CN1300213C - Ternary copoly ester capable of biological degradation and its preparation method - Google Patents
Ternary copoly ester capable of biological degradation and its preparation method Download PDFInfo
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- CN1300213C CN1300213C CNB2004100409147A CN200410040914A CN1300213C CN 1300213 C CN1300213 C CN 1300213C CN B2004100409147 A CNB2004100409147 A CN B2004100409147A CN 200410040914 A CN200410040914 A CN 200410040914A CN 1300213 C CN1300213 C CN 1300213C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920001634 Copolyester Polymers 0.000 title abstract description 8
- 230000015556 catabolic process Effects 0.000 title description 2
- 238000006731 degradation reaction Methods 0.000 title description 2
- -1 poly-succinic acid butanediol ester Chemical class 0.000 claims abstract description 98
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 45
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 63
- 229920002961 polybutylene succinate Polymers 0.000 claims description 60
- 239000004631 polybutylene succinate Substances 0.000 claims description 60
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 53
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 32
- 150000002148 esters Chemical class 0.000 claims description 31
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 31
- 229940051250 hexylene glycol Drugs 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 19
- 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 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 claims description 13
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 12
- 230000004927 fusion Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- 230000002045 lasting effect Effects 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001384 succinic acid Substances 0.000 abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 3
- 239000001361 adipic acid Substances 0.000 abstract 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract 1
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 abstract 1
- VJVOPINBJQWMNY-UHFFFAOYSA-N butanedioic acid;ethane-1,2-diol Chemical compound OCCO.OC(=O)CCC(O)=O VJVOPINBJQWMNY-UHFFFAOYSA-N 0.000 abstract 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 abstract 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract 1
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 56
- 238000012360 testing method Methods 0.000 description 30
- 239000000463 material Substances 0.000 description 22
- 239000002361 compost Substances 0.000 description 14
- 238000000748 compression moulding Methods 0.000 description 14
- 238000001746 injection moulding Methods 0.000 description 14
- 230000032050 esterification Effects 0.000 description 12
- 238000005886 esterification reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012660 binary copolymerization Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- IBMRTYCHDPMBFN-UHFFFAOYSA-N Mono-Me ester-Pentanedioic acid Natural products COC(=O)CCCC(O)=O IBMRTYCHDPMBFN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- RGCVYEOTYJCNOS-UHFFFAOYSA-N (4-cyano-2-methylphenyl)boronic acid Chemical compound CC1=CC(C#N)=CC=C1B(O)O RGCVYEOTYJCNOS-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- LNLCRJXCNQABMV-UHFFFAOYSA-N Dimethyl suberate Chemical compound COC(=O)CCCCCCC(=O)OC LNLCRJXCNQABMV-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- DRUKNYVQGHETPO-UHFFFAOYSA-N Nonanedioic acid dimethyl ester Natural products COC(=O)CCCCCCCC(=O)OC DRUKNYVQGHETPO-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- 229940014772 dimethyl sebacate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to biodegradable ternary copolyester and a preparation method thereof. The ternary copolyester is obtained by the method that raw materials for synthesizing poly-succinic acid butanediol ester, raw materials for synthesizing ethylene glycol succinate or poly-succinic acid hexanediol ester or poly-adipic acid butanediol easter or poly-adipic acid hexanediol ester and raw materials for synthesizing polyethylene glycol terephthalate or polybutylene terephthalate or poly-terephthalic acid propanediol carry out atactic copolymerization by provided simple, mature and easy-control technological methods and conditions. Thus, the mechanical performance, the thermal performance and the biodegradation performance of the obtained ternary copolyester are respectively superior to that of the dyadic copolyester of the prior art, and the ternary copolyester has low cost and application value.
Description
One, technical field
The invention belongs to biodegradable multicomponent copolyester product and preparation method's technical field, be specifically related to a kind of biodegradable three-element copolymerized ester and preparation method thereof.
Two, background technology
Poly butylene succinate (PBS) is a kind of polymkeric substance of totally biodegradable, and it can finally generate materials such as carbonic acid gas and water under the effect of bacterium or enzyme, at present, produces and puts goods on the market in Japan and Germany.But this material cost is higher, and its mechanical property still can not satisfy the actual needs of many industries.Therefore, people begin it has been carried out a large amount of study on the modification.As in order to improve the fragility shortcoming of PBS, people introduce phenyl ring in PBS, random copolymers (PBS-CO-PET) (the Darwin P.R Kint that has synthesized poly butylene succinate and polyethylene terephthalate, Abdelilah Alla, Polymer 44 (2003) 1321-1330.) and random copolymers (PBS-co-PBT) (the OKADA M.Prog.Polym.Sci. of poly butylene succinate and polybutylene terephthalate, 2002,27:87-133.), to give the product certain toughness.These products are compared with pure PBS product, though make its use range extended because of obtaining toughness, but, because the intervention of phenyl ring, the biodegradability of material then descends to some extent, simultaneously, in some industry that elongation at break is had higher requirements, PBS-CO-PET and PBS-CO-PBT still can not meet the demands.So, people carry out copolymerization with PBS and polyethylene glycol succinate (PES) again and have synthesized the random copolymers of poly butylene succinate and polyethylene glycol succinate (PBS-co-PES) (Amin Cao a, b, Takashi Okamurac, Polymer Degradation and Stability 78,2002,671-679), though the biological degradability of this material and elongation at break have raising greatly than pure PBS, PBS-CO-PET and PBS-CO-PBT, but regrettably, the fusing point of PBS-co-PES and intensity are all not high, promote the use of thereby had a strong impact on it.
Three, summary of the invention
The objective of the invention is at some shortcomings on existing pure PBS and the copolymer material property thereof, a kind of have actual application value and the comparatively cheap biodegradable three-element copolymerized ester of cost are provided.
Another object of the present invention provides the method for the described biodegradable three-element copolymerized ester of the last purpose of preparation.
Biodegradable three-element copolymerized ester provided by the invention, be by the structural unit of representing with poly butylene succinate, with with polyethylene glycol succinate, poly-succinic hexylene glycol ester, poly adipate succinic acid ester, the structural unit of any expression in the poly-hexanodioic acid hexylene glycol ester, and with polyethylene terephthalate, polybutylene terephthalate, the structural unit of any expression in the Poly(Trimethylene Terephthalate), constitute with the line style random arrangement, the molecular fraction of its each structural unit respectively is 7～34%, 43～62%, 5～50%, the intrinsic viscosity of this three-element copolymerized ester is 0.5～1.1dl/g, 90～120 ℃ of fusing points, tensile strength 12～36Mpa, elongation at break 850～1400%.
The tensile strength of biodegradable three-element copolymerized ester provided by the invention and elongation at break are to adopt the test of Britain LloYD-LR10K type stretching experiment machine; Fusing point is detected by differential scanning calorimeter; Intrinsic viscosity is to make solvent with trichloromethane, detects down for 20 ℃ in temperature with Ubbelohde viscometer; Each structural unit is to be solvent by deuterochloroform, characterizes combination again with Varian INOVA-400 type nuclear magnetic resonance analyser measured result
1The H-NMR spectrum can obtain the molar content of structural elements in the material.
The method of the above-mentioned biodegradable three-element copolymerized ester of preparation provided by the invention, its processing step and condition are as follows:
(1) prepolymer is synthetic
Join the raw material of synthetic poly butylene succinate and the raw material of synthetic polyethylene glycol succinate or poly-succinic hexylene glycol ester or poly adipate succinic acid ester or poly-hexanodioic acid hexylene glycol ester in the reactor together, after the intensification fusion is stirred and is mixed evenly, under protection of nitrogen gas, be warming up to 200 ℃, keep this temperature and continue to stir carrying out polycondensation, stopped reaction discharging behind 3～5h, promptly get the poly butylene succinate that intrinsic viscosity is 0.15～0.19dl/g and the pre-polymerization mixture of polyethylene glycol succinate or poly-succinic hexylene glycol ester or poly adipate succinic acid ester or poly-hexanodioic acid hexylene glycol ester, wherein requiring the butyleneglycol in the raw material of the raw material of synthetic poly butylene succinate and synthetic polyethylene glycol succinate or poly-succinic hexylene glycol ester or poly adipate succinic acid ester or poly-hexanodioic acid hexylene glycol ester and the mole proportioning of ethylene glycol or hexylene glycol is 15～35: 65～85;
Join the raw material of synthetic polyethylene terephthalate or polybutylene terephthalate or Poly(Trimethylene Terephthalate) in the reactor together, after the intensification fusion is stirred and is mixed evenly, be warming up to 200 ℃ again, simultaneously by adding nitrogen, make the still internal pressure rise to 5Mpa, keep this temperature and pressure, and lasting stirring reaction 3～5h, the stopped reaction discharging, promptly getting intrinsic viscosity is pre-polymerization polyethylene terephthalate or polybutylene terephthalate or the Poly(Trimethylene Terephthalate) of 0.15～0.17dl/g;
(2) polycondensation of multipolymer
Get the above-mentioned pre-polymerization polyethylene terephthalate for preparing or polybutylene terephthalate or Poly(Trimethylene Terephthalate); by making its final unit content molar content in three-element copolymerized ester is 5～50% to join in the reactor; under protection of nitrogen gas; stirring is warming up to 240～245 ℃; after treating that it melts fully; continue to keep temperature; in the time of stirring and nitrogen gas stream; the pre-polymerization mixture that adds above-mentioned poly butylene succinate for preparing and polyethylene glycol succinate or poly-succinic hexylene glycol ester or poly adipate succinic acid ester or poly-hexanodioic acid hexylene glycol ester again; it is 50～95% that its add-on should make its final unit content molar content in three-element copolymerized ester; after the complete fusion of the system for the treatment of; be cooled to 235～240 ℃; be incorporated as the catalyzer of prepolymer integral molar quantity 0.046-0.093% mole again; low whipping speed is 7～10r/s; temperature is 235～240 ℃; vacuum tightness is below the 60Pa, and reaction 3～7.5h promptly gets product.
Perhaps following processing step and condition preparation:
(1) precondensation
Is 50～95% adding reactors with the raw material of synthetic poly butylene succinate and the raw material of synthetic polyethylene glycol succinate or poly-succinic hexylene glycol ester or poly adipate succinic acid ester or poly-hexanodioic acid hexylene glycol ester by the molar content of these two kinds of structural units in three-element copolymerized ester, the mol ratio of its former with the latter is 15～35: 65～85, meanwhile, the raw material that also will synthesize polyethylene terephthalate or polybutylene terephthalate or Poly(Trimethylene Terephthalate) is that 5～50% amount joins in the reactor together by making its final structure unit molar content in three-element copolymerized ester, then under nitrogen protection, stirring is warming up to 200 ℃, reaction 3～4h;
(2) polycondensation
Continuation is incorporated as the catalyzer of prepolymer integral molar quantity 0.046-0.093% mole under nitrogen protection, low whipping speed is 7～10r/s, and temperature is 235～240 ℃, and vacuum tightness is below the 60Pa, and reaction 3～7.5h promptly gets product.
In above-mentioned preparation method, the raw material of synthetic poly butylene succinate is specially 1,4-Succinic Acid or 1,4-dimethyl succinate and 1,4-butyleneglycol; The raw material of synthetic polyethylene glycol succinate or poly-succinic hexylene glycol ester or poly adipate succinic acid ester or poly-hexanodioic acid hexylene glycol ester is according to synthetic prepolymer difference, specifically from oxalic acid, 1, the 3-propanedioic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, carbon atom quantities such as sebacic acid are in the individual di-carboxylic acid of 2-10, or from ethylene dimethyl, 1, the 3-dimethyl malonate, Methyl glutarate, dimethyl adipate, the suberic acid dimethyl ester, dimethyl azelate, carbon atom quantities such as dimethyl sebacate are in the individual dibasic ester of 2-10 and ethylene glycol, 1, ammediol, butyleneglycol, pentanediol, hexylene glycol, ethohexadiol, nonanediol, carbon atom quantities such as decanediol are to select for use in the individual dibasic alcohol of 2-10; The raw material of synthetic polyethylene terephthalate or polybutylene terephthalate or Poly(Trimethylene Terephthalate) also is according to synthetic prepolymer difference, specifically from terephthalic acid or dimethyl terephthalate (DMT), with ethylene glycol, 1, ammediol, 1, select for use in the 4-butyleneglycol.These comprise that various raw materials all are the known general knowledge of present technique field ordinary skill in collocation, the selection of synthetic concrete constitutional unit.
Employed catalyzer is at least a in tetrabutyl titanate, isopropyl titanate, antimonous oxide, germanic acid four butyl esters and the toluenesulphonic acids in above-mentioned preparation method.
Four, embodiment
Provide embodiment below to be described in more detail the present invention; but it is worthy of note that the present invention is not limited to these embodiment; the ordinary skill of this area to some nonessential improvement and adjustment that the present invention has done, still belongs to protection scope of the present invention according to the content of the invention described above.
Used following code name in an embodiment, hereby explanation.
PBS=poly butylene succinate PES=polyethylene glycol succinate
PET=polyethylene terephthalate PBT=polybutylene terephthalate
-CO-=random copolymerization DMT=dimethyl terephthalate (DMT)
ED=ethylene glycol SA=1, the 4-Succinic Acid
BD=1,4-butyleneglycol PHA=gathers hexanodioic acid hexylene glycol ester
PBA=poly adipate succinic acid ester PHO=gathers suberic acid hexylene glycol ester
PGS=gathers the sebacic acid pentadiol ester
Embodiment 1
What present embodiment prepared is the PBS-CO-PES-CO-PET multipolymer.
With take by weighing respectively 1; 0.54 mole of 4-Succinic Acid, 1,0.14 mole of 4-butyleneglycol; ethylene glycol joins in the reactor for 0.54 mole together; the intensification fusion under protection of nitrogen gas, is warming up to 200 ℃ after stirring and mixing evenly again; keep this temperature and under the stirring velocity of 3r/s; behind the reaction 4h, the stopped reaction discharging, promptly getting intrinsic viscosity is the low-molecular-weight poly butylene succinate of 0.16dl/g and the mixture of polyethylene glycol succinate.The mole proportioning of PBS/PES is about 79/21 in the mixture at this moment.
Join in the reactor together 0.50 mole of the terephthalic acid, the ethylene glycol that take by weighing for 0.64 mole, after the intensification fusion is stirred and is mixed evenly, be warming up to 200 ℃ again, simultaneously by adding nitrogen, make the still internal pressure rise to 5Mpa, keep this temperature and pressure, and lasting stirring reaction 3h, the stopped reaction discharging, promptly getting intrinsic viscosity is the pre-polymerization polyethylene terephthalate of 0.17dl/g.
Get 0.50 mole of the above-mentioned pre-polymerization polyethylene terephthalate for preparing; join in the reactor; under protection of nitrogen gas; stirring is warming up to 243 ℃; after treating that it melts fully; when continuing to keep temperature, stirring and nitrogen gas stream; add 0.75 mole in above-mentioned poly butylene succinate for preparing and polyethylene glycol succinate pre-polymerization mixture again; after treating that the three is melted fully mutually, be cooled to 235 ℃, add 0.00125 mole of tetrabutyl titanate again; low whipping speed is 7r/s; temperature is 235 ℃, and below the vacuum tightness 60Pa, reaction 5.5h promptly gets product.
After testing, the molar content of PET is 40% in the product, and the mole proportioning of PES and PBS is 79/21.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.67dL/g is behind the injection moulding machine compression molding, testing its tensile strength is 19MPa, elongation at break is 1130%, and fusing point is 96 ℃, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 11% in 11 weeks.
Embodiment 2
What present embodiment prepared is the PBS-CO-PES-CO-PET multipolymer.
With 2 moles of 1.4-Succinic Acid, 1,0.46 mole of 4-butyleneglycol, 1.64 moles of ethylene glycol, 1.34 moles of terephthalic acids, ethylene glycol joins in the reactor for 1.74 moles, under nitrogen protection, stirs and is warming up to 200 ℃, reaction 4h; Continuation adds 0.0038 mole of tetrabutyl titanate under nitrogen protection, low whipping speed is 8r/s, and temperature is 240 ℃, and below the vacuum tightness 60Pa, reaction 4h promptly gets product.
After testing, the molar content of PET is 40% in the product, and the mole proportioning of PES and PBS is 78/22.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.72dL/g is behind the injection moulding machine compression molding, testing its tensile strength is 20MPa, elongation at break is 1200%, and fusing point is 94 ℃, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 10% in 11 weeks.
Embodiment 3
What present embodiment prepared is the PBS-CO-PES-CO-PET multipolymer.
With 1 mole of 1.4-Succinic Acid, 1,0.23 mole of 4-butyleneglycol; 1.86 moles of ethylene glycol; 1.03 moles of adding reactors of dimethyl terephthalate (DMT) behind 200 ℃ of following esterification 4h, add totally 0.00195 mole (antimonous oxide: 0.0000596 mole of miscellany of antimonous oxide and tetrabutyl titanate; tetrabutyl titanate: 0.00134 mole); under nitrogen protection, stirring velocity is 8r/s, and temperature is 237 ℃; below the vacuum tightness 60Pa, reaction 3h promptly gets product.
After testing, the molar content of PET is 50% in the product, and the mole proportioning of PES and PBS is 78/22.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.64dL/g is behind the injection moulding machine compression molding, testing its tensile strength is 25MPa, elongation at break is 870%, and fusing point is 112 ℃, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 6% in 11 weeks.
Embodiment 4
What present embodiment prepared is the PBS-CO-PES-CO-PET multipolymer.
With 1 mole of 1.4-Succinic Acid, 1,0.23 mole of 4-butyleneglycol; 0.94 mole of ethylene glycol; 0.11 mole of adding reactor of dimethyl terephthalate (DMT) behind 200 ℃ of following esterification 5h, adds germanic acid four butyl esters and 0.00105 mole of (tetrabutyl titanate: 0.000703 mole of tetrabutyl titanate; 0.000347 mole); under nitrogen protection, stirring velocity is 9r/s, and temperature is 235 ℃; below the vacuum tightness 60Pa, reaction 7.5h promptly gets product.
After testing, the molar content of PET is 10% in the product, and the mole proportioning of PES and PBS is 82/18.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.63dL/g, behind the injection moulding machine compression molding, testing its tensile strength is 12MPa, and elongation at break is 1300%, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 20% in 11 weeks.
Embodiment 5
What present embodiment prepared is the PBS-CO-PES-CO-PBT multipolymer.
With 1 mole of 1.4-Succinic Acid, 1,0.38 mole of 4-butyleneglycol; 0.82 mole of ethylene glycol; 0.13 mole of adding reactor of dimethyl terephthalate (DMT) behind 200 ℃ of following esterification 3.5h, adds tetrabutyl titanate and 0.00052 mole of (0.00039 mole of tetrabutyl titanate of toluenesulphonic acids; 0.00013 mole of toluenesulphonic acids); under nitrogen protection, stirring velocity is 8r/s, and temperature is 237 ℃; below the vacuum tightness 60Pa, reaction 7h promptly gets product.
After testing, the molar content of PBT is 10% in the product, and the mole proportioning of PES and PBS is 77/23.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.82dL/g, behind the injection moulding machine compression molding, testing its tensile strength is 19MPa, and elongation at break is 977%, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 18% in 11 weeks.
Embodiment 6
What present embodiment prepared is the PBS-CO-PES-CO-PBT multipolymer.
With 1 mole of 1.4-Succinic Acid; 1,1.27 moles of 4-butyleneglycols, 0.82 mole of ethylene glycol; 1.03 moles of adding reactors of dimethyl terephthalate (DMT); behind 200 ℃ of following esterification 4h, add 0.00142 mole of isopropyl titanate, under nitrogen protection; stirring velocity is 10r/s; temperature is 240 ℃, and below the vacuum tightness 60Pa, reaction 3.5h promptly gets product.
After testing, the molar content of PBT is 50% in the product, and the mole proportioning of PES and PBS is 76/24.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.76dL/g is behind the injection moulding machine compression molding, testing its tensile strength is 28MPa, elongation at break is 940%, and fusing point is 120 ℃, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 8% in 11 weeks.
Embodiment 7
What present embodiment prepared is the PBS-CO-PES-CO-PBT multipolymer.
With 1 mole of 1.4-Succinic Acid, 1,0.965 mole of 4-butyleneglycol; 0.89 mole of ethylene glycol; 0.69 mole of adding reactor of dimethyl terephthalate (DMT) behind 200 ℃ of following esterification 3.5h, adds isopropyl titanate and 0.0157 mole of (isopropyl titanate: 0.011 mole of antimonous oxide; antimonous oxide: 0.0047 mole); under nitrogen protection, stirring velocity is 10r/s, and temperature is 240 ℃; below the vacuum tightness 60Pa, reaction 4.5h promptly gets product.
After testing, the molar content of PBT is 40% in the product, and the mole proportioning of PES and PBS is 85/15.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.76dL/g is behind the injection moulding machine compression molding, testing its tensile strength is 24MPa, elongation at break is 1084%, and fusing point is 112 ℃, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 10% in 11 weeks.
Embodiment 8
What present embodiment prepared is the PBS-CO-PES-CO-PBT multipolymer.
With take by weighing respectively 1; 0.70 mole of 4-Succinic Acid, 1,0.17 mole of 4-butyleneglycol; ethylene glycol joining in the reactor for 0.54 mole-; the intensification fusion under protection of nitrogen gas, is warming up to 200 ℃ after stirring and mixing evenly again; keep this temperature and under the stirring velocity of 10r/s; behind the reaction 4h, the stopped reaction discharging, promptly getting intrinsic viscosity is the low-molecular-weight poly butylene succinate of 0.15dl/g and the mixture of polyethylene glycol succinate.The mole proportioning of PBS/PES is about 75/25 in the mixture at this moment.
With 0.57 mole of the terephthalic acid that takes by weighing, 1, the 4-butyleneglycol joins in the reactor for 0.74 mole together, after the intensification fusion is stirred and is mixed evenly, be warming up to 200 ℃ again, by adding nitrogen, make the still internal pressure rise to 5Mpa simultaneously, keep this temperature and pressure, and lasting stirring reaction 5h, the stopped reaction discharging, promptly getting intrinsic viscosity is the pre-polymerization polybutylene terephthalate of 0.17dl/g.
Get 0.50 mole of the above-mentioned pre-polymerization polybutylene terephthalate for preparing; join in the reactor; under protection of nitrogen gas; stirring is warming up to 243 ℃; after treating that it melts fully; when continuing to keep temperature, stirring and nitrogen gas stream; add 1.17 moles in above-mentioned poly butylene succinate for preparing and polyethylene glycol succinate pre-polymerization mixture again; after treating that the three is melted fully mutually, be cooled to 240 ℃, add 0.014 mole of tetrabutyl titanate again; low whipping speed is 8r/s; temperature is 235 ℃, and vacuum tightness is below the 60Pa, and reaction 6.5h promptly gets product.
After testing, the molar content of PBT is 30% in the product, and the mole proportioning of PES and PBS is 75/25.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.67dL/g, behind the injection moulding machine compression molding, testing its tensile strength is 18MPa, and elongation at break is 1260%, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 15% in 11 weeks.
Embodiment 9
What present embodiment prepared is the PBS-CO-PES-CO-PET multipolymer.
With 4 moles of 14-Succinic Acid; 1,1.17 moles of 4-butyleneglycols, 4.22 moles of ethylene glycol; 1.03 moles of adding reactors of dimethyl terephthalate (DMT); behind 200 ℃ of following esterification 4h, add 0.025 mole of isopropyl titanate, under nitrogen protection; stirring velocity is 10r/s; temperature is 240 ℃, and vacuum tightness is below the 60Pa, and reaction 6h promptly gets product.
After testing, the molar content of PET is 20% in the product, and the mole proportioning of PES and PBS is 83/17.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.72dL/g, behind the injection moulding machine compression molding, testing its tensile strength is 16MPa, and elongation at break is 990%, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 7% in 11 weeks.
Embodiment 10
What present embodiment prepared is the PBS-CO-PHA-CO-PET multipolymer.
With 0.63 mole of 1.4-dimethyl succinate, 1,0.66 mole of 4-butyleneglycol; 1,1.17 moles of 6-hexanodioic acids, 1; 1.21 moles of 6-hexylene glycols, 0.23 mole of ethylene glycol, 0.20 mole of adding reactor of dimethyl terephthalate (DMT); behind 200 ℃ of following esterification 3.5h, add 0.0186 mole of isopropyl titanate, under nitrogen protection; stirring velocity is 10r/s; temperature is 240 ℃, and vacuum tightness is below the 60Pa, and reaction 6.5h promptly gets product.
After testing, the molar content of PET is 10% in the product, and the mole proportioning of PHA and PBS is 65/35.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.64dL/g, behind the injection moulding machine compression molding, testing its tensile strength is 29MPa, and elongation at break is 1040%, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 18% in 11 weeks.
Embodiment 11
What present embodiment prepared is the PBS-CO-PBA-CO-PBT multipolymer.
With 0.63 mole of 1.4-Succinic Acid, 1,3.10 moles of 4-butyleneglycols; 1; 1.17 moles of 6-hexanodioic acids, 1.20 moles of adding reactors of dimethyl terephthalate (DMT) are behind 200 ℃ of following esterification 4h; add 0.02 mole of tetrabutyl titanate; under nitrogen protection, stirring velocity is 9r/s, and temperature is 237 ℃; vacuum tightness is below the 60Pa, and reaction 6h promptly gets product.
After testing, the molar content of PBT is 40% in the product, and the mole proportioning of PBA and PBS is 75/25.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.70dL/g, behind the injection moulding machine compression molding, testing its tensile strength is 36MPa, and elongation at break is 880%, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 9% in 11 weeks.
Embodiment 12
What present embodiment prepared is the PBS-CO-PHO-CO-PET multipolymer.
With 0.59 mole of 1.4-dimethyl succinate, 1,0.63 mole of 4-butyleneglycol; 1,1.39 moles of 8-suberic acids, 1; 1.39 moles of 6-hexylene glycols, 0.84 mole of dimethyl terephthalate (DMT), 0.89 mole of adding reactor of ethylene glycol; behind 200 ℃ of following esterification 4h, add 0.0028 mole of isopropyl titanate, under nitrogen protection; stirring velocity is 10r/s; temperature is 240 ℃, and vacuum tightness is below the 60Pa, and reaction 6.5h promptly gets product.
After testing, the molar content of PET is 30% in the product, and the mole proportioning of PHO and PBS is 72/28.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.71dL/g, behind the injection moulding machine compression molding, testing its tensile strength is 21MPa, and elongation at break is 1336%, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 14% in 11 weeks.
Embodiment 13
What present embodiment prepared is the PBS-CO-PGS-CO-PET multipolymer.
With 1,0.54 mole of 4-Succinic Acid, 1; 0.57 mole of 4-butyleneglycol, 1,2.20 mole 1 of 6-sebacic acid; 2.32 moles of 6-pentanediols, 1.47 moles of dimethyl terephthalate (DMT), 1.54 moles of adding reactors of ethylene glycol; behind 200 ℃ of following esterification 3.5h, add 0.0024 mole of isopropyl titanate, under nitrogen protection; stirring velocity is 10r/s; temperature is 240 ℃, and vacuum tightness is below the 60Pa, and reaction 7h promptly gets product.
After testing, the molar content of PET is 35% in the product, and the mole proportioning of PGS and PBS is 80/20.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.61dL/g, behind the injection moulding machine compression molding, testing its tensile strength is 28MPa, and elongation at break is 991%, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 12% in 11 weeks.
Comparative Examples 1～4
What this Comparative Examples prepared is PBS-CO-PET or PBS-CO-PBT multipolymer
Press the listed molar ratio of table 1 with dimethyl terephthalate (DMT), ethylene glycol, 1; 4-Succinic Acid, 1; the 4-butyleneglycol adds reactor; behind 200 ℃ of following esterification 4h, add tetrabutyl titanate, under nitrogen protection; in 240 ℃; stirring velocity is 7～10r/s, and temperature is 240 ℃, and vacuum tightness is the following reaction of 60Pa 4h.
The data that obtain through correlation detection see Table 1.
Comparative Examples 5
What this Comparative Examples prepared is the PBS-CO-PES multipolymer.
With 1 mole of 1.4-Succinic Acid; 1; 0.87 mole of 4-butyleneglycol, 0.23 mole of adding reactor of ethylene glycol is behind 200 ℃ of following esterification 4h; add 0.0148 mole of tetrabutyl titanate; under nitrogen protection, stirring velocity is 10r/s, and temperature is 240 ℃; vacuum tightness is below the 60Pa, and reaction 7h promptly gets product.
After testing, the molar content of PES is 78% in the product, and the mole proportioning of PES and PBS is 78/22.Under 20 ℃ envrionment temperature, intrinsic viscosity 0.55dL/g is behind the injection moulding machine compression molding, testing its tensile strength is 10MPa, elongation at break is 1060%, and fusing point is 70 ℃, and the biodegradability of material is according to ASTMD5338 compost standard weightlessness 24% in 11 weeks.
In order to contrast the binary copolymerization ester that the present invention obtains biodegradable three-element copolymerized ester and prior art comparatively intuitively, difference aspect mechanical property, thermal characteristics, biodegradability changes, and the present invention is summarized in the test result of tensile strength, elongation at break, fusing point and biodegradability that embodiment and Comparative Examples 5 material that obtains carry out in the table 2.Can see that the elongation at break of ternary polyester of the present invention is generally higher from table 1,2 contrast, its value is than the high 80-300% of value of the binary PBS copolyesters of the aromatic polyester that contains equal molar content; The tensile strength of three-element copolymerized ester has improved 20-150% than fatty ester adoption ester PBS-CO-PES; The biodegradability of three-element copolymerized ester has surpassed the binary copolymerization ester PBS-CO-PET that contains isodose PET or PBT or the biodegradability of PBS-CO-PBT; Contain PET or PBT molar content more than or equal to the fusing point of 40% three-element copolymerized ester PBS-CO-PET-CO-PES or PBS-CO-PBT-CO-PES fusing point greater than binary copolymerization ester PBS-CO-PES, as when containing fusing point that PET or PBT molar content equal 40% three-element copolymerized ester PBS-CO-PET-CO-PES or PBS-CO-PBT-CO-PES all greater than 90 ℃, and the fusing point of PBS-CO-PES only is 70 ℃.Thereby, the above-mentioned performance of being not difficult to draw three-element copolymerized ester that the present invention obtains is better than the conclusion of the binary copolymerization ester of prior art respectively, and, also, the introducing of PET or PBT is lower than the PBS-CO-PES copolymer because making the present invention obtain the three-element copolymerized ester cost, and can be used as general-purpose plastics and use.Moreover, the synthesis technique maturation of its preparation method, simple is easy to control, and implementation is strong.
Table 1
| The material that makes | PBS-CO-PET | PBS-CO-PET | PBS-CO-PBT | PBS-CO-PBT |
| The molar content of PET or PBT | 10％PET | 40％PET | 40％PBT | 10％PBT |
| DMT(mol) | 0.1 | 1 | 1 | 0.1 |
| ED(mol) | 0.1 | 1.04 | 0 | 0 |
| SA(mol) | 0.9 | 1.5 | 1.5 | 0.9 |
| BD(mol) | 0.936 | 1.56 | 2.7 | 1.1 |
| Tensile strength (Mpa) | 26 | 24 | 18 | 34 |
| Elongation at break (%) | 300 | 560 | 500 | 294 |
| Biological degradation (weightless %) | 14 | 5 | 4 | 12 |
| Intrinsic viscosity (dl/g) | 0.61 | 0.66 | 0.65 | 0.70 |
Table 2
| Embodiment | Ratio (mol/mol) | The molar content of aromatic polyester | Tensile strength (Mpa) | Elongation at break (%) | Rate of weight loss (%) | Fusing point (℃) |
| 1 | PES/PBS 79/21 | 40％(PET) | 19 | 1130 | 11 | 96 |
| 2 | PES/PBS 78/22 | 40％(PET) | 20 | 1200 | 10 | 94 |
| 3 | PES/PBS 78/22 | 50％(PET) | 25 | 870 | 6 | 112 |
| 4 | PES/PBS 82/18 | 10％(PET) | 12 | 1300 | 20 | / |
| 5 | PES/PBS 77/23 | 10％(PBT) | 19 | 977 | 18 | / |
| 6 | PES/PBS 76/24 | 50％(PBT) | 28 | 940 | 8 | 120 |
| 7 | PES/PBS 85/15 | 40％(PBT) | 24 | 1084 | 10 | 112 |
| 8 | PES/PBS 75/25 | 30％(PBT) | 18 | 1260 | 15 | / |
| 9 | PES/PBS 83/17 | 20％(PET) | 16 | 990 | 7 | / |
| 10 | PHA/PBS 65/35 | 10％(PET) | 29 | 1040 | 18 | / |
| 11 | PBA/PBS 75/25 | 40％(PBT) | 36 | 880 | 9 | / |
| 12 | PHO/PBS 72/28 | 30％(PET) | 21 | 1366 | 14 | / |
| 13 | PGS/PBS 80/20 | 35％(PET) | 28 | 991 | 12 | / |
| Comparative Examples 5 | PBS/PES 78/22 | / | 10 | 1060 | 24 | 70 |
Claims (3)
1, a kind of biodegradable three-element copolymerized ester, be by the structural unit of representing with poly butylene succinate, with with polyethylene glycol succinate, poly-succinic hexylene glycol ester, poly adipate succinic acid ester, the structural unit of any expression in the poly-hexanodioic acid hexylene glycol ester, and with polyethylene terephthalate, polybutylene terephthalate, the structural unit of any expression in the Poly(Trimethylene Terephthalate), constitute with the line style random arrangement, the molecular fraction of its each structural unit respectively is 12.6～17.5%, 45～52.5%, 30～40%, the intrinsic viscosity of this three-element copolymerized ester under 20 ℃ of temperature is 0.67～0.70dl/g, 90～106 ℃ of fusing points, tensile strength 18～36Mpa, elongation at break 880～1260%.
2, a kind of method for preparing the described biodegradable three-element copolymerized ester of claim 1 is characterized in that its processing step and condition are as follows:
(1) prepolymer is synthetic
Join the raw material of synthetic poly butylene succinate and the raw material of synthetic polyethylene glycol succinate or poly-succinic hexylene glycol ester or poly adipate succinic acid ester or poly-hexanodioic acid hexylene glycol ester in the reactor together, after the intensification fusion is stirred and is mixed evenly, under protection of nitrogen gas, be warming up to 200 ℃ again, keep this temperature and continue to stir carrying out polycondensation, stopped reaction discharging behind 3～5h, promptly get the poly butylene succinate that intrinsic viscosity is 0.15～0.19dl/g and the pre-polymerization mixture of polyethylene glycol succinate or poly-succinic hexylene glycol ester or poly adipate succinic acid ester or poly-hexanodioic acid hexylene glycol ester, wherein requiring the butyleneglycol in the raw material of the raw material of synthetic poly butylene succinate and synthetic polyethylene glycol succinate or poly-succinic hexylene glycol ester or poly adipate succinic acid ester or poly-hexanodioic acid hexylene glycol ester and the mole proportioning of ethylene glycol or hexylene glycol is 15～35: 65～85;
Join the raw material of synthetic polyethylene terephthalate or polybutylene terephthalate or Poly(Trimethylene Terephthalate) in the reactor together, after the intensification fusion is stirred and is mixed evenly, be warming up to 200 ℃ again, simultaneously by adding nitrogen, make the still internal pressure rise to 5Mpa, keep this temperature and pressure, and lasting stirring reaction 3～5h, the stopped reaction discharging, promptly getting intrinsic viscosity is pre-polymerization polyethylene terephthalate or polybutylene terephthalate or the Poly(Trimethylene Terephthalate) of 0.15～0.17dl/g;
(2) polycondensation of multipolymer
Get the above-mentioned pre-polymerization polyethylene terephthalate for preparing or polybutylene terephthalate or Poly(Trimethylene Terephthalate); by making its final unit content molar content in three-element copolymerized ester is 5～50% to join in the reactor; under protection of nitrogen gas; stirring is warming up to 240～245 ℃; after treating that it melts fully; continue to keep temperature; in the time of stirring and nitrogen gas stream; the pre-polymerization mixture that adds above-mentioned poly butylene succinate for preparing and polyethylene glycol succinate or poly-succinic hexylene glycol ester or poly adipate succinic acid ester or poly-hexanodioic acid hexylene glycol ester again; it is 50～95% that its add-on should make its final unit content molar content in three-element copolymerized ester; after the complete fusion of the system for the treatment of; be cooled to 235～240 ℃; be incorporated as the catalyzer of prepolymer integral molar quantity 0.046-0.093% mole again; low whipping speed is 7～10r/s; temperature is 235～240 ℃; vacuum tightness is below the 60Pa, and reaction 3～7.5h promptly gets product.
3, the method for the biodegradable three-element copolymerized ester of preparation according to claim 2 is characterized in that catalyzer is at least a in tetrabutyl titanate, isopropyl titanate, antimonous oxide, germanic acid four butyl esters and the toluenesulphonic acids.
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| CN101628972B (en) * | 2008-07-14 | 2011-10-05 | 青岛生物能源与过程研究所 | Method for preparing poly (ethylene succinate) |
| CN101508771B (en) * | 2009-03-18 | 2011-08-24 | 马世金 | Method of preparing biodegradable multicomponent copolyester |
| CN101525425B (en) * | 2009-03-30 | 2011-04-27 | 东华大学 | Method for preparing biodegradable copolyester by direct esterification-polycondensation process |
| CN101660220B (en) * | 2009-08-24 | 2012-05-30 | 江苏鹰翔化纤股份有限公司 | Preparation method of poly-para-phenylene dioctyl phthalate 1, 3-trimethylene glycol ester and olybuthylenesuccinate sheath-core fiber |
| KR20130027095A (en) * | 2011-09-02 | 2013-03-15 | 삼성정밀화학 주식회사 | Method of preparation for biodegradable co-polyester resin |
| CN102443149B (en) * | 2011-10-28 | 2014-09-10 | 金发科技股份有限公司 | Continuous production method for biodegradable aliphatic-aromatic copolyester |
| CN102516517A (en) * | 2011-12-13 | 2012-06-27 | 金发科技股份有限公司 | Method for preparing polyester-polyester blocked copolyester |
| CN106939077B (en) * | 2017-05-12 | 2018-12-25 | 南京大学 | A kind of synthetic process of Biodegradable three-element copolymerized ester PBAST |
| CN109576813A (en) * | 2017-09-28 | 2019-04-05 | 中国石化仪征化纤有限责任公司 | A kind of preparation method of low melting point PBT copolyester fiber |
| CN110591058A (en) * | 2019-10-28 | 2019-12-20 | 浙江晟祺实业有限公司 | Method for catalytic polycondensation of degradable packaging material |
| CN111116874A (en) * | 2019-12-25 | 2020-05-08 | 重庆晟淦新材料科技有限公司 | Biodegradable PBST copolyester and synthetic method thereof |
| CN112280018A (en) * | 2020-09-30 | 2021-01-29 | 中国纺织科学研究院有限公司 | Preparation method of antistatic PBAT polymer and antistatic PBAT polymer |
| CN112457709B (en) * | 2020-11-30 | 2022-08-02 | 吉安天晟新材料有限公司 | Preparation method and application of degradable thermal transfer printing lettering film |
| CN115926123A (en) * | 2023-01-17 | 2023-04-07 | 辽宁东盛新材料研发中心有限公司 | Poly (butylene succinate) copolymerized and modified by poly (butylene adipate) and preparation method thereof |
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