CN102786673A - Cyclic aliphatic polyester preparation method - Google Patents
Cyclic aliphatic polyester preparation method Download PDFInfo
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- CN102786673A CN102786673A CN2012102647375A CN201210264737A CN102786673A CN 102786673 A CN102786673 A CN 102786673A CN 2012102647375 A CN2012102647375 A CN 2012102647375A CN 201210264737 A CN201210264737 A CN 201210264737A CN 102786673 A CN102786673 A CN 102786673A
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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 a class formation specific polymers, owing to there is not the constraint of end group, the structural unit on its molecular chain has identity property, and the polymer phase ratio with other topological frameworks has special physico-chemical property.Therefore, cyclic polymer is the problem that the researchist pays close attention to always.Cyclic polymer mainly obtains through intramolecular ring-closure reaction in the high dilute solution.According to ring-chain level theory, react in the solution under about 2 w/v % concentration, the cyclic polymer productive rate that obtains is the highest.Therefore, it is lower usually to utilize technology of closed loop to prepare the efficient of cyclic polymer, and is 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 with tradition ring-chain level theory is under any concentration, as long as the suitable feed ratio of regulating monomer and initiator can pass through kinetic control, to obtain being mainly the polymerisate of ring.Compare with technology of closed loop, the reaction of this kinetic control has improved the efficient of cyclization greatly, and has avoided the residual of simple linear polymer to a certain extent.But lactide monomers that this polymerization method is used and N-heterocycle carbine class catalyzer cost are higher, and 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 method that adopts is the phase-transfer catalysis polymerization of solid-liquid two in mutually; Under higher reaction density, obtained the annular aliphatic polyester of high yield; Improve the efficient of cyclization greatly, avoided traditional high weak solution method to prepare the solvent waste problem of cyclic polymer.
Technical scheme of the present invention is: at first solid-liquid two mutually in the synthetic polymerisate that contains high yield annular aliphatic polyester, remove simple linear polymer through the method for underpressure distillation again, thereby obtain highly purified annular aliphatic polyester.Specific embodiments is following:
(1) polymerization; 2-bromine carboxylate salt is placed organic solvent, and add the phase-transfer catalyst of 2-bromine carboxylate salt 0～30% mol ratio, the reaction times is not less than 3 hours; Reaction mixture is utilized ether and water extraction; Get ether layer, and use anhydrous magnesium sulfate drying, filter the back evaporation and remove organic solvent;
(2) purifying adds the stannous octoate of 0～10% mol ratio in the product of gained in polymerization process, under vacuum condition, progressively be warming up to 150～230 ℃ from 100 ℃, distills 15～24 hours.
In the aforesaid polymerization process, used monomer 2-bromine carboxylate salt is 2-bromoacetic acid potassium, 2-bromoacetic acid sodium, 2 bromopropionic acid potassium or 2 bromopropionic acid sodium.
Used organic solvent is chloroform, methylene dichloride, 1,2-ethylene dichloride, acetone, pimelinketone, THF, N, dinethylformamide, DMAC N,N, toluene or acetonitrile.
Used phase-transfer catalyst is 18-hat-6,15-hat-5, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, PEG 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 ring-type POLYACTIC ACID and ring-type Sodium bromoacetate homopolymer, SRU.The annular aliphatic polyester of gained can be applied to the living control polymerization field with the preparation high-molecular aliphatic polyester as cyclic monomer, has the potential economic benefit.
Embodiment
Be described in detail specific embodiment of the present invention 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 organic solvent, and add the phase-transfer catalyst of 2-bromine carboxylic acid potassium 0～30% molar weight, under 0～100 ℃ of condition; Reacted 3～48 hours; Reaction mixture is utilized ether and water extraction, get ether layer and use anhydrous magnesium sulfate drying, evaporation removes and desolvates after filtering.In polymerization process, add the stannous octoate of 0～10% molar weight then in the product of gained, under the reduced pressure of 10～15 mm Hg, progressively be warming up to 150～230 ℃, distillation is more than 15 hours.
Embodiment 1
The 2 bromopropionic acid potassium of 1.90 g and the 18-hat-6 of 0.264 g are added 1 of 50 ml backflow, in the 2-ethylene dichloride, reacted 8 hours.Utilize ether and water extraction 3 times, get organic layer, spend the night with anhydrous magnesium sulfate drying.After the filtration, the solvent in the filtrating is removed in evaporation, obtains faint yellow transparent thick liquid.Wherein, the massfraction of ring-type POLYACTIC ACID is 16.7%.
Above-mentioned light yellow viscous liquid is placed 50 ml flasks, and add the stannous octoate of 1% molar weight, feed nitrogen down earlier at 100 ℃ and vacuumize repeatable operation 3 times again.Under vacuum state, progressively be warming up to 150 ℃ then, underpressure distillation 15 hours obtains the faint yellow solid resistates, is the ring-type POLYACTIC ACID, characterizes through nuclear-magnetism and flight time mass spectrum, and its purity is greater than 99%.
Embodiment 2
The 2-bromoacetic acid potassium of 1.76 g and the 18-hat-6 of 0.264 g are added in the chloroform of 50 ml backflow, reacted 12 hours.Utilize ether and water extraction 3 times, get organic layer, spend the night with anhydrous magnesium sulfate drying.After the filtration, the solvent in the filtrating is removed in evaporation, obtains the transparent thick liquid of oyster white.Wherein, the massfraction of ring-type Sodium bromoacetate homopolymer, SRU is 33.3%.
Above-mentioned light yellow viscous liquid is placed 50 ml flasks, and add the stannous octoate of 1% molar weight, feed nitrogen down earlier at 100 ℃ and vacuumize repeatable operation 3 times again.Under vacuum state, progressively be warming up to 150 ℃ then, underpressure distillation 20 hours obtains the Off-white solid resistates, is the ring-type Sodium bromoacetate homopolymer, SRU, characterizes through nuclear-magnetism and flight time mass spectrum, and its purity is greater than 95.5 %.
Claims (5)
1. the preparation method of an annular aliphatic polyester is characterized in that concrete steps are following:
(1) polymerization places organic solvent with 2-bromine carboxylate salt, and adds 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 ether and water extraction; Get ether layer, and use anhydrous magnesium sulfate drying, filter the back evaporation and remove organic solvent;
(2) purifying adds 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.
2. preparation method according to claim 1 is characterized in that, described 2-bromine carboxylate salt is 2-bromoacetic acid potassium, 2-bromoacetic acid sodium, 2 bromopropionic acid potassium or 2 bromopropionic acid sodium.
3. preparation method according to claim 1 and 2; It is characterized in that described organic solvent is chloroform, methylene dichloride, 1,2-ethylene dichloride, acetone, pimelinketone, THF, N; Dinethylformamide, DMAC N,N, toluene or acetonitrile.
4. preparation method according to claim 1 and 2; It is characterized in that described phase-transfer catalyst is 18-hat-6,15-hat-5, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, PEG 400, Polyethylene Glycol-600, polyethylene glycol 1500 or Macrogol 2000.
5. preparation method according to claim 3; It is characterized in that described phase-transfer catalyst is 18-hat-6,15-hat-5, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, PEG 400, Polyethylene Glycol-600, polyethylene glycol 1500 or Macrogol 2000.
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| CN 201210264737 CN102786673B (en) | 2012-07-27 | 2012-07-27 | Cyclic aliphatic polyester preparation method |
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| CN 201210264737 CN102786673B (en) | 2012-07-27 | 2012-07-27 | Cyclic aliphatic polyester preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN115286778A (en) * | 2022-08-31 | 2022-11-04 | 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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Patent 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN115286778A (en) * | 2022-08-31 | 2022-11-04 | 天津大学 | Method for preparing polyester dihydric alcohol by reversible-inactivation ring-opening alternating copolymerization |
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| CN102786673B (en) | 2013-12-25 |
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Granted publication date: 20131225 Termination date: 20160727 |