CN1339512A - Polyhydrocarbon oxygen carbonyl carbene and its preparing method and use - Google Patents
Polyhydrocarbon oxygen carbonyl carbene and its preparing method and use Download PDFInfo
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- CN1339512A CN1339512A CN 01128454 CN01128454A CN1339512A CN 1339512 A CN1339512 A CN 1339512A CN 01128454 CN01128454 CN 01128454 CN 01128454 A CN01128454 A CN 01128454A CN 1339512 A CN1339512 A CN 1339512A
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Abstract
Through esterification between glycine and alcohol, reaction with sodium sulfate in the presence of catalyst to produce diazo acetate, catalytic reaction under the action of copper powder or copper salt to produce hydrocarbon oxygen carbonyl carbene, self-polymerization at 25-100 deg.c, and separation and extraction of polymer, polyhydrocarbon oxygen carbonyl carbene with weight-average molecular weight 2000-15000 and polydispersion 1.2-1.3 is obtained at yield over 75%. The said polymer has structure similar to that of polybutene diacid diester and it may be used in preparing LB film and as optical plastic material.
Description
Affiliated technical field
The present invention relates to a kind of Cabbeen polymkeric substance and its production and use, specifically is exactly polyhydrocarbon oxygen carbonyl carbene and its production and use, belongs to chemical field.
Background technology
Cabbeen takes place to the addition reaction of carbon-to-carbon double bond with to carbon-hydrogen, the single bonded insertion reaction of oxygen-hydrogen (J.Chem.Soc.2136 (1953), J.Am.Chem.Soc.83 easily as active intermediate, 1989 (1961), J.Am.Chem.Soc.83,4678 (1961), Tetrahedron 10,65 (1960), CN1151985 (1995)), but the auto-polymerization of hydrocarbon carbonyl oxygen Cabbeen reaction do not appear in the newspapers as yet.
The innovation and creation content
The object of the present invention is to provide a kind of Cabbeen polymkeric substance and its production and use, with the hydrocarbon carbonyl oxygen Cabbeen is the novel polymeric reaction of active intermediate, start a kind of new thinking for synthetic carbon chain polymer, resulting polymers is expected the material as development LB film and optical plastics
Concrete technical scheme is as follows:
A kind of name is called the polymkeric substance of polyhydrocarbon oxygen carbonyl carbene, and its general structure is:
Wherein R is an alkyl or alkenyl.
The chemical structure of above-mentioned polyhydrocarbon oxygen carbonyl carbene and polybutene two acid diesters are similar, therefore can be used for preparing LB film or optical plastics material.
A kind of method for preparing polyhydrocarbon oxygen carbonyl carbene:
Earlier esterification is taken place in glycine and alcohol, the ester that generates reacts with Sodium Nitrite under acid catalysis, generate diazonium acetate, with diazonium acetate under copper powder or mantoquita katalysis, generate the hydrocarbon carbonyl oxygen Cabbeen, carry out auto-polymerization in 25-100 ℃ again and react, polymerisate separation, extraction are promptly got polyhydrocarbon oxygen carbonyl carbene.
According to technical scheme of the present invention, described diazonium acetate is diazonium allyl acetate, ethyl diazoacetate or diazoacetic acid methyl esters.The polyreaction equation is:
R＝-CH
2CH＝CH
2，-CH
2CH
3，-CH
3
The structure of polymkeric substance is confirmed by NMR (Nuclear Magnetic Resonance) spectrum (comprising 1H-NMR and 13C-NMR) and infrared absorption spectrum (IR).The molecular weight of polymkeric substance and polydispersity index are measured by gel permeation chromatography (GPC), and moving phase is chloroform.
The specific embodiment
Embodiment 1
Glycine 3.375 grams and propenyl 23.40 grams are placed reaction bulb, add a hydration p-methyl benzenesulfonic acid 10.26 gram is made catalyst, take benzene as solvent, reflux dewatering 4 hours boils off most benzene and excessive then Propenyl. In reaction bulb, add an amount of ether, leave standstill, treat after product solidifies in ether it to be smashed to pieces, Suction filtration, vacuum drying obtains light yellow solid. 1H-NMR (heavy water, δ ppm): 2.31 (3H, s, CH3), (3.68 2H, m, CH2CO), 4.46 (2H, d, OCH2), 5.18 (2H, dd ,=CH2), 5.72 (1H, M, CH=), 7.16 and 7.70 (4H, dd, C6H4). This solid is glycine allyl ester tosilate.
0.7 gram natrium nitrosum and 4 milliliters of ether are placed reaction bulb, get glycine allyl ester tosilate 2.4 gram adds 4 ml water wiring solution-formings, is added drop-wise in the reaction bulb under stirring, and drips 0.2 milliliter after complete again 15% sulfuric acid, 0-5 ℃ of ice bath temperature control stirred 20 minutes, told the ether layer, added 4 milliliters in reaction bulb The sulfuric acid of ether and 0.2 milliliter 15%, the same temperature control stirring 20 minutes is told the ether layer, with the ether that obtains previously Also laminated, 3-4 time so repeatedly, until the ether layer is near colourless. The ether layer saturated aqueous common salt that merging is obtained Wash 2-3 time, ether is taken out in decompression, and residue is the diazonium allyl acetate. Restrain copper powder to wherein adding 0.05, Stir, have immediately nitrogen constantly to emit, when treating that emitting of nitrogen becomes slowly, be heated to 80 ℃ and also constantly stir Mix, do not emit until there is nitrogen. Add an amount of carrene lysate, filter, filtrate is concentrated, heavily heavy Form sediment in ether, centrifugal, drying gets solid polymer, and productive rate is 81%. (deuterium is imitative, δ for 1H-NMR Ppm): 3.19 (1H, t, CH), 4.68 (2H, q, CH2), 5.29 (2H, dd ,=CH2), 5.93 (1H, M, CH=). 13C-NMR (deuterium is imitative, δ ppm): 66.92 (CH), 77.42 (CH2), 119.79 (=CH2), 131.25 (CH=), 159.74 (COO). IR (v, cm-1): 1648 (CH=CH2), 1732 (COO). This solid is the polyene third oxygen carbonyl Cabbeen. The GPC test result shows that its weight average molecular weight is 2763, polydispersity index Be 1.24.
Embodiment 2
Get glycine allyl ester tosilate 2.4 gram that makes among the embodiment 1, following diazotising and to put nitrogen poly-Close step with embodiment 1, different is after adding copper powder, be heated to earlier 50-60 ℃ nitrogen is emitted rapidly, Stopped heating at room temperature carries out reaction then, does not emit until there is nitrogen. Polymer yield is 78%. 1H-NMR (deuterium is imitative, δ ppm): 3.19 (1H, t, CH), 4.67 (2H, q, CH2), 5.28 (2H, dd,=CH2), 5.92 (1H, m, CH=). 13C-NMR (deuterium is imitative, δ ppm): 66.49 (CH), 77.34 (CH2), 119.20 (=CH2), 131.31 (CH=), 159.72 (COO). IR (v, cm-1): 1648 (CH=CH2), 1735 (COO). This solid is the polyene third oxygen carbonyl Cabbeen. Weight average molecular weight 3052, polydispersity index 1.26.
Embodiment 3
6.0g glycine and 16 milliliters of absolute ethyl alcohols are placed reaction bulb, be warming up to gradually 60 ℃ under stirring. In addition Get there-necked flask, add 15 milliliters of concentrated hydrochloric acids, load onto the constant pressure funnel that fills 10 milliliters of concentrated sulfuric acids, three One side of mouth bottle connects a wireway. Along with splashing into of the concentrated sulfuric acid, the hydrogen chloride gas of generation is successively by dense sulphur Acid drying bottle and safety flack slowly pass in the reactant liquor equably. After becoming clear solution to reactant liquor, continue logical Enter hydrogen chloride and be reaction end until again separate out crystal. Pour out the pulpous state reactant liquor and under agitation cool off, crystallization, Suction filtration with absolute ethanol washing twice, namely gets white needle-like crystals after draining solvent. 1H-NMR (heavy water, δ ppm): 1.30 (3H, t, CH3), 3.97 (2H, s, CH2CO), 4.31 (2H, q, OCH2). Should Crystal is glycine ethyl ester hydrochloride.
Get glycine ethyl ester hydrochloride 13 gram, following diazotising and put the nitrogen polymerization procedure with embodiment 1, polymer Productive rate is 85%. 1H-NMR (deuterium is imitative, δ ppm): 1.29 (3H, t, CH3), 3.51 (1H, t, CH), (4.27 2H, q, CH2). 13C-NMR (deuterium is imitative, δ ppm): 14.6 (CH3), 29.1 (CH), 60.6 (CH2), 172.1 (COO). IR (v, cm-1): 1734 (COO). This solid is poly-ethoxy carbonyl Cabbeen. GPC Test result shows that its weight average molecular weight is 8704, and polydispersity index is 1.21.
Embodiment 4
Get glycine ethyl ester hydrochloride 1.3 gram that makes among the embodiment 3, following diazotising and put the nitrogen polymerization procedure with Embodiment 3, and different is when treating that emitting of nitrogen becomes slowly, to be heated to 100 ℃ and constantly stirring, until No nitrogen is emitted. Polymer yield is 87%. 1H-NMR (deuterium is imitative, δ ppm): (1.31 3H, t, CH3), 3.56 (1H, t, CH), 4.26 (2H, q, CH2). 13C-NMR (deuterium is imitative, δ ppm): 14.1 (CH3), 29.2 (CH), 61.4 (CH2), 170.8 (COO). IR (v, cm-1): 1736 (COO). This solid is poly-second Oxygen carbonyl Cabbeen. The GPC test result shows that its weight average molecular weight is 9472, and polydispersity index is 1.24.
Embodiment 5
Experimental procedure is with embodiment 4, and different is after adding copper powder, is heated to earlier 50-60 ℃ and makes nitrogen rapid Emit, stopped heating at room temperature carries out reaction then, does not emit until there is nitrogen. Polymer yield is 79%. 1H-NMR (deuterium is imitative, δ ppm): 1.33 (3H, t, CH3), 3.54 (1H, t, CH), 4.27 (2H, q, CH2). 13C-NMR (deuterium is imitative, δ ppm): 14.7 (CH3), 28.9 (CH), 59.8 (CH2), 172.5 (COO). IR (v, cm-1): 1734 (COO). This solid is poly-ethoxy carbonyl Cabbeen. The GPC test result shows its weight average molecular weight Be 12063, polydispersity index is 1.26.
Embodiment 6
6 milliliters of glycine 7.5 gram and methyl alcohol are placed reaction bulb, stir 4.5 milliliters of protochlorides of lower slowly dropping Sulfone, 65 ℃ of temperature controls, become clear solution to reactant liquor after, continue to add thermal agitation until reappear crystalline substance in the solution Body is reaction end. Add a small amount of methyl alcohol and make dissolution of crystals, add again excessive ether, then the adularescent flake crystalline Body is separated out. 1H-NMR (heavy water, δ ppm): 3.86 (3H, s, CH3), 3.99 (2H, s, CH2CO). This crystal is sweet The propylhomoserin methyl ester hydrochloride.
Get glycine methyl ester hydrochloride 1.17 gram, following diazotising and put the nitrogen polymerization procedure with embodiment 1, polymer Productive rate is 81%. 1H-NMR (deuterium is imitative, δ ppm): 2.49 (1H, t, CH), 3.64 (3H, s, CH3). 13C-NMR (deuterium is imitative, δ ppm): 28.7 (CH), 51.3 (CH3), 172.6 (COO). IR (v, cm-1): 1735 (COO). Should Solid is poly-methoxy carbonyl Cabbeen. The GPC test result shows that its weight average molecular weight is 8609, and polydispersity index is 1.21.
Embodiment 7
Experimental procedure is with embodiment 6, and different is when treating that emitting of nitrogen becomes slowly, to be heated to 100 ℃ also Constantly stir, until first nitrogen is emitted. Polymer yield is 84%. 1H-NMR (deuterium is imitative, δ ppm): 2.49 (1H, T, CH), 3.61 (3H, s, CH3). 13C-NMR (deuterium is imitative, δ ppm): 29.5 (CH), 51.9 (CH3), 173.1 (COO). IR (v, cm-1): 1732 (COO). This solid is poly-methoxy carbonyl Cabbeen. The GPC test The result shows that its weight average molecular weight is 9352, and polydispersity index is 1.25.
Embodiment 8
Implementation step is with embodiment 4, and different is that catalyst is anhydrous cupric sulfate, and polymer yield is 83%. 1H-NMR (deuterium is imitative, δ ppm): 1.28 (3H, t, CH3), 3.54 (1H, t, CH), 4.21 (2H, q, CH2). 13C-NMR (deuterium is imitative, δ ppm): 13.7 (CH3), 29.0 (CH), 60.2 (CH2), 168.8 (COO). IR (v, cm-1): 1735 (COO). This solid is poly-ethoxy carbonyl Cabbeen. The GPC test result shows its weight average molecular weight Be 9572, polydispersity index is 1.23.
Embodiment 9
Implementation step is with embodiment 5, and different is that catalyst is anhydrous cupric sulfate, and polymer yield is 76%. 1H-NMR (deuterium is imitative, δ ppm): 1.31 (3H, t, CH3), 3.58 (1H, t, CH), 4.22 (2H, q, CH2). 13C-NMR (deuterium is imitative, δ ppm): 14.3 (CH3), 29.8 (CH), 61.4 (CH2), 170.5 (COO). IR (v, cm-1): 1738 (COO). This solid is poly-ethoxy carbonyl Cabbeen. The GPC test result shows its weight average molecular weight Be 9736, polydispersity index is 1.25.
Claims (4)
1. a name is called the polymkeric substance of polyhydrocarbon oxygen carbonyl carbene, and its general structure is:
Wherein R is an alkyl or alkenyl.
2. the described polyhydrocarbon oxygen carbonyl carbene of claim 1 is used to prepare LB film or optical plastics material.
3. method for preparing the described polyhydrocarbon oxygen carbonyl carbene of claim 1, it is characterized in that: with diazonium acetate under copper powder or mantoquita katalysis, generate the hydrocarbon carbonyl oxygen Cabbeen, carry out auto-polymerization in 25-100 ℃ again and react, polymerisate separation, extraction are promptly got polyhydrocarbon oxygen carbonyl carbene.
4. method according to claim 3 is characterized in that described diazonium acetate is diazonium allyl acetate, ethyl diazoacetate or diazoacetic acid methyl esters.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977365A (en) * | 2012-12-03 | 2013-03-20 | 武汉大学 | Terpolymer of diazoacetate, carbethoxy cabbeen and cyclic lactone and preparation method thereof |
| CN102977364A (en) * | 2012-11-30 | 2013-03-20 | 武汉大学 | Diazoacetate-ethoxycarbonyl carbene copolymer and preparation method thereof |
| CN103319709A (en) * | 2013-07-04 | 2013-09-25 | 武汉大学 | Terpolymer of carbene-diazo compound-acraldehyde and preparation method thereof |
| CN104193970A (en) * | 2014-09-22 | 2014-12-10 | 武汉大学 | Three-dimensional regular poly (carbalkoxy carbene) and preparation method and application thereof |
| CN110003028A (en) * | 2019-04-25 | 2019-07-12 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of high-purity glycine ester hydrochloride |
| CN113061340A (en) * | 2021-06-04 | 2021-07-02 | 武汉柔显科技股份有限公司 | Display device, polyimide precursor composition, polyimide film, and laminate |
| WO2022051953A1 (en) * | 2020-09-09 | 2022-03-17 | 苏州大学 | Water-repellent fabric and preparation method therefor |
-
2001
- 2001-09-13 CN CNB011284544A patent/CN1156509C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977364A (en) * | 2012-11-30 | 2013-03-20 | 武汉大学 | Diazoacetate-ethoxycarbonyl carbene copolymer and preparation method thereof |
| CN102977365A (en) * | 2012-12-03 | 2013-03-20 | 武汉大学 | Terpolymer of diazoacetate, carbethoxy cabbeen and cyclic lactone and preparation method thereof |
| CN102977365B (en) * | 2012-12-03 | 2014-06-04 | 武汉大学 | Terpolymer of diazoacetate, carbethoxy cabbeen and cyclic lactone and preparation method thereof |
| CN103319709A (en) * | 2013-07-04 | 2013-09-25 | 武汉大学 | Terpolymer of carbene-diazo compound-acraldehyde and preparation method thereof |
| CN103319709B (en) * | 2013-07-04 | 2015-06-10 | 武汉大学 | Terpolymer of carbene-diazo compound-acraldehyde and preparation method thereof |
| CN104193970A (en) * | 2014-09-22 | 2014-12-10 | 武汉大学 | Three-dimensional regular poly (carbalkoxy carbene) and preparation method and application thereof |
| CN110003028A (en) * | 2019-04-25 | 2019-07-12 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of high-purity glycine ester hydrochloride |
| WO2022051953A1 (en) * | 2020-09-09 | 2022-03-17 | 苏州大学 | Water-repellent fabric and preparation method therefor |
| CN113061340A (en) * | 2021-06-04 | 2021-07-02 | 武汉柔显科技股份有限公司 | Display device, polyimide precursor composition, polyimide film, and laminate |
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|---|---|
| CN1156509C (en) | 2004-07-07 |
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