CN101524650A - Novel solid polymer catalyst for synthesizing dicyclohexylcarbodiimide - Google Patents
Novel solid polymer catalyst for synthesizing dicyclohexylcarbodiimide Download PDFInfo
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- CN101524650A CN101524650A CN200810069424A CN200810069424A CN101524650A CN 101524650 A CN101524650 A CN 101524650A CN 200810069424 A CN200810069424 A CN 200810069424A CN 200810069424 A CN200810069424 A CN 200810069424A CN 101524650 A CN101524650 A CN 101524650A
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Abstract
The invention discloses a preparation method for a solid organophosphorus catalyst for synthesizing dicyclohexylcarbodiimide and use. The preparation process for the solid polymer catalyst is characterized in that an intermediate obtained by reaction of PCl3 and propylene oxide is orderly reacted with isoprene, diethanolameine, alkali and allyl chloride to generate monomers of diallyl ether-1-diethanolamine-3-methyl-3-phosphol-1-oxides which are initiated by BPO to generate the solid organophosphorus polymer catalyst. The catalyst is used for catalyzing and condensing cyclohexyl isocyanate to obtain the dicyclohexylcarbodiimide, the dosage is between 0.1 and 0.5 percent, and the reaction temperature for removing carbon dioxide by condensation is between 50 and 170 DEG C. The catalyst has simple synthesis process and low cost and can be recycled.
Description
Technical field
The present invention relates to a kind of preparation method and use of organophosphor solid-phase catalyst of synthesizing dicyclohexylcarbodiimide.
Background technology
Along with the development of polypeptide, protein chemistry, people design, have synthesized polytype condensing agent to satisfy polypeptide, the synthetic requirement of protein.The condensing agent dicyclohexylcarbodiimide that nineteen fifty-five is proposed by Sheehan and Hess (Dicyclohexylcarbodiimide is called for short DCC) is representative.It is widely used in medicine, health products, cosmetics, biologic product and other organic synthesis fields.Therefore the catalyst that is used for synthetic DCC becomes the focus of people's research.The organic phosphates catalyst that the 60-80 age in 20th century constantly occurs, employing generates the carbodiimides route from the isocyanates condensation becomes main flow, not only be used for the synthetic carbodiimides of monoisocyanates, vulcabond synthesizes polycarbodiimide, is used for catalytic synthesis of C diimine modified isocyanate product simultaneously.This method yield is higher, and quality is better.
Because organophosphorus compound is poisonous, discarded object easily pollutes environment, so Upjohn company developed polymer graft organophosphor solid-phase catalyst, and the filtering catalyst is crossed in the reaction back, can get pure carbodiimides.Polymer graft organophosphor solid-phase catalyst catalytic efficiency height, the reaction condition gentleness; Catalyst separates from reactant easily, needn't add deactivator, can get comparatively pure carbodiimide, is the developing direction of catalyzing and condensing.
The synthesis technique complexity of US 4348337 disclosed solid polymer catalysts, step is various, the condition harshness, product is difficult for poisonous, the inflammable danger of used material in acquisition and the preparation process.Its technical process is with benzene and white phosphorus, after the dehydration, adds isoprene under nitrogen protection, phosphorus trichloride, iodine etc. react 1-chloro-3-methyl-3-phosphorus heterocycle amylene liquid (A).By (A) and expoxy propane, diethanol amine and polyformaldehyde reaction, get 1-diethanol amine ylmethyl-3-methyl-3-phosphorus heterocycle amylene-1-oxide (B).(B) react under protection of nitrogen gas with triethylamine, (methyl) acryloyl chloride, get two (methyl) acrylic acid-1-diethanol amine ylmethyl-3-methyl-3-phosphorus heterocycle amylene-1-oxide (C) of brown monomer.Monomer (III) and benzoyl peroxide (BPO) are dispersed in the water and promptly get needed organophosphor solid polymer catalyst after the reaction.
Summary of the invention
The problem that the present invention solves is:
1, the catalyst synthesis technique is simple relatively, and reaction condition is gentle realizes that easily raw material is easy to get, and cost is low;
2, product is a solid matter, and catalytic efficiency height in the application can be realized catalysis at low temperatures;
3, catalyst can be recycled and not lose catalytic activity.
The invention provides a kind of preparation method of new organophosphor solid catalyst, its technology is with PCl
3With expoxy propane (or oxirane, epoxy butane etc.) react intermediate (I) (PCl
3With expoxy propane mol ratio be 1: 1～2), this intermediate (I) again with isoprene react intermediate (II) (intermediate (I) is 1: 1～1.2 with isoprene mol ratio), intermediate (II) and diethanol amine (the mol ratio is 1～1.2: 1) react intermediate (III), intermediate (III) adds alkali, allyl chloride (intermediate (III), alkali, allyl chloride mol ratio is 1: 1～3: 1～1.5) reaction, obtain diallyl ether-1-diethanol amido-3-methyl-3-phosphorus heterocycle amylene-1-oxide monomer, with BPO initator (monomer 1～5%) cause the organophosphor solid polymer catalyst.
Below be the embodiment of patent of invention, but do not show present embodiment.
The specific embodiment:
Embodiment 1:
1) preparation of catalyst intermediate 1-chloro-3-methyl-3-phosphorus heterocycle amylene-1-oxide
With 137g (1mol) PCl
3Add in the three-necked bottle, drip 64g (1.1mol) propylene oxide reaction down after 1 hour in 25 ℃, the 70g isoprene is added drop-wise in the intermediate 25 ℃ of reactions after 1-2 hour, be heated to 100 ℃, 1 of generation is removed in decompression distillation, the 2-dichloropropane gets 150g 1-chloro-3-methyl-3-phosphorus heterocycle amylene-1-oxide.
2) preparation of monomer (diallyl ether-1-diethanol amido-3-methyl-3-phosphorus heterocycle amylene-1-oxide)
75.0g after (0.5mol) adding 53.0g diethanol amine, 55.0g triethylamine normal temperature react down in 1-chloro-3-methyl-3-phosphorus heterocycle amylene-1-oxide, filter desalination, add a certain amount of liquid caustic soda and drip the 85.0g chloropropene.Entire reaction below 50 ℃, drips reaction 1 hour in temperature, filtered brine, and the decompression distillation removal of impurity gets monomer C 160.0g.
3) preparation of phosphorus heterocycle solid-phase catalyst
10.0g monomer C and 0.40g benzoyl peroxide (BPO) are dispersed in the 50ml water, back flow reaction 1 hour, and cooled and filtered is separated, and with the acetone washing, the dry 6.0g yellow solid that gets is phosphorus heterocycle solid polymer catalyst.
Embodiment 2: phosphorus heterocycle solid polymer catalyst is used for synthetic DCC
Operating procedure: a certain amount of cyclohexyl isocyanate and solvent are added in the 500ml three-necked bottle, add the phosphorus heterocycle solid-phase catalyst again, there is tail gas to generate (tail gas absorbs with dilute NaOH solution) when slowly being warming up to uniform temperature, continued back flow reaction 8 hours, this moment emission-free substantially overflowing, stop heating, cooling.With this reacting liquid filtering, filter cake is a catalyst, recyclable utilization again.Filtrate is reduced pressure in distilling apparatus and is steamed front-end volatiles n-hexane solvent, and the cut of collecting under the 130-135 ℃/4-5mmHg promptly gets the product dicyclohexylcarbodiimide.Product is a white solid, the product recrystallization, and centrifugation obtains 99.0% DCC.
Claims (3)
- The novel solid polymer catalyst of 1 one kinds of synthesizing dicyclohexylcarbodiimides, described solid polymer catalyst preparation process is characterised in that: with PCl 3Get intermediate (I) (PCl with propylene oxide reaction 3With expoxy propane mol ratio be 1: 1～2), this intermediate (I) again with isoprene react intermediate (II) (intermediate (I) is 1: 1～1.2 with isoprene mol ratio), intermediate (II) and diethanol amine (the mol ratio is 1～1.2: 1) react intermediate (III), intermediate (III) adds alkali, allyl chloride (intermediate (III), alkali, allyl chloride mol ratio is 1: 1～3: 1～1.5) reaction, obtain diallyl ether-1-diethanol amido-3-methyl-3-phosphorus heterocycle amylene-1-oxide monomer, with BPO initator (monomer 1～5%) cause the organophosphor solid polymer catalyst.
- 2 organophosphor solid polymer catalysts as claimed in claim 1 are used for the cyclohexyl isocyanate catalyzing and condensing and get dicyclohexylcarbodiimide, and consumption is 0.1～5%, and the reaction temperature of condensation carbon dioxide removal is 50～170 ℃.
- 3 organophosphor solid polymer catalysts as claimed in claim 1 recycle more than 6 times.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200810069424A CN101524650A (en) | 2008-03-04 | 2008-03-04 | Novel solid polymer catalyst for synthesizing dicyclohexylcarbodiimide |
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| CN200810069424A CN101524650A (en) | 2008-03-04 | 2008-03-04 | Novel solid polymer catalyst for synthesizing dicyclohexylcarbodiimide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107250190A (en) * | 2015-02-26 | 2017-10-13 | 科思创德国股份有限公司 | The method for preparing the composition comprising poly- carbodiimide with improved storage stability |
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2008
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107250190A (en) * | 2015-02-26 | 2017-10-13 | 科思创德国股份有限公司 | The method for preparing the composition comprising poly- carbodiimide with improved storage stability |
| CN107250190B (en) * | 2015-02-26 | 2021-03-26 | 科思创德国股份有限公司 | Method for producing compositions comprising polycarbodiimides with improved storage stability |
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Open date: 20090909 |