CN1190103A - Biodegradable polyurethane material and its preparation - Google Patents
Biodegradable polyurethane material and its preparation Download PDFInfo
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- CN1190103A CN1190103A CN98100914A CN98100914A CN1190103A CN 1190103 A CN1190103 A CN 1190103A CN 98100914 A CN98100914 A CN 98100914A CN 98100914 A CN98100914 A CN 98100914A CN 1190103 A CN1190103 A CN 1190103A
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- tannin
- polyurethane material
- polyester
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- urethane
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Abstract
The present invention belongs to the field of polymer material technology and is one polyurethane material synthesized through the reaction of tannin as raw stock with diisocyanate. The said material is produced through simple pollution-less process and is biodegradable and thus results in no pollution of environment, so that it may be used to replace various polyurethane material available, such as hard heat-insulating material in refrigerator and building and soft vehicle cushion material. In addition, it may also find wide application in once-used material, artificial flower soil and water treatment.
Description
The invention belongs to technical field of polymer materials, is a kind of biodegradable polyurethane material and preparation method thereof.
In the various materials that the mankind use, macromolecular material is one of most important kind, and world's plastics annual production has at present broken through 100,000,000 tons.Simultaneously, various depleted macromolecular materials have occupied the overwhelming majority of waste cumulative volume, and the consumption of bringing thus to natural resources is given up and waste has caused the great attention of countries in the world to the pollution of environment.
Urethane is a kind of of macromolecular material, because of it has excellent abrasive and remarkable mechanical property, has become a kind of of the six big synthetic materialss given priority in the world so far.And in communications and transportation, metallurgy, building, light industry (papermaking, shoemaking, leather), industrial circles such as printing and printing and dyeing have future widely, still, after traditional polyurethane material is discarded, are difficult to back be subject to processing, and burn the cyanide gas of bringing back to life, and cause atmospheric pollution.Bury processing and be difficult to again decompose, make the soil deterioration, cause adverse consequences.Study a kind of can biodegradable polyurethane material, to further promoting the use of this material, avoid environmental pollution significant.
Be to provide a kind of polyurethane material and preparation technology thereof with biological degradability order of the present invention.
Tannin is a kind of natural polymer with a large amount of phenolic hydroxyl groups and a small amount of alcoholic extract hydroxyl group, and nature demonstrates good microbiological degradation again.The present invention utilizes the characteristic of tannin, comes synthesis of polyurethane with it, thereby makes urethane have biodegradable characteristic, and we are called tannin urethane.
In the past, general reaction by polyvalent alcohol and vulcabond came synthesis of polyurethane.The present invention replaces polyvalent alcohol commonly used and di-isocyanate reaction to come synthesis of polyurethane through lot of experiments with tannin.Its basic structure is:
Wherein: R=R '=CONHC
6H
5
Tannin is a kind of macromolecular material, and its molecular structural formula is:
R1=OH wherein, R2=OH, the synthesis step of tannin urethane is as follows among R3=H----catechin structure (Procyanidin) the present invention:
The tannin that in a unit weight (for example 1000 grams) polyester or polyethers (propylene oxide), adds the 10-30% weight percent, stirring in reactor and dissolving the back makes it expanded under 10-25 ' C condition, the amine that adds the 0.02-0.06% of polyester or polyethers (propylene oxide) amount then successively, the organo-metallic tin class catalyzer of 0.1-0.4%, the industrial silicone oil of 0.1-0.4% and 0.4-0.8% are as the water of whipping agent, stir, the technical pure vulcabond (TDI) that adds the polyester amount then and be 40-50% reacts, pour into through in the mould of preheating when having bubble to produce, put into baking oven, under 50-80 ' C condition, solidified 10-15 minute, promptly get required bark high elastic polyurethane material.Its polyreaction formula is as follows:
R=R '=CONHC wherein
6H
5
For the reaction of analysis and judgement tannin and carbimide, at first investigate the reaction of tannin and diisocyanate resin (diisocyanate) as model reaction with the repeated structural unit catechin (Catechin) of tannin and the reaction of benzene carbimide (Phenyl isocyanate).By the reaction of model compound, to the separation of resultant of reaction and a large amount of structural characterizations, proved 3 of catechin ', 4 ' phenolic hydroxyl group be easy to and carbimide reaction, generate the ammoniacum catechin.What is interesting is that 3 ' ammoniacumization exists in solution and can't separate with certain proportion all the time with 4 ' ammoniacum catechin, this phenomenon may be interpreted as the esterification of 3 ' ammonia and 4 ' ammonia esterification catechin has the tautomerism relation.In common ammonia esterification process, the reactivity of alcoholic extract hydroxyl group is bigger than phenolic hydroxyl group, but in this model compound, 3 alcoholic extract hydroxyl groups of catechin may be because due to the steric barrier of structure not by amination.Along with the amount of isocyanic ester increases, monoamine esterification catechin (CU-I) obviously reduces and two ammonia esterification catechins (CU-II) increase rapidly.Can infer it mainly is the phenolic hydroxyl group and the di-isocyanate reaction generation urethane of tannin by this phenomenon, be present in the polyurethane structural with hard disconnected form, and play a part crosslinked.
Above-mentioned tannin synthetic polyurethane material---a kind of elastomer material is arranged.The present invention analyzes and has examined or check its intensity and microbiological deterioration performance.
Urethane can be divided into polyester type and polyether-type substantially.Show according to existing data: polyester type is responsive to microbiological degradation, and polyethers is comparatively responsive to photolysis.Show by result of study: in the polyurethane elastomer, along with the increase of tannin content, the linear slow rising of elastomeric density, and its intensity and modulus of elasticity exponent function relation rise.This phenomenon explanation tannin has played cross-linking set really in foam.Because '-diphenylmethane diisocyanate (MDI), contain phenyl ring in the 2,4 toluene diisocyanate (TDI), so with the elastomerics intensity of their preparations with 1, the elastomerics that 6-hexane diisocyanate (HDI) prepares is big.Above presentation of results needs by purposes, can select suitable vulcabond and tannin content, obtains the polyurethane elastomer of varying strength.
In addition, in biology will be degraded test,, replace tannin with similar synthetic method, synthesized TMP polyurethane elastomer thing in contrast with TriMethylolPropane(TMP) (TMP) in order to compare with common polyurethane elastomer.Adopt several different wood-decaying fungus to carry out the microbiological deterioration controlled trial.From the result, TMP urethane is difficult to be decomposed, and the loss of the weight loss of tannin urethane and Young's modulus has clearly shown, illustrate that tannin urethane has kept the Biodegradable of tannin at occurring in nature, that is to say, after urethane carries out modification by the adding tannin, had microbiological degradation.
The stability of tannin urethane and chemical recovery probability analysis
By the stability and the chemical recovery possibility that add water decomposition experimental evaluation ammonia esterification tannin to ammonia esterification catechin (CU-I).Use phenylethyl alcohol (PA) to prepare the ammonia carboxylate as the model thing of common polyvalent alcohol simultaneously, (Phenethyl alcohol urethane PAU), characterizes conventional polyurethanes with this to the benzene isocyanic acid phenenyl B ester, the experiment of comparing property.The result shows that at normal temperatures CU-I has similar stability to PAU, both has been difficult to be decomposed.But during high temperature, under the effect of water, CU-I can be decomposed into catechin and aniline (Aniline), and this ammoniac compounds prepares the intermediate of isocyanic ester just, that is to say, it has the possibility of chemical recovery.If allow ammoniac compounds be retained in the system, and control certain condition, under its effect, the ammonia carboxylate can be continued ammonia to be separated, and generate carbamide compounds, and the PAU decomposition reaction is extremely slow so.Infer at normal temperatures that thus ammonia esterification tannin has the stability similar to conventional polyurethanes, and under the moisture situation of high temperature, is decomposed easily.Just because of at normal temperatures stable of tannin urethane and at high temperature relative unstable, make its operability and chemical recovery obtain unifying.
The character of tannin urethane and the field that is expected to develop
Both possessed the general property of conventional polyurethanes with the polyurethane material of tannin preparation, have above-mentioned property again, and production cost had been low, the complete greenization of production process, and solved the problem of environmental pollution of waste.So this material is expected in the refrigerator production, have a extensive future at aspects such as the car of the high resilience of development of new or the special-purpose cushions of motorcycle.And be expected in disposable material, to be used widely.
Owing to recently also find to be fixed in tannin composition in the urethane to zinc, copper, heavy metal ion such as cadmium and protein have good adsorption, and this material is expected to be applied to during Industrial Wastewater Treatment and purification of water quality handle.
Embodiment 1: synthesis condition: polyester: 100g, TDI:40g, TriMethylolPropane(TMP): 1.5g, tin
Catalyzer: 3g, amine catalyst: 0.5g, water: 2.5ml, silicone oil:
1g, tannin: 10g performance index: density: 100Kg/m3
Compressive strength: 0.158Kpa (compression 10%)
Young's modulus: 1.58Kpa embodiment 2: synthesis condition: polyester: 100g, TDI:43g, TriMethylolPropane(TMP): 1.5g, tin
Catalyzer: 3g, amine catalyst: 0.5g, water: 2.5ml, silicone oil:
1g, tannin: 15g performance index: density: 130Kg/m3
Compressive strength: 1.13Kpa (compression 10%)
Young's modulus: 11.22Kpa embodiment 3: synthesis condition: polyester: 100g, TDI:46g, TriMethylolPropane(TMP): 1.5g, tin
Catalyzer: 3g, amine catalyst: 0.5g, water: 2.5ml, silicone oil:
1g, tannin: 25g performance index: density: 193Kg/m3
Compressive strength: 69.5Kpa (compression 10%)
Young's modulus: 822Kpa
Claims (2)
1. a biodegradation type polyurethane material is characterized in that with the tannin being that raw material and vulcabond are polymerized.
Its basic structure formula is:
Wherein: R=R '=CONHC
6H
5
2. the preparation technology of a biodegradation type polyurethane material, it is characterized in that in the polyester of a weight unit or technical pure polyethers (propylene oxide), adding the tannin of 10-30% weight percent, stirring and dissolving in reactor, under 10-25 ' C condition, make it expanded, adding polyester or polyethers amount then successively is the amine of 0.02-0.06%, the organo-metallic tin class catalyzer of 0.1-0.4%, the technical pure silicone oil of 0.1-0.4% and 0.4-0.8% are as the water of whipping agent, stir, the technical pure vulcabond (TDI) that adds polyester or polyethers amount then and be 40-50% reacts, pour into through in the mould of preheating when having bubble to produce, put into baking oven, under 50-80 ' C condition, solidified 10-15 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98100914A CN1059217C (en) | 1998-03-17 | 1998-03-17 | Biodegradable polyurethane material and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98100914A CN1059217C (en) | 1998-03-17 | 1998-03-17 | Biodegradable polyurethane material and its preparation |
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| Publication Number | Publication Date |
|---|---|
| CN1190103A true CN1190103A (en) | 1998-08-12 |
| CN1059217C CN1059217C (en) | 2000-12-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98100914A Expired - Fee Related CN1059217C (en) | 1998-03-17 | 1998-03-17 | Biodegradable polyurethane material and its preparation |
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| Country | Link |
|---|---|
| CN (1) | CN1059217C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694140A (en) * | 2013-12-02 | 2014-04-02 | 艾达索高新材料无锡有限公司 | Degradable isocyanate and application thereof |
| CN105778075A (en) * | 2016-03-15 | 2016-07-20 | 长春工业大学 | Tannin-grafted biodegradable polyester |
| CN109503800A (en) * | 2018-10-30 | 2019-03-22 | 合肥科天水性科技有限责任公司 | A kind of modified aqueous polyurethane and preparation method thereof |
| CN110204679A (en) * | 2019-05-20 | 2019-09-06 | 齐鲁工业大学 | A kind of preparation method of modified environment-friendly aqueous polyurethane and its polyurethane of preparation |
| CN113234204A (en) * | 2021-05-28 | 2021-08-10 | 虚静科技(广州)有限责任公司 | Preparation method and application of plant polyphenol modified polyurethane foam |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3546199A (en) * | 1967-02-06 | 1970-12-08 | Kaiser Aluminium Chem Corp | Process for producing polyoxyalkylene ether-polyols from lignin |
| US4032483A (en) * | 1976-04-20 | 1977-06-28 | Champion International Corporation | Manufacture of polyurethanes from bark |
| JPS62874A (en) * | 1985-06-26 | 1987-01-06 | Nec Corp | Detecting circuit for cable trouble |
-
1998
- 1998-03-17 CN CN98100914A patent/CN1059217C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694140A (en) * | 2013-12-02 | 2014-04-02 | 艾达索高新材料无锡有限公司 | Degradable isocyanate and application thereof |
| CN103694140B (en) * | 2013-12-02 | 2016-09-28 | 艾达索高新材料无锡有限公司 | Degradable isocyanate and application thereof |
| CN105778075A (en) * | 2016-03-15 | 2016-07-20 | 长春工业大学 | Tannin-grafted biodegradable polyester |
| CN105778075B (en) * | 2016-03-15 | 2018-07-10 | 长春工业大学 | A kind of tannin is grafted biodegradable polyesters |
| CN109503800A (en) * | 2018-10-30 | 2019-03-22 | 合肥科天水性科技有限责任公司 | A kind of modified aqueous polyurethane and preparation method thereof |
| CN110204679A (en) * | 2019-05-20 | 2019-09-06 | 齐鲁工业大学 | A kind of preparation method of modified environment-friendly aqueous polyurethane and its polyurethane of preparation |
| CN110204679B (en) * | 2019-05-20 | 2021-08-31 | 齐鲁工业大学 | Preparation method of modified environment-friendly waterborne polyurethane and polyurethane prepared by same |
| CN113234204A (en) * | 2021-05-28 | 2021-08-10 | 虚静科技(广州)有限责任公司 | Preparation method and application of plant polyphenol modified polyurethane foam |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1059217C (en) | 2000-12-06 |
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