CN109337086B - Terpolymer composite material of functional graphene in-situ polymerization polyester, preparation method and special device thereof - Google Patents
Terpolymer composite material of functional graphene in-situ polymerization polyester, preparation method and special device thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 154
- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 48
- 229920000728 polyester Polymers 0.000 title claims abstract description 42
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 24
- 229920001897 terpolymer Polymers 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 84
- 238000005886 esterification reaction Methods 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 9
- 230000032050 esterification Effects 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims description 126
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 111
- 239000007788 liquid Substances 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 67
- 239000002994 raw material Substances 0.000 claims description 52
- 230000001804 emulsifying effect Effects 0.000 claims description 49
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 39
- 238000001914 filtration Methods 0.000 claims description 34
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 238000003860 storage Methods 0.000 claims description 25
- 238000011084 recovery Methods 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 239000002699 waste material Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 6
- 229960002684 aminocaproic acid Drugs 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
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- 239000002904 solvent Substances 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
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- 230000004913 activation Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000006473 carboxylation reaction Methods 0.000 claims description 3
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- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims 2
- 229910052718 tin Inorganic materials 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 23
- 235000019441 ethanol Nutrition 0.000 description 20
- 239000000835 fiber Substances 0.000 description 17
- 238000001816 cooling Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 239000004408 titanium dioxide Substances 0.000 description 11
- -1 Polyethylene terephthalate Polymers 0.000 description 9
- 238000009987 spinning Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
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- 230000008569 process Effects 0.000 description 5
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- 239000000203 mixture Substances 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 229920006027 ternary co-polymer Polymers 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 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 1
- VYVFQBFOMKEKBG-UHFFFAOYSA-L 3,3-dibutyl-2,4,3-benzodioxastannepine-1,5-dione Chemical compound O=C1O[Sn](CCCC)(CCCC)OC(=O)C2=CC=CC=C21 VYVFQBFOMKEKBG-UHFFFAOYSA-L 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a functional graphene in-situ polymerized polyester terpolymer composite material, a preparation method thereof and a special device, belonging to the technical field of composite material preparation. The composite material is prepared from dihydric alcohol, dibasic acid and functional graphene through esterification and polycondensation, wherein the molar ratio of the dihydric alcohol to the dibasic acid is (1.2-2): the functional graphene accounts for 0.01-2% of the ternary polymerization composite material by mass, and the number average molecular weight of the ternary polymerization composite material is 10000-150000. According to the invention, active functional groups are introduced to the surface of graphene, so that the graphene is grafted to the polyester chain segment, a stable covalent bond is formed between the graphene and the polyester, the polyester molecular chain is enhanced by utilizing the good physical and mechanical properties of graphene materials, and the composite material shows good mechanical properties and comprehensive properties.
Description
Technical Field
The invention belongs to the technical field of preparation of composite materials, and particularly relates to a functional graphene in-situ polymerized polyester ternary copolymer composite material, a preparation method thereof and a special device.
Background
Polyethylene terephthalate (PET) is one of the most important synthetic materials at present, and can be applied to the fields of fibers, films, plastics and the like. The PET film has high mechanical strength, good cold and heat resistance, stable shrinkage and excellent electrical insulation performance and optical performance, and is widely applied to the fields of packaging, industry, electricity, electronics, magnetism, sensitization and the like. The terylene is fiber prepared by taking polyethylene terephthalate (PET) as a raw material through spinning and post-treatment. The polyester fiber is the most widely used synthetic fiber in the world with the largest output, and occupies about 70 percent of the output of the synthetic fiber in the world. However, the molecular chains of the polyester fibers are closely connected, and the polyester fibers have high crystallinity and orientation degree and small polarity, so that the polyester fibers have the defects of poor hygroscopicity and poor hydrophilicity.
The graphene is a novel carbon nanometer light material, has a unique monoatomic layer two-dimensional crystal structure, a high specific surface area, high strength, high electrical conductivity and high thermal conductivity, and has high absorption efficiency on various light rays and an ideal shielding effect. Graphene is known as a miraculous material for changing the 21 st century, and along with the gradual maturity and perfection of relevant processes in the application field of graphene, the unquestionable matters of arbitrary bending of a mobile phone screen, instant charging of an electric automobile and transparency of a computer screen such as white paper become reality. The graphene material also draws wide attention in the aspect of textile function development, and the mechanical property and the electrical property of the fiber can be obviously improved by adding a small amount of graphene in the polymerization or spinning process of the textile fiber.
Chinese patent 201510430677.3 published as 2015, 10, month and 28 discloses a high-molecular composite functional fiber containing partially reduced graphene and a preparation method thereof, wherein the fiber comprises a component A and a component B, and the component A and the component B are partially exposed, parallel or skin-core phasesAnd (3) combining, wherein 20-100% of the external surface area of each fiber is a component B. The method comprises the steps of mixing 0.1-1 wt% of polyester containing partially reduced graphene and 4-20 wt% of polyester containing partially reduced graphene and TiO2The polyester of the nano composite filler is crystallized, dried, then melt composite spinning is carried out, then drafting and relaxation heat setting are carried out at 80-160 ℃, and reduction treatment is carried out to reduce part of reduced graphene in the fiber until the carbon/oxygen atomic ratio reaches 9/1-15/1. The fiber prepared by the method can be produced at a higher spinning speed, and the production efficiency is high; the antistatic fiber has lower single filament number, higher strength and lower resistivity, and meets the antistatic requirement; meanwhile, the coating has antibacterial and flame retardant properties, thereby having good application prospect.
Chinese patent 201510680473.5 published as 2015, 12 months and 30 days discloses a preparation method of graphene-polyester nano composite fiber, which comprises the following steps: the preparation method comprises the steps of preparing graphene-polyester composite master batches and preparing the graphene-polyester nano composite fibers from the composite master batches. Compared with other existing methods: the process is very simple, and the reinforced material has excellent performance and is cheap. In addition, the excellent mechanical property and functional property of graphene endow the nano composite fiber with high strength, antistatic performance and other functionalities. The good dispersibility and perfect interface compatibility of the surface-modified and modified graphene in the polyester polymer matrix enable the graphene and polyester chip matrix material to be efficiently and uniformly compounded. However, the content of the added graphene is large, which is not beneficial to resource saving and industrial large-scale production.
In the aspect of the performance of the graphene reinforced modified polyester, although relevant literature reports exist at home and abroad, the performance is realized by adopting a blending and adding mode, and the problems of large adding amount, difficult processing, unobvious performance improvement and the like exist.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a terpolymer composite material of functional graphene in-situ polymerized polyester, a second object of the present invention is to provide a method for preparing the composite material, and a third object of the present invention is to provide a special apparatus for preparing the composite material.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a special device for preparing a functional graphene in-situ polymerized polyester terpolymer composite material, which comprises a raw material adding device, a raw material preparing device, an esterification reaction device, a prepolymer filtering device, a polycondensation reaction device and a melt filtering device which are sequentially connected through pipelines, wherein the raw material adding device comprises a graphene adding device and an auxiliary material adding device; the device is characterized in that a high-shear emulsifying machine and an ultrasonic disperser are arranged in the graphene adding device, the auxiliary material adding device and the raw material preparing device at the same time, a high-pressure homogenizer is arranged between the graphene adding device and the raw material preparing device, waste ports of the esterification reaction device and the polycondensation reaction device are connected with the raw material preparing device through a recovery device, and a waste storage tank, a rectifying tower and a recovery storage tank are sequentially arranged in the recovery device.
The invention also relates to a preparation method of the ternary polymerization composite material of the functional graphene in-situ polymerization polyester by adopting the special device, which comprises the steps of dispersing the functional graphene and the auxiliary material in dihydric alcohol to respectively obtain a functional graphene dispersion liquid and an auxiliary material dispersion liquid; and then adding dihydric alcohol, dibasic acid, the functional graphene dispersion liquid and the auxiliary material dispersion liquid into a reaction kettle for dispersion, and then sequentially carrying out esterification and polycondensation reactions to obtain the ternary copolymerization composite material.
The method specifically comprises the following steps:
(1) dispersing functional graphene and dihydric alcohol in a graphene adding device in a mode of simultaneously using a high-shear emulsifying machine and an ultrasonic disperser to obtain functional graphene dispersion liquid, wherein the mass concentration of the functional graphene dispersion liquid is 0.1-10%;
(2) dispersing auxiliary materials and dihydric alcohol in an auxiliary material adding device by adopting a dispersion mode of simultaneously using a high-shear emulsifying machine and an ultrasonic disperser to obtain an auxiliary material dispersion liquid, wherein the mass concentration of the auxiliary material dispersion liquid is 0.1-35%;
(3) introducing the functional graphene dispersion liquid obtained in the step 1 into a raw material preparation device through a high-pressure homogenizer, introducing the auxiliary material dispersion liquid obtained in the step 2 into the raw material preparation device, simultaneously introducing dihydric alcohol and dibasic acid into the raw material preparation device, and then dispersing the materials in the device by adopting a mode that a high-shear emulsifying machine and an ultrasonic disperser are simultaneously used;
(4) introducing the material obtained in the step 3 into an esterification reaction device for esterification reaction;
(5) filtering the product obtained in the step 4 through a prepolymer filtering device, and then introducing the product into a polycondensation reaction device to perform polycondensation reaction;
(6) filtering the product obtained in the step 5 by a melt filtering device to obtain the ternary polymerization composite material;
(7) and (3) discharging gas-phase substances generated in the reaction processes in the step (4) and the step (5) to a waste storage tank, separating out dihydric alcohol through a rectifying tower, conveying the separated dihydric alcohol to a recovery storage tank, and recycling the dihydric alcohol to a raw material preparation device.
The binary alcohol is selected from one or more of ethylene glycol, propylene glycol, butanediol and cyclohexanediol, the binary acid is purified terephthalic acid, the functional graphene is carboxyl functional graphene or amino functional graphene, and the molar ratio of the binary alcohol to the binary acid is (1.2-2): 1, the functional graphene accounts for 0.01-2% of the ternary polymerization composite material by mass.
Preferably, the carboxyl functional graphene is prepared by one of the following two methods:
A. firstly, graphite oxide is dispersed in a good solvent by a mechanical dispersion mode that a high-shear emulsifying machine and an ultrasonic disperser operate simultaneously, then an amino acid compound is slowly added for reaction, and the graphite oxide is obtained after washing and drying;
B. firstly, dispersing and stripping graphene oxide in alkali liquor by a mechanical dispersion mode that a high-shear emulsifying machine and an ultrasonic disperser operate simultaneously, then activating the graphene oxide by adopting chloroacetic acid or sodium chloroacetate, and finally adding a carboxylation reagent to carry out carboxylation reaction;
the amino functional graphene is prepared by one of the following two methods:
C. firstly, graphite oxide is dispersed in a good solvent by a mechanical dispersion mode that a high-shear emulsifying machine and an ultrasonic disperser operate simultaneously, then a diamine compound is slowly added for reaction, and the graphite oxide is obtained after washing and drying;
D. the preparation method is referred to Chinese patent 201810212266.0.
The stirring speed of the high-shear emulsifying machine is more than or equal to 1000r/min, the ultrasonic power of the ultrasonic disperser is 1-20 kw, the dispersing time is 1-10 h, and the dispersing temperature is 10-40 ℃.
The auxiliary materials comprise catalysts, the catalysts are antimony trioxide, sodium germanate, germanium dioxide, dibutyltin phthalate, monobutyl tin oxide, dibutyl tin oxide chloride, dibutyl tin dilaurate, dibutyl tin diacetate, monobutyl tin trichloride and other antimony systems, titanium systems, tin systems or germanium systems, and the dosage of the catalysts is 0.05-0.25% of the total mass of the reaction materials.
The esterification reaction conditions are as follows: the reaction temperature is 250-265 ℃, the reaction pressure is 0.1-0.5 MPa, the reaction time is 0.5-2.5 h, and the esterification reaction rate is controlled to be not lower than 96%; the conditions of the polycondensation reaction are as follows: the reaction temperature is 265-280 ℃, the reaction vacuum degree is 0.1-25 kPa, the reaction time is 0.5-5 h, and the esterification reaction rate is controlled to be not less than 99.5%.
The invention also relates to a ternary polymerization composite material of the functional graphene in-situ polymerization polyester prepared by the method.
The composite material has a number average molecular weight of 10000-150000 and an intrinsic viscosity of 0.6-1.2 dL/g.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the functional graphene in-situ polymerization polyester ternary polymerization composite material, the active functional group is introduced to the surface of graphene, so that the graphene is grafted to the polyester chain segment, the purpose of in-situ modification of polyester is achieved, a stable covalent bond is formed between the graphene and the polyester, the polyester molecular chain is enhanced by utilizing the good physical and mechanical properties of the graphene material, and the composite material shows good mechanical properties and comprehensive properties.
(2) Compared with the polymer/graphene composite material in the prior art, the functional graphene can be uniformly dispersed in the polymer matrix, so that the performance of the composite material is greatly improved, and the required graphene content is low.
(3) When the functional graphene is dispersed in the dihydric alcohol, the functional graphene can be uniformly dispersed in a dihydric alcohol system without adding a surfactant or a dispersing auxiliary agent, so that the influence of the added auxiliary agent on in-situ polymerization is avoided; during dispersion, a high-shear emulsification and ultrasonic dispersion combined process is adopted, so that functional graphene can be well dispersed, peeled and sheared, the size is small and uniform, and graphene agglomeration is effectively avoided.
(4) The preparation method of the functional graphene in-situ polymerization polyester terpolymer composite material is simple in process and strong in operability, only needs basic modification on the existing industrial polyester production equipment, is low in investment, and is easy for industrial popularization.
Drawings
FIG. 1 is a schematic view of the preparation process of the ternary copolymer composite material of the present invention;
FIG. 2 is a schematic view of a special apparatus for preparing a terpolymer composite material according to the present invention;
in fig. 2: 1. a graphene adding device; 2. an auxiliary material adding device; 3. a high-pressure homogenizer; 4. a raw material preparation device; 5. an esterification reaction device; 6. a prepolymer filtration device; 7. a polycondensation reaction apparatus; 8. a melt filtration device; 9. a waste storage tank; 10. A rectifying tower; 11. a recovery storage tank; 12. a recovery device; 13. and (4) a granulating and drying device.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
The isolated plant of a preparation function graphite alkene in situ polymerization polyester's terpolymerization combined material of this embodiment, as shown in fig. 2, include that the raw materials that connect gradually through the pipeline add the device, the raw materials is prepared device 4, esterification reaction device 5, prepolymer filter equipment 6, polycondensation reaction device 7 and fuse-element filter equipment 8, the raw materials adds the device and includes that graphite alkene adds device 1 and auxiliary material and adds device 2, graphite alkene adds device 1, all be equipped with high shear emulsion machine and ultrasonic disperser in auxiliary material adding device 2 and the raw materials preparation device 4, be equipped with the high pressure homogenizer between graphite alkene adds device 1 and the raw materials preparation device 4. The waste material ports of the esterification reaction device 5 and the polycondensation reaction device 7 are connected with the raw material preparation device 4 through a recovery device 12; the recovery device 12 is provided with a waste storage tank 9, a rectifying tower 10 and a recovery storage tank 11 in sequence.
The auxiliary material adding device 2 is a place where auxiliary materials (such as titanium dioxide and a catalyst) are prepared in a dihydric alcohol system, is provided with a high-shear emulsifying machine and an ultrasonic dispersing device, can ensure the dispersion state of the auxiliary materials in the dihydric alcohol system, is internally provided with a cooling coil pipe, can effectively control the temperature of materials in a kettle during dispersion, ensures effective dispersion, and conveys the dispersed auxiliary material dispersion liquid obtained after dispersion to the raw material preparing device 4 through a bottom discharge pipeline.
The raw material preparation device 4 is a reaction kettle for mixing the dihydric alcohol, the dibasic acid, the functional graphene dispersion liquid and the auxiliary material dispersion liquid, and is provided with a high-shear emulsifying machine, an ultrasonic disperser and stirring equipment, so that the mixing uniformity of various raw materials can be effectively guaranteed. The top is equipped with material feed line, adds device 1, auxiliary material respectively with graphite alkene and adds device 2 and recovery unit 12 links to each other, and inside is equipped with heating coil, and the lower part is equipped with discharging pipeline, and lower part discharging pipeline connects esterification reaction device 5.
The esterification reaction device 5 comprises at least one reaction kettle for esterification reaction. Gas phase substances generated by the esterification reaction are discharged from a discharge port at the upper end of the reaction kettle to a waste storage tank 9 in a recovery device 12, a feeding pipeline at the upper end of the reaction kettle is connected with a raw material preparation device 4, a discharging pipeline at the lower end of the reaction kettle is connected with a prepolymer filtering device 6, and esterification reaction products are conveyed to a polycondensation reaction device 7 through a pipeline after passing through the prepolymer filtering device 6.
The polycondensation reaction apparatus 7 includes at least one reaction vessel for carrying out a polycondensation reaction. The polycondensation reaction kettle is a high-pressure kettle, gas-phase substances generated by reaction are discharged from a discharge port at the upper end of the reaction kettle to a waste storage tank 9 in a recovery device 12, a feeding pipeline at the upper end of the reaction kettle is connected with an esterification reaction device 5, a discharging pipeline at the lower end of the reaction kettle is connected with a melt filtering device 8, and polycondensation reaction products are conveyed to a granulating and drying device 13 through a pipeline after passing through the melt filtering device 8 or are directly conveyed to a spinning production line.
The recovery device 12 is used for conveying the waste liquid generated by the esterification reaction and the polycondensation reaction to the waste storage tank 9, separating, recovering and separating the dihydric alcohol by the rectification process tower 10, conveying the recovered dihydric alcohol monomer to the recovery storage tank 11 through a liquid conveying pipeline, and connecting the storage tank 11 with the raw material preparation device 4 through a pipeline, so that the recovered dihydric alcohol monomer is recycled.
The preparation method of the functional graphene in-situ polymerization polyester ternary polymerization composite material adopting the special device comprises the following steps: dispersing carboxyl functional graphene and auxiliary materials (comprising titanium dioxide and a catalyst) in ethylene glycol to respectively obtain a functional graphene dispersion liquid and an auxiliary material dispersion liquid; and then adding the residual ethylene glycol, purified terephthalic acid, the functional graphene dispersion liquid and the auxiliary material dispersion liquid into a reaction kettle for dispersion, and then sequentially carrying out esterification and polycondensation reactions to obtain the ternary polymerization composite material. Wherein the mass of the functional graphene accounts for 0.5 percent of that of the ternary polymerization composite material.
As shown in fig. 1, the method specifically comprises the following steps:
(1) in a graphene adding device, controlling the mass fraction of carboxyl functional graphene in functional graphene dispersion liquid to be 1% by a metering pump and controlling the mass fraction of the carboxyl functional graphene in the functional graphene dispersion liquid to be 1% by using a high-shear emulsifying machine and an ultrasonic disperser simultaneously for dispersing and stripping to obtain the carboxyl functional graphene dispersion liquid, wherein the dispersing temperature is controlled to be lower than 40 ℃ by a cooling coil pipe arranged inside, the rotating speed of the high-shear emulsifying machine is 2000r/min, the ultrasonic power is 8kW, and the dispersing time is 60 min.
(2) In the auxiliary material adding device, auxiliary materials (including titanium dioxide and antimony trioxide) and ethylene glycol are dispersed in a dispersion mode in which a high-shear emulsifying machine and an ultrasonic disperser are used simultaneously by controlling the using amount of the titanium dioxide to be 1.2% of the mass of the ternary polymerization composite material and the using amount of catalyst antimony trioxide to be 0.06% of the mass of the ternary polymerization composite material through a metering pump, the dispersion temperature is controlled to be lower than 40 ℃, the rotating speed of the high-shear emulsifying machine is 1400r/min, the ultrasonic power is 10kW, and the dispersion time is 30min through a cooling coil arranged inside the auxiliary material adding device to obtain an auxiliary material dispersion liquid, wherein the catalyst preparation concentration in the auxiliary material dispersion liquid is 1%, and the titanium dioxide preparation concentration is 20%.
(3) And (2) passing the functional graphene dispersion liquid obtained in the step (1) through a high-pressure homogenizer, introducing the functional graphene dispersion liquid into a raw material preparation device after the high-pressure action of the homogenizer, introducing the auxiliary material dispersion liquid obtained in the step (2) into the raw material preparation device, simultaneously introducing the rest ethylene glycol and all the purified terephthalic acid into the raw material preparation device, uniformly mixing various raw materials by adopting a mode of simultaneously using a high-shear emulsifying machine and an ultrasonic disperser, controlling the mixing temperature to be 80 ℃ through an internal heating coil, controlling the rotating speed of the high-shear emulsifying machine to be 1400r/min, controlling the ultrasonic power to be 10kW, and controlling the ultrasonic time to be 30min to obtain the raw material mixed slurry. Wherein the molar ratio of the sum of the ethylene glycol added in the step 1-3 to the total purified terephthalic acid is 1.6: 1, when ethylene glycol is added, the recovered ethylene glycol in the recovery tank 11 is preferably used.
(4) And (3) introducing the material obtained in the step (3) into an esterification reaction device to perform esterification reaction, wherein the reaction temperature of a reaction kettle is controlled to be 255 ℃, the reaction pressure is 0.1-0.5 MPa, the reaction time is 2.5h, and the esterification reaction rate is controlled to be 97.5%.
(5) And (3) filtering the product obtained in the step (4) through a prepolymer filtering device, introducing the product into a polycondensation reaction device, and carrying out polycondensation reaction, wherein the reaction temperature of a reaction kettle is 275 ℃, the reaction vacuum degree is 15kPa (absolute pressure), the reaction time is 4.5h, the esterification reaction rate is controlled to be 99.6%, and the intrinsic viscosity reaches 1.1 dL/g.
(6) And (4) filtering the product obtained in the step (5) through a melt filtering device, and then introducing into a granulating and drying device or directly conveying to a spinning production line.
(7) Discharging gas-phase substances (mainly a mixture of ethylene glycol and water) generated in the reaction processes in the step 4 and the step 5 to a waste storage tank, separating the ethylene glycol through a rectifying tower, conveying the separated ethylene glycol to a recovery storage tank, and recycling the ethylene glycol to a raw material preparation device.
The carboxyl functional graphene is prepared by the following method:
and 3, conveying the product obtained in the step 2 to a first filtering and washing tower through a pipeline, sequentially performing suction filtration and water washing, conveying the filtrate to a first storage tank through a discharge port pipeline, conveying the filtrate through a pipeline and controlling the filtrate through a valve, circularly using the filtrate in a first dispersion kettle for dispersion and stripping of the graphene oxide, and supplementing alkali liquor according to needs.
And 4, conveying the product washed in the step 3 to a second dispersing kettle through a pipeline, adding water, dispersing and stripping in a mode that a high-shear emulsifying machine and an ultrasonic dispersing device run simultaneously, controlling the dispersing temperature to be 30 ℃, the rotating speed of the high-shear emulsifying machine to be 600r/min, the ultrasonic power to be 10kW and the ultrasonic time to be 120min through a cooling coil arranged in the kettle, and obtaining the activated graphene oxide aqueous slurry, wherein the concentration of the slurry is 5 g/mL.
Step 5, conveying the slurry obtained in the step 4 into a reaction kettle through a pipeline, starting stirring, slowly adding certain mass of aminocaproic acid and N, N' -dicyclohexylcarbodiimide into the reaction kettle under the control of a valve, carrying out reflux reaction for 18 hours at 80 ℃ under the protection of nitrogen; wherein the mass ratio of the aminocaproic acid to the activated graphene oxide is 1.2: the dosage of 1, N, N' -dicyclohexylcarbodiimide is 80% of the mass of the activated graphene oxide.
And 6, introducing the product obtained in the step 5 into a second filtering and washing tower for suction filtration and water washing, conveying the filtrate into a second storage tank through a discharge port pipeline, and circularly using the filtrate in a second dispersion kettle through pipeline conveying and valve control.
And 7, conveying the product washed in the step 6 to a third dispersion kettle, adding water, dispersing and stripping in a mode that a high-shear emulsifying machine and an ultrasonic dispersion device run simultaneously, controlling the dispersion temperature to be 30 ℃, the rotating speed of the high-shear emulsifying machine to be 600r/min, the ultrasonic power to be 10kW and the ultrasonic time to be 120min through a cooling coil arranged in the kettle, and obtaining the carboxyl functionalized graphene aqueous slurry, wherein the concentration of the slurry is 1 g/mL.
And 8, conveying the slurry obtained in the step 7 into a drying tower through a pipeline, drying by adopting an upward-spraying airflow spray drying mode, setting the drying temperature to be 130 ℃, and collecting to obtain the carboxyl functionalized graphene powder.
In the embodiment, the number average molecular weight of the functional graphene in-situ polymerization polyester terpolymer composite material prepared by the special device and the method is 25000.
Example 2
The preparation device of the terpolymer composite material of the functional graphene in-situ polymerization polyester in the embodiment is the same as that in the embodiment 1, and the preparation method is as follows:
dispersing amino functional graphene and auxiliary materials (comprising titanium dioxide and a catalyst) in ethylene glycol to respectively obtain a functional graphene dispersion liquid and an auxiliary material dispersion liquid; and then adding the residual ethylene glycol, purified terephthalic acid, the functional graphene dispersion liquid and the auxiliary material dispersion liquid into a reaction kettle for dispersion, and then sequentially carrying out esterification and polycondensation reactions to obtain the ternary polymerization composite material. Wherein the mass of the functional graphene accounts for 0.5 percent of that of the ternary polymerization composite material.
As shown in fig. 1, the method specifically comprises the following steps:
(1) in a graphene adding device, amino functional graphene and ethylene glycol are controlled by a metering pump to have the mass fraction of 1% in functional graphene dispersion liquid, a high-shear emulsifying machine and an ultrasonic disperser are used simultaneously for dispersing and stripping, and the dispersion temperature is controlled to be lower than 40 ℃, the rotating speed of the high-shear emulsifying machine is 1200 r/min, the ultrasonic power is 10kW, and the dispersion time is 60min by a cooling coil arranged in the graphene adding device to obtain the amino functional graphene dispersion liquid.
(2) In the auxiliary material adding device, auxiliary materials (including titanium dioxide and a catalyst) and ethylene glycol are dispersed in a dispersion mode in which a high-shear emulsifying machine and an ultrasonic disperser are used simultaneously by controlling the using amount of the titanium dioxide to be 1.2% of the mass of the ternary polymerization composite material and the using amount of dibutyltin oxide as the catalyst to be 0.06% of the mass of the ternary polymerization composite material through a metering pump, and a cooling coil pipe is arranged in the auxiliary material adding device, wherein the dispersion temperature is controlled to be lower than 40 ℃, the rotating speed of the high-shear emulsifying machine is 1400r/min, the ultrasonic power is 10kW, and the dispersion time is 30min, so that an auxiliary material dispersion liquid is obtained, the catalyst preparation concentration in the auxiliary material dispersion liquid is 1%.
(3) And (2) passing the functional graphene dispersion liquid obtained in the step (1) through a high-pressure homogenizer, introducing the functional graphene dispersion liquid into a raw material preparation device after the high-pressure action of the homogenizer, introducing the auxiliary material dispersion liquid obtained in the step (2) into the raw material preparation device, simultaneously introducing the rest ethylene glycol and all the purified terephthalic acid into the raw material preparation device, uniformly mixing various raw materials by adopting a mode of simultaneously using a high-shear emulsifying machine and an ultrasonic disperser, controlling the mixing temperature to be 80 ℃ through an internal heating coil, controlling the rotating speed of the high-shear emulsifying machine to be 1400r/min, controlling the ultrasonic power to be 10kW, and controlling the ultrasonic time to be 30min to obtain the raw material mixed slurry. Wherein the molar ratio of the sum of the ethylene glycol added in the step 1-3 to the total purified terephthalic acid is 1.6: 1, when ethylene glycol is added, the recovered ethylene glycol in the recovery tank 11 is preferably used.
(4) And (3) introducing the material obtained in the step (3) into an esterification reaction device to perform esterification reaction, wherein the reaction temperature of a reaction kettle is controlled to be 255 ℃, the reaction pressure is 0.1-0.5 MPa, the reaction time is 3 hours, and the esterification reaction rate is controlled to be 98.5%.
(5) And (3) filtering the product obtained in the step (4) through a prepolymer filtering device, introducing the product into a polycondensation reaction device, and carrying out polycondensation reaction, wherein the reaction temperature of a reaction kettle is 275 ℃, the reaction vacuum degree is 18kPa (absolute pressure), the reaction time is 4.5h, the esterification reaction rate is controlled to be 99.6%, and the intrinsic viscosity reaches 1.08 dL/g.
(6) And (4) filtering the product obtained in the step (5) through a melt filtering device, and then introducing into a granulating and drying device or directly conveying to a spinning production line.
(7) Discharging gas-phase substances (mainly a mixture of ethylene glycol and water) generated in the reaction processes in the step 4 and the step 5 to a waste storage tank, separating the ethylene glycol through a rectifying tower, conveying the separated ethylene glycol to a recovery storage tank, and recycling the ethylene glycol to a raw material preparation device.
The amino functional graphene is prepared by the method described in the embodiment 1 of Chinese patent 201810212266.0.
In the embodiment, the number average molecular weight of the ternary polymerization composite material of the functional graphene in-situ polymerization polyester prepared by the special device and the method is 2450.
Example 3
The preparation device of the terpolymer composite material of the functional graphene in-situ polymerization polyester in the embodiment is the same as that in the embodiment 1, and the preparation method is as follows:
dispersing carboxyl functional graphene and auxiliary materials (including a catalyst) in ethylene glycol to respectively obtain a functional graphene dispersion liquid and an auxiliary material dispersion liquid; and then adding the residual ethylene glycol, purified terephthalic acid, the functional graphene dispersion liquid and the auxiliary material dispersion liquid into a reaction kettle for dispersion, and then sequentially carrying out esterification and polycondensation reactions to obtain the ternary polymerization composite material. Wherein the mass of the functional graphene accounts for 2% of that of the ternary polymerization composite material.
As shown in fig. 1, the method specifically comprises the following steps:
(1) in a graphene adding device, controlling the mass fraction of carboxyl functional graphene in functional graphene dispersion liquid to be 5% by a metering pump, dispersing and stripping by adopting a mode of using a high-shear emulsifying machine and an ultrasonic disperser simultaneously, controlling the dispersing temperature to be lower than 40 ℃, controlling the rotating speed of the high-shear emulsifying machine to be 2500 r/min, controlling the ultrasonic power to be 8kW and controlling the dispersing time to be 2h by a cooling coil arranged in the graphene adding device, and thus obtaining the carboxyl functional graphene dispersion liquid.
(2) In the auxiliary material adding device, auxiliary materials (including a catalyst) and ethylene glycol are controlled by a metering pump to enable the dosage of the catalyst monobutyl tin trichloride to be 0.1% of the mass of the ternary polymerization composite material, a dispersion mode that a high-shear emulsifying machine and an ultrasonic disperser are used simultaneously is adopted for dispersion, a cooling coil arranged in the auxiliary material adding device is used for controlling the dispersion temperature to be lower than 40 ℃, the rotating speed of the high-shear emulsifying machine is 1500r/min, the ultrasonic power is 5kW, and the dispersion time is 30min, so that an auxiliary material dispersion liquid is obtained, and the catalyst preparation concentration in the auxiliary material dispersion liquid is 1%.
(3) And (2) passing the functional graphene dispersion liquid obtained in the step (1) through a high-pressure homogenizer, introducing the functional graphene dispersion liquid into a raw material preparation device after the high-pressure action of the homogenizer, introducing the auxiliary material dispersion liquid obtained in the step (2) into the raw material preparation device, simultaneously introducing the rest ethylene glycol and all the purified terephthalic acid into the raw material preparation device, uniformly mixing various raw materials by adopting a mode of simultaneously using a high-shear emulsifying machine and an ultrasonic disperser, controlling the mixing temperature to be 80 ℃ through an internal heating coil, controlling the rotating speed of the high-shear emulsifying machine to be 1800r/min, controlling the ultrasonic power to be 10kW, and controlling the ultrasonic time to be 30min to obtain the raw material mixed slurry. Wherein the molar ratio of the sum of the ethylene glycol added in the step 1-3 to the total purified terephthalic acid is 1.5: 1, when ethylene glycol is added, the recovered ethylene glycol in the recovery tank 11 is preferably used.
(4) And (3) introducing the material obtained in the step (3) into an esterification reaction device to perform esterification reaction, wherein the reaction temperature of a reaction kettle is controlled at 260 ℃, the reaction pressure is 0.1-0.5 MPa, the reaction time is 2.5h, and the esterification reaction rate is controlled to reach 98%.
(5) And (3) filtering the product obtained in the step (4) through a prepolymer filtering device, introducing the product into a polycondensation reaction device, and carrying out polycondensation reaction, wherein the reaction temperature of a reaction kettle is 273 ℃, the reaction vacuum degree is 25kPa (absolute pressure), the reaction time is 5 hours, the esterification reaction rate is controlled to be 99.6%, and the intrinsic viscosity reaches 0.8 dL/g.
(6) And (4) filtering the product obtained in the step (5) through a melt filtering device, and then introducing into a granulating and drying device or directly conveying to a spinning production line.
(7) Discharging gas-phase substances (mainly a mixture of ethylene glycol and water) generated in the reaction processes in the step 4 and the step 5 to a waste storage tank, separating the ethylene glycol through a rectifying tower, conveying the separated ethylene glycol to a recovery storage tank, and recycling the ethylene glycol to a raw material preparation device.
The carboxyl functional graphene is prepared by the following method:
firstly, graphite oxide is dispersed and peeled in N, N-dimethylformamide with a certain volume in a mechanical dispersion mode that a high-shear emulsifying machine and an ultrasonic disperser operate simultaneously, the dispersion concentration is 0.5mg/mL, graphene oxide dispersion liquid is obtained, then a certain amount of aminocaproic acid is slowly added into the graphene oxide dispersion liquid, the using amount of the aminocaproic acid is 100% of the mass of the graphite oxide powder, reflux reaction is carried out at the temperature of 130 ℃ for 24 hours, black dispersion liquid is obtained, the obtained black dispersion liquid is fully washed by absolute ethyl alcohol, and then freeze drying is carried out, so that carboxyl functional graphene powder is obtained.
Example 4
The preparation device of the terpolymer composite material of the functional graphene in-situ polymerization polyester in the embodiment is the same as that in the embodiment 1, and the preparation method is as follows:
dispersing amino functional graphene and auxiliary materials (comprising titanium dioxide and a catalyst) in propylene glycol to respectively obtain a functional graphene dispersion liquid and an auxiliary material dispersion liquid; and then adding the residual propylene glycol, purified terephthalic acid, functional graphene dispersion liquid and auxiliary material dispersion liquid into a reaction kettle for dispersion, and then sequentially carrying out esterification and polycondensation reactions to obtain the ternary polymerization composite material. Wherein the mass of the functional graphene accounts for 0.1 percent of that of the ternary polymerization composite material.
As shown in fig. 1, the method specifically comprises the following steps:
(1) in a graphene adding device, amino functional graphene and propylene glycol are controlled by a metering pump to have the mass fraction of 2% in functional graphene dispersion liquid, a high-shear emulsifying machine and an ultrasonic disperser are used simultaneously for dispersing and stripping, and the amino functional graphene dispersion liquid is obtained by controlling the dispersing temperature to be lower than 40 ℃, controlling the rotating speed of the high-shear emulsifying machine to be 1500r/min, controlling the ultrasonic power to be 8kW and controlling the dispersing time to be 60min through a cooling coil arranged in the device.
(2) In the auxiliary material adding device, auxiliary materials (including titanium dioxide and a catalyst) and propylene glycol are dispersed in a dispersion mode in which a high-shear emulsifying machine and an ultrasonic disperser are used simultaneously by controlling the using amount of the titanium dioxide to be 0.5% of the mass of the ternary polymerization composite material and the using amount of the dibutyltin oxide as the catalyst to be 0.05% of the mass of the ternary polymerization composite material through a metering pump, and a dispersion liquid is obtained by controlling the dispersion temperature to be lower than 40 ℃, the rotating speed of the high-shear emulsifying machine to be 1500r/min, the ultrasonic power to be 10kW and the dispersion time to be 30min through a cooling coil pipe arranged inside the auxiliary material adding device, wherein the catalyst preparation concentration in the auxiliary material dispersion liquid is 0.5% and the titanium.
(3) And (2) passing the functional graphene dispersion liquid obtained in the step (1) through a high-pressure homogenizer, introducing the functional graphene dispersion liquid into a raw material preparation device after the high-pressure action of the homogenizer, introducing the auxiliary material dispersion liquid obtained in the step (2) into the raw material preparation device, simultaneously introducing the rest propylene glycol and all purified terephthalic acid into the raw material preparation device, uniformly mixing various raw materials by adopting a mode of simultaneously using a high-shear emulsifying machine and an ultrasonic disperser, controlling the mixing temperature to be 80 ℃ through an internal heating coil, controlling the rotating speed of the high-shear emulsifying machine to be 1500r/min, controlling the ultrasonic power to be 10kW, and controlling the ultrasonic time to be 60min to obtain raw material mixed slurry. Wherein the molar ratio of the sum of the propylene glycol added in the step 1-3 to the total purified terephthalic acid is 1.4: 1, when propylene glycol is added, the recovered propylene glycol in the recovery tank 11 is preferably used.
(4) And (3) introducing the material obtained in the step (3) into an esterification reaction device to perform esterification reaction, wherein the reaction temperature of a reaction kettle is controlled to be 255 ℃, the reaction pressure is 0.1-0.5 MPa, the reaction time is 2 hours, and the esterification reaction rate is controlled to be 98.5%.
(5) And (3) filtering the product obtained in the step (4) through a prepolymer filtering device, introducing the product into a polycondensation reaction device, and carrying out polycondensation reaction, wherein the reaction temperature of a reaction kettle is 275 ℃, the reaction vacuum degree is 20kPa (absolute pressure), the reaction time is 4.5h, the esterification reaction rate is controlled to be 99.6%, and the intrinsic viscosity reaches 0.78 dL/g.
(6) And (4) filtering the product obtained in the step (5) through a melt filtering device, and then introducing into a granulating and drying device or directly conveying to a spinning production line.
(7) Discharging gas-phase substances (mainly a mixture of ethylene glycol and water) generated in the reaction processes in the step 4 and the step 5 to a waste storage tank, separating out propylene glycol through a rectifying tower, conveying the separated propylene glycol to a recovery storage tank, and recycling the propylene glycol to a raw material preparation device.
The amino functional graphene is prepared by the following method:
firstly, dispersing graphite oxide in water with a certain volume in a mechanical dispersion mode that a high shear emulsifying machine and an ultrasonic disperser operate simultaneously, wherein the dispersion concentration is 0.8mg/mL to obtain graphene oxide dispersion liquid, slowly adding a certain amount of p-phenylenediamine into the graphene oxide dispersion liquid, wherein the amount of the p-phenylenediamine is 50% of the mass of the graphene oxide powder, carrying out reflux reaction at the temperature of 80 ℃ for 8 hours to obtain black dispersion liquid, fully washing the obtained black dispersion liquid with absolute ethyl alcohol, and then carrying out freeze drying to obtain amino functional graphene powder.
Comparative example
The preparation apparatus and the preparation method of the terpolymer composite material of graphene in-situ polymerized polyester of the present comparative example are substantially the same as those of example 1, except that the preparation is performed using the general graphene.
The ternary copolymer composite materials obtained in the examples and the comparative examples are subjected to related performance tests, and the test results are shown in Table 1.
Table 1 results of performance testing
As can be seen from the data in Table 1, the ternary polymerization composite material of the functional graphene in-situ polymerization polyester provided by the invention has superior performance, and compared with the ternary polymerization composite material which is not modified by functional graphene in-situ polymerization, the ternary polymerization composite material has the advantages of antistatic performance, antibacterial property, far infrared performance, ultraviolet resistance and excellent mechanical property.
Claims (8)
1. A preparation method of a functional graphene in-situ polymerized polyester terpolymer composite material is characterized in that functional graphene and auxiliary materials are dispersed in dihydric alcohol to respectively obtain a functional graphene dispersion liquid and an auxiliary material dispersion liquid; adding dihydric alcohol, dibasic acid, functional graphene dispersion liquid and auxiliary material dispersion liquid into a reaction kettle for dispersion, and then sequentially carrying out esterification and polycondensation reaction to obtain the ternary copolymerization composite material, wherein the functional graphene is carboxyl functional graphene or amino functional graphene;
the carboxyl functional graphene is prepared by one of the following two methods:
A. firstly, graphite oxide is dispersed in a good solvent by a mechanical dispersion mode that a high-shear emulsifying machine and an ultrasonic disperser operate simultaneously, then aminocaproic acid is slowly added for reaction, and the reaction product is obtained after washing and drying;
B. firstly, graphite oxide is dispersed and stripped in alkali liquor in a mechanical dispersion mode that a high-shear emulsifying machine and an ultrasonic disperser operate simultaneously, then chloroacetic acid or sodium chloroacetate is adopted to carry out activation treatment on graphene oxide, and finally aminocaproic acid and N, N' -dicyclohexylcarbodiimide are added to carry out carboxylation reaction;
the amino functional graphene is prepared by one of the following two methods:
C. firstly, graphite oxide is dispersed in a good solvent by a mechanical dispersion mode that a high-shear emulsifying machine and an ultrasonic disperser operate simultaneously, then p-phenylenediamine is slowly added for reaction, and the graphite oxide is obtained after washing and drying;
D. the preparation method is described in example 1 in Chinese patent 201810212266.0.
2. The method of claim 1, comprising the steps of:
(1) dispersing functional graphene and dihydric alcohol in a graphene adding device in a mode of simultaneously using a high-shear emulsifying machine and an ultrasonic disperser to obtain functional graphene dispersion liquid, wherein the mass concentration of the functional graphene dispersion liquid is 0.1-10%;
(2) dispersing auxiliary materials and dihydric alcohol in an auxiliary material adding device by adopting a dispersion mode of simultaneously using a high-shear emulsifying machine and an ultrasonic disperser to obtain an auxiliary material dispersion liquid, wherein the mass concentration of the auxiliary material dispersion liquid is 0.1-35%;
(3) introducing the functional graphene dispersion liquid obtained in the step 1 into a raw material preparation device through a high-pressure homogenizer, introducing the auxiliary material dispersion liquid obtained in the step 2 into the raw material preparation device, simultaneously introducing dihydric alcohol and dibasic acid into the raw material preparation device, and then dispersing the materials in the device by adopting a mode that a high-shear emulsifying machine and an ultrasonic disperser are simultaneously used;
(4) introducing the material obtained in the step 3 into an esterification reaction device for esterification reaction;
(5) filtering the product obtained in the step 4 through a prepolymer filtering device, and then introducing the product into a polycondensation reaction device to perform polycondensation reaction;
(6) filtering the product obtained in the step 5 by a melt filtering device to obtain the ternary polymerization composite material;
(7) and (3) discharging gas-phase substances generated in the reaction processes in the step (4) and the step (5) to a waste storage tank, separating out dihydric alcohol through a rectifying tower, conveying the separated dihydric alcohol to a recovery storage tank, and recycling the dihydric alcohol to a raw material preparation device.
3. The preparation method according to claim 1 or 2, characterized in that the diol is one or more selected from ethylene glycol, propylene glycol, butanediol, cyclohexanediol, the diacid is purified terephthalic acid, and the mole ratio of the diol to the diacid is (1.2-2): 1, the functional graphene accounts for 0.01-2% of the ternary polymerization composite material by mass.
4. The preparation method of claim 2, wherein the stirring speed of the high shear emulsifying machine is not less than 1000r/min, the ultrasonic power of the ultrasonic disperser is 1-20 kw, the dispersing time is 1-10 h, and the dispersing temperature is 10-40 ℃.
5. The preparation method of claim 2, wherein the auxiliary material comprises a catalyst, the catalyst is antimony, titanium, tin or germanium, and the amount of the catalyst is 0.05-0.25% of the total mass of the reaction materials.
6. The method according to claim 2, wherein the esterification reaction is carried out under the following conditions: the reaction temperature is 250-265 ℃, the reaction pressure is 0.1-0.5 MPa, the reaction time is 0.5-2.5 h, and the esterification reaction rate is controlled to be not lower than 96%; the conditions of the polycondensation reaction are as follows: the reaction temperature is 265-280 ℃, the reaction vacuum degree is 0.1-25 kPa, the reaction time is 0.5-5 h, and the esterification reaction rate is controlled to be not less than 99.5%.
7. The functional graphene in-situ polymerization polyester ternary polymerization composite material prepared by the method of any one of claims 1 to 6.
8. The terpolymer composite according to claim 7, wherein the composite has a number average molecular weight of 10000-150000 and an intrinsic viscosity of 0.6-1.2 dL/g.
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