CN101812175A - Nonisocyanate polyurethane synthesized by using carbon dioxide(CO2) as raw material - Google Patents
Nonisocyanate polyurethane synthesized by using carbon dioxide(CO2) as raw material Download PDFInfo
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- CN101812175A CN101812175A CN200910105394A CN200910105394A CN101812175A CN 101812175 A CN101812175 A CN 101812175A CN 200910105394 A CN200910105394 A CN 200910105394A CN 200910105394 A CN200910105394 A CN 200910105394A CN 101812175 A CN101812175 A CN 101812175A
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Abstract
The invention provides a catalyst for the synthesis of nonisocyanate polyurethane. The catalyst consists of metal salt, imidazole-type ionic liquid, pyridine-type ionic liquid and quaternary ammonium salt. The invention also provides a method for preparing the nonisocyanate polyurethane. In the method, multi-ring shaped carbonic ester is catalytically synthesized by using the catalyst, and then the multi-ring shaped carbonic ester is reacted with organic amines to form the nonisocyanate polyurethane. The catalyst has the advantages of simple catalyst system, low cost, high reaction activity and good selectivity; and the preparation method has the advantages of mild reaction conditions, simple process flow and easy operation.
Description
[technical field]
The present invention relates to novel non-isocyanate polyurethane synthetic technology, especially a kind of employing carbonic acid gas and polyepoxy compound synthesize the polycyclic carbonic ether, the method for this then polycyclic carbonic ether and the novel non-isocyanate polyurethane of organic amine prepared in reaction and be used for the catalyzer of this method.
[background technology]
Urethane (PU) is meant and contains a plurality of ammonia ester bonds (general name of polymkeric substance NH-COO-) in the molecular chain.Ammonia ester bond is generally obtained by isocyanate group and hydroxyl reaction.Urethane is since being invented by Germanization scholar O.Bayer the thirties in 20th century, be used to rapidly since over half a century make porous plastics, fiber, elastomerics, synthetic leather, coating, sizing agent, pavement material and medical material etc., be widely used in fields such as traffic, building, light industry, weaving, electromechanics, aviation, health care.Along with constantly widening of polyurethane chemistry research, product manufacturing and application art development of technology and Application Areas, formed the industrial system that occupies the 6th big synthetic materials status (P E, P P, P V C, P S, P E T, P U) at present in the world gradually.Over nearly more than 20 years, polyurethane products kind, Application Areas, industry size enlarge rapidly, have become one of high molecular synthetic material industry with fastest developing speed.Especially in recent years China becomes urethane market centre with fastest developing speed in the world, and the technical progress of producing simultaneously, use, researching and developing is also advanced by leaps and bounds.
According to the report of the expert Angelar Austin of Britain IAL consulting firm in the international urethane meeting of in March, 2006 Europe UTECH, world's polyurethane products ultimate production was about 1,000 ten thousand t in 2000, was about 1,370 ten thousand t, and predicted 2010 and reach 1,700 ten thousand t in 2005.2000～2005 years average annual rate of increase 6.7% are predicted 2005～2010 years average annual rate of increase 4.2%.According to the data of IAL, China's nineteen eighty-two urethane output 7000t only, and reached 2,900,000 t by 2005, average growth rate per annum is 25%, estimates will reach 4,300,000 t in 2010, average growth rate per annum is 8.1%.
But isocyanic ester is to environment and the deleterious high toxic material of HUMAN HEALTH, particularly TD I, and the raw material phosgene toxicity of preparation isocyanic ester is bigger, is in particular in the processing of starting material production process and coating, the coating process.Along with the enhancing of people's environmental protection, Occupational Health and Safety consciousness, cause that society pays close attention to greatly, corresponding laws and regulations increasingly stringent in recent years.In coating, use isocyanate material, all limitation are arranged.Require the content of limiting the quantity of＜0.5% of its free monomers TDI, HDI as GB; Polyisocyanates generates carbon dioxide to moisture-sensitive in the environment with the water reaction, causes coating bubble and closure to reduce, thereby influences its resistant to chemical media and ornamental; Inherent amino-formate bond hydrolytic resistance is limited on the main chain of urethane, thereby has limited PU coating in application that weighs corrosion-resistant field or the like.Under above-mentioned background, since the nineties in 20th century, chemical engineering circle is paid attention to the development and application of non-isocyanate polyurethane material, relates to fundamental research---chemical reagents reaction kinetics such as cyclic carbonate ester and amine; The exploitation of basic raw material cyclic carbonate ester monomer, oligopolymer, polyamine; NIPU is in the application in fields such as plastic foam, coating, rubber and tackiness agent.Wherein U.S. Biotech company maintains the leading position in the research and development of NIPU, has set up the suitability for industrialized production base in Israel.The exploitation of China's non-isocyanate polyurethane also is in the starting stage, and the research report is less.
Carbon dioxide is one of topmost greenhouse gases in the atmosphere, and CO2 emissions constantly increases in recent years, has caused huge pressure to environment.But from the angle of resource, carbonic acid gas is again a kind of safe, nontoxic, abundant carbon resource, and a most typical catalytic process is utilized CO exactly in the conversion reaction of carbonic acid gas
2Synthesize the cyclic carbonate that contains carbonyl by cycloaddition reaction with epoxy compounds.If do not use any organic solvent in reaction and last handling process, this reaction will be " atom economy " and " Green Chemistry " reaction of a standard, and all atoms have all obtained 100% utilization in the reactant, produce without any by product.
[summary of the invention]
The invention provides a kind of Catalyst And Method of synthesizing new non-isocyanate polyurethane, the reaction by the synthetic polycyclic carbonic ether of cycloaddition reaction of carbonic acid gas and polyepoxy compound can be under relatively mild condition, and efficient, environmental protection, economy, technology realize simply.The non-isocyanate polyurethane that synthesizes has higher stability to hydrolysis, outstanding chemical-resistant, low perviousness, outstanding glueability and imporosity.
Novel non-isocyanate polyurethane of the present invention adopts following method preparation
1, catalyzer and polyepoxy compound are added reactor, feed carbonic acid gas,, produce the polycyclic carbonic ether under the temperature of reaction in reaction pressure;
2, with polycyclic carbonic ether and organic primary amine reaction, preparation non-isocyanate polyurethane.
As 1 described catalyzer is the common catalyst system of one or more formation in metal-salt, glyoxaline ion liquid, pyridines ionic liquid and the quaternary ammonium salt
The chemical formula of aforesaid metal-salt is MX, and wherein M represents Ca
2+, Mg
2+, Ba
2+, Zn
2+, Fe
2+, Fe
3+, Na
+, K
+, Ni
2+, Zr
4+, Co
2+, Cu
+, Cu
2+, X represents CO
3 2-, SO
4 2-, NO
3 -, halogen, CH
3COO
-
The structure of glyoxaline ion liquid is as mentioned above:
X=Cl, Br, I, BF
4Or PF
6
Aforesaid catalyzer is characterized in that: the ion liquid structure of described pyridines is:
X=Cl, Br, I, BF
4Or PF
6
As above-mentioned quaternary ammonium salt is one or more combination in tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, 4 bromide, tetraethylammonium bromide, tetraethyl ammonium iodide, benzyl trimethyl ammonium chloride and the benzyltrimethylammonium bromide.
As 1 described catalyst levels is the 1x10 of polyepoxide
-6To 1x10
-1Mol%.
As 1 described reaction pressure is 0.1-10MPa, and temperature of reaction is 50-200 ℃, reaction times 0.5-20 hour.
As polyepoxy compound as described in 1 be: 1,4 butanediol diglycidyl ethers, 1,6 hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, ethylene glycol diglycidylether, propylene glycol diglycidylether, trihydroxymethylpropanyltri diglycidyl ether, polypropylene glycol diglycidyl ether, polyethyleneglycol diglycidylether, epoxy soybean oil, diglycidylether, tetramethylolmethane glycidyl ether, epoxy chloropropane, glycidyl allyl ether, vinylformic acid glycidyl ether, methyl propenoic acid glycidyl ether, sorbyl alcohol polyglycidyl ether.
As organic primary amine as described in 2 be: diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, isophorone diamine, ditan diamines, polyetheramine.
Catalyzer of the present invention and employing carbonic acid gas and synthetic polycyclic carbonic ether of polyepoxy compound and then nonisocyanate polyurethane synthesized method can realize under relatively mild condition under the situation that does not add any organic solvent.
The invention has the beneficial effects as follows:
1. catalyst system is simple, cost is low, and reactive behavior height, selectivity are good;
2. reaction conditions gentleness, technological process are simple, are convenient to operation.
[embodiment]
Embodiment 1:
In effective volume is 1000 milliliters stainless steel autoclave, add the 2g zirconium carbonate successively, 1-methyl-3-butyl imidazole villaumite 5g, 1,4 butanediol diglycidyl ether 200g, under magnetic agitation by 150 ℃ of temperature controller control reaction temperature, charge into carbonic acid gas then to 2MPa, reacted 10 hours, be cooled to room temperature, get product 1,4 butyleneglycol 2-glycidyl carbonic ether.
1,4 butyleneglycol 2-glycidyl carbonic ether and stoichiometric tetraethylene pentamine prepared in reaction non-isocyanate polyurethane.
Embodiment 2:
In effective volume is 1000 milliliters stainless steel autoclave, add the 2g zirconium carbonate successively, 1-methyl-3-butyl imidazole villaumite 5g, propylene glycol diglycidylether 200g, under magnetic agitation,, charge into carbonic acid gas then, reacted 10 hours to 2MPa by 150 ℃ of temperature controller control reaction temperature, be cooled to room temperature, get product propylene glycol 2-glycidyl carbonic ether.
Propylene glycol 2-glycidyl carbonic ether and stoichiometric tetraethylene pentamine prepared in reaction non-isocyanate polyurethane.
Embodiment 3:
In effective volume is 1000 milliliters stainless steel autoclave, add positive zirconium sulfate 2.5g successively, 1-methyl-3-butyl imidazole villaumite 5g, 1,4 butanediol diglycidyl ether 200g, under magnetic agitation by 150 ℃ of temperature controller control reaction temperature, charge into carbonic acid gas then to 2MPa, reacted 10 hours, be cooled to room temperature, get product 1,4 butyleneglycol 2-glycidyl carbonic ether.
1,4 butyleneglycol 2-glycidyl carbonic ether and stoichiometric diethylenetriamine prepared in reaction non-isocyanate polyurethane.
Embodiment 4:
In effective volume is 1000 milliliters stainless steel autoclave, add positive zirconium sulfate 2.5g successively, 1-methyl-3-butyl imidazole villaumite 5g, 1,6 hexanediol diglycidyl ether 200g, under magnetic agitation by 150 ℃ of temperature controller control reaction temperature, charge into carbonic acid gas then to 3MPa, reacted 20 hours, be cooled to room temperature, get product 1,6 hexylene glycol 2-glycidyl carbonic ether.
1,6 hexylene glycol 2-glycidyl carbonic ether and stoichiometric reacting ethylenediamine prepare non-isocyanate polyurethane.
Embodiment 5:
In effective volume is 1000 milliliters stainless steel autoclave, add positive zirconium sulfate 2.5g successively, 1-methyl-3-butyl imidazole villaumite 5g, ethylene glycol diglycidylether 200g, under magnetic agitation,, charge into carbonic acid gas then, reacted 24 hours to 3MPa by 150 ℃ of temperature controller control reaction temperature, be cooled to room temperature, get product ethylene glycol bisthioglycolate Racemic glycidol carbonic ether.
Ethylene glycol bisthioglycolate Racemic glycidol carbonic ether and stoichiometric hexanediamine prepared in reaction non-isocyanate polyurethane.
Embodiment 6
In effective volume is 1000 milliliters stainless steel autoclave, add zinc bromide 2g successively, 1-methyl-3-butyl imidazole villaumite 5g, trihydroxymethylpropanyltri diglycidyl ether 200g, under magnetic agitation,, charge into carbonic acid gas then, reacted 30 hours to 2MPa by 150 ℃ of temperature controller control reaction temperature, be cooled to room temperature, get product trimethylolpropane tris Racemic glycidol carbonic ether.
Trimethylolpropane tris Racemic glycidol carbonic ether and stoichiometric diethylenetriamine prepared in reaction non-isocyanate polyurethane.
Embodiment 7
In effective volume is 1000 milliliters stainless steel autoclave, add zinc bromide 2g successively, 1-methyl-3-butyl imidazole villaumite 5g, 1,4 butanediol diglycidyl ether 200g, under magnetic agitation by 150 ℃ of temperature controller control reaction temperature, charge into carbonic acid gas then to 2MPa, reacted 20 hours, be cooled to room temperature, get product 1,4 butyleneglycol 2-glycidyl carbonic ether.
1,4 butyleneglycol 2-glycidyl carbonic ether and stoichiometric diethylenetriamine prepared in reaction non-isocyanate polyurethane.
Embodiment 8
In effective volume is 1000 milliliters stainless steel autoclave, add zinc bromide 2g successively, 1-methyl-3-butyl imidazole villaumite 5g, 1,4 butanediol diglycidyl ether 200g, under magnetic agitation by 150 ℃ of temperature controller control reaction temperature, charge into carbonic acid gas then to 2MPa, reacted 10 hours, be cooled to room temperature, get product 1,4 butyleneglycol 2-glycidyl carbonic ether.
1,4 butyleneglycol 2-glycidyl carbonic ether and stoichiometric reacting ethylenediamine prepare non-isocyanate polyurethane.
Embodiment 9
In effective volume is 1000 milliliters stainless steel autoclave, add the 2g zinc bromide successively, 1-methyl-3-butyl imidazole villaumite 5g, 1,6 hexanediol diglycidyl ether 200g, under magnetic agitation by 150 ℃ of temperature controller control reaction temperature, charge into carbonic acid gas then to 2MPa, reacted 20 hours, be cooled to room temperature, get product 1,6 hexylene glycol 2-glycidyl carbonic ether.
1,6 hexylene glycol 2-glycidyl carbonic ether and stoichiometric diethylenetriamine prepared in reaction non-isocyanate polyurethane.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (11)
1. a novel non-isocyanate polyurethane is characterized in that it being to adopt following method preparation
(1), catalyzer and polyepoxy compound are added reactor, feed carbonic acid gas,, produce the polycyclic carbonic ether under the temperature of reaction in reaction pressure;
(2), with polycyclic carbonic ether and organic primary amine reaction, preparation non-isocyanate polyurethane.
2. catalyzer according to claim 1; It is characterized in that: catalyzer adopts the common catalyst system of one or more formation in metal-salt, glyoxaline ion liquid, pyridines ionic liquid and the quaternary ammonium salt.
3. according to claim 1,2 described catalyzer, it is characterized in that: the chemical formula of metal-salt is MX, and wherein M represents Ca
2+, Mg
2+, Ba
2+, Zn
2+, Fe
2+, Fe
3+, Na
+, K
+, Ni
2+, Zr
4+, Co
2+, Cu
+, Cu
2+, X represents CO
3 2-, SO
4 2-, NO
3 -, halogen, CH
3COO
-
4. according to claim 1,2 or 3 described catalyzer, it is characterized in that: the structure of described glyoxaline ion liquid is:
X=Cl, Br, I, BF
4Or PF
6
5. according to claim 1,2,3 or 4 described catalyzer, it is characterized in that: the ion liquid structure of described pyridines is:
X=Cl, Br, I, BF
4Or PF
6
6. according to claim 1,2,3,4 or 5 described catalyzer, it is characterized in that: quaternary ammonium salt is one or more the combination in tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, 4 bromide, tetraethylammonium bromide, tetraethyl ammonium iodide, benzyl trimethyl ammonium chloride and the benzyltrimethylammonium bromide.
7. catalyzer according to claim 1 and 2 is characterized in that: catalyst levels is the 1x10 of polyepoxide
-6To 1x10
-1Mol%.
8. according to the preparation method of the described a kind of novel non-isocyanate polyurethane of claim 1, it is characterized in that:
(1), catalyzer and polyepoxy compound are added reactor, feed carbonic acid gas, in reaction pressure, reaction generates the polycyclic carbonic ether under temperature of reaction and the stirring condition;
(2), with polycyclic carbonic ether and organic primary amine reaction, preparation non-isocyanate polyurethane.
9. method according to claim 7 is characterized in that: reaction pressure is 0.1-10MPa, and temperature of reaction is 50-200 ℃, reaction times 0.5-30 hour.
10. according to claim 7 or 8 described methods, it is characterized in that: described polyepoxy compound is:
1,4 butanediol diglycidyl ethers, 1,6 hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, ethylene glycol diglycidylether, propylene glycol diglycidylether, trihydroxymethylpropanyltri diglycidyl ether, polypropylene glycol diglycidyl ether, polyethyleneglycol diglycidylether, epoxy soybean oil, diglycidylether, tetramethylolmethane glycidyl ether, epoxy chloropropane, glycidyl allyl ether, vinylformic acid glycidyl ether, methyl propenoic acid glycidyl ether, sorbyl alcohol polyglycidyl ether.
11. according to claim 1 or 7 described methods, it is characterized in that: described organic primary amine is: diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, isophorone diamine, ditan diamines, polyetheramine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910105394A CN101812175A (en) | 2009-02-20 | 2009-02-20 | Nonisocyanate polyurethane synthesized by using carbon dioxide(CO2) as raw material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910105394A CN101812175A (en) | 2009-02-20 | 2009-02-20 | Nonisocyanate polyurethane synthesized by using carbon dioxide(CO2) as raw material |
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|---|---|
| CN101812175A true CN101812175A (en) | 2010-08-25 |
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|---|---|---|---|
| CN200910105394A Pending CN101812175A (en) | 2009-02-20 | 2009-02-20 | Nonisocyanate polyurethane synthesized by using carbon dioxide(CO2) as raw material |
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| CN115820090A (en) * | 2022-11-14 | 2023-03-21 | 中国科学院山西煤炭化学研究所 | Single-component hybrid non-isocyanate polyurethane coating and preparation method thereof |
| CN115820090B (en) * | 2022-11-14 | 2024-04-05 | 中国科学院山西煤炭化学研究所 | Single-component hybrid non-isocyanate polyurethane coating and preparation method thereof |
| CN116444710A (en) * | 2023-02-03 | 2023-07-18 | 武汉工程大学 | Nonmetal dynamic iminium polyion liquid catalyst and preparation method and application method thereof |
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