CN110396189A - A kind of method of organic catalysis synthesis of polyester amide material - Google Patents
A kind of method of organic catalysis synthesis of polyester amide material Download PDFInfo
- Publication number
- CN110396189A CN110396189A CN201910513815.2A CN201910513815A CN110396189A CN 110396189 A CN110396189 A CN 110396189A CN 201910513815 A CN201910513815 A CN 201910513815A CN 110396189 A CN110396189 A CN 110396189A
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- Prior art keywords
- polyester amide
- amide material
- synthesis
- organic catalysis
- catalysis synthesis
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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
-
- 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
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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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)
- Polyamides (AREA)
Abstract
The present invention provides a kind of methods of organic catalysis synthesis of polyester amide material, in the presence of phosphazene catalyst, Formulas I compound represented reacted with Formula II compound represented to get.The advantages of present invention is using phosphonitrile organic catalyst, synthesis of polyester amide material under the conditions of one kettle way, it is made to integrate polyester and polyamide, preparation method is simple, low in cost.
Description
Technical field
The invention belongs to synthesis of polyester amide Material Field, in particular to a kind of organic catalysis synthesis of polyester amide material
Method.
Background technique
Polyamide (PA is commonly called as nylon) is with excellent mechanical property, lubricity and rub resistance are good, fusing point is high, to change
The advantages that learning reagent (in addition to strong acid, highly basic) stable, heat-resisting good, electrical insulating property and weatherability is that yield is maximum in the world, uses
The most wide engineering plastics in way, thousand auto industrys that are widely used, electronic apparatus industry, transportation, machine industry,
The fields such as wire and cable communications industry, packaging and articles for daily use.However, polyamide that there is also impact strengths under dry state or low temperature is low,
Opaque, the disadvantages of dissolubility is poor, which has limited its applications.
Aliphatic polyester includes polylactic acid (PLA), polyglycolide (PGA), polycaprolactone (PCL), polyhydroxyalkanoate
(PHA) and its copolymer, be a kind of high molecular material with good physical and mechanical property and processing performance, can biology drop
Solution is eventually converted into carbon dioxide and water, and the fields such as daily plastic, fiber and packaging material are widely applied；In Human Physiology ring
In border it is also degradable and absorb, have good biocompatibility, because and be widely used in medical field, such as surgical implantation
Material, slow releasing carrier of medication and tissue engineering bracket etc..Many researchers are dedicated to design and synthesis using aliphatic polyester as base
The functional material of plinth, control its molecular weight, and molecular weight distribution, composition and end of the chain function base reach different application purposes.It can
The aliphatic polyester of control usually passes through cyclic annular esters monomer to the metallic catalyst catalysis based on Al, Zn, Ti, Sn and Ca
It polymerize and obtains.
These methods can synthesize the aliphatic polyester or copolyesters of various different structures, performance, to meet different purposes
Requirement.But since they have cytotoxicity, and metal residual is had to organism nocuousness, the polyester material of synthesis is uncomfortable
Together in medical material, while polymerization process needs heating and carrying out under reduced pressure, and the reaction time is long, point of product
Son amount is difficult to be effectively controlled.And for being catalyzed the polymerization with functional group monomer, high reaction temperature is easy to draw
Many side reactions are played, the structure of function monomer are destroyed, or even it is made to lose functional group, so finding metal-free biology
Highly-safe catalyst is explored and can be effectively controlled molecular weight and the simple synthetic method of operating procedure, is that medical polyesters are closed
At field problem anxious to be resolved.
It is a kind of novel biodegradable polymer that aliphatic poly, which drinks amide (PEA), compared with aliphatic polyester,
Due to introducing amide group, hydrogen bond is formed between amide group, makes polymer that there is better mechanical property and intensity, while ester
The presence of key assigns material good biodegradability again, makes it have broad application prospect.
Summary of the invention
In order to achieve the above objectives, the present invention provides a kind of method of organic catalysis synthesis of polyester amide material, step is such as
Under: in the presence of phosphazene catalyst, Formulas I compound represented reacted with Formula II compound represented to get；Reaction equation
It is as follows:
As an improvement, 150~200 DEG C of reaction temperature, 30~90min of reaction time.
As an improvement, the dosage of the phosphazene catalyst is 1~5mol%.
As an improvement, the dosage of the benzoyl caprolactam is 1~5mol%.
The utility model has the advantages that the present invention uses phosphonitrile organic catalyst, synthesis of polyester amide material, makes it under the conditions of one kettle way
The advantages of comprehensive polyester and polyamide, preparation method is simple, low in cost.
Specific embodiment
With reference to embodiment, the embodiment of the present invention is furthur described in detail.Following embodiment is used for
Illustrate the present invention, but is not intended to limit the scope of the invention.
Embodiment 1
Synthesis for poly- (epsilon-caprolactams), by 3g epsilon-caprolactams and 1mol% catalyst phosphonitrile in glove box
And the benzoyl caprolactam mixing of 1mol%, mixture is mixed into the ampoule that flame dry is passed through in magnetic stir bar addition
In bottle.Synthesis for poly- (L- lactide) mixes 3g L- lactide and 1mol% catalyst phosphonitrile according to identical step
Conjunction is put into ampoule bottle.The reaction vessel (ampoule bottle) of sealing is placed in 180 DEG C of pre- hot oil bath.After reacting 60min, use
Liquid nitrogen, which is quickly cooled down, terminates reaction.
Poly- (epsilon-caprolactams) purify 48 hours in THF；Poly- (L- lactide) is dissolved in THF and in H2It sinks in O
It forms sediment.All samples are dried in vacuo 24 hours at 40 DEG C.
Embodiment 2
For the bulk copolymerization of epsilon-caprolactams and L- lactide, by 3g epsilon-caprolactams, 3g L- in glove box
Lactide is mixed with the benzoyl caprolactam of 1mol% catalyst phosphonitrile and 1mol%, and mixture is mixed magnetic agitation
Son is added in the ampoule bottle by flame dry and the reaction vessel (ampoule bottle) of sealing is placed in 180 DEG C of pre- hot oil bath.
After reacting 60min, it is quickly cooled down with liquid nitrogen and terminates reaction.
It purifies and there is a high proportion of copolymer in epsilon-caprolactams by being washed in THF, and will have high L- third
The copolymer of glycolide ratios is dissolved in THF and in H2It is precipitated in O.Before characterization, by all copolymers at 40 DEG C vacuum
It is 24 hours dry.
Embodiment 3
For the bulk copolymerization of epsilon-caprolactams and L- lactide, by 3g epsilon-caprolactams, 3g L- in glove box
Lactide is mixed with the benzoyl caprolactam of 5mol% catalyst phosphonitrile and 2.5mol%, and mixture is mixed magnetic force and is stirred
Sub- addition is mixed by the reaction vessel (ampoule bottle) of sealing to be placed in 150 DEG C of pre- hot oil bath in the ampoule bottle of flame dry
In.After reacting 90min, it is quickly cooled down with liquid nitrogen and terminates reaction.
It purifies and there is a high proportion of copolymer in epsilon-caprolactams by being washed in THF, and will have high L- third
The copolymer of glycolide ratios is dissolved in THF and in H2It is precipitated in O.Before characterization, by all copolymers at 40 DEG C vacuum
It is 24 hours dry.
Embodiment 4
For the bulk copolymerization of epsilon-caprolactams and L- lactide, by 3g epsilon-caprolactams, 3g L- in glove box
Lactide is mixed with the benzoyl caprolactam of 2.5mol% catalyst phosphonitrile and 5mol%, and mixture is mixed magnetic force and is stirred
Sub- addition is mixed by the reaction vessel (ampoule bottle) of sealing to be placed in 200 DEG C of pre- hot oil bath in the ampoule bottle of flame dry
In.After reacting 30min, it is quickly cooled down with liquid nitrogen and terminates reaction.
It purifies and there is a high proportion of copolymer in epsilon-caprolactams by being washed in THF, and will have high L- third
The copolymer of glycolide ratios is dissolved in THF and in H2It is precipitated in O.Before characterization, by all copolymers at 40 DEG C vacuum
It is 24 hours dry.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (4)
1. a kind of method of organic catalysis synthesis of polyester amide material, which is characterized in that in phosphazene catalyst and initiator benzene
In the presence of formyl caprolactam, Formulas I compound represented reacted with Formula II compound represented to get；Reaction equation is as follows:
2. a kind of method of organic catalysis synthesis of polyester amide material according to claim 1, which is characterized in that reaction temperature
150~200 DEG C of degree, 30~90min of reaction time.
3. a kind of method of organic catalysis synthesis of polyester amide material according to claim 1, which is characterized in that the phosphorus
The dosage of nitrile catalyst is 1~5mol%.
4. a kind of method of organic catalysis synthesis of polyester amide material according to claim 1, which is characterized in that the benzene
The dosage of formyl caprolactam is 1~5mol%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910513815.2A CN110396189A (en) | 2019-06-14 | 2019-06-14 | A kind of method of organic catalysis synthesis of polyester amide material |
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| CN201910513815.2A CN110396189A (en) | 2019-06-14 | 2019-06-14 | A kind of method of organic catalysis synthesis of polyester amide material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321821A (en) * | 2020-10-29 | 2021-02-05 | 南京先进生物材料与过程装备研究院有限公司 | Recyclable polyester polyamide and preparation method thereof |
| CN113024781A (en) * | 2021-03-03 | 2021-06-25 | 深圳市鑫元素新材料科技有限公司 | Preparation method of cyclic polylactone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174128A (en) * | 2011-01-21 | 2011-09-07 | 华南理工大学 | Polymerization with strong alkali phosphazene compound as catalyst |
| CN105646876A (en) * | 2016-04-08 | 2016-06-08 | 南京工业大学 | Method for preparing polyesteramide |
| CN108467411A (en) * | 2018-04-09 | 2018-08-31 | 青岛科技大学 | A kind of method of phosphonitrile and the catalysis controllable ring-opening polymerisation of cyclic ester monomers of urea binary system |
-
2019
- 2019-06-14 CN CN201910513815.2A patent/CN110396189A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174128A (en) * | 2011-01-21 | 2011-09-07 | 华南理工大学 | Polymerization with strong alkali phosphazene compound as catalyst |
| CN105646876A (en) * | 2016-04-08 | 2016-06-08 | 南京工业大学 | Method for preparing polyesteramide |
| CN108467411A (en) * | 2018-04-09 | 2018-08-31 | 青岛科技大学 | A kind of method of phosphonitrile and the catalysis controllable ring-opening polymerisation of cyclic ester monomers of urea binary system |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321821A (en) * | 2020-10-29 | 2021-02-05 | 南京先进生物材料与过程装备研究院有限公司 | Recyclable polyester polyamide and preparation method thereof |
| CN113024781A (en) * | 2021-03-03 | 2021-06-25 | 深圳市鑫元素新材料科技有限公司 | Preparation method of cyclic polylactone |
| CN113024781B (en) * | 2021-03-03 | 2022-01-04 | 深圳市鑫元素新材料科技有限公司 | Preparation method of cyclic polylactone |
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