CN113583401B - Preparation method of transparent PET composite material - Google Patents
Preparation method of transparent PET composite material Download PDFInfo
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- CN113583401B CN113583401B CN202111006055.XA CN202111006055A CN113583401B CN 113583401 B CN113583401 B CN 113583401B CN 202111006055 A CN202111006055 A CN 202111006055A CN 113583401 B CN113583401 B CN 113583401B
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- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 27
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 229920001864 tannin Polymers 0.000 claims abstract description 11
- 235000018553 tannin Nutrition 0.000 claims abstract description 11
- 239000001648 tannin Substances 0.000 claims abstract description 11
- 229920002770 condensed tannin Polymers 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 4
- 239000008187 granular material Substances 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- -1 dihydroxy ethyl terephthalate Chemical compound 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- 230000032050 esterification Effects 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 10
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 229910052709 silver Inorganic materials 0.000 abstract description 5
- 239000004332 silver Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000007822 coupling agent Substances 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 38
- 239000005020 polyethylene terephthalate Substances 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- JMGCAHRKIVCLFW-UHFFFAOYSA-N 1-O-Galloylcastalagin Natural products Oc1cc(cc(O)c1O)C(=O)OC2C3OC(=O)c4c2c(O)c(O)c(O)c4c5c(O)c(O)c(O)c6c5C(=O)OC3C7OC(=O)c8cc(O)c(O)c(O)c8c9c(O)c(O)c(O)cc9C(=O)OCC7OC(=O)c%10cc(O)c(O)c(O)c6%10 JMGCAHRKIVCLFW-UHFFFAOYSA-N 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229920001968 ellagitannin Polymers 0.000 description 3
- JMGCAHRKIVCLFW-CNWXVVPTSA-N ellagitannin Chemical compound OC1=C(O)C(O)=CC(C(=O)O[C@H]2C3=C4C(=O)O[C@@H]2[C@@H]2[C@@H]5OC(=O)C6=CC(O)=C(O)C(O)=C6C6=C(O)C(O)=C(O)C=C6C(=O)OC[C@H]5OC(=O)C5=CC(O)=C(O)C(O)=C5C=5C(O)=C(O)C(O)=C(C=5C(=O)O2)C4=C(O)C(O)=C3O)=C1 JMGCAHRKIVCLFW-CNWXVVPTSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 101001135375 Homo sapiens Protein PET117 homolog, mitochondrial Proteins 0.000 description 1
- 102100033074 Protein PET117 homolog, mitochondrial Human genes 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002834 transmittance Methods 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for preparing transparent PET composite material, which comprises bonding graphene sheets modified by coupling agent in a chain in PET synthesis, mixing the graphene-modified particles with hydrolyzed tannin and condensed tannin plant polyphenol for modifying again, adsorbing graphene and plant polyphenol on the surface of a graphene sheet layer by pi-pi interaction, hydrogen bond interaction and the like, combining amino groups on nano silicon dioxide and nano silver particles with phenolic hydroxyl groups in plant polyphenol to combine the PET particles of silicon dioxide, nano silver and the like into functional particle auxiliary agent, improving the compatibility when the functional agent is mixed with PET and PBT, dispersing the particles of silicon dioxide, silver and the like more uniformly, improving the performance of the material under a small amount, mixing PBT to improve the crystallization speed of the material, and the material prepared by the method has higher transparency, high surface hardness and small friction coefficient, the phenomena of scratches on the surface and the like caused by the collision of sundries can be effectively avoided.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a preparation method of a transparent PET composite material.
Background
PET, namely polyethylene terephthalate, is low in price and has the advantages of excellent wear resistance, heat resistance, electrical insulation, mechanical strength and the like, but has the defects of long molding cycle, insufficient surface hardness, easiness in scratching and the like due to the fact that a conjugated structure exists in a molecular chain, the rigidity of the molecular chain is high, the crystallization speed is low, and the like.
PBT, graphene or carbon nanotubes and the like are added to the enterprises to improve the crystallization speed of the PET material, and various additives are added to improve the physical properties of the PET, for example, a PET-based graphene composite material is disclosed in the patent with the publication number CN105820519, and graphene is bonded in a PET chain to improve the tensile strength and the barrier property. For example, patent No. CN102766320 discloses a PET/PBT alloy material with improved flexibility and crystallization speed.
The problem to be solved by this document is how to adjust the components and how to improve the inorganic filler so as to meet the requirements for functions such as hardness and transparency, and the like, because the crystallization speed and the like are actually improved when the shell such as lipstick and cosmetic pencil is prepared according to the scheme, but the defect that the shell is easily scratched due to insufficient surface hardness still exists, and after the inorganic filler is added, the defect that the filler is poor in dispersion uniformity during preparation is found, and the performance of the material is easily changed greatly.
Disclosure of Invention
In order to solve at least one technical defect, the invention provides the following technical scheme:
the application document discloses a preparation method of a transparent PET composite material, which comprises the following steps:
1) bonding the KH560 modified graphene sheets in PET in an esterification and in-situ polymerization manner and pelletizing;
2) mixing the terminal granules obtained in the step 1) with a solution containing hydrolyzed tannin or condensed tannin, stirring for more than 4 hours at the temperature of 60-75 ℃, and filtering and washing to obtain plant polyphenol modified granules;
3) mixing KH550 modified nano-silica and plant polyphenol modified granules in a solvent, stirring, filtering and drying to form a first functional auxiliary agent;
mixing KH550 modified nano-silver particles and plant polyphenol modified granules in a solvent, stirring, filtering and drying to form a second functional auxiliary agent;
4) mixing 120 parts of PET 110-containing material, 5-8 parts of PBT, 3-10 parts of first functional auxiliary agent, 2-4 parts of second functional auxiliary agent, 1-3 parts of slipping agent and 0.4-0.7 part of antioxidant, and melting and extruding to form the composite material.
In the scheme, the preparation and the composition of the PET material auxiliary agent are mainly improved, and the composition and the proportion of the PET material formula are selected in a targeted manner, and the general idea lies in that: graphene sheets modified by a coupling agent are bonded in a chain in PET synthesis, then graphene modified granules are mixed with hydrolyzed tannin and condensed tannin plant polyphenol for secondary modification, graphene and plant polyphenol are adsorbed on the surface of a graphene sheet layer through pi-pi interaction, hydrogen bond interaction and the like, then amino in KH550 on nano silicon dioxide and nano silver particles are combined with phenolic hydroxyl in the plant polyphenol to form a functional particle auxiliary agent, the compatibility is improved when the functional agent is mixed with PET and PBT, the particles of silicon dioxide, silver and the like are dispersed more uniformly, the performance of the material can be improved under a small amount, meanwhile, PBT is added to improve the crystallization speed of the material, graphene can also improve the insulativity of the PET material, the surface adsorption of impurities is avoided, the material has the sterilization performance due to the addition of nano silver, the migration effect of a slipping agent is reduced by the surface friction coefficient, the material prepared by the method has higher transparency, high surface hardness and small friction coefficient, can effectively avoid the phenomena of scratches and the like on the surface caused by sundry collision, has good aesthetic property, and has heat resistance and crystallization speed superior to those of similar products.
Further, KH560 and graphene are added into the ethylene glycol solution in the step 1) for ultrasonic dispersion to form a graphene dispersion solution, so that the dispersion effect is improved, and the modification amount of the coupling agent is increased.
Further, in the step 1), terephthalic acid, ethylene glycol antimony, a stabilizer and KH560 modified graphene dispersion liquid are mixed, emulsified and pulped, wherein the graphene raw material accounts for 0.15-0.25%, the mass ratio of the terephthalic acid to ethylene glycol in the graphene dispersion liquid is 1:1.2-1.4, then the slurry is added into a polymerization kettle to synthesize dihydroxy ethyl terephthalate by a direct esterification method, the esterification time is 120-245 min under the protection of nitrogen, and the esterification temperature is 220-245 ℃; then carrying out polycondensation on the dihydroxy ethyl terephthalate to obtain PET resin under the vacuum condition, wherein the polycondensation temperature is 280-290 ℃, the time is 120-160min, the intrinsic viscosity value of the product PET is 0.6-0.65dL/g, and the PET material is synthesized in an esterification and polycondensation manner, so that the synthesis process and the related technology are mature, controllable and low in risk, and more favorable for bonding graphene in a chain.
Furthermore, the hydrolyzed tannin or the condensed tannin is dissolved in the alcoholic solution, the concentration is 10-15%, and the hydrolyzed tannin or the condensed tannin is mixed and stirred with the terminal granules accounting for 35-45% of the mass of the alcoholic solution of the hydrolyzed tannin or the condensed tannin, so that the full contact is facilitated, the modification effect is good, the concentration ratio is preferably 13%, and the terminal granules account for preferably 40%.
Further, in the step 3), the mass ratio of the nano silicon dioxide modified by KH550 to the plant polyphenol modified granular material is 1:2.5-4, the mass ratio of the nano silver particles modified by KH550 to the plant polyphenol modified granular material is 1:4-5, the joint amount of nano silver and silicon dioxide is controlled, and the compatibility of the functional additive and the PET raw material is better.
Further, KH550 modified nano-silica and plant polyphenol modified granular materials, and KH550 modified nano-silver particles and plant polyphenol modified granular materials are all placed in an alcohol solution to be mixed and stirred.
And further, mixing and stirring part of the slipping agent with PET and PBT, mixing and stirring the rest of the slipping agent with the first functional auxiliary agent, the second functional auxiliary agent and the antioxidant, and then mixing the two parts of materials step by step, which is favorable for improving the uniformity of material mixing.
Furthermore, the slipping agent comprises polytetrafluoroethylene micro powder and oleamide in a mass ratio of 1:1, and the combination of the oleamide and the polytetrafluoroethylene micro powder is favorable for improving the dispersion uniformity of the materials.
Further, a screw extruder is used for extruding and molding the composite material, wherein the temperature of a first zone is 185 ℃ plus the temperature of a second zone is 185 ℃ plus the temperature of 190 ℃ plus the temperature of a third zone is 215 ℃ plus the temperature of a fourth zone is 255 ℃, the temperature of a fifth zone is 250 ℃ plus the temperature of 260 ℃, the temperature of a sixth zone is 250 ℃ plus the temperature of a seventh zone is 250 ℃ plus the temperature of 260 ℃, the temperature of an eighth zone is 250 ℃ plus the temperature of a ninth zone, the temperature of a die head is 255-65 ℃, the extrusion parameters are preferably selected to avoid the ester exchange reaction, the preferred zone parameters are 175 ℃ in the first zone, 187 ℃ in the second zone, 220 ℃ in the third zone, 250 ℃ in the fourth zone, 255 ℃ in the fifth zone, 255 ℃ in the sixth zone, 255 ℃ in the seventh zone, 245 ℃ in the eighth zone and 245 ℃ in the ninth zone, and the temperature of the die head is 260 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention improves the preparation and the composition of the material components, and selects the composition of the PET material formula in a targeted manner, thereby being beneficial to improving the surface hardness of the PET material, reducing the surface friction coefficient and improving the aesthetic property.
Detailed Description
The present invention will be further described with reference to the following specific examples.
For the PET material forming method, the PET material is synthesized by polycondensation after esterification, the technical maturity is high, all the technical parameters are easy to obtain, and the intrinsic viscosity of the selected PET raw material is 0.642dL/g and is detected by the national standard GB 17931-2003; ethylene glycol antimony is used as a catalyst, the ethylene glycol antimony, terephthalic acid and ethylene glycol are all selected from industrial grade, the coupling agent is analytically pure, the graphene is selected from SE1430 with the specification of 7.0 +/-1.0 mu m (Hezhou Sexiu materials science and technology Co., Ltd.), the plant polyphenol is selected from hydrolyzed tannin, namely ellagitannin, the particle size of nano-silver and silicon dioxide particles is 80-100nm, the antioxidant is selected from 1010, and the PBT is selected from Beihua institute 301GO type and has the particle size of 10-15 mu m.
The graphene-modified PET pellets were synthesized as follows:
1.1, adding KH560 and graphene into an ethylene glycol solution to perform ultrasonic dispersion for 40min to form a graphene dispersion solution.
1.2, mixing terephthalic acid, ethylene glycol antimony, a stabilizer and KH560 modified graphene dispersion liquid, emulsifying and pulping, wherein the proportion of the graphene raw material is 0.15-0.25% (calculated according to the theoretical yield of synthesis), the proportion of the ethylene glycol antimony raw material is 0.018%, the stabilizer is phosphoric acid, the proportion of the raw material is 0.0012%, and the mass ratio of the terephthalic acid to the ethylene glycol in the graphene dispersion liquid is 1: 1.4.
1.3, then adding the slurry into a polymerization kettle to synthesize the dihydroxy ethyl terephthalate by a direct esterification method, under the protection of nitrogen, wherein the esterification time is 140min, and the esterification temperature is 235-240 ℃.
1.4, then carrying out polycondensation on the dihydroxy ethyl terephthalate to obtain PET resin under the vacuum condition, wherein the polycondensation temperature is 285 +/-1 ℃, the time is 150min, the intrinsic viscosity value of the product PET is 0.645dL/g, and the product PET is extruded and granulated, and the particle size is 15-18 mu m.
The polyphenol modified pellets were prepared as follows:
2.1, dissolving ellagitannin in 13% ethanol water solution, mixing and stirring with 40% of terminal granules of the mass of the solution of ellagitannin in batches, at 70 ℃, for 6h, filtering, washing and drying in vacuum.
The functional assistant is synthesized as follows:
3.1, adding KH550 into the ethanol solution, adding nano-silica, fully stirring, wherein the mass ratio of the KH550 to the silica is 1:4, and carrying out vacuum drying;
adding KH550 into an ethanol solution, adding nano-silver particles, fully stirring, and performing vacuum drying, wherein the mass ratio of the KH550 to the nano-silver is 1: 4;
3.2, mixing the polyphenol modified granules and KH550 modified nano-silica in an ethanol (alcohol-water ratio is 1:1) solvent, adding 3 drops of 40% sodium bisulfite solution to improve the reaction activity, wherein the mass of the granules is 3 times of that of the silica, and filtering and drying to form a first functional auxiliary agent;
mixing the granules dried in the second step and KH550 modified nano-silver particles in an ethanol (alcohol-water ratio of 1:1) solvent, adding 3 drops of 40% sodium bisulfite solution to improve the reaction activity, wherein the granules are 4.5 times of the nano-silver particles in mass, filtering and drying to form the second functional auxiliary agent.
The transparent PET material was prepared as follows
Example 1
3 parts of the prepared first functional auxiliary agent, 2 parts of the prepared second functional auxiliary agent, 0.5 part of slipping agent (1: 1 of polytetrafluoroethylene micro powder and oleamide) and 0.4 part of antioxidant are mixed; 110 parts of PET, 5 parts of PBT and 0.5 part of slipping agent are mixed.
The two parts of materials are placed in a screw extruder to be uniformly mixed and melted to be extruded to form a composite material, and the interval parameters are as follows: the temperature of the first zone is 175 ℃, the temperature of the second zone is 187 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 255 ℃, the temperature of the sixth zone is 255 ℃, the temperature of the seventh zone is 255 ℃, the temperature of the eighth zone is 245 ℃ and the temperature of the die head is 260 ℃.
Example 2
Mixing 7 parts of the prepared first functional auxiliary agent, 3 parts of the prepared second functional auxiliary agent, 0.6 part of slipping agent (1: 1 of polytetrafluoroethylene micro powder and oleamide) and 0.5 part of antioxidant; mixing 115 parts of PET, 6 parts of PBT and 0.6 part of slipping agent.
The two parts of materials which are uniformly mixed are placed in a screw extruder to be uniformly mixed and melted to be extruded to form a composite material, and the interval parameters are as follows: the temperature of the first zone is 180 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 255 ℃, the temperature of the fifth zone is 257 ℃, the temperature of the sixth zone is 255 ℃, the temperature of the seventh zone is 255 ℃, the temperature of the eighth zone is 245 ℃ and the temperature of the die head is 260 ℃.
Example 3
Mixing 10 parts of the prepared first functional auxiliary agent, 4 parts of the prepared second functional auxiliary agent, 1.5 parts of a slipping agent (1: 1 of polytetrafluoroethylene micro powder and oleamide) and 0.7 part of an antioxidant; 120 parts of PET, 8 parts of PBT and 1.5 parts of slipping agent are mixed.
The two parts of materials which are uniformly mixed are placed in a screw extruder to be uniformly mixed and melted to be extruded to form a composite material, and the interval parameters are as follows: the temperature of the first zone is 180 ℃, the temperature of the second zone is 187 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 255 ℃, the temperature of the fifth zone is 255 ℃, the temperature of the sixth zone is 255 ℃, the temperature of the seventh zone is 255 ℃, the temperature of the eighth zone is 245 ℃ and the temperature of the die head is 260 ℃.
Example 4
Mixing the prepared first functional auxiliary agent 8, the prepared second functional auxiliary agent 2 parts, a slipping agent (1: 1 of polytetrafluoroethylene micro powder and oleamide) 1.2 parts and an antioxidant 0.4 part; PET117 parts, PBT5 parts and 1.2 parts of a slipping agent are mixed.
The two parts of materials which are uniformly mixed are placed in a screw extruder to be uniformly mixed and melted to be extruded to form a composite material, and the interval parameters are as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 187 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 245 ℃, the temperature of the fifth zone is 255 ℃, the temperature of the sixth zone is 255 ℃, the temperature of the seventh zone is 255 ℃, the temperature of the eighth zone is 245 ℃ and the temperature of the die head is 260 ℃.
Comparative example 1
Compared with example 4, the difference is that: mixing 15 parts of the prepared first functional auxiliary, 2 parts of the prepared second functional auxiliary, 1.2 parts of a slipping agent (1: 1 of polytetrafluoroethylene micro powder and oleamide) and 0.4 part of an antioxidant; 98 parts of PET, 5 parts of PBT and 1.2 parts of a slipping agent are mixed.
Comparative example 2
Compared with example 4, the difference is that: mixing 2 parts of the prepared first functional auxiliary agent, 2 parts of the prepared second functional auxiliary agent, 1.2 parts of a slipping agent (1: 1 of polytetrafluoroethylene micro powder and oleamide) and 0.4 part of an antioxidant; 98 parts of PET, 5 parts of PBT and 0.5 part of slipping agent are mixed.
Comparative example 3
Compared with example 4, the difference is that: the PET component, the graphene and the tannin in the first functional auxiliary agent and the second functional auxiliary agent are independently mixed with the rest components and are subjected to melt extrusion, and the ratio of each component is unchanged.
Detection of
The sheet materials prepared in the above examples and comparative examples were tested for their properties, as shown in the following table, hardness GB/T6739-2006, transmittance GB/T2410-2008, and haze GB/T2410-2008.
It can be seen that the hardness was better in examples 1 to 4, and the scratch resistance was found to be excellent in use, with the lowest surface friction coefficient in example 3 and the best scratch resistance in use.
In addition, silver particles are added in the scheme, sterilization test is carried out on the silver particles, detection is carried out according to the enterprise standard Q/02GZS001, detection strains are escherichia coli and staphylococcus aureus in sequence, and it is found that the antibacterial property of the samples in examples 1-4 exceeds 65%, and relatively speaking, the antibacterial property of the sample in comparative example 3 is poor, and the silver particles are distributed unevenly and have small surface quantity.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (7)
1. The preparation method of the transparent PET composite material is characterized by comprising the following steps:
1) bonding a KH560 modified graphene sheet in PET in an esterification and in-situ polymerization manner and pelletizing, wherein the graphene raw material accounts for 0.15-0.25%, and the intrinsic viscosity value of the product PET is 0.6-0.65 dL/g;
2) mixing the terminal granules obtained in the step 1) with a solution containing hydrolyzed tannin or condensed tannin, stirring for more than 4 hours at the temperature of 60-75 ℃, and filtering and washing to obtain plant polyphenol modified granules; dissolving hydrolyzed tannin or condensed tannin in alcohol solution with concentration of 10-15%, and mixing with terminal granules accounting for 35-45% of the mass of the alcohol solution of hydrolyzed tannin or condensed tannin;
3) mixing KH550 modified nano-silica and plant polyphenol modified granules in a solvent, stirring, filtering and drying to form a first functional auxiliary agent;
mixing KH550 modified nano-silver particles and plant polyphenol modified granules in a solvent, stirring, filtering and drying to form a second functional auxiliary agent; the mass ratio of the KH550 modified nano silicon dioxide to the plant polyphenol modified granular material is 1:2.5-4, and the mass ratio of the KH550 modified nano silver particles to the plant polyphenol modified granular material is 1: 4-5;
4) mixing 120 parts of PET 110-containing material, 5-8 parts of PBT, 3-10 parts of first functional auxiliary agent, 2-4 parts of second functional auxiliary agent, 1-3 parts of slipping agent and 0.4-0.7 part of antioxidant, and melting and extruding to form the composite material.
2. The process for preparing a transparent PET composite material according to claim 1, wherein: adding KH560 and graphene into an ethylene glycol solution in the step 1) to perform ultrasonic dispersion to form a graphene dispersion solution.
3. The method of claim 2 for preparing a transparent PET composite, wherein: mixing terephthalic acid, ethylene glycol antimony, a stabilizer and KH560 modified graphene dispersion liquid in the step 1), emulsifying and pulping, wherein the proportion of the graphene raw material is 0.15-0.25%, the mass ratio of the terephthalic acid to ethylene glycol in the graphene dispersion liquid is 1:1.2-1.4, then adding the slurry into a polymerization kettle to synthesize dihydroxy ethyl terephthalate by a direct esterification method, and carrying out nitrogen protection, wherein the esterification time is 120-150min and the esterification temperature is 220-245 ℃; then carrying out polycondensation on the dihydroxy ethyl terephthalate to obtain PET resin under the vacuum condition, wherein the polycondensation temperature is 280-290 ℃, the polycondensation time is 120-160min, and the intrinsic viscosity value of the product PET is 0.6-0.65 dL/g.
4. The process for preparing a transparent PET composite material according to claim 1, wherein: KH550 modified nano-silica and plant polyphenol modified granular materials, and KH550 modified nano-silver particles and plant polyphenol modified granular materials are placed in an alcohol solution to be mixed and stirred.
5. The process for preparing a transparent PET composite material according to claim 1, wherein: mixing and stirring part of the slipping agent with PET and PBT, mixing and stirring the rest of the slipping agent with the first functional auxiliary agent, the second functional auxiliary agent and the antioxidant, and then mixing the two parts of materials.
6. The process for preparing a transparent PET composite material according to claim 1, wherein: the slipping agent comprises polytetrafluoroethylene micro powder and oleamide, and the mass ratio of the polytetrafluoroethylene micro powder to the oleamide is 1:1.
7. The process for preparing a transparent PET composite material according to claim 1, wherein: the composite material is extruded and molded by a screw extruder, wherein the temperature of the first zone is 160-.
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