CN1362437A - Synthesis of degradable poly-beta-oxybate - Google Patents
Synthesis of degradable poly-beta-oxybate Download PDFInfo
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- CN1362437A CN1362437A CN 02100406 CN02100406A CN1362437A CN 1362437 A CN1362437 A CN 1362437A CN 02100406 CN02100406 CN 02100406 CN 02100406 A CN02100406 A CN 02100406A CN 1362437 A CN1362437 A CN 1362437A
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Abstract
The method for synthesizing completely-degradable plastics poly beta-hydroxybutyrate includes the folloiwng steps: adopting acetaldehyde as raw material to prepare beta-hydroxybutanal; oxidizing it to prepare beta-hydroxybutyric acid; esterifying it to prepare ethyl beta-hydroxybutyrate and polymerizing it to prepare poly beta-hydroxybutyrate. It is characterized by that preparation of beta-hydroxybutanal adopts benzene as solvent, sodium hydroxide as catalyst, its reaction temp. is 1-15 deg.C and the organic acid is used as neutralizing reagent, the preparation of beta-hydroxybutyric acid adopts ethyl acetate as solvent, cobalt acetate as catalyst, its reaction temp. is 40-100 deg.c and reaction pressure is 0.3-1.5 MPa, the preparation of ethyl ebeta-hydroxybutyrate adopts cresulsulfonic acid as catalyst and ethyl alcohol as solvent and polymerization preparation of beta-hydroxybutyrate uses isopropyl titanate as catalyst.
Description
Technical field
The invention belongs to the technology that adopts a kind of complete-degradable plastic of chemical process synthetic, exactly belong to a kind of poly-beta-hydroxy-butanoic acid ester of acetaldehyde preparation technology of plastics fully that adopts.
Background technology
Poly-beta-hydroxy-butanoic acid ester (PHB) is a kind of widely used adip cluster polyester biological degradation polyalcohol, no matter under aerobic still is oxygen free condition, all can be degraded by microorganisms.Under excess oxygen, the PHB degraded is except that the beta-hydroxy-butanoic acid that produces minute quantity, and great majority are oxidized to carbonic acid gas and water; Degradation production is etheric acid and beta-hydroxy-butanoic acid under the weary oxygen condition.As seen the PHB degraded product can directly enter the ecological circulation system, fundamentally solves problem of environmental pollution
[1,2]
Producing the PHB main method both at home and abroad at present is biochemical process or biological fermentation process
[2,3,4]The storage material of the PHB synthetic cell internal carbon source that is many prokaryotic organism under non-equilibrium growth (as lacking nitrogen phosphorus magnesia etc.) condition and the energy.So far kind of autotrophy and heterotrophic bacterium can produce PHB surplus having found 60, and for example alkali bacillus belongs to (Slcaligenes), false unicellular Pseudomonas (Pseudonlonos), methylotrophy Pseudomonas (Methylotrophs) etc.Reports such as Capon can comprise separation and Extraction PHB and PHV the blue green algae matrix from a kind of fresh water cyano group bacterium (Aphanothece species) or seawater cyano group bacterium.1976, Britain ICI company used Alealegenes Entropls bacterium, has synthesized PHB in the common fermentation jar.Improvement to biochemical process at present comprises that utilizing price to hang down wide agricultural byproducts or the waste in source produces PHB as saccharine material, and utilizes recombinant DNA technology, to improve output.
Above-mentioned biochemical process and biological fermentation process, because the production cost height causes costing an arm and a leg of PHB, for example PHBV is more expensive more than 10 times than general-purpose plastics such as PE, and biological fermentation process is the macromolecule mixture that makes multiple compound mostly.Therefore be difficult to large-scale production.Utilize chemical catalysis can prepare PHB.Ohta etc.
[5]Report adopts diketene to carry out asymmetric hydrogenation under the effect of catalyzer and can make and have optically active beta-butyrolactone, and beta-butyrolactone is at catalyzer Ru
2Cl
4[(S)-binap]
2Et
3The N effect is the poly-beta-hydroxy-butanoic acid ester of open loop preparation down.This method is owing to the activity of diketene, difficult control of reaction conditions.
U.S. Patent No. 5 281 691 has reported that the employing beta-butyrolactone prepares beta substitution-β-Bing Chunsuanneizhi, produces PHB by beta substitution-β-Bing Chunsuanneizhi polymerization.The main drawback of this method is that the toxicity of beta substitution-β-Bing Chunsuanneizhi is very strong.
All adopted beta-butyrolactone as raw material in above-mentioned two kinds of technologies,, brought danger to operation because of beta-butyrolactone is a kind of very strong carcinogenic substance.In addition, prepare and require (S)-beta-butyrolactone or (R)-beta-butyrolactone to have higher purity in the polyester process of three-dimensional isomorphism, therefore preparing monomer needs higher cost.
Seebach etc.
[6]Reported that the employing acetylacetic ester produces beta-hydroxy-butanoic acid; adopt the hydroxyl of phenylate protection hydroxy acid, adopt butyl ester protection carboxyl, then through taking off the phenylate base, taking off four-step reaction such as butyl ester base; can produce the polyester of polymerization degree n=2, further polymerization can obtain the higher polyester of the polymerization degree.The raw material methyl aceto acetate that adopts in this technology contains active methylene radical, and reactions such as condensation, decomposition easily take place.Because the reaction process complexity, the polymerization degree of product polymer is lower.
Summary of the invention
The object of the present invention is to provide a kind of chemical synthesis process of degradable poly-beta-oxybate.This method have the product of advantages of nontoxic raw materials, production of employing inexpensive, and can be in atmosphere degraded and do not produce the characteristics of secondary pollution fully.
For achieving the above object, the present invention is realized by following proposal.Adopting acetaldehyde is the feedstock production acetaldol; Prepare beta-hydroxy-butanoic acid by the acetaldol oxidation; Prepare the beta-hydroxy-butanoic acid ethyl ester by the beta-hydroxy-butanoic acid esterification; Method by the poly-beta-hydroxy-butanoic acid ester of beta-hydroxy-butanoic acid polymerizable methacrylate preparation.It is characterized in that: acetaldehyde prepares acetaldol, and employing benzene is solvent, and consumption is the 60-100% of acetaldehyde quality; Catalyzer is an aqueous sodium hydroxide solution, and consumption is the 5-10% of acetaldehyde molar weight, adds in 1 hour; Temperature of reaction is 1-15 ℃, and the reaction times is 1-5 hour, and neutralization reagent adopts organic acid.Acetaldol prepares beta-hydroxy-butanoic acid, and solvent is an ethyl acetate, and consumption is the 50-150% of acetaldol quality; Catalyzer is acetic acid Cobalt, and consumption is the 0.1-1% of acetaldol quality; Temperature of reaction is 40-100 ℃, 5 hours reaction times, reaction pressure 0.3-1.5Mpa.The beta-hydroxy-butanoic acid esterification prepares the beta-hydroxy-butanoic acid ethyl ester, and tosic acid is a catalyzer, is solvent with ethanol, alcohol: beta-hydroxy-butanoic acid: the mol ratio of tosic acid is 24: 20: 1, and the reaction times is 3 hours.The poly-beta-hydroxy-butanoic acid ester of beta-hydroxy-butanoic acid polymerizable methacrylate preparation; catalyzer is an isopropyl titanate; the concentration of titanium ion is 1,000,000/50-500 in the reactant; reaction times is 20-30 hour; absolute pressure in the reactive system progressively is reduced to 7Pa from 1KPa; kept 5-10 hour, and after reaction finishes, fed nitrogen protection.
Above-mentioned acetaldehyde prepares in the acetaldol process, and the organic acid of employing is formic acid, acetate, propionic acid and butanic acid.The present invention puies forward advantage and is: 1. the source of raw material acetaldehyde is abundant, and low price and output are big.2. the cost of product is low, can be controlled in below 20,000 yuan/ton.3. the quality height of product, the molecular weight of the polymer P HB of production is controlled within the specific limits.4. the output of suitability for industrialized production PHB can reach and produce per year more than ten thousand tons.5. acetaldehyde is mainly used in production acetic acid at present, and acetic acid will change by the production of methyl alcohol carbonyl process, and latter's cost is low, has a clear superiority in.
The present invention is put into production and will be made the original device of acetaldehyde continue to play a role, and helps adjusting improving the petrochemicals production distribution.
Embodiment
The preparation of embodiment 1 (1) acetaldol
Reactant acetaldehyde 88g, solvent benzol 88g, catalyst n aOH aqueous solution 26.7g, temperature of reaction 4-5 ℃, 1.0 hours reaction times, adopt the acetate catalyst neutralisation, acetaldehyde is 19.36g in the resultant, and olefine aldehydr is 0.89g, and acetaldol is 61.68g, reaction yield is: 70.1%, and acetaldehyde conversion is: 78.0%.(2) preparation of beta-hydroxy-butanoic acid
Reactant acetaldol 161g, solvent ethyl acetate 144.7ml, catalyst acetic acid cobalt 1.5852g, 5 hours reaction times, 90 ℃ of temperature of reaction, reaction pressure 10MPa, beta-hydroxy-butanoic acid is 165.57g in the resultant, crotonaldehyde is 14.75g, and reaction yield is: 88.9%, and transformation efficiency is: 90.9%.(3) preparation of beta-hydroxy-butanoic acid ethyl ester
Reactant beta-hydroxy-butanoic acid 10.41g, ethanol 3.84g, catalyzer tosic acid 1g, the reaction times is 3 hours, and temperature of reaction is 80 ℃, and the beta-hydroxy-butanoic acid ethyl ester is 12.77g in the resultant, and yield is 96.6%.(4) preparation of polymer poly beta-hydroxy-butanoic acid ester (PHB)
Reactant beta-hydroxy-butanoic acid ethyl ester is 50ml, catalyst Ti isopropyl propionate 0.072ml, and 160 ℃ of temperature of reaction, 20 hours reaction times, resultant PHB, sample size 0.6854g, the polymerization degree is 12.2, molecular weight is 1095.2.
The preparation of embodiment 2 (1) acetaldols
Reactant acetaldehyde 90g, solvent benzol 54g, catalyst n aOH50.7g, reacted 1.0-1.5 hour by temperature of reaction 4-5 ℃, adopt the acetate catalyst neutralisation, acetaldehyde is 25.19g in the resultant, and olefine aldehydr is 2.73g, and acetaldol is 48.24g, reaction yield is: 53.60%, and acetaldehyde conversion is: 72.01%.(2) preparation of beta-hydroxy-butanoic acid
Reactant acetaldol 176.8g, solvent ethyl acetate 117.9ml, catalyst acetic acid cobalt 1.2434,3 hours reaction times, 60 ℃ of temperature of reaction, reaction pressure 10MPa, beta-hydroxy-butanoic acid is 43.12g in the resultant, butenoic acid 7.20g, reaction yield is: 47.83%, transformation efficiency is: 50.32%.(3) preparation of beta-hydroxy-butanoic acid ethyl ester
Reactant beta-hydroxy-butanoic acid 12.19g, ethanol 4.51g, catalyzer tosic acid 1.5g, the reaction times is 5 hours, and temperature of reaction is 80 ℃, and the beta-hydroxy-butanoic acid ethyl ester is 13.59g in the resultant, and yield is 86.51%.(4) preparation of polymer poly beta-hydroxy-butanoic acid ester (PHB)
Reactant beta-hydroxy-butanoic acid ethyl ester is 50ml, catalyst Ti isopropyl propionate 0.091ml, and 150 ℃ of temperature of reaction, 10 hours reaction times, resultant PHB, sample size 0.8129g, the polymerization degree is 9.1, molecular weight is 816.9.
The preparation of embodiment 3 (1) acetaldols
Reactant acetaldehyde 75g, solvent benzol 60g, catalyst n aOH aqueous solution 22.8g, temperature of reaction 7-8 ℃, acetaldehyde is 10.45g in the resultant, and olefine aldehydr is 3.19g, and acetaldol is 35.16g, and reaction yield is: 46.88%, acetaldehyde conversion is: 86.06%.(2) preparation of beta-hydroxy-butanoic acid
Reactant acetaldol 168g, solvent ethyl acetate 150ml, catalyst acetic acid cobalt 1.1760g, 1 hour reaction times, 50 ℃ of temperature of reaction, reaction pressure 10MPa, beta-hydroxy-butanoic acid is 26.77g in the resultant, crotonaldehyde is 8.16g, and reaction yield is: 28.42%, and transformation efficiency is: 33.47%.(3) preparation of beta-hydroxy-butanoic acid ethyl ester
Reactant beta-hydroxy-butanoic acid 8.15g, ethanol 1.05g, catalyzer tosic acid 0.73g, the reaction times is 1 hour, and temperature of reaction is 80 ℃, and the beta-hydroxy-butanoic acid ethyl ester is 5.45g in the resultant, and yield is 51.9%.(4) preparation of polymer poly beta-hydroxy-butanoic acid ester (PHB)
Reactant beta-hydroxy-butanoic acid ethyl ester is 50ml, catalyst Ti isopropyl propionate 0.093ml (200ppm), and 170 ℃ of temperature of reaction, 30 hours reaction times, resultant PHB, sample size 0.7254g, the polymerization degree is 15.4, molecular weight is 1382.4.
Claims (2)
1, a kind of chemical synthesis process of degradable poly-beta-oxybate, it is the feedstock production acetaldol that this method adopts acetaldehyde; Prepare beta-hydroxy-butanoic acid by the acetaldol oxidation; Prepare the beta-hydroxy-butanoic acid ethyl ester by the beta-hydroxy-butanoic acid esterification; By the poly-beta-hydroxy-butanoic acid ester of beta-hydroxy-butanoic acid polymerizable methacrylate preparation, it is characterized in that: acetaldehyde prepares acetaldol, and employing benzene is solvent, and consumption is the 60-100% of acetaldehyde quality; Catalyzer is an aqueous sodium hydroxide solution, and consumption is the 5-10% of acetaldehyde molar weight, adds in 1 hour; Temperature of reaction is 1-15 ℃, and the reaction times is 1-5 hour, and neutralization reagent adopts organic acid; Acetaldol prepares beta-hydroxy-butanoic acid, and solvent is an ethyl acetate, and consumption is the 50-150% of acetaldol quality; Catalyzer is acetic acid Cobalt, and consumption is the 0.1-1% of acetaldol quality; Temperature of reaction is 40-100 ℃, 5 hours reaction times, reaction pressure 0.3-1.5Mpa; The beta-hydroxy-butanoic acid esterification prepares the beta-hydroxy-butanoic acid ethyl ester, and tosic acid is a catalyzer, is solvent with ethanol, alcohol: beta-hydroxy-butanoic acid: the mol ratio of tosic acid is 24: 20: 1, and the reaction times is 3 hours; The poly-beta-hydroxy-butanoic acid ester of beta-hydroxy-butanoic acid polymerizable methacrylate preparation; catalyzer is an isopropyl titanate; the concentration of titanium ion is 1,000,000/50-500 in the reactant; reaction times is 20-30 hour; absolute pressure in the reactive system progressively is reduced to 7Pa from 1KPa; kept 5-10 hour, and after reaction finishes, fed nitrogen protection.
2, by the chemical synthesis process of the described degradable poly-beta-oxybate of claim 1, it is characterized in that: acetaldehyde prepares in the acetaldol process, and the organic acid of employing is formic acid, acetate, propionic acid and butanic acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467715A (en) * | 2013-09-26 | 2013-12-25 | 南京年吉冷冻食品有限公司 | Synthetic method of biodegradable polyhydroxybutyrate copolymerization mixture |
| CN103739835A (en) * | 2013-12-20 | 2014-04-23 | 苏州市万泰真空炉研究所有限公司 | Preparation method of carboxymethyl chitosan modified polyhydroxybutyrate biodegradable material |
| CN103788359A (en) * | 2014-01-14 | 2014-05-14 | 广州优塑塑料科技有限公司 | Method for preparing 3D (three-dimensional) degradable printing material from chitosan-modified hydroxybutyrate |
-
2002
- 2002-01-24 CN CN 02100406 patent/CN1216090C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467715A (en) * | 2013-09-26 | 2013-12-25 | 南京年吉冷冻食品有限公司 | Synthetic method of biodegradable polyhydroxybutyrate copolymerization mixture |
| CN103739835A (en) * | 2013-12-20 | 2014-04-23 | 苏州市万泰真空炉研究所有限公司 | Preparation method of carboxymethyl chitosan modified polyhydroxybutyrate biodegradable material |
| CN103739835B (en) * | 2013-12-20 | 2015-08-19 | 苏州市万泰真空炉研究所有限公司 | A kind of preparation method of polyhydroxybutyrate biodegradable material of cm-chitosan modification |
| CN103788359A (en) * | 2014-01-14 | 2014-05-14 | 广州优塑塑料科技有限公司 | Method for preparing 3D (three-dimensional) degradable printing material from chitosan-modified hydroxybutyrate |
| CN103788359B (en) * | 2014-01-14 | 2015-10-28 | 广州优塑塑料科技有限公司 | The 3D printed material preparation method of the chitin modified butyric ester of a kind of degradable |
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