CN1457926A - Molecule print high molecular super-nucleophilic catalyst and its preparing method - Google Patents
Molecule print high molecular super-nucleophilic catalyst and its preparing method Download PDFInfo
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- CN1457926A CN1457926A CN 03124083 CN03124083A CN1457926A CN 1457926 A CN1457926 A CN 1457926A CN 03124083 CN03124083 CN 03124083 CN 03124083 A CN03124083 A CN 03124083A CN 1457926 A CN1457926 A CN 1457926A
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- nitrobenzophenone
- acid phosphate
- methyl acid
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Abstract
The molecular print polymer super-nucleophilic catalyst consists of 4-amino pyridine 32-36 wt%, epoxy chloropropane 32-36 wt%, 4-nitrophenylmethyl phosphoric acid 9-13 wt% and crosslinking agent tolylene diisocyanate 19-23 wt%. The preparation process of the catalyst includes preparing di(4-nitrophenyl) methyl phosphate ester; preparing 4-nitrophenylmethyl phosphoric acid; preparing epoxy molecular print polymer with the materials including 4-amino pyridine, 4-nitrophenylmethyl phosphoric acid, epoxy chloropropane and crosslinking agent tolylene diisocyanate; and final catalytic activity test. The present invention has the advantages of the introducing of efficient acidylation catalyzing radical into the molecular print polymer catalyst to raise the activity; and the using of transition state analog print polymer to make the catalyst obtain the specificity on the substrate like artificial enzyme.
Description
(1) field under:
The invention belongs to a kind of polymer catalyst and preparation method thereof, particularly a kind of molecular engram macromolecule super-nucleophilic Catalysts and its preparation method.
(2) background technology:
At present, the molecular engram catalyst is the cross one another fields of front subject such as current molecular recognition, manual simulation's enzyme, abzyme.It is to simulate immune organism and a kind of method of the catalytic antibody that obtains with synthetic polymer catalyst, and the macromolecule that is obtained has single-minded catalytic activity.In vivo, antibody is in immunologic process, the protein that can combine with the antigen molecule selectivity.According to the Pauling principle, the antibody combination be stable ground state molecule, and the enzyme combination is unsettled transition state.Enzymatic promptly is by the transition state intermediate of stablizing substrate reaction to be quickened.So, the stable compound that is similar to the transition state intermediate on certain structure (is called the transition state analogies, TSA) as antigen, be used for immune organism, " trick " go out with TSA at complementary in shape antibody, this antibody has demonstrated the catalytic activity to this substrate immediately, is called as catalytic antibody or abzyme.In Polymer Synthesizing, TSA as template, is dissolved in it in liquid monomer.After monomer polymerization solidifies, formed the macroporous type crosslinked resin, if with TSA molecule wash-out from macromolecular network, will make the surface of macroreticular resin and inside stay many and " hole " complementation of TSA molecule space.In catalysis system, when substrate forms the transition state intermediate will with the narrow spectrum identification of this hole, temporarily live away from home hole and being stablized of intermediate has reduced the activation energy of reaction, thereby has improved reaction rate.Here it is so-called " molecular engram polymer catalyst ".The high molecular research of molecular engram that contains imidazole radicals appears in the newspapers.The super-nucleophilic catalyst is a kind of catalyst that has than the general stronger catalytic capability of nucleophilic catalyst such as imidazoles and pyridine.It refers in particular to 4-(N, the N-dialkyl amido) high activity of pyridine group in various acidylates and hydrolysis.Various super-nucleophilic catalyst are synthesized.They are widely used in the reaction of high steric hindrance substrate in the fine chemicals such as quickening those medicines are synthetic, spices.
(3) summary of the invention:
The object of the present invention is to provide a kind of molecular engram macromolecule super-nucleophilic Catalysts and its preparation method, it is that super-nucleophilic catalytic activity group is introduced in the molecular engram macromolecule, to strengthen the catalysis selectivity and the specificity of super-nucleophilic catalyst, be about to mix with monomer as the 4-nitrobenzophenone methyl acid phosphate of TSA, by polymerization, obtaining the macromolecule super-nucleophilic catalyst of TSA trace.
Technical scheme of the present invention: a kind of molecular engram macromolecule super-nucleophilic catalyst, it is characterized in that it is by 4-aminopyridine, epoxychloropropane, 4-nitrobenzophenone methyl acid phosphate and adds crosslinking agent and constituted, said 4-aminopyridine occupies 36%～32%, epoxychloropropane occupies 36%～32%, 4-nitrobenzophenone methyl acid phosphate occupies 9%～13%, add the crosslinking agent toluene di-isocyanate(TDI) simultaneously occupies 19%～23%.
Above-mentioned said molecular engram macromolecule super-nucleophilic Preparation of catalysts method is characterized in that it is made of following steps:
[step 1] produces two (4-nitrobenzophenone) methyl phosphorodithioates by raw material methyl acid phosphate dichloro, 4-nitrophenol;
[step 2] produces 4-nitrobenzophenone methyl acid phosphate by two (4-nitrobenzophenone) methyl phosphorodithioates of raw material, sodium hydroxide solution;
[step 3] produces the epoxy type molecularly imprinted polymer by raw material 4-aminopyridine, 4-nitrobenzophenone methyl acid phosphate, epoxychloropropane and crosslinking agent toluene di-isocyanate(TDI).
[step 4] catalytic activity test.
The above-mentioned said method of producing the epoxy type molecularly imprinted polymer adds 9%～13% 4-nitrobenzophenone methyl acid phosphate in 36%～32% 4-aminopyridine solution, stirs 30min.The epoxychloropropane of adding 36%～32% stirs 3～5h under 50～70 ℃ of temperature.Be cooled to 0 ℃, add 19%～23% toluene di-isocyanate(TDI) again, stir until the system gel; Solid is washed 20～30h in apparatus,Soxhlet's, obtain yellow solid after the vacuum drying.
Operation principle of the present invention is: the template that is made of 4-nitrobenzophenone methyl acid phosphate with the cross-linked epoxy macromolecule embedding that contains the super-nucleophilic catalytic group.Then, eccysis 4-nitrobenzophenone methyl acid phosphate has formed the netted macromolecular structure that contains a large amount of cavities.Discern specifically and bound substrates with the cavity, with the super-nucleophilic group catalysis is carried out in the reaction of substrate again.Come the hydrolysis of catalysis acetate 4-nitro phenyl ester with synthetic molecular engram macromolecule super-nucleophilic catalyst, the process of following the tracks of hydrolysis with ultraviolet-visible spectrophotometer just can be estimated and compares the catalytic activity of catalyst.Studies show that the reaction constant of molecular engram macromolecule super-nucleophilic catalyst increases than non-molecular engram analogies, its effect is suitable with imidazoles molecular engram polymer catalyst.
Superiority of the present invention is: 1, efficient acidylate catalytic group is introduced the molecular engram polymer catalyst, catalytic activity is improved; 2,, make catalyst as the artificial enzyme, obtain selectivity to substrate with the big molecule of TSA trace.
(4) specific embodiment:
Embodiment: a kind of molecular engram macromolecule super-nucleophilic catalyst, it is characterized in that it is by 4-aminopyridine, epoxychloropropane, 4-nitrobenzophenone methyl acid phosphate and adds crosslinking agent and constituted, said 4-aminopyridine occupies 34%, epoxychloropropane occupies 34%, 4-nitrobenzophenone methyl acid phosphate occupies 11%, add the crosslinking agent toluene di-isocyanate(TDI) simultaneously occupies 21%.
Above-mentioned said molecular engram macromolecule super-nucleophilic Preparation of catalysts method is characterized in that it is made of following steps:
[step 1] produces two (4-nitrobenzophenone) methyl phosphorodithioates: raw material is got methyl acid phosphate dichloro, 4-nitrophenol; Method is in 10g methyl acid phosphate dichloro, adds the 20g4-nitrophenol; System slow room temperature to 160 ℃ in 3h is kept reaction 1h.The dark oil thing is dissolved in toluene, uses activated carbon decolorizing, recrystallization obtains two (4-nitrobenzophenone) methyl phosphorodithioates of 11.3g for 2 times in solvent toluene-ether mixed liquor;
[step 2] produces 4-nitrobenzophenone methyl acid phosphate: raw material is got two (4-nitrobenzophenone) methyl phosphorodithioates, sodium hydroxide solution; Method is in 100mL 10% sodium hydroxide solution, adds two (4-nitrobenzophenone) methyl phosphorodithioates of 5.0g, and heating systems is to boiling, and two (4-nitrobenzophenone) methyl phosphorodithioates are dissolved behind the 5min; After cool off, be acidified to pH 3.5, divide with the 150mL ether to extract for 3 times; Collect the ether phase, add anhydrous magnesium sulfate, standing over night; Freezing and crystallizing then; From the ether that refluxes, be recrystallized, obtain 1.6g white needle-like crystals 4-nitrobenzophenone methyl acid phosphate.
[step 3] produces the epoxy type molecularly imprinted polymer: raw material is got 4-aminopyridine, 4-nitrobenzophenone methyl acid phosphate, epoxychloropropane and crosslinking agent toluene di-isocyanate(TDI); Method is in 34% 4-aminopyridine solution, adds 11% 4-nitrobenzophenone methyl acid phosphate, stirs 30min.The epoxychloropropane of adding 34% stirs 3h under 60 ℃ of temperature.Be cooled to 0 ℃, add 21% toluene di-isocyanate(TDI) again, stir until the system gel.Solid is washed 20h in apparatus,Soxhlet's, obtain yellow solid after the vacuum drying.
[step 4] catalytic activity test: raw material is got epoxy type molecularly imprinted polymer, acetate 4-nitro phenyl ester and buffer solution; Method is in system, contains the molecular engram polymer catalyst, 2.5 * 10 of 0.23g/L
-5Acetate 4-nitro phenyl ester and the buffer solution of g/L react under 30 ℃ of normal pressures, with the variation of ultraviolet spectra at 400 nanometers tracking 4-nitrophenol negative ion concentration, obtain reaction rate constant thus; Come comparison this case gained activity of such catalysts according to the size of reaction rate constant.
Claims (3)
1, a kind of molecular engram macromolecule super-nucleophilic catalyst, it is characterized in that it is by 4-aminopyridine, epoxychloropropane, 4-nitrobenzophenone methyl acid phosphate and adds crosslinking agent and constituted, said 4-aminopyridine occupies 36%～32%, epoxychloropropane occupies 36%～32%, 4-nitrobenzophenone methyl acid phosphate occupies 9%～13%, add the crosslinking agent toluene di-isocyanate(TDI) simultaneously occupies 19%～23%.
2, a kind of molecular engram macromolecule super-nucleophilic Preparation of catalysts method is characterized in that it is made of following steps:
[step 1] produces two (4-nitrobenzophenone) methyl phosphorodithioates by raw material methyl acid phosphate dichloro, 4-nitrophenol;
[step 2] produces 4-nitrobenzophenone methyl acid phosphate by two (4-nitrobenzophenone) methyl phosphorodithioates of raw material, sodium hydroxide solution;
[step 3] produces the epoxy type molecularly imprinted polymer by raw material 4-aminopyridine, 4-nitrobenzophenone methyl acid phosphate, epoxychloropropane and crosslinking agent toluene di-isocyanate(TDI).
[step 4] catalytic activity test.
3, according to the said a kind of molecular engram macromolecule super-nucleophilic Preparation of catalysts method of claim 2, it is characterized in that the said method of epoxy type molecularly imprinted polymer of producing is in 36%～32% 4-aminopyridine solution, the 4-nitrobenzophenone methyl acid phosphate of adding 9%～13% stirs 30min.The epoxychloropropane of adding 36%～32% stirs 3～5h under 50～70 ℃ of temperature.Be cooled to 0 ℃, add 19%～23% toluene di-isocyanate(TDI) again, stir until the system gel; Solid is washed 20～30h in apparatus,Soxhlet's, obtain yellow solid after the vacuum drying.
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| CN111574720A (en) * | 2019-02-18 | 2020-08-25 | 南开大学 | Preparation method of molecularly imprinted polymer microspheres suitable for complex water sample analysis |
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| CN108031453A (en) * | 2017-12-13 | 2018-05-15 | 太原理工大学 | Microwave radiation technology magnetism fly ash loading p-nitrophenol molecular engram solid phase extraction material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111574720A (en) * | 2019-02-18 | 2020-08-25 | 南开大学 | Preparation method of molecularly imprinted polymer microspheres suitable for complex water sample analysis |
| CN111574720B (en) * | 2019-02-18 | 2022-06-17 | 南开大学 | Preparation method of molecularly imprinted polymer microspheres suitable for complex water sample analysis |
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