CN108034215B - High-low temperature alternating-resistant modified polyester alloy material and preparation method thereof - Google Patents
High-low temperature alternating-resistant modified polyester alloy material and preparation method thereof Download PDFInfo
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- CN108034215B CN108034215B CN201711460722.5A CN201711460722A CN108034215B CN 108034215 B CN108034215 B CN 108034215B CN 201711460722 A CN201711460722 A CN 201711460722A CN 108034215 B CN108034215 B CN 108034215B
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- 239000000956 alloy Substances 0.000 title claims abstract description 46
- 229920000728 polyester Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003365 glass fiber Substances 0.000 claims abstract description 32
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 28
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 25
- 239000004417 polycarbonate Substances 0.000 claims abstract description 25
- -1 polybutylene terephthalate Polymers 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000012764 mineral filler Substances 0.000 claims abstract description 9
- 239000012745 toughening agent Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 23
- 150000002148 esters Chemical group 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
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- 238000001035 drying Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229920001744 Polyaldehyde Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 3
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 2
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 235000019820 disodium diphosphate Nutrition 0.000 claims description 2
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 125000004185 ester group Chemical group 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 14
- 229920006778 PC/PBT Polymers 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 10
- 239000008187 granular material Substances 0.000 description 9
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 5
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- 229920006351 engineering plastic Polymers 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 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 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle 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
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention discloses a high and low temperature alternating resistant modified polyester alloy material and a preparation method thereof, wherein the modified polyester alloy material comprises the following materials in parts by weight: 20-60 parts of polycarbonate, 20-60 parts of polybutylene terephthalate, 10-50 parts of glass fiber, 5-20 parts of toughening agent, 0.5-5 parts of nano mineral filler, 0.1-3 parts of ester exchange inhibitor, 0.5-5 parts of reactive monomer, 0.2-2 parts of antioxidant and 0.2-2 parts of lubricant. The modified polyester alloy material obtained by the invention has the characteristics of good high and low temperature alternating property resistance and stable mechanical property, and can be used for automobile interior and exterior decorative structural members, precise-sized electronic parts and the like.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to a high-temperature and low-temperature alternating-resistant modified polyester alloy material and a preparation method thereof.
Background
Polycarbonate (PC) belongs to a typical amorphous and non-crystalline polymer material, has the advantages of good high and low temperature resistance, good toughness and low shrinkage, but also has the defect of poor molding processability; polybutylene terephthalate (PBT) belongs to a typical crystalline polymer material, has the advantage of good molding processability, but also has the disadvantages of poor high-temperature resistance effect, poor notch toughness, large shrinkage and the like; the front and back polyester materials are subjected to different types of blending modification by adding glass fibers, ester exchange inhibitors, toughening agents and the like, so that a general-purpose engineering plastic alloy with relatively excellent comprehensive performance and good temperature resistance, toughness and processability can be prepared, and the general-purpose engineering plastic alloy is mainly used for overcoming the defects of PC/ABS alloy materials in certain applications.
The patent document with the application number of CN201410266869.0 at present introduces a halogen-free flame-retardant glass fiber reinforced PC/PBT alloy material and a preparation method thereof, wherein the halogen-free glass fiber flame-retardant PC/PBT alloy material is prepared by PC and PBT in a double-screw extruder through blending modification and is used for appearance parts such as liquid crystal inner frames, television modules and the like; the patent document with the application number of CN201410172491.8 introduces a glass fiber reinforced PBT/PC alloy material and a preparation method thereof, and the glass fiber reinforced alloy material prepared by PCT and PBT in a double-screw extruder has better comprehensive performance and wider application range than non-reinforced materials; the patent document with the application number of CN104530681A introduces a high-performance and uvioresistant PC/PBT composite material and a preparation method thereof, the performance stability of the composite material is ensured by adding an ester exchange inhibitor, the binding force among all components of the composite material is improved by adding a compatilizer and a flexibilizer so as to improve the toughness and other mechanical properties of the composite material, and the uvioresistant property of the composite material is met by adding a light stabilizer; the patent document with the application number of CN201310306825.1 introduces the preparation method of toughened PC/PBT alloy engineering plastics and plastic products, and a thermoplastic polyester alloy nano composite material is obtained by PC, PBT and nano particles through a double-screw extruder.
The invention patents above mainly adopt various additives to improve the strength, toughness, flame retardance and weather resistance of the prepared PC/PBT alloy material, but because the transesterification reaction between PC and PBT is an unstable state process which is difficult to control, especially the unstable state reaction is further aggravated by high and low temperature alternation, the transesterification reaction between PC and PBT is aggravated if the material is subjected to high and low temperature transformation during the use process, and the material performance fluctuation is caused, thereby the strength, toughness, flame retardance and weather resistance of the material are all worsened.
Disclosure of Invention
The invention provides a high and low temperature alternating resistant modified polyester alloy material and a preparation method thereof, and aims to solve the problem that the performance of a PC/PBT alloy material is influenced by the fact that the ester exchange reaction between PC and PBT is easily aggravated after the existing PC/PBT alloy material is subjected to high and low temperature alternating.
In order to solve the technical problems, the technical scheme adopted by the invention is summarized as follows:
the high and low temperature alternating resistant modified polyester alloy material comprises the following components in parts by weight: 20-60 parts of Polycarbonate (PC); 20-60 parts of polybutylene terephthalate (PBT); 10-50 parts of glass fiber; 5-20 parts of a toughening agent; 0.5-5 parts of nano mineral filler; 0.1-3 parts of ester exchange inhibitor; 0.5-5 parts of reactive monomer; 0.2-2 parts of antioxidant; 0.2-2 parts of a lubricant.
Further, the reactive monomer is one or more of difunctional, trifunctional or multifunctional polyaldehyde, polyalcohol, polycarboxylic acid or polyester and the like.
Further, the transesterification inhibitor is any one of sodium dihydrogen phosphate, disodium hydrogen phosphate, disodium dihydrogen pyrophosphate, triphenyl phosphate, triphenyl phosphite, and the like.
Further, the polycarbonate has a melt index of 10 to 22g/10min (test conditions 300 ℃,1.2 kg); the polybutylene terephthalate has an intrinsic viscosity of 0.7 to 1.2dl/g (test conditions 25 ℃).
Further, the diameter of the glass fiber is 7-15 μm, and the glass fiber is one or both of a continuous glass fiber and a chopped yarn.
Furthermore, the particle size of the nano mineral filler is 0.01-1 um, and the nano mineral filler is one or more of calcium carbonate, talcum powder, barium sulfate, wollastonite and kaolin.
Still further, the toughening agent is one or more of ethylene-methyl acrylate-glycidyl methacrylate random terpolymer (AX8900), ethylene-butyl acrylate-glycidyl methacrylate copolymer (PTW), Acrylate Copolymer (ACR), methyl methacrylate-butadiene-styrene (MBS).
Furthermore, the lubricant is a mixture consisting of one or more of Ethylene Bis Stearamide (EBS), pentaerythritol stearate (PETS), polyethylene wax, oxidized polyethylene wax, silicone powder and silicone master batch, and the antioxidant is one or more of hindered phenol compounds (such as antioxidant tetra [ β - (3, 5-di-tert-butyl-4-hydroxy-phenyl) propionic acid ] pentaerythritol ester (1010), β - (3, 5-di-tert-butyl-4-hydroxy-phenyl) propionic acid octadecyl ester (1076)) or phosphite compounds (such as antioxidant tri (nonylphenyl) phosphite (TNPP), tri (2, 4-di-tert-butylphenyl) phosphite (168) and tetra (2, 4-di-tert-butylphenyl-4, 4' -biphenyl) bisphosphonate (P-EPQ)).
The preparation method of the high and low temperature alternating resistant modified polyester alloy material comprises the following steps:
(1) weighing raw materials according to the weight ratio, and uniformly mixing the weighed polycarbonate, polybutylene terephthalate, toughening agent, nano mineral filler, ester exchange inhibitor, reactive monomer, antioxidant and lubricant in a high-speed mixer, wherein the mixing temperature is 20-50 ℃, the mixing time is 2-4min, and the rotating speed is 600-plus-material 1000 rpm/min;
the inventor summarizes experience in practice and finds that the control of the mixing temperature of the materials in a reasonable range is beneficial to keeping the original form of each component and avoiding local bonding or caking affecting the uniformity of the materials in a high-speed mixer; meanwhile, the rotating speed of the high-speed mixer is increased, so that the raw material components can be mixed more fully, and the effect of uniform texture is achieved. For some auxiliary agents, too low a rotational speed does not facilitate uniform mixing, while too high a rotational speed tends to result in cracking of the structure itself. The rotation speed of the high-speed mixer is preferred by the inventor according to the physical properties of the raw material components, and within the range, the components of the raw material can be uniformly mixed, and the raw material can be effectively prevented from cracking and losing effectiveness.
(2) Melting and mixing the uniformly mixed material in the step (1) on a double-screw extruder, and adding continuous glass fiber from a long glass fiber feed opening or adding chopped yarn from a side feed opening for melting and mixing, wherein the first-stage temperature of the extruder is 200-260 ℃, the second-stage temperature is 230-250 ℃, the third-stage temperature is 240-260 ℃, the fourth-stage temperature is 240-260 ℃, the fifth-stage temperature is 240-260 ℃, the head temperature is 230-250 ℃, and the host frequency is 25-40 Hz;
the smelting temperature of the invention is selected according to the properties of various raw materials, and in the temperature range, various raw materials can be completely melted and fully mixed, and the appearance of the final product cannot be influenced by cracking or color change caused by overhigh temperature. The raw materials can be fully mixed and melted to obtain the high-quality performance required by the invention under the synergistic action.
(3) And (3) extruding, drawing, cooling, granulating and drying the material further mixed in the extruder in the step (2) to obtain the high and low temperature alternating resistant modified polyester alloy material, wherein the rotating speed of the granulator is 600-.
The inventor of the invention finds in practice and research that too high rotating speed of the granulator can lead to small volume of the granules and easy breakage in the subsequent strand pulling process, and too low rotating speed of the granulator can lead to large granules, thus affecting the appearance of the final granules and increasing the processing difficulty in the application of the granules. The granules of each component have the proper granule size, and for the invention, the rotating speed of the granulator of 600-.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. in a PC and PBT resin blending system, by adding bifunctional, trifunctional or polyfunctional polyaldehyde, polyalcohol, polycarboxylic acid or polyester and other reactive monomers, the two monomers and an ester exchange inhibitor can be matched with each other in a synergistic manner, so that the inhibition effect on the ester exchange reaction between PC and PBT is further enhanced, and the influence of high-temperature and low-temperature alternation on the ester exchange reaction between PC and PBT is reduced;
2. by adding the glass fiber, the toughening agent and the nano mineral filler, the temperature resistance and the stability of the PC/PBT alloy material are improved, so that the temperature resistance and the stability of the PC/PBT alloy material are greatly improved compared with those of a common PC/PBT alloy material;
3. the modified polyester alloy material provided by the invention has the characteristics of good temperature change resistance (100 ℃, 0.5h → -40 ℃, 0.5h, one cycle per 1 hour, and total 1000h), and stable mechanical properties, and can be used for automobile interior and exterior decorative structural members, precise-sized electronic parts and the like.
4. The preparation method provided by the invention is obtained by optimizing the process parameters such as the rotating speed of a high-speed mixer, the melting temperature, the rotating speed of a granulator and the like according to the characteristics of the raw material components, and the prepared high-low temperature alternating-resistant PC/PBT alloy material product can realize the technical effect sought by the invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. Embodiments of the present invention include, but are not limited to, the following examples.
Example 1
30 parts of PC, 20 parts of PBT, 8 parts of AX8900, 0.1 part of 1010, 0.1 part of 168, 0.1 part of sodium dihydrogen pyrophosphate, 0.5 part of adipic acid, 0.5 part of EBS and 5 parts of talcum powder are put into a high-speed mixer to be mixed for 3min, the mixing temperature is 30 ℃, and the rotating speed is 800 rpm/min; after being uniformly mixed, the mixture is extruded and granulated by a double-screw extruder, continuous glass fiber is added from a glass fiber charging port, the weight parts of the continuous glass fiber are controlled to be 50 parts, and the temperatures of one section to five sections of the double-screw extruder are respectively as follows: 220 ℃, 250 ℃, 260 ℃, 240 ℃, 250 ℃ of head temperature, 40Hz of rotating speed and 800r/min of rotating speed of a granulator.
Wherein the melt index of PC is 10-22g/10min (test condition 300 ℃,1.2 kg); the intrinsic viscosity of the PBT is 0.7-1.2dl/g (test condition 25 ℃), which is the more preferable raw material property determined by the inventor through a plurality of experiments, so that the prepared product has more excellent high-temperature and low-temperature cross-denaturation resistance.
Drying the modified polyester granular material in an oven at 100-140 ℃ for 4-6h, and performing injection molding by using an injection molding machine to obtain a standard performance sample strip for performance test. Wherein, the adopted conditions of the embodiment are drying at 120 ℃ for 4h, and the injection molding temperature is 230-260 ℃.
Example 2
30 parts of PC, 25 parts of PBT, 0.5 part of AX8900, 0.5 part of 1010, 1 part of 168, 1 part of sodium dihydrogen pyrophosphate, 1 part of disodium hydrogen phosphate, 1 part of triphenyl phosphate, 0.5 part of adipic acid, 0.5 part of polyethylene wax and 3 parts of talcum powder are put into a high-speed mixer to be mixed for 3min, the mixing temperature is 30 ℃, and the rotating speed is 800 rpm/min; after being uniformly mixed, the mixture is extruded and granulated by a double-screw extruder, continuous glass fiber is added from a glass fiber feeding port, and the weight part of the continuous glass fiber is controlled to be 37 parts; the temperatures of the first section to the fifth section of the double-screw extruder are respectively as follows: 200 ℃, 240 ℃, 255 ℃, 245 ℃, 240 ℃, 230 ℃ of head temperature, 35Hz of rotating speed and 800r/min of rotating speed of a granulator.
The extruded granules were dried at 120 ℃ for 4 hours. The dried polyester alloy particles were injection molded by an injection molding machine to perform the test at an injection molding temperature of 220 ℃ and 260 ℃.
Example 3
Putting 25 parts of PC, 24 parts of PBT, 10 parts of AX8900, 1 part of 1010, 1 part of 168, 0.5 part of triphenyl phosphite, 1 part of adipic acid, 0.5 part of polyethylene wax and 3 parts of talcum powder into a high-speed mixer to mix for 4min, wherein the mixing temperature is 20 ℃, and the rotating speed is 1000 rpm/min; after uniformly mixing, extruding and granulating by using a double-screw extruder, adding chopped yarns from a side feeding port, and controlling the weight parts of the chopped yarns to be 35 parts; the temperatures of the first section to the fifth section of the double-screw extruder are respectively as follows: 220 ℃, 250 ℃, 260 ℃, 250 ℃, 240 ℃, 230 ℃ of head temperature, 35Hz of rotating speed and 600r/min of rotating speed of the granulator.
The extruded granules were dried at 100 ℃ for 4 h. The dried polyester alloy particles were injection molded by an injection molding machine to perform the test at an injection molding temperature of 220 ℃ and 260 ℃.
Example 4
Putting 20 parts of PC, 38 parts of PBT, 5 parts of AX8900, 5 parts of PTW, 10 parts of MBS, 0.8 part of 1010, 0.5 part of triphenyl phosphite, 0.1 part of PETS and 1 part of kaolin into a high-speed mixer to mix for 2min, wherein the mixing temperature is 50 ℃ and the rotating speed is 1000 rpm/min; after being uniformly mixed, the mixture is extruded and granulated by a double-screw extruder, continuous glass fiber is added from a glass fiber charging port, and the weight part of the continuous glass fiber is controlled to be 32 parts; the temperatures of the first section to the fifth section of the double-screw extruder are respectively as follows: 220 ℃, 260 ℃, 250 ℃, 240 ℃ and 230 ℃ of the head temperature; the rotating speed is 35Hz, and the rotating speed of the granulator is 1000 r/min.
The extruded particles were dried at 100 ℃ for 6h, and the dried polyester alloy particles were injection molded by an injection molding machine for testing at an injection temperature of 220 ℃ and 260 ℃.
Example 5
Placing 22 parts of PC, 60 parts of PBT, 4 parts of AX8900, 0.4 part of 1010, 0.2 part of 168, 1 part of triphenyl phosphite, 4 parts of adipic acid, 1 part of adipic dialdehyde, 1 part of oxidized polyethylene wax and 1 part of calcium carbonate into a high-speed mixer to mix for 3min, wherein the mixing temperature is 40 ℃, and the rotating speed is 600 rpm/min; after uniformly mixing, extruding and granulating by using a double-screw extruder, adding chopped yarns from a side feeding port, and controlling the weight parts of the chopped yarns to be 10 parts; the temperatures of the first section to the fifth section of the double-screw extruder are respectively as follows: 220 ℃, 250 ℃, 260 ℃, 250 ℃, 240 ℃, the head temperature is 240 ℃, the rotating speed is 35Hz, and the rotating speed of the granulator is 900 r/min.
The extruded particles were dried at 140 ℃ for 4h, and the dried polyester alloy particles were injection molded by an injection molding machine for testing at an injection temperature of 220 ℃ and 260 ℃.
Example 6
Putting 60 parts of PC, 28 parts of PBT, 2 parts of AX8900, 1 part of 1010, 1 part of 168, 0.5 part of sodium dihydrogen pyrophosphate, 1.25 parts of adipic acid, 1 part of EBS and 0.5 part of talcum powder into a high-speed mixer, and mixing for 4min at the mixing temperature of 40 ℃ and the rotating speed of 700 rpm/min; after being uniformly mixed, the mixture is extruded and granulated by a double-screw extruder, continuous glass fiber is added from a glass fiber charging port, and the weight part of the continuous glass fiber is controlled to be 30 parts; the temperatures of the first section to the fifth section of the double-screw extruder are respectively as follows: 210 ℃, 230 ℃, 240 ℃, 260 ℃, 240 ℃, 230 ℃ of head temperature, 25Hz of rotating speed and 1000r/min of rotating speed of the granulator.
Wherein the melt index of PC is 10-22g/10min (test condition 300 ℃,1.2 kg); the PBT has an intrinsic viscosity of 0.7 to 1.2dl/g (test conditions 25 ℃).
The extruded particles were dried at 110 ℃ for 6h, and the dried polyester alloy particles were injection molded by an injection molding machine for testing at an injection temperature of 220 ℃ and 260 ℃.
The tensile strength, flexural strength, impact strength, and strength and toughness retention after 1000h high and low temperature alternation (100 ℃, 0.5h → -40 ℃, 0.5h) test of the high and low temperature alternation resistant modified polyester alloys obtained in examples 1 to 6 were measured, and the results are shown in table 1 below:
TABLE 1 Properties of ordinary PC/PBT alloy and high and Low temperature resistant modified polyester alloys obtained in examples 1 to 6
As can be seen from Table 1, the high and low temperature alternation resistant modified polyester alloy prepared by selecting different types and amounts of reactive monomers, ester exchange inhibitors, glass fibers, minerals and toughening agents according to different polyester proportions has the strength and toughness retention rate after high and low temperature alternation which is obviously higher than that of the common PC/PBT alloy material.
The preparation method of the high-temperature and low-temperature resistant alternating modified polyester alloy, which is disclosed by the invention, adopts a double-screw extrusion process for preparation, and has the advantages of simple and continuous flow, high production efficiency and stable product quality; the composite material is more suitable for general structural parts or other parts with high and low temperature resistance and high dimensional stability requirements.
The above description is an embodiment of the present invention. The present invention is not limited to the above embodiments, and any structural changes made under the teaching of the present invention shall fall within the protection scope of the present invention, which is similar or similar to the technical solutions of the present invention.
Claims (7)
1. The high and low temperature alternating resistant modified polyester alloy material is characterized by comprising the following components in parts by weight: 20-60 parts of polycarbonate; 20-60 parts of polybutylene terephthalate; 10-50 parts of glass fiber; 5-20 parts of a toughening agent; 0.5-5 parts of nano mineral filler; 0.1-3 parts of ester exchange inhibitor; 0.5-5 parts of reactive monomer; 0.2-2 parts of antioxidant; 0.2-2 parts of a lubricant; the reactive monomer is one or more of polyaldehyde, polyalcohol, polycarboxylic acid or polyester;
the preparation method comprises the following steps:
(1) weighing raw materials according to the weight ratio, and uniformly mixing the weighed polycarbonate, polybutylene terephthalate, flexibilizer, nano mineral filler, ester exchange inhibitor, reactive monomer, antioxidant and lubricant in a high-speed mixer, wherein the mixing temperature is 20-50 ℃;
(2) melting and mixing the uniformly mixed material in the step (1) on a double-screw extruder, and adding continuous glass fiber from a long glass fiber feed opening or adding chopped yarn from a side feed opening for melting and mixing, wherein the first-stage temperature of the extruder is 200-260 ℃, the second-stage temperature is 230-250 ℃, the third-stage temperature is 240-260 ℃, the fourth-stage temperature is 240-260 ℃, the fifth-stage temperature is 240-260 ℃, the head temperature is 230-250 ℃, and the host frequency is 25-40 Hz;
(3) and (3) extruding, drawing, cooling, granulating and drying the material further mixed in the extruder in the step (2) to obtain the high and low temperature alternating resistant modified polyester alloy material, wherein the rotating speed of the granulator is 600-.
2. The high and low temperature alternation resistant modified polyester alloy material as claimed in claim 1, wherein the ester exchange inhibitor is any one of sodium dihydrogen phosphate, disodium hydrogen phosphate, disodium dihydrogen pyrophosphate, triphenyl phosphate, triphenyl phosphite, etc.
3. The high and low temperature alternation resistant modified polyester alloy material as claimed in claim 1, wherein the melt index of the polycarbonate is 10-22g/10 min; the intrinsic viscosity of the polybutylene terephthalate is 0.7-1.2 dl/g.
4. The high and low temperature alternation resistant modified polyester alloy material as claimed in claim 1, wherein the diameter of the glass fiber is 7-15 μm, and the glass fiber is one or both of continuous glass fiber and chopped yarn.
5. The high and low temperature alternation resistant modified polyester alloy material as claimed in claim 1, wherein the nano mineral filler has a particle size of 0.01um-1um, and is one or more of calcium carbonate, talc, barium sulfate, wollastonite and kaolin.
6. The high and low temperature alternation resistant modified polyester alloy material as claimed in claim 1, wherein the toughening agent is one or more of ethylene-methyl acrylate-glycidyl methacrylate random terpolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, acrylate copolymer, and methyl methacrylate-butadiene-styrene.
7. The high and low temperature alternation resistant modified polyester alloy material as claimed in claim 1, wherein the lubricant is a mixture of one or more of ethylene bis stearamide, pentaerythritol stearate, polyethylene wax, oxidized polyethylene wax, silicone powder and silicone master batch; the antioxidant is one or more of hindered phenol compounds or phosphite ester compounds.
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| CN110183835A (en) * | 2019-04-30 | 2019-08-30 | 南通开普乐工程塑料有限公司 | A kind of high pressure resistant high temperature resistant PC/PBT and preparation method thereof |
| CN110093018A (en) * | 2019-05-20 | 2019-08-06 | 福建师范大学 | It is a kind of to utilize the polyester alloy and preparation method thereof for recycling blended textile fabric preparation |
| CN111548613A (en) * | 2020-06-17 | 2020-08-18 | 湖北合聚高分子材料有限公司 | High-strength flame-retardant aging-resistant PBT/PC alloy resin material and preparation method thereof |
| CN111995856A (en) * | 2020-07-16 | 2020-11-27 | 天津金发新材料有限公司 | PC composition |
| CN112480613B (en) * | 2020-11-30 | 2021-11-30 | 金发科技股份有限公司 | Damping halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof |
| CN112795164B (en) * | 2021-01-14 | 2023-01-13 | 万华化学(四川)有限公司 | PC/PBA alloy material and preparation method thereof |
| CN112812522B (en) * | 2021-02-07 | 2022-04-22 | 深圳鑫富艺科技股份有限公司 | Internal explosion-proof membrane material and preparation process thereof |
| CN115651372A (en) * | 2022-10-12 | 2023-01-31 | 河南天海合聚新材料有限公司 | High-weather-resistance material for air inlet grille, preparation method and air inlet grille |
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