CN118344569A - PET-CL copolyester and preparation method thereof - Google Patents
PET-CL copolyester and preparation method thereof Download PDFInfo
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- CN118344569A CN118344569A CN202410366778.8A CN202410366778A CN118344569A CN 118344569 A CN118344569 A CN 118344569A CN 202410366778 A CN202410366778 A CN 202410366778A CN 118344569 A CN118344569 A CN 118344569A
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title abstract description 56
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims abstract description 86
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000003381 stabilizer Substances 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 82
- 239000002904 solvent Substances 0.000 claims description 56
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 52
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 24
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 14
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 10
- 229960001545 hydrotalcite Drugs 0.000 claims description 10
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 38
- 229920000728 polyester Polymers 0.000 abstract description 24
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 21
- 230000009477 glass transition Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000002845 discoloration Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 68
- 238000003756 stirring Methods 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- 239000011541 reaction mixture Substances 0.000 description 48
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 238000001035 drying Methods 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000945 filler Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- -1 terephthalic acid glycol ester Chemical class 0.000 description 2
- SBMYBOVJMOVVQW-UHFFFAOYSA-N 2-[3-[[4-(2,2-difluoroethyl)piperazin-1-yl]methyl]-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCN(CC1)CC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SBMYBOVJMOVVQW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
The invention relates to the technical field of polyester synthesis, and discloses PET-CL copolyester and a preparation method thereof, wherein the raw materials of the material are cyclic ethylene terephthalate oligomer, ɛ -caprolactone, a catalyst and a stabilizer, the degradability of the material is obviously improved, the glass transition temperature is obviously reduced, and the material has higher hot processing performance; according to the method, the ring-opening copolymerization reaction is directly carried out on the mixture of the cyclic ethylene terephthalate oligomer, ɛ -caprolactone, the catalyst and the stabilizer, the temperature of the ring-opening copolymerization reaction can be reduced to 220-270 ℃, compared with the ring-opening copolymerization temperature of the single cyclic ethylene terephthalate oligomer exceeding 330 ℃, the ring-opening copolymerization temperature of the single cyclic ethylene terephthalate oligomer is obviously reduced, the problems of increased side reaction, increased polyester viscosity, polyester discoloration and the like caused by overhigh cyclic ethylene terephthalate oligomer can be avoided, and the quality of the PET-CL copolyester is obviously improved.
Description
Technical Field
The invention relates to the technical field of polyester synthesis, in particular to PET-CL copolyester and a preparation method thereof.
Background
The Chinese name of PET-CL copolyester is terephthalic acid glycol ester-caprolactone copolyester, wherein terephthalic acid glycol ester is hard segment caprolactone and soft segment, and the terephthalic acid glycol ester with high mechanical property and degradable caprolactone are polymerized, so that the PET-CL has degradability and high mechanical property, is a good degradable high-strength high-molecular material, the PET-CL copolyester in the prior art is used for preparing a safety belt, the impact resistance of the safety belt is obviously increased, and the PET-CL copolyester has low production cost and extremely high application value compared with a commercial ether/ester copolymerized thermoplastic elastomer.
At present, PET-CL copolyester is prepared by mainly copolymerizing PET polyester monomer and epsilon-caprolactone polyester monomer, but the PET polyester monomer is synthesized by mainly adopting a method of polycondensation of terephthalic acid or dimethyl terephthalate and ethylene glycol, and the method can also generate water, methanol and other small molecule byproduct impurities, and meanwhile, the implementation engineering difficulty of completely removing the small molecule byproducts is high. In recent years, the prior art indicates that the cyclic oligomer can reform high molecular weight linear polyester through ring-opening polymerization, and has the advantages of high ring-opening polymerization rate, no polymerization reaction heat, no byproducts and the like, so that the problem that the byproducts are difficult to obtain high-purity PET polyester in the production process of the direct conventional PET polyester monomer can be solved by preparing PET polyester monomer by utilizing the cyclic ethylene terephthalate oligomer and then copolymerizing the PET polyester monomer with epsilon-caprolactone polyester monomer to prepare PET-CL copolyester; although the cyclic ethylene terephthalate oligomer has a high value, the ring-opening polymerization temperature of the cyclic ethylene terephthalate oligomer is generally high, and the problem of the polyester stability being lowered and the color being changed due to the increase of side reactions caused by the excessively high ring-opening temperature occurs, so that the problem of the cyclic ethylene terephthalate oligomer that the ring-opening polymerization temperature is high is needed to be studied intensively after the preparation of the PET polyester by using the cyclic ethylene terephthalate oligomer and the copolymerization of the PET polyester with the epsilon-caprolactone polyester.
Disclosure of Invention
Aiming at the problem of high ring-opening polymerization temperature of the cyclic ethylene terephthalate oligomer, the invention provides a PET-CL copolyester and a preparation method thereof, the PET-CL copolyester is directly synthesized by adopting the cyclic ethylene terephthalate oligomer and epsilon-caprolactone as raw materials under the conditions of a catalyst and a stabilizer, and the PET-CL copolyester has low impurity and remarkably improved biodegradability, mechanical property, heat resistance and hot workability.
The preparation method directly carries out ring-opening copolymerization reaction on the cyclic ethylene terephthalate oligomer and epsilon-caprolactone, and the epsilon-caprolactone can obviously reduce the ring-opening temperature of the cyclic ethylene terephthalate oligomer, reduce the generation of reaction byproducts and improve the stability of the copolyester.
The specific technical scheme of the invention is as follows:
The PET-CL copolyester comprises the following raw materials in parts by mass: 30 to 70 parts of cyclic ethylene terephthalate oligomer, 30 to 70 parts of epsilon-caprolactone, 0.2 to 2.5 parts of catalyst and 0 to 0.02 part of stabilizer.
The invention provides PET-CL copolyester, which is prepared from cyclic ethylene terephthalate oligomer and epsilon-caprolactone, wherein epsilon-caprolactone can obviously reduce the crystallinity of the polymer, increase the content of amorphous molecular chains and thus the volume of loose amorphous regions in a crystal structure in the process of the cyclic ethylene terephthalate oligomer ring-opening polymer reaction, and is beneficial for oxygen and water to enter the molecular chains, so that the copolyester has better degradability, the glass transition temperature of the PET-CL copolyester can be obviously reduced, and the PET-CL copolyester has good heat resistance and hot processing performance.
Preferably, the catalyst is selected from one or more of dibutyl tin oxide, antimony trioxide, dibutyl tin dilaurate, dioctyl tin dilaurate and stannous octoate.
Preferably, the one or more selected from phosphoric acid, trimethyl phosphate, triethyl phosphate and triphenyl phosphate.
Preferably, the raw material further includes an inorganic filler.
Preferably, the inorganic filler is 1 to 50 parts by mass.
Preferably, the inorganic filler is hydrotalcite.
Compared with PET polymer, the cyclic ethylene terephthalate oligomer provided by the invention has better compatibility with filler, so that the filler can be added in the process of preparing PET-CL copolyester by taking the cyclic ethylene terephthalate oligomer and epsilon-caprolactone as raw materials, the filler can be better dispersed in the finally formed PET-CL copolyester, and the physical properties of the PET-CL copolyester can be obviously improved.
The preparation method of the PET-CL copolyester takes cyclic ethylene terephthalate oligomer and epsilon-caprolactone as raw materials, and the raw materials react under the conditions of a catalyst and a stabilizer to prepare the PET-CL copolyester.
Preferably, the reaction conditions are: the reaction temperature is 220-270 ℃, and the reaction time is 10-60 min in an inert atmosphere.
Preferably, the cyclic ethylene terephthalate oligomer, epsilon-caprolactone as raw materials, a catalyst and a stabilizer are dissolved in a solvent before the reaction, and the solvent is evaporated and then the reaction is performed.
Preferably, the solvent is chloroform.
The invention also provides a preparation method of the PET-CL copolyester, which is characterized in that the mixture of the cyclic ethylene terephthalate oligomer, epsilon-caprolactone, the catalyst and the stabilizer is placed in a reaction vessel, and ring-opening copolymerization is carried out under the inert atmosphere condition to prepare the PET-CL copolyester, the ring-opening copolymerization temperature of the method is between 220 ℃ and 270 ℃, compared with the ring-opening copolymerization temperature of the PET prepared by the ring-opening copolymerization of the single cyclic ethylene terephthalate oligomer, the ring-opening copolymerization temperature of the PET is obviously reduced, the epsilon-caprolactone plays a role of reducing the ring-opening temperature in the ring-opening copolymerization process of the cyclic ethylene terephthalate oligomer, and meanwhile, the method is also used as a raw material for preparing the PET-CL copolyester, so that the problems of polyester color change and the like caused by the high ring-opening temperature of the cyclic ethylene terephthalate oligomer are obviously reduced, and the quality of the PET-CL copolyester is improved.
Compared with the prior art, the application has the following technical effects:
(1) The invention provides PET-CL copolyester, which is prepared from cyclic ethylene terephthalate oligomer, epsilon-caprolactone, a catalyst and a stabilizer, wherein the material has the advantages of remarkably improved degradability, remarkably reduced glass transition temperature and higher hot processing performance;
(2) The cyclic ethylene terephthalate oligomer in the PET-CL copolyester raw material provided by the invention has good compatibility with the filler, so that the filler can be directly added into the ring-opening copolymerization reaction of the cyclic ethylene terephthalate oligomer, the dispersibility of the filler in the PET-CL copolyester can be obviously improved, and the performance of the PET-CL copolyester is obviously improved;
(3) The invention also provides a preparation method of the PET-CL copolyester, which directly carries out ring-opening copolymerization reaction on the mixture of the cyclic ethylene terephthalate oligomer, epsilon-caprolactone, the catalyst and the stabilizer, the temperature of the ring-opening copolymerization reaction of the method can be reduced to 220-270 ℃, compared with the ring-opening copolymerization temperature of the single cyclic ethylene terephthalate oligomer exceeding 330 ℃, the ring-opening copolymerization temperature of the single cyclic ethylene terephthalate oligomer is obviously reduced, the problems of side reaction increase, polyester viscosity increase, polyester discoloration and the like caused by overhigh cyclic ethylene terephthalate oligomer can be avoided, the quality of the PET-CL copolyester is obviously improved, and meanwhile, the method can also reduce the reaction energy consumption.
Detailed Description
The invention is further described below with reference to examples.
Example 1:
a PET-CL copolyester comprising 70 parts cyclic ethylene terephthalate oligomer, 30 parts epsilon-caprolactone, and 2.5 parts catalyst (antimony trioxide).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone and antimony trioxide into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring to dissolve, distilling to remove the solvent, drying in an oven to constant weight to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere gas (nitrogen), heating to 270 ℃, stirring and starting to react, reacting for 10 minutes, and ending the reaction to prepare the PET-CL copolyester.
Example 2:
A PET-CL copolyester comprising 70 parts cyclic ethylene terephthalate oligomer, 30 parts epsilon-caprolactone, and 0.5 parts catalyst (antimony trioxide).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone and antimony trioxide into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring to dissolve, distilling to remove the solvent, drying in an oven to constant weight to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere gas (nitrogen), heating to 270 ℃, stirring and starting to react, reacting for 30min, and ending the reaction to prepare the PET-CL copolyester.
Example 3:
a PET-CL copolyester comprising 60 parts of a refined water-removed cyclic ethylene terephthalate oligomer, 40 parts of epsilon-caprolactone, 1.0 part of a catalyst (antimony trioxide) and 0.005 parts of a stabilizer (triphenyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triphenyl phosphate into a container with a magneton according to the parts by weight, adding a solvent (chloroform), stirring until the mixture is dissolved, distilling the solvent, drying the mixture in an oven until the weight is constant to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere gas (nitrogen) and heating to 260 ℃, stirring and starting the reaction, reacting for 45min, and ending the reaction to prepare the PET-CL copolyester.
Example 4:
A PET-CL copolyester comprising 60 parts of a refined dehydrated cyclic ethylene terephthalate oligomer, 40 parts of epsilon-caprolactone, 1.0 part of a catalyst (antimony trioxide) and 0.005 parts of a stabilizer (phosphoric acid).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and phosphoric acid into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring to dissolve, distilling to remove the solvent, drying in an oven to constant weight to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere (nitrogen), heating to 260 ℃, stirring and starting to react, reacting for 30min, and ending the reaction to prepare the PET-CL copolyester.
Example 5:
A PET-CL copolyester comprising 60 parts of a refined dehydrated cyclic ethylene terephthalate oligomer, 40 parts of epsilon-caprolactone, 1.5 parts of a catalyst (antimony trioxide) and 0.005 parts of a stabilizer (trimethyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and trimethyl phosphate into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring to dissolve, distilling to remove the solvent, drying in an oven to constant weight to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere gas (nitrogen), heating to 260 ℃, stirring and starting to react, reacting for 20 minutes, and ending the reaction to prepare the PET-CL copolyester.
Example 6:
A PET-CL copolyester comprising 60 parts of a cyclic ethylene terephthalate oligomer, 40 parts of epsilon-caprolactone, 2.5 parts of a catalyst (antimony trioxide) and 0.01 parts of a stabilizer (trimethyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and trimethyl phosphate into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring to dissolve, distilling to remove the solvent, drying in an oven to constant weight to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere (nitrogen) and heating to 250 ℃, stirring and starting to react, reacting for 30min, and ending the reaction to prepare the PET-CL copolyester.
Example 7:
A PET-CL copolyester comprising 60 parts of a cyclic ethylene terephthalate oligomer, 40 parts of epsilon-caprolactone, 1.5 parts of a catalyst (dibutyltin oxide) and 0.01 parts of a stabilizer (trimethyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, dibutyl tin oxide and trimethyl phosphate into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring to dissolve, distilling to remove the solvent, drying in an oven to constant weight to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere (nitrogen) and heating to 260 ℃, stirring and starting to react, reacting for 20min, and ending the reaction to prepare the PET-CL copolyester.
Example 8:
a PET-CL copolyester comprising 50 parts of a cyclic ethylene terephthalate oligomer, 50 parts of epsilon-caprolactone, 1.5 parts of a catalyst (dibutyltin dilaurate) and 0.01 parts of a stabilizer (trimethyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, dibutyl tin dilaurate and trimethyl phosphate into a container with a magneton according to the parts by weight, adding a solvent (chloroform), stirring until the mixture is dissolved, distilling the solvent, drying the mixture in an oven until the weight is constant to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere gas (nitrogen), heating to 250 ℃, stirring and starting the reaction, reacting for 20min, and ending the reaction to prepare the PET-CL copolyester.
Example 9:
a PET-CL copolyester comprising 50 parts of a cyclic ethylene terephthalate oligomer, 50 parts of epsilon-caprolactone, 1.5 parts of a catalyst (dioctyl tin dilaurate) and 0.01 parts of a stabilizer (trimethyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, dioctyl tin dilaurate and trimethyl phosphate into a container with a magneton according to the parts by weight, adding a solvent (chloroform), stirring until the mixture is dissolved, distilling the solvent, drying the mixture in an oven until the weight is constant to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere gas (nitrogen), heating to 250 ℃, stirring and starting the reaction, reacting for 20min, and ending the reaction to prepare the PET-CL copolyester.
Example 10:
a PET-CL copolyester comprising 50 parts of a cyclic ethylene terephthalate oligomer, 50 parts of epsilon-caprolactone, 1.5 parts of a catalyst (stannous octoate) and 0.01 parts of a stabilizer (trimethyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, stannous octoate and trimethyl phosphate into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring to dissolve, distilling to remove the solvent, drying in an oven to constant weight to prepare a reaction mixture, placing the reaction mixture into the reaction container, introducing inert atmosphere (nitrogen), heating to 250 ℃, stirring and starting to react, reacting for 20 minutes, and ending the reaction to prepare the PET-CL copolyester.
Example 11:
a PET-CL copolyester comprising 50 parts of a cyclic ethylene terephthalate oligomer, 50 parts of epsilon-caprolactone, 1.5 parts of a catalyst (antimony trioxide) and 0.01 parts of a stabilizer (triethyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triethyl phosphate into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring to dissolve, distilling to remove the solvent, drying in an oven to constant weight to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere (nitrogen) and heating to 260 ℃, stirring and starting to react, reacting for 10 minutes, and ending the reaction to prepare the PET-CL copolyester.
Example 12:
A PET-CL copolyester comprising 40 parts of a cyclic ethylene terephthalate oligomer, 60 parts of epsilon-caprolactone, 0.5 parts of a catalyst (antimony trioxide) and 0.01 parts of a stabilizer (triethyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triethyl phosphate into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring to dissolve, distilling to remove the solvent, drying in an oven to constant weight to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere (nitrogen) and heating to 240 ℃, stirring and starting to react, reacting for 30min, and ending the reaction to prepare the PET-CL copolyester.
Example 13:
A PET-CL copolyester comprising 40 parts of a cyclic ethylene terephthalate oligomer, 60 parts of epsilon-caprolactone, 0.5 parts of a catalyst (antimony trioxide) and 0.015 parts of a stabilizer (triphenyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triphenyl phosphate into a container with a magneton according to the parts by weight, adding a solvent (chloroform), stirring until the mixture is dissolved, distilling the solvent, drying the mixture in an oven until the weight is constant to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere gas (nitrogen) and heating to 240 ℃, stirring and starting the reaction, reacting for 30min, and ending the reaction to prepare the PET-CL copolyester.
Example 14:
A PET-CL copolyester comprising 40 parts of a cyclic ethylene terephthalate oligomer, 60 parts of epsilon-caprolactone, 0.5 parts of a catalyst (antimony trioxide) and 0.01 parts of a stabilizer (triethyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triethyl phosphate into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring to dissolve, distilling to remove the solvent, drying in an oven to constant weight to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere (nitrogen) and heating to 240 ℃, stirring and starting to react, reacting for 30min, and ending the reaction to prepare the PET-CL copolyester.
Example 15:
A PET-CL copolyester comprising 40 parts of a cyclic ethylene terephthalate oligomer, 60 parts of epsilon-caprolactone, 0.5 parts of a catalyst (antimony trioxide) and 0.01 parts of a stabilizer (triphenyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triphenyl phosphate into a container with a magneton according to the parts by weight, adding a solvent (chloroform), stirring until the mixture is dissolved, distilling the solvent, drying the mixture in an oven until the weight is constant to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere gas (nitrogen) and heating to 240 ℃, stirring and starting the reaction, reacting for 30min, and ending the reaction to prepare the PET-CL copolyester.
Example 16:
A PET-CL copolyester comprising 30 parts of a cyclic ethylene terephthalate oligomer, 70 parts of epsilon-caprolactone, 0.5 parts of a catalyst (antimony trioxide) and 0.015 parts of a stabilizer (triphenyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triphenyl phosphate into a container with a magneton according to the parts by weight, adding a solvent (chloroform), stirring until the mixture is dissolved, distilling the solvent, drying the mixture in an oven until the weight is constant to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere gas (nitrogen), heating to 220 ℃, stirring and starting the reaction, reacting for 60 minutes, and ending the reaction to prepare the PET-CL copolyester.
Example 17:
A PET-CL copolyester comprising 30 parts of a cyclic ethylene terephthalate oligomer, 70 parts of epsilon-caprolactone, 0.5 parts of a catalyst (antimony trioxide) and 0.015 parts of a stabilizer (triphenyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triphenyl phosphate into a container with a magneton according to the parts by weight, adding a solvent (chloroform), stirring until the mixture is dissolved, distilling the solvent, drying the mixture in an oven until the weight is constant to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere gas (nitrogen), heating to 220 ℃, stirring and starting the reaction, reacting for 40min, and ending the reaction to prepare the PET-CL copolyester.
Example 18:
A PET-CL copolyester comprising 30 parts of a cyclic ethylene terephthalate oligomer, 70 parts of epsilon-caprolactone, 0.5 parts of a catalyst (antimony trioxide) and 0.02 parts of a stabilizer (triphenyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triphenyl phosphate into a container with a magneton according to the parts by weight, adding a solvent (chloroform), stirring until the mixture is dissolved, distilling the solvent, drying the mixture in an oven until the weight is constant to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere gas (nitrogen) and heating to 240 ℃, stirring and starting the reaction, reacting for 40min, and ending the reaction to prepare the PET-CL copolyester.
Example 19:
A PET-CL copolyester comprising 30 parts of a cyclic ethylene terephthalate oligomer, 70 parts of epsilon-caprolactone, 0.5 parts of a catalyst (antimony trioxide) and 0.02 parts of a stabilizer (triphenyl phosphate).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triphenyl phosphate into a container with a magneton according to the parts by weight, adding a solvent (chloroform), stirring until the mixture is dissolved, distilling the solvent, drying the mixture in an oven until the weight is constant to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere gas (nitrogen), heating to 220 ℃, stirring and starting the reaction, reacting for 30min, and ending the reaction to prepare the PET-CL copolyester.
Example 20:
A PET-CL copolyester comprising 50 parts of a cyclic ethylene terephthalate oligomer, 50 parts of epsilon-caprolactone, 0.5 parts of a catalyst (antimony trioxide), 0.01 parts of a stabilizer (triphenyl phosphate) and 5 parts of a filler (hydrotalcite).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triphenyl phosphate into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring until the mixture is dissolved, adding hydrotalcite, continuously stirring and dispersing uniformly, distilling the mixture to remove the solvent, drying the mixture in an oven until the mixture is constant in weight to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere (nitrogen), heating to 250 ℃, stirring and starting to react for 30 minutes, and ending the reaction to prepare the PET-CL copolyester.
Example 21:
A PET-CL copolyester comprising 50 parts of a cyclic ethylene terephthalate oligomer, 50 parts of epsilon-caprolactone, 1.5 parts of a catalyst (antimony trioxide), 0.01 parts of a stabilizer (triphenyl phosphate) and 10 parts of a filler (hydrotalcite).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triphenyl phosphate into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring until the mixture is dissolved, adding hydrotalcite, continuously stirring and dispersing uniformly, distilling the mixture to remove the solvent, drying the mixture in an oven until the mixture is constant in weight to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere (nitrogen), heating to 250 ℃, stirring and starting to react for 30 minutes, and ending the reaction to prepare the PET-CL copolyester.
Example 22:
A PET-CL copolyester comprising 50 parts of a cyclic ethylene terephthalate oligomer, 50 parts of epsilon-caprolactone, 1.5 parts of a catalyst (antimony trioxide), 0.01 parts of a stabilizer (triphenyl phosphate) and 25 parts of a filler (hydrotalcite).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triphenyl phosphate into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring until the mixture is dissolved, adding hydrotalcite, continuously stirring and dispersing uniformly, distilling the mixture to remove the solvent, drying the mixture in an oven until the mixture is constant in weight to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere (nitrogen), heating to 250 ℃, stirring and starting to react, reacting for 40 minutes, and ending the reaction to prepare the PET-CL copolyester.
Example 23:
A PET-CL copolyester comprising 50 parts of a cyclic ethylene terephthalate oligomer, 50 parts of epsilon-caprolactone, 1.5 parts of a catalyst (antimony trioxide), 0.01 parts of a stabilizer (triphenyl phosphate) and 50 parts of a filler (hydrotalcite).
The preparation method of the PET-CL copolyester comprises the following preparation steps:
Adding the refined and dehydrated cyclic ethylene terephthalate oligomer, epsilon-caprolactone, antimony trioxide and triphenyl phosphate into a container with magnetons according to the parts by weight, adding a solvent (chloroform), stirring until the mixture is dissolved, adding hydrotalcite, continuously stirring and dispersing uniformly, distilling the mixture to remove the solvent, drying the mixture in an oven until the mixture is constant in weight to prepare a reaction mixture, placing the reaction mixture into a reaction container, introducing inert atmosphere (nitrogen), heating to 250 ℃, stirring and starting to react, reacting for 60 minutes, and ending the reaction to prepare the PET-CL copolyester.
Comparative example 1:
the comparative example is a cyclic ethylene terephthalate oligomer polymerized alone to PET comprising the steps of:
100 parts of cyclic ethylene terephthalate oligomer and 2 parts of stabilizer antimony trioxide are added into a container with magnetons, a solvent (chloroform) is added and stirred until the solvent is dissolved, the solvent is distilled off, the mixture is dried in an oven until the weight is constant to prepare a reaction mixture, the reaction mixture is placed into a reaction container, inert atmosphere gas (nitrogen) is introduced and heated to 330 ℃, stirring is carried out, the reaction is started, the reaction is carried out for 10 minutes, and the reaction is finished to prepare the PET polyester.
Detection example:
The polyester materials prepared in examples 1 to 23 and comparative example 1 above were tested for glass transition temperature (T g), melting point (T m) and intrinsic viscosity (η);
Glass transition temperature and melting point were measured using a differential scanning calorimeter;
The intrinsic viscosity test method is referred to GB/T14189 93, and comprises the following steps: using an automatic viscosimeter to test, using 3:2 phenol/tetrachloroethane as a solvent, wherein the dissolution temperature of slices is 90-100 ℃, the temperature control range of a viscosimeter water bath is 25+/-0.01 ℃, and the test results are shown in table 1;
TABLE 1 glass transition temperature, melting point and intrinsic viscosity of polyester materials
| Tg(℃) | Tm(℃) | η(dL/g) | |
| Example 1 | 33.4 | 186 | 0.299 |
| Example 2 | 34.2 | 185.8 | 0.289 |
| Example 3 | 27.9 | / | 0.356 |
| Example 4 | 27.1 | / | 0.288 |
| Example 5 | 26.8 | / | 0.314 |
| Example 6 | 27.5 | / | 0.335 |
| Example 7 | 28 | / | 0.299 |
| Example 8 | 3.1 | / | 0.384 |
| Example 9 | 3.4 | / | 0.324 |
| Example 10 | 2.9 | / | 0.319 |
| Example 11 | 3.3 | / | 0.333 |
| Example 12 | -13 | / | 0.300 |
| Example 13 | -12.5 | / | 0.453 |
| Example 14 | -12.3 | / | 0.398 |
| Example 15 | -11.9 | / | 0.394 |
| Example 16 | -25.2 | 84.3 | 0.430 |
| Example 17 | -25.9 | 83.7 | 0.537 |
| Example 18 | -26.1 | 84.6 | 0.617 |
| Example 19 | -25.9 | 83.5 | 0.614 |
| Example 20 | 3.5 | / | 0.324 |
| Example 21 | 3.9 | / | 0.335 |
| Example 22 | 4.2 | / | 0.346 |
| Example 23 | 4.0 | / | 0.340 |
| Comparative example 1 | 165.8 | 256.2 | 0.640 |
As shown in Table 1, the results of examples 1 to 23, each PET-CL copolyester was indexed by one glass transition temperature, and the thermal behavior of the cyclic ethylene terephthalate oligomer and the epsilon caprolactone polyester was not observed for each PET-CL copolyester, indicating that the PET-CL copolyesters were formed for examples 1 to 23.
The glass transition temperature regularly changes along with the increase of the addition content of the hard segment annular ethylene terephthalate oligomer, and the glass transition temperature of the PET-CL copolyester gradually decreases along with the increase of the addition amount of the soft segment epsilon-caprolactone monomer, so that the hot processing capability is obviously enhanced; as the amount of the soft segment epsilon-caprolactone monomer added is increased, the viscosity characteristics of the PET-CL copolyesters are also increased, and the results show that the viscosity characteristics of the PET-CL copolyesters prepared in examples 1 to 23 are between 0.3 dL/g and 0.62dL/g, which shows that the PET-CL copolyesters have a certain molecular weight.
Comparative example 1 is a PET produced by polymerization of a cyclic ethylene terephthalate oligomer alone, comparative example 2 is a PET-CL copolyester produced by copolymerization of epsilon-caprolactone produced in comparative example 1, the copolyesters produced in comparative examples 1-23 exhibit a transparent pale yellow color, and comparative example 1 exhibits an opaque yellowish brown color; in addition, comparative example 1 has significantly improved glass transition temperature, viscosity characteristics, and also has significantly increased polymer size and viscosity with increasing reaction time, compared with example 2, due to side reactions of esterification reaction between polymer segments.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The PET-CL copolyester is characterized by comprising the following raw materials in parts by mass: 30-70 parts of cyclic ethylene terephthalate oligomer, 30-70 parts of ɛ -caprolactone, 0.2-2.5 parts of catalyst and 0-0.02 part of stabilizer.
2. The PET-CL copolyester of claim 1, wherein the catalyst is selected from one or more of dibutyltin oxide, antimony trioxide, dibutyltin dilaurate, dioctyltin dilaurate, and stannous octoate.
3. The PET-CL copolyester of claim 1, wherein the copolyester is selected from one or more of phosphoric acid, trimethyl phosphate, triethyl phosphate, and triphenyl phosphate.
4. The PET-CL copolyester of claim 1, wherein the feedstock further comprises an inorganic filler.
5. The PET-CL copolyester according to claim 4, wherein the mass part of the inorganic filler is 1 to 50.
6. The PET-CL copolyester of claim 4 or 5, characterized in that the inorganic filler is hydrotalcite.
7. A process for preparing a PET-CL copolyester according to any one of claims 1 to 6, characterized in that the PET-CL copolyester is prepared by reacting a cyclic ethylene terephthalate oligomer and ɛ -caprolactone as raw materials in the presence of a catalyst and a stabilizer.
8. The process for preparing a PET-CL copolyester according to claim 7, characterized in that the reaction conditions are: the reaction temperature is 220-270 ℃, the inert atmosphere is adopted, and the reaction time is 10-60 min.
9. The method for preparing PET-CL copolyester according to claim 7, wherein the reaction is carried out by dissolving a cyclic ethylene terephthalate oligomer, ɛ -caprolactone as a raw material, a catalyst and a stabilizer in a solvent before the reaction is carried out, and evaporating the solvent before the reaction.
10. The method for preparing the PET-CL copolyester according to claim 9, wherein the solvent is chloroform.
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