index is 30g/10min, the content of terminal hydroxyl is 1200PPM, and the content of BPA is 110PPM;
polycarbonate (virgin) 1#: PC S-2000F (Japan brightening, phosgene method), melt index is 10g/10min;
polycarbonate (new material) 2#: PC WY-111BR (Lihuayi, ester exchange method), melt index is 10g/10min;
the solid phase tackifying process of the recovered polyethylene glycol terephthalate of the invention is as follows: the recovered polyethylene terephthalate is put into a rotary drum system (comprising a heating system) and heated to a temperature (generally lower than the temperature of 10-40 ℃ below the melting point) which is lower than the glass transition temperature of the recovered polyethylene terephthalate, so as to carry out polycondensation reaction, vacuum is formed in the rotary drum through a vacuum system, by-products formed by the reaction are pumped away, the polycondensation reaction is continued, the viscosity of the material is increased along with the increase of the tackifying time, the tackifying time is generally controlled to be 5-10 hours, and the viscosity of the material can reach 0.85-1.1 (the viscosity can be monitored on line through an Ubbelohde viscometer).
Polyethylene terephthalate 1#: the reclaimed materials, PET-YH002 and Fujian jin Jiang Yonghong, have viscosity of 0.90dL/g after solid-phase tackifying (the tackifying time is 6 hours);
polyethylene terephthalate 2#: the reclaimed materials, PET-YH002 and Fujian jin Jiang Yonghong, have viscosity of 1.0dL/g after solid-phase tackifying (the tackifying time is 8 hours);
polyethylene terephthalate # 3: reclaimed materials, PET-YH002, fujian jin Jiang Yonghong, the viscosity of the reclaimed materials reaches 1.1dL/g after solid-phase tackifying (the tackifying time is 10 hours);
polyethylene terephthalate 4#: reclaimed materials, PET-YH002, fujian jin Jiang Yonghong, and the viscosity of the reclaimed materials reaches 0.85dL/g after solid-phase tackifying (the tackifying time is 5 hours);
polyethylene terephthalate 5#: reclaimed materials, PET CEV413 and Zhenjiang Seville, the viscosity of the reclaimed materials reaches 0.90dL/g after solid-phase tackifying (the tackifying time is 6 hours);
polyethylene terephthalate 6#: a new material, CR-8828, changzhou Huarun, with the viscosity of 0.86dL/g;
polyethylene terephthalate 7#: the reclaimed material PET-YH002, fujian jin Jiang Yonghong, with the viscosity of 0.62dL/g;
1# of filler: the laminated structure has a laminated thickness of 2.5-5 μm, HTPUltra5L, and Liaoning Eihai sea;
and 2# of filler: kaolin, needle structure, TRANSLINK 445, basf;
flame retardant: bisphenol a bis (diphenyl phosphate), commercially available;
flexibilizer 1#: s-2001, mitsubishi yang, a core-shell structure toughening agent, wherein the core is silicon rubber, and the shell is an acrylic copolymer;
flexibilizer # 2: m-521, japanese mediterrain, a core-shell structure toughening agent, wherein the core is butadiene-styrene rubber, and the shell is methyl methacrylate;
anti-dripping agent: polytetrafluoroethylene, commercially available;
other auxiliary agents: pentaerythritol stearate, lubricant, commercially available;
metal passivator # 1: basf, MD1024,1, 2-bis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine;
metal passivator 2#: adico, CAD-6, dodecanedioic acid bis [2- (2-hydroxybenzoyl) hydrazide ];
transesterification inhibitor # 1: sodium dihydrogen pyrophosphate (SAPP), shanghai chemical agents corporation, china medicine group;
transesterification inhibitor # 2: shanghai, yuannao, anhydrous sodium dihydrogen phosphate (AMSP);
antioxidant: antioxidant 1076, commercially available;
the composite stabilizer 1-9 # is prepared by self-made method as follows: the components are mixed according to the formula of the table 1 to obtain the composite stabilizer.
TABLE 1 composite stabilizer formulation (parts by weight)
The components (e.g., flame retardant, and other auxiliaries) selected in each of the parallel examples and comparative examples were the same commercial product, unless otherwise specified.
The polycarbonate compositions provided in the examples and comparative examples of the present invention were subjected to the following test methods for their performance:
1. and (3) processing stability: the fixed injection molding temperature is 270 ℃, the injection molding pressure is 50%, the injection molding speed is 50%, the quality of the injection molding is judged by calculating the change of the length of the spiral line through a continuous injection molding 30 die, wherein the smaller the change is, the better the processing stability is; conversely, the greater the variation, the poorer the processing stability.
2. Flexural modulus: according to the ASTM D790-2018B standard, the test sample bars after injection molding are reversely placed in an environment with the temperature of 25 ℃ and the humidity of 50 percent for more than 48 hours, then the test is carried out, and the results are recorded.
3. Shrinkage (mold shrinkage): and fixing the injection molding temperature at 265 ℃, the injection molding pressure at 50%, the injection molding speed at 50%, and injecting a 2.0mm cross shrinkage rate plate, adjusting the cross shrinkage rate plate for more than 48 hours in an environment with the room temperature of 25 ℃ and the humidity of 50% after injection molding, measuring through a quadratic element, and recording the result to obtain the shrinkage rate.
The preparation process of the polycarbonate composite material of each example and comparative example of the present invention is as follows: weighing the components according to the proportion, adding the components into a high-speed mixer, stirring and blending to obtain a premix, then extruding the premix in a double-screw extruder, and performing a melting and granulating process to obtain the polycarbonate composition. Wherein the stirring speed is 150 r/min, the length-diameter ratio of the double-screw extruder is 40, the temperature of the screw cylinder is 260 ℃, and the screw speed is 400 r/min.
Examples 1 to 22
Examples 1-22 provide a series of polycarbonate compositions having the formulations shown in tables 2 and 3.
TABLE 2 formulations (parts by weight) of examples 1 to 10
TABLE 3 formulations (parts by weight) of examples 11 to 22
Comparative example 1
This comparative example provides a polycarbonate composition having a formulation which differs from that of example 1 in that: the compound stabilizer 1# is replaced by the compound stabilizer 6# with the same dosage.
Comparative example 2
This comparative example provides a polycarbonate composition having a formulation which differs from that of example 1 in that: the compound stabilizer 1# is replaced by the compound stabilizer 7# with the same dosage.
Comparative example 3
This comparative example provides a polycarbonate composition having a formulation which differs from that of example 1 in that: the compound stabilizer 1# is replaced by the compound stabilizer 8# with the same dosage.
Comparative example 4
This comparative example provides a polycarbonate composition having a formulation which differs from that of example 1 in that: the compound stabilizer 1# is replaced by the compound stabilizer 9# with the same dosage.
Comparative example 5
This comparative example provides a polycarbonate composition having a formulation which differs from that of example 1 in that: and replacing the composite stabilizer 1# with the metal passivator 1# with the same dosage.
Comparative example 6
This comparative example provides a polycarbonate composition having a formulation which differs from that of example 1 in that: replacing the compound stabilizer 1# with the ester exchange inhibitor 1# with the same dosage.
Comparative example 7
This comparative example provides a polycarbonate composition having a formulation which differs from that of example 1 in that: no. 1 composite stabilizer was not added.
Comparative example 8
This comparative example provides a polycarbonate composition having a formulation which differs from that of example 1 in that: the polyethylene terephthalate No. 1 is replaced by the polyethylene terephthalate No. 7 with the same dosage.
The properties of the polycarbonate compositions of the respective examples and comparative examples were measured in accordance with the above-mentioned test methods, and the results are shown in Table 4.
TABLE 4 results of performance test of polycarbonate composites of examples and comparative examples
From table 4, it can be seen that:
the polycarbonate composites of examples 1 to 22 had a helical length of 17 or less, a flexural modulus of 3600MPa or more and a shrinkage of 0.3 to 0.45%, indicating that the polycarbonate composition of the present invention can maintain a shrinkage of 0.3 to 0.45%, meet the requirements for processing, and have excellent rigidity and good processing stability. Wherein, the closer the shrinkage of the polycarbonate composition is to 0.375% (i.e., the median value of the range of 0.3 to 0.45%), the more the shrinkage is considered to meet the processing requirements; when the amounts of the respective components are controlled within appropriate ranges as compared with examples 1 to 5 (examples 1, 4 and 5), the shrinkage of the resulting polycarbonate composition is closer to 0.375%, which is more satisfactory for processing.
The composite stabilizer 6# is added in the comparative example 1, the composite stabilizer 7# is added in the comparative example 2, the mass ratio of the metal passivator and the ester exchange inhibitor of the composite stabilizer 6# and the composite stabilizer 7# is unreasonable, so that the polycarbonate composition has the defects of high spiral line length, processing stability deviation, shrinkage rate less than 0.3 percent and small shrinkage rate, the product has large size, is subjected to interference assembly, causes an end product to have uneven appearance, is easy to deform under the action of long-term internal stress, shortens the service life and does not meet the processing requirement. The composite stabilizer No. 8 is added in the comparative example 3, and the composite stabilizer No. 8 is obtained by compounding the metal passivator and the antioxidant, so that the polycarbonate composition has long peptide with the spiral line length, poor processing stability and shrinkage of less than 0.3 percent, and does not meet the processing requirement. Comparative example 4 was added with composite stabilizer No. 9, and composite stabilizer No. 9 was obtained by compounding the ester interchange inhibitor and the antioxidant, resulting in a shrinkage of the polycarbonate composition of less than 0.3%, which did not meet the processing requirements. Comparative example 5 replacement of composite stabilizer # 1 with an equivalent amount of metal deactivator resulted in polycarbonate compositions with long helix length peptides and poor processing stability. Comparative example 6 replacement of composite stabilizer # 1 with an equivalent amount of transesterification inhibitor resulted in polycarbonate compositions with long helix length peptides and poor processing stability. Comparative example 7 no addition of the composite stabilizer resulted in a polycarbonate composition with a long helical length peptide and poor processing stability. The polyethylene terephthalate added in comparative example 8 has too low a viscosity, resulting in a polycarbonate composition having a high helical length, a poor processing stability, and a shrinkage of less than 0.3%, which is not satisfactory for processing.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The polycarbonate composition with good processing stability is characterized by comprising the following components in parts by weight:
the composite stabilizer is prepared from a metal passivator and an ester exchange inhibitor in a mass ratio of 1: (0.33-4) compounding; the viscosity of the polyethylene terephthalate is more than or equal to 0.85dL/g.
2. The polycarbonate composition of claim 1, wherein the polycarbonate is virgin polycarbonate and/or recycled polycarbonate.
3. The polycarbonate composition of claim 2, wherein the recycled polycarbonate has a BPA content of 45 to 100PPM and a terminal hydroxyl group content of 300 to 1100PPM.
4. The polycarbonate composition of claim 2, wherein the virgin polycarbonate is prepared by a phosgene process.
5. The polycarbonate composition of claim 1, wherein the polyethylene terephthalate has a viscosity of 0.9 to 1.1dL/g.
6. The polycarbonate composition of claim 1, wherein the filler is a filler having a platelet structure.
7. The polycarbonate composition of claim 1, wherein the metal deactivator is at least one of 1, 2-bis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl ] hydrazine or dodecanedioic acid bis [2- (2-hydroxybenzoyl) hydrazide ].
8. The polycarbonate composition of claim 1, wherein the transesterification inhibitor is at least one of anhydrous sodium dihydrogen phosphate, sodium dihydrogen pyrophosphate, or sodium dihydrogen phosphate.
9. The method for preparing the polycarbonate composition of any one of claims 1-8, comprising the steps of: mixing the components, melting, extruding and granulating to obtain the polycarbonate composition.
10. Use of the polycarbonate composition according to any one of claims 1 to 8 for the preparation of household electrical appliances.
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