CN107778469B - A kind of 2,5- furandicarboxylic acid base polyester/phyllosilicate nano-composite material and its preparation method and application - Google Patents
A kind of 2,5- furandicarboxylic acid base polyester/phyllosilicate nano-composite material and its preparation method and application Download PDFInfo
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- CN107778469B CN107778469B CN201710899317.7A CN201710899317A CN107778469B CN 107778469 B CN107778469 B CN 107778469B CN 201710899317 A CN201710899317 A CN 201710899317A CN 107778469 B CN107778469 B CN 107778469B
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- CN
- China
- Prior art keywords
- furandicarboxylic acid
- phyllosilicate
- acid base
- composite material
- base polyester
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- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 71
- 229920000728 polyester Polymers 0.000 title claims abstract description 67
- 229910052615 phyllosilicate Inorganic materials 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 89
- 230000004048 modification Effects 0.000 claims description 54
- 238000012986 modification Methods 0.000 claims description 54
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 47
- -1 2,5-furandicarboxylic acid diester Chemical class 0.000 claims description 46
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 44
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 35
- 238000002425 crystallisation Methods 0.000 claims description 32
- 230000008025 crystallization Effects 0.000 claims description 32
- 239000000725 suspension Substances 0.000 claims description 30
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 27
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical class CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 23
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006068 polycondensation reaction Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 238000011065 in-situ storage Methods 0.000 claims description 13
- 239000003760 tallow Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 230000002687 intercalation Effects 0.000 claims description 10
- 238000009830 intercalation Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical class CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 claims description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- FQXGHZNSUOHCLO-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-cyclobutanediol Chemical compound CC1(C)C(O)C(C)(C)C1O FQXGHZNSUOHCLO-UHFFFAOYSA-N 0.000 claims description 2
- XVBXJBGOQQLLAO-UHFFFAOYSA-J [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O Chemical compound [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O XVBXJBGOQQLLAO-UHFFFAOYSA-J 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- CYDRXTMLKJDRQH-UHFFFAOYSA-N benzododecinium Chemical compound CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CYDRXTMLKJDRQH-UHFFFAOYSA-N 0.000 claims description 2
- FWLORMQUOWCQPO-UHFFFAOYSA-N benzyl-dimethyl-octadecylazanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 FWLORMQUOWCQPO-UHFFFAOYSA-N 0.000 claims description 2
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 125000006182 dimethyl benzyl group Chemical group 0.000 claims description 2
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical class CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 claims description 2
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 241000549556 Nanos Species 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000006177 alkyl benzyl group Chemical group 0.000 claims 1
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000004299 exfoliation Methods 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 4
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 229910017059 organic montmorillonite Inorganic materials 0.000 description 37
- 238000002156 mixing Methods 0.000 description 26
- 238000005809 transesterification reaction Methods 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 16
- 229910052787 antimony Inorganic materials 0.000 description 15
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 238000002604 ultrasonography Methods 0.000 description 13
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910000271 hectorite Inorganic materials 0.000 description 6
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 241000446313 Lamella Species 0.000 description 5
- 150000005690 diesters Chemical class 0.000 description 5
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical class NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
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- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 3
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- 238000004458 analytical method Methods 0.000 description 2
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- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical class CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
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- 150000002334 glycols Chemical class 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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- 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
- C08K7/00—Use of ingredients characterised by shape
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of 2,5-furandicarboxylic acid base polyester/phyllosilicate nano-composite material and its preparation method and application, the composite material, which includes 2,5-furandicarboxylic acid base polyester and phyllosilicate, to be prepared by situ aggregation method.Phyllosilicate through organic-treating is high in the intracorporal extent of exfoliation of products therefrom base, and molecular weight is higher, and tensile strength is big, has certain crystal property.The preparation method simple possible, advantageously accounts for the slow problem of 2,5-furandicarboxylic acid base crystallizing polyester rate, at the same can further expansion its application in high-gas resistance packaging market, the industrialization after being lays a good foundation.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of high performance 2,5-furandicarboxylic acid base is poly-
Ester/laminated nm-silicate composite material and its preparation method and application.
Background technique
There is weight in polymer industry based on the polyester that petroleum base monomers terephthalic acid or bis- terephthalate synthesize
The status wanted, such as polyethylene terephthalate (Poly (ethylene terephthalate), english abbreviation PET) year
Nearly 70,000,000 tons of yield, it is widely used in fiber, film and plastic bottle etc..However, traditional fossil resources due to
It is non-renewable to face shortage or even exhausted danger, therefore it is a kind of for developing a kind of reproducible resource part substitution fossil resources
The method of effective sustainable development.Currently, being determined as 12 kinds of most competitive biomass in 2004 by U.S. Department of Energy
The 2,5-furandicarboxylic acid and its diester of one of monomer, due to having structure similar with terephthalic acid (TPA) and its diester and property
Matter has vast potential for future development.
2,5-furandicarboxylic acid or its diester can 2,5-furandicarboxylic acid base polyester corresponding with dihydric alcohol generation, with poly- 2,
5- furandicarboxylic acid glycol ester (Poly (ethylene 2,5-furandicarboxylate), english abbreviation PEF) is
Example, is made by 2,5-furandicarboxylic acid or its diester and ethylene glycol by melt polycondensation.The polyester PEF and petroleum base of biology base
Polyester PET compare, the two have comparable physical property, but PEF not only have higher glass transition temperature and
Tensile strength, and it is to the gas permeability coefficient of oxygen and carbon dioxide 11 times low compared with PET and 19 times, the i.e. gas of PEF respectively
Body barrier property is better than PET, more holds promise for packing the substance to gas sensitization, such as fruit juice, beer etc..However, due to furans
Oxygen atom in ring, which imparts the stronger polarity of 2,5- furandicarboxylic acid base polyester and the asymmetry of furan nucleus, leads to difference
The crystalline rate of molecule segment activity, 2,5-furandicarboxylic acid base polyester is slower, such as " Polymer " periodical (2016,87:
148-158) in a text, the PEF of synthesis does not occur melt crystallization peak under the rate of temperature fall of 10 DEG C/min.2,5- furandicarboxylic acid
Although base crystallizing polyester rate is conducive to the transparency that sample keeps certain slowly, it is detrimental to injection molding, is also unfavorable for leading to
It crosses solid phase polycondensation and improves its molecular weight.
Phyllosilicate has length and width about 100nm, the lamellar structure of thickness about 1nm, by being mingled among two oxygen-octahedrons
One layer of aluminum-oxygen tetrahedron is constituted, and by a shared oxygen atom connection, interlayer dissociates a large amount of Na the two+、Ca2+And Mg2+
Equal cations.In order to be dispersed in the lamella of phyllosilicate in macromolecule matrix, generally all had using positively charged
The inorganic cation of machine molecule (such as alkylammonium salt) and interlayer carries out ion-exchange reactions and generates organic modified sheet silicate, so
It is nano combined with polymer progress afterwards, to improve polymer performance.Prepare nano composite polymer/laminated silicate material
Technology path mainly has three kinds of solution blending, melt blending and in-situ polymerization methods, wherein needs to remove in solution blending process
A large amount of solvents, it is difficult to industrialize；Since polymer and phyllosilicate are difficult to form active force during melt blending, will lead to
Polyalcohol intercalation is insufficient, and the dispersity of silicate granules is bad；Reaction monomers or oligomer be gradually during in-situ polymerization
Insertion silicate plate interlayer is reacted, and lamella is caused gradually to be softened, and is conducive to be uniformly distributed in a polymer matrix, be formed
Intercalation/exfoliated polymer/laminated nm-silicate composite material.
By the phyllosilicate of organic modifiers intercalation modifying with based on terephthalic acid (TPA) or secondly Lipase absobed polyester
Carrying out nano combined research has many patent applications.Such as application No. is 200910147596.7 Chinese patent literatures to pass through
The montmorillonite of the quaternary ammonium salt treatment of 5wt% and PET carry out melt blending, polyester/phyllosilicate nano-composite material obtained
With higher tensile strength；As the Chinese patent literature of application number 02123499.X passes through the octadecyl benzyl two of 3wt%
The modified montmorillonite of methyl bromide ammonium and PBT carry out melt blending, and polyester/phyllosilicate nano-composite material obtained has
Higher impact strength；As the Chinese patent literature of application number 201210044664.9 is made by the method for in-situ polymerization
Polyester/phyllosilicate nano-composite material, Nano-silicate particles are scattered in polyester matrix with the of uniform size of 10-100nm
In；Phyllosilicate and terephthalic acid (TPA) that the Chinese patent literature of application number 01113754.1 is handled by organic modifiers,
Ethylene glycol monomers carry out in-situ polymerization, and the OTR oxygen transmission rate of the polyester/phyllosilicate nano-composite material of synthesis reduces one
Times.
However, the research now for 2,5-furandicarboxylic acid base polyester focuses primarily upon synthesis aspect, and for its property
Can modified aspect research it is less, carry out especially by phyllosilicate with it nano combined for promoting grinding for its performance
Study carefully.Through consulting, domestic temporarily without related application, only several external documents are had been reported, such as " RSC Advances " phase
It prints in (2016,6:59800-59807) text, the PEF/ montmorillonite-based nano composite wood of intercal type has been synthesized by solution blended process
Material effectively increases the thermal stability and crystallinity of PEF, but solvent used is expensive hexafluoroisopropanol, and
Promote the effect of PEF crystallization unobvious, for raw material PEF under the rate of temperature fall of 2 DEG C/min, melt crystallization enthalpy has 9.3J/g, and
PEF nanocomposite containing 4wt% organic modification montmonrillonite, under the rate of temperature fall of 2 DEG C/min, melt crystallization enthalpy
Only 14.5J/g；As closed by melt-blending process in " Composites Part B " periodical (2017,110:96-105) text
At the PEF/ Nano composite material of montmorillonite of intercal type, the thermal stability of PEF is effectively increased, but to the crystallinity of PEF
Facilitation is had no, and sheet surfaces have the organic modification montmonrillonite of a large amount of hydrophilic hydroxy groups, in melt-processed process
Middle meeting is so that the molecular weight of PEF has largely reduces.In addition, at present existing PEF and amido multi-walled carbon nano-tube and
The report of nano silica, titanium dioxide in-situ polymerization, equally exists that molecular weight is not high enough and crystal property is imperfect
It is insufficient.
In conclusion different nanoparticles and nano combined preparation method influence the performance of nanometer composite polyester material
It is larger.For 2,5-furandicarboxylic acid base nanometer composite polyester material, there are still certain deficiencies at present, main to show
Are as follows: the 2,5-furandicarboxylic acid base nanometer composite polyester material molecular weight of synthesis is lower, and characteristic Nian Shuo≤0.5dL/g causes to receive
Influence of the rice corpuscles to its mechanical property has not been reported；Promote the effect of 2,5-furandicarboxylic acid base crystallizing polyester still not good enough,
, can only be in rate of temperature fall (≤5 DEG C/min at a slow speed such as PEF nanocomposite) under melt crystallization, and fast cooling rate (>=
10 DEG C/min) under crystallization facilitating effect it is bad or have not been reported.Therefore, suitable nanoparticle and nano combined side are chosen
The 2,5-furandicarboxylic acid base nanometer composite polyester material that method prepares easily crystallization, molecular weight is high and mechanical strength is big, is one
Urgent problem to be solved.
Summary of the invention
Slow for 2,5-furandicarboxylic acid base crystallizing polyester rate in the prior art, the small deficiency of molecular weight proposes one kind
High performance 2,5-furandicarboxylic acid base polyester/phyllosilicate nano-composite material and its preparation method and application, gained is multiple
Condensation material easily crystallizes, molecular weight is high and mechanical strength is big.
The technical solution adopted by the invention is as follows:
A kind of 2,5-furandicarboxylic acid base polyester/phyllosilicate nano-composite material, including 2,5-furandicarboxylic acid base
Polyester and phyllosilicate are led to by 2,5-furandicarboxylic acid or 2,5-furandicarboxylic acid dimethyl ester, dihydric alcohol and phyllosilicate
In-situ polymerization is crossed to obtain.
It is based on 100% 2 by 2,5-furandicarboxylic acid or the quality summation of 2,5-furandicarboxylic acid dimethyl ester and dihydric alcohol,
The dosage of 5- furandicarboxylic acid or 2,5-furandicarboxylic acid dimethyl ester is 20~80wt%, the dosage of dihydric alcohol is 20~
80wt%, the dosage of phyllosilicate be 2,5-furandicarboxylic acid or 2,5-furandicarboxylic acid dimethyl ester dosage 0.01~
10wt%, preferably, the dosage of phyllosilicate is 2,5-furandicarboxylic acid or 2,5-furandicarboxylic acid dimethyl ester dosage
1.5~5wt% is supplied to the nucleation of 2,5-furandicarboxylic acid base crystallizing polyester if the dosage of phyllosilicate is lower than this range
Site is very few, if dosage is higher than this range, phyllosilicate aggregate structure easy to form in the course of the polymerization process leads to 2,5- furans
The intracorporal dispersion of diformyl polyester base is uneven, is unfavorable for its crystal property and mechanical property.And the use of phyllosilicate
In preferred scope, phyllosilicate is uniformly dispersed amount in matrix and extent of exfoliation is higher, is conducive to promotion 2,5- furans
The crystal property and mechanical property of diformyl polyester.
The dihydric alcohol is ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,6-HD, 1,4-
Cyclohexanedimethanol, 1,4- cyclohexanediol, 2,2,4,4- tetramethyl -1,3- cyclobutanediol, polyethylene glycol, polypropylene glycol and poly- four
One or more of hydrogen furans ether glycol.Wherein, for the polyethylene glycol of polyether Glycols, polypropylene glycol and polytetrahydrofuran
Ether glycol, number-average molecular weight 450-6000, preferably, the number-average molecular weight of polyether Glycols is 1000-3000.
The phyllosilicate is by the montmorillonite of organic intercalation agent modification, saponite or Meccah stone.At this
In invention, the modification of phyllosilicate can use method in the prior art, and it is modified i.e. to can be realized organic intercalation agent
It can.
The organic intercalation agent is dodecyl trimethyl ammonium salt, cetyltrimethyl ammonium salt, octadecyl trimethyl
Ammonium salt, cetyl double hydroxyethyl methyl ammonium salt, octadecyl double hydroxyethyl methyl ammonium salt, dodecylbenzyl dimethyl ammonium
Salt, cetyl benzyl dimethyl ammonium salt, octadecyl benzyl dimethyl ammonium salt, double octadecyldimethyl ammonium salts, methyl are double
(2- ethoxy) hydrogenated tallow based quaternary ammonium salt, double hydrogenated-tallow group dimethyl quaternary ammoniums or double hydrogenated-tallow group dimethyl benzyl seasons
Ammonium salt.
The intrinsic viscosity of the 2,5- furandicarboxylic acid base polyester/phyllosilicate nano-composite material is not less than
0.6dL/g, melt crystallization enthalpy under 10 DEG C/min cooling rate compared with its 2,5-furandicarboxylic acid base polyester ontology growth not
Lower than 5J/g, growth of the tensile strength compared with its 2,5-furandicarboxylic acid base polyester ontology is not less than 10Mpa.As comparative example 1 synthesizes
Intrinsic viscosity be 0.7dL/g PEF, do not crystallized under 10 DEG C/min cooling rate, tensile strength 85Mpa；And implement
The comparable PEF/ laminated nm-silicate composite material of intrinsic viscosity that example 2 synthesizes, the knot under 10 DEG C/min cooling rate
Brilliant enthalpy is 27J/g, and tensile strength reaches 113Mpa.
The present invention also provides a kind of above-mentioned 2,5- furandicarboxylic acid base polyester/phyllosilicate nano-composite materials
Preparation method, comprising the following steps:
(1) phyllosilicate is mixed with dihydric alcohol, is dispersed, the dihydric alcohol suspension containing phyllosilicate is made；
(2) in atmosphere of inert gases, put into reactor 2,5-furandicarboxylic acid or 2,5-furandicarboxylic acid diester,
The resulting dihydric alcohol suspension of step (1) and catalyst 1, and 1~10h is reacted at 150~210 DEG C, intermediate is made；
(3) catalyst 2 is added into the intermediate of step (2), heats up and carries out depressurization condensation reaction, reaction temperature is
210~250 DEG C, system pressure≤200Pa, the polycondensation time is 1~8h, can be obtained 2,5-furandicarboxylic acid base polyester/stratiform
Silicate nanometer composite material.
Present invention introduces the hydroxyl phyllosilicates through organic modifiers intercalation modifying of sheet surfaces, by situ poly-
It is legal that it is made to form certain active force with 2,5-furandicarboxylic acid base polyester, so that phyllosilicate lamella nanoparticle exists
The intracorporal dispersion of 2,5-furandicarboxylic acid base polyester machine is more uniform, forms the higher 2,5-furandicarboxylic acid base of extent of exfoliation
Polyester/phyllosilicate nano-composite material.
The catalyst 1 be tetrabutyl titanate, isopropyl titanate, stannous octoate, stannous oxalate, Dibutyltin oxide,
Compound, earth silicon/titanic oxide/nitrogenous compound compound and the silica/dioxy of earth silicon/titanic oxide
Change one or more of titanium/phosphorus-containing compound compound, dosage is 2,5-furandicarboxylic acid or 2,5-furandicarboxylic acid
0.01~0.4mol% of diester dosage.
The catalyst 2 is tetrabutyl titanate, isopropyl titanate, titanium ethylene glycolate, titanium acetylacetone, antimony glycol, three
Aoxidize two antimony, the compound of earth silicon/titanic oxide, earth silicon/titanic oxide/nitrogenous compound compound and dioxy
One or more of SiClx/titanium dioxide/phosphorus-containing compound compound, the amount of coming into operation are 2,5-furandicarboxylic acid or 2,5- furan
0.01~0.4mol% of dicarboxylate dosage of muttering.
The catalyst activity that the present invention selects is high, is conducive to improve esterification or ester exchange rate, promotes polycondensation reaction, mention
High molecular weight.
The present invention also provides a kind of above-mentioned 2,5- furandicarboxylic acid base polyester/phyllosilicate nano-composite materials to make
Application in standby high-gas resistance packaging material.
Compared with prior art, the invention has the following advantages:
(1) the 2,5- furandicarboxylic acid base polyester/phyllosilicate nano that the present invention is synthesized using situ aggregation method is compound
Material molecule amount is higher, and intrinsic viscosity is above 0.6dL/g；
(2) present invention introduces the hydroxyl phyllosilicate through organic modifiers intercalation modifying of sheet surfaces, pass through original
Position polymerization makes it form certain active force with 2,5-furandicarboxylic acid base polyester, thus phyllosilicate lamella nanoparticle
Son is more uniform in the intracorporal dispersion of 2,5-furandicarboxylic acid base polyester machine, forms higher 2, the 5- furans diformazan of extent of exfoliation
Acid based polyester/laminated nm-silicate composite material；
(3) the 2,5- furandicarboxylic acid base polyester/phyllosilicate nano that the present invention is synthesized using situ aggregation method is compound
Material has certain crystallizing power, as containing montmorillonite of the 2.5wt% through octadecyl double hydroxyethyl methyl ammonium salt treatment
PEF nanocomposite, intrinsic viscosity 0.73dL/g can be with melt crystallization under 10 DEG C/min rate of temperature fall, and crystallizes
Enthalpy reaches 27.3J/g；
(4) the 2,5- furandicarboxylic acid base polyester/phyllosilicate nano that the present invention is synthesized using situ aggregation method is compound
Material has better tensile strength, as containing montmorillonite of the 2.5wt% through octadecyl double hydroxyethyl methyl ammonium salt treatment
PEF nanocomposite, intrinsic viscosity 0.73dL/g, tensile strength is up to 113Mpa.
(5) the method for the present invention simple possible advantageously accounts for the slow problem of 2,5-furandicarboxylic acid base crystallizing polyester rate,
Simultaneously can further expansion its application in high-gas resistance packaging market, the industrialization after being lays a good foundation.
Detailed description of the invention
Fig. 1 is sample DSC temperature lowering curve prepared by comparative example 1~2 and Examples 1 to 4；
Fig. 2 is sample DSC heating curve prepared by comparative example 1~2 and Examples 1 to 4；
Fig. 3 is the XRD diffraction pattern of sample and organic modification montmonrillonite used prepared by embodiment 2 and embodiment 3；
Fig. 4 is sample TEM figure prepared by embodiment 2.
Specific embodiment
Method for testing and analyzing employed in following embodiment and comparative examples is as follows:
Intrinsic viscosity: using the intrinsic viscosity of Hangzhou Zhong Wang automatic viscosity instrument measurement embodiment sample, test temperature 25
DEG C, solvent for use is phenol/tetrachloroethanes (mass ratio w/w=3/2).
Infrared spectrum analysis: Fourier is carried out to embodiment sample using Thermo scientific nicolet 6700
Transformation decaying In situ ATR-FTIR analysis, test scope is 4000~400cm-1。
Heat deflection: DSC measurement is carried out to embodiment sample using TA-Q200 thermal analyzer, using heating-drop of standard
Temperature-temperature program.It is warming up to 250 DEG C from 30 DEG C with the heating rate of 10 DEG C/min first, keeps 5min；Then with 10 DEG C/min
Rate of temperature fall be cooled to 30 DEG C, keep the temperature 5min；Finally 250 DEG C are warming up to the heating rate of 10 DEG C/min again.
Tensile strength: using the dumbbell shape batten of HaakeMiniJet II miniature injection machine preparation thickness 2mm, width 4mm.Root
According to ASTM D638 standard, using German Zwick company Roell Z020 model universal testing machine, in 25 DEG C and 10mm/
Extension test is carried out under the conditions of the rate of extension of min.5 battens of each sample test, take its average value as test result.
Transmission electron microscope TEM experiment: JEM-1200EX transmission electron microscope instrument, ultra-thin section after sample embedding are used.
X-ray diffraction XRD experiment: use D/max-rc type x-ray diffractometer, CuK alpha ray, 1-10 ° of scanning range,
Scanning speed is 1 °/min, is pressed into thin slice after sample melted.
Combined with specific embodiments below, the present invention is further specifically described.Following embodiment is merely to illustrate the present invention, but
The present invention is not limited to these embodiments.
Comparative example 1
(1) into the reactor of nitrogen atmosphere be added 66.28g 2,5- furandicarboxylic acid dimethyl ester, 44.67g ethylene glycol and
0.08g stannous oxalate reacts 1 hour in 170 DEG C, and 180 DEG C are reacted 1 hour, and 190 DEG C are reacted 1 hour, and 200 DEG C are reacted 1 hour,
Obtain transesterification product；
(2) into transesterification product obtained in step (2) be added 0.1g antimony glycol, 240 DEG C, high vacuum (≤
Polycondensation 3 hours under conditions of 133Pa) obtain poly- 2,5-furandicarboxylic acid glycol ester (being denoted as PEF), and performance is shown in Table 1.
Comparative example 2
The poly- 2,5- furandicarboxylic acid glycol ester and 0.125g that 5g comparative example 1 is obtained are through octadecyl double hydroxyethyl first
The montmorillonite (being denoted as OMMT) of base ammonium salt modification is blended in the miniature blending instrument of MiniLab, and it is 250 that instrument temperature, which is blended,
DEG C, revolving speed 80r/min, be blended time 5min, obtain melt blending formation poly- 2,5-furandicarboxylic acid glycol ester/it is organic
Nano composite material of montmorillonite (is denoted as PEF/OMMT nanocomposite), at the modification of octadecyl double hydroxyethyl methyl ammonium salt
The montmorillonite dosage of reason is the 2.5wt% of poly- 2,5-furandicarboxylic acid glycol ester quality, and performance is shown in Table 1.
Embodiment 1
(1) montmorillonite by the 0.67g after drying through octadecyl double hydroxyethyl methyl ammonium salt modification and 44.67g
Ethylene glycol mixing, is vigorously stirred to be placed within 2 hours under ultrasound environments and disperse 15 minutes, is made containing through octadecyl double hydroxyethyl
The glycolic suspension of the montmorillonite of methyl ammonium salt treatment；
(2) under nitrogen atmosphere, step (1) resulting glycolic suspension, 66.28g 2,5- furan are added into reactor
It mutters dicarboxylic acid dimethyl ester and 0.08g stannous oxalate, is reacted in 170 DEG C 1 hour, 180 DEG C are reacted 1 hour, and 190 DEG C are reacted 1 hour,
200 DEG C are reacted 1 hour, and transesterification product is obtained；
(3) into transesterification product obtained in step (2) be added 0.1g antimony glycol, and 240 DEG C, high vacuum (≤
Polycondensation 3 hours under conditions of 133Pa) obtain poly- 2,5-furandicarboxylic acid glycol ester/organic montmorillonite nano composite material,
The dosage of montmorillonite through octadecyl double hydroxyethyl methyl ammonium salt modification is 2,5- furandicarboxylic acid dimethyl ester dosage
1wt%, performance are shown in Table 1.
Embodiment 2
(1) montmorillonite by the 1.66g after drying through octadecyl double hydroxyethyl methyl modification and 44.67g second two
Alcohol mixing, is vigorously stirred to be placed within 2 hours under ultrasound environments and disperse 15 minutes, is made containing through octadecyl double hydroxyethyl methyl
The glycolic suspension of the montmorillonite of ammonium salt modification；
(2) under nitrogen atmosphere, step (1) resulting glycolic suspension, 66.28g 2,5- furan are added into reactor
It mutters dicarboxylic acid dimethyl ester and 0.08g stannous oxalate, is reacted in 170 DEG C 1 hour, 180 DEG C are reacted 1 hour, and 190 DEG C are reacted 1 hour,
200 DEG C are reacted 1 hour, and transesterification product is obtained；
(3) into transesterification product obtained in step (2) be added 0.1g antimony glycol, and 240 DEG C, high vacuum (≤
Polycondensation 3 hours under conditions of 133Pa) obtain poly- 2,5-furandicarboxylic acid glycol ester/organic montmorillonite nano composite material,
The dosage of montmorillonite through octadecyl double hydroxyethyl methyl ammonium salt modification is 2,5- furandicarboxylic acid dimethyl ester dosage
2.5wt%, performance are shown in Table 1.
Embodiment 3
(1) montmorillonite by the 2.32g after drying through 18 double hydroxyethyl methyl ammonium salt modifications and 44.67g second two
Alcohol mixing, is vigorously stirred to be placed within 2 hours under ultrasound environments and disperse 15 minutes, is made containing through octadecyl double hydroxyethyl methyl
The glycolic suspension of the montmorillonite of ammonium salt modification；
(2) under nitrogen atmosphere, step (1) resulting glycolic suspension, 66.28g 2,5- furan are added into reactor
It mutters dicarboxylic acid dimethyl ester and 0.08g stannous oxalate, is reacted in 170 DEG C 1 hour, 180 DEG C are reacted 1 hour, and 190 DEG C are reacted 1 hour,
200 DEG C are reacted 1 hour, and transesterification product is obtained；
(3) into transesterification product obtained in step (2) be added 0.1g antimony glycol, and 240 DEG C, high vacuum (≤
Polycondensation 3 hours under conditions of 133Pa) obtain poly- 2,5-furandicarboxylic acid glycol ester/organic montmorillonite nano composite material,
The dosage of montmorillonite through octadecyl double hydroxyethyl methyl ammonium salt modification is 2,5- furandicarboxylic acid dimethyl ester dosage
3.5wt%, performance are shown in Table 1.
Embodiment 4
(1) montmorillonite by the 3.98g after drying through octadecyl double hydroxyethyl methyl ammonium salt modification and 44.67g
Ethylene glycol mixing, is vigorously stirred to be placed within 2 hours under ultrasound environments and disperse 15 minutes, is made containing through octadecyl double hydroxyethyl
The glycolic suspension of the montmorillonite of methyl ammonium salt modification；
(2) under nitrogen atmosphere, step (1) resulting glycolic suspension, 66.28g 2,5- furan are added into reactor
It mutters dicarboxylic acid dimethyl ester and 0.08g stannous oxalate, is reacted in 170 DEG C 1 hour, 180 DEG C are reacted 1 hour, and 190 DEG C are reacted 1 hour,
200 DEG C are reacted 1 hour, and transesterification product is obtained；
(3) into transesterification product obtained in step (2) be added 0.1g antimony glycol, and 240 DEG C, high vacuum (≤
Polycondensation 3 hours under conditions of 133Pa) obtain poly- 2,5-furandicarboxylic acid glycol ester/organic montmorillonite nano composite material,
The dosage of montmorillonite through octadecyl double hydroxyethyl methyl ammonium salt modification is 2,5- furandicarboxylic acid dimethyl ester dosage
6wt%, performance are shown in Table 1.
Properties of sample parameter list prepared by table 1
Comparative example 1 and comparative example 2 are not add the pure PEF of organic modification montmonrillonite synthesis and prepared by melt blending respectively
Additive amount be 2.5wt% PEF/OMMT nanocomposite, Examples 1 to 4 be by in-situ polymerization synthesize PEF/
The organic modification montmonrillonite type of OMMT nanocomposite, addition is identical as comparative example 2, and dosage be respectively 1wt%,
2.5wt%, 3.5wt% and 6wt%.
Intrinsic viscosity test is carried out to sample made above, the results are shown in Table 1.Test shows to pass through in-situ polymerization
Technology can with composite character viscosity number 0.7dL/g or so PEF/OMMT nanocomposite, and add organo montmorillonite simultaneously
There is not apparent influence to its intrinsic viscosity, and the PEF/OMMT nanocomposite prepared by melt blending, characteristic are viscous
Number reduces 0.08dL/g compared with PEF raw material, illustrates that organic modification montmonrillonite can cause the drop of PEF molecular weight in melt blending process
Low, possible reason is that montmorillonite layer surface has a large amount of hydrophilic hydroxyls, the melting carried out at high temperature with PEF
The water being easy in absorption air in Blending Processes leads to the hydrolysis of PEF, the reduction of molecular weight, and then influences the power of material itself
Learn performance.
Heat deflection test is carried out to sample made above, obtained temperature lowering curve is as shown in Figure 1, second of heating curve
As shown in Fig. 2, specific data are as shown in table 1, wherein Tc、ΔHcIt respectively represents the melt crystallization temperature in temperature-fall period and melts
Body crystallization enthalpy, Tcc、ΔHcc、Tm、ΔHmRespectively represent cold crystallization temperature in second of temperature-rise period, cold crystallization enthalpy, fusing point with
And melting enthalpy.Test shows that the pure PEF of comparative example 1 is not crystallized under the cooling rate of 10 DEG C/min, and comparative example 2 passes through melt blending
The PEF/OMMT nanocomposite of 2.5% organic modification montmonrillonite of addition of preparation is basic under the cooling rate of 10 DEG C/min
It does not crystallize, but occurs faint cold crystallization peak during subsequent secondary temperature elevation, cold crystallization enthalpy is 4J/g.
Examples 1 to 4 is addition 1wt%, 2.5wt% respectively, 3.5wt% and 6wt% organic modification montmonrillonite and is passed through
The PEF/OMMT nanocomposite of in-situ polymerization synthesis.From Fig. 1,2 and table 1 as can be seen that when organic modification montmonrillonite
Additive amount in a certain range when, the crystallinity of the PEF/OMMT nanocomposite synthesized by in-situ polymerization is significantly better than molten
Melt the PEF/OMMT nanocomposite that preparation is blended, and the additive amount of its crystallinity and organic modification montmonrillonite has certain pass
System.When additive amount is 1wt%, melt crystallization of the PEF/OMMT nanocomposite under the cooling rate of 10 DEG C/min is simultaneously unknown
It is aobvious, it is only to occur apparent cold crystallization peak during subsequent secondary temperature elevation, cold crystallization enthalpy is 10J/g；Additive amount is
When 2.5wt% and 3.5wt%, PEF/OMMT nanocomposite occurs significantly molten under the cooling rate of 10 DEG C/min
Body peak crystallization, and melt crystallization enthalpy is respectively 27J/g and 10J/g；When additive amount is 6wt%, PEF/OMMT nanocomposite
Do not occur melt crystallization peak, not occurring cold crystallization peak during subsequent secondary temperature elevation in temperature-fall period yet.The above results are said
Bright organic modification montmonrillonite adding too much or the too low crystal property that will affect PEF/OMMT nanocomposite, mainly
Reason is that organic modification montmonrillonite additive amount is too low and is easy to cause the site for providing PEF nucleation inadequate, and adding too much is easy
Montmorillonite is caused to be reunited, and additive amount such as adds the embodiment 2 of 2.5wt% and 3.5wt% respectively and implements in OK range
Example 3, XRD diffraction pattern illustrate this additive amount as shown in figure 3, the two does not occur the d001 characteristic peak of organo montmorillonite used
Organo montmorillonite it is higher in the intracorporal extent of exfoliation of PEF base and it is dispersed uniformly, provide PEF nucleation site it is enough, from
And the effect for promoting PEF to crystallize is good.In addition, Fig. 4 is the TEM figure for the PEF/OMMT nanocomposite that embodiment 2 synthesizes, from figure
In it can be seen that in Filamentous monolithic layer in matrix large percentage, and be uniformly dispersed, illustrate organo montmorillonite in the base
Extent of exfoliation is higher, has further proved the test result of XRD experiment.
Tensile property test is carried out to sample made above, as shown in table 1.The comparative example 2PEF/ of melt blending preparation
OMMT nanocomposite decreases compared with the tensile property of comparative example 1PEF raw material, main reason is that with sheet surfaces containing parent
Aqueous hydroxyl, which carries out melt blending, will lead to the reduction of PEF molecular weight.The embodiment 1,2,3PEF/OMMT of in-situ polymerization synthesis
It is suitable that nanocomposite and comparative example 1 are not added with the PEF molecular weight of organic modification montmonrillonite, but the former tensile property have it is aobvious
It writes and improves, especially add the PEF/OMMT nanocomposite of 2.5wt% organic modification montmonrillonite, tensile strength reaches
113Mpa, main reason is that one side nanoscale twins are uniformly dispersed in its matrix, equally distributed nanometer in drawing process
Lamella can undertake the loading force of a part, further aspect is that its good crystallinity, is conducive to the raising of mechanical strength.However, real
It applies the PEF/OMMT nanocomposite tensile strength that example 4 adds 6wt% organic modification montmonrillonite and only has 84Mpa, and be not added with
The PEF raw material of organic modification montmonrillonite is suitable, main reason is that adding too much makes limellar stripping degree not high, dispersibility
It is bad, cause to be easy to appear stress concentration in drawing process, is unfavorable for its mechanical property.
Embodiment 5
(1) montmorillonite and 65.85g second two by the 1.66g after drying through double octadecyldimethyl ammonium salt modifications
Alcohol mixing, is vigorously stirred to be placed within 2 hours under ultrasound environments and disperse 15 minutes, is made containing through double octadecyldimethyl ammonium salts
The glycolic suspension of the montmorillonite of modification；
(2) under nitrogen atmosphere, step (1) resulting glycolic suspension, 66.28g 2,5- furan are added into reactor
It mutters dioctyl phthalate and 0.1g stannous oxalate, is reacted in 170 DEG C 1 hour, 180 DEG C are reacted 1 hour, and 190 DEG C are reacted 1 hour, and 200 DEG C anti-
It answers 1 hour, obtains esterification products；
(3) into esterification products obtained in step (2) be added 0.1g antimony glycol, and 240 DEG C, high vacuum (≤
Polycondensation 3 hours under conditions of 133Pa) obtain poly- 2,5-furandicarboxylic acid glycol ester/organic montmorillonite nano composite material,
Montmorillonite dosage through double octadecyldimethyl ammonium salt modifications is the 2.5wt% of 2,5- furandicarboxylic acid dosage.
Through detecting, the characteristic of poly- 2,5-furandicarboxylic acid glycol ester/organic montmorillonite nano composite material of synthesis is viscous
Number is 0.73dL/g, and the melt crystallization enthalpy under 10 DEG C/min rate of temperature fall is 8J/g, tensile strength 105Mpa.
Embodiment 6
(1) montmorillonite by the 1.99g after drying through double hydrogenated-tallow group dimethyl quaternary ammonium modifications and 39.51g
Ethylene glycol mixing, is vigorously stirred to be placed within 2 hours under ultrasound environments and disperse 15 minutes, is made containing through double hydrogenated-tallow group diformazans
The glycolic suspension of the montmorillonite of based quaternary ammonium salt modification；
(2) under nitrogen atmosphere, step (1) resulting glycolic suspension, 66.28g 2,5- furan are added into reactor
It mutters dioctyl phthalate and 0.1g stannous oxalate, is reacted in 170 DEG C 1 hour, 180 DEG C are reacted 1 hour, and 190 DEG C are reacted 1 hour, and 200 DEG C anti-
It answers 1 hour, obtains esterification products；
(3) into esterification products obtained in step (2) be added 0.1g antimony glycol, and 240 DEG C, high vacuum (≤
Polycondensation 3 hours under conditions of 133Pa) obtain poly- 2,5-furandicarboxylic acid glycol ester/organic montmorillonite nano composite material,
Montmorillonite dosage through double hydrogenated-tallow group dimethyl quaternary ammonium modifications is the 3wt% of 2,5- furandicarboxylic acid dosage.
Through detecting, the characteristic of poly- 2,5-furandicarboxylic acid glycol ester/organic montmorillonite nano composite material of synthesis is viscous
Number is 0.65dL/g, and the melt crystallization enthalpy under 10 DEG C/min rate of temperature fall is 5J/g, tensile strength 82Mpa.
Embodiment 7
(1) hectorite and 44.67g by the 1.66g after drying through cetyl double hydroxyethyl methyl ammonium salt modification
Ethylene glycol mixing, is vigorously stirred to be placed within 2 hours under ultrasound environments and disperse 15 minutes, is made containing through cetyl double hydroxyethyl
The glycolic suspension of the hectorite of methyl ammonium salt modification；
(2) under nitrogen atmosphere, step (1) resulting glycolic suspension, 66.28g 2,5- furan are added into reactor
It mutters dicarboxylic acid dimethyl ester and 0.08g tetrabutyl titanate, is reacted in 170 DEG C 1 hour, 180 DEG C are reacted 1 hour, and 190 DEG C of reactions 1 are small
When, 200 DEG C are reacted 2 hours, and transesterification product is obtained；
(3) into transesterification product obtained in step (2) be added 0.15g antimony glycol, and 240 DEG C, high vacuum (≤
Polycondensation 3 hours under conditions of 133Pa) obtain poly- 2,5-furandicarboxylic acid glycol ester/organic lithium soapstone nanocomposite,
Hectorite dosage through cetyl double hydroxyethyl methyl ammonium salt modification is 2,5- furandicarboxylic acid dimethyl ester dosage
2.5wt%.
Through detecting, the characteristic of poly- 2,5-furandicarboxylic acid glycol ester/organic lithium soapstone nanocomposite of synthesis is viscous
Number is 0.62dL/g, and the melt crystallization enthalpy under 10 DEG C/min rate of temperature fall is 3J/g, tensile strength 79Mpa.
Embodiment 8
(1) hectorite by the 1.33g after drying through octadecyltrimethylammonium salt modification and 52.68g ethylene glycol
Mixing, is vigorously stirred to be placed within 2 hours under ultrasound environments and disperse 15 minutes, is made containing modified through octadecyltrimethylammonium salt
The glycolic suspension of the hectorite of processing；
(2) under nitrogen atmosphere, step (1) resulting glycolic suspension, 66.28g 2,5- furan are added into reactor
It mutters dioctyl phthalate and 0.1g stannous oxalate, is reacted in 170 DEG C 1 hour, 180 DEG C are reacted 1 hour, and 190 DEG C are reacted 1 hour, and 200 DEG C anti-
It answers 2 hours, obtains esterification products；
(3) into esterification products obtained in step (2) be added 0.1g antimony glycol, and 240 DEG C, high vacuum (≤
Polycondensation 4 hours under conditions of 133Pa) obtain poly- 2,5-furandicarboxylic acid glycol ester/organic lithium soapstone nanocomposite,
Hectorite dosage through octadecyltrimethylammonium salt treatment is the 2.0wt% of 2,5- furandicarboxylic acid dosage.
Through detecting, the characteristic of poly- 2,5-furandicarboxylic acid glycol ester/organic lithium soapstone nanocomposite of synthesis is viscous
Number is 0.72dL/g, and the melt crystallization enthalpy under 10 DEG C/min rate of temperature fall is 1J/g, tensile strength 94Mpa.
Embodiment 9
(1) montmorillonite by the 1.66g after drying through octadecyl double hydroxyethyl methyl ammonium salt modification and 54.75g
1,3-PD mixing, is vigorously stirred to be placed within 2 hours under ultrasound environments and disperse 15 minutes, is made containing through the double hydroxyls of octadecyl
The propylene glycol suspension of the montmorillonite of ethyl-methyl ammonium salt modification；
(2) under nitrogen atmosphere, step (1) resulting propylene glycol suspension, 66.28g 2,5- furan are added into reactor
It mutters dicarboxylic acid dimethyl ester and 0.1g stannous oxalate, is reacted in 170 DEG C 1 hour, 180 DEG C are reacted 1 hour, and 190 DEG C are reacted 1 hour,
200 DEG C are reacted 2 hours, and transesterification product is obtained；
(3) 0.1g antimony oxide is added into transesterification product obtained in step (2), and in 240 DEG C, high vacuum
(≤133Pa) under conditions of polycondensation 3 hours, obtain poly- 2,5-furandicarboxylic acid propylene glycol ester/organic montmorillonite nano composite wood
Material, the montmorillonite dosage through octadecyl double hydroxyethyl methyl ammonium salt modification are 2,5-furandicarboxylic acid dimethyl ester dosage
2.5wt%.
Through detecting, the characteristic of poly- 2,5-furandicarboxylic acid propylene glycol ester/organic montmorillonite nano composite material of synthesis is viscous
Number is 0.62dL/g, and the melt crystallization enthalpy under 10 DEG C/min rate of temperature fall is 13J/g, tensile strength 83Mpa.
Embodiment 10
(1) montmorillonite by the 0.99g after drying through octadecyl double hydroxyethyl methyl ammonium salt modification and 81.05g
1,4-butanediol mixing, is vigorously stirred to be placed within 2 hours under ultrasound environments and disperse 15 minutes, is made containing through the double hydroxyls of octadecyl
The butanediol suspension of the montmorillonite of ethyl-methyl ammonium salt modification；
(2) under nitrogen atmosphere, step (1) resulting butanediol suspension, 66.28g 2,5- furan are added into reactor
It mutters dicarboxylic acid dimethyl ester and 0.1g stannous oxalate, is reacted in 170 DEG C 1 hour, 180 DEG C are reacted 1 hour, and 190 DEG C are reacted 1 hour,
200 DEG C are reacted 1 hour, and transesterification product is obtained；
(3) into transesterification product obtained in step (2) be added 0.1g antimony glycol, and 240 DEG C, high vacuum (≤
Polycondensation 3 hours under conditions of 133Pa) obtain poly- 2,5-furandicarboxylic acid butanediol ester/organic montmorillonite nano composite material,
Montmorillonite dosage through octadecyl double hydroxyethyl methyl ammonium salt modification is 2,5- furandicarboxylic acid dimethyl ester dosage
1.5wt%.
Through detecting, the characteristic of poly- 2,5-furandicarboxylic acid butanediol ester/organic montmorillonite nano composite material of synthesis is viscous
Number is 0.67dL/g, and the melt crystallization enthalpy under 10 DEG C/min rate of temperature fall is 11J/g, tensile strength 63Mpa.
Embodiment 11
(1) under the conditions of 40 DEG C, the 1.99g after drying is quaternary ammonium salt-modified through bis- (2- ethoxy) hydrogenated-tallow groups of methyl
The montmorillonite of processing is mixed with 91.9g 1,4-CHDM, is vigorously stirred to be placed within 2 hours under ultrasound environments and is dispersed 15
Minute, Isosorbide-5-Nitrae-hexamethylene two containing the montmorillonite through the quaternary ammonium salt-modified processing of bis- (2- ethoxy) hydrogenated-tallow groups of methyl is made
Methanol suspension；
(2) under nitrogen atmosphere, be added into reactor step (1) resulting 1,4-CHDM suspension,
66.28g 2,5-furandicarboxylic acid dimethyl ester and 0.1g stannous oxalate, in 170 DEG C react 1 hour, 180 DEG C react 1 hour, 190
DEG C reaction 1 hour, 200 DEG C react 2 hours, obtain transesterification product；
(3) into transesterification product obtained in step (2) be added 0.1g antimony glycol, and 240 DEG C, high vacuum (≤
Polycondensation 3 hours under conditions of 133Pa) obtain poly- 2,5-furandicarboxylic acid 1,4-CHDM ester/organic montmorillonite nano
Composite material, the montmorillonite dosage through the quaternary ammonium salt-modified processing of bis- (2- ethoxy) hydrogenated-tallow groups of methyl are 2,5- furans diformazan
The 2.5wt% of dimethyl phthalate dosage.
Through detecting, poly- 2,5-furandicarboxylic acid 1,4-CHDM ester/organic montmorillonite nano composite wood of synthesis
The intrinsic viscosity of material is 0.71dL/g, and the melt crystallization enthalpy under 10 DEG C/min rate of temperature fall is 45J/g, and tensile strength is
73Mpa。
Embodiment 12
(1) illiteracy under the conditions of 40 DEG C, by the 0.67g after drying through octadecyl double hydroxyethyl methyl ammonium salt modification
The polytetrahydrofuran ether glycol (PTMG) that de- soil, 55.84g ethylene glycol and 28.1g number-average molecular weight are 1000, it is small to be vigorously stirred 5
When be placed under ultrasound environments and disperse 30 minutes, the montmorillonite containing octadecyl double hydroxyethyl methyl ammonium salt modification is made
Suspension；
(2) under nitrogen atmosphere, step (1) resulting suspension, 66.28g 2,5- furans diformazan are added into reactor
Dimethyl phthalate and 0.15g stannous oxalate react 1 hour in 170 DEG C, and 180 DEG C are reacted 1 hour, and 190 DEG C are reacted 1 hour, 200 DEG C
Reaction 2 hours, obtains transesterification product；
(3) into transesterification product obtained in step (2) be added 0.2g antimony glycol, and 240 DEG C, high vacuum (≤
Polycondensation 3 hours under conditions of 133Pa) obtain PEF-PTMG polyester/organic montmorillonite nano composite material, double through octadecyl
The montmorillonite dosage of hydroxyethyl methyl ammonium salt modification is the 1wt% of 2,5- furandicarboxylic acid dimethyl ester dosage.
Through detecting, PEF-PTMG polyester/organic montmorillonite nano composite material intrinsic viscosity of synthesis is 0.98dL/g,
Melt crystallization enthalpy under 10 DEG C/min rate of temperature fall is 3J/g, tensile strength 48Mpa.
Embodiment 13
(1) under the conditions of 60 DEG C, the 0.99g after drying is taken off through the illiteracy of double octadecyldimethyl ammonium salt modifications
The polyethylene glycol (PEG) that soil, 44.67g ethylene glycol and 16.4g number-average molecular weight are 2000 mixes, and is vigorously stirred 5 hours and is placed on
Disperse 30 minutes under ultrasound environments, the suspension of the montmorillonite containing double octadecyldimethyl modifications is made；
(2) under nitrogen atmosphere, step (1) resulting suspension, 66.28g 2,5- furans diformazan are added into reactor
Dimethyl phthalate and 0.15g stannous oxalate react 1 hour in 170 DEG C, and 180 DEG C are reacted 1 hour, and 190 DEG C are reacted 1 hour, 200 DEG C
Reaction 2 hours, obtains transesterification product；
(3) into transesterification product obtained in step (2) be added 0.2g antimony glycol, and 240 DEG C, high vacuum (≤
Polycondensation 5 hours under conditions of 133Pa) obtain PEF-PEG polyester/organic montmorillonite nano composite material, through double octadecyls two
The montmorillonite dosage of methyl ammonium salt modification is the 1.5wt% of 2,5- furandicarboxylic acid dimethyl ester dosage.
Through detecting, PEF-PEG polyester/organic montmorillonite nano composite material intrinsic viscosity of synthesis is 0.88dL/g,
Melt crystallization enthalpy under 10 DEG C/min rate of temperature fall is 8J/g, tensile strength 57Mpa.
Claims (10)
1. a kind of 2,5-furandicarboxylic acid base polyester/phyllosilicate nano-composite material, which is characterized in that 2, the 5- furans
Diformyl polyester/laminated nm-silicate composite material includes 2,5-furandicarboxylic acid base polyester and phyllosilicate, by 2,
5- furandicarboxylic acid or 2,5- furandicarboxylic acid dimethyl ester, dihydric alcohol and phyllosilicate are obtained by in-situ polymerization；The layer
The dosage of shape silicate is 1.5~5wt% of 2,5- furandicarboxylic acid or 2,5- furandicarboxylic acid dimethyl ester dosage.
2. 2,5-furandicarboxylic acid base polyester/phyllosilicate nano-composite material according to claim 1, feature exist
In being 2,5- furans based on 100% by 2,5-furandicarboxylic acid or the quality summation of 2,5-furandicarboxylic acid dimethyl ester and dihydric alcohol
The dosage of dioctyl phthalate or 2,5-furandicarboxylic acid dimethyl ester is 20~80wt%, and the dosage of dihydric alcohol is 20~80wt%.
3. 2,5-furandicarboxylic acid base polyester/phyllosilicate nano-composite material according to claim 1, feature exist
In the dihydric alcohol is ethylene glycol, 1,3-PD, 1,4-butanediol, 1,5-PD, 1,6- hexylene glycol, Isosorbide-5-Nitrae-hexamethylene
Alkane dimethanol, 1,4- cyclohexanediol, 2,2,4,4- tetramethyl -1,3- cyclobutanediol, polyethylene glycol, polypropylene glycol and poly- tetrahydro furan
It mutters one or more of ether glycol.
4. 2,5-furandicarboxylic acid base polyester/phyllosilicate nano-composite material according to claim 1, feature exist
In the phyllosilicate is by the montmorillonite of organic intercalation agent modification, saponite or Meccah stone.
5. 2,5-furandicarboxylic acid base polyester/phyllosilicate nano-composite material according to claim 4, feature exist
In, the organic intercalation agent be dodecyl trimethyl ammonium salt, cetyltrimethyl ammonium salt, octadecyltrimethylammonium salt,
Cetyl double hydroxyethyl methyl ammonium salt, octadecyl double hydroxyethyl methyl ammonium salt, dodecylbenzyl dimethyl ammonium, 16
Bis- (the 2- hydroxyl second of alkyl benzyl dimethyl ammonium salt, octadecyl benzyl dimethyl ammonium salt, double octadecyldimethyl ammonium salts, methyl
Base) hydrogenated tallow based quaternary ammonium salt, double hydrogenated-tallow group dimethyl quaternary ammoniums or double hydrogenated-tallow group dimethylbenzyl based quaternary ammonium salts.
6. 2,5-furandicarboxylic acid base polyester/phyllosilicate nano-composite material according to claim 1, feature exist
In, the intrinsic viscosity of the 2,5-furandicarboxylic acid base polyester/phyllosilicate nano-composite material is not less than 0.6dL/g,
Growth of the melt crystallization enthalpy compared with 2,5-furandicarboxylic acid base polyester ontology under 10 DEG C/min cooling rate is not less than 5J/g, draws
Growth of the intensity compared with 2,5- furandicarboxylic acid base polyester ontology is stretched not less than 10Mpa.
7. a kind of 2,5- furandicarboxylic acid base polyester/phyllosilicate nanos described in any item according to claim 1~6 are compound
The preparation method of material, which comprises the following steps:
(1) phyllosilicate is mixed with dihydric alcohol, is dispersed, the dihydric alcohol suspension containing phyllosilicate is made；
(2) in atmosphere of inert gases, 2,5-furandicarboxylic acid or 2,5-furandicarboxylic acid diester, step are put into reactor
(1) resulting dihydric alcohol suspension and catalyst 1, and 1~10h is reacted at 150~210 DEG C, intermediate is made；
(3) catalyst 2 is added into the intermediate of step (2), heat up and carries out depressurization condensation reaction, reaction temperature is 210~
250 DEG C, system pressure≤200Pa, the polycondensation time is 1~8h, can be obtained 2,5-furandicarboxylic acid base polyester/phyllosilicate
Nanocomposite.
8. the preparation side of 2,5- furandicarboxylic acid base polyester/phyllosilicate nano-composite material according to claim 7
Method, which is characterized in that the catalyst 1 is tetrabutyl titanate, isopropyl titanate, stannous octoate, stannous oxalate, dibutyl oxygen
Change tin, the compound of earth silicon/titanic oxide, earth silicon/titanic oxide/nitrogenous compound compound and titanium dioxide
One or more of silicon/titanium dioxide/phosphorus-containing compound compound, dosage are 2,5-furandicarboxylic acid or 2,5- furans
0.01~0.4mol% of dicarboxylate dosage.
9. the preparation side of 2,5- furandicarboxylic acid base polyester/phyllosilicate nano-composite material according to claim 7
Method, which is characterized in that the catalyst 2 is tetrabutyl titanate, isopropyl titanate, titanium ethylene glycolate, titanium acetylacetone, ethylene glycol
Antimony, antimony oxide, the compound of earth silicon/titanic oxide, earth silicon/titanic oxide/nitrogenous compound compound
One or more of with earth silicon/titanic oxide/phosphorus-containing compound compound, the amount of coming into operation be 2,5-furandicarboxylic acid or
0.01~0.4mol% of 2,5- furandicarboxylic acid diester dosage.
10. a kind of 2,5- furandicarboxylic acid base polyester/phyllosilicate nanos described in any item according to claim 1~6 are multiple
Condensation material is preparing the application in high-gas resistance packaging material.
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