CN106349467A - Preparation method of easy-to-degrade adipic acid polyethylene glycol polyester - Google Patents
Preparation method of easy-to-degrade adipic acid polyethylene glycol polyester Download PDFInfo
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- CN106349467A CN106349467A CN201610792209.5A CN201610792209A CN106349467A CN 106349467 A CN106349467 A CN 106349467A CN 201610792209 A CN201610792209 A CN 201610792209A CN 106349467 A CN106349467 A CN 106349467A
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- Prior art keywords
- polyethylene glycol
- adipic acid
- preparation
- polyester
- acid
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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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
-
- 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
- C08G2230/00—Compositions for preparing biodegradable polymers
Abstract
The invention relates to a preparation method of easy-to-degrade adipic acid polyethylene glycol polyester and belongs to the technical field of ester compounds in organic chemistry. The preparation method includes: adding part of polyethylene glycol into adipic acid, stirring, adding a catalyst, and raising temperature; removing generated water in a vacuum condition, holding temperature of 120-140 DEG C for reaction for 2-5h, lowering temperature, adding remaining polyethylene glycol, and stirring at 70-80 DEG C for 0.5-2.5h to obtain a finished product. When being applied to adipic acid polyethylene glycol polyester, the preparation method has the advantages that the process is reasonable, operation is simple, and the product is stable, short in reaction period and shallow in color.
Description
Technical field
The present invention relates to a kind of preparation method of degradable type adipic acid polyethylene glycol polyester, belong to esters in organic chemistry
Technical field of compound preparation.
Background technology
Adipic acid polyethylene glycol polyester is that a kind of polymer is used as to spread lubricant in Metal Cutting, uses rubber production
Make releasing agent, have well smooth, dispersion, isolating film as demolding film, have good environment-friendly type, used than independent Polyethylene Glycol
Preferably stripping result.Due to the unique properties of oils surfactant, of many uses, add oil and fat product low toxicity itself,
Low irritant, therefore developmental research oils surfactant are increasingly subject to people's attention.Improve surfactant simultaneously
Biological degradability be the important guarantee realizing ecological environment good circulation.
The synthesis report of adipic acid polyethylene glycol polyester has much at present.
Li Xianhong has delivered " synthesis of PEG-polyadipic anhydride " in chemistry world, with Polyethylene Glycol, acetic anhydride,
Adipic acid synthesizes a kind of new medical macromolecular material polyethylene glycol-polyadipate acid anhydride.Wang Ying has delivered " poly- on Chemical Engineering Technology
The synthesis of hexanediol glycol ester " spent glycol does the product of raw material, and ethylene glycol has loss, and molecular weight is difficult to do height.
10PE27, PEG-polyadipic anhydride, adipic acid polyethylene glycol polyester is all a kind of polymerization
Thing, complex structure, biological degradability will hardly possible with respect to other esters products and alkyl ether.How to improve the life of surfactant
The research of thing degradability is significant.
Based on this, make the application.
Content of the invention
For the above-mentioned technical problem of prior art, the present invention provides a kind of adipic acid Polyethylene Glycol of easily biological-degradable to gather
The preparation method of ester, this preparation method, rational technology, simple to operate, product are stable, of light color, easily biological-degradable, have preferably
The advantages of serviceability.
For reaching above-mentioned purpose, the technical solution used in the present invention is as follows:
A kind of preparation method of adipic acid polyethylene glycol polyester, adds partly poly- second two to being added with adipic acid flask
Alcohol, stirring is lower to add catalyst, and (the too violent Polyethylene Glycol of fast response that heats up follows water to take out of for slow intensification；3-4 hour is warmed up to
120 DEG C is optimal) remove the water generating in time under conditions of vacuum, it is incubated 2-5 under the reaction condition of temperature 120-140 DEG C
After hour, it is cooled to 80 DEG C, adds remaining Polyethylene Glycol, stir 0.5-2.5 hour at 70-80 DEG C, obtain slightly yellow
Bright product.
Further, as preferred:
The molecular weight 200-600 of described Polyethylene Glycol, and the mol ratio of adipic acid and total Polyethylene Glycol is 1:1-2.
Described catalyst is the mixture of p-methyl benzenesulfonic acid and phosphorous acid, and the weight of p-methyl benzenesulfonic acid and phosphorous acid ratio is for 1:
0.3-1.
The addition of described composite catalyst is the 0.1-0.9% of adipic acid and Polyethylene Glycol gross weight.
The weight of the Polyethylene Glycol that described second adds is the 15-50% of the weight of total Polyethylene Glycol.
The acquisition modes of degradation rate: take the aqueous solution 50ml that product design is 5% to be loaded in 250ml conical flask, add
25% connect bacterium amount, at 30 DEG C shaking table process 7h, survey cod, calculate degradation rate (%).
Dehydration esterification reaction equation in above-mentioned preparation method is:
Wherein, m:n=1:1-2.
The preparation method of adipic acid polyethylene glycol polyester of the present invention, with adipic acid and Polyethylene Glycol as raw material, to toluene
Carry out esterification under the catalytic action of sulfonic acid and phosphorous acid, control esterification yield, add remaining Polyethylene Glycol to stir, system
Obtain adipic acid polyethylene glycol polyester.
Beneficial effects of the present invention are as follows:
1) the adipic acid polyethylene glycol polyester being obtained by the present invention, has excellent smooth diffusibility, isolating film as demolding film effect
Good it is often more important that easily biological-degradable.
2) present invention is the process is simple using the dehydration esterification reaction under acidic catalyst effect, can effective reduces cost,
Improve yield.Improve production efficiency, product appearance is improved.
3) reaction condition of the present invention is gentle, and adopted equipment is simple, so that equipment investment and energy consumption are more saved.
4) preparation technology of the present invention does not almost pollute to environment, meets current environmental requirement, is worthy to be popularized.
Whole reaction is allocated as three steps and carries out: add part Polyethylene Glycol to carry out primary response in adipic acid flask, and should
The water removing that in reaction, dehydration esterification is formed, then the continuation reaction that heats up, add in the adipic acid polyethylene glycol polyester synthesizing the most backward
Enter remaining Polyethylene Glycol, after adipic acid polyethylene glycol polyester and Polyethylene Glycol compound in proportion, the property that monomer has does not have
Change, but improve biological degradability.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
Polyethylene Glycol mean molecule quantity used in following embodiments is 200-600, limited by Zhejiang Real Madrid science and technology share
Company produces；Adipic acid is bought in Shanghai Pu along import and export corporation；Other raw materials, such as p-methyl benzenesulfonic acid, phosphorous acid can adopt
On market, conventional method is obtained, it would however also be possible to employ commercially available prod.
In the preparation method of the present embodiment, esterification equation is:
M:n=1:1-2.
The compounding method with adding while stirring adds remaining Polyethylene Glycol.
Embodiment 1
Add 1.3 grams of addition under the Polyethylene Glycol that 528 gram-molecular weights are 528 and the stirring of 146 g of adipic acid right in flask
Toluenesulfonic acid and the catalyst of 0.4 gram of phosphorous acid, are warmed up to 135 DEG C for 4 hours, vacuum -0.096mpa removes the water of generation in time,
After being incubated 3 hours under the reaction condition of temperature 135-140 DEG C, it is cooled to 80 DEG C, the Polyethylene Glycol of 264 grams of addition, 70-80 DEG C
Stirring 1 hour, obtains slightly yellow (color and luster is less than 50 platinum cobalt standards) transparent product. and the present embodiment has rational technology, operation
Simply, product is stable, and product has excellent smooth diffusion lubricity, and isolating film as demolding film effect is good, easily biological-degradable.
Take the aqueous solution 50ml that product design is 10% to be loaded in 250ml conical flask, add 25% connect bacterium amount, at 30 DEG C
Shaking table processes 5h, surveys cod, calculates degradation rate 58.2%.
Comparative example 1
As other conditions of embodiment 1, simply Polyethylene Glycol all disposably adds reaction, and same condition is measured
Degradation rate is 31.5%.Polyethylene Glycol adds after staying part cooling, and degradation rate 58.2% is apparently higher than the disposable fall adding
Solution rate 31.5%.
Embodiment 2
Add 1.3 grams of addition under the Polyethylene Glycol that 528 gram-molecular weights are 528 and the stirring of 146 g of adipic acid right in flask
Toluenesulfonic acid and the catalyst of 0.4 gram of phosphorous acid, are warmed up to 135 DEG C for 4 hours, vacuum -0.096mpa removes the water of generation in time,
After being incubated 3 hours under the reaction condition of temperature 135-140 DEG C, it is cooled to 80 DEG C, the Polyethylene Glycol of 422 grams of addition, 70-80 DEG C
Stirring 1 hour, obtains slightly yellow (color and luster is less than 50 platinum cobalt standards) transparent product. and the present embodiment has rational technology, operation
Simply, product is stable, and product has excellent smooth diffusion lubricity, and isolating film as demolding film effect is good, easily biological-degradable.
Take the aqueous solution 50ml that product design is 10% to be loaded in 250ml conical flask, add 25% connect bacterium amount, at 30 DEG C
Shaking table processes 5h, surveys cod, calculates degradation rate 67.8%.
Comparative example 2
As other conditions of embodiment 2, simply Polyethylene Glycol all disposably adds reaction, and same condition is measured
Degradation rate is 39.6%.Polyethylene Glycol adds after staying part cooling, and degradation rate 67.8% is apparently higher than the disposable fall adding
Solution rate 39.6%.
Embodiment 3
Add 1.0 grams of addition under the Polyethylene Glycol that 400 gram-molecular weights are 400 and the stirring of 146 g of adipic acid right in flask
Toluenesulfonic acid and the catalyst of 0.3 gram of phosphorous acid, slow intensification, it is warmed up within 3 hours 125 DEG C, vacuum -0.096mpa removes in time
The water generating, after being incubated 4 hours, is cooled to 80 DEG C under the reaction condition of temperature 125-130 DEG C, adds 200 grams of poly- second two
Alcohol, 70-80 DEG C is stirred 1 hour, obtains slightly yellow (color and luster is less than 50 platinum cobalt standards) transparent product. and the present embodiment has technique
Rationally, simple to operate, product is stable, and product has excellent smooth diffusion lubricity, and isolating film as demolding film effect is good, easily biological fall
Solution.
Take the aqueous solution 50ml that product design is 10% to be loaded in 250ml conical flask, add 25% connect bacterium amount, at 30 DEG C
Shaking table processes 5h, surveys cod, calculates degradation rate 56.5%.
Comparative example 3
As other conditions of embodiment 3, simply Polyethylene Glycol starts plus 480 grams of reactions, adds 120 grams after cooling,
Total amount keeps constant.It is 46.2% that same condition measures degradation rate.Polyethylene Glycol total amount is the same, and the amount adding after cooling is many
, the degradation rate 56.5% in same amount of time is apparently higher than the low degradation rate of addition 46.2%.
Embodiment 4
Add 0.5 gram of addition under the Polyethylene Glycol that 300 gram-molecular weights are 300 and the stirring of 146 g of adipic acid right in flask
Toluenesulfonic acid and the catalyst of 0.2 gram of phosphorous acid, slow intensification, it is warmed up within 3 hours 120 DEG C, vacuum -0.096mpa removes in time
The water generating, after being incubated 5 hours, is cooled to 80 DEG C under the reaction condition of temperature 120-125 DEG C, adds 200 grams of poly- second two
Alcohol, 70-80 DEG C is stirred 1.0 hours, obtains slightly yellow (color and luster is less than 50 platinum cobalt standards) transparent product. and the present embodiment has work
Rationally, simple to operate, product is stable, and product has excellent smooth diffusion lubricity, and isolating film as demolding film effect is good for skill, easily biological fall
Solution.
Take the aqueous solution 50ml that product design is 10% to be loaded in 250ml conical flask, add 25% connect bacterium amount, at 30 DEG C
Shaking table processes 5h, surveys cod, calculates degradation rate 60.3%.
Comparative example 4
As other conditions of embodiment 4, simply the molecular weight of Polyethylene Glycol is 450, and same condition measures degraded
Rate is 52.3%.The low degradation rate 60.3% in same amount of time of molecular weight polyethylene glycol is apparently higher than peg molecule
Measure high degradation rate 52.3%.
The preparation method of adipic acid polyethylene glycol polyester of the present invention, with adipic acid and Polyethylene Glycol as raw material, to toluene
Carry out esterification under the catalytic action of sulfonic acid and phosphorous acid, add remaining Polyethylene Glycol to stir, prepared adipic acid gathers
Polyglycol ester.The present invention is using the dehydration condensation under acidic catalyst effect, process is simple, can effectively reduce into
This, improve yield.Product biological degradability is improved, and serviceability is good.Reaction condition of the present invention is gentle, adopted equipment letter
Single, so that equipment investment and energy consumption are more saved.The adipic acid polyethylene glycol polyester being obtained by the present invention, has excellent putting down
Sliding diffusion lubricity, isolating film as demolding film effect good it is often more important that easily biological-degradable.The preparation technology of the present invention is to environment almost
Do not pollute, meet current environmental requirement, be worthy to be popularized.
Above content be preferred implementation with reference to the invention provided technical scheme is made detailed further
Describe in detail bright it is impossible to assert that the invention is embodied as being confined to these explanations above-mentioned, the affiliated technology for the invention
For the those of ordinary skill in field, without departing from the concept of the premise of the invention, some simple deductions can also be made
Or replace, all should be considered as belonging to the protection domain of the invention.
Claims (5)
1. a kind of preparation method of degradable type adipic acid polyethylene glycol polyester it is characterised in that: in adipic acid add part
Polyethylene Glycol, after stirring and adding catalyst, heats up；Then remove the water of generation under vacuum, be 120-140 in temperature
After insulation reaction 2-5 hour under conditions of DEG C, cooling, add remaining Polyethylene Glycol, stirring 0.5-2.5 is little at 70-80 DEG C
When, that is, obtain finished product.
2. as claimed in claim 1 a kind of preparation method of degradable type adipic acid polyethylene glycol polyester it is characterised in that: institute
State the molecular weight 200-600 of Polyethylene Glycol, and adipic acid is 1:1-2 with the mol ratio of total Polyethylene Glycol.
3. as claimed in claim 1 a kind of preparation method of degradable type adipic acid polyethylene glycol polyester it is characterised in that: institute
State the mixture that catalyst is p-methyl benzenesulfonic acid and phosphorous acid, the weight of p-methyl benzenesulfonic acid and phosphorous acid ratio is for 1:0.3-1.
4. the preparation method of a kind of degradable type adipic acid polyethylene glycol polyester as described in claim 1 or 3, its feature exists
In: the addition of described composite catalyst is the 0.1-0.9 % of adipic acid and Polyethylene Glycol gross weight.
5. as claimed in claim 1 a kind of preparation method of degradable type adipic acid polyethylene glycol polyester it is characterised in that: institute
State the Polyethylene Glycol of second addition weight be total Polyethylene Glycol weight 15-50%.
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| CN201610792209.5A CN106349467B (en) | 2016-08-31 | 2016-08-31 | A kind of preparation method of degradable type adipic acid polyethylene glycol polyester |
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| CN201610792209.5A CN106349467B (en) | 2016-08-31 | 2016-08-31 | A kind of preparation method of degradable type adipic acid polyethylene glycol polyester |
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| CN106349467B CN106349467B (en) | 2018-06-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159520A (en) * | 2020-09-29 | 2021-01-01 | 浙江皇马科技股份有限公司 | Preparation method of modified poly (ethylene glycol adipate) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087015A (en) * | 2012-12-19 | 2013-05-08 | 湖北葛店人福药用辅料有限责任公司 | Preparation method of sorbitan oleate servicing as medicinal auxiliary material |
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- 2016-08-31 CN CN201610792209.5A patent/CN106349467B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087015A (en) * | 2012-12-19 | 2013-05-08 | 湖北葛店人福药用辅料有限责任公司 | Preparation method of sorbitan oleate servicing as medicinal auxiliary material |
Non-Patent Citations (3)
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| 李先红等: "聚乙二醇-聚己二酸酐的合成", 《化学世界》 * |
| 李幸: "聚醚酯增塑剂的合成及在橡胶中应用研究", 《中国优秀硕士学位论文全文数据库（工程科技I辑）》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159520A (en) * | 2020-09-29 | 2021-01-01 | 浙江皇马科技股份有限公司 | Preparation method of modified poly (ethylene glycol adipate) |
| CN112159520B (en) * | 2020-09-29 | 2022-10-14 | 浙江皇马科技股份有限公司 | Preparation method of modified poly (ethylene glycol adipate) |
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