CN106349467B - A kind of preparation method of degradable type adipic acid polyethylene glycol polyester - Google Patents
A kind of preparation method of degradable type adipic acid polyethylene glycol polyester Download PDFInfo
- Publication number
- CN106349467B CN106349467B CN201610792209.5A CN201610792209A CN106349467B CN 106349467 B CN106349467 B CN 106349467B CN 201610792209 A CN201610792209 A CN 201610792209A CN 106349467 B CN106349467 B CN 106349467B
- Authority
- CN
- China
- Prior art keywords
- polyethylene glycol
- adipic acid
- preparation
- polyester
- glycol polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of preparation methods of degradable type adipic acid polyethylene glycol polyester, belong to ester type compound preparing technical field in organic chemistry.Part polyethylene glycol is added in into adipic acid, after stirring and adding in catalyst, heating；Then remove the water of generation under vacuum, when temperature is small for insulation reaction 25 under conditions of 120 140 DEG C after, cooling adds in remaining polyethylene glycol, stirred at 70 80 DEG C 0.5 2.5 it is small when to get to finished product.The application is applied to adipic acid polyethylene glycol polyester, has many advantages, such as that rational technology, easy to operate, product are stablized, reaction time is short, of light color.
Description
Technical field
The present invention relates to a kind of preparation methods 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 spreading lubricant in Metal Cutting, uses rubber production
Releasing agent is made, there is good smooth, scattered, isolating film as demolding film, have good environment-friendly type, used than independent polyethylene glycol
Better stripping result.It is widely used due to the unique properties of grease type surfactant, and oil and fat product in itself low toxicity,
Low irritant, therefore developmental research grease type surfactant is increasingly valued by people.Improve surfactant simultaneously
Biological degradability be realize ecological environment good circulation important guarantee.
The synthesis report of adipic acid polyethylene glycol polyester has many at present.
Li Xianhong is delivered in chemistry world《The synthesis of PEG-polyadipic anhydride》, with polyethylene glycol, acetic anhydride,
Adipic acid synthesizes a kind of new medical macromolecular material polyethylene glycol-polyadipate acid anhydride.Wang Ying is delivered on Chemical Engineering Technology《It is poly-
The synthesis of hexylene glycol glycol ester》Spent glycol does the product of raw material, and ethylene glycol has loss, and molecular weight is difficult to do height.
Polyethylene glycol adipate, PEG-polyadipic anhydride, adipic acid polyethylene glycol polyester are all a kind of polymerizations
Object, complicated, biological degradability will hardly possible compared with other esters products and alkyl ether.How the life of surfactant is improved
The research of object degradability is significant.
Based on this, the application is made.
The content of the invention
For the above-mentioned technical problem of the prior art, the present invention provides a kind of adipic acid polyethylene glycol of easily biological-degradable and gathers
The preparation method of ester, the preparation method, rational technology, easy to operate, product are stablized, and of light color, easily biological-degradable has preferable
The advantages that performance.
In order to achieve the above objectives, the technical solution adopted by the present invention is as follows：
A kind of preparation method of adipic acid polyethylene glycol polyester, to added with the addition poly- second two in part in adipic acid flask
Alcohol is added with stirring catalyst, and slowly (the heating too violent polyethylene glycol of fast response is taken out of with dampening for heating；It is warming up to when 3-4 is small
120 DEG C are optimal) remove the water of generation in time under conditions of vacuum, keep the temperature 2-5 under the reaction condition of 120-140 DEG C of temperature
After hour, 80 DEG C are cooled to, adds in remaining polyethylene glycol, when stirring 0.5-2.5 is small at 70-80 DEG C, obtained yellowish
Bright product.
Further, as preferred：
The molecular weight 200-600 of the polyethylene glycol, and the molar ratio of adipic acid and total polyethylene glycol is 1：1-2.
The catalyst is the mixture of p-methyl benzenesulfonic acid and phosphorous acid, and the weight ratio of p-methyl benzenesulfonic acid and phosphorous acid is 1：
0.3-1。
The addition of the composite catalyst is adipic acid and the 0.1-0.9% of polyethylene glycol total weight.
The weight of second of polyethylene glycol added in is the 15-50% of the weight of total polyethylene glycol.
The acquisition modes of degradation rate：The aqueous solution 50ml that product design is 5% is taken to be added loaded in 250ml conical flasks
25% connects bacterium amount, and shaking table processing 7h, surveys COD at 30 DEG C, 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, using adipic acid and polyethylene glycol as raw material, to toluene
Esterification is carried out under the catalytic action of sulfonic acid and phosphorous acid, esterification yield is controlled, adds in remaining polyethylene glycol and stir evenly, is made
Obtain adipic acid polyethylene glycol polyester.
Beneficial effects of the present invention are as follows：
1) by adipic acid polyethylene glycol polyester produced by the present invention, there is excellent smooth diffusivity, isolating film as demolding film effect
It is good, it is often more important that easily biological-degradable.
2) present invention be using the dehydration esterification reaction under acidic catalyst effect, it is simple for process, can effectively reduce cost,
Improve yield.Production efficiency is improved, product appearance is improved.
3) reaction condition of the present invention is mild, uses equipment simple, so that equipment investment and energy consumption are more saved.
4) preparation process of the invention meets current environmental requirement, is worthy to be popularized to environment almost without pollution.
Entire reaction is allocated as the progress of three steps：Part polyethylene glycol is added in adipic acid flask and carries out initial reaction, and should
The water removing that dehydration esterification is formed in reaction, then heat up that the reaction was continued, in the adipic acid polyethylene glycol polyester most synthesized backward plus
Enter remaining polyethylene glycol, after adipic acid polyethylene glycol polyester compounds in proportion with polyethylene glycol, 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 average molecular weight used is 200-600 in following embodiments, limited by Zhejiang Real Madrid science and technology share
Company produces；Adipic acid purchase is in Shanghai Pu along import and export corporation；Other raw materials, as p-methyl benzenesulfonic acid, phosphorous acid may be employed
Conventional method is made in the market, can also use commercial product.
In the preparation method of the present embodiment, esterification equation is：
m:N=1:1-2.
Compounding adds in remaining polyethylene glycol with the method added in while stirring.
Embodiment 1
Added in flask 528 gram-molecular weights be 528 polyethylene glycol and 146 g of adipic acid be added with stirring 1.3 grams it is right
The catalyst of toluenesulfonic acid and 0.4 gram of phosphorous acid, 4 are warming up to 135 DEG C when small, vacuum -0.096MPa removes the water of generation in time,
After when heat preservation 3 is small under the reaction condition of 135-140 DEG C of temperature, 80 DEG C are cooled to, adds in 264 grams of polyethylene glycol, 70-80 DEG C
Stir 1 it is small when, obtaining yellowish (color and luster be less than 50 platinum cobalt standards) transparent product the present embodiment has rational technology, operation
Simply, product is stablized, and product has excellent smooth diffusion lubricity, and isolating film as demolding film effect is good, easily biological-degradable.
Aqueous solution 50ml that product design is 10% is taken loaded on the bacterium amount that connects in 250ml conical flasks, adding 25%, at 30 DEG C
Shaking table handles 5h, surveys COD, calculates degradation rate 58.2%.
Comparative example 1
As other conditions of embodiment 1, simply polyethylene glycol is all disposable adds in reaction, and same condition is measured
Degradation rate is 31.5%.Polyethylene glycol stays a part to be added in after cooling down, and degradation rate 58.2% is apparently higher than the drop disposably added in
Solution rate 31.5%.
Embodiment 2
Added in flask 528 gram-molecular weights be 528 polyethylene glycol and 146 g of adipic acid be added with stirring 1.3 grams it is right
The catalyst of toluenesulfonic acid and 0.4 gram of phosphorous acid, 4 are warming up to 135 DEG C when small, vacuum -0.096MPa removes the water of generation in time,
After when heat preservation 3 is small under the reaction condition of 135-140 DEG C of temperature, 80 DEG C are cooled to, adds in 422 grams of polyethylene glycol, 70-80 DEG C
Stir 1 it is small when, obtaining yellowish (color and luster be less than 50 platinum cobalt standards) transparent product the present embodiment has rational technology, operation
Simply, product is stablized, and product has excellent smooth diffusion lubricity, and isolating film as demolding film effect is good, easily biological-degradable.
Aqueous solution 50ml that product design is 10% is taken loaded on the bacterium amount that connects in 250ml conical flasks, adding 25%, at 30 DEG C
Shaking table handles 5h, surveys COD, calculates degradation rate 67.8%.
Comparative example 2
As other conditions of embodiment 2, simply polyethylene glycol is all disposable adds in reaction, and same condition is measured
Degradation rate is 39.6%.Polyethylene glycol stays a part to be added in after cooling down, and degradation rate 67.8% is apparently higher than the drop disposably added in
Solution rate 39.6%.
Embodiment 3
Added in flask 400 gram-molecular weights be 400 polyethylene glycol and 146 g of adipic acid be added with stirring 1.0 grams it is right
The catalyst of toluenesulfonic acid and 0.3 gram of phosphorous acid slowly heats up, and 3 are warming up to 125 DEG C when small, vacuum -0.096MPa is removed in time
The water of generation, when heat preservation 4 is small under the reaction condition of 125-130 DEG C of temperature after, be cooled to 80 DEG C, add in 200 grams of poly- second two
Alcohol, when 70-80 DEG C of stirring 1 is small, obtaining yellowish (color and luster is less than 50 platinum cobalt standards) transparent product the present embodiment has technique
Rationally, easy to operate, product is stablized, and product has excellent smooth diffusion lubricity, and isolating film as demolding film effect is good, easily biology drop
Solution.
Aqueous solution 50ml that product design is 10% is taken loaded on the bacterium amount that connects in 250ml conical flasks, adding 25%, at 30 DEG C
Shaking table handles 5h, surveys COD, calculates degradation rate 56.5%.
Comparative example 3
As other conditions of embodiment 3, simply polyethylene glycol starts plus 480 grams are reacted, and 120 grams are added in after cooling,
Total amount remains unchanged.Same condition measures degradation rate as 46.2%.Polyethylene glycol total amount is the same, and the amount added in after cooling is more
, degradation rate 56.5% in same amount of time is apparently higher than the low degradation rate 46.2% of addition.
Embodiment 4
Added in flask 300 gram-molecular weights be 300 polyethylene glycol and 146 g of adipic acid be added with stirring 0.5 gram it is right
The catalyst of toluenesulfonic acid and 0.2 gram of phosphorous acid slowly heats up, and 3 are warming up to 120 DEG C when small, vacuum -0.096MPa is removed in time
The water of generation, when heat preservation 5 is small under the reaction condition of 120-125 DEG C of temperature after, be cooled to 80 DEG C, add in 200 grams of poly- second two
Alcohol, when 70-80 DEG C of stirring 1.0 is small, obtaining yellowish (color and luster is less than 50 platinum cobalt standards) transparent product the present embodiment has work
Skill is reasonable, easy to operate, and product is stablized, and product has excellent smooth diffusion lubricity, and isolating film as demolding film effect is good, easily biology drop
Solution.
Aqueous solution 50ml that product design is 10% is taken loaded on the bacterium amount that connects in 250ml conical flasks, adding 25%, at 30 DEG C
Shaking table handles 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 degradation
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, using adipic acid and polyethylene glycol as raw material, to toluene
Esterification is carried out under the catalytic action of sulfonic acid and phosphorous acid, remaining polyethylene glycol is added in and stirs evenly, obtained adipic acid gathers
Polyglycol ester.The present invention be using the dehydration condensation under acidic catalyst effect, it is simple for process, can effectively reduce into
This, improves yield.Product biological degradability is improved, and performance is good.Reaction condition of the present invention is mild, uses equipment simple
It is single, so that equipment investment and energy consumption are more saved.By adipic acid polyethylene glycol polyester produced by the present invention, there is excellent put down
Sliding diffusion lubricity, isolating film as demolding film effect are good, it is often more important that easily biological-degradable.The present invention preparation process to environment almost
It does not pollute, meets current environmental requirement, be worthy to be popularized.
There is provided technical solution is made the above content is the preferred embodiment for combining the invention further detailed
It describes in detail bright, it is impossible to assert that the invention specific implementation is confined to these above-mentioned explanations, for the affiliated technology of the invention
For the those of ordinary skill in field, without departing from the concept of the premise of the invention, several simple deductions can also be made
Or replace, it should all 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：Part is added in into adipic acid
Polyethylene glycol, after stirring and adding in catalyst, heating；Then the water of generation is removed under vacuum, is 120-140 in temperature
After when insulation reaction 2-5 is small under conditions of DEG C, cooling adds in remaining polyethylene glycol, and it is small that 0.5-2.5 is stirred at 70-80 DEG C
When to get to finished product.
2. a kind of preparation method of degradable type adipic acid polyethylene glycol polyester as described in claim 1, it is characterised in that：Institute
The molecular weight 200-600 of polyethylene glycol is stated, and the molar ratio of adipic acid and total polyethylene glycol is 1：1-2.
3. a kind of preparation method of degradable type adipic acid polyethylene glycol polyester as described in claim 1, it is characterised in that：Institute
Catalyst is stated as p-methyl benzenesulfonic acid and the mixture of phosphorous acid, the weight ratio of p-methyl benzenesulfonic acid and phosphorous acid is 1：0.3-1.
4. a kind of preparation method of degradable type adipic acid polyethylene glycol polyester as described in claim 1 or 3, feature exist
In：The addition of the catalyst is adipic acid and the 0.1-0.9 % of polyethylene glycol total weight.
5. a kind of preparation method of degradable type adipic acid polyethylene glycol polyester as described in claim 1, it is characterised in that：Institute
State 15-50% of the weight of the polyethylene glycol of second of addition for the weight of total polyethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610792209.5A CN106349467B (en) | 2016-08-31 | 2016-08-31 | A kind of preparation method of degradable type adipic acid polyethylene glycol polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610792209.5A CN106349467B (en) | 2016-08-31 | 2016-08-31 | A kind of preparation method of degradable type adipic acid polyethylene glycol polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106349467A CN106349467A (en) | 2017-01-25 |
| CN106349467B true CN106349467B (en) | 2018-06-05 |
Family
ID=57856818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610792209.5A Active CN106349467B (en) | 2016-08-31 | 2016-08-31 | A kind of preparation method of degradable type adipic acid polyethylene glycol polyester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106349467B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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) |
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 |
-
2016
- 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)
| Title |
|---|
| 聚乙二醇-聚己二酸酐的合成;李先红等;《化学世界》;20070125(第1期);第23-25页 * |
| 聚己二酸乙二醇酯的合成;王颖等;《化学工业与工程》;20030430;第20卷(第2期);第116-118页 * |
| 聚醚酯增塑剂的合成及在橡胶中应用研究;李幸;《中国优秀硕士学位论文全文数据库（工程科技I辑）》;20130115(第1期);第B016-B319页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106349467A (en) | 2017-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106190512B (en) | A kind of concrete water-based release agent and preparation method thereof | |
| CN102391592B (en) | Environmental-friendly calcium-zinc stabilizer for PVC (Polyvinyl Chloride) rolling film and preparation method thereof | |
| CN103613745B (en) | A kind of energy-conservation vibrin of phase-transfer catalysis functional type and preparation method and use thereof | |
| CN103214618B (en) | thermoplastic acrylic resin and preparation method thereof | |
| CN102205390B (en) | Environmentally-friendly casting mold-releasing agent and preparation method thereof | |
| CN101319058B (en) | Method for producing wood-plastic composite material and produced wood-plastic composite material | |
| CN102516435A (en) | Method for preparing porous material by reversible addition fragmentation chain transfer polymerization of high internal phase emulsion | |
| CN104726071A (en) | Composite low-temperature coolant and preparation method and applications thereof | |
| CN103409219B (en) | Waste oil-based environment-friendly mold separating agent and preparation method thereof | |
| CN103045044A (en) | Energy-saving and environment-friendly powder coating and preparation method thereof | |
| CN105236798A (en) | Preparation method of naphthalene-series water reducing agent | |
| CN106349467B (en) | A kind of preparation method of degradable type adipic acid polyethylene glycol polyester | |
| JP2013503740A5 (en) | ||
| CN103073707B (en) | Alkyd resin and preparation method thereof | |
| CN106280442A (en) | A kind of ortho position acid imide functionalization benzoxazine resins carbon fiber laminating composite material and preparation method thereof | |
| CN100488939C (en) | Preparation process of pentaerythritol mixed acid ester | |
| CN107723429A (en) | A kind of low oil smoke overspeed quenching oil and preparation method thereof | |
| CN102167772B (en) | Fluorine-containing easily processed acrylate rubber and preparation method thereof | |
| CN104877510A (en) | Anticorrosion antibacterial paint and preparation method thereof | |
| CN106221082A (en) | A kind of composite of Gemini surface active modified calcium carbonate filled polytetrafluoroethylene and preparation method thereof | |
| CN108060003A (en) | A kind of self-emulsifying type vegetable oil/fatty acid aluminium/triethanolamine compound system high efficient demoulding agent | |
| CN104402720A (en) | Preparation method of castor oil polyoxyethylene ether oleate | |
| CN104356176A (en) | Preparation method of tannins ether stearate | |
| CN111269116B (en) | Method for realizing preparation and in-situ separation of ricinoleic acid oligomer | |
| CN102898623A (en) | Cashew amine epoxy curing agent for marine heavy anti-corrosion coating and preparation method for curing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |