CN102731779B - Synthetic method of hybrid non-isocyanate polyurethane - Google Patents
Synthetic method of hybrid non-isocyanate polyurethane Download PDFInfo
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- CN102731779B CN102731779B CN201110450438.6A CN201110450438A CN102731779B CN 102731779 B CN102731779 B CN 102731779B CN 201110450438 A CN201110450438 A CN 201110450438A CN 102731779 B CN102731779 B CN 102731779B
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- isocyanate polyurethane
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Abstract
The invention discloses a synthetic method of hybrid non-isocyanate polyurethane, comprising the following steps: adding epoxy resin and catalyst in a high pressure reaction vessel, sealing the high pressure reaction vessel, and opening to stir, heating up to 60-150 DEG C under continuously stirring, continuously introducing air to keep the CO2 pressure at 0.5-2 MPa, reacting for 1-4 h to generate epoxy-terminated cyclic carbonate, then reacting the epoxy-terminated cyclic carbonate with amine in the presence of a solvent at 30-60 DEG C for 2-10 h to obtain a hybrid non-isocyanate polyurethane solution, wherein the additional amount of the catalyst is 0.1-2 wt% of that of the epoxy resin; pouring the non-isocyanate polyurethane solution in a mold, and removing the solvent to obtain a non-isocyanate polyurethane solution film. The synthetic method of the invention has the advantages of environmental protection and simpleness, and the synthetic product has excellent performances of epoxy resin and polyurethane simultaneously, and has excellent caking property, acid and alkali corrosion resistance, solvent resistance, mechanical strength and other physical properties.
Description
Technical field
The invention belongs to a kind of synthetic method field of superpolymer.What be specifically related to is a kind of synthetic method of hydridization non-isocyanate polyurethane.
Background technology
Conventional urethane is generally to react with dihydroxyl or polyol the macromolecular compound forming by organic diisocyanate or polyisocyanates, it with excellent property, form is various, forming process is simple and famous.Utilize urethane resin, people can make the multiple products such as porous plastics, elastomerics, coating, tackiness agent, fiber, synthetic leather, water-proof material and surfacing material, are widely used in the fields such as communications and transportation, building, machinery, electronics, furniture, food-processing, clothes, weaving, synthetic leather, printing, mineral, petrochemical complex, water conservancy, national defence, physical culture, medicine equipment.
But the technique that adopts isocyanic ester synthesis of polyurethane exists some problems to need to solve: isocyanic ester itself has very large toxicity, in production and use procedure, can work the mischief to human body and environment; Produce isocyanic ester raw material phosgene toxicity larger; Very responsive to envrionment conditions by the course of processing of isocyanic ester synthesis of polyurethane, for example, the existence of moisture can induce side reaction to occur, thereby makes product occur micropore, mechanical property variation.
Polyurethane industrial forward adapts to the future developments such as environmental protection, safety and sanitation, resource recovery at present, develops the important research direction that nontoxic environment-friendly materials have become current polyurethane synthetic material.Therefore about the research of this respect, also more and more paid attention to.In nineteen nineties, started to develop environment-protecting polyurethane abroad.Non-isocyanate polyurethane is a kind of environment-protecting polyurethane, and it is subject to scientific research personnel's extensive concern and is devoted to applied research with its excellent over-all properties.At present, China also launches the research of this respect gradually, CN 1880360 is used epoxy soybean oils to synthesize non-isocyanate polyurethane for raw material, CN 101812175 be take epoxy resin and has been synthesized non-isocyanate polyurethane as raw material, CN 101260232A mixes with epoxy resin after epoxy soybean oil is converted into cyclic carbonate ester, then this mixture is reacted and has prepared mixing type nonisocyanate polyurethane with amine.
Above-mentioned these inventions, all only in the preliminary study stage, also differ greatly from practical application in industry.CN 1880360 generated times are longer, and the synthetic mixing type nonisocyanate polyurethane of CN 101260232A can cause urethane separated with the two-phase system of epoxy resin, thereby affect the mechanical property of material.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, a kind of synthetic method environmental protection, simple is provided, synthetic product has the premium properties of epoxy resin and urethane simultaneously, the synthetic method of the hydridization non-isocyanate polyurethane that the physicalies such as its cohesiveness, acid-alkali-corrosive-resisting, solvent resistance, physical strength are more excellent.
Design philosophy of the present invention is by epoxy resin and CO
2certain temperature with under pressure, react for some time and generate the cyclic carbonate ester that end group contains epoxy group(ing).Then this compound is mixed with primary amine, by epoxy group(ing), react and cyclocarbonate radical and the amino generation hydridization non-isocyanate polyurethane that reacts with amino.
Synthetic method step of the present invention is as follows:
(1) epoxy resin and catalyzer are added in autoclave, sealing autoclave, opens stirring, is warming up to 60～150 ℃, uses CO
2gas displacement continues afterwards ventilation for three times and keeps CO
2pressure is 0.5～2MPa reaction, 1～4h, generates the cyclic carbonate ester that end group contains epoxy group(ing); Wherein the transformation efficiency of epoxy group(ing) is 20%～80%.
(2) by cyclic carbonate ester and amine under solvent exists 30～60 ℃ react 2～10h, obtain hydridization non-isocyanate polyurethane solution.
(3) pour hydridization non-isocyanate polyurethane solution into mould, after desolventizing, make hydridization non-isocyanate polyurethane film.
Described in step (1), epoxy resin is epoxy resin E-21, E-44, E-51.
Described in step (1), catalyzer comprises organic amine salt, inorganic salts or their mixture.Described organic amine salt is four butyl bromation amine, tetrabutylammonium chloride, tetrabutyl iodate amine or two or more mixture arbitrarily wherein.Described inorganic salt are Sodium Bromide, potassiumiodide or calcium chloride.Described catalyzer, the 0.1-2 that its add-on is epoxy resin (wt) %.
In step (2), amine is organic amine.Described organic amine is quadrol, hexanediamine, polyethylene polyamine or two or more mixture arbitrarily wherein.
Described in step (2), solvent is organic polar solvent, and described organic polar solvent is DMF, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane.
In described step (3), pour hydridization non-isocyanate polyurethane solution into tetrafluoroethylene mould, vacuum desolventizes rear room temperature and places 24h, and 50 ℃ of baking ovens are placed 48h, make hydridization non-isocyanate polyurethane film.
Advantage of the present invention: the present invention utilizes epoxy resin and CO
2reaction is reacted generation hydridization non-isocyanate polyurethane after generating the cyclic carbonate ester that contains epoxy group(ing) with amine.Synthetic line is simple, environmental protection, and synthetic product has inierpeneirating network structure, does not have phenomenon of phase separation.Product has the excellent properties of epoxy resin and urethane simultaneously, can be widely used in the industries such as elastomerics, coating, tackiness agent.
Embodiment
embodiment 1
By 200g epoxy resin E-44,1g four butyl bromation amine adds in autoclave, and sealed reactor is opened induction stirring and stirs condensing works, is warming up to 80 ℃, uses CO
2gas displacement three times, continues ventilate and keep CO
2pressure is 1.0MPa reaction 3h, makes the cyclic carbonate ester that end group contains epoxy group(ing).The transformation efficiency that records epoxy group(ing) is 0.47.
Take the above-mentioned cyclic carbonate ester of 100g, 200g1,4-dioxane, 0.5g triethylamine, 12g quadrol add in 500ml four-hole boiling flask, and under normal temperature, stirring reaction 9h makes hydridization non-isocyanate polyurethane solution, and solution is light yellow transparent liquid.
Pour above-mentioned solution into tetrafluoroethylene mould, vacuum desolventizes under rear room temperature and places 24h, and 50 ℃ of baking ovens are placed 48h and made hydridization non-isocyanate polyurethane film.
Film physical property is as follows: second-order transition temperature: 16 ℃; Tensile strength: 1.7MPa; Elongation at break: 211%.
embodiment 2
By 200g epoxy resin E-44,1g four butyl bromation amine adds in autoclave, and sealed reactor is opened induction stirring and stirs condensing works, is warming up to 100 ℃, uses CO
2gas displacement three times, continues ventilate and keep CO
2pressure is 0.5MPa reaction 3h, makes the cyclic carbonate ester that end group contains epoxy group(ing).The transformation efficiency that records epoxy group(ing) is 0.48.
Take the above-mentioned cyclic carbonate ester of 100g, 200g tetrahydrofuran (THF), 0.5g triethylamine, 23.2g1,6-hexanediamine adds in 500ml four-hole boiling flask, and under normal temperature, stirring reaction 6h makes hydridization non-isocyanate polyurethane solution, and solution is light yellow transparent liquid.
Pour above-mentioned solution into mould, vacuum desolventizes under rear room temperature and places 24h, and 50 ℃ of baking ovens are placed 48h and made hydridization non-isocyanate polyurethane film.
Film physical property is as follows: second-order transition temperature: 13.5 ℃; Tensile strength: 0.66MPa; Elongation at break: 193%.
embodiment 3
By 300g epoxy resin E-44,1.5g tetrabutylammonium chloride, 0.03g Potassium Bromide adds in autoclave, and sealed reactor is opened induction stirring and stirs condensing works, is warming up to 100 ℃, uses CO
2gas displacement three times, continues ventilate and keep CO
2pressure is 2.0MPa reaction 1h, makes the cyclic carbonate ester that end group contains epoxy group(ing).The transformation efficiency that records epoxy group(ing) is 0.46.
Take the above-mentioned cyclic carbonate ester of 100g, 200gN, dinethylformamide, 17.4g1,6-hexanediamine adds in 500ml four-hole boiling flask, and stirring reaction 2h makes hydridization non-isocyanate polyurethane solution at 60 ℃, and solution is light yellow transparent liquid.
After above-mentioned solution is desolventized, pour tetrafluoroethylene mould into, under room temperature, place 24h, 50 ℃ of baking ovens are placed 48h and are made hydridization non-isocyanate polyurethane film.
Film physical property is as follows: second-order transition temperature :-21.5 ℃; Tensile strength: 1.08MPa; Elongation at break: 97%.
embodiment 4
By 200g epoxy resin E-44,2g tetrabutyl iodate amine adds in autoclave, and sealed reactor is opened induction stirring and stirs condensing works, is warming up to 150 ℃, uses CO
2gas displacement three times, continues ventilate and keep CO
2pressure is 1.5MPa reaction 1h, makes the cyclic carbonate ester that end group contains epoxy group(ing).The transformation efficiency that records epoxy group(ing) is 0.51.
Take the above-mentioned cyclic carbonate ester of 100g, 200g1,4-dioxane, 0.5g triethylamine, 8.2g quadrol add in 500ml four-hole boiling flask, and under normal temperature, stirring reaction 10h makes hydridization non-isocyanate polyurethane solution, and solution is light yellow transparent liquid.
After above-mentioned solution is desolventized, pour tetrafluoroethylene mould into, under room temperature, place 24h, 50 ℃ of baking ovens are placed 48h and are made hydridization non-isocyanate polyurethane film.
Film physical property is as follows: second-order transition temperature: 5 ℃; Tensile strength: 1.47MPa; Elongation at break: 67%.
Claims (10)
1. a synthetic method for hydridization non-isocyanate polyurethane, is characterized in that its synthetic method step is as follows:
(1) epoxy resin and catalyzer are added in autoclave, sealing autoclave, opens stirring, is warming up to 60～150 ℃, uses CO
2gas displacement continues afterwards ventilation for three times and keeps CO
2pressure is 0.5～2MPa reaction, 1～4h, generates the cyclic carbonate ester that end group contains epoxy group(ing);
(2) by cyclic carbonate ester and amine under solvent exists 30～60 ℃ react 2～10h, obtain hydridization non-isocyanate polyurethane solution;
(3) pour hydridization non-isocyanate polyurethane solution into mould, after desolventizing, make hydridization non-isocyanate polyurethane film.
2. the synthetic method of hydridization non-isocyanate polyurethane as claimed in claim 1, is characterized in that: described in step (1), epoxy resin is epoxy resin E-21, E-44, E-51.
3. the synthetic method of hydridization non-isocyanate polyurethane as claimed in claim 1, is characterized in that: described in step (1), catalyzer comprises organic amine salt, inorganic salts or their mixture.
4. the synthetic method of hydridization non-isocyanate polyurethane as claimed in claim 3, is characterized in that: described organic amine salt is four butyl bromation amine, tetrabutylammonium chloride, tetrabutyl iodate amine or two or more mixture arbitrarily wherein.
5. hydridization non-isocyanate polyurethane synthetic method as claimed in claim 3, is characterized in that: described inorganic salt are Sodium Bromide, potassiumiodide or calcium chloride.
6. the synthetic method of hydridization non-isocyanate polyurethane as claimed in claim 3, is characterized in that: described catalyzer, 0.1～2wt% that its add-on is epoxy resin.
7. the synthetic method of hydridization non-isocyanate polyurethane as claimed in claim 1, is characterized in that: in step (2), amine is organic amine.
8. the synthetic method of hydridization non-isocyanate polyurethane as claimed in claim 7, is characterized in that: described organic amine is quadrol, hexanediamine, polyethylene polyamine or two or more mixture arbitrarily wherein.
9. the synthetic method of hydridization non-isocyanate polyurethane as claimed in claim 1, it is characterized in that: described in step (2), solvent is organic polar solvent, described organic polar solvent is DMF, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane.
10. the synthetic method of hydridization non-isocyanate polyurethane as claimed in claim 1, it is characterized in that: in described step (3), pour hydridization non-isocyanate polyurethane solution into mould, vacuum desolventizes rear room temperature and places 24h, 50 ℃ of baking ovens are placed 48h, make hydridization non-isocyanate polyurethane film.
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| CN201110450438.6A CN102731779B (en) | 2011-12-29 | 2011-12-29 | Synthetic method of hybrid non-isocyanate polyurethane |
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| CN201110450438.6A CN102731779B (en) | 2011-12-29 | 2011-12-29 | Synthetic method of hybrid non-isocyanate polyurethane |
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| CN102731779A CN102731779A (en) | 2012-10-17 |
| CN102731779B true CN102731779B (en) | 2014-02-26 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013322B (en) * | 2013-01-07 | 2015-07-22 | 中北大学 | Preparation method of epoxy non-isocyanate polyurethane heavy anti-corrosion coating |
| CN105219125B (en) * | 2015-10-26 | 2017-06-16 | 江南大学 | A kind of preparation method of cold curing non-isocyanate water polyurethane base high molecular dye |
| CN105399948A (en) * | 2015-12-08 | 2016-03-16 | 王景泉 | Isocyanate-free polyurethane UV resin and preparation method thereof |
| CN106008966B (en) * | 2016-07-01 | 2018-11-23 | 中国科学院山西煤炭化学研究所 | The method of carbon dioxide preparation hybrid non-isocyanate polyurethane |
| CN109467664B (en) * | 2017-09-08 | 2021-01-26 | 汪上晓 | Preparation method of polyurethane resin |
| CN111662626B (en) * | 2020-07-04 | 2021-08-27 | 上海暄洋化工材料科技有限公司 | Isocyanate-free high-wear-resistance polyurethane coating and preparation process thereof |
| CN111909360B (en) * | 2020-08-11 | 2023-08-01 | 深圳市宝安区新材料研究院 | High-elasticity epoxy curing agent, preparation method and epoxy resin |
| 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 |
| CN115594842A (en) * | 2022-09-16 | 2023-01-13 | 浙江众立合成材料科技股份有限公司（Cn） | Method for preparing non-isocyanate polyurethane by using disulfide bicyclocarbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100593547C (en) * | 2006-05-12 | 2010-03-10 | 中国科学院山西煤炭化学研究所 | Method for generating nonisocyanate polyurethane using natural reproducible resource |
| CN101260232A (en) * | 2008-04-15 | 2008-09-10 | 中国科学院山西煤炭化学研究所 | Mixing type nonisocyanate polyurethane and preparation method thereof |
| CN101812175A (en) * | 2009-02-20 | 2010-08-25 | 任旭 | Nonisocyanate polyurethane synthesized by using carbon dioxide(CO2) as raw material |
| JP5069737B2 (en) * | 2009-11-19 | 2012-11-07 | 大日精化工業株式会社 | imitation leather |
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