CN102786673B - Cyclic aliphatic polyester preparation method - Google Patents
Cyclic aliphatic polyester preparation method Download PDFInfo
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- CN102786673B CN102786673B CN 201210264737 CN201210264737A CN102786673B CN 102786673 B CN102786673 B CN 102786673B CN 201210264737 CN201210264737 CN 201210264737 CN 201210264737 A CN201210264737 A CN 201210264737A CN 102786673 B CN102786673 B CN 102786673B
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- Prior art keywords
- aliphatic polyester
- bromine
- cyclic
- hours
- organic solvent
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- 229920003232 aliphatic polyester Polymers 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 125000004122 cyclic group Chemical group 0.000 title abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 230000008020 evaporation Effects 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 6
- 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 abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MONMFXREYOKQTI-UHFFFAOYSA-N 2-bromopropanoic acid Chemical compound CC(Br)C(O)=O MONMFXREYOKQTI-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000003809 water extraction Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- CEVRHGVQRGAUIR-UHFFFAOYSA-N [K].BrCC(=O)O Chemical group [K].BrCC(=O)O CEVRHGVQRGAUIR-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 2
- QKRAOTCLMXZGQF-UHFFFAOYSA-N [Na].BrCC(=O)O Chemical compound [Na].BrCC(=O)O QKRAOTCLMXZGQF-UHFFFAOYSA-N 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 229960003511 macrogol Drugs 0.000 claims description 2
- -1 poly(oxyethylene glycol) Polymers 0.000 claims description 2
- 229940093430 polyethylene glycol 1500 Drugs 0.000 claims description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 229920000954 Polyglycolide Polymers 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 4
- 239000004633 polyglycolic acid Substances 0.000 abstract description 4
- 239000004626 polylactic acid Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 229920005565 cyclic polymer Polymers 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000237502 Ostreidae Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
A cyclic aliphatic polyester preparation method belongs to the chemical field of high polymer syntheses. The method is characterized by comprising the following steps: placing 2-bromine carboxylate in an organic solvent, adding a phase-transfer catalyst of 0-30 percent of the 2-bromine carboxylate by molar weight so as to react for 3-48 hours, extracting the reaction mixture with ethyl ether and water, taking a diethyl ether layer to be dried with anhydrous magnesium sulfate, and removing the solvent through evaporation after filtering; and then, adding 0-10 percent of stannous octoate by molar weight in the production obtained from the polymerization process, and distilling the mixture for more than 15 hours under a pressure reduction condition when the temperature is gradually increased to 150-230 DEG C. The method has the benefits that high-yield and high-purity cyclic polylactic acid and cyclic polyglycolic acid can be obtained under a mild reaction condition through using a lower-cost monomer. The cyclic aliphatic polyester, as a cyclic monomer, can be applied to the field of active controllable polymerization field so as to prepare the high molecular weight aliphatic polyester, and has potential economic benefits.
Description
Technical field
The invention belongs to the macromolecule synthesising technology field, specially refer to a kind of preparation method of annular aliphatic polyester.
Background technology
Cyclic polymer is the special polymkeric substance of a class formation, and due to the constraint that there is no end group, the structural unit on its molecular chain has identity property, and the polymer phase ratio with other topological frameworks, have special physico-chemical property.Therefore, cyclic polymer is the problem that the researchist pays close attention to always.Cyclic polymer mainly obtains by intramolecular ring-closure reaction in high dilute solution.According to ring-chain level theory, in the solution under about 2 w/v % concentration, react, the cyclic polymer productive rate obtained is the highest.Therefore, utilize technology of closed loop to prepare the efficiency of cyclic polymer usually lower, and be difficult to avoid the residual of simple linear polymer.
In recent years, Germany scientist Kricheldorf etc. have proposed a kind of new ring level theory (Macromolecules, Vol. 41, No. 21, p7812-7816,2008).Different from tradition ring-chain level theory, under any concentration, as long as suitably regulate the feed ratio of monomer and initiator, can pass through kinetic control, obtain being mainly the polymerisate of ring.With technology of closed loop, compare, the reaction of this kinetic control has improved the efficiency of cyclization greatly, and has avoided to a certain extent the residual of simple linear polymer.But the lactide monomers that this polymerization process is used and N-heterocycle carbine class catalyzer cost are higher, its synthesis technique is also comparatively complicated.
Summary of the invention
The invention provides a kind of preparation method of annular aliphatic polyester, its polymerization process adopted is the phase-transfer catalysis polymerization in the solid-liquid two-phase, obtained the annular aliphatic polyester of high yield under higher reaction density, greatly improve the efficiency of cyclization, avoided traditional high weak solution method to prepare the solvent waste problem of cyclic polymer.
Technical scheme of the present invention is: at first in the solid-liquid two-phase, synthesize the polymerisate that contains high yield annular aliphatic polyester, then remove simple linear polymer by the method for underpressure distillation, thereby obtain highly purified annular aliphatic polyester.Specific embodiments is as follows:
(1) polymerization, 2-bromine carboxylate salt is placed in to organic solvent, and add the phase-transfer catalyst of 2-bromine carboxylate salt 0～30% mol ratio, reaction times is not less than 3 hours, reaction mixture is utilized to ether and water extraction, get ether layer, and use anhydrous magnesium sulfate drying, after filtering, organic solvent is removed in evaporation;
(2) purifying adds the stannous octoate of 0～10% mol ratio in polymerization process in the product of gained, under vacuum condition, progressively be warming up to 150～230 ℃ from 100 ℃, distills 15～24 hours.
In aforesaid polymerization process, monomer 2-bromine carboxylate salt used is 2-bromoacetic acid potassium, 2-bromoacetic acid sodium, 2 bromopropionic acid potassium or 2 bromopropionic acid sodium.
Organic solvent used is chloroform, methylene dichloride, 1,2-ethylene dichloride, acetone, pimelinketone, tetrahydrofuran (THF), DMF, N,N-dimethylacetamide, toluene or acetonitrile.
Phase-transfer catalyst used is 18-hat-6,15-hat-5, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, polyethylene glycol 1500 or Macrogol 2000.
Effect of the present invention and benefit are under mild reaction conditions, utilize lower-cost monomer, can obtain high yield, highly purified cyclic polylactic acid and ring-type polyglycolic acid.The annular aliphatic polyester of gained can be applied to the living control polymerization field to prepare high-molecular aliphatic polyester as cyclic monomer, has potential economic benefit.
Embodiment
Describe specific embodiments of the invention in detail below in conjunction with technical scheme.
The present invention relates to a kind of preparation method of annular aliphatic polyester, it is characterized in that 2-bromine carboxylate salt is placed in to organic solvent, and add the phase-transfer catalyst of 2-bromine carboxylic acid potassium 0～30% molar weight, under 0～100 ℃ of condition, react 3～48 hours, reaction mixture is utilized to ether and water extraction, get ether layer and use anhydrous magnesium sulfate drying, after filtering, evaporation is except desolventizing.Then add the stannous octoate of 0～10% molar weight in the product of gained in polymerization process, under the reduced pressure of 10～15 mm Hg, progressively be warming up to 150～230 ℃, distill more than 15 hours.
Embodiment 1
The 18-of the 2 bromopropionic acid potassium of 1.90 g and 0.264 g hat-6 is added to 1 of 50 ml backflows, in the 2-ethylene dichloride, react 8 hours.Utilize ether and water extraction 3 times, get organic layer, spend the night with anhydrous magnesium sulfate drying.After filtration, the solvent in filtrate is removed in evaporation, obtains faint yellow transparent thick liquid.Wherein, the massfraction of cyclic polylactic acid is 16.7%.
Above-mentioned light yellow viscous liquid is placed in to 50 ml flasks, and adds the stannous octoate of 1% molar weight, first pass into nitrogen and vacuumize again under 100 ℃, repeatable operation 3 times.Then progressively be warming up to 150 ℃ under vacuum state, underpressure distillation 15 hours, obtain the faint yellow solid resistates, is cyclic polylactic acid, by nuclear-magnetism and flight time mass spectrum, characterizes, and its purity is greater than 99%.
Embodiment 2
In the chloroform that adds 50 ml to reflux the 18-of the 2-bromoacetic acid potassium of 1.76 g and 0.264 g hat-6, react 12 hours.Utilize ether and water extraction 3 times, get organic layer, spend the night with anhydrous magnesium sulfate drying.After filtration, the solvent in filtrate is removed in evaporation, obtains the transparent thick liquid of oyster white.Wherein, the massfraction of ring-type polyglycolic acid is 33.3%.
Above-mentioned light yellow viscous liquid is placed in to 50 ml flasks, and adds the stannous octoate of 1% molar weight, first pass into nitrogen and vacuumize again under 100 ℃, repeatable operation 3 times.Then progressively be warming up to 150 ℃ under vacuum state, underpressure distillation 20 hours, obtain the Off-white solid resistates, is the ring-type polyglycolic acid, by nuclear-magnetism and flight time mass spectrum, characterizes, and its purity is greater than 95.5 %.
Claims (2)
1. the preparation method of an annular aliphatic polyester is characterized in that concrete steps are as follows:
(1) polymerization, be placed in organic solvent by 2-bromine carboxylate salt, and add the phase-transfer catalyst of 2-bromine carboxylate salt 0～30% mol ratio, and the reaction times is not less than 3 hours, and reaction mixture is utilized to ether and water extraction; Get ether layer, and use anhydrous magnesium sulfate drying, after filtering, organic solvent is removed in evaporation;
(2) purifying, add the stannous octoate of 0～10% mol ratio in the product that step (1) is obtained, under vacuum condition, progressively be warming up to 150～230 ℃ from 100 ℃, distills 15～24 hours;
Described 2-bromine carboxylate salt is 2-bromoacetic acid potassium, 2-bromoacetic acid sodium, 2 bromopropionic acid potassium or 2 bromopropionic acid sodium;
Described phase-transfer catalyst is 18-hat-6,15-hat-5, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, polyethylene glycol 1500 or Macrogol 2000.
2. preparation method according to claim 1, is characterized in that, described organic solvent is chloroform, methylene dichloride, 1,2-ethylene dichloride, acetone, pimelinketone, tetrahydrofuran (THF), DMF, N,N-dimethylacetamide, toluene or acetonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210264737 CN102786673B (en) | 2012-07-27 | 2012-07-27 | Cyclic aliphatic polyester preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210264737 CN102786673B (en) | 2012-07-27 | 2012-07-27 | Cyclic aliphatic polyester preparation method |
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| CN102786673A CN102786673A (en) | 2012-11-21 |
| CN102786673B true CN102786673B (en) | 2013-12-25 |
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| CN 201210264737 Expired - Fee Related CN102786673B (en) | 2012-07-27 | 2012-07-27 | Cyclic aliphatic polyester preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113019124A (en) * | 2019-12-24 | 2021-06-25 | 天津膜天膜科技股份有限公司 | Membrane process for preparing and purifying cyclic polymers |
| CN115286778B (en) * | 2022-08-31 | 2023-04-07 | 天津大学 | Method for preparing polyester dihydric alcohol by reversible-inactivation ring-opening alternating copolymerization |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640910A (en) * | 2004-12-22 | 2005-07-20 | 华南理工大学 | Unsaturated polyester synthesizing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640910A (en) * | 2004-12-22 | 2005-07-20 | 华南理工大学 | Unsaturated polyester synthesizing method |
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| CN102786673A (en) | 2012-11-21 |
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Granted publication date: 20131225 Termination date: 20160727 |