CN100593547C - Method for generating nonisocyanate polyurethane using natural reproducible resource - Google Patents
Method for generating nonisocyanate polyurethane using natural reproducible resource Download PDFInfo
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- CN100593547C CN100593547C CN200610012702A CN200610012702A CN100593547C CN 100593547 C CN100593547 C CN 100593547C CN 200610012702 A CN200610012702 A CN 200610012702A CN 200610012702 A CN200610012702 A CN 200610012702A CN 100593547 C CN100593547 C CN 100593547C
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Abstract
This invention relates to a method for producing non-isocyanate polyurethane using renewable natural resources, comprising: add epoxy soybean oil and catalyst into the reactor, wherein the amount of catalyst added is 3-5mol% of epoxy soybean oil, and then aerate in carbon dioxide gas, with reaction temperature 100-140Deg C, and reaction pressure 6-14 atmospheric pressure, start the reaction with magnetic stirring . for 25-40h. The produced cyclic carbonates are mixed with amine at 70-80Deg C, perform flaking at 100-110Deg C for 7-8h, perform sulfidization at 90-110Deg C for 24-72h, and are placed at room temperature for 7-9d. This invention synthesizes non-isocyanate polyurethane by replacing petrochemical products with epoxy soybean oil and CO2 via two-step reactions, forming a green, clean, high efficient and simple line for producing non-isocyanate polyurethane.
Description
Technical field
The invention belongs to a kind of method that generates non-isocyanate polyurethane, what be specifically related to is that epoxy soybean oil generates five-membered cyclic carbonate ester as natural reproducible resource and carbonic acid gas cycloaddition, and this then five-membered cyclic carbonate ester and the reaction of primary amine compounds generate non-isocyanate polyurethane.
Technical background
Since the thirties in last century Germany Baeyer has been found reaction by isocyanic ester and polyvalent alcohol synthesis of polyurethane, through nearly 80 years effort, urethane has become one of the world's six big important synthetic materialss, is used more and more widely in fields such as automobile, mine, shoemaking, building, medical treatment and furniture.Isocyanic ester as main raw material is also developed fast, and the output of global isocyanic ester in 2005 has reached 4,000,000 tons.Though use till today with the isocyanic ester synthesis of polyurethane always, this technology also exists some problems to be needed to solve:
1. isocyanic ester itself has great toxicity, and respiratory organs, skin, the eyes to the people have stronger stimulation in process of production, even poisons.
2. present, the industrial production of isocyanic ester adopts the phosgene of corresponding amine and severe toxicity to react under high temperature, high pressure bar none and makes, and the hydrochloric acid that produces in the reaction is serious to equipment corrosion, causes environmental pollution and loss of life and personal injury easily.Along with the continuous enhancing of people's environmental consciousness with to the pursuit of cleaner production, abroad each major company and domestic part unit all carry out the research of non-phosgene synthesizing isocyanate one after another.Though obtained certain progress, owing to be subjected to the influence of cost of material and technology maturation degree, the industrialization of this route needs time.
3. with isocyanic ester synthetic urethane, the anti-hydrolysis ability of particularly present widely used PAUR product is very poor, and this performance to polyurethane products such as water-borne coatings and footwear material has a strong impact on.
4. the conventional processes with the isocyanic ester synthesis of polyurethane is sensitive to envrionment conditions very much, and for example the existence of moisture can be induced the generation of side reaction, thereby obtains the product of unwanted porous and bad mechanical property.
Though become traditional, a fixed pattern with the isocyanic ester synthesis of polyurethane, people seek to come the effort of synthesis of polyurethane never to stop with the isocyanic ester surrogate, this also becomes one of direction of polyurethane industrial Future Development.In this field, carried out a large amount of work abroad, propose the thinking of non-isocyanate polyurethane (NIPU) and obtained good progress, U.S.pat.6,120, Figovsky cyclic carbonate and amine prepared in reaction non-isocyanate polyurethane in 951, propose the cyclic carbonate ester oligomer in the literary composition and still have the part epoxy group(ing), epoxy group(ing) also can be reacted with Ammonia, thereby generates the non-isocyanate polyurethane (HNIPU) of hydridization.American chemical monomer company (ChemonolLtd) has been used to NIPU to prepare car surface modifier, material of construction, aircraft coating, anti-benzene tackiness agent etc.Europe technology company (Eurotech.Ltd) has also developed some high-grade non-isocyanate polyurethane products (HNIPU), produces new coating, semihard bubble, tackiness agent etc. and predict to can be used on later fascia, noise abatement fabric etc.The novel NIPU resin of U.S. Lyondell company exploitation, existing better manufacturability has higher functional again.Above raw materials used petrochemicals that still all come from the report, because petroleum resources are very limited, therefore seeking the renewable resources that substitutes petrochemicals is a very urgent task with the dependence that reduces petroleum chemicals.At present, serve as that the polymkeric substance that the basis obtains obtains extensive concern with renewable resourcess such as natural product and derivatives thereof.Vegetables oil is as natural reproducible resource, and its kind is a lot, as: soybean oil, rapeseed oil, Oleum Gossypii semen, corn wet goods are the renewable raw materials of the wide material sources of cheapness.And soybean oil is to be easy to most in the world use and the most cheap vegetables oil, and it is rich in fatty acid triglyceride, it is changed into the polymer materials useful as intermediates have significant science, economy, Significance for Environment.
CO
2Be carbon source inexhaustible on the earth, strengthen CO
2Development and use are strategic problems that are significant.At present, CO
2Because special chemistry, all respects that physical properties has been applied to productive life.Use CO
2The report that generates organism or superpolymer is also a lot.
So far the report that does not have the NIPU aspect at home.China is polyurethane industrial country with the fastest developing speed in the world, have urethane market the biggest in the world, the urethane that synthesizes excellent combination property with eco-friendly raw material substitution isocyanic ester has been a urgent task, and it meets the general requirement of green, cleaner production and Sustainable development.Therefore seize the opportunity, developing this new production process as early as possible will be significant to seizing the market share and improving China's polyurethane industrial aggregate level.
Summary of the invention
The invention provides a kind of preparation method who uses natural reproducible resource to generate non-isocyanate polyurethane.Specifically be to use the epoxy soybean oil of natural reproducible resource and the cycloaddition reaction of carbonic acid gas to generate five-membered cyclic carbonate ester, the reaction of five-membered ring shape carbonic ether and primary amine class generates non-isocyanate polyurethane then.
Production method of the present invention is as follows:
(1) epoxy soybean oil and catalyzer are added in the reactor, the amount that adds catalyzer is the 3-5mol% of epoxy soybean oil, feed carbon dioxide then, temperature of reaction is at 100 ℃-140 ℃, reaction pressure is a 6-14 normal atmosphere, begin reaction under the effect of stirring, the reaction times is 25-40 hour, generates cyclic carbonate;
(2) cyclic carbonate is mixed under 70-80 ℃ with amine, mixing is back to be descended 7-8 in blocks hour at 100-110 ℃, and sulfuration is 24-72 hour under 90-110 ℃ of temperature, at room temperature places 7-9 days.
Go back useful catalyst as mentioned above in (2) step, add-on is the 1-2mol% of cyclic carbonate.Catalyzer is quaternary ammonium salt such as Tetrabutyl amonium bromide, triethylamine, organic tin, alkali metal halide, and wherein catalytic effect is reasonable is Tetrabutyl amonium bromide.
As above (1) step described catalyzer comprise organism, inorganic salt solution or some the common catalyst system of the two.
Aforesaid organism comprise amine, guanidinesalt class, phenols,, pyridine, organic alkali metal class or quaternary ammonium salt.
Described amine is triethylene diamine, triethylamine etc.
Described guanidinesalt class is a Guanidinium hydrochloride, and phenols is a phenol, and pyridines is a Dimethylamino pyridine.
Described organic alkali metal class is potassium alcoholate, sodium alkoxide.
Described quaternary ammonium salt is Tetrabutyl amonium bromide, Tetramethylammonium iodide, two C
8-C
10Alkyl-dimethyl ammonium chloride or dodecyl benzyl dimethyl ammonium chloride etc.
Aforesaid inorganic salt solution comprises that metal halide, metal oxide or hydrotalcite are dissolved in the inorganic salt solution that organic solvent forms.
Aforesaid metal halide is KI, NaI, LiBr, CaCl
2, MgCl
2, ZnCl
2, CoCl
2Or NbCl
5Deng.
Aforesaid metal oxide is a magnesium oxide etc.
Aforesaid organic solvent is dehydrated alcohol, N, dinethylformamide, N,N-dimethylacetamide, tetrahydrofuran (THF), pyrrolidone or dimethyl sulfoxide (DMSO).
Best in the described catalyzer is common catalysis, the CaCl of common catalysis, NaI and the Tetrabutyl amonium bromide of Tetrabutyl amonium bromide, KI, NaI, KI and Tetrabutyl amonium bromide
2Common catalysis, MgCl with Tetrabutyl amonium bromide
2Common catalysis, ZnCl with Tetrabutyl amonium bromide
2Common catalysis, CoCl with Tetrabutyl amonium bromide
2Common catalysis with common catalysis, magnesium oxide and the Tetrabutyl amonium bromide of Tetrabutyl amonium bromide.
Aforesaid amine comprises quadrol (EDA), hexanediamine (HA), diethylenetriamine (DETA), isophorone diamine (IPDA), ditan diamines (MDA), triethylene tetramine or tetraethylene pentamine etc.
Advantage of the present invention: the present invention is the plant resources that utilizes natural reproducible---epoxy soybean oil and CO
2Substitute petrochemicals through two-step reaction with nonisocyanate polyurethane synthesized, form green, cleaning, the production route of non-isocyanate polyurethane efficiently, experimental technique is simple.
Embodiment
Embodiment one
Add the epoxy soybean oil of 84.91g in the autoclave that a volume of being furnished with magnetic agitation, ventpipe and stopple coupon is 100ml, triethylene diamine 1.79g (5mol%) is warming up to 140 ℃, begins to feed CO
2Gas keeps pressure 14atm, discharging behind the reaction 40h,
Raw material epoxy soybean oil oxirane value is 0.376, and it is 0.201 that reaction finishes back survey product oxirane value.To behind the catalyzer flush away product cyclic carbonate be mixed with stoichiometric quadrol (EDA), mixing temperature is 80 ℃, after the deaeration at mould top-pour sheet, temperature 100-110 ℃ in flakes, time 7-8 hour in flakes, sulfuration was at room temperature placed and was surveyed its physical and mechanical properties in 7 days after 24 hours in 90 ℃ of baking ovens.
The test piece rerum natura is as follows: hardness (ShoreA), 82; Resilience, 12%; Elongation, 163%; Tensile strength, 5.9MPa; 100% modulus, 4.2MPa; Pull apart forever and become 16.7%; Tear strength, 20.8KN/m.
Embodiment two
Add the epoxy soybean oil of 81.47g in the autoclave that a volume of being furnished with magnetic agitation, ventpipe and stopple coupon is 100ml, phenol 1.44g (5mol%) is warming up to 120 ℃, feeds CO
2Gas, discharging behind the maintenance pressure 12atm reaction 30h.
Raw material epoxy soybean oil oxirane value is 0.376, and it is 0.205 that reaction finishes back survey product oxirane value.The product cyclic carbonate is mixed with stoichiometric hexanediamine (HA), and mixing temperature is 80 ℃, after the deaeration at mould top-pour sheet, temperature 100-110 ℃ in flakes, time 7-8 hour in flakes, sulfuration was 24 hours in 90 ℃ of baking ovens, after at room temperature place and surveyed its physical and mechanical properties in 8 days.
The test piece rerum natura is as follows: hardness (ShoreA), 85; Resilience, 9%; Elongation, 196%; Tensile strength, 5.7MPa; 100% modulus, 2.8MPa; Pull apart forever and become 10%; Tear strength, 21.5KN/m.
Embodiment three
Add the epoxy soybean oil of 91.62g in the autoclave that volume of being furnished with magnetic agitation, ventpipe and stopple coupon is 100ml, sodium methylate 0.93g (5mol%) is warming up to 120 ℃, feeds CO
2Gas, discharging behind the maintenance pressure 10atm reaction 25h.
The oxirane value of epoxy soybean oil is 0.376, and it is 0.202 that reaction finishes back survey product oxirane value.To behind the catalyzer flush away product cyclic carbonate be mixed with stoichiometric diethylenetriamine (DETA), add Tetrabutyl amonium bromide 1.5g, mixing temperature is 70 ℃, after the deaeration at mould top-pour sheet, temperature 100-110 ℃ in flakes, time 7-8 hour in flakes, sulfuration was 24 hours in 90 ℃ of baking ovens, after at room temperature place and surveyed its physical and mechanical properties in 9 days.
The test piece rerum natura is as follows: hardness (ShoreA), 85; Resilience, 9%; Elongation, 165%; Tensile strength, 6.5MPa; 100% modulus, 4.3MPa; Pull apart forever and become 11%; Tear strength, 21.1KN/m.
Embodiment four
In the autoclave that a volume of being furnished with magnetic agitation, ventpipe and stopple coupon is 100ml, add the epoxy soybean oil of 94.62g, add Tetrabutyl amonium bromide 4.59g (4mol%), be warming up to 120 ℃, feed CO
2Gas, discharging behind the maintenance pressure 8atm reaction 25h.
The oxirane value of epoxy soybean oil is 0.376, and it is 0.066 that reaction finishes back survey product oxirane value.To behind the catalyzer flush away product cyclic carbonate be mixed with stoichiometric triethylene tetramine (DETA), add triethylamine (1-1.5mol%), mixing temperature is 70 ℃, after the deaeration at mould top-pour sheet, in the still life-span 20min temperature 100-110 in blocks ℃, time 7-8 hour in flakes, sulfuration was 24 hours in 90 ℃ of baking ovens, after at room temperature place and surveyed its physical and mechanical properties in 8 days.
The test piece rerum natura is as follows: hardness (ShoreA), 80; Resilience, 8%; Elongation, 144%; Tensile strength, 3.08MPa; 100% modulus, 2.02MPa; Pull apart forever and become 106%; Tear strength, 11.1KN/m.
Embodiment five
In the autoclave that a volume of being furnished with magnetic agitation, ventpipe and stopple coupon is 100ml, add the epoxy soybean oil of 75.80g, add KI 1.41g (3mol%) and solvents tetrahydrofurane 15g, be warming up to 120 ℃, feed CO
2Gas, discharging behind the maintenance pressure 6atm reaction 25h.
The oxirane value of epoxy soybean oil is 0.376, and it is 0.06 that reaction finishes back survey product oxirane value.Catalyzer flush away after product cyclic carbonate is mixed with stoichiometric tetraethylene pentamine (DETA), add Tetrabutyl amonium bromide (1-2mol%), mixing temperature is 70 ℃, after the deaeration at mould top-pour sheet, in the still life-span 30min temperature 100-110 in blocks ℃, time 7-8 hour in flakes, sulfuration was 24 hours in 90 ℃ of baking ovens, after at room temperature place a week and survey its physical and mechanical properties.
The test piece rerum natura is as follows: hardness (ShoreA), 89; Resilience, 7%; Elongation, 168,8%; Tensile strength, 3.9MPa; 100% modulus, 2.76MPa; Pull apart forever and become 110%; Tear strength, 11.9KN/m.
Embodiment six
In the autoclave that a volume of being furnished with magnetic agitation, ventpipe and stopple coupon is 100ml, add the epoxy soybean oil of 91.91g, add CaCl
21.15g (3mol%), and solvent N, N dimethyl formamide 15g is warming up to 120 ℃, feeds CO
2Gas, discharging behind the maintenance pressure 10atm reaction 25h.
The oxirane value of epoxy soybean oil is 0.376, and it is 0.041 that reaction finishes back survey product oxirane value.To behind the catalyzer flush away product cyclic carbonate be mixed with stoichiometric quadrol (EDA), mixing temperature is 80 ℃, after the deaeration at mould top-pour sheet, temperature 100-110 ℃ in flakes, time 7-8 hour in flakes, sulfuration was at room temperature placed and was surveyed its physical and mechanical properties in 7 days after 24 hours in 90 ℃ of baking ovens.
The test piece rerum natura is as follows: hardness (ShoreA), 92; Resilience, 12%; Elongation, 163%; Tensile strength, 6.9MPa; 100% modulus, 5.2MPa; Pull apart forever and become 16.7%; Tear strength, 27.8KN/m.
Embodiment seven
The epoxy soybean oil that in the autoclave that a volume of being furnished with magnetic agitation, ventpipe and stopple coupon is 100ml, adds 101g, MgO 0.46g (3mol%), and solvent N, N dimethyl formamide 15g is warming up to 120 ℃, feeds CO
2Gas, discharging behind the maintenance pressure 10atm reaction 25h.
Raw material epoxy soybean oil oxirane value is 0.376, and it is 0.076 that reaction finishes back survey product oxirane value.The product cyclic carbonate is mixed with stoichiometric hexanediamine (HA), and mixing temperature is 70 ℃, after the deaeration at mould top-pour sheet, temperature 100-110 ℃ in flakes, time 7-8 hour in flakes, sulfuration was 24 hours in 90 ℃ of baking ovens, after at room temperature place and surveyed its physical and mechanical properties in 8 days.
The test piece rerum natura is as follows: hardness (ShoreA), 95; Resilience, 9%; Elongation, 206%; Tensile strength, 5.7MPa; 100% modulus, 2.8MPa; Pull apart forever and become 10%; Tear strength, 29.5KN/m.
Embodiment eight
Add the epoxy soybean oil of 80g in the autoclave that a volume of being furnished with magnetic agitation, ventpipe and stopple coupon is 100ml, KI1.24g (2.5mol%) and Tetrabutyl amonium bromide 2.42g (2.5mol%) and dimethyl sulfoxide (DMSO) 15g are warming up to 120 ℃, feed CO
2Gas, discharging behind the maintenance pressure 10atm reaction 25h.
The oxirane value of epoxy soybean oil is 0.376, and it is 0.062 that reaction finishes back survey product oxirane value.To behind the catalyzer flush away product cyclic carbonate be mixed with stoichiometric diethylenetriamine (DETA), add Tetrabutyl amonium bromide 1.5g, mixing temperature is 80 ℃, after the deaeration at mould top-pour sheet, temperature 100-110 ℃ in flakes, time 7-8 hour in flakes, sulfuration was 24 hours in 90 ℃ of baking ovens, after at room temperature place and surveyed its physical and mechanical properties in 9 days.
The test piece rerum natura is as follows: hardness (ShoreA), 95; Resilience, 9%; Elongation, 165%; Tensile strength, 6.5MPa; 100% modulus, 4.3MPa; Pull apart forever and become 11%; Tear strength, 29.1KN/m.
Embodiment nine
The epoxy soybean oil that in the autoclave that a volume of being furnished with magnetic agitation, ventpipe and stopple coupon is 100ml, adds 90.5g, CaCl
20.76g (2mol%) with common catalysis and the N of Tetrabutyl amonium bromide 2.19g (2mol%), N dimethyl formamide 15g is warming up to 120 ℃, feeds CO
2Gas, discharging behind the maintenance pressure 10atm reaction 25h.
The oxirane value of epoxy soybean oil is 0.376, and it is 0.046 that reaction finishes back survey product oxirane value.To behind the catalyzer flush away product cyclic carbonate be mixed with stoichiometric triethylene tetramine (DETA), add triethylamine (1-1.5mol%), mixing temperature is 80 ℃, after the deaeration at mould top-pour sheet, in the still life-span 20min temperature 100-110 in blocks ℃, time 7-8 hour in flakes, sulfuration was 24 hours in 90 ℃ of baking ovens, after at room temperature place a week and survey its physical and mechanical properties.
The test piece rerum natura is as follows: hardness (ShoreA), 90; Resilience, 8%; Elongation, 144%; Tensile strength, 3.08MPa; 100% modulus, 2.02MPa; Pull apart forever and become 106%; Tear strength, 21.1KN/m.
Embodiment ten
The epoxy soybean oil that in the autoclave that a volume of being furnished with magnetic agitation, ventpipe and stopple coupon is 100ml, adds 86.3g, common catalysis and the N of MgO 0.19g (1.5mol%) and Tetrabutyl amonium bromide 1.57g (1.5mol%), N dimethyl formamide 15g is warming up to 120 ℃, feeds CO
2Gas, discharging behind the maintenance pressure 10atm reaction 25h.
The oxirane value of epoxy soybean oil is 0.376, and it is 0.052 that reaction finishes back survey product oxirane value.Catalyzer flush away after product cyclic carbonate is mixed with stoichiometric tetraethylene pentamine (DETA), add Tetrabutyl amonium bromide (1-2mol%), mixing temperature is 80 ℃, after the deaeration at mould top-pour sheet, in the still life-span 30min temperature 100-110 in blocks ℃, time 7-8 hour in flakes, sulfuration was 24 hours in 90 ℃ of baking ovens, after at room temperature place a week and survey its physical and mechanical properties.
The test piece rerum natura is as follows: hardness (ShoreA), 89; Resilience, 7%; Elongation, 198.8%; Tensile strength, 3.9MPa; 100% modulus, 2.76MPa; Pull apart forever and become 110%; Tear strength, 21.9KN/m.
Claims (20)
1, a kind of use natural reproducible resource generates the non-isocyanate polyurethane method, it is characterized in that
(1) epoxy soybean oil and catalyzer are added in the reactor, the amount that adds catalyzer is the 3-5mol% of epoxy soybean oil, feed carbon dioxide then, temperature of reaction is at 100 ℃-140 ℃, reaction pressure is a 6-14 normal atmosphere, begin reaction under the effect of stirring, the reaction times is 25-40 hour, generates cyclic carbonate;
(2) cyclic carbonate is mixed under 70-80 ℃ with amine, mixing is back to be descended 7-8 in blocks hour at 100-110 ℃, and sulfuration is 24-72 hour under 90-110 ℃ of temperature, at room temperature places 7-9 days.
2, a kind of use natural reproducible resource as claimed in claim 1 generates the non-isocyanate polyurethane method, it is characterized in that also using catalyzer in described (2) step, and its add-on is the 1-2mol% of cyclic carbonate.
3, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 1 is characterized in that the temperature of reaction in described (1) step is 120 ℃-140 ℃, and reaction pressure is a 10-14 normal atmosphere.
4, as each described a kind of method of using natural reproducible resource to generate cyclic carbonate of claim 1-3, it is characterized in that as described catalyzer of (1) step be organism, inorganic salt solution or the common catalysis of the two.
5, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 4 is characterized in that described organism comprises amine, guanidinesalt class, phenols, pyridine, organic alkali metal class or quaternary ammonium salt.
6, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 5 is characterized in that described amine is triethylene diamine or triethylamine.
7, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 5 is characterized in that described guanidinesalt class is a Guanidinium hydrochloride.
8, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 5 is characterized in that described phenols is a phenol.
9, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 5 is characterized in that described pyridines is a Dimethylamino pyridine.
10, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 5 is characterized in that described organic alkali metal class is potassium alcoholate or sodium alkoxide.
11, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 5 is characterized in that described quaternary ammonium salt is Tetrabutyl amonium bromide, Tetramethylammonium iodide, two C
8-C
10Alkyl-dimethyl ammonium chloride or dodecyl benzyl dimethyl ammonium chloride.
12, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 4 is characterized in that described inorganic salt solution is that metal halide, metal oxide or hydrotalcite are dissolved in the inorganic salt solution that organic solvent forms.
13, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 12 is characterized in that described metal halide is KI, NaI, LiBr, CaCl
2, MgCl
2, ZnCl
2, Co Cl
2Or NbCl
5
14, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 12 is characterized in that described metal oxide is a magnesium oxide.
15, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 12, it is characterized in that described organic solvent is dehydrated alcohol, N, dinethylformamide, N,N-dimethylacetamide, tetrahydrofuran (THF), pyrrolidone or dimethyl sulfoxide (DMSO).
16, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 4 is characterized in that catalyzer is common catalysis, the CaCl of common catalysis, NaI and the Tetrabutyl amonium bromide of Tetrabutyl amonium bromide, KI, NaI, KI and Tetrabutyl amonium bromide in described (1) step
2Common catalysis, MgCl with Tetrabutyl amonium bromide
2Common catalysis, ZnCl with Tetrabutyl amonium bromide
2Common catalysis, CoCl with Tetrabutyl amonium bromide
2With the common catalysis of Tetrabutyl amonium bromide or the common catalysis of magnesium oxide and Tetrabutyl amonium bromide.
17, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 2 is characterized in that the catalyzer in described (2) step is quaternary ammonium salt, triethylamine, organic tin, alkali metal halide.
18, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 17 is characterized in that described quaternary ammonium salt is Tetrabutyl amonium bromide, Tetramethylammonium iodide, two C
8-C
10Alkyl-dimethyl ammonium chloride or dodecyl benzyl dimethyl ammonium chloride.
19, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 17 is characterized in that described alkali metal halide is KI, NaI, LiBr, CaCl
2, MgCl
2, ZnCl
2, CoCl
2Or NbCl
5
20, a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 2 is characterized in that described amine is quadrol, hexanediamine, diethylenetriamine, isophorone diamine, ditan diamines, triethylene tetramine or tetraethylene pentamine.
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| CN111393627B (en) * | 2020-04-28 | 2023-05-30 | 广东珠江化工涂料有限公司 | Non-isocyanate polyurethane modified waterborne alkyd resin and preparation method thereof |
| CN111484613B (en) * | 2020-06-09 | 2022-07-12 | 广西民族大学 | Temperature-sensitive non-isocyanate polyurethane and preparation method and application thereof |
| CN112209772A (en) * | 2020-11-09 | 2021-01-12 | 吉林大学 | Preparation method of oil-based polyurethane slow-release nitrogen fertilizer |
| CN112979943B (en) * | 2021-02-25 | 2021-12-14 | 中国林业科学研究院林产化学工业研究所 | Preparation method of recyclable and renewable all-bio-based non-isocyanate polyurethane |
| CN113549214B (en) * | 2021-07-19 | 2022-11-22 | 中国林业科学研究院林产化学工业研究所 | Non-isocyanate polyurethane capable of realizing recycling and reprocessing under mild condition and preparation method thereof |
| CN115490851B (en) * | 2022-08-29 | 2024-01-26 | 湖北好口福食品有限公司 | Vegetable oil-based non-isocyanate polyurethane resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1334278A (en) * | 2000-07-19 | 2002-02-06 | 纳幕尔杜邦公司 | Polyurethane having hydroxy function of t-amino-formate bond |
| CN1432563A (en) * | 2001-12-28 | 2003-07-30 | 三井武田化学株式会社 | Prepn process of carbamate and prepn process of isocyanate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1334278A (en) * | 2000-07-19 | 2002-02-06 | 纳幕尔杜邦公司 | Polyurethane having hydroxy function of t-amino-formate bond |
| CN1432563A (en) * | 2001-12-28 | 2003-07-30 | 三井武田化学株式会社 | Prepn process of carbamate and prepn process of isocyanate |
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