CN113831496A - Glycolic acid-based polyurethane foam and preparation method thereof - Google Patents
Glycolic acid-based polyurethane foam and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
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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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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Abstract
The invention provides glycolic acid-based polyurethane foam and a preparation method thereof, belonging to the field of green manufacturing processes of biomedical degradable porous materials. The invention provides a glycolic acid-based foam porous material and a preparation method thereof, aiming at the defects that polyglycolic acid material has excellent biodegradability, but is crisp and hard in texture and difficult to process. The preparation method comprises the following steps: glycolic acid is used as a raw material, and glycolide is prepared by oligomerization-pyrolysis; preparing polyester polyol by copolymerizing glycolide and epsilon-caprolactone; the obtained polyol, isocyanate and an auxiliary agent are synthesized into degradable polyurethane foam under the action of a catalyst. The glycolic acid-based polyurethane foam and the preparation method thereof provided by the invention have the advantages of simple method, easiness in operation and degradability. The obtained polyurethane foam has the compression strength of 200-350 kPa and the apparent density as low as 40-60 kg/m3, and has certain application prospect in the field of tissue engineering scaffolds.
Description
Technical Field
The invention belongs to the cross field of medical degradable materials and green chemistry, and particularly relates to a preparation method of glycollic acid-based polyurethane foam.
Background
Polyglycolic acid (PGA) has excellent biocompatibility, and is a completely biodegradable medical material. Compared with other degradable materials such as polylactic acid (PLA), Polydioxanone (PDS), Polycaprolactone (PCL) and the like, the PGA is high in degradation speed and can be degraded in 60 days. The PGA degradation products are carbon dioxide and water, are nontoxic and harmless to human bodies, and can be used in high-end medical fields such as absorbable surgical sutures, drug carriers, bone fixation and the like. With the rapid development and the continuous improvement of the productivity of the process for preparing the glycollic acid by the coal chemical industry in China, the material obtains unprecedented development opportunities. PGA has high crystallinity, high melting point and difficult processing and forming, and the application range of the PGA is limited to a certain extent. In order to meet different requirements, the design and adjustment of the molecular chain structure of PGA are usually required.
The polyurethane foam is prepared by polymerizing and foaming isocyanate and hydroxyl compounds, has excellent mechanical, physical and chemical properties, and resists a plurality of solvents and oils; the wear resistance is excellent; and also has excellent processability, heat insulation property, adhesiveness and the like, and is a cushioning material with excellent performance. Most of the polyols synthesized by polyurethane at present are from petroleum and are not degradable. While the development of degradable polyurethanes has focused primarily on the synthesis of degradable polyols.
The glycolic acid is used for preparing polyester polyol to replace the traditional petroleum-based product, so that the problem that the petroleum-based product is not degradable can be solved, and the raw materials are sufficient and environment-friendly; related studies have not been reported. Currently, degradable polyols are mainly classified into the following 3 types: (1) natural polymer type; (2) vegetable oil-based; (3) molecular chain design.
The method prepares the rice straw liquefaction product by taking rice straws as a research object, polyethylene glycol 400 (PEG-400) and glycerol as liquefaction agents and concentrated sulfuric acid as a catalyst. The liquefaction rate of the prepared rice straw liquefaction product is 55%, the acid value of the liquefaction product is 3 mg/g, the hydroxyl value is 450 mg/g, and the prepared liquefaction product can be directly used for synthesizing polyurethane foam. Fourier transform infrared spectroscopy analysis shows that the liquefied product is polyether rich in hydroxyl, and the polyether polyol can be used for replacing polyether polyol to react with isocyanate to prepare the rice straw-based polyurethane foam. (Fouwenxing. preparation and modification of rice straw based polyurethane foam [ D ]. Haikou: Hainan university, 2017: 1-55.).
The preparation method comprises the steps of reacting homemade epoxidized soybean oil with methanol to generate soybean oil-based polyol under the condition that tetrafluoroboric acid is used as a catalyst. Uniformly mixing soybean oil-based polyol, trihydroxymethyl phosphorus oxide (THPO), a surfactant (AK 8805) and water under vigorous stirring, uniformly stirring the mixture with Toluene Diisocyanate (TDI), foaming the mixture, and placing the mixture into an oven at 60 ℃ for curing for a period of time to obtain the phosphorus-containing polyurethane foam. (wantinging. preparation and modification of rice straw based polyurethane foam [ D ]. Wuhan: Hubei university, 2016: 1-59.).
Wei ice, which is prepared by taking fermentation residues (hereinafter referred to as fermentation residues) obtained by preparing fuel ethanol from corn straws as raw materials, carrying out liquefaction reaction in polyhydric alcohols such as polyethylene glycol and the like by taking concentrated sulfuric acid as a catalyst to obtain plant fiber-based polyol, and replacing part of polyether polyol with the liquefied product for preparing polyurethane rigid foam. The resulting polyurethane had a density and compressive strength of 34.84 kg/m3 and 137 kPa, respectively. (Weibing, research on preparation of polyurethane foam by liquefaction of ethanol fermentation residues of corn straws [ D ]. Guangzhou: university of south China's marble and trade, 2013: 1-55.).
Halorales utilizes polyethylene glycol 2000 to graft and modify alkali lignin, so that phenolic hydroxyl groups on the alkali lignin are converted into alcoholic hydroxyl groups, and the reactivity of lignin and isocyanate is improved. Due to the introduction of the long chain of the polyoxyethylene ether, the total hydroxyl content is reduced, but the alcoholic hydroxyl content is increased, and the high-resilience lignin-based polyurethane foam is synthesized by partially replacing petrochemical polyol. (Halorales preparation of Lignin-based polyurethane elastic materials and Structure and Performance Studies thereof [ D ]. Guangzhou: university of south China, 2013: 1-55.).
Disclosure of Invention
Aiming at the problems of high crystallinity, high melting point and difficult processing and forming of PGA, the invention provides glycolic acid-based polyurethane foam and a preparation method thereof. Glycolic acid is used as a raw material, and glycolide is prepared by oligomerization-pyrolysis; preparing polyester polyol by copolymerizing glycolide and epsilon-caprolactone; the obtained polyol, isocyanate and an auxiliary agent are synthesized into degradable polyurethane foam under the action of a catalyst.
The invention adopts the following technical scheme:
a process for preparing glycollic acid-base polyurethane foam includes oligomerizing glycollic acid, and vacuum cracking at 260 deg.C under the action of depolymerizing catalyst to obtain glycolide.
Glycolide, an epsilon-caprolactone monomer, 1, 4-butanediol and stannous octoate are sequentially added into a three-port glass reactor according to a proportion. Firstly introducing nitrogen to replace the air in the reactor, and then heating the system to the temperature of 120-160 ℃ for reaction for 8-20h to obtain the glycollic acid based polyester polyol.
Sequentially adding glycollic acid polyester polyol, polyether 4110, silicone oil, water and diisobutyltin dilaurate into a plastic beaker, stirring at a high speed to uniformly mix, then adding a certain amount of isocyanate, stirring at a high speed to uniformly mix, and standing for 1-2 minutes to obtain the polyurethane foam.
The polyol is polyester polyol (self-made) and polyether 4110 (industrial grade), m (polyester polyol): m (polyether 4110) =1:1 to 5, preferably 1:2 to 4.
The amount of water used is 0.5 to 1.5%, preferably 0.8 to 1.2% of the total mass of the polyol.
The amount of silicone oil used is 0.5 to 1.5%, preferably 0.7 to 1.1% of the total mass of the polyol.
The isocyanate index is from 1 to 1.5, preferably from 1.1 to 1.3.
The invention has the beneficial effects that:
the polyester polyol is a green degradable material and is non-toxic and harmless.
Secondly, different soft polyurethane segment structures can be obtained by adjusting the proportion of the polyester polyol to the polyether 4110, so that polyurethane materials with different performances can be obtained.
And thirdly, the preparation process is clean, and no by-product or pollutant is generated. The obtained polyurethane foam has the compression strength of 370 kPa and the apparent density of 51.2 kg/m3, and meets the quality requirement of the polyurethane foam.
Drawings
FIG. 1 shows the IR spectra of the polyurethanes prepared in examples 1 and 2 of the present invention.
FIG. 2 is a photograph of polyurethane foams prepared according to examples 1, 2 and 3 of the present invention.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the following will clearly and completely describe the technical solutions of the present invention with reference to the embodiments of the present invention. But should not be construed to limit the scope of the invention.
Example 1
8.0 g of polyester polyol (self-made), 411012.0 g of polyether, 0.4 g of silicone oil, 0.4 g of water and 0.04g of diisobutyltin dilaurate are put into a 500 ml plastic beaker, stirred at a high speed to uniformly mix the materials, then 16.3 g of toluene diisocyanate is added, stirred at a high speed until the materials are uniformly mixed, and the stirring is stopped and the mixture is kept stand for a few minutes to obtain the polyurethane foam. The polyurethane foam had an apparent density of 58.5 kg/m3 and a compressive strength of 330 kPa.
Example 2
4.0 g of polyester polyol (self-made), 411016.0 g of polyether, 0.4 g of silicone oil, 0.4 g of water and 0.04g of diisobutyltin dilaurate are put into a 500 ml plastic beaker, stirred at a high speed to uniformly mix the materials, then 17.2 g of toluene diisocyanate is added, stirred at a high speed until the materials are uniformly mixed, and the stirring is stopped and the mixture is kept stand for a few minutes to obtain the polyurethane foam. The polyurethane foam had an apparent density of 58.0 kg/m3 and a compressive strength of 170 kPa.
Example 3
6.0 g of polyester polyol (self-made), 411016.0 g of polyether, 0.4 g of silicone oil, 0.3 g of water and 0.04g of diisobutyltin dilaurate are put into a 500 ml plastic beaker, stirred at a high speed to uniformly mix the materials, then 16.8 g of toluene diisocyanate is added, stirred at a high speed until the materials are uniformly mixed, and the stirring is stopped and the mixture is kept stand for a few minutes to obtain the polyurethane foam. The polyurethane foam had an apparent density of 55.7 kg/m3 and a compressive strength of 280 kPa.
Example 4
4.0 g of polyester polyol (self-made), 411016.0 g of polyether, 0.4 g of silicone oil, 0.4 g of water and 0.04g of diisobutyltin dilaurate are put into a 500 ml plastic beaker, stirred at a high speed to uniformly mix the materials, then 16.3 g of toluene diisocyanate is added, stirred at a high speed until the materials are uniformly mixed, and the stirring is stopped and the mixture is kept stand for a few minutes to obtain the polyurethane foam. The polyurethane foam had an apparent density of 41.1 kg/m3 and a compressive strength of 170 kPa.
Example 5
4.0 g of polyester polyol (self-made), 411016.0 g of polyether, 0.3 g of silicone oil, 0.4 g of water and 0.04g of diisobutyltin dilaurate are put into a 500 ml plastic beaker, stirred at a high speed to uniformly mix the materials, then 17.4 g of toluene diisocyanate is added, stirred at a high speed until the materials are uniformly mixed, and the stirring is stopped and the mixture is kept stand for a few minutes to obtain the polyurethane foam. The polyurethane foam had an apparent density of 53.1 kg/m3 and a compressive strength of 370 kPa.
Example 6
4.0 g of polyester polyol (self-made), 411016.0 g of polyether, 0.4 g of silicone oil, 0.4 g of water and 0.04g of diisobutyltin dilaurate are put into a 500 ml plastic beaker, stirred at a high speed to uniformly mix the materials, then 17.4 g of toluene diisocyanate is added, stirred at a high speed until the materials are uniformly mixed, and the stirring is stopped and the mixture is kept stand for a few minutes to obtain the polyurethane foam. The polyurethane foam had an apparent density of 50.7 kg/m3 and a compressive strength of 330 kPa.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. The glycolic acid-based polyurethane foam is characterized by being prepared by foaming polyester polyol and isocyanate, wherein the polyester polyol is mainly prepared by using glycolic acid as a main raw material, the foam has good biodegradability, the compression strength can reach 200-350 kPa, and the apparent density is as low as 40-60 kg/m 3.
2. A preparation method of glycolic acid-based polyurethane foam comprises the following steps: glycolic acid is used as a raw material, and glycolide is prepared by oligomerization-pyrolysis; preparing polyester polyol by copolymerizing glycolide and epsilon-caprolactone; adding polyester polyol, polyether 4110, silicone oil, water and diisobutyltin dilaurate into a foaming container, stirring at a high speed to uniformly mix, adding a certain amount of isocyanate, stirring at a high speed again to uniformly mix, and standing for 1-2 minutes to obtain the polyurethane foam.
3. The method of claim 2, wherein the glycolic acid-based polyurethane foam is prepared by: the polyester polyol is prepared by taking glycolide and epsilon-caprolactone as raw materials, 1, 4-butanediol as an initiator and stannous octoate as a catalyst through a polycondensation reaction.
4. The method of claim 2, wherein the glycolic acid-based polyurethane foam is prepared by: the mass ratio of the polyester polyol to the polyether 4110 is 1: 1-5.
5. The method of claim 2, wherein the glycolic acid-based polyurethane foam is prepared by: the isocyanate includes Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI) and other common isocyanates.
6. The method of claim 2, wherein the glycolic acid-based polyurethane foam is prepared by: the isocyanate index is 1-1.5.
7. The method of claim 2, wherein the glycolic acid-based polyurethane foam is prepared by: the amount of water is 0.5-1.5% of the total mass of the polyol.
8. The method of claim 2, wherein the glycolic acid-based polyurethane foam is prepared by: the amount of the silicone oil is 0.5-1.5% of the total mass of the polyhydric alcohol.
9. The method of claim 2, wherein the glycolic acid-based polyurethane foam is prepared by: the foaming temperature is 20-30 ℃, and the reaction time is 1-2 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115678097A (en) * | 2022-10-11 | 2023-02-03 | 中山欣必康生物科技有限公司 | Medical high-absorption polyurethane foam dressing and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115678097A (en) * | 2022-10-11 | 2023-02-03 | 中山欣必康生物科技有限公司 | Medical high-absorption polyurethane foam dressing and preparation method thereof |
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