CN108503803B - A method of poly- γ-fourth lactones is prepared using urea/alkoxide - Google Patents
A method of poly- γ-fourth lactones is prepared using urea/alkoxide Download PDFInfo
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- CN108503803B CN108503803B CN201810289807.XA CN201810289807A CN108503803B CN 108503803 B CN108503803 B CN 108503803B CN 201810289807 A CN201810289807 A CN 201810289807A CN 108503803 B CN108503803 B CN 108503803B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Poly- γ-fourth lactones method is prepared using urea/alkoxide the invention discloses a kind of.The following steps are included: catalyst system and γ-fourth lactones are mixed, ring-opening polymerisation is carried out under conditions of anhydrous and oxygen-free, is used sour quenching reaction after reaction, is obtained poly- fourth lactones after precipitating；The catalyst system is the mixture of urea and alkoxide, shown in the structural formula of urea such as following formula (Ι).R, R ' group are aliphatic group, phenyl or naphthenic base.Catalyst system used in the present invention has been commercialized, cheap, has very high catalytic activity to poly- γ-fourth lactones of preparation high molecular weight, chemical catalysis method large scale preparation polyphosphazene polymer γ-fourth lactones blank can not be used by having filled up.
Description
Technical field
The present invention relates to polymeric material fields, specifically, being related to a kind of urea/alkoxide catalyst γ-fourth lactones open loop
The method of polymerization.
Background technique
Aliphatic polyester is drawn on packaging material and biomedical applications due to its biocompatibility and biodegradability
Play very big concern.Polyester can be degraded in human body by the hydrolysis of ester bond on polymer backbone, be participated in normal new old
Metabolism.So they are widely used in drug release, degradable suture and organizational project.
The polyester for preparing controllable molecular weight at present is generally obtained by corresponding annular lactone or lactide ring-opening polymerisation.Wherein
γ-fourth lactones can be prepared by the biomass succinic acid that yield ranks the first, so the relatively other annular lactones of price
Or lactide is cheap many.But since the ring strain of its five-membered ring structure is very low, the controllable ring-opening polymerisation of γ-fourth lactones has very
Big challenge.Until this 2 years, synthesize high score at low temperature with rare earth metal complex and super base organic catalytic system
Poly- γ-fourth lactones of son.But rare earth metal complex and super basic catalyst, there is structure is complicated, preparation is difficult, at high cost
And the disadvantage that property is unstable, so the catalyst system of exploitation simple cheap is large scale preparation high-molecular-weight poly γ-fourth lactones
Essential step.
Thiocarbamide and urea are to pay close attention to more organic catalyst recently, need alcohols/organic base or alkoxide as co-catalysis
Agent all has greater activity to annular lactone and lactide.Most urea structure and alkoxide have all been commercialized, and price is just
Preferably, it can be found by the type of change urea and alkoxide to γ-highest catalyst system of fourth lactones ring-opening polymerisation activity, and
There is the possibility of further industrialization.
Summary of the invention
It is an object of the invention to for it is existing prepare poly- γ-fourth lactones there are the shortcomings that, a kind of utilization is provided and novel is urged
Change system, poly- γ-fourth lactones method of large scale preparation high molecular weight, this method is cheap, is easy large-scale production.
Above-mentioned purpose of the invention is achieved by following scheme:
A method of poly- γ-fourth lactones is prepared using urea/alkoxide, comprising the following steps: by catalyst system and γ-Ding Nei
Rouge mixing, carries out ring-opening polymerisation under conditions of anhydrous and oxygen-free, uses sour quenching reaction after reaction, obtains in poly- fourth after precipitating
Rouge；The catalyst system is the mixture of urea and alkoxide, shown in the structural formula of urea such as following formula (Ι):
R, R ' group are aliphatic group, phenyl or naphthenic base.
Preferably, in above-mentioned preparation method: the alkoxide be alkali metal alcoholates, alkali metal be lithium, sodium or potassium,
Alcohol is methanol, ethyl alcohol or Bian alcohol.
Preferably, in above-mentioned preparation method: the molar ratio of urea and alkoxide is 1-10:1.
Preferably, in above-mentioned preparation method: γ-fourth lactones and the molar ratio for urging system are 500-10000:
1.
Preferably, in above-mentioned preparation method: adding solvent when polymerization, the solvent is tetrahydrofuran, toluene
Or methylene chloride.
Preferably, in above-mentioned preparation method: the reaction temperature of polymerization is -60~0 DEG C, reaction time 1-
12h。
Preferably, in above-mentioned preparation method: obtained poly- γ-fourth lactones molecular weight is 1000-70000.
Compared with prior art, the invention has the following beneficial effects:
1, γ-fourth lactones can be prepared by the biomass succinic acid that yield ranks the first, so price is with respect to other
Annular lactone or lactide it is cheap many.So being had by poly- γ-fourth lactones that γ-fourth lactones ring-opening polymerisation obtains very big
Market potential.
2, γ-fourth lactones due to the ring strain of five-membered ring structure it is low, controllable ring-opening polymerisation have very big challenge.Directly
To this 2 years, synthesize high molecular poly- γ-Ding Nei at low temperature with rare earth metal complex and super base organic catalytic system
Rouge.But rare earth metal complex and super basic catalyst, there is structure is complicated, preparation is difficult, and at high cost and property is unstable
Disadvantage, and urea/alkoxide catalyst architecture is simple, and has been commercialized, it is cheap.
3, the ring-opening polymerisation of the p- fourth lactones of urea/alkoxide catalyst system is highly active, and conversion ratio is reachable in a short time
To 95%, most urea structure and alkoxide have all been commercialized, therefore can be found pair by changing the type of urea and alkoxide
γ-highest the catalyst system of fourth lactones ring-opening polymerisation activity, there is the possibility of further industrialization.
4, alkali metal alcoholates are not easy to remain in the polymer, and its cytotoxicity very little, are conducive to poly- γ-fourth lactones and exist
Application in biomedicine.
Specific embodiment
The present invention can be explained further and illustrate in conjunction with following specific embodiments, but specific embodiment is not to the present invention
There is any type of restriction.
Using Schlenk technology, catalyst system and γ-fourth lactones or solvent are quantitatively put into flask, at room temperature after
After mixing evenly, it is placed into the constant temperature low-temp reaction bath set, starting stirring, starts polymerization instead after reaching assigned temperature
It answers.After reacting 1-12h, the chloroformic solution quenching reaction of acid is added in polymeric reaction temperature -60~0 DEG C, with methanol extraction product,
Obtained polymer is poly- γ-fourth lactones, is dried under vacuum to constant weight at room temperature, and then sampling carries out dependency structure and performance
Test.
Embodiment 1~12 provides in above-mentioned preparation method, uses different urea structure and alkoxide as catalyst, Yi Ji
Poly- γ-fourth lactones is prepared under the parameters such as different catalyst/γ-fourth lactones molar ratio, differential responses condition, specifically such as 1 institute of table
Show, while structural analysis test is carried out to the poly- γ of the preparation gained of embodiment 1~12-fourth lactones material, the results are shown in Table 1.
The response parameter and product analysis of each embodiment of table 1
Urea structure U1~U4 in table 1 is as follows:
Examples 1 to 8 changes alkoxide type and urea structure, to γ-fourth lactones ring-opening polymerisation activity and prepares poly- γ-
The molecular weight of fourth lactones has larger impact.Embodiment 9~15 optimizes reaction condition and catalysis using the highest U2 urea structure of activity
Agent/monomer ratio can prepare poly- γ-fourth lactones of super high molecular weight.
Claims (6)
1. a kind of prepare poly- γ-fourth lactones method using urea/alkoxide, feature is the following steps are included: by catalyst system and γ-
The mixing of fourth lactones, carries out ring-opening polymerisation under conditions of anhydrous and oxygen-free, uses sour quenching reaction after reaction, is gathered after precipitating
Fourth lactones；The catalyst system is the mixture of urea and alkoxide, shown in the structural formula of urea such as following formula (Ι):
R, R ' group are aliphatic group or phenyl.
2. preparation method according to claim 1, it is characterized in that: the alkoxide is alkali metal alcoholates, alkali metal is lithium, sodium
Or potassium, alcohol are methanol, ethyl alcohol or Bian alcohol.
3. preparation method according to claim 1 or 2, it is characterized in that: the molar ratio of urea and alkoxide is 1-10:1.
4. preparation method according to claim 1, it is characterized in that: γ-fourth lactones and the molar ratio for urging system are 500-
10000:1.
5. preparation method according to claim 1, it is characterized in that: add solvent when polymerization, the solvent be tetrahydrofuran,
Toluene or methylene chloride.
6. preparation method according to claim 1, it is characterised in that: the reaction temperature of polymerization is -60~0 DEG C, the reaction time
For 1-12h.
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| CN109627429B (en) * | 2018-10-23 | 2024-04-16 | 青岛博远高分子材料研究院有限公司 | Preparation method of high molecular weight poly (gamma-butyrolactone) |
| CN110283464A (en) * | 2019-07-10 | 2019-09-27 | 佛山市巴盛诺新材料科技有限公司 | A kind of high-barrier aliphatic polyester-polycarbonate compound film material and preparation method thereof |
| CN110227390A (en) * | 2019-07-10 | 2019-09-13 | 佛山市巴盛诺新材料科技有限公司 | A kind of device and method preparing poly- gamma-butyrolacton using urea and alkoxide |
Citations (2)
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|---|---|---|---|---|
| CN1687176A (en) * | 2005-04-15 | 2005-10-26 | 浙江大学 | Method for preparing aliphatic polyester |
| CN105367763A (en) * | 2015-12-14 | 2016-03-02 | 南京工业大学 | Method for preparing polyester by ring opening polymerization |
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| JP3379841B2 (en) * | 1994-10-28 | 2003-02-24 | 高砂香料工業株式会社 | Block copolymerized poly (ester-carbonate) and method for producing the same |
| US6423850B1 (en) * | 1999-06-18 | 2002-07-23 | E.I. Du Pont De Nemours And Company | Preparation and use of gamma-butyrolactones as cross-linking agents |
| JP3648550B2 (en) * | 2002-03-05 | 2005-05-18 | 独立行政法人産業技術総合研究所 | Process for producing polyγ-butyrolactone using metal complex catalyst |
| FR2893325B1 (en) * | 2005-11-15 | 2010-04-02 | Arkema | PROCESS FOR THE PREPARATION OF POLYHYDROXYALKANOATES POLYMERS THUS OBTAINED, COMPOSITIONS COMPRISING THEM AND USES THEREOF |
| CN102643301B (en) * | 2011-02-22 | 2014-12-24 | 中国石油天然气股份有限公司 | Alkoxy aluminum complex, and preparation and application thereof |
| CN107827915B (en) * | 2017-11-23 | 2020-04-17 | 吉林大学 | Amine bisphenol tetradentate ligand trivalent rare earth metal complex and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687176A (en) * | 2005-04-15 | 2005-10-26 | 浙江大学 | Method for preparing aliphatic polyester |
| CN105367763A (en) * | 2015-12-14 | 2016-03-02 | 南京工业大学 | Method for preparing polyester by ring opening polymerization |
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