CN102115531A - Preparation method of ABA-type triblock polyester-ether copolymer - Google Patents
Preparation method of ABA-type triblock polyester-ether copolymer Download PDFInfo
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- CN102115531A CN102115531A CN2009102476539A CN200910247653A CN102115531A CN 102115531 A CN102115531 A CN 102115531A CN 2009102476539 A CN2009102476539 A CN 2009102476539A CN 200910247653 A CN200910247653 A CN 200910247653A CN 102115531 A CN102115531 A CN 102115531A
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229920001577 copolymer Polymers 0.000 title claims abstract description 17
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims abstract description 146
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 229920000151 polyglycol Polymers 0.000 claims abstract description 9
- 239000010695 polyglycol Substances 0.000 claims abstract description 9
- 150000002148 esters Chemical group 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 28
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 25
- 229920000728 polyester Polymers 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 150000003384 small molecules Chemical class 0.000 claims description 20
- -1 2,2,6,6-tetramethyl--4-piperidyl Chemical group 0.000 claims description 17
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000005809 transesterification reaction Methods 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004246 zinc acetate Substances 0.000 claims description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000012544 monitoring process Methods 0.000 claims description 7
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 4
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 claims description 4
- 150000001463 antimony compounds Chemical class 0.000 claims description 4
- 150000002291 germanium compounds Chemical class 0.000 claims description 4
- 229940119177 germanium dioxide Drugs 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 claims description 2
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 2
- BPTAFUFSKASLJF-UHFFFAOYSA-N OP(O)OP(O)O.C1=CC=CC=2C3=CC=CC=C3C12 Chemical class OP(O)OP(O)O.C1=CC=CC=2C3=CC=CC=C3C12 BPTAFUFSKASLJF-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 abstract description 3
- 229920005604 random copolymer Polymers 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 2
- 239000012760 heat stabilizer Substances 0.000 abstract 2
- 239000004611 light stabiliser Substances 0.000 abstract 2
- 150000002009 diols Chemical class 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 11
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 239000008118 PEG 6000 Substances 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 241001515806 Stictis Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- TZBAVQKIEKDGFH-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]-1-benzothiophene-2-carboxamide;hydrochloride Chemical compound [Cl-].C1=CC=C2SC(C(=O)NCC[NH+](CC)CC)=CC2=C1 TZBAVQKIEKDGFH-UHFFFAOYSA-N 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a preparation method of an ABA-type triblock polyester-ether copolymer, which comprises the following steps: mixing dimethyl terephthalate, small-molecular diol and a first catalyst, and carrying out ester exchange reaction; supplementally adding a second catalyst, a first heat stabilizer and a first light stabilizer, and carrying out prepolymerization; and finally, adding polyglycol, a second heat stabilizer and a second light stabilizer, regulating the temperature and pressure, and carrying out polycondensation reaction to obtain the ABA-type polyester-ether block copolymer. Compared with the prior art, the structure and molecular weight of the ABA-type triblock polyester-ether copolymer are basically controllable, and the molecular weight of the copolymer is 30000-40000. The polymerization method is melt polycondensation which is convenient for industrial production, and is a great breakthrough on the basis of the prior polyester-ether random copolymer.
Description
Technical field
The present invention relates to a kind of preparation method of multipolymer, especially relate to the preparation method of a kind of ABA type triblock polyester-ether type multipolymer.
Background technology
Polyester-ether thermoplastic elastomer is meant the segmented copolymer of polyether block and alternately arrangement formation of polyester block, at present the polyethers section mainly is meant soft section of the polytetrahydrofuran, polyoxyethylene glycol etc. of different molecular weight, and polyester segments mainly is polyethylene terephthalate, polybutylene terephthalate and has just risen soon hard sections such as Poly(Trimethylene Terephthalate).This thermoplastic elastomer is mainly used in the moulded parts of making high tenacity, warp resistance and medium thermotolerance and medium chemical-resistant, especially aspect polymer toughening and the blend increase-volume vital role is being arranged.But up to the present, say on the polyester of these suitability for industrialized production-ether type copolymer thermoplastic elastomerics stricti jurise and belong to many blocks random copolymers.The block polyester of compound with regular structure-ether type multipolymer, block polyester-ether type the multipolymer of compound with regular structure that especially can suitability for industrialized production yet there are no report, certainly, the solution self-assembly, can prepare the polyester-ether type multipolymer of compound with regular structure by chainextender, but up to the present only limit to laboratory scope.
The present invention utilizes sophisticated melt phase polycondensation technology, innovative point is that the amount of the small molecules glycol that steams by polycondensation process control pressure and monitoring decompression or the variation of system viscosity judge the degree that polycondensation is carried out, and then infer the different sizes of system molecular weight constantly, thereby decision adds the optimum time point of polyglycol.Prepare ABA type polyester-ether type multipolymer.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of sophisticated melt phase polycondensation technology of utilizing for the defective that overcomes above-mentioned prior art existence, innovative point is that the amount of the small molecules glycol that steams by polycondensation process control pressure and monitoring decompression or the variation of system viscosity judge the degree that polycondensation is carried out, and then the different sizes of system molecular weight constantly of deduction, thereby decision adds the optimum time point of polyglycol, prepares the method for ABA type polyester-ether type multipolymer.
Purpose of the present invention can be achieved through the following technical solutions:
The preparation method of a kind of ABA type triblock polyester-ether type multipolymer is characterized in that this method may further comprise the steps:
(1) transesterify: dimethyl terephthalate (DMT) and small molecules glycol mixed in molar ratio≤0.5 obtaining mixture, in the reactor that has whipping appts, control reaction temperature is 140-205 ℃ and carries out transesterification reaction behind first catalyzer of the 1-10wt ‰ of adding dimethyl terephthalate (DMT) weight;
(2) prepolymerization: treat to add second catalyzer, first thermo-stabilizer and first photostabilizer after the quantity of methyl alcohol that steams in the transesterification reaction reaches theoretical value, temperature is increased to 235 ℃, progressively regulates vacuum tightness to carrying out prepolymerization reaction below the 100Pa and monitoring the amount that steams the small molecules glycol;
(3) polymerization: after the amount that steams the small molecules glycol reaches desirable value; under nitrogen protection, add polyglycol, second thermo-stabilizer and second photostabilizer; elevated temperature is to 250-270 ℃; regulate vacuum tightness to carrying out polycondensation 3-5h below the 20Pa, prepare ABA type polyester-ether type segmented copolymer.
Described small molecules glycol is selected from 1,1, ammediol or 1, one or more in the 4-butyleneglycol.
The concrete material of described first catalyzer and second catalyzer can be the same or different, all be selected from acetate type compound, antimony compounds, titanium compound or the germanium compounds one or more, described acetate type compound is selected from zinc acetate, described antimony compounds is selected from antimonous oxide, described titanium compound is selected from one or both in titanium dioxide or the tetra-n-butyl titanate, and described germanium compounds is selected from germanium dioxide.
The concrete material of described first photostabilizer and second photostabilizer can be the same or different, and all is selected from photostabilizer 944 (poly--{ [6-[(1,1,3,3 ,-tetramethyl butyl)-amido] 1,3,5 ,-triazine-2,4-two bases] [(2,2,6, the 6-tetramethyl-piperidyl)-and imido grpup]-1,6-hexane two bases-[(2,2,6, the 6-tetramethyl-piperidyl)-imido grpup]), photostabilizer 622 (poly-[1-(2 '-hydroxyethyl)-2,2,6,6-tetramethyl--4-hydroxy piperidine Succinic Acid fat]), photostabilizer 770 (sebacic acid two 2,2,6,6-tetramethyl piperidine alcohol ester) or photostabilizer 783 (poly-{ [6-[(1,1,3, the 3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-two [(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1, oneself two supports [(2 of 6-, 2,6,6-tetramethyl--4-piperidyl) imino-] and poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines ethanol) one or more the mixture of ester).
The concrete material of described first thermo-stabilizer and second thermo-stabilizer can be the same or different, all be selected from triphenyl phosphite, four (2,4-two-tert.-butylbenzene) 4,4 ' biphenylene-diphosphites, oxidation inhibitor 168 (tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester), antioxidant 264 (2, the 6-toluene di-tert-butyl phenol), oxidation inhibitor Topanol-A (2,4-dimethyl-6-tert.-butyl phenol) or oxidation inhibitor IRGANOX 1330 (3,3,3,5,5,5-six tertiary butyls-a, a, a-(1,3,5-Three methyl Benzene-2,4,6-three bases) one or more three-p-cresols).
Described polyglycol is selected from one or more in polyoxyethylene glycol, polypropylene glycol or the polytetrahydrofuran.
The theoretical value that steams methyl alcohol in the described step (2) is the twice of dimethyl terephthalate (DMT) molar weight.
The amount that adds second catalyzer in the described step (2) is 1 ‰ of a dimethyl terephthalate (DMT) weight-10 ‰, the amount that adds first thermo-stabilizer be after the transesterify co-mixing system gross weight 2 ‰-10 ‰, the amount that adds first photostabilizer be after the transesterify co-mixing system gross weight 0 ‰-10 ‰.
Steaming small molecules glycol amount in the described step (3) is the 99%-99.5% of dimethyl terephthalate (DMT) molar weight.
The polyglycol that adds in the described step (3) and the mol ratio of dimethyl terephthalate (DMT) are 1: (50-75), the amount that adds second thermo-stabilizer be after the precondensation co-mixing system gross weight 2 ‰-10 ‰, the amount that adds second photostabilizer be after the precondensation co-mixing system gross weight 2 ‰-10 ‰.
Compared with prior art, the ABA type polyester-ether block copolymers of the present invention's preparation, because pressure-controlling, viscosity controller or small molecules glycol all are easy to by the control of the amount of steaming in the reaction process, thereby make that the ABA type polyester-ether block copolymers structure and the molecular weight of preparation are controlled substantially, the resulting polymers molecular weight is between 30000-40000, and polymerization process is melt phase polycondensation, is convenient to suitability for industrialized production, be on the basis of former polyester-ether type random copolymers once than quantum jump.
With the 78g dimethyl terephthalate (DMT), 60g small molecules glycol reaction system is an example, steams small molecules glycol amount (is example with the propylene glycol) and polyester segment molecular weight and has linear relationship in the following table:
| Steam propylene glycol amount (g) | Polyester segment molecular weight (Mn) |
| 28 | 17500～18000 |
| 28.5 | 26000～30500 |
| 30 | 32000～35000 |
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
The preparation method of a kind of ABA type block polyester of compound with regular structure-ether type multipolymer may further comprise the steps:
(1) transesterify: with dimethyl terephthalate (DMT) and 1, ammediol is 0.5 to mix 1 ‰ positive four butyl esters of metatitanic acid that the back adds dimethyl terephthalate (DMT) weight in molar ratio, in the reactor that has whipping appts, control reaction temperature is 140 ℃ and carries out transesterification reaction then;
(2) prepolymerization: treat that the quantity of methyl alcohol that steams in the transesterification reaction reaches the triphenyl phosphite of co-mixing system gross weight 2 ‰ after the zinc acetate of adding dimethyl terephthalate (DMT) weight 1 ‰ after the theoretical value (twice of dimethyl terephthalate (DMT) molar weight), the transesterify, temperature is increased to 235 ℃, progressively regulates vacuum tightness to carrying out prepolymerization reaction below the 100Pa and monitoring the amount that steams the small molecules glycol;
(3) polymerization: when steaming 1; after the amount of ammediol reaches desirable value (dimethyl terephthalate (DMT) molar weight 99%); the photostabilizer 770 that under nitrogen protection, adds co-mixing system gross weight 2 ‰ after the triphenyl phosphite of co-mixing system gross weight 2 ‰ after polyoxyethylene glycol, the precondensation and the precondensation; the polyoxyethylene glycol that adds and the mol ratio of dimethyl terephthalate (DMT) are 1: 50; elevated temperature to 250 ℃; regulate vacuum tightness to carrying out polycondensation below the 20Pa 3 hours, obtain ABA type polyester-ether type segmented copolymer.
The skeleton symbol of this method gained segmented copolymer is: PEG2000-b-PTT-b-PEG2000.By GPC test as can be known its number-average molecular weight (Mn) between 31000-40000.
Embodiment 2
The preparation method of a kind of ABA type block polyester of compound with regular structure-ether type multipolymer may further comprise the steps:
(1) with the 78g dimethyl terephthalate (DMT), 65g 1, ammediol, and churned mechanically 250ml three-necked flask is equipped with in the positive four butyl esters adding of 0.1g metatitanic acid, and 200 ℃ are carried out transesterify;
(2) treat that it is after the 32.4ml that quantity of methyl alcohol reaches theoretical value, add positive four butyl esters of 0.1g metatitanic acid and 0.1g zinc acetate, and adding 0.7g triphenyl phosphite, slowly temperature is increased to 235 ℃, and slowly reduce vacuum tightness below 100Pa, when 1, ammediol steams and reaches 28.9g and can carry out next step reaction later on;
(3) behind the completing steps (2), removal vacuum under nitrogen protection adds 21.3g Macrogol 4000 (PEG4000); add 0.2g triphenyl phosphite and 0.9g photostabilizer 770; slowly temperature is increased to 260 ℃, control vacuum tightness is carried out post polymerization 4h and is got final product below 20Pa.
The skeleton symbol of this method gained segmented copolymer is: PEG4000-b-PTT-b-PEG4000.By GPC test as can be known its number-average molecular weight (Mn) between 35000-44000.
Embodiment 3
The preparation method of a kind of ABA type block polyester of compound with regular structure-ether type multipolymer may further comprise the steps:
(1) with the 78g dimethyl terephthalate (DMT), 65g 1, ammediol, and churned mechanically 250ml three-necked flask is equipped with in the positive four butyl esters adding of 0.15g metatitanic acid, and 200 ℃ are carried out transesterify;
(2) treat that it is after the 32.4ml that quantity of methyl alcohol reaches theoretical value, add positive four butyl esters of 0.15g metatitanic acid and 0.15g zinc acetate, and adding 0.45g triphenyl phosphite, slowly temperature is increased to 235 ℃, and slowly reduce vacuum tightness below 100Pa, when 1, ammediol steams and reaches 28.9g and can carry out next step reaction later on;
(3) behind the completing steps (2), removal vacuum under nitrogen protection adds 48g polyethylene glycol 6000 (PEG6000) and adds 0.45g triphenyl phosphite and 0.9g photostabilizer 770, slowly temperature is increased to 250 ℃, control vacuum tightness is carried out post polymerization 4h and is got final product below 20Pa;
The skeleton symbol of this method gained segmented copolymer is: PEG6000-b-PTT-b-PEG6000.By GPC test as can be known its number-average molecular weight (Mn) between 33000-45000.
Embodiment 4
The preparation method of a kind of ABA type block polyester of compound with regular structure-ether type multipolymer may further comprise the steps:
(1) with the 78g dimethyl terephthalate (DMT), 65g 1, ammediol, and churned mechanically 250ml three-necked flask is equipped with in the positive four butyl esters adding of 0.2g metatitanic acid, and 200 ℃ are carried out transesterify;
(2) treat that it is after the 32.4ml that quantity of methyl alcohol reaches theoretical value, add positive four butyl esters of 0.2g metatitanic acid and 0.2g zinc acetate, and adding 0.2g triphenyl phosphite and 0.2g photostabilizer 770, slowly temperature is increased to 235 ℃, and slowly reduce vacuum tightness below 100Pa, when 1, ammediol steams and reaches 28.9g and can carry out next step reaction later on;
(3) behind the completing steps (2); removal vacuum under nitrogen protection adds 10.7g polytetramethylene ether diol 2000 (PTMEG2000) and adds 0.2g triphenyl phosphite and 0.6g photostabilizer 770, slowly temperature is increased to 255 ℃; control vacuum tightness is carried out post polymerization 4h and is got final product below 20Pa.
The skeleton symbol of this method gained segmented copolymer is: PTMEG2000-b-PTT-b-PTMEG2000.By GPC test as can be known its number-average molecular weight (Mn) between 30000-40000.
Embodiment 5
The preparation method of a kind of ABA type block polyester of compound with regular structure-ether type multipolymer may further comprise the steps:
(1) with the 78g dimethyl terephthalate (DMT), 65g 1, ammediol, and churned mechanically 250ml three-necked flask is equipped with in the positive four butyl esters adding of 0.08g metatitanic acid, and 200 ℃ are carried out transesterify;
(2) treat that it is after the 32.4ml that quantity of methyl alcohol reaches theoretical value, add positive four butyl esters of 0.08g metatitanic acid and 0.3g zinc acetate, and adding 0.5g triphenyl phosphite and 0.2g photostabilizer 770, slowly temperature is increased to 235 ℃, and slowly reduce vacuum tightness below 100Pa, when 1, ammediol steams and reaches 28.9g and can carry out next step reaction later on;
(3) behind the completing steps (2); removal vacuum under nitrogen protection adds 24g polypropylene glycol 3000 (PPG3000) and adds 0.5g triphenyl phosphite and 0.65g photostabilizer 770, slowly temperature is increased to 260 ℃; control vacuum tightness is carried out post polymerization 4.5h and is got final product below 20Pa.
The skeleton symbol of this method gained segmented copolymer is: PPG3000-b-PTT-b-PPG3000.By GPC test as can be known its number-average molecular weight (Mn) between 30000-40000.
Embodiment 6
The preparation method of a kind of ABA type block polyester of compound with regular structure-ether type multipolymer may further comprise the steps:
(1) with the 78g dimethyl terephthalate (DMT), 60g 1, ammediol, and churned mechanically 250ml three-necked flask is equipped with in the positive four butyl esters adding of 0.3g metatitanic acid, and 200 ℃ are carried out transesterify;
(2) treat that it is after the 32.4ml that quantity of methyl alcohol reaches theoretical value, add positive four butyl esters of 0.3g metatitanic acid and 0.03g zinc acetate, and add the 1g triphenyl phosphite and, slowly temperature is increased to 235 ℃, and slowly reduce vacuum tightness below 100Pa, when 1, ammediol steams and reaches 28.9g and can carry out next step reaction later on;
(3) behind the completing steps (2); removal vacuum under nitrogen protection adds 32g polypropylene glycol 4000 (PPG4000) and adds 0.3g triphenyl phosphite and 1g photostabilizer 770, slowly temperature is increased to 265 ℃; control vacuum tightness is carried out post polymerization 5h and is got final product below 20Pa.
The skeleton symbol of this method gained segmented copolymer is: PPG4000-b-PTT-b-PPG4000.By GPC test as can be known its number-average molecular weight (Mn) between 32000-41000.
Embodiment 7
The preparation method of a kind of ABA type triblock polyester-ether type multipolymer, this method may further comprise the steps:
(1) transesterify: with dimethyl terephthalate (DMT) and 1,2-ethylene glycol 0.4 mixing in molar ratio obtains mixture, in the reactor that has whipping appts, control reaction temperature is 180 ℃ and carries out transesterification reaction behind the zinc acetate of adding dimethyl terephthalate (DMT) 5wt ‰;
(2) prepolymerization: after treating that the quantity of methyl alcohol that steams in the transesterification reaction reaches the twice of dimethyl terephthalate (DMT) molar weight, add antimonous oxide, oxidation inhibitor 168 and photostabilizer 944, the add-on of antimonous oxide is 4 ‰ of a dimethyl terephthalate (DMT) weight, the add-on of oxidation inhibitor 168 be after the transesterify co-mixing system gross weight 6 ‰, the add-on of photostabilizer 944 be after the transesterify co-mixing system gross weight 2 ‰, temperature is increased to 235 ℃, progressively regulates vacuum tightness to carrying out prepolymerization reaction below the 100Pa and monitoring the amount that steams the small molecules glycol;
(3) polymerization: when the amount that steams the small molecules glycol reach the dimethyl terephthalate (DMT) molar weight 99.2% after; under nitrogen protection, add polypropylene glycol; antioxidant 264 and photostabilizer 622; the polypropylene glycol that adds and the mol ratio of dimethyl terephthalate (DMT) are 1: 65; the add-on of antioxidant 264 be after the precondensation co-mixing system gross weight 5 ‰; the add-on of photostabilizer 622 be after the precondensation co-mixing system gross weight 6 ‰; elevated temperature to 260 ℃; regulate vacuum tightness to carrying out polycondensation 4h below the 20Pa, prepare ABA type polyester-ether type segmented copolymer.
Embodiment 8
The preparation method of a kind of ABA type triblock polyester-ether type multipolymer, this method may further comprise the steps:
(1) transesterify: with dimethyl terephthalate (DMT) and 1,4-butyleneglycol 0.2 mixing in molar ratio obtains mixture, in the reactor that has whipping appts, control reaction temperature is 205 ℃ and carries out transesterification reaction behind the titanium dioxide of the 10wt ‰ of adding dimethyl terephthalate (DMT) weight;
(2) prepolymerization: after treating that the quantity of methyl alcohol that steams in the transesterification reaction reaches the twice of dimethyl terephthalate (DMT) molar weight, add germanium dioxide, oxidation inhibitor Topanol-A and photostabilizer 783, the add-on of germanium dioxide is the 10wt ‰ of dimethyl terephthalate (DMT), the add-on of oxidation inhibitor Topanol-A be after the transesterify co-mixing system gross weight 10 ‰, the add-on of photostabilizer 783 be after the transesterify co-mixing system gross weight 10 ‰, temperature is increased to 235 ℃, progressively regulates vacuum tightness to carrying out prepolymerization reaction below the 100Pa and monitoring the amount that steams the small molecules glycol;
(3) polymerization: when the amount that steams the small molecules glycol reach the dimethyl terephthalate (DMT) molar weight 99.5% after; under nitrogen protection, add polytetrahydrofuran; oxidation inhibitor Topanol-A and photostabilizer 783; the polytetrahydrofuran that adds and the mol ratio of dimethyl terephthalate (DMT) are 1: 75; the add-on of oxidation inhibitor Topanol-A be after the precondensation co-mixing system gross weight 10 ‰; the add-on of photostabilizer 783 be after the precondensation co-mixing system gross weight 10 ‰; elevated temperature to 270 ℃; regulate vacuum tightness to carrying out polycondensation 5h below the 20Pa, prepare ABA type polyester-ether type segmented copolymer.
Claims (10)
1. the preparation method of ABA type triblock polyester-ether type multipolymer is characterized in that this method may further comprise the steps:
(1) transesterify: dimethyl terephthalate (DMT) and small molecules glycol mixed in molar ratio≤0.5 obtaining mixture, in the reactor that has whipping appts, control reaction temperature is 140-205 ℃ and carries out transesterification reaction behind first catalyzer of the 1-10wt ‰ of adding dimethyl terephthalate (DMT) weight;
(2) prepolymerization: treat to add second catalyzer, first thermo-stabilizer and first photostabilizer after the quantity of methyl alcohol that steams in the transesterification reaction reaches theoretical value, temperature is increased to 235 ℃, progressively regulates vacuum tightness to carrying out prepolymerization reaction below the 100Pa and monitoring the amount that steams the small molecules glycol;
(3) polymerization: after the amount that steams the small molecules glycol reaches desirable value; under nitrogen protection, add polyglycol, second thermo-stabilizer and second photostabilizer; elevated temperature is to 250-270 ℃; regulate vacuum tightness to carrying out polycondensation 3-5h below the 20Pa, prepare ABA type polyester-ether type segmented copolymer.
2. the preparation method of a kind of ABA type triblock polyester according to claim 1-ether type multipolymer is characterized in that described small molecules glycol is selected from 1,1, ammediol or 1, one or more in the 4-butyleneglycol.
3. the preparation method of a kind of ABA type triblock polyester according to claim 1-ether type multipolymer, it is characterized in that, the concrete material of described first catalyzer and second catalyzer can be the same or different, all be selected from the acetate type compound, the antimony compounds, in titanium compound or the germanium compounds one or more, described acetate type compound is selected from zinc acetate, described antimony compounds is selected from antimonous oxide, described titanium compound is selected from one or both in titanium dioxide or the tetra-n-butyl titanate, and described germanium compounds is selected from germanium dioxide.
4. the preparation method of a kind of ABA type triblock polyester according to claim 1-ether type multipolymer is characterized in that the concrete material of described first photostabilizer and second photostabilizer can be the same or different, all be selected from photostabilizer 944 (poly--{ [6-[(1,1,3,3 ,-tetramethyl butyl)-amido] 1,3,5 ,-triazine-2,4-two bases] [(2,2,6, the 6-tetramethyl-piperidyl)-imido grpup]-1,6-hexane two bases-[(2,2,6, the 6-tetramethyl-piperidyl)-imido grpup]), photostabilizer 622 (poly-[1-(2 '-hydroxyethyl)-2,2,6,6-tetramethyl--4-hydroxy piperidine Succinic Acid fat]), photostabilizer 770 (sebacic acid two 2,2,6,6-tetramethyl piperidine alcohol ester) or photostabilizer 783 (poly-{ [6-[(1,1,3, the 3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-two [(2,2,6,6,-tetramethyl-4-piperidyl) imino-]-1,6-oneself two the support [(2,2,6,6-tetramethyl--4-piperidyl) imino-] } and poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines ethanol) one or more the mixture of ester).
5. the preparation method of a kind of ABA type triblock polyester according to claim 1-ether type multipolymer, it is characterized in that, the concrete material of described first thermo-stabilizer and second thermo-stabilizer can be the same or different, all be selected from triphenyl phosphite, four (2,4-two-tert.-butylbenzene) 4,4 ' biphenylene-diphosphites, oxidation inhibitor 168 (tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester), antioxidant 264 (2, the 6-toluene di-tert-butyl phenol), oxidation inhibitor Topanol-A (2,4-dimethyl-6-tert.-butyl phenol) or oxidation inhibitor IRGANOX1330 (3,3,3,5,5,5-six tertiary butyls-a, a, a-(1,3,5-Three methyl Benzene-2,4,6-three bases) one or more three-p-cresols).
6. the preparation method of a kind of ABA type triblock polyester according to claim 1-ether type multipolymer is characterized in that described polyglycol is selected from one or more in polyoxyethylene glycol, polypropylene glycol or the polytetrahydrofuran.
7. the preparation method of a kind of ABA type triblock polyester according to claim 1-ether type multipolymer is characterized in that the theoretical value that steams methyl alcohol in the described step (2) is the twice of dimethyl terephthalate (DMT) molar weight.
8. the preparation method of a kind of ABA type triblock polyester according to claim 1-ether type multipolymer, it is characterized in that, the amount that adds second catalyzer in the described step (2) is 1 ‰ of a dimethyl terephthalate (DMT) weight-10 ‰, the amount that adds first thermo-stabilizer be after the transesterify co-mixing system gross weight 2 ‰-10 ‰, the amount that adds first photostabilizer be after the transesterify co-mixing system gross weight 0 ‰-10 ‰.
9. the preparation method of a kind of ABA type triblock polyester according to claim 1-ether type multipolymer is characterized in that steaming small molecules glycol amount in the described step (3) is the 99%-99.5% of dimethyl terephthalate (DMT) molar weight.
10. the preparation method of a kind of ABA type triblock polyester according to claim 1-ether type multipolymer, it is characterized in that, the polyglycol that adds in the described step (3) and the mol ratio of dimethyl terephthalate (DMT) are 1: (50-75), the amount that adds second thermo-stabilizer be after the precondensation co-mixing system gross weight 2 ‰-10 ‰, the amount that adds second photostabilizer be after the precondensation co-mixing system gross weight 2 ‰-10 ‰.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964579A (en) * | 2012-12-06 | 2013-03-13 | 盘锦科隆精细化工有限公司 | Reinforced thermoplastic polyester elastomer and preparation method thereof |
| CN105585701A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | A continuous preparing method for polyether modified copolyester |
| CN105585702A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Polyester used for plates and preparing method thereof |
| CN109354837A (en) * | 2018-09-19 | 2019-02-19 | 常州钟恒新材料有限公司 | The preparation method of high ductibility polyester material and the method that composite membrane-forming is prepared using the material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1177606A (en) * | 1996-09-20 | 1998-04-01 | 中国科学院化学研究所 | Polyester-polyether multi-block copolymer, preparation method and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1177606A (en) * | 1996-09-20 | 1998-04-01 | 中国科学院化学研究所 | Polyester-polyether multi-block copolymer, preparation method and use thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964579A (en) * | 2012-12-06 | 2013-03-13 | 盘锦科隆精细化工有限公司 | Reinforced thermoplastic polyester elastomer and preparation method thereof |
| CN102964579B (en) * | 2012-12-06 | 2015-04-22 | 盘锦科隆精细化工有限公司 | Reinforced thermoplastic polyester elastomer and preparation method thereof |
| CN105585701A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | A continuous preparing method for polyether modified copolyester |
| CN105585702A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Polyester used for plates and preparing method thereof |
| CN105585701B (en) * | 2014-10-22 | 2019-11-29 | 中国石油化工股份有限公司 | A kind of polyether-modified copolyesters continuous preparation method |
| CN109354837A (en) * | 2018-09-19 | 2019-02-19 | 常州钟恒新材料有限公司 | The preparation method of high ductibility polyester material and the method that composite membrane-forming is prepared using the material |
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