CN105646317A - Preparation method for trimethylolpropane tri[3-(2-methyl aziridinyl)propionic ester] - Google Patents
Preparation method for trimethylolpropane tri[3-(2-methyl aziridinyl)propionic ester] Download PDFInfo
- Publication number
- CN105646317A CN105646317A CN201610031335.9A CN201610031335A CN105646317A CN 105646317 A CN105646317 A CN 105646317A CN 201610031335 A CN201610031335 A CN 201610031335A CN 105646317 A CN105646317 A CN 105646317A
- Authority
- CN
- China
- Prior art keywords
- methylaziridine
- propionic ester
- preparation
- trimethylolpropane tris
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 title claims abstract description 27
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 6
- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylaziridine Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 claims description 32
- 239000007983 Tris buffer Substances 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002274 desiccant Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 208000035126 Facies Diseases 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 238000005406 washing Methods 0.000 abstract description 6
- -1 2-methyl aziridinyl Chemical group 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000047 product Substances 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 241000283898 Ovis Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012501 chromatography medium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method for trimethylolpropane tri[3-(2-methyl aziridinyl)propionic ester]. The problems that in the prior art, highly toxic products are adopted, and the yield is low are mainly solved. According to the technical scheme for solving the problem, the preparation method for trimethylolpropane tri[3-(2-methyl aziridinyl)propionic ester] comprises the steps that trimethylolpropane tri-acrylic ester and a 2-methyl aziridinyl water solution are adopted as raw materials, a catalyst is added in an organic solvent system for a Michael addition reaction, and the product is obtained through aftertreatment of skimming, washing, skimming, drying and solvent removal. The method can be used for preparing trimethylolpropane tri[3-(2-methyl aziridinyl)propionic ester].
Description
Technical field
The preparation method that the present invention relates to a kind of trimethylolpropane tris [3-(2-methylaziridine base) propionic ester].
Background technology
Trimethylolpropane tris [3-(2-methylaziridine base) propionic ester] is a kind of cross-linking agent and firming agent, and structural formula is as follows:
English name Trimethylolpropanetris [3-(2-methylaziridinyl) propionate], referred to as: TTMAP, its CAS:64265-57-2, molecular weight is 467.6, is clear amber liquid under room temperature, and density is 1.07g/mL, boiling point is 532.1 DEG C, flash-point is 275.6 DEG C, and refractive index is 1.477, and aziridine content is 6.0. The aziridine functional group of trimethylolpropane tris [3-(2-methylaziridine base) propionic ester] and special molecular structure, make it have good water solublity and oil-soluble simultaneously, the goods of the polymer such as Polypropionate, polyethylene, polyurethane, polystyrene-maleic anhydride, protein and polysaccharide there are good crosslinking and curing performance, are widely used in the fields such as coating, adhesive, ink, imaging (Photography), optical fiber, military project initiator.
Coating is that trimethylolpropane tris [3-(2-methylaziridine base) propionic ester] applies maximum field, has outstanding water solublity and oil-soluble due to TTMAP, gives it and have multi-functional coreactivity. TTMAP is usable in the middle of almost all of polymeric system, after adding TTMAP, it is possible to improve the adhesiveness of coating, intensity, mechanical performance, dissolubility and water resistance. Modified coating is usable in magnetic recording material, timber, prevents scrawling material, paper, eyeglass, it is also possible to be used for improving the adhesiveness of base layer dope.
Adhesive field is the third-largest application of TTMAP, with the addition of TTMAP and can improve the mechanical performance of tradition adhesive. Such as, mixing the polymerization catalyst that can prepare a kind of acrylic monomers with TTMAP with organic boron-amine, the adhesiveness improving propionic ester is had extraordinary effect by this catalyst, and the high polymer binder obtained only has only small surface energy.
Ink and print field mainly improve the cohesive of lipid aggregate thing with TTMAP, including Polypropionate, dispersions of polyurethanes, polrvinyl chloride and lacca etc.
In sensitive material field, TTMAP has a wide range of applications.The egative film of film is usually rolled on carrier film (usually macromolecular material) two sides by multilayer material, including many levels, such as pigment, non-pigment lining, basic unit, antistatic layer, silver layer, imaging layer and wear-resistant friction layer. TTMAP almost can apply to all of layer.
TTMAP can also be applied to temperature-sensitive and electrophotographic image forming field, for reducing the resistance on top layer and improving the sensitivity of record. Heat transfer material is transmitted ink layer by the heat on polyester counterdie upper strata and a solid lower membrane forms. Lower membrane is to be prepared by styrene-maleic acid copolymer and TTMAP, and ink layer is to be prepared by Brazil wax and white carbon black, and this combination table reveals extraordinary anticreep performance and high heat sensitivity.
In fiber treatment field, with the addition of the fiber of TTMAP and can form the protecting film of one layer of property on the surface of fiber, thus improving the resistance to dry-cleaning of fiber and the performance of washing, can be applicable in Pilus Caprae seu Ovis, knitting wool, polyester and nylon.
Other field can be used for the chromatography media of military industry field propellant. TTMAP, as the firming agent of a kind of novel high added value and cross-linking agent, has application in the army and the people two. Both can whereby deeper into intervention military industry field, have again the demand purpose of relative maturity, carry out its research and there is good feasibility.
Li Fengze etc., the synthesis [J] of three (��-'-aziridino propanoic acid) trihydroxymethyl propane ester. University of the Inner Mongol's journal, 1985,16 (4): 631-632; R.R.Roesler, K.Danielmeier.Tris-3-(1-aziridino) propionatesandtheiruseinformulatedproducts.ProgressinOrg anicCoatings, 2004,50:1-27 refer to two kinds of primary synthetic methods of TTMAP. They are: route 1 mainly acrylic acid and trimethylolpropane first make trimethylolpropane trimethacrylate, then carrying out Michael addition reaction with 2-methylaziridine, obtain last product, post-reaction treatment is fairly simple, and yield is also higher, the ratio that reaction carries out is more thoroughly. Route 2 is mainly and 2-methylaziridine generation Michael addition reaction first with acrylic acid methyl ester., then carries out ester exchange with trimethylolpropane again, and ester exchange is difficult to carry out, and unreacted raw material completely and by-product are difficult to separate. Therefore, two sections of documents are all to select route 1 as best route. Wherein the technique of route 1 is all again to carry out Michael addition reaction with anhydrous 2-methylaziridine, referring to: Sun great Qing, Li Yanfeng, Zhou Xiangdong. the synthesis of Multi-functional Binder for Leather Finish and applied research. Chinese leather, 1999,28 (7): 11-14.; He Xiaoqiang. the synthesis of multi-group crosslink agent and performance study. Central China Normal University's master thesis, 2008.
Preparing anhydrous 2-methylaziridine needs with solid sodium hydroxide, 2-methylaziridine aqueous solution to be carried out the layering of 2-methylaziridine and water to adopt anhydrous 2-methylaziridine to have following defects that in route 1, complex operation, owing to anhydrous 2-methylaziridine boiling point is low, volatility is big, itself has hypertoxicity, operator are injured greatly, potential safety hazard is very big, thus adopts the synthetic route actual production of anhydrous 2-methylaziridine not have feasibility, can only at laboratory lab scale.
Summary of the invention
The technical problem to be solved is the problem using toxic articles, yield relatively low in prior art, it is provided that the preparation method of a kind of new trimethylolpropane tris [3-(2-methylaziridine base) propionic ester].The method has the advantage not using toxic articles, yield higher.
For solving the problems referred to above, the technical solution used in the present invention is as follows: the preparation method of a kind of trimethylolpropane tris [3-(2-methylaziridine base) propionic ester], comprises the steps:
(1) by 2-methylaziridine aqueous solution organic solvent diluting, temperature controls at 0-5 DEG C, standby;
(2) by trimethylolpropane trimethacrylate at room temperature with organic solvent diluting, standby;
(3) to adding catalyst in the 2-methylaziridine aqueous solution of organic solvent diluting;
(4) control temperature in reaction system and be 0-5 DEG C, the solution obtained in (2) is added in the solution that (1) and (3) forms, carry out Michael addition reaction, the solution that obtains in (2) add terminate after continue at 15-25 DEG C at stirring reaction 12-16h;
(5) reaction terminates, carry out separatory operation, separate organic facies, use deionized water wash organic facies again, separatory again, after gained organic facies desiccant is dried, through collecting by filtration clear liquid, gained residue after the de-organic solvent of concentrating under reduced pressure clear liquid, is trimethylolpropane tris [3-(2-methylaziridine base) propionic ester].
In technique scheme, it is preferable that in step (1), the concentration of 2-methylaziridine aqueous solution is 30%-80%.
In technique scheme, it is preferable that the organic solvent described in step (1) and (2) is selected from dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethanes, benzene, toluene, hexamethylene, petroleum ether, normal hexane.
In technique scheme, it is preferable that the catalyst described in step (3) is selected from Feldalat NM, Sodium ethylate, sodium hydride, Sodamide., triethylamine, pyridine.
In technique scheme, it is preferable that the desiccant described in step (5) is selected from anhydrous magnesium sulfate, anhydrous calcium chloride, molecular sieve; Concentrating under reduced pressure temperature described in step (5) controls at 30-45 DEG C.
In technique scheme, it is preferable that in step (4), trimethylolpropane trimethacrylate is 1:1.001-1.1 with the mol ratio of 2-methylaziridine.
In technique scheme, it is preferable that consumption of organic solvent is the 25%-60% of reactant liquor gross mass.
In technique scheme, it is preferable that catalyst amount is the 0.05%-0.20% of reactant liquor gross mass.
In technique scheme, it is more preferred to, the organic solvent described in step (1) and (2) is 1,2-dichloroethanes.
In technique scheme, it is more preferred to, the catalyst described in step (3) is triethylamine.
The trimethylolpropane tris [3-(2-methylaziridine base) propionic ester] obtained by the preparation method of the present invention, productivity more than 95%. The present invention is compared with prior art, it is possible to avoiding using the anhydrous 2-methylaziridine of severe toxicity, process operability is strong, and yield is high, and cost is low, is suitable for industrialized production, achieves good technique effect.
The invention will be further elaborated by the examples below, but is not limited only to the present embodiment.
Detailed description of the invention
In the present invention, trimethylolpropane trimethacrylate has commercialization, it is possible to directly buy, and 2-methylaziridine aqueous solution is prepared voluntarily according to document.
[comparative example]
Anhydrous 2-methylaziridine synthesizes
Putting into isopropanolamine 125g (1.664mol), water 200g in glass reaction bottle, open low temperature bath, drip 170g98% sulphuric acid (1.699mol) after cooling, interior temperature control is below 30 DEG C. Dropwise, continue stirring 30min.
All feed liquids being transferred in another bigger glass reaction bottle, water is steamed in decompression, and outer temperature is set to 110 DEG C, drop temperature about 40 DEG C, and after water outlet terminates, solidifying occurs in reaction, and white solid improves temperature to 150 DEG C, solidifies 2h.
Adding 30%NaOH (4.950mol) solution of 660g, outer temperature is set to 110 DEG C, carries out air-distillation, and solid slowly dissolves, and stirring continues, and when T=80 DEG C, 2-methylaziridine aqueous solution out flows into reception still, and amount is about 150 milliliters.
End product is poured in beaker and is made 2-methylaziridine and aqueous phase layering with solid sodium hydroxide, to prepare anhydrous 2-methylaziridine, cools down with ice-water bath, altogether about need sodium hydroxide 50g outside beaker. Collecting upper strata 2-methylaziridine clear liquid, then dry with solid NaOH, its purity of gas chromatographic analysis, purity is about 98%, and stable yield, about 78%, does not contain moisture, obtains anhydrous 2-methylaziridine and is about 75g.
The synthesis of TTMAP
In glass reaction bottle add trimethylolpropane trimethacrylate 25g (0.084mol), 1,2-dichloroethanes 15g, open stirring and jacket refrigerating, interior temperature is set to 5 DEG C, slowly drip anhydrous 2-methylaziridine 15g (0.263mol), dropwise after 20 DEG C of stirring reaction 12h, carry out decompression distillation, remove unnecessary 2-methylaziridine and solvent, obtain end product 37.3g, yield 95%.
[embodiment 1]
Have jacket refrigerating brine-cooled, with mechanical agitation, thermocouple, head tank Dropping feeder reactor in, closed conduit is utilized to add 70%2-methylaziridine aqueous solution 79.2kG (0.971kmol), add 1,2-dichloroethanes 85kG, mix homogeneously under mechanical agitation, add 500g triethylamine, make temperature in system be cooled to 0-5 DEG C; The solution of dropping 90kG trimethylolpropane trimethacrylate (0.304kmol) and 96kG1,2-dichloroethanes subsequently, in controlling, temperature is less than 5 DEG C, is added dropwise to complete continuation at 20 DEG C of stirring reaction 12h; The product that post processing obtains after separatory, washing, separatory, dry, desolventizing, is the target product of the present invention, obtains 140kG, yield 98.6%. Wherein, desiccant adopts anhydrous magnesium sulfate, and concentrating under reduced pressure temperature controls at 40 DEG C.
[embodiment 2]
Have jacket refrigerating brine-cooled, with mechanical agitation, thermocouple, head tank Dropping feeder reactor in, closed conduit is utilized to add 75%2-methylaziridine aqueous solution 81kG (1.064kmol), add chloroform 80kG, mix homogeneously under mechanical agitation, add 500g triethylamine, make temperature in system be cooled to 0-5 DEG C; The solution of dropping 100kG trimethylolpropane trimethacrylate (0.337kmol) and 80kG chloroform subsequently, in controlling, temperature is less than 5 DEG C, is added dropwise to complete continuation at 20 DEG C of stirring reaction 16h; The product that post processing obtains after separatory, washing, separatory, dry, desolventizing, is the target product of the present invention, obtains 154kG, yield 97.6%. Wherein, desiccant adopts anhydrous magnesium sulfate, and concentrating under reduced pressure temperature controls at 40 DEG C.
[embodiment 3]
Have jacket refrigerating brine-cooled, with mechanical agitation, thermocouple, head tank Dropping feeder reactor in, closed conduit is utilized to add 60%2-methylaziridine aqueous solution 100kG (1.051kmol), add benzene 75kG, mix homogeneously under mechanical agitation, add 500g pyridine, make temperature in system be cooled to 0-5 DEG C; The solution of dropping 95kG trimethylolpropane trimethacrylate (0.321kmol) and 75kG benzene subsequently, in controlling, temperature is less than 5 DEG C, is added dropwise to complete continuation at 20 DEG C of stirring reaction 14h; The product that post processing obtains after separatory, washing, separatory, dry, desolventizing, is the target product of the present invention, obtains 145kG, yield 96.6%.Wherein, desiccant adopts anhydrous calcium chloride, and concentrating under reduced pressure temperature controls at 45 DEG C.
[embodiment 4]
Have jacket refrigerating brine-cooled, with mechanical agitation, thermocouple, head tank Dropping feeder reactor in, closed conduit is utilized to add 40%2-methylaziridine aqueous solution 200kG (1.401kmol), add toluene 90kG, mix homogeneously under mechanical agitation, add 500g Feldalat NM, make temperature in system be cooled to 0-5 DEG C; The solution of dropping 130kG trimethylolpropane trimethacrylate (0.439kmol) and 90kG toluene subsequently, in controlling, temperature is less than 5 DEG C, is added dropwise to complete continuation at 20 DEG C of stirring reaction 16h; The product that post processing obtains after separatory, washing, separatory, dry, desolventizing, is the target product of the present invention, obtains 200kG, yield 97.4%. Wherein, desiccant adopts molecular sieve, and concentrating under reduced pressure temperature controls at 45 DEG C.
Obviously, the present invention is compared with prior art, it is possible to avoiding using the anhydrous 2-methylaziridine of severe toxicity, process operability is strong, and yield is high, and cost is low, is suitable for industrialized production, achieves good technique effect.
Claims (10)
1. a preparation method for trimethylolpropane tris [3-(2-methylaziridine base) propionic ester], comprises the steps:
(1) by 2-methylaziridine aqueous solution organic solvent diluting, temperature controls at 0-5 DEG C, standby;
(2) by trimethylolpropane trimethacrylate at room temperature with organic solvent diluting, standby;
(3) to adding catalyst in the 2-methylaziridine aqueous solution of organic solvent diluting;
(4) control temperature in reaction system and be 0-5 DEG C, the solution obtained in (2) is added in the solution that (1) and (3) forms, carry out Michael addition reaction, the solution that obtains in (2) add terminate after continue at 15-25 DEG C at stirring reaction 12-16h;
(5) reaction terminates, carry out separatory operation, separate organic facies, use deionized water wash organic facies again, separatory again, after gained organic facies desiccant is dried, through collecting by filtration clear liquid, gained residue after the de-organic solvent of concentrating under reduced pressure clear liquid, is trimethylolpropane tris [3-(2-methylaziridine base) propionic ester].
2. the preparation method of trimethylolpropane tris [3-(2-methylaziridine base) propionic ester] according to claim 1, it is characterised in that in step (1), the concentration of 2-methylaziridine aqueous solution is 30%-80%.
3. the preparation method of trimethylolpropane tris [3-(2-methylaziridine base) propionic ester] according to claim 1, it is characterized in that the organic solvent described in step (1) and (2) is selected from dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethanes, benzene, toluene, hexamethylene, petroleum ether, normal hexane.
4. the preparation method of trimethylolpropane tris [3-(2-methylaziridine base) propionic ester] according to claim 1, it is characterised in that the catalyst described in step (3) is selected from Feldalat NM, Sodium ethylate, sodium hydride, Sodamide., triethylamine, pyridine.
5. the preparation method of trimethylolpropane tris [3-(2-methylaziridine base) propionic ester] according to claim 1, it is characterised in that the desiccant described in step (5) is selected from anhydrous magnesium sulfate, anhydrous calcium chloride, molecular sieve; Concentrating under reduced pressure temperature described in step (5) controls at 30-45 DEG C.
6. the preparation method of trimethylolpropane tris [3-(2-methylaziridine base) propionic ester] according to claim 1, it is characterised in that in step (4), trimethylolpropane trimethacrylate is 1:1.001-1.1 with the mol ratio of 2-methylaziridine.
7. the preparation method of trimethylolpropane tris [3-(2-methylaziridine base) propionic ester] according to claim 1, it is characterised in that consumption of organic solvent is the 25%-60% of reactant liquor gross mass.
8. the preparation method of trimethylolpropane tris [3-(2-methylaziridine base) propionic ester] according to claim 1, it is characterised in that catalyst amount is the 0.05%-0.20% of reactant liquor gross mass.
9. the preparation method of trimethylolpropane tris [3-(2-methylaziridine base) propionic ester] according to claim 3, it is characterised in that the organic solvent described in step (1) and (2) is 1,2-dichloroethanes.
10. the preparation method of trimethylolpropane tris [3-(2-methylaziridine base) propionic ester] according to claim 4, it is characterised in that the catalyst described in step (3) is triethylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610031335.9A CN105646317A (en) | 2016-01-18 | 2016-01-18 | Preparation method for trimethylolpropane tri[3-(2-methyl aziridinyl)propionic ester] |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610031335.9A CN105646317A (en) | 2016-01-18 | 2016-01-18 | Preparation method for trimethylolpropane tri[3-(2-methyl aziridinyl)propionic ester] |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105646317A true CN105646317A (en) | 2016-06-08 |
Family
ID=56486868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610031335.9A Pending CN105646317A (en) | 2016-01-18 | 2016-01-18 | Preparation method for trimethylolpropane tri[3-(2-methyl aziridinyl)propionic ester] |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105646317A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947860A (en) * | 2018-06-25 | 2018-12-07 | 同济大学 | Trimethylolpropane tris ((N, N- bis- (6- amino hexylidene)) -3- aminopropan acid esters) and preparation method thereof |
| CN109180509A (en) * | 2018-06-25 | 2019-01-11 | 上海龙灯环保科技有限公司 | Trimethylolpropane tris ((N, N- bis- (2- amino-ethyl)) -3- aminopropan acid esters) and preparation method and application |
| CN111960982A (en) * | 2020-08-28 | 2020-11-20 | 湖南长岭石化科技开发有限公司 | Synthetic method of aromatic aziridine crosslinking agent |
| CN113999559A (en) * | 2020-03-30 | 2022-02-01 | 欧朋(深圳)环保涂料有限公司 | Water-based primer for vehicle |
| CN114276706A (en) * | 2020-03-30 | 2022-04-05 | 欧朋(深圳)环保涂料有限公司 | Water-based varnish for vehicle |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5712331A (en) * | 1995-08-15 | 1998-01-27 | Rockwell International Corporation | Curable epoxy compositions containing aziridine in supercritical fluid carbon dioxide |
| US20070066709A1 (en) * | 2005-09-20 | 2007-03-22 | Tamkang University | Manufacturing method for ambient temperature self-curable system of water borne-based polymeric ink |
| CN102643452A (en) * | 2011-02-16 | 2012-08-22 | 中国中化股份有限公司 | Method for improving aziridine cross-linking agent stability |
| CN104478776A (en) * | 2014-12-19 | 2015-04-01 | 上海浩登材料科技有限公司 | Preparation method of aziridine cross-linking agent |
| CN104788721A (en) * | 2015-04-04 | 2015-07-22 | 成都育芽科技有限公司 | Aziridine crosslinker containing composition and preparation method thereof |
-
2016
- 2016-01-18 CN CN201610031335.9A patent/CN105646317A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5712331A (en) * | 1995-08-15 | 1998-01-27 | Rockwell International Corporation | Curable epoxy compositions containing aziridine in supercritical fluid carbon dioxide |
| US20070066709A1 (en) * | 2005-09-20 | 2007-03-22 | Tamkang University | Manufacturing method for ambient temperature self-curable system of water borne-based polymeric ink |
| CN102643452A (en) * | 2011-02-16 | 2012-08-22 | 中国中化股份有限公司 | Method for improving aziridine cross-linking agent stability |
| CN104478776A (en) * | 2014-12-19 | 2015-04-01 | 上海浩登材料科技有限公司 | Preparation method of aziridine cross-linking agent |
| CN104788721A (en) * | 2015-04-04 | 2015-07-22 | 成都育芽科技有限公司 | Aziridine crosslinker containing composition and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李逢泽，边占喜: "三(β-氮丙啶基丙酸)三甲醇丙烷酯的合成", 《内蒙古大学学报(自然科学版)》 * |
| 郭保国，赵文献 主编: "《有机合成重要单元反应》", 30 June 2009 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947860A (en) * | 2018-06-25 | 2018-12-07 | 同济大学 | Trimethylolpropane tris ((N, N- bis- (6- amino hexylidene)) -3- aminopropan acid esters) and preparation method thereof |
| CN109180509A (en) * | 2018-06-25 | 2019-01-11 | 上海龙灯环保科技有限公司 | Trimethylolpropane tris ((N, N- bis- (2- amino-ethyl)) -3- aminopropan acid esters) and preparation method and application |
| CN113999559A (en) * | 2020-03-30 | 2022-02-01 | 欧朋(深圳)环保涂料有限公司 | Water-based primer for vehicle |
| CN114276706A (en) * | 2020-03-30 | 2022-04-05 | 欧朋(深圳)环保涂料有限公司 | Water-based varnish for vehicle |
| CN111960982A (en) * | 2020-08-28 | 2020-11-20 | 湖南长岭石化科技开发有限公司 | Synthetic method of aromatic aziridine crosslinking agent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105646317A (en) | Preparation method for trimethylolpropane tri[3-(2-methyl aziridinyl)propionic ester] | |
| CN107089914B (en) | Cardanol-based acrylate reactive diluent and preparation method and application thereof | |
| CN101284805A (en) | Production method for 2-acryloylamino-2-methylpropane sulfonic acid | |
| WO2019099944A1 (en) | Recyclable and reconfigurable high-performance polymer networks and uses thereof | |
| CN107056828B (en) | A kind of preparation method of the star-like compound based on three polyindenes | |
| Sunitha et al. | Shape memory polymers (SMPs) derived from phenolic cross-linked epoxy resin via click chemistry | |
| Li et al. | Novel halogen-free deep eutectic solvents for efficient extraction of phenolic compounds from real coal tar | |
| CN101407450A (en) | Chemical recovery method for waste polycarbonate material | |
| CN108623543B (en) | Furan derivative-containing triarylethene-based photochromic material and its synthesis method and application | |
| Tao et al. | Preparation of modified polylactic acid melt coated urea material and its green coating technique | |
| CN106478381A (en) | A kind of method that bis ether fluorenes is prepared by catalyzing epoxyethane | |
| Tu et al. | A porous thienyl cyclodextrin polymer synthesized in a homogeneous ionic liquid catalytic system for the rapid removal of pharmaceuticals and personal care products (PPCPs) | |
| Long et al. | Synthesis of pyrogallol triglycidyl ether: A bio-based epoxy resin monomer with low viscosity, high activity, and good thermomechanical properties | |
| CN108503669A (en) | A kind of efficient diarylethene light-operated switch molecule and preparation method thereof | |
| CN106823984B (en) | A kind of abietyl tertiary amine class surfactant and its preparation method and application | |
| CN102942444B (en) | Synthesis method of 2,2'-dibromo-9,9'-spirobifluorene | |
| Liu et al. | Green synthesis of a typical chiral stationary phase of cellulose-tris (3, 5-dimethylphenylcarbamate) | |
| CN113412835A (en) | Synthesis method of novel chlamydomonas pheromone component | |
| CN101747162A (en) | Synthetic process of p-methoxystyrene | |
| Chen et al. | Microwave-assisted synthesis and properties of sodium glycol bis-(isooctyl) sulfosuccinate | |
| CN108484435B (en) | Modified azobenzene derivative for dyeing and finishing fabric and preparation method thereof | |
| CN102030650A (en) | Novel process for synthesizing dimethylcyclopropanecarboxylate | |
| Miyajima et al. | New fluorous gelators for perfluorodecalin | |
| CN107629033A (en) | A kind of synthetic method of [60] fullerene benzothiophene derivative that DDQ promotes | |
| CN102675148A (en) | Preparation method of hydroxybenzyl cyanide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160608 |