CN115975367B - 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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- CN115975367B CN115975367B CN202310164206.7A CN202310164206A CN115975367B CN 115975367 B CN115975367 B CN 115975367B CN 202310164206 A CN202310164206 A CN 202310164206A CN 115975367 B CN115975367 B CN 115975367B
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 106
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 106
- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 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 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000012745 toughening agent Substances 0.000 claims abstract description 9
- 239000003063 flame retardant Substances 0.000 claims abstract description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000013329 compounding Methods 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims abstract description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 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 7
- 239000006078 metal deactivator Substances 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 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
- 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
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 30
- 239000000463 material Substances 0.000 description 21
- 238000009472 formulation Methods 0.000 description 13
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 238000001746 injection moulding Methods 0.000 description 10
- 239000007790 solid phase Substances 0.000 description 10
- 239000003381 stabilizer Substances 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 108090000765 processed proteins & peptides Proteins 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method 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
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 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
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 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
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a polycarbonate composition with good processing stability, and 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 comprises a metal passivating agent and an ester interchange inhibitor according to the mass ratio of 1: (0.33-4) compounding to obtain the compound; the viscosity of the polyethylene terephthalate is more than or equal to 0.85. The shrinkage of the polycarbonate composition can be maintained in the range of 0.3 to 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 for the production of products in the fields of electronics and electricity, vehicles, medical devices, construction, lighting, and the like, and are also liable to cause serious environmental pollution after disposal.
Polyethylene terephthalate (PET) resins are widely used to produce PET bottles, PET films, and the like. As the human living standard increases, a large number of these PET bottles and PET films are used and discarded after use, and thus, research into recycling thereof is also required.
PC/PET resin is one of the most commonly used resins in the engineering plastics field. In some applications of precision injection molding, for example: in the 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 assembly, and meanwhile, the PC/PET resin has excellent rigidity; in addition, because some household electrical appliances have larger shells (such as television backshell with the size of more than 60 inches), some larger injection molding machines (1600 tons or more) can be selected, and the residence time of the materials in the screw cylinder is long, so that the materials are required to have good processing stability, and the conventional PC/PET resin materials are difficult to meet the requirements. Chinese patent entitled flame retardant modified polycarbonate/polyethylene terephthalate provides a PC/PET resin material, but it does not pay attention to shrinkage, rigidity, processing stability, etc.
Therefore, the problems of inadequate shrinkage range, poor rigidity and poor processing stability of the existing PC/PET resin are to be solved.
Disclosure of Invention
The primary purpose of the invention is to overcome the problems of unsuitable shrinkage range, poor rigidity and poor processing stability of the existing PC/PET resin. A polycarbonate composition having good processing stability is provided. The shrinkage of the polycarbonate composition can be maintained in the range of 0.3 to 0.45%, which 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.
It is a further object of the present invention to provide the use of the above polycarbonate composition for the 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 comprises a metal passivating agent and an ester interchange inhibitor according to the mass ratio of 1: (0.33-4) compounding to obtain the compound; 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, and the filler is added to reduce the shrinkage of the polycarbonate composition to a certain extent, and on the basis, the viscosity of the polyethylene terephthalate is further regulated and controlled and the composite stabilizer is added to keep the shrinkage of the obtained polycarbonate composition within 0.3-0.45%, and the material has excellent rigidity and good processing stability. The reason for this is: the transesterification inhibitor can further stabilize the polycarbonate composition system, and the existence of the metal passivating agent can slow down the catalytic reaction caused by the metal impurities remained in the polyethylene terephthalate, and the cooperation of the metal passivating agent and the polyethylene terephthalate ensures that the polycarbonate composition has good compatibility and stability, thereby improving the rigidity and processing stability of the polycarbonate composition and reducing the shrinkage rate; the viscosity of the polyethylene terephthalate is further regulated, on one hand, the transesterification reaction of the self ester groups of the PC and PET resins can be reduced, so that a polycarbonate composition system is kept stable, the processing stability is further improved, and on the other hand, the polyethylene terephthalate has lower crystallinity, and the stable shrinkage rate of the polycarbonate composition is kept in the range of 0.3-0.45% by the cooperation of the two aspects. Since the transesterification inhibitor and the polyethylene terephthalate of a specific viscosity act on the end 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 recycling polycarbonate and recycling polyethylene terephthalate.
Namely, 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 measured according to GB/T10247-2008 standard.
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 recycled polycarbonate refers to recycled material obtained by sorting and collecting waste polycarbonate according to physical recycling processes conventional in the art.
More preferably, the recycled polycarbonate has a BPA content of 45 to 100ppm and a hydroxyl terminated content of 300 to 1100ppm.
The recycled polycarbonate with the BPA content and the hydroxyl-terminated content is selected, and the obtained polycarbonate composition has better processing stability and higher flexural modulus.
The BPA content of the recycled polycarbonate of the present invention can be measured according to GB/T32889-2016 and the hydroxyl end group content can be measured according to HG/T2709-1995.
More preferably, the virgin polycarbonate is prepared by the phosgene process.
Preferably, the viscosity of the polyethylene terephthalate is from 0.9 to 1.1dL/g.
The polycarbonate composition obtained by selecting the viscosity in the viscosity range has better processing stability and higher flexural modulus.
Preferably, the polyethylene terephthalate is virgin polyethylene terephthalate or recycled polyethylene terephthalate.
The viscosity of the recycled polyethylene terephthalate is generally from 0.6 to 0.75, and can be brought to the desired viscosity of the present invention by the prior art, such as solid phase viscosification. Solid phase tackifying is also known as solid phase polycondensation, which is a polycondensation reaction carried out in the solid state. The solid phase tackifying process for recovering polyethylene terephthalate is as follows: the recycled polyethylene terephthalate is placed in a rotary drum system (comprising a heating system) and heated to a temperature which is higher than the glass transition temperature of the melting point (249-260 ℃), the temperature is usually lower than the temperature of the melting point (10-40 ℃), the polycondensation is carried out, vacuum is formed in the rotary drum through a vacuum system, byproducts formed by the reaction are pumped out, the polycondensation is continued, the viscosity of the material is increased along with the prolongation of the tackifying time, the tackifying time is controlled to be 5-10 hours generally, and the viscosity of the material can reach 0.85-1.1 dL/g (the viscosity can be monitored on line through a 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-like structure.
The filler with a flaky structure is selected, and the processing stability of the obtained polycarbonate composition is better.
More preferably, the filler is at least one of talc, wollastonite, kaolin or glass frit.
Preferably, the toughening agent is at least one of a silicone rubber-acrylic copolymer, a high rubber powder, or a methyl methacrylate-butadiene-styrene type toughening agent.
Preferably, the flame retardant is at least one of bisphenol a bis (diphenyl phosphate), triphenyl phosphate, or resorcinol-bis (biphosphate).
Preferably, the metal deactivator is at least one of 1, 2-bis [ beta- (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 [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine.
The metal passivating agent is 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 transesterification 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 further 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: and mixing the components, carrying out melt extrusion and granulation to obtain the polycarbonate composite material.
More preferably, the rotation speed of stirring and mixing is 100-150 rpm; the length-diameter ratio of the double-screw extruder is 40-48:1, the temperature of the screw cylinder is 240-280 ℃, and the rotating speed of the screw is 400-600 revolutions per mm.
The application of the polycarbonate composition in preparing household appliances is also within the protection scope of the invention.
Preferably, the home appliance is a television housing or an audio housing.
Compared with the prior art, the invention has the beneficial effects that:
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.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples for the purpose of illustration and not limitation, and various modifications may be made within the scope of the present invention as defined by the appended claims.
The reagents selected for the examples and comparative examples of the present invention are described below:
Polycarbonate (recovery) 1#: PC-TJ17CR01ST (torch, source is bucket), physical recovery, melt finger 5g/10min, hydroxyl end content 300PPM, BPA content 45PPM;
polycarbonate (recovery) 2#: PC ASL-06 (Orsel, water bucket) is physically recovered, the melt index is 10g/10min, the hydroxyl end content is 650PPM, and the BPA content is 55PPM;
Polycarbonate (recovery) 3#: PC 1800 (Oncolor, source is car light), physical recovery, 20g/10min of melt finger, 1100PPM of hydroxyl end content and 100PPM of BPA content;
Polycarbonate (recovery) 4#: PC-TJ17CR01BT (torch, plate material) is physically recovered, the melt finger is 30g/10min, the hydroxyl end content is 1200PPM, and the BPA content is 110PPM;
Polycarbonate (New material) No. 1: PC S-2000F (Japanese light emitting, phosgene method), melt index 10g/10min;
Polycarbonate (New material) 2#: PC WY-111BR (Li Huayi, transesterification method), melt index 10g/10min;
The solid phase tackifying process of the recycled polyethylene terephthalate is as follows: the recycled polyethylene terephthalate is placed in a rotary drum system (comprising a heating system) and heated to a temperature which is higher than the glass transition temperature of the melting point (249-260 ℃), the temperature is usually lower than the temperature of the melting point by 10-40 ℃) to carry out polycondensation, vacuum is formed in the rotary drum through a vacuum system, byproducts formed by the reaction are pumped out, the polycondensation is continued, the viscosity of the materials is increased along with the prolongation of the tackifying time, the general tackifying time is controlled to be 5-10 hours, and the viscosity of the materials can reach 0.85-1.1 (the viscosity can be monitored on line through an Ubbelohde viscometer).
Polyethylene terephthalate 1#: the viscosity of the reclaimed materials, PET-YH002 and Fujian Jinjiang Yonghong, after solid phase tackifying (the tackifying time is 6 hours) reaches 0.90dL/g;
polyethylene terephthalate # 2: the viscosity of the reclaimed materials, PET-YH002 and Fujian Jinjiang permanent macros, reaches 1.0dL/g after solid phase tackifying (the tackifying time is 8 hours);
Polyethylene terephthalate 3#: the viscosity of the reclaimed materials, PET-YH002 and Fujian Jinjiang Yonghong, after solid phase tackifying (the tackifying time is 10 hours) reaches 1.1dL/g;
Polyethylene terephthalate # 4: the viscosity of the reclaimed materials, PET-YH002 and Fujian Jinjiang permanent macros, reaches 0.85dL/g after solid phase tackifying (the tackifying time is 5 hours);
polyethylene terephthalate 5#: the viscosity of the reclaimed material, PET CEV413 and Zhenjiang Saifer after solid phase tackifying (the tackifying time is 6 hours) reaches 0.90dL/g;
polyethylene terephthalate 6#: new material, CR-8828, changzhou Huarun, viscosity 0.86dL/g;
polyethylene terephthalate 7#: recovering material, PET-YH002, fujian Jinjiang Yonghong, viscosity of 0.62dL/g;
Filler 1#: a lamellar structure, wherein the lamellar thickness is 2.5-5 μm, HTPUltra L, liaoning Ai Hai;
Filler 2#: kaolin, needle structure, TRANSLINK, 445, basf;
Flame retardant: bisphenol a bis (diphenyl phosphate), commercially available;
toughening agent 1#: s-2001, mitsubishi yang, a toughening agent with a core-shell structure, wherein the core is silicon rubber, and the shell is an acrylic copolymer;
Toughening agent # 2: m-521, japanese Zhongyuan, the core-shell structure toughener, the core is butadiene-styrene rubber, the shell is methyl methacrylate;
Anti-drip agent: polytetrafluoroethylene, commercially available;
Other auxiliaries: pentaerythritol stearate, lubricants, commercially available;
metal passivating agent # 1: basf, MD1024,1, 2-bis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine;
Metal passivating agent # 2: ai Dike CAD-6, dodecanedioic acid bis [2- (2-hydroxybenzoyl) hydrazide ];
transesterification inhibitor # 1: sodium dihydrogen pyrophosphate (SAPP) is available from Shanghai chemical reagent company, china medicine group;
Transesterification inhibitor # 2: shanghai is repaired, anhydrous sodium dihydrogen phosphate (AMSP);
An antioxidant: antioxidant 1076, commercially available;
the composite stabilizer is 1 # to 9# and self-made, and the preparation method is as follows: the components were mixed according to the formulation of table 1 to obtain a composite stabilizer.
Table 1 Complex stabilizer formulation (parts by weight)
The components (e.g., flame retardants, and other adjuvants) selected in each of the parallel examples and comparative examples are the same commercially available products, unless otherwise specified.
The polycarbonate compositions provided in the examples and comparative examples of the present invention were subjected to performance measurements according to the following test methods:
1. Processing stability: fixing the injection molding temperature to 270 ℃, the injection molding pressure to 50%, and the injection molding speed to 50%, judging whether the continuous injection molding 30 die is good or not by calculating the change of the spiral line length, 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: the molded test bars were reverse conditioned for more than 48 hours at 25 c and 50% humidity according to ASTM D790-2018B, then tested and the results recorded.
3. Shrinkage (molding shrinkage): the injection molding temperature is fixed at 265 ℃, the injection molding pressure is 50%, the injection molding speed is 50%, the cross shrinkage rate plate with the thickness of 2.0mm is injected, the plate is placed in an environment with the room temperature of 25 ℃ and the humidity of 50% for more than 48 hours after injection molding, and then the shrinkage rate is obtained by measuring and recording the result through a secondary element.
The preparation process of the polycarbonate composite material of each example and comparative example of the present invention is as follows: the components are weighed according to the proportion, added into a high-speed mixer for stirring and blending to obtain premix, then extruded in a double-screw extruder, and melted and granulated to obtain the polycarbonate composition. Wherein the stirring speed is 150 revolutions per minute, the length-diameter ratio of the double-screw extruder is 40:1, the temperature of the screw barrel is 260 ℃, and the screw rotating speed is 400 revolutions per minute.
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 different from that of example 1 in that: the composite stabilizer 1# is replaced by composite stabilizer 6# with the same dosage.
Comparative example 2
This comparative example provides a polycarbonate composition having a formulation different from that of example 1 in that: the composite stabilizer 1# is replaced by composite stabilizer 7# with the same dosage.
Comparative example 3
This comparative example provides a polycarbonate composition having a formulation different from that of example 1 in that: the composite stabilizer 1# is replaced by composite stabilizer 8# with the same dosage.
Comparative example 4
This comparative example provides a polycarbonate composition having a formulation different from that of example 1 in that: the composite stabilizer 1# is replaced by composite stabilizer 9# with the same dosage.
Comparative example 5
This comparative example provides a polycarbonate composition having a formulation different from that of example 1 in that: the composite stabilizer 1# is replaced by the metal passivating agent 1# with the same dosage.
Comparative example 6
This comparative example provides a polycarbonate composition having a formulation different from that of example 1 in that: the composite stabilizer 1# is replaced by the transesterification inhibitor 1# with the same dosage.
Comparative example 7
This comparative example provides a polycarbonate composition having a formulation different from that of example 1 in that: no compound stabilizer # 1 was added.
Comparative example 8
This comparative example provides a polycarbonate composition having a formulation different from that of example 1 in that: polyethylene terephthalate # 1 was replaced with an equivalent amount of polyethylene terephthalate # 7.
The properties of the polycarbonate compositions of the examples and comparative examples were determined according to the test methods mentioned above, and the test results are shown in Table 4.
Table 4 results of performance testing of polycarbonate composites of examples and comparative examples
From table 4, it can be seen that:
The polycarbonate composite materials of examples 1 to 22 have a spiral length of 17 or less, a flexural modulus of 3600MPa or more, and a shrinkage in the range of 0.3 to 0.45%, indicating that the shrinkage of the polycarbonate composition of the present invention can be maintained in the range of 0.3 to 0.45%, meets the processing requirements, and has 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 were controlled within the appropriate ranges (examples 1, 4 and 5) in comparison with examples 1 to 5, the shrinkage of the obtained polycarbonate composition was closer to 0.375%, thereby more conforming to the processing requirements.
The composite stabilizer 6# added in the comparative example 1, the composite stabilizer 7# and the metal passivating agent and the transesterification inhibitor of the composite stabilizer 6# and the composite stabilizer 7# are added in the comparative example 2, and have unreasonable mass ratio, so that the spiral line length of the polycarbonate composition is higher, the processing stability is deviated, the shrinkage rate is smaller than 0.3%, the shrinkage rate is too small, the product size is larger, the interference fit is carried out, the appearance of the terminal product is uneven, the terminal product is easy to deform under the action of long-term internal stress, the service life is shortened, and the processing requirement is not met. The compound stabilizer 8# is added in the comparative example 3, and the compound stabilizer 8# is obtained by compounding a metal passivating agent and an antioxidant, so that the polycarbonate composition has long spiral line length peptide, poor processing stability and shrinkage less than 0.3 percent, and does not meet the processing requirement. Comparative example 4 was added with a compound stabilizer # 9, which was obtained by compounding a transesterification inhibitor and an antioxidant, resulting in a shrinkage of less than 0.3% of the polycarbonate composition, which did not meet the processing requirements. Comparative example 5 the replacement of the complex stabilizer 1# with an equivalent amount of metal deactivator resulted in a polycarbonate composition with long helix length peptide and poor processing stability. Comparative example 6 the replacement of the complex stabilizer 1# with an equivalent amount of transesterification inhibitor resulted in a polycarbonate composition with long helix length peptide and poor processing stability. Comparative example 7, without the addition of a compound stabilizer, resulted in a polycarbonate composition with long helix length peptide and poor processing stability. The polyethylene terephthalate added in comparative example 8 had too low a viscosity, resulting in a polycarbonate composition with a higher spiral length, a deviation in processing stability, and a shrinkage of less than 0.3% and not meeting the processing requirements.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (11)
1. A polycarbonate composition with good processing stability is characterized by comprising the following components in parts by weight:
50-100 parts of polycarbonate,
5-30 Parts of polyethylene terephthalate,
1-18 Parts of a toughening agent,
10-25 Parts of a filler,
9-15 Parts of a flame retardant,
0.01 To 5 parts of anti-dripping agent,
0.01-2 Parts of a composite stabilizer;
the composite stabilizer comprises a metal passivating agent and an ester interchange inhibitor according to the mass ratio of 1: (0.33-4) compounding to obtain; 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 hydroxyl terminated 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 lamellar structure.
7. The polycarbonate composition of claim 1, wherein the metal deactivator is at least one of 1, 2-bis [ beta- (3, 5-di-tert-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 sodium dihydrogen pyrophosphate or sodium dihydrogen phosphate.
9. The polycarbonate composition of claim 8, wherein the sodium dihydrogen phosphate is anhydrous sodium dihydrogen phosphate.
10. The method for preparing the polycarbonate composition according to any one of claims 1 to 9, characterized by comprising the steps of: and mixing the components, carrying out melt extrusion and granulation to obtain the polycarbonate composition.
11. Use of the polycarbonate composition according to any one of claims 1 to 9 for the preparation of household appliances.
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