CN113429758A - Hydrolysis-resistant and anti-aging PET modified material and preparation method thereof - Google Patents
Hydrolysis-resistant and anti-aging PET modified material and preparation method thereof Download PDFInfo
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- CN113429758A CN113429758A CN202110787198.2A CN202110787198A CN113429758A CN 113429758 A CN113429758 A CN 113429758A CN 202110787198 A CN202110787198 A CN 202110787198A CN 113429758 A CN113429758 A CN 113429758A
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- 239000000463 material Substances 0.000 title claims abstract description 92
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 67
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 67
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000011347 resin Substances 0.000 claims abstract description 77
- 229920005989 resin Polymers 0.000 claims abstract description 77
- 239000003365 glass fiber Substances 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000011521 glass Substances 0.000 claims abstract description 33
- 239000011324 bead Substances 0.000 claims abstract description 31
- 238000011049 filling Methods 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000032683 aging Effects 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 18
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 59
- 239000000203 mixture Substances 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 25
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 24
- 239000012745 toughening agent Substances 0.000 claims description 21
- 239000003963 antioxidant agent Substances 0.000 claims description 19
- 230000003078 antioxidant effect Effects 0.000 claims description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 14
- 239000005995 Aluminium silicate Substances 0.000 claims description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims description 12
- 229960000892 attapulgite Drugs 0.000 claims description 12
- 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 12
- 229910052625 palygorskite Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 238000007664 blowing Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 9
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 7
- POYODSZSSBWJPD-UHFFFAOYSA-N 2-methylprop-2-enoyloxy 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOOC(=O)C(C)=C POYODSZSSBWJPD-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
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- 238000000034 method Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 claims 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
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- 229920001155 polypropylene Polymers 0.000 claims 1
- 229920001634 Copolyester Polymers 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 3
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 90
- 239000005020 polyethylene terephthalate Substances 0.000 description 90
- 239000003112 inhibitor Substances 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- JKBYAWVSVVSRIX-UHFFFAOYSA-N octadecyl 2-(1-octadecoxy-1-oxopropan-2-yl)sulfanylpropanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)C(C)SC(C)C(=O)OCCCCCCCCCCCCCCCCCC JKBYAWVSVVSRIX-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 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
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- 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)
Abstract
The invention discloses a hydrolysis-resistant and anti-aging PET modified material, and particularly relates to the technical field of PET materials, which comprises the following raw materials: modified PET resin, filling resin, acrylic acid, modified glass fiber, glass beads, a hydrolysis resistant agent, nano boron nitride and an auxiliary agent. According to the invention, the modified PET resin is used as a base material, and the filling resin, the modified glass fiber, the glass beads and the auxiliary agent are added, so that the mechanical property of the PET modified material is good, the ageing resistance of the PET modified material is obviously improved under the action of the nano titanium dioxide and the nano silicon dioxide, the glass beads can promote the microfibrillation of the liquid crystal copolyester in the PET material, the mechanical property of the PET modified material is improved, the heat resistance and hydrolysis resistance of the PET modified material can be effectively improved by adding the hydrolysis resistance agent, the terminal carboxyl content in the PET material can be effectively reduced by adding the nano boron nitride, the water resistance of the PET material is better, and the mechanical property of the PET material is improved.
Description
Technical Field
The invention relates to the technical field of PET materials, in particular to a hydrolysis-resistant anti-aging PET modified material and a preparation method thereof.
Background
The PET (polyethylene terephthalate) resin is the least expensive of five common engineering plastic matrix resins, the price of the modified PET resin is only 50% of that of the PA6 resin, and the price of the PET slice is only 40% of that of the PA66 resin. Today, the selection of materials with high cost performance is very critical when the price of raw materials rises. Many large synthesis plants in China are industrialized, and the PA6 and PA66 slices are rarely produced in the factories in China. However, the modified PET resin which is not modified has the defects of slow crystallization speed, long molding period, poor toughness, low heat resistance, easy warping when heated and fiber floating on the surface of a workpiece at low molding temperature, and the defects seriously influence the industrial use of the modified PET resin.
PET is poly terephthalic acid plastic, and the modified PET resin has high glass transition temperature, low crystallization speed, long molding period, large molding shrinkage, poor dimensional stability, brittle crystallized molding, low heat resistance and the like. PET is the highest of thermoplastic general purpose engineering plastics in heat distortion temperature and long-term use temperature through improvement of nucleating agent and crystallizing agent and glass fiber reinforcement; therefore, the PET alloy is more and more widely applied to automobile parts, and simultaneously, in order to improve the performance of PET, the PET can form an alloy with PC, ABS and PA, so that the performance of the alloy is more variable, and the requirements of different performances are met.
When the existing PET modified material is applied to the automobile industry, the anti-aging effect is insufficient, and the hydrolysis resistance is poor due to relatively high ester bond content in PET molecules, so that the mechanical property of the PET material is reduced.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides a hydrolysis-resistant anti-aging PET modified material and a preparation method thereof, and the invention aims to solve the following problems: how to improve the aging resistance and the hydrolysis resistance of the PET material.
In order to achieve the purpose, the invention provides the following technical scheme: a hydrolysis-resistant and anti-aging PET modified material comprises the following raw materials in percentage by weight: 40-48% of modified PET resin, 8-15% of filling resin, 3-5% of acrylic acid, 15-20% of modified glass fiber, 15-20% of glass bead, 0.1-0.6% of hydrolysis resistance agent, 1-3% of nano boron nitride and 2-5% of auxiliary agent.
In a preferred embodiment, the composition comprises the following raw materials in percentage by weight: 42-46% of modified PET resin, 10-13% of filling resin, 3-4% of acrylic acid, 17-18% of modified glass fiber, 17-18% of glass bead, 0.2-0.4% of hydrolysis resistance agent, 2-3% of nano boron nitride and 3-4% of auxiliary agent.
In a preferred embodiment, the composition comprises the following raw materials in percentage by weight: 44% of modified PET resin, 11% of filling resin, 4% of acrylic acid, 17.5% of modified glass fiber, 17.5% of glass bead, 0.3% of hydrolysis resistance agent, 2.2% of nano boron nitride and 3.5% of auxiliary agent.
In a preferred embodiment, the filling resin is one or more of PC, PA or epoxy methacrylate resin, the glass beads are hollow glass beads, the auxiliary agent comprises a toughening agent, a compatilizer, an antioxidant and an aging inhibitor, and the weight ratio of the toughening agent, the compatilizer, the antioxidant and the aging inhibitor is 1: (0.7-1): (1.2-1.4) and (0.8-1.2).
In a preferred embodiment, the hydrolysis resistant agent is polycarbodiimide, the toughening agent is a graft copolymer of ethylene polyolefin and acrylate monomers, the compatilizer is PP-g-MA with a grafting rate of 1-1.5%, the antioxidant is one of antioxidant 1010 or antioxidant 168, and the aging inhibitor is dioctadecyl thiodipropionate.
The invention also provides a preparation method of the hydrolysis-resistant and anti-aging PET modified material, which comprises the following specific preparation steps:
the method comprises the following steps: weighing 20 parts of styrene butadiene rubber grafted with maleic anhydride, placing the styrene butadiene rubber in a reaction container, adding 80 parts of PET resin into the reaction container, then adding 5 parts of vinylidene fluoride and 5 parts of tetrafluoroethylene, stirring, adding the mixture into a double-screw extruder after uniform stirring, extruding and granulating to obtain modified PET resin, weighing the raw materials according to the weight percentage, introducing the weighed modified PET resin, filling resin, acrylic acid and nano boron nitride into a mixing container, and uniformly stirring and mixing to obtain premix A for later use;
step two: uniformly stirring and mixing the weighed toughening agent, compatilizer, antioxidant, anti-aging agent and hydrolysis resistance agent, slowly adding the mixture into the premix A, stirring and adding the mixture in a spiral stirring manner, and uniformly mixing to obtain a premix B;
step three: weighing glass fiber with the diameter of 1-2um, mixing the glass fiber with the modified material, stirring for 20-40 minutes at normal temperature, heating and melting the mixture in a double-screw extruder, and extruding and granulating the mixture to obtain modified glass fiber for later use;
step four: introducing the premix B into a double-screw extruder, injecting the modified glass fiber obtained in the step three into the double-screw extruder through a front side feeding bin, and injecting the hollow glass beads into the double-screw extruder through a rear side feeding bin after the injection of the modified glass fiber is finished;
step five: and (3) heating and melting the mixed material, extruding and granulating by using a double-screw extruder, removing water in the material by using a double-blowing device, selecting by using a three-layer vibrating screen, removing powder and drawing, and selecting qualified granules to obtain the hydrolysis-resistant and anti-aging PET modified material.
In a preferred embodiment, the spiral stirring in the second step adopts alternate stirring of horizontal stirring and vertical stirring, the stirring speed is 100-.
In a preferred embodiment, the modifier in the third step comprises nano titanium dioxide, nano silica, nano kaolin, nano attapulgite and a silane coupling agent, wherein the weight ratio of the nano titanium dioxide, the nano silica, the nano kaolin, the nano attapulgite and the silane coupling agent is 1: (1.2-1.4): (1.8-2.4): (1.5-2): (0.2-0.4).
In a preferred embodiment, when the styrene-butadiene rubber is grafted with maleic anhydride in the first step, the styrene-butadiene rubber is plasticated on a low-temperature open mill for 5-10min, then zinc oxide, stearic acid, maleic anhydride, antioxidant 1010 and an accelerator are added, the temperature is increased to 60-70 ℃, the plastication is continued for 10-15min, and the roll gap is adjusted to obtain the styrene-butadiene rubber grafted with maleic anhydride.
In a preferred embodiment, the twin-screw extruder in the fifth step comprises eleven temperature zones arranged in sequence, wherein the temperature of the first zone is 245 ℃, the temperature of the second zone is 255 ℃, the temperature of the third zone and the temperature of the fourth zone are 265 ℃, the temperature of the fifth zone to the eleven zone is 255 ℃, the head temperature of the twin-screw extruder is 265 ℃, and an auxiliary air blowing device is used at the head of the twin-screw extruder to assist in preventing the generation of the derivatives of the die head, and the diameter of the screw of the twin-screw extruder is 44: 1, the rotating speed of the screw extruder is 450-550rpm, and a phi plate is 3.0X15 holes, wherein the modified glass fiber is fed by vibration in the fourth step.
The invention has the technical effects and advantages that:
1. the hydrolysis-resistant and aging-resistant PET modified material prepared by adopting the raw material formula adopts modified PET resin as a base material, is added with filling resin, modified glass fiber, glass beads and an auxiliary agent, is modified by utilizing grafted styrene butadiene rubber, is added with vinylidene fluoride and tetrafluoroethylene, and has better thermal stability and impact strength after modification, the vinylidene fluoride and the tetrafluoroethylene can increase granulation viscosity of the PET resin and the grafted styrene butadiene rubber and improve the limit oxygen index of the PET modified material, and the acrylic acid is utilized to promote the fusion of the modified PET resin, the filling resin and the toughening agent, so that the PET material has better toughness, the modified glass fiber not only ensures that the mechanical property of the PET modified material is good, but also obviously improves the aging resistance of the PET modified material through the action of nano titanium dioxide and nano silicon dioxide, the addition of the nano kaolin and the nano attapulgite can reduce the cost of the PET modified material and improve the stability of the PET material, and the glass beads can promote the microfibrillation of the liquid crystal copolyester in the PET material and improve the mechanical property of the PET modified material;
2. according to the invention, PC, PA or epoxy methacrylate resin is used as filling resin, hydrolysis resistance agent and nano boron nitride are added, resin with good compatibility and strong hydrolysis resistance is combined with PET, so that the hydrolysis resistance of the PET modified material can be effectively improved, the heat resistance and hydrolysis resistance of the PET modified material can be effectively improved by adding the hydrolysis resistance agent, the content of terminal carboxyl groups in the PET material can be effectively reduced by using the nano boron nitride, the water resistance of the PET material is better, and the mechanical property is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides a hydrolysis-resistant and anti-aging PET modified material, which comprises the following raw materials in percentage by weight: 42% of modified PET resin, 14% of filling resin, 4% of acrylic acid, 16% of modified glass fiber, 16% of glass bead, 0.2% of hydrolysis resistance agent, 3% of nano boron nitride and 4.8% of auxiliary agent.
In a preferred embodiment, the filling resin is one or more of PC, PA or epoxy methacrylate resin, the glass beads are hollow glass beads, the auxiliary agent comprises a toughening agent, a compatilizer, an antioxidant and an aging inhibitor, and the weight ratio of the toughening agent, the compatilizer, the antioxidant and the aging inhibitor is 1: 0.9: 1.3 and 1.
In a preferred embodiment, the hydrolysis resistant agent is polycarbodiimide, the toughening agent is a graft copolymer of ethylene polyolefin and acrylate monomers, the compatilizer is PP-g-MA with a grafting rate of 1-1.5%, the antioxidant is one of antioxidant 1010 or antioxidant 168, and the aging inhibitor is dioctadecyl thiodipropionate.
The invention also provides a preparation method of the hydrolysis-resistant and anti-aging PET modified material, which comprises the following specific preparation steps:
the method comprises the following steps: weighing 20 parts of styrene butadiene rubber grafted with maleic anhydride, placing the styrene butadiene rubber in a reaction container, adding 80 parts of PET resin into the reaction container, then adding 5 parts of vinylidene fluoride and 5 parts of tetrafluoroethylene, stirring, adding the mixture into a double-screw extruder after uniform stirring, extruding and granulating to obtain modified PET resin, weighing the raw materials according to the weight percentage, introducing the weighed modified PET resin, filling resin, acrylic acid and nano boron nitride into a mixing container, and uniformly stirring and mixing to obtain premix A for later use;
step two: uniformly stirring and mixing the weighed toughening agent, compatilizer, antioxidant, anti-aging agent and hydrolysis resistance agent, slowly adding the mixture into the premix A, stirring and adding the mixture in a spiral stirring manner, and uniformly mixing to obtain a premix B;
step three: weighing glass fiber with the diameter of 1-2um, mixing the glass fiber with the modified material, stirring the mixture for 30 minutes at normal temperature, putting the mixture into a double-screw extruder after the mixture is completely mixed, heating and melting the mixture, and extruding and granulating the mixture to obtain modified glass fiber for later use;
step four: introducing the premix B into a double-screw extruder, injecting the modified glass fiber obtained in the step three into the double-screw extruder through a front side feeding bin, and injecting the hollow glass beads into the double-screw extruder through a rear side feeding bin after the injection of the modified glass fiber is finished;
step five: and (3) heating and melting the mixed material, extruding and granulating by using a double-screw extruder, removing water in the material by using a double-blowing device, selecting by using a three-layer vibrating screen, removing powder and drawing, and selecting qualified granules to obtain the hydrolysis-resistant and anti-aging PET modified material.
In a preferred embodiment, in the second step, the spiral stirring is performed by alternately stirring transversely and stirring vertically, the stirring speed is 200 rpm, and the stirring mode is changed every 2 minutes.
In a preferred embodiment, the modifier in the third step comprises nano titanium dioxide, nano silica, nano kaolin, nano attapulgite and a silane coupling agent, wherein the weight ratio of the nano titanium dioxide, the nano silica, the nano kaolin, the nano attapulgite and the silane coupling agent is 1: 1.2: 2: 1.8: 0.3.
in a preferred embodiment, when the styrene-butadiene rubber is grafted with maleic anhydride in the first step, the styrene-butadiene rubber is plasticated on a low-temperature open mill for 8min, then zinc oxide, stearic acid, maleic anhydride, an antioxidant 1010 and an accelerator are added, the temperature is increased to 65 ℃, the plastication is continued for 13min, and the roll gap is adjusted to discharge sheets, so that the styrene-butadiene rubber grafted with maleic anhydride is obtained.
In a preferred embodiment, the twin-screw extruder in the fifth step comprises eleven temperature zones arranged in sequence, wherein the temperature of the first zone is 245 ℃, the temperature of the second zone is 255 ℃, the temperature of the third zone and the temperature of the fourth zone are 265 ℃, the temperature of the fifth zone to the eleven zone is 255 ℃, the head temperature of the twin-screw extruder is 265 ℃, and an auxiliary air blowing device is used at the head of the twin-screw extruder to assist in preventing the generation of the derivatives of the die head, and the diameter of the screw of the twin-screw extruder is 44: 1, the rotating speed of a screw of the screw extruder is 500rpm, and phi 3.0X15 holes are reserved in a pinch plate, and vibration blanking is adopted when the modified glass fiber is injected in the step four.
Example 2:
different from the embodiment 1, the hydrolysis-resistant anti-aging PET modified material comprises the following raw materials in percentage by weight: 44% of modified PET resin, 11% of filling resin, 4% of acrylic acid, 17.5% of modified glass fiber, 17.5% of glass bead, 0.3% of hydrolysis resistance agent, 2.2% of nano boron nitride and 3.5% of auxiliary agent.
Example 3:
different from the embodiment 1-2, the hydrolysis-resistant anti-aging PET modified material comprises the following raw materials in percentage by weight: 46% of modified PET resin, 14% of filling resin, 4% of acrylic acid, 15% of modified glass fiber, 15% of glass bead, 0.5% of hydrolysis resistance agent, 2% of nano boron nitride and 3.5% of auxiliary agent.
Example 4:
the invention provides a hydrolysis-resistant and anti-aging PET modified material, which comprises the following raw materials in percentage by weight: 45% of modified PET resin, 14% of filling resin, 4% of acrylic acid, 16% of modified glass fiber, 16% of glass bead, 0.2% of hydrolysis resistance agent and 4.8% of auxiliary agent.
In a preferred embodiment, the filling resin is one or more of PC, PA or epoxy methacrylate resin, the glass beads are hollow glass beads, the auxiliary agent comprises a toughening agent, a compatilizer, an antioxidant and an aging inhibitor, and the weight ratio of the toughening agent, the compatilizer, the antioxidant and the aging inhibitor is 1: 0.9: 1.3 and 1.
In a preferred embodiment, the hydrolysis resistant agent is polycarbodiimide, the toughening agent is a graft copolymer of ethylene polyolefin and acrylate monomers, the compatilizer is PP-g-MA with a grafting rate of 1-1.5%, the antioxidant is one of antioxidant 1010 or antioxidant 168, and the aging inhibitor is dioctadecyl thiodipropionate.
The invention also provides a preparation method of the hydrolysis-resistant and anti-aging PET modified material, which comprises the following specific preparation steps:
the method comprises the following steps: weighing 20 parts of styrene butadiene rubber grafted with maleic anhydride, placing the styrene butadiene rubber in a reaction container, adding 80 parts of PET resin into the reaction container, then adding 5 parts of vinylidene fluoride and 5 parts of tetrafluoroethylene, stirring, adding the mixture into a double-screw extruder after uniform stirring, extruding and granulating to obtain modified PET resin, weighing the raw materials according to the weight percentage, introducing the weighed modified PET resin, filling resin, acrylic acid and nano boron nitride into a mixing container, and uniformly stirring and mixing to obtain premix A for later use;
step two: uniformly stirring and mixing the weighed toughening agent, compatilizer, antioxidant, anti-aging agent and hydrolysis resistance agent, slowly adding the mixture into the premix A, stirring and adding the mixture in a spiral stirring manner, and uniformly mixing to obtain a premix B;
step three: weighing glass fiber with the diameter of 1-2um, mixing the glass fiber with the modified material, stirring the mixture for 30 minutes at normal temperature, putting the mixture into a double-screw extruder after the mixture is completely mixed, heating and melting the mixture, and extruding and granulating the mixture to obtain modified glass fiber for later use;
step four: introducing the premix B into a double-screw extruder, injecting the modified glass fiber obtained in the step three into the double-screw extruder through a front side feeding bin, and injecting the hollow glass beads into the double-screw extruder through a rear side feeding bin after the injection of the modified glass fiber is finished;
step five: and (3) heating and melting the mixed material, extruding and granulating by using a double-screw extruder, removing water in the material by using a double-blowing device, selecting by using a three-layer vibrating screen, removing powder and drawing, and selecting qualified granules to obtain the hydrolysis-resistant and anti-aging PET modified material.
In a preferred embodiment, in the second step, the spiral stirring is performed by alternately stirring transversely and stirring vertically, the stirring speed is 200 rpm, and the stirring mode is changed every 2 minutes.
In a preferred embodiment, the modifier in the third step comprises nano titanium dioxide, nano silica, nano kaolin, nano attapulgite and a silane coupling agent, wherein the weight ratio of the nano titanium dioxide, the nano silica, the nano kaolin, the nano attapulgite and the silane coupling agent is 1: 1.2: 2: 1.8: 0.3.
in a preferred embodiment, when the styrene-butadiene rubber is grafted with maleic anhydride in the first step, the styrene-butadiene rubber is plasticated on a low-temperature open mill for 8min, then zinc oxide, stearic acid, maleic anhydride, an antioxidant 1010 and an accelerator are added, the temperature is increased to 65 ℃, the plastication is continued for 13min, and the roll gap is adjusted to discharge sheets, so that the styrene-butadiene rubber grafted with maleic anhydride is obtained.
In a preferred embodiment, the twin-screw extruder in the fifth step comprises eleven temperature zones arranged in sequence, wherein the temperature of the first zone is 245 ℃, the temperature of the second zone is 255 ℃, the temperature of the third zone and the temperature of the fourth zone are 265 ℃, the temperature of the fifth zone to the eleven zone is 255 ℃, the head temperature of the twin-screw extruder is 265 ℃, and an auxiliary air blowing device is used at the head of the twin-screw extruder to assist in preventing the generation of the derivatives of the die head, and the diameter of the screw of the twin-screw extruder is 44: 1, the rotating speed of a screw of the screw extruder is 500rpm, and phi 3.0X15 holes are reserved in a pinch plate, and vibration blanking is adopted when the modified glass fiber is injected in the step four.
Example 5:
the invention provides a hydrolysis-resistant and anti-aging PET modified material, which comprises the following raw materials in percentage by weight: 45% of PET resin, 14% of filling resin, 4% of acrylic acid, 16% of modified glass fiber, 16% of glass bead, 0.2% of hydrolysis resistance agent and 4.8% of auxiliary agent.
In a preferred embodiment, the filling resin is one or more of PC, PA or epoxy methacrylate resin, the glass beads are hollow glass beads, the auxiliary agent comprises a toughening agent, a compatilizer, an antioxidant and an aging inhibitor, and the weight ratio of the toughening agent, the compatilizer, the antioxidant and the aging inhibitor is 1: 0.9: 1.3 and 1.
In a preferred embodiment, the hydrolysis resistant agent is polycarbodiimide, the toughening agent is a graft copolymer of ethylene polyolefin and acrylate monomers, the compatilizer is PP-g-MA with a grafting rate of 1-1.5%, the antioxidant is one of antioxidant 1010 or antioxidant 168, and the aging inhibitor is dioctadecyl thiodipropionate.
The invention also provides a preparation method of the hydrolysis-resistant and anti-aging PET modified material, which comprises the following specific preparation steps:
the method comprises the following steps: weighing the raw materials according to the weight percentage, introducing the weighed PET resin, filling resin and acrylic acid into a mixing container, and uniformly stirring and mixing to obtain premix A for later use;
step two: uniformly stirring and mixing the weighed toughening agent, compatilizer, antioxidant, anti-aging agent and hydrolysis resistance agent, slowly adding the mixture into the premix A, stirring and adding the mixture in a spiral stirring manner, and uniformly mixing to obtain a premix B;
step three: weighing glass fiber with the diameter of 1-2um, mixing the glass fiber with the modified material, stirring the mixture for 30 minutes at normal temperature, putting the mixture into a double-screw extruder after the mixture is completely mixed, heating and melting the mixture, and extruding and granulating the mixture to obtain modified glass fiber for later use;
step four: introducing the premix B into a double-screw extruder, injecting the modified glass fiber obtained in the step three into the double-screw extruder through a front side feeding bin, and injecting the hollow glass beads into the double-screw extruder through a rear side feeding bin after the injection of the modified glass fiber is finished;
step five: and (3) heating and melting the mixed material, extruding and granulating by using a double-screw extruder, removing water in the material by using a double-blowing device, selecting by using a three-layer vibrating screen, removing powder and drawing, and selecting qualified granules to obtain the hydrolysis-resistant and anti-aging PET modified material.
In a preferred embodiment, in the second step, the spiral stirring is performed by alternately stirring transversely and stirring vertically, the stirring speed is 200 rpm, and the stirring mode is changed every 2 minutes.
In a preferred embodiment, the modifier in the third step comprises nano titanium dioxide, nano silica, nano kaolin, nano attapulgite and a silane coupling agent, wherein the weight ratio of the nano titanium dioxide, the nano silica, the nano kaolin, the nano attapulgite and the silane coupling agent is 1: 1.2: 2: 1.8: 0.3.
in a preferred embodiment, the twin-screw extruder in the fifth step comprises eleven temperature zones arranged in sequence, wherein the temperature of the first zone is 245 ℃, the temperature of the second zone is 255 ℃, the temperature of the third zone and the temperature of the fourth zone are 265 ℃, the temperature of the fifth zone to the eleven zone is 255 ℃, the head temperature of the twin-screw extruder is 265 ℃, and an auxiliary air blowing device is used at the head of the twin-screw extruder to assist in preventing the generation of the derivatives of the die head, and the diameter of the screw of the twin-screw extruder is 44: 1, the rotating speed of a screw of the screw extruder is 500rpm, and phi 3.0X15 holes are reserved in a pinch plate, and vibration blanking is adopted when the modified glass fiber is injected in the step four.
The hydrolysis-resistant and aging-resistant PET modified materials prepared in the above examples 1 to 5 were respectively used as an experimental group 1, an experimental group 2, an experimental group 3, an experimental group 4, and an experimental group 5, and the mechanical properties, the thermal properties, and the hydrolysis resistance of the selected PET materials were respectively tested by using the conventional PET materials as a control group. The test results are shown in table one:
watch 1
As shown in the table I, compared with the traditional PET material, the hydrolysis-resistant and anti-aging PET modified material produced by the invention has higher mechanical property, better thermal deformation temperature and flow rate performance and obviously improved hydrolysis resistance, compared with example 1, example 4 lacks nanometer boron nitride, the hydrolysis resistance of the PET material is obviously reduced compared with example 1, example 5 adopts common PET resin as the raw material, the thermal property is obviously reduced, so that the hydrolysis-resistant and anti-aging PET modified material prepared by adopting the raw material formula of the invention adopts the modified PET resin as the base material, is added with filling resin, modified glass fiber, glass microsphere and auxiliary agent, the modified PET resin is modified by utilizing grafted styrene butadiene rubber, is added with vinylidene fluoride and tetrafluoroethylene, and the thermal stability and impact strength of the PET modified material are better after modification, vinylidene fluoride and tetrafluoroethylene can increase the granulation viscosity of PET resin and grafted styrene-butadiene rubber, the limiting oxygen index of the PET modified material is improved, the fusion of the modified PET resin and the filling resin and the toughening agent is promoted by utilizing acrylic acid, so that the PET material has better toughness, the mechanical property of the PET modified material is good by utilizing the modified glass fiber, the ageing resistance of the PET modified material is obviously improved under the action of nano titanium dioxide and nano silicon dioxide, the cost of the PET modified material can be reduced by adding nano kaolin and nano attapulgite, the stability of the PET material is improved, the glass microspheres can promote the microfibrillation of liquid crystal copolyester in the PET material, and the mechanical property of the PET modified material is improved.
And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. The hydrolysis-resistant and anti-aging PET modified material is characterized in that: comprises the following raw materials in percentage by weight: 40-48% of modified PET resin, 8-15% of filling resin, 3-5% of acrylic acid, 15-20% of modified glass fiber, 15-20% of glass bead, 0.1-0.6% of hydrolysis resistance agent, 1-3% of nano boron nitride and 2-5% of auxiliary agent.
2. The hydrolysis-resistant and aging-resistant PET modified material as claimed in claim 1, characterized in that: comprises the following raw materials in percentage by weight: 42-46% of modified PET resin, 10-13% of filling resin, 3-4% of acrylic acid, 17-18% of modified glass fiber, 17-18% of glass bead, 0.2-0.4% of hydrolysis resistance agent, 2-3% of nano boron nitride and 3-4% of auxiliary agent.
3. The hydrolysis-resistant and aging-resistant PET modified material as claimed in claim 1, characterized in that: comprises the following raw materials in percentage by weight: 44% of modified PET resin, 11% of filling resin, 4% of acrylic acid, 17.5% of modified glass fiber, 17.5% of glass bead, 0.3% of hydrolysis resistance agent, 2.2% of nano boron nitride and 3.5% of auxiliary agent.
4. The hydrolysis-resistant and aging-resistant PET modified material as claimed in claim 1, characterized in that: the filling resin is one or more of PC, PA or epoxy methacrylate resin, the glass beads are hollow glass beads, the auxiliary agent comprises a toughening agent, a compatilizer, an antioxidant and an anti-aging agent, and the weight ratio of the toughening agent to the compatilizer to the antioxidant to the anti-aging agent is 1: (0.7-1): (1.2-1.4) and (0.8-1.2).
5. The hydrolysis-resistant and aging-resistant PET modified material as claimed in claim 4, characterized in that: the anti-aging agent is composed of a stabilizer, a compatibilizer, an antioxidant 1010 or 168, a stabilizer, a polyethylene glycol ether, a polypropylene.
6. The preparation method of the hydrolysis-resistant and aging-resistant PET modified material according to any one of claims 1 to 5, characterized by comprising the following steps: the preparation method comprises the following specific steps:
the method comprises the following steps: weighing 20 parts of styrene butadiene rubber grafted with maleic anhydride, placing the styrene butadiene rubber in a reaction container, adding 80 parts of PET resin into the reaction container, then adding 5 parts of vinylidene fluoride and 5 parts of tetrafluoroethylene, stirring, adding the mixture into a double-screw extruder after uniform stirring, extruding and granulating to obtain modified PET resin, weighing the raw materials according to the weight percentage, introducing the weighed modified PET resin, filling resin, acrylic acid and nano boron nitride into a mixing container, and uniformly stirring and mixing to obtain premix A for later use;
step two: uniformly stirring and mixing the weighed toughening agent, compatilizer, antioxidant, anti-aging agent and hydrolysis resistance agent, slowly adding the mixture into the premix A, stirring and adding the mixture in a spiral stirring manner, and uniformly mixing to obtain a premix B;
step three: weighing glass fiber with the diameter of 1-2um, mixing the glass fiber with the modified material, stirring for 20-40 minutes at normal temperature, heating and melting the mixture in a double-screw extruder, and extruding and granulating the mixture to obtain modified glass fiber for later use;
step four: introducing the premix B into a double-screw extruder, injecting the modified glass fiber obtained in the step three into the double-screw extruder through a front side feeding bin, and injecting the hollow glass beads into the double-screw extruder through a rear side feeding bin after the injection of the modified glass fiber is finished;
step five: and (3) heating and melting the mixed material, extruding and granulating by using a double-screw extruder, removing water in the material by using a double-blowing device, selecting by using a three-layer vibrating screen, removing powder and drawing, and selecting qualified granules to obtain the hydrolysis-resistant and anti-aging PET modified material.
7. The preparation method of the hydrolysis-resistant and anti-aging PET modified material as claimed in claim 6, characterized in that: and in the second step, the spiral stirring adopts alternate stirring of horizontal stirring and vertical stirring, the stirring speed is 100-300 revolutions per minute, and the stirring mode is replaced once every 1-3 minutes.
8. The preparation method of the hydrolysis-resistant and anti-aging PET modified material as claimed in claim 6, characterized in that: the modified material in the third step comprises nano titanium dioxide, nano silicon dioxide, nano kaolin, nano attapulgite and a silane coupling agent, wherein the weight ratio of the nano titanium dioxide to the nano silicon dioxide to the nano kaolin to the nano attapulgite to the silane coupling agent is 1: (1.2-1.4): (1.8-2.4): (1.5-2): (0.2-0.4).
9. The preparation method of the hydrolysis-resistant and anti-aging PET modified material as claimed in claim 6, characterized in that: and in the step one, when maleic anhydride is grafted on styrene-butadiene rubber, plasticating the styrene-butadiene rubber on a low-temperature open mill for 5-10min, then adding zinc oxide, stearic acid, maleic anhydride, an antioxidant 1010 and an accelerator, heating to 60-70 ℃, continuing to plasticate for 10-15min, adjusting the roller distance, and discharging sheets to obtain the styrene-butadiene rubber grafted with maleic anhydride.
10. The preparation method of the hydrolysis-resistant and anti-aging PET modified material as claimed in claim 6, characterized in that: the screw diameter of the twin-screw extruder in the step five is 44: 1, the rotating speed of a screw of the screw extruder is 450-550rpm, holes phi of the buckle plate are 3.0X15, vibration blanking is adopted when the modified glass fiber is injected in the fourth step, the double-screw extruder comprises eleven temperature zones which are sequentially arranged, the temperature of the first zone is 245 ℃, the temperature of the second zone is 255 ℃, the temperature of the third zone and the temperature of the fourth zone are 265 ℃, the temperature of the fifth zone to the eleven zone is 255 ℃, the head temperature of the double-screw extruder is 265 ℃, and an auxiliary blowing device is used at the head of the double-screw extruder to assist in preventing generation of a flow derivative of a die head.
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| CN115594953A (en) * | 2022-09-22 | 2023-01-13 | 苏州易昇光学材料股份有限公司（Cn） | Anti-ultraviolet PET (polyethylene terephthalate) film for solar cell back plate and preparation method thereof |
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| CN103497490A (en) * | 2013-09-27 | 2014-01-08 | 深圳市科聚新材料有限公司 | PET (polyethylene terephthalate) composite material and preparation method thereof |
| CN107177173A (en) * | 2017-06-09 | 2017-09-19 | 东莞市联洲知识产权运营管理有限公司 | A kind of hydrolysis resistant PET composite material |
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| CN102344654A (en) * | 2011-06-17 | 2012-02-08 | 深圳市科聚新材料有限公司 | Hydrolysis resistant PET composite material and preparation method thereof |
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