CN113461921A - Low-melting-point thermoplastic polyester elastomer and preparation method thereof - Google Patents
Low-melting-point thermoplastic polyester elastomer and preparation method thereof Download PDFInfo
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- CN113461921A CN113461921A CN202110812013.9A CN202110812013A CN113461921A CN 113461921 A CN113461921 A CN 113461921A CN 202110812013 A CN202110812013 A CN 202110812013A CN 113461921 A CN113461921 A CN 113461921A
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- 229920006346 thermoplastic polyester elastomer Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 107
- 125000003118 aryl group Chemical group 0.000 claims abstract description 89
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 28
- 238000005886 esterification reaction Methods 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000003077 polyols Chemical class 0.000 claims abstract description 14
- 230000032050 esterification Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 40
- 125000001931 aliphatic group Chemical group 0.000 claims description 27
- 150000007824 aliphatic compounds Chemical group 0.000 claims description 24
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 24
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 238000006482 condensation reaction Methods 0.000 claims description 7
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 5
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims 1
- 229940035437 1,3-propanediol Drugs 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 7
- 229920000728 polyester Polymers 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 239000000806 elastomer Substances 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- -1 small molecule polyol Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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
The invention relates to the technical field of polyester elastomer preparation, in particular to a low-melting-point thermoplastic polyester elastomer and a preparation method thereof, wherein the low-melting-point thermoplastic polyester elastomer is obtained by the following steps: the first step is as follows: esterification, mixing the aromatic dibasic acid, 1, 4-butanediol, polytetramethylene ether glycol and the fourth component in required amount, and carrying out esterification reaction under the action of a catalyst I to obtain an esterified product; the second step is that: pre-shrinking, namely adding a catalyst II, an antioxidant and micromolecular polyol into the esterified substance to perform pre-shrinking reaction to obtain a prepolymer; the third step: and finally, carrying out polycondensation reaction on the prepolymer to obtain the low-melting-point thermoplastic polyester elastomer. The low-melting-point thermoplastic polyester elastomer is polymerized and synthesized by adopting a one-step method, has simple process and convenient operation, has the melting point of 130-160 ℃, the hardness of 30-55D, the product melt index within 30 g/10min, good physical properties, wide application range and flexible and adjustable product index, and can meet the processing requirements of different application products.
Description
Technical Field
The invention relates to the technical field of preparation of plastic polyester elastomers, in particular to a low-melting-point thermoplastic polyester elastomer and a preparation method thereof.
Background
Thermoplastic polyester elastomers (hereinafter referred to as TPEE) are linear block copolymers containing PBT polyester hard segments and polyether soft segments. The rigidity, polarity and crystallinity of the PBT polyester hard segment ensure that the PBT polyester hard segment has outstanding strength and better high temperature resistance, creep resistance, solvent resistance and impact resistance; the low glass transition temperature and saturation of the soft segment of polyether make it have excellent low temperature resistance and aging resistance. Therefore, TPEE combines excellent elasticity of rubber and easy processability of thermoplastic plastics.
The thermoplastic polyester elastomer TPEE has the characteristics of excellent heat resistance, oil resistance, bending fatigue performance at high and low temperatures, abrasion resistance, high strength and toughness, outstanding chemical resistance, excellent weather resistance and aging resistance, easy processing and forming and the like, and is widely applied to the fields of rail transit, automobiles, electronics and electrical, industrial products, sports goods and the like.
The low-melting-point thermoplastic polyester elastomer is TPEE with a lower melting point, meets the requirement of a product on low processing temperature, and simultaneously reserves the characteristics of impact resistance, oil resistance, wear resistance, chemical resistance and the like of the thermoplastic polyester elastomer. The product is mainly used in the fields of spinning, shock absorption materials, foaming materials, sports goods, automotive interior and the like, and at present, the one-step polymerization synthesis of the melting point thermoplastic polyester elastomer is not reported.
Disclosure of Invention
The invention provides a low-melting-point thermoplastic polyester elastomer and a preparation method thereof, overcomes the defects of the prior art, and has good physical properties and wide application range.
One of the technical schemes of the invention is realized by the following measures: a low-melting-point thermoplastic polyester elastomer is obtained by the following method: the first step is as follows: and (2) esterification, namely mixing required amount of aromatic dibasic acid, 1, 4-butanediol, polytetramethylene ether glycol and a fourth component, and carrying out esterification reaction under the action of a catalyst I to obtain an esterified product, wherein the molar ratio of the aromatic dibasic acid to the 1, 4-butanediol is 1.0: 1.1 to 2.0, the addition amount of the polytetramethylene ether glycol is 5 to 50 percent of the total mass of the aromatic dibasic acid, the fourth component is an aliphatic compound, the addition amount of the aliphatic compound is 5 to 25 percent of the mole number of the aromatic dibasic acid, and the addition amount of the first catalyst is 0.05 to 0.11 percent of the total mass of the aromatic dibasic acid; the second step is that: pre-shrinking, namely adding a catalyst II, an antioxidant and micromolecular polyol into the esterified product to perform pre-shrinking reaction to obtain a prepolymer, wherein the addition amount of the catalyst II is 0.03-0.06% of the total mass of the aromatic dibasic acid, the addition amount of the antioxidant is 0.1-0.5% of the total mass of the aromatic dibasic acid, and the addition amount of the micromolecular polyol is 0.04-0.08% of the total mass of the aromatic dibasic acid; the third step: and finally, carrying out polycondensation reaction on the prepolymer to obtain the low-melting-point thermoplastic polyester elastomer.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
the aromatic dibasic acid is one or more of terephthalic acid, isophthalic acid and phthalic acid.
The aromatic dibasic acid is mixed in a molar ratio of 1 to 9: 1 in a mixture or molar ratio of terephthalic acid and isophthalic acid of 1 from 1 to 9: 1 of a mixture of terephthalic acid and phthalic acid.
The aromatic dibasic acid is mixed in a molar ratio of 15 to 85: 15 in a mixture or molar ratio of terephthalic acid to isophthalic acid of 15 to 85: 15 of terephthalic acid and phthalic acid.
The molecular weight of the polytetramethylene ether glycol is 250 to 3000.
The molecular weight of the polytetramethylene ether glycol is 650 to 2000.
The fourth component is an aliphatic compound, the aliphatic compound is one of aliphatic dibasic acid or aliphatic dihydric alcohol, the addition amount of the aliphatic dibasic acid is 5 to 15 percent of the mole number of the aromatic dibasic acid, the addition amount of the aliphatic dihydric alcohol is 5 to 25 percent of the mole number of the aromatic dibasic acid, the aliphatic dibasic acid is more than one of succinic acid, adipic acid and sebacic acid, and the aliphatic dihydric alcohol is more than one of ethylene glycol, 1, 3-propylene glycol and 1, 6-hexanediol.
The catalyst I and the catalyst II are both titanium catalysts, and the titanium catalysts are more than one of tetraethyl titanate, tetrabutyl titanate and tetraisopropyl titanate.
The antioxidant is more than one of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168 and antioxidant 1330.
The small molecular polyol is more than one of 1, 2, 3-glycerol, pentaerythritol, neopentyl glycol and 1, 2, 6-hexanetriol.
In the first step, the esterification reaction temperature is 200-250 ℃, the reaction pressure is 50-85 KPa, and the reaction time is 2-4 hours.
In the second step, the pre-shrinking reaction temperature is 230-260 ℃, the reaction pressure is 3-6 KPa, and the reaction time is 1.5-2.5 hours.
In the third step, the final condensation reaction temperature is 240-265 ℃, the reaction pressure is 100-350 Pa, and the reaction time is 2-3 hours.
The second technical scheme of the invention is realized by the following measures: a preparation method of a low-melting-point thermoplastic polyester elastomer comprises the following steps: the first step is as follows: and (2) esterification, namely mixing required amount of aromatic dibasic acid, 1, 4-butanediol, polytetramethylene ether glycol and a fourth component, and carrying out esterification reaction under the action of a catalyst I to obtain an esterified product, wherein the molar ratio of the aromatic dibasic acid to the 1, 4-butanediol is 1.0: 1.1 to 2.0, the addition amount of the polytetramethylene ether glycol is 5 to 50 percent of the total mass of the aromatic dibasic acid, the fourth component is an aliphatic compound, the addition amount of the aliphatic compound is 5 to 25 percent of the mole number of the aromatic dibasic acid, and the addition amount of the first catalyst is 0.05 to 0.11 percent of the total mass of the aromatic dibasic acid; the second step is that: pre-shrinking, namely adding a catalyst II, an antioxidant and micromolecular polyol into the esterified product to perform pre-shrinking reaction to obtain a prepolymer, wherein the addition amount of the catalyst II is 0.03-0.06% of the total mass of the aromatic dibasic acid, the addition amount of the antioxidant is 0.1-0.5% of the total mass of the aromatic dibasic acid, and the addition amount of the micromolecular polyol is 0.04-0.08% of the total mass of the aromatic dibasic acid; the third step: and finally, carrying out polycondensation reaction on the prepolymer to obtain the low-melting-point thermoplastic polyester elastomer.
The following is further optimization or/and improvement of the second technical scheme of the invention:
the aromatic dibasic acid is one or more of terephthalic acid, isophthalic acid and phthalic acid.
The aromatic dibasic acid is mixed in a molar ratio of 1 to 9: 1 in a mixture or molar ratio of terephthalic acid and isophthalic acid of 1 from 1 to 9: 1 of a mixture of terephthalic acid and phthalic acid.
The aromatic dibasic acid is mixed in a molar ratio of 15 to 85: 15 in a mixture or molar ratio of terephthalic acid to isophthalic acid of 15 to 85: 15 of terephthalic acid and phthalic acid.
The molecular weight of the polytetramethylene ether glycol is 250 to 3000.
The molecular weight of the polytetramethylene ether glycol is 650 to 2000.
The fourth component is an aliphatic compound, the aliphatic compound is one of aliphatic dibasic acid or aliphatic dihydric alcohol, the addition amount of the aliphatic dibasic acid is 5 to 15 percent of the mole number of the aromatic dibasic acid, the addition amount of the aliphatic dihydric alcohol is 5 to 25 percent of the mole number of the aromatic dibasic acid, the aliphatic dibasic acid is more than one of succinic acid, adipic acid and sebacic acid, and the aliphatic dihydric alcohol is more than one of ethylene glycol, 1, 3-propylene glycol and 1, 6-hexanediol.
The catalyst I and the catalyst II are both titanium catalysts, and the titanium catalysts are more than one of tetraethyl titanate, tetrabutyl titanate and tetraisopropyl titanate.
The antioxidant is more than one of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168 and antioxidant 1330.
The small molecular polyol is more than one of 1, 2, 3-glycerol, pentaerythritol, neopentyl glycol and 1, 2, 6-hexanetriol.
In the first step, the esterification reaction temperature is 200-250 ℃, the reaction pressure is 50-85 KPa, and the reaction time is 2-4 hours.
In the second step, the pre-shrinking reaction temperature is 230-260 ℃, the reaction pressure is 3-6 KPa, and the reaction time is 1.5-2.5 hours.
In the third step, the final condensation reaction temperature is 240-265 ℃, the reaction pressure is 100-350 Pa, and the reaction time is 2-3 hours.
The low-melting-point thermoplastic polyester elastomer is polymerized and synthesized by adopting a one-step method, has simple process and convenient operation, has the melting point of 130-160 ℃, the hardness of 30-55D, the product melt index within 30 g/10min, good physical properties, wide application range and flexible and adjustable product index, and can meet the processing requirements of different application products.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the present invention are all mass percentages unless otherwise specified.
The invention is further described below with reference to the following examples:
example 1: the low-melting-point thermoplastic polyester elastomer is obtained by the following method: the first step is as follows: and (2) esterification, namely mixing required amount of aromatic dibasic acid, 1, 4-butanediol, polytetramethylene ether glycol and a fourth component, and carrying out esterification reaction under the action of a catalyst I to obtain an esterified product, wherein the molar ratio of the aromatic dibasic acid to the 1, 4-butanediol is 1.0: 1.1 to 2.0, the addition amount of the polytetramethylene ether glycol is 5 to 50 percent of the total mass of the aromatic dibasic acid, the fourth component is an aliphatic compound, the addition amount of the aliphatic compound is 5 to 25 percent of the mole number of the aromatic dibasic acid, and the addition amount of the first catalyst is 0.05 to 0.11 percent of the total mass of the aromatic dibasic acid; the second step is that: pre-shrinking, namely adding a catalyst II, an antioxidant and micromolecular polyol into the esterified product to perform pre-shrinking reaction to obtain a prepolymer, wherein the addition amount of the catalyst II is 0.03-0.06% of the total mass of the aromatic dibasic acid, the addition amount of the antioxidant is 0.1-0.5% of the total mass of the aromatic dibasic acid, and the addition amount of the micromolecular polyol is 0.04-0.08% of the total mass of the aromatic dibasic acid; the third step: and finally, carrying out polycondensation reaction on the prepolymer to obtain the low-melting-point thermoplastic polyester elastomer.
Example 2: in the optimization of the above embodiment, the aromatic dibasic acid is one or more of terephthalic acid, isophthalic acid and phthalic acid.
Example 3: as an optimization of the above examples, the aromatic dibasic acid is a mixture of aromatic dibasic acid in a molar ratio of 1 to 9: 1 in a mixture or molar ratio of terephthalic acid and isophthalic acid of 1 from 1 to 9: 1 of a mixture of terephthalic acid and phthalic acid.
Example 4: as an optimization of the above examples, the aromatic dibasic acid is in a molar ratio of 15 to 85: 15 in a mixture or molar ratio of terephthalic acid to isophthalic acid of 15 to 85: 15 of terephthalic acid and phthalic acid.
Example 5: as an optimization of the above examples, the polytetramethylene ether glycol has a molecular weight of 250 to 3000.
Example 6: as an optimization of the above examples, the polytetramethylene ether glycol has a molecular weight of 650 to 2000.
Example 7: in the optimization of the above embodiment, the fourth component is an aliphatic compound, the aliphatic compound is one of aliphatic dibasic acid or aliphatic diol, the addition amount of the aliphatic dibasic acid is 5 to 15% of the mole number of the aromatic dibasic acid, the addition amount of the aliphatic diol is 5 to 25% of the mole number of the aromatic dibasic acid, the aliphatic dibasic acid is one or more of succinic acid, adipic acid and sebacic acid, and the aliphatic diol is one or more of ethylene glycol, 1, 3-propylene glycol and 1, 6-hexanediol.
Example 8: in the optimization of the above embodiment, the first catalyst and the second catalyst are both titanium-based catalysts, and the titanium-based catalyst is one or more of tetraethyl titanate, tetrabutyl titanate, and tetraisopropyl titanate.
Example 9: in the optimization of the embodiment, the antioxidant is more than one of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168 and antioxidant 1330.
Example 10: as optimization of the above embodiment, the small molecule polyol is more than one of 1, 2, 3-propanetriol, pentaerythritol, neopentyl glycol and 1, 2, 6-hexanetriol.
Example 11: as optimization of the above embodiment, in the first step, the esterification reaction temperature is 200 ℃ to 250 ℃, the reaction pressure is 50KPa to 85KPa, and the reaction time is 2 hours to 4 hours.
Example 12: as optimization of the above embodiment, in the second step, the pre-shrinking reaction temperature is 230 ℃ to 260 ℃, the reaction pressure is 3KPa to 6KPa, and the reaction time is 1.5 hours to 2.5 hours.
Example 13: as optimization of the above examples, in the third step, the final condensation reaction temperature is 240 ℃ to 265 ℃, the reaction pressure is 100Pa to 350Pa, and the reaction time is 2 hours to 3 hours.
Example 14: the low-melting-point thermoplastic polyester elastomer is obtained by the following method: the first step is as follows: and (2) esterification, namely mixing required amount of aromatic dibasic acid, 1, 4-butanediol, polytetramethylene ether glycol and a fourth component, and carrying out esterification reaction under the action of tetraethyl titanate to obtain an esterified product, wherein the molar ratio of the aromatic dibasic acid to the 1, 4-butanediol is 1.0: 1.1, the adding amount of polytetramethylene ether glycol is 5 percent of the total mass of the aromatic dibasic acid, the adding amount of tetraethyl titanate is 0.05 percent of the total mass of the aromatic dibasic acid, and the molar ratio of the aromatic dibasic acid is 15: 15, the molecular weight of polytetramethylene ether glycol is 650, the fourth component is an aliphatic compound, the aliphatic compound is aliphatic dibasic acid, the addition amount of the aliphatic dibasic acid is 5% of the mole number of the aromatic dibasic acid, the aliphatic dibasic acid is succinic acid, the esterification reaction temperature is 200 ℃, the reaction pressure is 50KPa, and the reaction time is 2 hours; the second step is that: pre-shrinking, namely adding tetraethyl titanate, an antioxidant 1010 and 1, 2, 3-glycerol into an esterified product to perform a pre-shrinking reaction to obtain a prepolymer, wherein the addition amount of the tetraethyl titanate is 0.03 percent of the total mass of the aromatic dibasic acid, the addition amount of the antioxidant 1010 is 0.1 percent of the total mass of the aromatic dibasic acid, the addition amount of the 1, 2, 3-glycerol is 0.04 percent of the total mass of the aromatic dibasic acid, the pre-shrinking reaction temperature is 230 ℃, the reaction pressure is 3KPa, and the reaction time is 1.5 hours; the third step: and final condensation, namely performing polycondensation reaction on the prepolymer to obtain the low-melting-point thermoplastic polyester elastomer, wherein the final condensation reaction temperature is 240 ℃, the reaction pressure is 100Pa, and the reaction time is 2 hours.
Example 15: the low-melting-point thermoplastic polyester elastomer is obtained by the following method: the first step is as follows: and (2) esterification, namely mixing the required amount of aromatic dibasic acid, 1, 4-butanediol, polytetramethylene ether glycol and a fourth component, and carrying out esterification reaction under the action of tetrabutyl titanate to obtain an esterified product, wherein the molar ratio of the aromatic dibasic acid to the 1, 4-butanediol is 1.0: 2.0, the addition amount of polytetramethylene ether glycol is 50% of the total mass of the aromatic dibasic acid, the addition amount of tetrabutyl titanate is 0.11% of the total mass of the aromatic dibasic acid, and the molar ratio of the aromatic dibasic acid is 85: 15, the molecular weight of polytetramethylene ether glycol is 2000, the fourth component is an aliphatic compound, the aliphatic compound is aliphatic dihydric alcohol, the addition amount of the aliphatic dihydric alcohol is 25 percent of the mole number of aromatic dibasic acid, the aliphatic dihydric alcohol is 1, 3-propylene glycol, the esterification reaction temperature is 250 ℃, the reaction pressure is 85KPa, and the reaction time is 4 hours; the second step is that: pre-shrinking, namely adding tetrabutyl titanate, an antioxidant 1076 and pentaerythritol into the esterified product to perform pre-shrinking reaction to obtain a prepolymer, wherein the addition amount of a catalyst II is 0.06 percent of the total mass of the aromatic dibasic acid, the addition amount of the antioxidant 1076 is 0.5 percent of the total mass of the aromatic dibasic acid, the addition amount of pentaerythritol is 0.08 percent of the total mass of the aromatic dibasic acid, the pre-shrinking reaction temperature is 260 ℃, the reaction pressure is 6KPa, and the reaction time is 2.5 hours; the third step: and final condensation, namely performing polycondensation reaction on the prepolymer to obtain the low-melting-point thermoplastic polyester elastomer, wherein the final condensation reaction temperature is 265 ℃, the reaction pressure is 350Pa, and the reaction time is 3 hours.
Example 16: the low-melting-point thermoplastic polyester elastomer is obtained by the following method: the first step is as follows: and (2) esterification, namely mixing required amount of aromatic dibasic acid, 1, 4-butanediol, polytetramethylene ether glycol and a fourth component, and carrying out esterification reaction under the action of tetraisopropyl titanate to obtain an esterified product, wherein the molar ratio of the aromatic dibasic acid to the 1, 4-butanediol is 1.0: 1.5, the addition amount of the polytetramethylene ether glycol is 20 percent of the total mass of the aromatic dibasic acid, the addition amount of the tetraisopropyl titanate is 0.08 percent of the total mass of the aromatic dibasic acid, and the molar ratio of the aromatic dibasic acid is 50: 15, the molecular weight of polytetramethylene ether glycol is 1000, the fourth component is an aliphatic compound, the aliphatic compound is aliphatic dibasic acid, the addition amount of the aliphatic dibasic acid is 10 percent of the mole number of the aromatic dibasic acid, the aliphatic dibasic acid is sebacic acid, the esterification reaction temperature is 235 ℃, the reaction pressure is 75KPa, and the reaction time is 3 hours; the second step is that: pre-shrinking, namely adding tetraisopropyl titanate, an antioxidant 1098 and neopentyl glycol into the esterified product to perform pre-shrinking reaction to obtain a prepolymer, wherein the adding amount of a catalyst II is 0.05 percent of the total mass of the aromatic dibasic acid, the adding amount of the antioxidant 1098 is 0.3 percent of the total mass of the aromatic dibasic acid, the adding amount of neopentyl glycol is 0.06 percent of the total mass of the aromatic dibasic acid, the pre-shrinking reaction temperature is 240 ℃, the reaction pressure is 4.5KPa, and the reaction time is 2.0 hours; the third step: and final condensation, namely performing polycondensation reaction on the prepolymer to obtain the low-melting-point thermoplastic polyester elastomer, wherein the final condensation reaction temperature is 245 ℃, the reaction pressure is 200Pa, and the reaction time is 3 hours.
Example 17: the low melting point thermoplastic polyester elastomers prepared in examples 14 to 16 of the present invention were examined for physical properties including melting point, hardness and melt index. The physical property test method is carried out according to the detection method in the ISO1133 standard. As shown in Table 1, the low melting point thermoplastic polyester elastomers prepared in examples 14 and 16 have a melting point of 130 ℃ to 160 ℃, a hardness of 30D to 55D, a melt index of 30 g/10min or less, and good physical properties.
In conclusion, the low-melting-point thermoplastic polyester elastomer is polymerized and synthesized by adopting a one-step method, has simple process and convenient operation, has the melting point of 130-160 ℃, the hardness of 30-55D and the melt index within 30 g/10min, has good physical properties, wide application range and flexible and adjustable product indexes, and can meet the processing requirements of different application products.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
Claims (9)
1. A low-melting thermoplastic polyester elastomer, characterized in that it is obtained by the following process: the first step is as follows: and (2) esterification, namely mixing required amount of aromatic dibasic acid, 1, 4-butanediol, polytetramethylene ether glycol and a fourth component, and carrying out esterification reaction under the action of a catalyst I to obtain an esterified product, wherein the molar ratio of the aromatic dibasic acid to the 1, 4-butanediol is 1.0: 1.1 to 2.0, the addition amount of the polytetramethylene ether glycol is 5 to 50 percent of the total mass of the aromatic dibasic acid, the fourth component is an aliphatic compound, the addition amount of the aliphatic compound is 5 to 25 percent of the mole number of the aromatic dibasic acid, and the addition amount of the first catalyst is 0.05 to 0.11 percent of the total mass of the aromatic dibasic acid; the second step is that: pre-shrinking, namely adding a catalyst II, an antioxidant and micromolecular polyol into the esterified product to perform pre-shrinking reaction to obtain a prepolymer, wherein the addition amount of the catalyst II is 0.03-0.06% of the total mass of the aromatic dibasic acid, the addition amount of the antioxidant is 0.1-0.5% of the total mass of the aromatic dibasic acid, and the addition amount of the micromolecular polyol is 0.04-0.08% of the total mass of the aromatic dibasic acid; the third step: and finally, carrying out polycondensation reaction on the prepolymer to obtain the low-melting-point thermoplastic polyester elastomer.
2. The low melting point thermoplastic polyester elastomer according to claim 1, wherein the aromatic dibasic acid is one or more of terephthalic acid, isophthalic acid and phthalic acid; or/and, the polytetramethylene ether glycol has a molecular weight of 250 to 3000.
3. A low-melting thermoplastic polyester elastomer according to claim 2, characterized in that the aromatic dibasic acid is present in a molar ratio of 1 to 9: 1 in a mixture or molar ratio of terephthalic acid and isophthalic acid of 1 from 1 to 9: 1 of a mixture of terephthalic acid and phthalic acid; or/and, the polytetramethylene ether glycol has a molecular weight of 650 to 2000.
4. A low-melting thermoplastic polyester elastomer according to claim 3, characterized in that the aromatic dibasic acid is present in a molar ratio of 15 to 85: 15 in a mixture or molar ratio of terephthalic acid to isophthalic acid of 15 to 85: 15 of terephthalic acid and phthalic acid.
5. The thermoplastic polyester elastomer with a low melting point as claimed in any one of claims 1 to 4, wherein the fourth component is an aliphatic compound, the aliphatic compound is one of aliphatic dibasic acid or aliphatic diol, the amount of the aliphatic dibasic acid added is 5 to 15% of the mole number of the aromatic dibasic acid, the amount of the aliphatic diol added is 5 to 25% of the mole number of the aromatic dibasic acid, the aliphatic dibasic acid is one or more of succinic acid, adipic acid and sebacic acid, and the aliphatic diol is one or more of ethylene glycol, 1, 3-propanediol and 1, 6-hexanediol.
6. The thermoplastic polyester elastomer with a low melting point according to any one of claims 1 to 5, wherein the first catalyst and the second catalyst are both titanium-based catalysts, and the titanium-based catalysts are one or more of tetraethyl titanate, tetrabutyl titanate, and tetraisopropyl titanate; and/or the antioxidant is more than one of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168 and antioxidant 1330.
7. The thermoplastic polyester elastomer with low melting point according to any one of claims 1 to 6, wherein the small-molecular polyol is one or more of 1, 2, 3-propanetriol, pentaerythritol, neopentyl glycol and 1, 2, 6-hexanetriol; or/and in the first step, the esterification reaction temperature is 200-250 ℃, the reaction pressure is 50-85 KPa, and the reaction time is 2-4 hours.
8. The low melting point thermoplastic polyester elastomer according to any one of claims 1 to 7, wherein in the second step, the preshrinking reaction temperature is 230 ℃ to 260 ℃, the reaction pressure is 3KPa to 6KPa, and the reaction time is 1.5 hours to 2.5 hours; or/and in the third step, the final condensation reaction temperature is 240-265 ℃, the reaction pressure is 100-350 Pa, and the reaction time is 2-3 hours.
9. A process for the preparation of a low melting thermoplastic polyester elastomer according to any of claims 2 to 8, characterized in that the ammonia is carried out by the following process: the first step is as follows: and (2) esterification, namely mixing required amount of aromatic dibasic acid, 1, 4-butanediol, polytetramethylene ether glycol and a fourth component, and carrying out esterification reaction under the action of a catalyst I to obtain an esterified product, wherein the molar ratio of the aromatic dibasic acid to the 1, 4-butanediol is 1.0: 1.1 to 2.0, the addition amount of the polytetramethylene ether glycol is 5 to 50 percent of the total mass of the aromatic dibasic acid, the fourth component is an aliphatic compound, the addition amount of the aliphatic compound is 5 to 25 percent of the mole number of the aromatic dibasic acid, and the addition amount of the first catalyst is 0.05 to 0.11 percent of the total mass of the aromatic dibasic acid; the second step is that: pre-shrinking, namely adding a catalyst II, an antioxidant and micromolecular polyol into the esterified product to perform pre-shrinking reaction to obtain a prepolymer, wherein the addition amount of the catalyst II is 0.03-0.06% of the total mass of the aromatic dibasic acid, the addition amount of the antioxidant is 0.1-0.5% of the total mass of the aromatic dibasic acid, and the addition amount of the micromolecular polyol is 0.04-0.08% of the total mass of the aromatic dibasic acid; the third step: and finally, carrying out polycondensation reaction on the prepolymer to obtain the low-melting-point thermoplastic polyester elastomer.
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