CN116715834A - High-strength high-toughness 2, 5-furandicarboxylic acid copolyester and preparation method thereof - Google Patents
High-strength high-toughness 2, 5-furandicarboxylic acid copolyester and preparation method thereof Download PDFInfo
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- CN116715834A CN116715834A CN202310714321.7A CN202310714321A CN116715834A CN 116715834 A CN116715834 A CN 116715834A CN 202310714321 A CN202310714321 A CN 202310714321A CN 116715834 A CN116715834 A CN 116715834A
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- furandicarboxylic acid
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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 113
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 6
- -1 aromatic diols Chemical class 0.000 claims abstract description 51
- 229920000728 polyester Polymers 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims description 22
- 238000005886 esterification reaction Methods 0.000 claims description 21
- 125000001424 substituent group Chemical group 0.000 claims description 20
- 230000032050 esterification Effects 0.000 claims description 19
- 238000006068 polycondensation reaction Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 10
- 150000002009 diols Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 8
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- 108090000790 Enzymes Proteins 0.000 claims description 4
- 102000004190 Enzymes Human genes 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims description 2
- JODJLOUEMNZRNF-UHFFFAOYSA-N 3,4-diethylfuran-2,5-dicarboxylic acid Chemical compound CCC1=C(C(O)=O)OC(C(O)=O)=C1CC JODJLOUEMNZRNF-UHFFFAOYSA-N 0.000 claims description 2
- NVWMHICCPUEWLL-UHFFFAOYSA-N 3,4-dimethylfuran-2,5-dicarboxylic acid Chemical compound CC=1C(C)=C(C(O)=O)OC=1C(O)=O NVWMHICCPUEWLL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 108010031797 Candida antarctica lipase B Proteins 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 230000009477 glass transition Effects 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 3
- 125000002723 alicyclic group Chemical group 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009864 tensile test Methods 0.000 description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 5
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 5
- 229940035437 1,3-propanediol Drugs 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 5
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 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 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- VNAWKNVDKFZFSU-UHFFFAOYSA-N 2-ethyl-2-methylpropane-1,3-diol Chemical compound CCC(C)(CO)CO VNAWKNVDKFZFSU-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- KDNOCIDNIPWRLT-UHFFFAOYSA-N ethene;furan-2,5-dicarboxylic acid Chemical compound C=C.OC(=O)C1=CC=C(C(O)=O)O1 KDNOCIDNIPWRLT-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- DVVGBNZLQNDSPA-UHFFFAOYSA-N 3,6,11-trioxabicyclo[6.2.1]undeca-1(10),8-diene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1O2 DVVGBNZLQNDSPA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OMXWMKAHNWDBRJ-UHFFFAOYSA-N OCC(C)(CO)C.O1C(=CC=C1C(=O)O)C(=O)O Chemical compound OCC(C)(CO)C.O1C(=CC=C1C(=O)O)C(=O)O OMXWMKAHNWDBRJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 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
- 230000009471 action Effects 0.000 description 1
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940094938 stannous 2-ethylhexanoate Drugs 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 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 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
- MBWVCEZZJUXUHB-UHFFFAOYSA-I zinc antimony(3+) pentaacetate Chemical compound [Sb+3].C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] MBWVCEZZJUXUHB-UHFFFAOYSA-I 0.000 description 1
Classifications
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Aiming at the problem that the polyester prepared by reacting a 2, 5-furandicarboxylic acid structural unit with short-chain aliphatic dihydric alcohol or rigid alicyclic dihydric alcohol or heterocyclic dihydric alcohol or aromatic dihydric alcohol is brittle, the application discloses high-strength high-toughness 2, 5-furandicarboxylic acid copolyester and a preparation method thereof. The structure is as followsR in the structural formula 1 Is thatRepeating units, R in the formula 2 Structural units belonging to residues of short-chain aliphatic or rigid cycloaliphatic or heterocyclic or aromatic diols, R 3 The structural unit belongs to the residue of 2, 2-disubstituted-1, 3-propanediol. The application is thatThe modified polyester has higher Young modulus, tensile strength and glass transition temperature, and improves heat resistance and thermal processing stability at the same time of realizing toughening. The high-strength high-toughness 2, 5-furandicarboxylic acid copolyester provided by the application can be applied to the field of high-performance bio-based polyesters.
Description
Technical Field
The application relates to the technical field of bio-based polyester modification, in particular to high-strength high-toughness 2, 5-furandicarboxylic acid copolyester and a preparation method thereof.
Background
The bio-based 2, 5-furandicarboxylic acid polyester has excellent barrier property and excellent mechanical property, can be used as packaging materials in the industries of beverages, foods, medicines and the like, and is a potential substitute material for petroleum-based terephthalic acid polyester. The polyester prepared by reacting the 2, 5-furandicarboxylic acid structural unit with short-chain aliphatic diol, rigid alicyclic diol, heterocyclic diol or aromatic diol, such as poly (ethylene-2, 5-furandicarboxylic acid) glycol ester, poly (propylene-2, 5-furandicarboxylic acid) glycol ester, poly (neopentyl glycol-2, 5-furandicarboxylic acid) ester, poly (2, 4-tetramethyl-1, 3-cyclobutanediol) and the like, has higher Young modulus and tensile strength, higher glass transition temperature and strong barrier capability to carbon dioxide, oxygen and water. However, polyesters prepared by reacting 2, 5-furandicarboxylic acid building blocks with short-chain aliphatic diols, rigid cycloaliphatic diols, heterocyclic diols or aromatic diols have a significant disadvantage, namely brittle fracture, and elongation at break of typically only 5 to 10%, which greatly influences their processing and use.
There is a great interest in improving the brittle fracture characteristics and increasing the tensile elongation at break of the above-mentioned 2, 5-furandicarboxylic acid polyesters. The prior art scheme mainly introduces a flexible monomer (such as lactone, long carbon chain aliphatic dihydric alcohol and the like) or a polyether block structure (such as polyethylene glycol, polytetrahydrofuran and the like) into the 2, 5-furandicarboxylic acid polyester molecular chain to improve the flexibility of the molecular chain, and the advantages of the 2, 5-furandicarboxylic acid polyester are reduced at the cost of losing Young modulus and glass transition temperature although the flexibility of the molecular chain can be greatly improved by increasing the flexibility of the molecular chain. How to improve the tensile breaking elongation of the 2, 5-furandicarboxylic acid polyester and retain the advantageous characteristics thereof is a problem to be solved in the field.
It is generally believed that rigid diols are less toughening than flexible monomers (lactones, long carbon chain aliphatic diols, etc.) or polyether block structures (polyethylene glycol, polytetrahydrofuran, etc.) as co-modifying monomers. If 2, 4-tetramethyl-1, 3-cyclobutanediol is copolymerized with 2, 5-furandicarboxylic acid and ethylene glycol, the Young's modulus of the copolymer is increased from 2800+ -120 MPa of polyethylene 2, 5-furandicarboxylic acid to 3300+ -100 MPa, but the elongation at break (4+ -1%) of the copolymer is not improved as compared with the elongation at break (5+ -1%) of polyethylene 2, 5-furandicarboxylic acid [ Polymers, 2017, 9 (9): 305-320 ]. It can be seen that the rigid diol acts primarily to increase the Young's modulus.
In summary, aiming at the problem that the polyester prepared by reacting the 2, 5-furandicarboxylic acid structural unit with the short-chain aliphatic diol, the rigid alicyclic diol, the heterocyclic diol or the aromatic diol is brittle to break, the prior solution is mainly to introduce a flexible monomer for copolymerization or a polyether block structure for copolymerization, so that the Young modulus is inevitably reduced or the glass transition temperature is reduced when the breaking elongation of the corresponding polyester is improved, and the problem that the tensile toughness is improved and the original advantage characteristic is maintained by introducing the rigid monomer is needed to be solved.
Disclosure of Invention
Aiming at the problem that the polyester prepared by reacting a 2, 5-furandicarboxylic acid structural unit with short-chain aliphatic diol, rigid alicyclic diol, heterocyclic diol or aromatic diol is brittle fracture, the application provides high-strength high-toughness 2, 5-furandicarboxylic acid copolyester and a preparation method thereof, and aims at: the polyester prepared by reacting the 2, 5-furan dicarboxylic acid structural unit with short-chain aliphatic dihydric alcohol, rigid alicyclic dihydric alcohol, heterocyclic dihydric alcohol or aromatic dihydric alcohol has higher breaking elongation and higher Young modulus or glass transition temperature.
The technical scheme adopted by the application is as follows:
a high-strength high-toughness 2, 5-furandicarboxylic acid copolyester has the following structural formula:r in the structural formula 1 Is->A repeating unit; r in the structural formula 2 Residues belonging to short-chain aliphatic diols, rigid cycloaliphatic diols, heterocyclic diols or aromatic diols; r is R 3 Residues belonging to the rigid 2, 2-disubstituted-1, 3-propanediol group.
The R is 2 The structural unit is、/>、/>、、/>、/>One or more of the following. At said R 2 The structural unit comprises: substituent R 4 Is alkyl, substituted alkyl or phenyl with 1-50 carbon atoms or any substituent thereof; substituent R 5 ~R 8 Is alkyl, substituted alkyl or phenyl with 1-50 carbon atoms or any substituent thereof; substituent R 9 ~R 16 Is an alkyl group having 1 to 50 carbon atoms, a substituted alkyl group, an H atom, a phenyl group, or any substituent thereof. Identical R 2 The number or the type of the substituent groups in the structural unit can be flexibly changed and combined according to actual needs under the condition of not violating the rule of the chemical structural formula.
The R is 3 The structural unit isWherein the substituents R 4 And R is 17 Is one of alkyl, substituted alkyl or phenyl with 1-50 carbon atoms or any substituent thereof, and the substituent R 4 And R is 17 May be the same or different.
After the technical scheme is adopted, R in the prepared 2, 5-furandicarboxylic acid polyester molecular chain 2 Structural unit and R 3 Structural units are randomly distributed, and the original structure only containing R is destroyed 2 Or R is 3 The molecular chain structure of the polyester of a single structural unit,in particular R 3 The 2, 2-disubstituted group in the structural unit increases the free volume of the polyester molecular chain and also destroys the original R-only structure 2 Or R is 3 Forces between and within the molecular chains of the single structural unit polyester, R 2 Structural unit and R 3 The combined action of the structural units improves the flexibility of the molecular chain of the 2, 5-furandicarboxylic acid polyester, thereby improving the elongation at break of the 2, 5-furandicarboxylic acid polyester. On the other hand, R 2 Residues belonging to the group consisting of short-chain aliphatic diols, rigid cycloaliphatic diols, heterocyclic diols or aromatic diols, R 3 Residues belonging to rigid 2, 2-disubstituted-1, 3-propanediol, which have higher Young's modulus, tensile strength and higher glass transition temperature with the polyester synthesized by the 2, 5-furandicarboxylic acid structural unit respectively, thus being capable of maintaining the higher Young's modulus, tensile strength and glass transition temperature of the 2, 5-furandicarboxylic acid polyester. For the reasons, the polyester prepared by the reaction of the 2, 5-furandicarboxylic acid structural unit and the short-chain aliphatic diol, the rigid alicyclic diol, the heterocyclic diol or the aromatic diol has higher elongation at break and higher Young modulus or glass transition temperature, and breaks through the fact that the polyester only contains R originally 2 Or R is 3 Bottleneck problem of brittle fracture of single structural unit 2, 5-furandicarboxylic acid polyesters.
The application also aims to provide a preparation method of the high-strength high-toughness 2, 5-furandicarboxylic acid copolyester, which comprises the following steps:
(1) 2, 5-furandicarboxylic acid, dimethyl 2, 5-furandicarboxylic acid, diethyl 2, 5-furandicarboxylic acid, or mixtures thereof under inert gas atmosphere, containing R 2 、R 3 The dihydric alcohol of the structural unit, an esterification catalyst or a polycondensation catalyst are mixed according to a proportion, and are subjected to esterification reaction at the temperature of 80-260 ℃ for 1-6 hours to obtain an esterification product;
(2) Adding a polycondensation catalyst into the esterification product, further increasing the reaction temperature, reducing the pressure of the reaction system from the atmospheric pressure to below 100 Pa, performing polycondensation reaction at 80-280 ℃ for 1-8 hours, and obtaining the polyester product.
Wherein, the molar ratio of the 2, 5-furandicarboxylic acid structural monomer to the dihydric alcohol is 1: 1-1: 5, a step of; the R-containing 2 Diols of structural units and R-containing compounds 3 The molar ratio of the dihydric alcohol of the structural unit is 1:99-99:1. The catalyst is used in an amount of 0.01-5% of the mole number of the 2, 5-furandicarboxylic acid structural monomer.
The catalyst is simple substance based on at least one element of Ti, si, sn, sb, pb, ge, zn, fe, mn, co, zr, mg, V, al or rare earth elements, or a compound or a mixture. The catalyst is an enzyme or an organic base catalyst, the enzyme is candida antarctica lipase B immobilized on acrylic resin, and the organic base catalyst is one or more of 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene or 1, 4-diazabicyclo [2.2.2] octane.
Further preferred, the Ti element-based compound or mixture is one or more of tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetrabutyl titanate, tetraisooctyl titanate, amorphous titanium dioxide, or titanium silicalite catalyst; the Sn-based compound or mixture is one or more of monobutyl tin oxide, dibutyl tin oxide, stannous 2-ethylhexanoate, dibutyl tin dilaurate or stannous chloride; the Sb-based compound or mixture is one or more of antimony trioxide or antimony acetate; the Pb element-based compound or mixture is one or more of lead oxide or lead acetate.
In summary, due to the adoption of the technical scheme, compared with the prior art, the application has the beneficial effects that:
(1) The application takes the rigid 2, 2-disubstituted-1, 3-propanediol as a copolymerization toughening modified monomer, and reacts with the 2, 5-furandicarboxylic acid structural unit, the short-chain aliphatic diol or the rigid alicyclic diol or the heterocyclic diol or the aromatic diol, thereby realizing the toughening of the 2, 5-furandicarboxylic acid polyester, and simultaneously leading the copolyester to have higher Young modulus, tensile strength, glass transition temperature and excellent gas barrier property.
(2) According to the application, good modification effect can be realized by only introducing 10-25 mol% of 2, 2-disubstituted-1, 3-propanediol into the rigid dihydric alcohol ingredient, and the intrinsic viscosity of the prepared copolyester is higher than 0.7dL/g. By adjusting the amount of 2, 2-disubstituted-1, 3-propanediol and the polycondensation reaction time, even high molecular weight copolyesters having an intrinsic viscosity exceeding 1.0dL/g can be obtained. The copolyester provided by the application can meet the conventional application without subsequent solid-state polycondensation tackifying.
(3) The heat resistance and the thermal processing stability of the copolyester are greatly improved by introducing 2, 2-disubstituted-1, 3-propanediol into the molecular chain of the 2, 5-furandicarboxylic acid polyester.
Drawings
FIG. 1 is a drawing of a polyester synthesized from ethylene glycol, 2-dimethyl-1, 3-propanediol and 2, 5-furandicarboxylic acid catalyzed by anhydrous zinc acetate-antimony trioxide.
FIG. 2 is a drawing of a polyester synthesized from ethylene glycol, 2-dimethyl-1, 3-propanediol and dimethyl 2, 5-furandicarboxylate catalyzed by dibutyltin oxide.
FIG. 3 is a stretch plot of a polyester synthesized from tetrabutyl titanate catalyzed by diethyl 2, 4-tetramethyl-1, 3-cyclobutanediol, ethylene glycol, 2-ethyl-2-methyl-1, 3-propanediol, and 2, 5-furandicarboxylic acid.
Description of the embodiments
The present application will be described in further detail with reference to examples and comparative examples in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
Examples
Ethylene glycol, 2-dimethyl-1, 3-propanediol and 2, 5-furandicarboxylic acid (molar ratio 1.75:0.25:1) are placed in a three-neck flask, anhydrous zinc acetate (molar ratio of 0.05% of 2, 5-furandicarboxylic acid) is added as an esterification catalyst, nitrogen is introduced to replace air for 3 times, nitrogen atmosphere is maintained, and stirring is fully carried out. The evenly mixed reactants are heated to 180 ℃ for reaction for 3 hours, and the esterified product is obtained. Antimony trioxide (the mole number is 0.1 percent of 2, 5-furandicarboxylic acid) is added into the esterification product, the temperature is raised to 230 ℃, the pressure of a reaction system is slowly reduced from atmospheric pressure to below 100 Pa within 0.5 hour, and the reaction is carried out for 3.5 hours, so that poly (ethylene 2, 5-furandicarboxylic acid) glycol ester-co-poly (2, 5-furandicarboxylic acid) -2, 2-dimethyl-1, 3-propanediol ester is obtained. The polyester sample was subjected to an intrinsic viscosity test (the solvent was phenol/tetrachloroethane, the mass ratio was 3:2), resulting in 0.73. 0.73 dL/g.
The polyester samples were subjected to tensile testing at 25℃and a tensile rate of 10 mm/min using a hot press (160℃10MPa 0.5 min) to prepare dumbbell bars. As determined by tensile experiments, the Young's modulus E of the poly (ethylene 2, 5-furandicarboxylate-co-poly (2, 5-furandicarboxylate) -2, 2-dimethyl-1, 3-propanediol) obtained in the example is 1565+ -90 Mpa, and the tensile strength sigma M Is 95+ -4 Mpa, elongation at break epsilon b 34.+ -. 2%. The stretching curve is shown in fig. 1. And the intrinsic viscosity of the hot-pressed drawn bar was measured to be 0.72. 0.72 dL/g.
Examples
Ethylene glycol, 2-dimethyl-1, 3-propanediol and dimethyl 2, 5-furandicarboxylate (molar ratio 1.4:0.6:1) are placed in a three-neck flask, dibutyl tin oxide (molar ratio of 0.15% of 2, 5-furandicarboxylic acid) is added as an esterification and polycondensation catalyst, nitrogen is introduced to replace air for 3 times, nitrogen atmosphere is maintained, and stirring is fully carried out. The evenly mixed reactants are heated to 190 ℃ to react for 1 hour, and the reaction time is 200 ℃ to react for 2 hours, thus obtaining the esterification product. Heating the esterification product to 235 ℃, slowly reducing the pressure of a reaction system from atmospheric pressure to below 100 Pa within 0.5 hour, and reacting for 5 hours to obtain the poly (ethylene 2, 5-furandicarboxylic acid) co-poly (2, 5-furandicarboxylic acid) 2, 2-dimethyl-1, 3-propanediol ester. The polyester sample was subjected to an intrinsic viscosity test, resulting in 1.07 dL/g.
The polyester samples were subjected to tensile testing at 25℃and a tensile rate of 10 mm/min using a hot press (160℃10MPa 0.5 min) to prepare dumbbell bars. The implementation is determined by tensile experimentsThe Young's modulus E of the obtained poly (ethylene 2, 5-furandicarboxylate) -co-poly (2, 5-furandicarboxylic acid) -2, 2-dimethyl-1, 3-propanediol) was 1430.+ -. 60 MPa, and the tensile strength sigma M Is 100+ -10 Mpa, elongation at break epsilon b 110 plus or minus 15 percent. The stretching curve is shown in fig. 2. The hot-pressed tensile bars were tested for intrinsic viscosity, resulting in 1.07 dL/g.
Examples
2, 4-tetramethyl-1, 3-cyclobutanediol, ethylene glycol, 2-ethyl-2-methyl-1, 3-propanediol and diethyl 2, 5-furandicarboxylate (molar ratio 0.2:1.7:0.2:1) are placed in a three-neck flask, tetrabutyl titanate (molar ratio 0.20% of 2, 5-furandicarboxylate) is added as an esterification and polycondensation catalyst, nitrogen is introduced to replace air for 3 times, nitrogen atmosphere is maintained, and stirring is fully carried out. The evenly mixed reactants are heated to 190 ℃ to react for 1 hour, 200 ℃ to react for 2 hours, 210 ℃ to react for 1 hour, and the esterified product is obtained. Heating the esterification product to 245 ℃, slowly reducing the pressure of a reaction system from atmospheric pressure to below 100 Pa within 0.5 hour, and reacting for 5 hours to obtain a polyester product. The polyester sample was subjected to an intrinsic viscosity test, resulting in 0.88 dL/g.
The polyester samples were subjected to tensile testing at 25℃and a tensile rate of 10 mm/min using a hot press (180 ℃, 10MPa, 0.5 min) to prepare dumbbell bars. As measured by tensile test, the Young's modulus E of the polyester obtained in this example is 1670+ -70 Mpa, and the tensile strength sigma M Is 95+ -15 Mpa, elongation at break epsilon b 55.+ -. 10%. The stretching curve is shown in fig. 3. The intrinsic viscosity of the hot-pressed tensile bars was measured and found to be 0.87. 0.87 dL/g.
Comparative example 1
Ethylene glycol and dimethyl 2, 5-furandicarboxylate (molar ratio 2:1) were placed in a three-necked flask, dibutyltin oxide (molar ratio of 0.15% of 2, 5-furandicarboxylic acid) was added as an esterification and polycondensation catalyst, nitrogen was introduced to replace air for 3 times, nitrogen atmosphere was maintained, and stirring was sufficient. The evenly mixed reactants are heated to 190 ℃ to react for 1 hour, and the reaction time is 200 ℃ to react for 2 hours, thus obtaining the esterification product. And heating the esterification product to 235 ℃, slowly reducing the pressure of a reaction system from atmospheric pressure to below 100 Pa within 0.5 hour, and reacting for 5 hours to obtain the polyethylene 2, 5-furandicarboxylate. The polyester sample was subjected to an intrinsic viscosity test, resulting in 0.68 dL/g.
The polyester samples were subjected to tensile testing at 25℃and a tensile rate of 10 mm/min using a hot press (160℃10MPa 0.5 min) to prepare dumbbell bars. As determined by tensile experiments, the Young's modulus E of the polyethylene 2, 5-furandicarboxylate obtained in the embodiment is 2030+ -80 Mpa and the tensile strength sigma M Is 87+ -12 Mpa, elongation at break epsilon b 6+/-2 percent. The intrinsic viscosity of the hot-pressed tensile bars was measured and found to be 0.57 dL/g.
Comparative example 2
2, 2-dimethyl-1, 3-propanediol and 2, 5-furandicarboxylic acid dimethyl ester (molar ratio 2:1) are placed in a three-neck flask, dibutyl tin oxide (0.15% of 2, 5-furandicarboxylic acid) is added as an esterification and polycondensation catalyst, nitrogen is introduced to replace air for 3 times, nitrogen atmosphere is maintained, and stirring is fully carried out. The evenly mixed reactants are heated to 190 ℃ to react for 1 hour, and the reaction time is 200 ℃ to react for 2 hours, thus obtaining the esterification product. Heating the esterification product to 235 ℃, slowly reducing the pressure of a reaction system from atmospheric pressure to below 100 Pa within 0.5 hour, and reacting for 5 hours to obtain the poly-2, 5-furandicarboxylic acid-2, 2-dimethyl-1, 3-propanediol. The polyester sample was subjected to an intrinsic viscosity test, resulting in 0.88 dL/g.
The polyester samples were subjected to tensile testing at 25℃and a tensile rate of 10 mm/min using a hot press (160℃10MPa 0.5 min) to prepare dumbbell bars. As determined by tensile experiments, the Young's modulus E of the poly (2, 5-furandicarboxylic acid) -2, 2-dimethyl-1, 3-propanediol ester obtained in the embodiment is 1455+/-50 Mpa and the tensile strength sigma M Is 80+ -12 Mpa, elongation at break epsilon b 15.+ -. 3%. The intrinsic viscosity of the hot-formed tensile bars was measured and found to be 0.88 dL/g.
It can be seen that the polyester products obtained in examples 1 to 3 above are excellent in mechanical properties, have high Young's modulus, tensile strength and elongation at break, and successfully convert the tensile fracture mode from brittle fracture to ductile fracture. In addition, the prepared polyester also has good heat resistance and thermal processing stability.
As can be seen from the comparison of example 2 and comparative examples 1 and 2: the polyethylene 2, 5-furandicarboxylic acid glycol ester and the polyethylene 2, 5-furandicarboxylic acid-2, 2-dimethyl-1, 3-propanediol ester synthesized by ethylene glycol or 2, 2-dimethyl-1, 3-propanediol and 2, 5-furandicarboxylic acid structural units have higher Young's modulus and tensile strength, but have lower elongation at break and are brittle fracture; the copolyester prepared by copolymerizing ethylene glycol, 2-dimethyl-1, 3-propanediol and 2, 5-furandicarboxylic acid structural units has high Young's modulus and tensile strength, and obviously improves the elongation at break, and the tensile breaking mode is changed from brittle fracture to ductile fracture.
Comparative examples 1 to 3 and comparative examples 1 to 2 show that: according to the application, good toughening modification effect can be realized by only introducing 2, 2-disubstituted-1, 3-propanediol into the rigid dihydric alcohol ingredient, and the intrinsic viscosity of the prepared copolyester is higher than 0.7dL/g; adjusting the amount of 2, 2-disubstituted-1, 3-propanediol and the polycondensation reaction time, even high molecular weight copolyesters having intrinsic viscosities exceeding 1.0dL/g can be obtained; the heat resistance and the thermal processing stability of the copolyester are greatly improved by introducing 2, 2-disubstituted-1, 3-propanediol into the molecular chain of the 2, 5-furandicarboxylic acid polyester.
The above examples merely illustrate specific embodiments of the application, which are described in more detail and are not to be construed as limiting the scope of the application. It should be noted that it is possible for a person skilled in the art to make several variants and modifications without departing from the technical idea of the application, which fall within the scope of protection of the application.
Claims (10)
1. A high-strength high-toughness 2, 5-furandicarboxylic acid copolyester has the following structural formula:r in the structural formula 1 Is->A repeating unit; r in the structural formula 2 Structural units are residues of short chain aliphatic diols, rigid cycloaliphatic diols, heterocyclic diols or aromatic diols; r is R 3 The structural unit belongs to the residue of 2, 2-disubstituted-1, 3-propanediol.
2. A high strength, high toughness 2, 5-furandicarboxylic acid copolyester according to claim 1, characterized in that: the R is 2 The structural unit is、/>、/>、/>、、/>One or more of the following.
3. A high strength, high toughness 2, 5-furandicarboxylic acid copolyester according to claim 2, characterized in that R 2 The structural unit comprises: substituent R 4 Is alkyl, substituted alkyl or phenyl with 1-50 carbon atoms or any substituent thereof; substituent R 5 ~R 8 Is alkyl, substituted alkyl or phenyl with 1-50 carbon atoms or any substituent thereof; substituent R 9 ~R 16 Is an alkyl group having 1 to 50 carbon atoms, a substituted alkyl group, an H atom, a phenyl group, or any substituent thereof.
4. According toR as claimed in claim 3 2 A structural unit, the structural unit being characterized by; identical R 2 The number or the type of the substituent groups in the structural unit can be flexibly changed and combined according to actual needs under the condition of not violating the rule of the chemical structural formula.
5. A high strength, high toughness 2, 5-furandicarboxylic acid copolyester according to claim 1, characterized in that: the R is 3 The structural unit isWherein the substituents R 4 And R is 17 Is one of alkyl, substituted alkyl or phenyl with 1-50 carbon atoms or any substituent thereof, and the substituent R 4 And R is 17 May be the same or different.
6. A process for preparing a high strength, high toughness 2, 5-furandicarboxylic acid copolyester according to claim 1, comprising the steps of:
(1) 2, 5-furandicarboxylic acid, dimethyl 2, 5-furandicarboxylic acid, diethyl 2, 5-furandicarboxylic acid, or mixtures thereof under inert gas atmosphere, containing R 2 、R 3 The dihydric alcohol of the structural unit, an esterification catalyst or a polycondensation catalyst are mixed according to a proportion, and are subjected to esterification reaction at the temperature of 80-260 ℃ for 1-6 hours to obtain an esterification product;
(2) Adding a polycondensation catalyst into the esterification product, further increasing the reaction temperature, reducing the pressure of the reaction system from the atmospheric pressure to below 100 Pa, performing polycondensation reaction at 80-280 ℃ for 1-8 hours, and obtaining the polyester product.
7. The process for preparing a high strength, high toughness 2, 5-furandicarboxylic acid copolyester according to claim 6, characterized in that: the molar ratio of the 2, 5-furandicarboxylic acid structural monomer to the amount of diol in step (1) is 1: 1-1: 5, a step of; the R-containing 2 Diols of structural units and R-containing compounds 3 The molar ratio of the dihydric alcohol of the structural unit is 1:99-99:1.
8. The process for preparing a high strength, high toughness 2, 5-furandicarboxylic acid copolyester according to claim 6, characterized in that: the amount of the catalyst in the step (1) is 0.01% -5% of the mole number of the 2, 5-furandicarboxylic acid structural monomer.
9. The process for preparing a high strength, high toughness 2, 5-furandicarboxylic acid copolyester according to claim 6, characterized in that: the catalyst is simple substance based on at least one element of Ti, sn, sb, pb, ge, zn, fe, mn, co, zr, mg, V, al or rare earth elements, or a compound or a mixture.
10. The process for preparing a high strength, high toughness 2, 5-furandicarboxylic acid copolyester according to claim 6, characterized in that: the catalyst is an enzyme or an organic base catalyst, the enzyme is candida antarctica lipase B immobilized on acrylic resin, and the organic base catalyst is one or more of 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene or 1, 4-diazabicyclo [2.2.2] octane.
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