CN112625406B - Cold-heat shock resistant polybutylene terephthalate composition - Google Patents
Cold-heat shock resistant polybutylene terephthalate composition Download PDFInfo
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- CN112625406B CN112625406B CN202011437086.6A CN202011437086A CN112625406B CN 112625406 B CN112625406 B CN 112625406B CN 202011437086 A CN202011437086 A CN 202011437086A CN 112625406 B CN112625406 B CN 112625406B
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- 229920001707 polybutylene terephthalate Polymers 0.000 title claims abstract description 50
- -1 polybutylene terephthalate Polymers 0.000 title claims abstract description 35
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 230000035939 shock Effects 0.000 title abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000004014 plasticizer Substances 0.000 claims abstract description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000012765 fibrous filler Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 229920001634 Copolyester Polymers 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- 238000012545 processing Methods 0.000 abstract description 9
- 238000003466 welding Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 14
- 239000004033 plastic Substances 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000314 lubricant Substances 0.000 description 7
- 150000001718 carbodiimides Chemical class 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000874 polytetramethylene terephthalate Polymers 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CTJJGIVJOBVMEO-UHFFFAOYSA-N tetraoctyl benzene-1,2,4,5-tetracarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC(C(=O)OCCCCCCCC)=C(C(=O)OCCCCCCCC)C=C1C(=O)OCCCCCCCC CTJJGIVJOBVMEO-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a cold and hot shock resistant polybutylene terephthalate composition, which comprises the following components: PBT resin, PCTG resin, fluorine processing aid, plasticizer and reinforcing agent. The polybutylene terephthalate mixture has the characteristics of excellent cold and heat shock resistance, low processing smell, high welding strength and excellent comprehensive performance.
Description
Technical Field
The invention belongs to the field of polybutylene terephthalate composition materials, and particularly relates to a polybutylene terephthalate composition with cold and hot shock resistance.
Background
Polybutylene terephthalate (PBT), also known as polytetramethylene terephthalate, has excellent mechanical properties, high heat resistance, excellent chemical solvent resistance, fatigue resistance and creep resistance, and is fast in crystallization and easy to process. In China, the synthesis technology of the PBT resin is mature, and raw material resources are sufficient, so that the PBT resin is low in price, and the modified plastic produced by taking the PBT as a base material has high cost performance, and is widely applied to a plurality of fields of automobiles, industry, electronics and electrics, household appliances, IT, OA and the like.
The biggest defect of the PBT material is notch sensitivity and poor deformation resistance. Even if the toughness is improved, the material is difficult to meet the use requirements when being used in special fields, particularly electronic and electrical equipment products with severe temperature difference change in use working conditions, such as motors. The motor product is usually a molded product embedded with metal, the metal insert is usually composed of an iron core and magnetic sheets which are formed by stamping and laminating, the iron core has sharp edges, and the PBT material plays roles in coating, fixing and insulating. Because the metal insert is used in an environment with violent temperature rise and drop caused by temperature change of a natural environment, self working temperature rise or energy transfer of a refrigeration module and the like, the plastic part is easy to crack due to the difference of linear expansion coefficients of the metal insert and the PBT material, and the plastic cracking is accelerated by the corner structure of the iron core. Therefore, products for such applications require plastic materials having thermal shock resistance. Currently, there are few reports on improving the thermal shock resistance of PBT materials. CN 102056986B reports that the cold and heat shock resistance of reinforced PBT material is improved by adding carbodiimide and elastomer. CN 104830033B reports the improvement of the cold and hot shock resistance of reinforced PBT material by adding carbodiimide. US 6512027B2 reports improved thermal shock resistance by the addition of a toughening agent and an aromatic multivalent carboxylate. However, there is a problem in that the imine group of carbodiimide reacts with active hydrogen during processing, and the intermediate isocyanate thereof has an offensive odor, resulting in intolerable production environment. Further, when the thermal shock resistance is improved by the elastomer, the mechanical strength and fluidity of the material are remarkably reduced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a cold and hot shock resistant polybutylene terephthalate composition, which overcomes the defects of unfriendly processing smell caused by carbodiimide and reduced comprehensive physical properties caused by excessive elastomers in the prior art.
The polybutylene terephthalate composition comprises the following raw materials in percentage by mass:
the PBT resin has a relative density of 1.30-1.35 and a carboxyl end group content of less than or equal to 30mol/t;
the PCTG resin is amorphous copolyester formed by condensing PTA, EG and 1,4-cyclohexanedimethanol CHDM.
Preferably, the PBT resin has a carboxyl end group content of less than or equal to 25mol/t, and more preferably, the carboxyl end group content of less than or equal to 15mol/t.
The intrinsic viscosity of the PBT resin is not particularly limited, but is preferably 0.6 to 1.35dl/g, more preferably 0.7 to 1.1dl/g. The PBT resin can be a single resin with a specified intrinsic viscosity, or can be a mixed resin with two or more resins which are blended to obtain the specified intrinsic viscosity. For example, a PBT resin having an intrinsic viscosity of 0.85dl/g is obtained by mixing two PBT resins having intrinsic viscosities of 0.8dl/g and 1.0 dl/g.
The mass of CHDM in the PCTG accounts for more than 50 percent of the total mass of the PCTG, and the increase of the CHDM proportion destroys the molecular regularity, so that the melting point is reduced, the glass transition temperature is increased, and the crystallinity is reduced.
The content of the PCTG is within the content range required by the invention, and the product can obtain the optimal comprehensive mechanical property. It should be noted that when the PCTG content is more than 20%, the heat resistance of the material is drastically lowered.
The fluorine processing aid is a processing aid based on a fluorine-containing polymer elastomer, and can improve the extrusion processing performance of the polymer and improve the quality of an extruded product. The fluorine processing aid in the invention is different from common fluorine-containing compounds (such as wear-resistant aid polytetrafluoroethylene and compatilizer hydroxyl-terminated fluorine-containing polyester polysiloxane) in modified plastics in types and functions. In the present invention, the fluorine processing aid and the plasticizer have a synergistic effect in improving the cold and hot impact properties and reducing the odor during processing. The fluorine processing aid may be selected from FX-59 series of 3M company.
Preferably, the FX-59-series auxiliary agent is one or more of FX-5911, FX-5920A, FX-5912, FX-5920B, FX-5924 and FX-5922.
The plasticizer is one or more of a meta-benzene plasticizer, an epoxy plasticizer, a fatty acid ester plasticizer, a p-benzene plasticizer, a pyromellitic plasticizer and a polyester plasticizer; preferred are the pyromellitic plasticizers and the trimellitic plasticizers.
The reinforcing agent is a fibrous filler.
The fibrous filler is one or more of glass fiber, carbon fiber, potassium titanate fiber, silica/alumina fiber, zirconia fiber, silica fiber, boron nitride fiber, silicon nitride fiber, aluminum borate fiber, metal fiber and organic fiber. The fibrous reinforcing agent is not affected by the diameter of the fiber, the shape of the cross section (round, flat, irregular), the form of the fiber (such as strand, grit, grinding), and glass fiber and carbon fiber are preferable in view of the effect of the mechanical properties obtained.
The composition also contains a processing aid.
Furthermore, the polybutylene terephthalate composition can also comprise 0.1-1.0wt% of antioxidant and 0.1-1.0wt% of lubricant and other common processing aids based on the total weight of the polybutylene terephthalate composition.
Further, the antioxidant includes, but is not limited to, one or more of hindered phenol antioxidants, phosphite antioxidants, diphenylamine antioxidants, copper salt antioxidants and thioether antioxidants.
The lubricant comprises one or more of ester lubricant, polyethylene wax lubricant or Meng Dan ester lubricant.
The invention discloses a preparation method of a polybutylene terephthalate composition, which comprises the following steps:
weighing the raw materials according to the proportion, uniformly mixing all the components, adding the mixture into a double-screw extruder, cooling after extrusion, and granulating.
Further, the components are uniformly mixed according to the weight percentage and then added into a double-screw extruder. The liquid components may also be added to the twin screw extruder using liquid metering equipment, preferably where there is an opening between the first zone and the fifth zone of the twin screw extruder, without affecting the mixing, dispersion of the components and the synergistic effect of the lubricant and plasticizer. Wherein the temperature of the first zone of the double-screw extruder is 30-200 ℃, the temperature of the second zone is 220-260 ℃, the temperature of the third zone is 220-260 ℃, the temperature of the fourth zone is 200-240 ℃, the temperature of the fifth zone is 200-240 ℃, the temperature of the sixth zone is 200-240 ℃, the temperature of the seventh zone is 200-240 ℃, the temperature of the eighth zone is 200-240 ℃, the temperature of the ninth zone is 200-240 ℃, the temperature of the head is 220-260 ℃, the retention time is 1-3 minutes, the rotating speed of the main machine is 300-500 revolutions per minute, and the double-screw extruder is cooled and granulated after extrusion.
The polybutylene terephthalate composition is applied to electronic, electric and electrical equipment, for example, products with metal inserts in severe temperature alternation places such as cold and hot impact or high and low temperature circulation, particularly plastic, such as motors, pump bodies, electromagnetic valves, copper bar connectors and the like; and can also be applied to products with high welding strength requirements, such as household appliance parts, electrical parts, low-voltage electrical appliance products and the like.
Advantageous effects
The polybutylene terephthalate composition has the characteristics of excellent cold and hot shock resistance, low processing smell, high welding strength, high comprehensive performance and strong processability.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
(1) Source of raw materials
The PBT resin is PBT GX121, has the relative density of 1.31, the intrinsic viscosity of 1.00dl/g and the terminal carboxyl group content of 19mol/t, and is purchased from China petrochemical group asset management Limited company;
the PBT resin is PBT GX121J, has the relative density of 1.31, the intrinsic viscosity of 1.02dl/g and the terminal carboxyl content of 9mol/t, and is purchased from China petrochemical group asset management Co., ltd;
PCTG resin with model number of PCTG DN011 and density of 1.23g/cm 3 Purchased from eastman chemical limited, usa;
a fluorine processing aid, model FX-5920A, purchased from 3M china ltd;
fluoro Compound 1, polytetrafluoroethylene, model F-5AEX, available from Suwei (Shanghai) Inc.;
fluorine compound 2, hydroxyl terminated fluoropolyester polysiloxane, model IOTA 3375F, available from anshi Ai Yaoda silicone oil ltd;
a plasticizer, trioctyl trimellitate, model TOTM, available from kyxing chemical ltd, shandong;
a plasticizer, tetraoctyl pyromellitate, model TOPM, available from Shanghai Hua Yi Chemicals Co., ltd;
an elastomer, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, model No. AX8900, purchased from arkema china investment ltd;
a reinforcing agent, alkali-free chopped glass fiber, model number ECS11-4.5-534A, purchased from megalite group, inc.;
hydrolysis resistance auxiliaries, carbodiimide, type Stabilizer9000, commercially available from Raschig GmbH.
Antioxidant, namely pentaerythritol tetrakis [ beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], the type of which is antioxidant Y001, purchased from wind and light chemical company Limited in Yingkou city;
lubricant, acrylic polyethylene wax, model A-C540A, available from Honeywell (China) Inc
(2) Test standards and methods
Tensile properties were tested according to ISO 527-2 with a specimen size of 150 x 10 x 4mm and a tensile speed of 10mm/min; the bending performance test was performed according to ISO 178, with a sample size of 80 x 10 x 4mm, a bending speed of 2mm/min and a span of 64mm; notched izod impact strength was performed according to ISO 180 with test specimen size 80 x 10 x 4mm and notch depth 2mm. The melt flow rate test was carried out according to ISO 1133, under test conditions of 250 ℃ 2.16kg; the welding strength was performed according to ISO 527-2, the specimen size was 150 x 10 x 4mm, the sample was filled with glue at both ends, the bond line was located in the middle of the specimen, and the drawing speed was 10mm/min.
Adopt a frequency conversion air conditioner motor rotor as metal insert test article, this rotor test article comprises rotor core, magnetic sheet, polybutylene terephthalate mixture, puts into the mould with rotor core, magnetic sheet in advance, carries out mould injection moulding with polybutylene terephthalate mixture, and polybutylene terephthalate mixture plays fixed and insulating effect. Wherein, rotor core height 40mm, external diameter 60mm, internal diameter 20mm, along its a week evenly distributed 8 slots are used for placing the magnetic sheet, and magnetic sheet thickness 10mm. Rotor core possesses sharp-pointed edges and corners structure, and plastic minimum wall thickness is 0.9mm in the rotor test article. The rotor test articles are only used for the explanation of the cold thermal shock test of the examples and the comparative examples, and are not to be construed as limiting the cold thermal shock test method of the present invention.
The cold and hot impact resistance test is carried out in a cold and hot impact test box, the test box is divided into two boxes, the temperature can be set to be high and low, and the switching time of a test sample between the two boxes is less than 8s. According to the common test conditions in the industry, the rotor test product is placed in a cold and hot impact test box, after staying for 1H at 140 ℃, the temperature is quickly switched to minus 40 ℃ for staying for 1H, then the temperature is quickly switched to 140 ℃, the temperature is switched to 140 ℃ for 1H and minus 40 ℃ for 1H as a cycle, the test is carried out repeatedly until the plastic part of the rotor test product cracks, and the cycle times are recorded. Rotor test articles were inspected every 48H and the number of cycles to crack was recorded as multiples of 24 (24 cycles per 48H test), with more than 600 cycles with no cracks noted as > 600.
The overspeed rotation test uses a rotor test article to run at 23000rpm for 5min, and the rotor appearance after overspeed rotation is judged: the plastic is qualified (PASS) as having no cracks and no metal falling off; the plastic is judged to be unqualified (NG) due to cracks or metal falling.
The odor test was evaluated and rated with reference to the general criteria PV3900, with at least three professional evaluators giving odor scores and odor sensations with self-perception. The evaluation principle is as follows: 1 minute, no odor; 2 points, has smell but does not disturb people; 3 points, has obvious smell but is still not disturbing; 4 points, disturbing smell exists; 5 points, strong disturbing smell exists; 6 points, it is intolerable.
Examples 1 to 9
The preparation method comprises the following steps of weighing raw materials according to the proportion shown in Table 1, uniformly mixing the dried PBT resin and other raw materials in proportion, adding the mixture into a double-screw extruder, adding the liquid plasticizer into a feed opening or an opening between a first zone and a fifth zone of the extruder by using a metering pump, adding the glass fiber into a special feed opening of the double-screw extruder, and processing conditions are as follows: the temperature of the first zone is 60 ℃, the temperature of the second zone is 250 ℃, the temperature of the third zone is 250 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 230 ℃, the temperature of the sixth zone is 230 ℃, the temperature of the seventh zone is 230 ℃, the temperature of the eighth zone is 230 ℃, the temperature of the ninth zone is 230 ℃, the temperature of a machine head is 240 ℃, the retention time is 2 minutes, the rotating speed of a main machine is 400 revolutions per minute, and the extruded materials are cooled and granulated. And (3) putting the prepared granules into a blast oven, drying for 4 hours at the temperature of 120-140 ℃, and preparing the dried granules into a mechanical sample strip by using an injection molding machine. The injection molding temperature is 50-70 ℃.
Comparative examples 1 to 7
The raw materials are weighed according to the mixture ratio in the table 2, and then the dried PBT resin and other raw materials are uniformly mixed according to the proportion for preparation, and the specific preparation process is the same as the above example.
Table 1 formulations and material testing results for examples 1-9
TABLE 2 formulations and material testing results for comparative examples 1-7
As can be seen from Table 1, the polybutylene terephthalate mixtures of examples 1 to 9 have excellent cold and hot impact resistance, high levels of tensile strength, notched Izod impact strength, flexural modulus, and weld strength, excellent overall properties, low odor level during processing, and high processability. Example 4 using a PBT resin having a carboxyl end group content of 19mol/t had a slightly poorer thermal shock effect than the PBT resin of example 9 having a carboxyl end group content of < 15mol/t.
As can be seen from comparative examples 1-2, when the fluorine processing aid and the plasticizer were not added simultaneously, the impact properties and the cold-heat impact effects of the resulting products were poor. Example 5 demonstrates a synergistic effect with comparative examples 1 and 2, where the simultaneous addition of a fluorine processing aid and a plasticizer exhibits significantly improved impact, cold and hot impact properties and significantly improved process odor ratings. From comparative examples 3 to 4, it is understood that the addition of other fluorine compounds (e.g., polytetrafluoroethylene, hydroxyl-terminated fluorine-containing polyester polysiloxane) does not improve the cold and hot impact properties and reduce the odor grade during processing. Comparative examples 4 and 6 resulted in unacceptable pungent odor during the manufacturing process due to the introduction of hydroxyl terminated fluoro polyester polysiloxane or carbodiimide. Comparative examples 5 to 6 significantly improved the toughness of the material due to the introduction of the elastomer, but greatly reduced the rigidity, flow properties and weld strength of the material, and reduced the injection processability. Comparative example 7 has lower weld strength without adding PCTG, and example 5 has significantly improved weld strength with adding PCTG, which proves that PCTG can improve weld strength of polybutylene terephthalate composition.
Claims (9)
1. The polybutylene terephthalate composition is characterized by comprising the following raw material components in percentage by mass:
28-82wt% of PBT resin,
5 to 20 percent of PCTG resin,
1.0-6.0wt% of fluorine processing aid,
2.0 to 6.0 weight percent of plasticizer,
10-40wt% of reinforcing agent; wherein the PBT resin has a relative density of 1.30-1.35 and a carboxyl end group content of less than or equal to 30mol/t; the fluorine processing aid is one or more of FX-5911, FX-5920A, FX-5912, FX-5920B, FX-5924 and FX-5922.
2. The composition of claim 1, wherein the PCTG resin is an amorphous copolyester condensed from PTA, ethylene glycol EG, and 1, 4-cyclohexanedimethanol CHDM.
3. The composition of claim 1, wherein the PBT resin has a carboxyl end group content of less than or equal to 25mol/t.
4. The composition of claim 2, wherein the mass of CHDM in the PCTG is greater than 50% of the total mass of the PCTG.
5. The composition of claim 1, wherein the plasticizer is one or more of a meta-benzene plasticizer, an epoxy plasticizer, a fatty acid ester plasticizer, a para-benzene plasticizer, a pyromellitic plasticizer and a polyester plasticizer; the reinforcing agent is a fibrous filler.
6. The composition according to claim 5, wherein the fibrous filler is one or more of glass fiber, carbon fiber, potassium titanate fiber, silica/alumina fiber, zirconia fiber, silica fiber, boron nitride fiber, silicon nitride fiber, aluminum borate fiber, metal fiber, and organic fiber.
7. The composition of claim 1, further comprising a processing aid.
8. A method of making a polybutylene terephthalate composition, comprising:
weighing the raw materials according to the proportion of claim 1, uniformly mixing the components, adding the mixture into a double-screw extruder, cooling after extrusion, and granulating.
9. Use of the polybutylene terephthalate composition of claim 1 in electrical and electronic equipment.
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| CN114539732B (en) * | 2022-02-21 | 2023-08-11 | 江苏金发科技新材料有限公司 | Polybutylene terephthalate composition and application thereof |
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