CN118085251A - Preparation method of biodegradable block polyester material - Google Patents
Preparation method of biodegradable block polyester material Download PDFInfo
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- CN118085251A CN118085251A CN202211459847.7A CN202211459847A CN118085251A CN 118085251 A CN118085251 A CN 118085251A CN 202211459847 A CN202211459847 A CN 202211459847A CN 118085251 A CN118085251 A CN 118085251A
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- isosorbide
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 229920000728 polyester Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229960002479 isosorbide Drugs 0.000 claims abstract description 96
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims abstract description 88
- 239000010936 titanium Substances 0.000 claims abstract description 86
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 85
- -1 polybutylene succinate Polymers 0.000 claims abstract description 67
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 51
- 229920002961 polybutylene succinate Polymers 0.000 claims abstract description 48
- 239000004631 polybutylene succinate Substances 0.000 claims abstract description 48
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims abstract description 45
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 67
- 239000001361 adipic acid Substances 0.000 claims description 34
- 235000011037 adipic acid Nutrition 0.000 claims description 34
- 229910052710 silicon Inorganic materials 0.000 claims description 31
- 239000010703 silicon Substances 0.000 claims description 31
- 239000001384 succinic acid Substances 0.000 claims description 20
- 229940014800 succinic anhydride Drugs 0.000 claims description 16
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 34
- 229920000642 polymer Polymers 0.000 abstract description 13
- 150000002148 esters Chemical class 0.000 abstract description 11
- 229920001577 copolymer Polymers 0.000 abstract description 10
- 239000000178 monomer Substances 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 56
- 239000003054 catalyst Substances 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000010438 heat treatment Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 7
- 229920003232 aliphatic polyester Polymers 0.000 description 7
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- 229910052751 metal Inorganic materials 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229960005196 titanium dioxide Drugs 0.000 description 5
- 229920000704 biodegradable plastic Polymers 0.000 description 4
- 229920000229 biodegradable polyester Polymers 0.000 description 4
- 239000004622 biodegradable polyester Substances 0.000 description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
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- 235000013305 food Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 239000000155 melt Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VPVXHAANQNHFSF-UHFFFAOYSA-N 1,4-dioxan-2-one Chemical compound O=C1COCCO1 VPVXHAANQNHFSF-UHFFFAOYSA-N 0.000 description 1
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- YHTLGFCVBKENTE-UHFFFAOYSA-N 4-methyloxan-2-one Chemical compound CC1CCOC(=O)C1 YHTLGFCVBKENTE-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 1
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
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- 238000012828 global research and development Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920006030 multiblock copolymer Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002463 poly(p-dioxanone) polymer Polymers 0.000 description 1
- 229920001896 polybutyrate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
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- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
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- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a preparation method of a biodegradable block polyester material, which comprises the following steps: and (3) completely melting the polybutylene succinate and the isosorbide adipate oligomer, and then adding titanium-containing mesoporous silica to perform polycondensation reaction to obtain the biodegradable block polyester material. The invention takes bio-based succinic acid, 1, 4-butanediol and isosorbide as polymerization monomers, firstly, the butanediol succinate ester and the isosorbide and butanediol ester are respectively obtained through esterification reaction, the two ester are further respectively polycondensated to form polybutylene succinate and isosorbide succinate oligomer, the two oligomers are further polycondensated to synthesize a segmented copolymer polyester polymer, and the novel segmented biodegradable copolymer polyester material prepared by the method has the characteristics of high impact strength, tensile strength and elongation at break, good toughness, degradability, wide bio-based sources, carbon reduction and the like.
Description
Technical Field
The invention belongs to the field of new polymer materials, and particularly relates to a preparation method of a biodegradable block polyester material.
Background
Plastic development has so far brought convenience and benefit to life and industrial production of people, and meanwhile, due to the non-degradability, the problem of environmental pollution is more and more serious, and biodegradable plastic is an important way for solving the problem, and finally, under specific conditions, the biodegradable plastic is completely degraded into plastic of carbon dioxide, water, methane or mineralized inorganic salt. With the gradual implementation of plastic limiting and plastic inhibition regulations, the demand for biodegradable material products is increasing, and biodegradable plastics are an emerging industry with economic and low-carbon ecological significance and have become a hot spot for global research and development and popularization.
Poly (butylene succinate) (PBS) is used as one of main varieties of biodegradable plastics, and is obtained by esterification and polycondensation of succinic acid and butanediol, wherein the raw material succinic acid and butanediol can be derived from fossil base and biological base. PBS has good heat resistance and mechanical processing property, can be suitable for the conventional plastic processing technology at present, is widely used in the fields of packaging, agriculture, transportation, food, medical treatment and the like, can replace the traditional plastic to be widely applied to various fields of human life, and is greatly researched and developed. However, PBS itself still has some drawbacks, such as low glass transition temperature, insufficient mechanical properties such as tear strength and toughness, etc., and thus, in order to expand the application range of PBS, it is necessary to carry out copolymerization or blending modification.
Copolymerization is a common method for modifying a polymer, and the introduction of a rigid benzene ring into a polymer molecular chain is one of the most common methods for improving the mechanical properties of aliphatic polymers at present, but a serious transesterification reaction exists in the copolymerization process, so that a random copolymer is usually generated, and the melting point is greatly reduced. Meanwhile, the degradation performance of the aliphatic polyester is severely reduced due to the introduction of the non-degradation benzene ring.
Polymer International 200655,545 reports that the PBS modification is realized by copolymerization with maleic anhydride, and the flexural strength and tensile strength of the copolymerization product are greatly improved, but the impact strength is not obviously improved. The preparation of the segmented copolymer by introducing polyether prepolymers such as polyethylene glycol, polypropylene glycol and the like into the aliphatic polyester molecular chain is a main mode for improving the biodegradability of the aliphatic polyester at present, but the strength of the segmented copolymer is greatly reduced while the biodegradability and toughness of the aliphatic polyester are improved.
Chinese patent documents CN101649045A and CN102020772a respectively report that a multiblock copolymer is prepared by modifying crystalline aliphatic polyester by introducing amorphous or glassy aliphatic polyester soft segments into a crystalline aliphatic polyester molecular chain, and a high-performance biodegradable material is prepared, but the improvement of impact strength is extremely limited.
Chinese patent document CN104072954a discloses a poly 2, 5-isosorbide ethylene glycol ester composite material and a method for preparing the same, the poly 2, 5-isosorbide ethylene glycol ester composite material is prepared from a first poly 2, 5-isosorbide ethylene glycol ester; the first polymer is formed by blending with an auxiliary agent; the auxiliary agent is formed by sequentially grafting second polymer 2, 5-isosorbide glycol ester and second polymer after cellulose beads or cellulose whiskers are modified by a silane coupling agent with amino groups at the tail ends. The invention carries out modification by blending, toughens the poly-2, 5-isosorbide glycol ester and improves the impact strength; by adding the auxiliary agent, the interfacial compatibility of the blend is improved, and cellulose beads or cellulose whiskers in the auxiliary agent can play a role in enhancing the blend, but the addition of the auxiliary agent can influence the biocompatibility, transparency and degradation speed of the material.
The Chinese patent document CN107955142 discloses a preparation method of polyester containing isosorbide, relates to a preparation method of polyester containing ethylene glycol, isosorbide and terephthalic acid, and mainly solves the problems that in the prior art, isosorbide is easy to decompose in the polymerization process and the loss rate is high. The preparation method of the isosorbide polyester comprises the following steps: a) Terephthalic acid and glycol are used as raw materials, wherein the molar ratio of the glycol to the terephthalic acid is 1.05:1-1.3:1, a catalyst is added, and esterification reaction is carried out under the conditions that the esterification reaction temperature is 220-250 ℃ and the esterification reaction pressure is 10.4 KPa-0.5 MPa, so as to obtain a prepolymer; b) The technical scheme of obtaining the polymerization product by carrying out melt polycondensation reaction on the obtained prepolymer under the vacuum condition that the melt polycondensation reaction temperature is 250-265 ℃ and the melt polycondensation reaction pressure is less than 150Pa better solves the problem, and can be used in the industrial production of the polyester product containing isosorbide. Wherein the catalyst used comprises the reaction product of: a) an organotitanium compound, b) a hydroxy compound, c) a metal organic salt, wherein the metal element is selected from at least one metal element of group IA metal elements, group IIA metal elements, aluminium, tin, zinc, zirconium, lanthanum or hafnium, d) a phosphorus compound; preferably, the preparation method comprises the following steps: reacting the organic titanium compound with a hydroxyl compound at 0-200 ℃ for 0.1-24 hours, adding the metal organic salt and the phosphorus compound into the product, reacting at 0-200 ℃ for 0.1-24 hours, and removing low-carbon alcohol and/or water in the system to obtain the catalyst for preparing the polyester. The proposal adopts terephthalic acid as raw material, so that the obtained copolymer contains benzene ring substances, which limits the application of the copolymer in high-end fields such as medical use, food and the like, and the obtained copolymer has no biodegradation characteristic and is liable to cause unnecessary pollution.
Chinese patent document CN107522852a discloses a bio-based biodegradable triblock copolymer comprising dimer acid polyester segments, the triblock copolymer having the general formula a-B-a; wherein the chain segment A is a polymer chain segment formed by at least one of polylactic acid, polyglycolide, polydioxanone, polycaprolactone, poly-beta-methyl-valerolactone and polycarbonate; the chain segment B is a polyester chain segment formed by dicarboxylic acid or ester thereof and aliphatic dihydric alcohol; b represents a block structure; the dicarboxylic acid or ester thereof forming the segment B contains dimer acid or ester thereof, and the mole percentage of the dimer acid or ester thereof in the dicarboxylic acid or ester thereof is in the range of 0.1-100%. The preparation method comprises the following steps: (1) Adding the dibasic acid or the ester thereof and the aliphatic dihydric alcohol into a reactor, adding an esterification catalyst or an ester exchange catalyst to perform esterification reaction or ester exchange reaction to obtain an esterification product or an ester exchange product, and then adding a polycondensation catalyst into the esterification product or the ester exchange product to perform melt polycondensation reaction to obtain polyester with terminal hydroxyl groups; (2) Adding a cyclic monomer E (at least one of lactide, glycolide, p-dioxanone, epsilon-caprolactone, beta-methyl-valerolactone and cyclic carbonate) into the polyester obtained in the step (1), and obtaining the bio-based biodegradable triblock copolymer containing dimer acid polyester through ring opening reaction under the action of a ring opening polymerization catalyst. According to the technical scheme, two different catalysts are required to be added for polymerization reaction, the addition amount of the catalysts is increased, residues which are difficult to avoid in a polymerization product are caused, the product performance is influenced, the application range of the product in the fields of medical treatment, food and the like is influenced, the monomers adopted in the scheme are all annular monomers for ring-opening polymerization, the molecular chain structure in the polymer is mainly linear chains, the flexibility is outstanding, but the rigidity group is absent, and the strength is weak.
Disclosure of Invention
Aiming at the defects existing in the prior art, the main purpose of the invention is to provide a preparation method of a biodegradable block polyester material, which does not use auxiliary agents or other additives, and the prepared block polyester material has the characteristics of high tensile strength, high elongation at break, high transparency, degradability, wide biological base sources, carbon reduction and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a biodegradable block polyester material comprises the following steps:
And (3) completely melting the polybutylene succinate and the isosorbide adipate oligomer, and then adding titanium-containing mesoporous silica to perform polycondensation reaction to obtain the biodegradable block polyester material.
Optionally, the number average molecular weight of the poly (butylene succinate) is 5000-15000; the number average molecular weight of the adipic acid isosorbide oligomer is 5000-15000.
Optionally, in the mesoporous silica containing titanium, the molar ratio of titanium to silicon is 0.01-1:1, preferably 0.01-0.5:1.
Optionally, the titanium-containing mesoporous silica is added in an amount of 0.05 to 0.1wt% of the total amount of reactants (the total mass of the polybutylene succinate and the isosorbide adipate oligomer).
When the biodegradable block polyester material is formed by polycondensation of the polybutylene succinate and the isosorbide adipate oligomer, the dosage ratio and parameters of the raw materials can be adjusted according to the requirements on the molecular weight, the performance and the like of the biodegradable block polyester material, for example, the molar ratio of the polybutylene succinate to the isosorbide adipate oligomer can be limited to be 0.05-5:1, preferably 0.5-2:1;
The temperature of the polycondensation reaction is 220-300 ℃, the pressure is 0-100 Pa, and the time is 0.5-10 h.
Optionally, the preparation method of the polybutylene succinate comprises the following steps:
The bio-based succinic acid and/or succinic anhydride reacts with 1, 4-butanediol under the catalysis of mesoporous silica containing titanium (the molar ratio of titanium to silicon is 0.01-1:1, preferably 0.01-0.5:1) to obtain the polybutylene succinate.
Optionally, the titanium-containing mesoporous silica is added in an amount of 0.005 to 0.1wt% of the total amount of reactants (the total mass of bio-based succinic acid and/or succinic anhydride and 1, 4-butanediol).
Preferably, in the preparation method of the poly (butylene succinate), the bio-based succinic acid and/or the succinic anhydride are mixed with the 1, 4-butanediol, and then the mesoporous silica containing titanium is added.
Preferably, the bio-based succinic acid and/or succinic anhydride and 1, 4-butanediol are subjected to esterification reaction under the catalysis of titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.01-1:1, preferably 0.01-0.5:1) at constant temperature and normal pressure to obtain succinic acid 1, 4-butanediol ester, and then vacuumizing is carried out, and the reaction is continued under negative pressure to obtain the polybutylene succinate.
In the preparation method of the poly (butylene succinate), the parameters which are conventional in the industry are adopted, and the reaction temperature and parameters of each step can be adjusted according to actual requirements, for example, the temperature for the esterification reaction of bio-based succinic acid and/or succinic anhydride and 1, 4-butanediol at constant temperature and normal pressure is limited to be 140-180 ℃ and the time is 2-4 hours;
The reaction temperature is 200-280 ℃ under the negative pressure, the pressure is 20-200 Pa, and the reaction time is 1-4 h;
The mol ratio of the bio-based succinic acid and/or succinic anhydride to the 1, 4-butanediol is 1:1-1.6; the specific parameters can be adjusted according to actual requirements.
Optionally, the bio-based succinic acid is a "C4 platform compound" which can be used as an organic chemical raw material and intermediate.
Optionally, the preparation method of the adipic acid isosorbide oligomer comprises the following steps:
the isosorbide and adipic acid are subjected to esterification reaction under the catalysis of mesoporous silicon dioxide containing titanium (the molar ratio of titanium to silicon is 0.01-1:1, preferably 0.01-0.5:1) to obtain isosorbide adipate, and then the isosorbide adipate is subjected to polycondensation reaction to obtain an isosorbide adipate oligomer;
the adding amount of the mesoporous silica containing titanium is 0.005-0.1 wt% of the total amount of the isosorbide and the adipic acid.
Optionally, the molar ratio of the adipic acid to the isosorbide is 1:1.0-1.5.
Optionally, in the preparation method of the adipic acid isosorbide oligomer, the esterification reaction temperature is 150-210 ℃ and the time is 2-5 h.
Optionally, in the preparation method of the adipic acid isosorbide oligomer, the pressure of the polycondensation reaction is 0-1000 Pa, the temperature is 220-300 ℃ and the time is 0.5-10 h.
The above-mentioned titanium-containing mesoporous silica is a highly dispersed titanium-based catalyst formed by supporting a titanium-containing catalyst by mesoporous silica, the titanium-containing catalyst may be selected from titanium or titanium dioxide, preferably titanium dioxide, and the titanium fatty acid may be selected from at least one of titanium acid including n-butyl titanate, isopropyl titanate, n-pentyl titanate, isopentyl titanate, n-octyl titanate, isooctyl titanate, and the like.
According to the invention, the bio-based isosorbide monomer is introduced, and the novel block biodegradable polyester material poly (butylene succinate) co-isosorbide adipate is synthesized by reacting with dibasic acid such as succinic acid, butanediol, adipic acid and the like and dihydric alcohol, so that the novel block biodegradable polyester material poly (butylene succinate) co-isosorbide adipate has better transparency, strength and toughness compared with the existing poly (butylene succinate) (PBS).
Compared with the prior art, the invention has the following beneficial effects:
1. According to the invention, by introducing the bio-based isosorbide monomer, directly utilizing the dibasic acid and the dihydric alcohol as raw materials and combining the titanium-containing mesoporous silica catalyst with small particle size, high activity and good dispersion, a novel block biodegradable polyester material with high intrinsic viscosity, namely the polybutylene succinate and the isosorbide adipate oligomer, is synthesized in a direct esterification and segmented polycondensation mode, and the polymer with different series of molecular structures is synthesized, so that the molecular structure is controlled more accurately, the material is ensured to keep a block structure, the flexibility and the operability are higher, the product performance is ensured, and the adjustable range of the product performance is large. Compared with the existing polybutylene succinate (PBS), the PBS has better impact strength and toughness, improves the comprehensive performance of PBS products, and expands the application range. The method replaces the conventional method of carrying out copolymerization modification by introducing petroleum-based terephthalic acid and butanediol reaction, reduces side effects brought by benzene rings, increases the bio-based attribute of the material, and expands the material source.
2. The invention takes bio-based succinic acid, 1, 4-butanediol and isosorbide as polymerization monomers, firstly obtains butanediol succinate ester and adipic acid isosorbide ester through esterification reaction and distribution, further respectively carries out polycondensation reaction on the two ester compounds to generate polybutylene succinate and adipic acid isosorbide oligomer, and finally carries out polycondensation reaction on the polybutylene succinate and the adipic acid isosorbide oligomer to synthesize the segmented copolymer polyester polymer. The novel block biodegradable copolyester material prepared by the method has the characteristics of high tensile strength and elongation at break, high transparency, degradability, wide biological base sources, carbon reduction and the like.
3. According to the preparation method, the green monomer isosorbide is introduced, and the characteristic of the cyclic structure of the isosorbide monomer is utilized to replace benzene rings in the conventional PBAT (polybutylene terephthalate-adipate) biodegradable material, so that the rigidity and strength of the novel copolyester material are improved, and meanwhile, the negative influence caused by the existence of the benzene rings can be avoided. The modified PBS material prepared by the preparation method not only does not change the performance advantages of biodegradability and biocompatibility of the PBS, but also improves the compatibility among copolymers compared with the physical modification by adding corresponding compatilizer, and the chemically modified copolyester has better chain segment compatibility, transparency, tensile strength, elongation at break and other mechanical properties.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
The implementation of the technical scheme of the invention can be satisfied by loading the mesoporous silica with a titanium-containing catalyst (at least one of titanium dioxide, n-butyl titanate, isopropyl titanate, n-pentyl titanate, isopentyl titanate, n-octyl titanate, isooctyl titanate and the like) to form a highly dispersed titanium-based catalyst, namely titanium-containing mesoporous silica. For comparison, the titanium-containing mesoporous silica of each of the following examples and comparative examples was obtained by uniformly mixing silica having a particle size of less than 100nm with titania having a particle size of less than 100nm at room temperature. The mass ratio of the specific silicon dioxide to the titanium dioxide can be correspondingly adjusted according to the mol ratio of titanium to silicon in the target titanium-containing mesoporous silicon dioxide.
For comparison, the vacuum degree of melt polycondensation of polybutylene succinate and isosorbide adipate oligomer in the following step (3) of each example was set to 50Pa, the temperature was set to 260℃and the time was set to 3 hours.
The molecular weights in each of the examples and comparative examples are number average molecular weights.
Example 1
(1) The preparation method comprises the steps of placing bio-based succinic acid and 1, 4-butanediol in a reaction vessel according to a molar ratio of 1:1, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 1) serving as a catalyst with the total mass of 0.1% of the bio-based succinic acid and the 1, 4-butanediol under the protection of nitrogen, stirring and heating to 180 ℃ to perform constant-temperature normal-pressure esterification reaction, vacuumizing to 50Pa after 2 hours, heating to 250 ℃ to continue the reaction for 4 hours, and stopping the reaction to obtain the polybutylene succinate with the molecular weight of 15000.
(2) Placing isosorbide and adipic acid into a reactor at a molar ratio of 1.0, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.03) serving as a catalyst with the total mass of 0.005% of the isosorbide and the adipic acid under the protection of nitrogen, carrying out constant-temperature normal-pressure esterification reaction for 3 hours at 140 ℃, vacuumizing to 100Pa, and after the temperature is raised to 245 ℃ for continuous reaction for 3 hours, stopping the reaction to obtain the isosorbide adipate oligomer with the molecular weight of 5000.
(3) Adding polybutylene succinate and isosorbide adipate oligomer into a dry reactor in a molar ratio of 0.05:1, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.5:1) serving as a catalyst with the total mass of 0.05% of the polybutylene succinate and the isosorbide adipate oligomer after the polybutylene succinate and the isosorbide adipate oligomer are completely melted, carrying out melt polycondensation reaction for 3 hours at the vacuum degree of 50Pa and the temperature of 260 ℃, stopping the reaction, and carrying out extrusion granulation to obtain the biodegradable block polyester material.
Example 2
(1) The preparation method comprises the steps of placing bio-based succinic acid and 1, 4-butanediol in a reaction vessel according to a molar ratio of 1:1.3, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.3) serving as a catalyst with the total mass of 0.05% of the bio-based succinic acid and the 1, 4-butanediol under the protection of nitrogen, stirring and heating to 170 ℃ to perform constant temperature and normal pressure esterification reaction for 3 hours, vacuumizing to 100Pa, heating to 230 ℃ to continue the reaction for 2 hours, and stopping the reaction to obtain the polybutylene succinate with the molecular weight of 10000.
(2) Placing isosorbide and adipic acid into a reactor at a molar ratio of 1:1.3, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.3) serving as a catalyst with the total mass of 0.05% of the isosorbide and the adipic acid under the protection of nitrogen, carrying out constant-temperature normal-pressure esterification reaction for 3 hours at 170 ℃, vacuumizing to 100Pa, heating to 245 ℃ for continuous reaction for 3 hours, and stopping the reaction to obtain the isosorbide adipate oligomer with the molecular weight of 10000.
(3) Adding polybutylene succinate and isosorbide adipate oligomer into a dry reactor in a molar ratio of 1:1, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.3:1) serving as a catalyst accounting for 0.05% of the total mass of the polybutylene succinate and the isosorbide adipate oligomer after the polybutylene succinate and the isosorbide adipate oligomer are completely melted, carrying out melt polycondensation reaction for 3 hours at the vacuum degree of 50Pa and the temperature of 260 ℃, stopping the reaction, and extruding and granulating to obtain the biodegradable block polyester material.
Example 3
(1) The preparation method comprises the steps of placing bio-based succinic acid and 1, 4-butanediol in a reaction vessel according to a molar ratio of 1:1.6, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.03) serving as a catalyst with the total mass of the bio-based succinic acid and the 1, 4-butanediol under the protection of nitrogen, stirring and heating to 160 ℃ to perform constant-temperature normal-pressure esterification reaction for 2 hours, vacuumizing to 100Pa, heating to 230 ℃ to continue the reaction for 2 hours, and stopping the reaction to obtain the polybutylene succinate with the molecular weight of 5000.
(2) Placing isosorbide and adipic acid into a reactor at a molar ratio of 1:1.5, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.03) serving as a catalyst with the total mass of isosorbide and adipic acid being 0.005% under the protection of nitrogen, carrying out constant-temperature normal-pressure esterification reaction for 3 hours at 170 ℃, vacuumizing to 100Pa, and after the temperature is raised to 245 ℃ for continuous reaction for 3 hours, stopping the reaction to obtain the isosorbide adipate oligomer with the molecular weight of 7000.
(3) Adding polybutylene succinate and isosorbide adipate oligomer into a dry reactor in a molar ratio of 2:1, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.5) serving as a catalyst accounting for 0.05% of the total mass of the polybutylene succinate and the isosorbide adipate oligomer after the polybutylene succinate and the isosorbide adipate oligomer are completely melted, performing melt polycondensation reaction for 3 hours at the vacuum degree of 50Pa and the temperature of 260 ℃, stopping the reaction, and extruding and granulating to obtain the biodegradable block polyester material.
Example 4
(1) The preparation method comprises the steps of placing bio-based succinic acid and 1, 4-butanediol in a reaction vessel according to a molar ratio of 1:1.3, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.03) serving as a catalyst with the total mass of the bio-based succinic acid and the 1, 4-butanediol under the protection of nitrogen, stirring and heating to 150 ℃ to perform constant-temperature normal-pressure esterification reaction for 3 hours, vacuumizing to 100Pa, heating to 260 ℃ to continue the reaction for 1 hour, and stopping the reaction to obtain the polybutylene succinate with the molecular weight of 8000.
(2) Placing isosorbide and adipic acid into a reactor at a molar ratio of 1:1.3, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.03) serving as a catalyst with the total mass of 0.1% of the isosorbide and the adipic acid under the protection of nitrogen, carrying out constant-temperature normal-pressure esterification reaction for 3 hours at 170 ℃, vacuumizing to 100Pa, heating to 245 ℃ for continuous reaction for 2 hours, and stopping the reaction to obtain the isosorbide oligomer with the molecular weight of 8000 adipic acid.
(3) Adding polybutylene succinate and isosorbide adipate oligomer into a dry reactor in a molar ratio of 1:1, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 1) serving as a catalyst accounting for 0.1% of the total mass of the polybutylene succinate and the isosorbide adipate oligomer after the polybutylene succinate and the isosorbide adipate oligomer are completely melted, and carrying out melt polycondensation reaction for 3 hours at a vacuum degree of 50Pa and a temperature of 260 ℃, stopping the reaction, and extruding and granulating to obtain the biodegradable block polyester material.
Example 5
(1) The preparation method comprises the steps of placing bio-based succinic anhydride and 1, 4-butanediol in a reaction vessel according to a molar ratio of 1:1, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.03) serving as a catalyst with the total mass of the bio-based succinic anhydride and the 1, 4-butanediol under the protection of nitrogen, stirring and heating to 180 ℃ to perform constant-temperature normal-pressure esterification reaction for 4 hours, vacuumizing to 100Pa, heating to 230 ℃ to continue the reaction for 2 hours, and stopping the reaction to obtain the polybutylene succinate with the molecular weight of 6000.
(2) Placing isosorbide and adipic acid into a reactor with a molar ratio of 1.0, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.03) serving as a catalyst with the total mass of 0.005% of the isosorbide and the adipic acid under the protection of nitrogen, carrying out constant-temperature normal-pressure esterification reaction for 3 hours at 170 ℃, vacuumizing to 100Pa, and after the temperature is raised to 245 ℃ for continuous reaction for 3 hours, stopping the reaction to obtain the isosorbide adipate oligomer with the molecular weight of 5000.
(3) Adding polybutylene succinate and isosorbide adipate oligomer into a dry reactor in a molar ratio of 0.5:1, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.2) serving as a catalyst accounting for 0.05% of the total mass of the polybutylene succinate and the isosorbide adipate oligomer after the polybutylene succinate and the isosorbide adipate oligomer are completely melted, performing melt polycondensation reaction for 3 hours at the vacuum degree of 50Pa and the temperature of 260 ℃, stopping the reaction, and extruding and granulating to obtain the biodegradable block polyester material.
Example 6
(1) Placing the bio-based succinic anhydride and the 1, 4-butanediol in a reaction vessel according to a molar ratio of 1:1.3, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.03) serving as a catalyst with the total mass of 0.005% of the bio-based succinic anhydride and the 1, 4-butanediol under the protection of nitrogen, stirring and heating to 160 ℃ to perform constant temperature and normal pressure esterification reaction for 2 hours, vacuumizing to 100Pa, heating to 250 ℃ to continue the reaction for 3 hours, and stopping the reaction to obtain the polybutylene succinate with the molecular weight of 9000.
(2) Placing isosorbide and adipic acid into a reactor at a molar ratio of 1:1.3, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.6) serving as a catalyst with the total mass of isosorbide and adipic acid being 0.07% under the protection of nitrogen, carrying out constant-temperature normal-pressure esterification reaction for 3 hours at 170 ℃, vacuumizing to 100Pa, and after the temperature is raised to 245 ℃ for continuous reaction for 3 hours, stopping the reaction to obtain the isosorbide adipate oligomer with the molecular weight of 11000.
(3) Adding polybutylene succinate and isosorbide adipate oligomer into a dry reactor in a molar ratio of 1:1, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.2) serving as a catalyst accounting for 0.05% of the total mass of the polybutylene succinate and the isosorbide adipate oligomer after the polybutylene succinate and the isosorbide adipate oligomer are completely melted, performing melt polycondensation reaction for 3 hours at the vacuum degree of 50Pa and the temperature of 260 ℃, stopping the reaction, and extruding and granulating to obtain the biodegradable block polyester material.
Example 7
(1) The preparation method comprises the steps of placing bio-succinic anhydride and1, 4-butanediol in a reaction vessel according to a molar ratio of 1:1.6, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.03) serving as a catalyst with the total mass of the bio-succinic anhydride and the 1, 4-butanediol under the protection of nitrogen, stirring and heating to 160 ℃ for constant temperature and normal pressure esterification reaction for 2 hours, vacuumizing to 100Pa, heating to 230 ℃ for continuous reaction for 2 hours, and stopping the reaction to obtain the polybutylene succinate with the molecular weight of 7500.
(2) Placing isosorbide and adipic acid into a reactor at a molar ratio of 1:1.5, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.03) serving as a catalyst with the total mass of isosorbide and adipic acid being 0.005% under the protection of nitrogen, carrying out constant-temperature normal-pressure esterification reaction for 3 hours at 170 ℃, vacuumizing to 100Pa, and raising the temperature to 245 ℃ for continuous reaction for 3 hours, and stopping the reaction to obtain the isosorbide adipate oligomer with the molecular weight of 6000.
(3) Adding polybutylene succinate and isosorbide adipate oligomer into a dry reactor in a molar ratio of 2:1, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.5) serving as a catalyst accounting for 0.05% of the total mass of the polybutylene succinate and the isosorbide adipate oligomer after the polybutylene succinate and the isosorbide adipate oligomer are completely melted, performing melt polycondensation reaction for 3 hours at the vacuum degree of 50Pa and the temperature of 260 ℃, stopping the reaction, and extruding and granulating to obtain the biodegradable block polyester material.
Comparative example 1
The specific preparation process of the comparative PBS is as follows:
(1) Adding succinic acid and 1, 4-butanediol into a pulping kettle in a molar ratio of 1.2:1, starting stirring, heating to 120 ℃, and mixing for 10 minutes;
(2) Adding a titanium-containing mesoporous silica catalyst (the molar ratio of titanium to silicon is 0.01) into the material (1) in a proportion of 0.05 percent by weight, uniformly mixing, and then transferring the material to an esterification kettle;
(3) Heating the esterification kettle to 170 ℃, and stirring for reaction for 3h;
(4) After the esterification reaction is finished, introducing the materials into a pre-polycondensation reaction kettle for pre-polycondensation reaction, wherein the reaction temperature is 220 ℃, and stirring and reacting for 1h;
(5) After the preshrinking reaction is finished, introducing preshrinking products into a final polycondensation reaction kettle, adding a titanium-containing mesoporous silica catalyst (the molar ratio of titanium to silicon is 0.5) accounting for 0.1 percent of the total mass of the materials (1), heating to 240 ℃, vacuumizing to 60Pa, and carrying out the final polycondensation reaction for 3 hours;
(6) And stopping stirring after the reaction is finished, discharging and granulating.
Comparative example 2
(1) Placing the bio-based succinic anhydride and the 1, 4-butanediol in a reaction vessel according to a molar ratio of 1:1.3, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.03) serving as a catalyst with the total mass of 0.005% of the bio-based succinic anhydride and the 1, 4-butanediol under the protection of nitrogen, stirring and heating to 160 ℃ to perform constant temperature and normal pressure esterification reaction for 2 hours, vacuumizing to 100Pa, heating to 250 ℃ to continue the reaction for 3 hours, and stopping the reaction to obtain the polybutylene succinate with the molecular weight of 9000.
(2) Placing isosorbide and adipic acid into a reactor at a molar ratio of 1:1.3, adding titanium-containing mesoporous silica (the molar ratio of titanium to silicon is 0.6) serving as a catalyst with the total mass of 0.07% of the isosorbide and the adipic acid under the protection of nitrogen, carrying out constant-temperature normal-pressure esterification reaction for 3 hours at 170 ℃, vacuumizing to 100Pa, heating to 245 ℃ for continuous reaction for 3 hours, and stopping the reaction to obtain the isosorbide adipate polymer with the molecular weight of 11000.
(3) And (3) blending the PBS polyester, the isosorbide and the adipic acid polyester according to the mass ratio of 1:1 by using a double-screw extruder, extruding and granulating to obtain the blend of the PBS polyester, the isosorbide and the adipic acid polyester.
Performance test and results
The dynamic thermo-mechanical properties of the polyester materials prepared in each example and comparative example were analyzed using a DMA-Q800 dynamic mechanical analyzer from TA company in the united states. The selected test mode is Multi-frequencestrain, the test frequency is 1Hz, the temperature range is-80-110 ℃, and the temperature rising rate is 3K/min.
Table 1 mechanical properties of examples and comparative examples samples
| Sample of | Breaking strength (MPa) | Elongation at break (%) | Young's modulus (MPa) | Transparency of the film |
| Example 1 | 52.3 | 753 | 473 | Good (good) |
| Example 2 | 49.6 | 880 | 396 | Preferably, it is |
| Example 3 | 43.4 | 989 | 266 | In general |
| Example 4 | 51.7 | 912 | 412 | Preferably, it is |
| Example 5 | 51.5 | 713 | 434 | Good (good) |
| Example 6 | 48.2 | 828 | 343 | Preferably, it is |
| Example 7 | 44.9 | 928 | 223 | In general |
| Comparative example 1 | 35.6 | 325 | 326 | In general |
| Comparative example 2 | 39.1 | 189 | 314 | Low and low |
Note that: transparency is the average of 30 randomly selected individuals for visual observation.
The transparency criteria in the above table are as follows:
and (3) good: the light-transmitting type particle size analyzer can allow most light to transmit, and when a following object is observed through the particle size analyzer, the outline and detail of the object can be clearly seen;
the method is better: more light can be allowed to pass through, and when the following objects are observed through the granules, the outlines of the objects can be clearly seen, but the details cannot be clearly seen;
Generally: can allow part of light to pass through, and only shadows of the outline of the object can be seen when the object behind is observed through the granules;
Low: substantially no light is allowed to pass through.
From the data in the table, the novel copolymerized biodegradable polyester material obtained by the preparation method provided by the invention has good mechanical properties and high transparency, and particularly the breaking strength and the breaking elongation are obviously improved. Compared with the traditional PBS material, the segmented copolymer polyester prepared by the preparation method provided by the invention has good compatibility, good transparency, higher breaking strength and better mechanical property.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The preparation method of the biodegradable block polyester material is characterized by comprising the following steps:
And (3) completely melting the polybutylene succinate and the isosorbide adipate oligomer, and then adding titanium-containing mesoporous silica to perform polycondensation reaction to obtain the biodegradable block polyester material.
2. The method according to claim 1, wherein the polybutylene succinate has a number average molecular weight of 5000 to 15000; the number average molecular weight of the adipic acid isosorbide oligomer is 5000-15000.
3. The method of claim 1, wherein the molar ratio of titanium to silicon in the titanium-containing mesoporous silica is 0.01 to 1:1, preferably 0.01 to 0.5:1.
4. The method of claim 1, wherein the titanium-containing mesoporous silica is added in an amount of 0.05wt% to 0.1wt% based on the total amount of the reactants.
5. The process according to claim 1, wherein the molar ratio of polybutylene succinate to isosorbide adipate oligomer is from 0.05 to 5:1, preferably from 0.5 to 2:1.
6. The preparation method of any one of claims 1 to 5, wherein the preparation method of the polybutylene succinate comprises the following steps:
The bio-based succinic acid and/or succinic anhydride react with 1, 4-butanediol under the catalysis of mesoporous silica containing titanium to obtain the poly butylene succinate.
7. The method of claim 6, wherein the titanium-containing mesoporous silica is added in an amount of 0.005wt% to 0.1wt% based on the total amount of the reactants.
8. The method according to claim 6, wherein the molar ratio of the bio-based succinic acid and/or succinic anhydride to the 1, 4-butanediol is 1:1 to 1.6.
9. The method of any one of claims 1-5, wherein the method of preparing isosorbide adipate oligomer comprises the steps of:
Esterifying isosorbide and adipic acid under the catalysis of titanium-containing mesoporous silica to obtain isosorbide adipate, and performing polycondensation reaction to obtain isosorbide adipate oligomer;
the adding amount of the mesoporous silica containing titanium is 0.005-0.1 wt% of the total amount of the isosorbide and the adipic acid.
10. The method of claim 9, wherein the molar ratio of adipic acid to isosorbide is 1:1.0 to 1.5.
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