CN111116880B - Full-bio-based thermoplastic polyester elastomer based on furan ring and preparation method thereof - Google Patents
Full-bio-based thermoplastic polyester elastomer based on furan ring and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—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
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
- C08G63/58—Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
Abstract
A furan ring-based full-bio-based thermoplastic polyester elastomer and a preparation method thereof, a thermoplastic polyester elastomer and a preparation method thereof, wherein the thermoplastic polyester elastomer comprises a hard segment made of 2, 5-furandicarboxylic acid polyester and a soft segment made of bio-based polyester; the invention also provides a preparation method of the furan ring-based full-bio-based thermoplastic polyester elastomer; the all-biobased thermoplastic polyester elastomer has excellent mechanical properties, the mechanical properties, crystallization and thermal properties of the thermoplastic polyester elastomer can be adjusted by changing the ratio of the hard section and the soft section of the biobased polyester of the 2, 5-furandicarboxylic acid polyester, the elastomer from hard plastics to soft elastomers can be obtained, all monomer raw materials of the elastomer are from renewable resources, and the elastomer is independent of petroleum-based monomers and is a novel green high polymer material.
Description
Technical Field
The invention relates to a thermoplastic polyester elastomer and a preparation method thereof, in particular to a furan ring-based all-bio-based thermoplastic polyester elastomer and a preparation method thereof.
Background
The thermoplastic elastomer has the characteristics of both rubber and plastic, shows high elasticity of the traditional vulcanized rubber at normal temperature, and can be repeatedly processed and plasticized like thermoplastic resin at high temperature. The thermoplastic elastomer generally comprises two phases at the use temperature, wherein one phase is a hard segment (the Tg of the hard segment is higher than the use temperature), the other phase is a soft segment (the Tg of the soft segment is lower than the use temperature), reversible physical cross-linking points are formed between the hard segments to bear stress, the soft segment is a freely distributed high-elasticity chain segment to contribute to elasticity, interaction exists between the hard segment and the soft segment, and the thermoplastic elastomers with different properties can be obtained by adjusting the composition and the proportion of the hard segment and the soft segment. The thermoplastic polyester elastomer is a typical and interesting thermoplastic elastomer, and has been widely applied to the fields of automobile industrial products, cable and wire, stationery, electronic and electric products, biological materials and the like.
At present, most of thermoplastic polyester elastomers are prepared from aromatic compounds derived from fossil resources, for example, aromatic polyesters such as polybutylene terephthalate (PBT), polytrimethylene terephthalate (PPT) and polybutylene naphthalate (PBN) are used as a hard segment, and polyesters such as polyoxyalkylene glycols (e.g., polytetramethylene glycol, PTMG), polycaprolactone and polycarbonate are used as a soft segment. Although the thermoplastic polyester elastomer has the characteristic of recycling, most of the main raw materials (such as terephthalic acid) of the synthetic thermoplastic polyester elastomer are derived from non-renewable fossil resources, the manufacturing process of the monomer is highly polluted and toxic to the environment, and a large amount of greenhouse gas CO2 is released in the production process. Therefore, the preparation of a novel full-bio-based thermoplastic elastomer to replace the traditional petroleum-based thermoplastic elastomer is a problem which needs to be solved urgently in the field of high polymer materials.
2, 5-Furanedicarboxylic acid (FDCA), a biobased monomer available from renewable resources, such as polysaccharides, starches, lignocelluloses, and the like, has attracted considerable attention in both academia and industry. 2, 5-Furanedicarboxylic acid (FDCA) is similar in structure to terephthalic acid (PTA) and contains a rigid ring structure, and FDCA is considered to be an alternative to PTA for the synthesis of bio-based polymers with high performance. There are also some patents reporting furan ring-containing thermoplastic elastomers, such as: CN 109134835 a, CN 107973904 a, CN 107973904 a. However, the soft segment of the thermoplastic elastomer reported in these patents is petrochemical products such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or polytetrahydrofuran. Therefore, the preparation of the furan ring-based full-bio-based thermoplastic polyester elastomer has important significance for saving petroleum resources, protecting the environment and the like.
Disclosure of Invention
The invention aims to provide a furan ring-based all-biobased thermoplastic polyester elastomer and a preparation method thereof, the prepared furan ring-based all-biobased thermoplastic polyester elastomer has excellent mechanical properties, and the mechanical properties, crystallization and thermal properties of the thermoplastic polyester elastomer can be adjusted by changing the ratio of the hard segment of 2, 5-furandicarboxylic acid polyester to the soft segment of biobased polyester, so that the elastomer from hard plastic to soft plastic can be obtained.
The purpose of the invention is realized by the following technical scheme:
the invention provides a furan ring-based full-bio-based thermoplastic polyester elastomer, which has a structural formula shown in a formula (I):
in the formula (I), R is bio-based diol,
the chain segment is hydroxyl-terminated bio-based polyester, and x, y and m are integers.
The bio-based thermoplastic polyester elastomer comprises hard segments of 2, 5-furandicarboxylic acid polyester and soft segments of bio-based polyester.
The thermoplastic polyester elastomer is completely independent of petrochemical resources and has biodegradability.
The invention also provides a preparation method of the full-bio-based thermoplastic polyester elastomer based on furan rings, which adopts the following technical scheme:
(1) the preparation method of the hydroxyl-terminated bio-based polyester comprises the following steps: stirring and mixing various bio-based diols and dibasic acid, adding a stabilizer, carrying out esterification reaction for 1-4 h at 160-190 ℃ under the protection of nitrogen, then adding a catalyst, carrying out polycondensation reaction for 1-4 h at 100-300 Pa and 180-220 ℃, adding bio-based diols accounting for 10% of the total amount of alcohols, and carrying out end capping to prepare the hydroxyl-terminated bio-based polyester soft segment.
(2) The preparation method of the full-bio-based thermoplastic polyester elastomer based on furan rings comprises the following steps: stirring and mixing 2, 5-furan dicarboxylic acid or ester thereof, bio-based dihydric alcohol and hydroxyl-terminated bio-based polyester according to a proportion, adding a stabilizer, carrying out esterification or transesterification reaction for 3-6 h at 150-190 ℃ under the protection of nitrogen, then adding a catalyst, and carrying out polycondensation reaction for 2-10 h at 100-300 Pa and 200-240 ℃ to prepare the furan ring-based all-bio-based thermoplastic polyester elastomer.
The molar ratio of the dihydric alcohol to the dibasic acid in the hydroxyl-terminated bio-based polyester is 1.05: 1-1.7: 1, the total reacted monomers are at least 3 and more than 3 dibasic acids and dihydric alcohol mixtures (at least 1 dibasic acid and 1 dihydric alcohol), the dosage of the stabilizer is 0.05-0.2% of the total mass of the reacted monomers, and the dosage of the catalyst is 0.05-0.5% of the total mass of the reacted monomers.
The hydroxyl-terminated bio-based polyester has the number average molecular weight of 1000-8000 g/mol, the molecular weight distribution of 1.2-3, the glass transition temperature of-60 to-30 ℃, and is an amorphous polymer at normal temperature.
In the furan ring-based total bio-based thermoplastic polyester elastomer, the reaction molar ratio of dihydric alcohol to dibasic acid (containing 2, 5-furandicarboxylate) is 1.1: 1-2.2: 1, the hydroxyl-terminated bio-based polyester accounts for 50-90% of the total bio-based thermoplastic polyester elastomer, the dosage of the stabilizer is 0.01-0.2% of the total mass of the reaction monomer, and the dosage of the catalyst is 0.1-0.5% of the total mass of the reaction monomer.
Preferably, the bio-based diol is 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 2, 3-butanediol, isosorbide, 1, 5-pentanediol, 1, 6-hexanediol, 1, 10-decanediol.
Preferably, the bio-based dibasic acid is 1, 4-succinic acid, fumaric acid, isosorbide, 1, 5-glutaric acid, 1, 6-adipic acid, itaconic acid, 1, 10-sebacic acid, dodecanedioic acid, tridecanedioic acid, pentadecanedioic acid.
The stabilizer is one or a mixture of more of phosphoric acid, triphenyl phosphate, triethyl phosphate, p-hydroxyanisole, hydroquinone, o-methyl hydroquinone, p-benzoquinone or benzoquinone triphenyl phosphite.
The catalyst is one or a mixture of more of n-butyl titanate, tetrabutyl titanate, titanium tetraisopropoxide, tetraethyl titanate, stannous oxide, stannous octoate, stannous chloride, stannous bromide, stannous iodide, stannous acetate, stannous oxalate, stannous sulfate or stannous hydroxide.
The invention has the advantages and effects that:
1. the furan ring-based full-bio-based thermoplastic polyester elastomer prepared by the invention has excellent mechanical properties, and the mechanical properties, crystallization and thermal properties of the thermoplastic polyester elastomer can be adjusted by changing the ratio of the hard segment and the soft segment of the bio-based polyester of the 2, 5-furandicarboxylic acid polyester, so that the elastomer from hard plastics to soft plastics can be obtained.
2. All monomer raw materials of the furan ring-based full-bio-based thermoplastic polyester elastomer prepared by the invention are derived from renewable resources, do not depend on petroleum-based monomers, and are a novel green high polymer material.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the all-bio based thermoplastic polyester elastomer prepared in example 1 and a comparative example;
FIG. 2 is an infrared spectrum of the all bio-based thermoplastic polyester elastomer prepared in example 1 and a comparative example;
FIG. 3 is a thermogravimetric plot of the fully bio-based thermoplastic polyester elastomer prepared in example 1 versus a comparative example;
fig. 4 is a stress-strain curve of the all bio-based thermoplastic polyester elastomer prepared in example 1 and a comparative example.
Detailed Description
The scheme of the invention is further detailed below with reference to examples:
example 1
Preparing hydroxyl-terminated bio-based polyester: adding 1, 2-propylene glycol, 1, 4-butanediol, 1, 4-succinic acid, 1, 10-sebacic acid and p-hydroxyanisole (0.2% of total mass of reaction monomers) into a three-neck flask, stirring uniformly, wherein the ratio of dihydric alcohol: the molar ratio of the dibasic acid is 1.2: 1, 1, 2-propanediol: the molar ratio of 1, 4-butanediol is 0.5: 0.5, 1, 4-succinic acid: 1, 10-sebacic acid molar ratio of 0.7: 0.3, heating to 180 ℃ under the nitrogen atmosphere, reacting for 2 hours at the temperature, adding tetrabutyl titanate (0.05 percent of the total mass of the reaction monomers), reacting for 1.5 h under the condition of reduced pressure (300 Pa), adding 1, 4-butanediol accounting for 10 percent of the total amount of the alcohol for end capping, and finally obtaining the hydroxyl-terminated bio-based polyester (Mn =2700-3000 g/mol).
Preparing a furan ring-based all-bio-based thermoplastic polyester elastomer: putting 2, 5-furan diformate, 1, 4-butanediol, hydroxyl-terminated bio-based polyester and p-hydroxyanisole (0.2% of the total mass of reaction monomers) into a three-neck flask, uniformly stirring, wherein the molar ratio of the dihydric alcohol to the dibasic acid is 1.3: 1, the hydroxyl-terminated bio-based polyester accounts for 80% of the total mass of the bio-based thermoplastic polyester elastomer, stirring and melting under the protection of nitrogen, then carrying out transesterification reaction at 160 ℃ for 1 h, transesterification reaction at 170 ℃ for 1 h and transesterification reaction at 180 ℃ for 2 h in sequence, then adding tetrabutyl titanate (0.05% of the total mass of the reaction monomers), heating to 220 ℃, carrying out vacuum pumping and polycondensation reaction for 4 h, and taking out the product while the product is hot.
Example 2
Preparing hydroxyl-terminated bio-based polyester: the same as in example 1.
Preparing a furan ring-based all-bio-based thermoplastic polyester elastomer: putting 2, 5-furan diformate, 1, 4-butanediol, hydroxyl-terminated bio-based polyester and p-hydroxyanisole (0.2% of the total mass of reaction monomers) into a three-neck flask, uniformly stirring, wherein the molar ratio of the dihydric alcohol to the dibasic acid is 1.5: 1, the hydroxyl-terminated bio-based polyester accounts for 90% of the total mass of the all-bio-based thermoplastic polyester elastomer, stirring and melting under the protection of nitrogen, then carrying out transesterification reaction at 160 ℃ for 1 h, transesterification reaction at 170 ℃ for 1 h and transesterification reaction at 180 ℃ for 2 h, then adding tetrabutyl titanate (0.05% of the total mass of the reaction monomers), heating to 220 ℃, carrying out vacuum pumping reaction for 6 h, and taking out polycondensation products when the reactants are hot.
Example 3
Preparing hydroxyl-terminated bio-based polyester: the same as in example 1.
Preparing a furan ring-based all-bio-based thermoplastic polyester elastomer: putting 2, 5-furan diformate, 1, 4-butanediol, hydroxyl-terminated bio-based polyester and p-hydroxyanisole (0.2% of the total mass of reaction monomers) into a three-neck flask, uniformly stirring, wherein the molar ratio of the dihydric alcohol to the dibasic acid is 1.3: 1, the hydroxyl-terminated bio-based polyester accounts for 50% of the total mass of the all-bio-based thermoplastic polyester elastomer, stirring and melting under the protection of nitrogen, then carrying out transesterification reaction at 160 ℃ for 1 h, transesterification reaction at 170 ℃ for 1 h and transesterification reaction at 180 ℃ for 2 h, then adding tetrabutyl titanate (0.05 wt% of the total mass of the reaction monomers), heating to 210 ℃, carrying out vacuum pumping reaction for 10 h, and taking out polycondensation products when the reactants are hot.
Example 4
Preparing hydroxyl-terminated bio-based polyester: adding 1, 3-propylene glycol, 1, 4-butanediol, 1, 4-succinic acid, 1, 10-sebacic acid and p-hydroxyanisole (0.2% of total mass of reaction monomers) into a three-neck flask, stirring uniformly, wherein the ratio of dihydric alcohol: the molar ratio of the dibasic acid is 1.5: 1, 1, 3-propanediol: the molar ratio of 1, 4-butanediol is 0.7: 0.3, 1, 4-succinic acid: 1, 10-sebacic acid molar ratio of 0.5: 0.5, heating to 190 ℃ in a nitrogen atmosphere, reacting for 2 hours at the temperature, adding tetrabutyl titanate (0.1 percent of the total mass of the reaction monomers), reacting for 3 h under the condition of reduced pressure (600 Pa), adding 1, 3-propylene glycol accounting for 10% of the total amount of alcohol for end capping, and finally obtaining hydroxyl-terminated bio-based polyester (Mn = 4500-5000 g/mol).
Preparing a furan ring-based all-bio-based thermoplastic polyester elastomer: putting 2, 5-furandicarboxylic acid, 1, 3-propylene glycol, hydroxyl-terminated bio-based polyester and p-hydroxyanisole (0.2% of the total mass of reaction monomers) into a three-neck flask, uniformly stirring, wherein the molar ratio of the dihydric alcohol to the dibasic acid is 1.5: 1, the hydroxyl-terminated bio-based polyester accounts for 60% of the total mass of the bio-based thermoplastic polyester elastomer, stirring and melting under the protection of nitrogen, carrying out ester exchange reaction at 180 ℃ for 3 h, then adding tetrabutyl titanate (0.1% of the total mass of the reaction monomers), heating to 230 ℃, carrying out vacuum polycondensation reaction for 4 h, and taking out a product while the product is hot.
Example 5
Preparing hydroxyl-terminated bio-based polyester: adding 1, 3-propylene glycol, 1, 4-butanediol, 1, 4-succinic acid, 1, 10-sebacic acid, itaconic acid and p-hydroxyanisole (0.2 percent of the total mass of reaction monomers) into a three-neck flask, uniformly stirring, wherein the molar ratio of the dihydric alcohol to the dibasic acid is 1.5: 1, the molar ratio of the 1, 3-propanediol to the 1, 4-butanediol is 0.5: 0.5, the molar ratio of the 1, 4-succinic acid to the 1, 10-sebacic acid to the itaconic acid is 0.3: 0.5: 0.2, heating to 180 ℃ under a nitrogen atmosphere, reacting for 2 hours at the temperature, adding stannous octoate (0.1 percent of the total mass of the reaction monomers), reacting for 3 hours under a reduced pressure (600 Pa), adding 1, 3-propanediol accounting for 10 percent of the total mass of the alcohol for blocking, finally, hydroxyl-terminated bio-based polyester (Mn = 8000 g/mol) is obtained.
Preparing a furan ring-based all-bio-based thermoplastic polyester elastomer: putting 2, 5-furandicarboxylic acid, isosorbide, hydroxyl-terminated bio-based polyester and p-hydroxyanisole (0.1% of the total mass of reaction monomers) into a three-neck flask, uniformly stirring, wherein the molar ratio of diol to dibasic acid is 1.6: 1, the hydroxyl-terminated bio-based polyester accounts for 70% of the total mass of the bio-based thermoplastic polyester elastomer, stirring and melting under the protection of nitrogen, then carrying out transesterification reaction at 170 ℃ for 2 hours and transesterification reaction at 180 ℃ for 1 hour in sequence, then adding tetrabutyl titanate (0.1% of the total mass of the reaction monomers), heating to 230 ℃, carrying out vacuum-pumping polycondensation reaction for 4 hours, and taking out the product while the product is hot.
Comparative example
Adding dimethyl 2, 5-furandicarboxylate, 1, 4-butanediol, p-hydroxyanisole (0.2% of the total mass of reaction monomers) and tetrabutyl titanate (0.05% of the total mass of reaction monomers) into a three-neck flask, uniformly stirring, wherein the molar ratio of dihydric alcohol to dibasic acid is 1.4: 1, heating to 180 ℃ under the protection of a nitrogen atmosphere, and reacting for 2 hours at the temperature. Then raising the temperature to 220 ℃, and carrying out vacuum polycondensation for 2 h to obtain the product.
Claims (9)
1. A furan ring-based all-bio-based thermoplastic polyester elastomer is characterized in that:
the full thermoplastic polyester elastomer is composed of hard segments of 2, 5-furandicarboxylic acid polyester and soft segments of bio-based polyester, and has a polymer main chain structure shown in the following formula:
wherein R is a bio-based diol residue,
the chain segment is hydroxyl-terminated bio-based polyester residue, and x, y and m are integers.
2. A preparation method of a furan ring-based all-bio-based thermoplastic polyester elastomer is characterized by comprising the following steps of:
(1) the preparation method of the hydroxyl-terminated bio-based polyester comprises the following steps: stirring and mixing various bio-based diols and bio-based diacids, adding a stabilizer, carrying out esterification reaction for 1-4 h at 160-190 ℃ under the protection of nitrogen, then adding a catalyst, carrying out polycondensation reaction for 1-4 h at 100-300 Pa and 180-220 ℃, adding bio-based diols accounting for 10% of the total amount of alcohols, and carrying out end capping to prepare a hydroxyl-terminated bio-based polyester soft segment;
(2) the preparation method of the full-bio-based thermoplastic polyester elastomer based on furan rings comprises the following steps: stirring and mixing 2, 5-furan dicarboxylic acid or ester thereof, bio-based dihydric alcohol and hydroxyl-terminated bio-based polyester according to a proportion, adding a stabilizer, carrying out esterification or transesterification reaction for 3-6 h at 150-190 ℃ under the protection of nitrogen, then adding a catalyst, and carrying out polycondensation reaction for 2-10 h at 100-300 Pa and 200-240 ℃ to prepare the furan ring-based all-bio-based thermoplastic polyester elastomer.
3. The method for preparing the furan ring-based fully bio-based thermoplastic polyester elastomer as claimed in claim 2, wherein the molar ratio of the reaction of the dibasic alcohol and the dibasic acid in the hydroxyl-terminated bio-based polyester is 1.05: 1 to 1.7: 1, the total reaction monomers comprise more than 3 kinds of dibasic acid and dibasic alcohol mixture, wherein the mixture comprises at least 1 kind of dibasic acid and 1 kind of dibasic alcohol, the amount of the stabilizer is 0.05 to 0.2 percent of the total mass of the reaction monomers, and the amount of the catalyst is 0.05 to 0.5 percent of the total mass of the reaction monomers.
4. The method for preparing the furan ring-based all-bio-based thermoplastic polyester elastomer as claimed in claim 2, wherein the hydroxyl-terminated bio-based polyester has a number average molecular weight of 1000 to 8000 g/mol, a molecular weight distribution of 1.2 to 3, a glass transition temperature of-60 to-30 ℃, and is an amorphous polymer at room temperature.
5. The method for preparing the furan ring-based all-bio-based thermoplastic polyester elastomer according to claim 2, wherein the molar ratio of the diol to the 2, 5-furandicarboxylic acid or 2, 5-furandicarboxylate in the furan ring-based all-bio-based thermoplastic polyester elastomer is 1.1: 1 to 2.2: 1, the hydroxyl-terminated bio-based polyester accounts for 50 to 90 percent of the total mass of the all-bio-based thermoplastic polyester elastomer, the amount of the stabilizer accounts for 0.01 to 0.2 percent of the total mass of the reaction monomers, and the amount of the catalyst accounts for 0.1 to 0.5 percent of the total mass of the reaction monomers.
6. The method for preparing the furan ring-based all-bio-based thermoplastic polyester elastomer as claimed in claim 2, wherein the bio-based diol is 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 2, 3-butanediol, isosorbide, 1, 5-pentanediol, 1, 6-hexanediol, 1, 10-decanediol.
7. The method for preparing the furan ring-based all-biobased thermoplastic polyester elastomer as claimed in claim 2, wherein the biobased dibasic acid is 1, 4-succinic acid, fumaric acid, isosorbide, 1, 5-glutaric acid, 1, 6-adipic acid, itaconic acid, 1, 10-sebacic acid, dodecanedioic acid, tridecanedioic acid, pentadecanedioic acid.
8. The method for preparing the furan ring-based all-bio-based thermoplastic polyester elastomer as claimed in claim 2, wherein the stabilizer is one or more of phosphoric acid, triphenyl phosphate, triethyl phosphate, p-hydroxyanisole, hydroquinone, o-methyl hydroquinone, p-benzoquinone or benzoquinone triphenyl phosphite.
9. The method for preparing the furan ring-based all-bio-based thermoplastic polyester elastomer as claimed in claim 2, wherein the catalyst is one or more of n-butyl titanate, tetra-isopropyl titanate, tetraethyl titanate, stannous oxide, stannous octoate, stannous chloride, stannous bromide, stannous iodide, stannous acetate, stannous oxalate, stannous sulfate or stannous hydroxide.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1481406A (en) * | 2001-10-31 | 2004-03-10 | ��Ļ���Ű˾ | Polyether ester elastomer comprising polytrimethylene ether ester soft segment and tetramethylene ester hard segment |
| CN102432847A (en) * | 2011-08-25 | 2012-05-02 | 中国科学院长春应用化学研究所 | 2,5-furandicarboxylic-terephthalic-aliphatic copolyester and preparation method thereof |
| CN104341585A (en) * | 2014-05-13 | 2015-02-11 | 浙江大学 | Triblock copolymer using furandicarboxylic acid flexible random copolyester as soft block and preparation method thereof |
| CN106854274A (en) * | 2016-12-23 | 2017-06-16 | 清华大学 | A kind of preparation method of multi-block copolyesters and preparation method thereof and its compound |
| CN107312167A (en) * | 2016-04-26 | 2017-11-03 | 中国科学院理化技术研究所 | A kind of thermoplastic polyester elastomer based on biomass-based 2,5- furandicarboxylic acids and preparation method thereof |
| CN107973904A (en) * | 2017-12-15 | 2018-05-01 | 中国科学院长春应用化学研究所 | A kind of more block furyl polyether ester shape-memory materials and preparation method thereof |
| CN108059715A (en) * | 2017-12-21 | 2018-05-22 | 中国科学院宁波材料技术与工程研究所 | A kind of thermoplastic polyester elastomer and preparation method thereof |
| CN108192105A (en) * | 2017-12-29 | 2018-06-22 | 王肖桦 | A kind of biology base Biodegradable multiblock polymer and its preparation method and application |
| CN108727575A (en) * | 2018-05-21 | 2018-11-02 | 东华大学 | A kind of preparation method of biology base 2,5- furandicarboxylic acids base copolyesters |
| CN108997568A (en) * | 2018-06-21 | 2018-12-14 | 浙江大学 | A kind of biological poly ester material and its preparation method and application |
| CN109134835A (en) * | 2018-07-11 | 2019-01-04 | 中国科学院宁波材料技术与工程研究所 | A kind of thermoplastic polyester elastomer and preparation method thereof |
| CN110183633A (en) * | 2019-04-15 | 2019-08-30 | 中国科学院化学研究所 | 1,4;The modified furandicarboxylic acid base random copolymer of bis- shrink hexitol of 3,6- and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018156859A1 (en) * | 2017-02-24 | 2018-08-30 | E. I. Du Pont De Nemours And Company | Process for preparing poly(trimethylene furandicarboxylate) using zinc catalyst |
-
2020
- 2020-01-17 CN CN202010050872.4A patent/CN111116880B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1481406A (en) * | 2001-10-31 | 2004-03-10 | ��Ļ���Ű˾ | Polyether ester elastomer comprising polytrimethylene ether ester soft segment and tetramethylene ester hard segment |
| CN102432847A (en) * | 2011-08-25 | 2012-05-02 | 中国科学院长春应用化学研究所 | 2,5-furandicarboxylic-terephthalic-aliphatic copolyester and preparation method thereof |
| CN104341585A (en) * | 2014-05-13 | 2015-02-11 | 浙江大学 | Triblock copolymer using furandicarboxylic acid flexible random copolyester as soft block and preparation method thereof |
| CN107312167A (en) * | 2016-04-26 | 2017-11-03 | 中国科学院理化技术研究所 | A kind of thermoplastic polyester elastomer based on biomass-based 2,5- furandicarboxylic acids and preparation method thereof |
| CN106854274A (en) * | 2016-12-23 | 2017-06-16 | 清华大学 | A kind of preparation method of multi-block copolyesters and preparation method thereof and its compound |
| CN107973904A (en) * | 2017-12-15 | 2018-05-01 | 中国科学院长春应用化学研究所 | A kind of more block furyl polyether ester shape-memory materials and preparation method thereof |
| CN108059715A (en) * | 2017-12-21 | 2018-05-22 | 中国科学院宁波材料技术与工程研究所 | A kind of thermoplastic polyester elastomer and preparation method thereof |
| CN108192105A (en) * | 2017-12-29 | 2018-06-22 | 王肖桦 | A kind of biology base Biodegradable multiblock polymer and its preparation method and application |
| CN108727575A (en) * | 2018-05-21 | 2018-11-02 | 东华大学 | A kind of preparation method of biology base 2,5- furandicarboxylic acids base copolyesters |
| CN108997568A (en) * | 2018-06-21 | 2018-12-14 | 浙江大学 | A kind of biological poly ester material and its preparation method and application |
| CN109134835A (en) * | 2018-07-11 | 2019-01-04 | 中国科学院宁波材料技术与工程研究所 | A kind of thermoplastic polyester elastomer and preparation method thereof |
| CN110183633A (en) * | 2019-04-15 | 2019-08-30 | 中国科学院化学研究所 | 1,4;The modified furandicarboxylic acid base random copolymer of bis- shrink hexitol of 3,6- and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| "微观结构与生物降解性能可控的热塑性聚酯弹性体 ";杨丽博等;《中国科学》;20161231;第46卷(第6期);第579-585页 * |
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