CN1156509C - 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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- CN1156509C CN1156509C CNB011284544A CN01128454A CN1156509C CN 1156509 C CN1156509 C CN 1156509C CN B011284544 A CNB011284544 A CN B011284544A CN 01128454 A CN01128454 A CN 01128454A CN 1156509 C CN1156509 C CN 1156509C
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Abstract
The present invention discloses a polyhydrocarbon oxygen carbonyl carbene and a preparing method and the applications thereof. Glycine and alcohol are esterified; the obtained matter reacts with sodium nitrite under the action of acid catalysis into diazo acetate; hydrocarbon oxygen carbonyl carbene is generated under the actions of copper powder or salts; the seft-polyreaction is carried out at 25 to 100 DEG C; polymerisates are separated and extracted to obtain polyhydrocarbon oxygen carbonyl carbene whose yield is more than 75%, weight average molecular weight is from 2000 to 15000 and polydispersity index is from1.2 to 1.3. The structure of the polymers is similar to the structure of polybutene diacid diester; the polyhydrocarbon oxygen carbonyl carbene can be used for preparing LB membranes or optical plastic material in the future.
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:
Hydrocarbon carbonyl oxygen Cabbeen polyhydrocarbon oxygen carbonyl carbene
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.
Embodiment
Embodiment 1
Glycine 3.375 grams and vinylcarbinol 23.40 grams being placed reaction flask, add a hydration tosic acid 10.26 grams and make catalyzer, is solvent with benzene, and reflux dewatering 4 hours boils off the benzene of the overwhelming majority and excessive vinylcarbinol then.In reaction flask, 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 a glycine allyl ester tosilate.
0.7 gram Sodium Nitrite and 4 milliliters of ether are placed reaction flask, get glycine allyl ester tosilate 2.4 grams, add 4 ml water wiring solution-formings, be added drop-wise in the reaction flask under stirring, drip 0.2 milliliter 15% sulfuric acid after finishing again, 0-5 ℃ of ice bath temperature control, stirred 20 minutes, tell the ether layer, add the sulfuric acid of 4 milliliters of ether and 0.2 milliliter 15% in reaction flask, the same temperature control stirred 20 minutes, tell the ether layer, also laminated with the ether that obtains previously, 3-4 time so repeatedly, approaching colourless until the ether layer.With ether layer saturated common salt water washing 2-3 time that merging obtains, ether is taken out in decompression, and residue is the diazonium allyl acetate.To wherein adding 0.05 gram copper powder, stir, there is nitrogen constantly to emit immediately, when treating that emitting of nitrogen becomes slowly, be heated to 80 ℃ and also constantly stir, emit until no nitrogen.Add an amount of methylene dichloride lysate, filter, filtrate is concentrated, reprecipitation is in ether, and is centrifugal, and drying gets solid polymer, and productive rate is 81%.1H-NMR (deuterium is imitative, δ 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, 8ppm): 66.92 (CH), 77.42 (CH2), 119.79 (=CH2), 131.25 (CH=), 159.74 (COO).IR(ν，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, and polydispersity index is 1.24.
Embodiment 2
Get glycine allyl ester tosilate 2.4 grams that make among the embodiment 1, following diazotization and put the nitrogen polymerization procedure with embodiment 1, different is after adding copper powder, being heated to 50-60 ℃ earlier emits nitrogen rapidly, stop heating then, reaction is at room temperature carried out, emitted until no 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(ν，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 dehydrated alcohols are placed reaction flask, stir down and be warming up to 60 ℃ gradually.Other gets there-necked flask, adds 15 milliliters of concentrated hydrochloric acids, loads onto the constant pressure funnel that fills 10 milliliters of vitriol oils, and a side of there-necked flask connects an airway.Along with splashing into of the vitriol oil, the hydrogen chloride gas of generation slowly feeds in the reaction solution equably by vitriol oil drying bottle and safety flack successively.After becoming clear solution to reaction solution, continue to feed hydrogenchloride and be reaction end until separating out crystal again.Pour out the pulpous state reaction solution and under agitation cool off, crystallization, suction filtration with absolute ethanol washing twice, promptly 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).This crystal is a glycine ethyl ester hydrochloride.
Get glycine ethyl ester hydrochloride 1.3 gram, following diazotization and put the nitrogen polymerization procedure with embodiment 1, polymer yield 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(ν，cm-1)：1734(COO)。This solid is poly-ethoxy carbonyl Cabbeen.The GPC test result shows that its weight-average molecular weight is 8704, and polydispersity index is 1.21.
Embodiment 4
Get the glycine ethyl ester hydrochloride that makes among the embodiment 3 1.3 grams, following diazotization and put the nitrogen polymerization procedure with embodiment 3, different is when treating that emitting of nitrogen becomes slowly, is heated to 100 ℃ and constantly stir, and emits until no nitrogen.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(ν，cm-1)：1736(COO)。This solid is poly-ethoxy 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 50-60 ℃ earlier nitrogen is emitted rapidly, stops heating then, and reaction is at room temperature carried out, and emits until no 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(ν，cm-1)：1734(COO)。This solid is poly-ethoxy carbonyl Cabbeen.The GPC test result shows that its weight-average molecular weight is 12063, and polydispersity index is 1.26.
Embodiment 6
Glycine 7.5 gram and methyl alcohol are placed reaction flask for 6 milliliters, stir and slowly drip 4.5 milliliters of sulfur oxychlorides down, 65 ℃ of temperature controls, become clear solution to reaction solution after, the continuation heated and stirred reappears crystal and is reaction end in solution.Add small amount of methanol and make dissolution of crystals, add excessive ether again, then the adularescent tabular crystal is separated out.1H-NMR (heavy water, δ ppm): 3.86 (3H, s, CH3), 3.99 (2H, s, CH2CO).This crystal is a glycine methyl ester hydrochloride.
Get glycine methyl ester hydrochloride 1.17 gram, following diazotization and put the nitrogen polymerization procedure with embodiment 1, polymer yield 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(ν，cm-1)：1735(COO)。This 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 ℃ and constantly stirring, emits until no nitrogen.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(ν，cm-1)：1732(COO)。This solid is poly-methoxy carbonyl Cabbeen.The GPC test 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 catalyzer is an 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(ν，cm-1)：1735(COO)。This solid is poly-ethoxy carbonyl Cabbeen.The GPC test result shows that its weight-average molecular weight is 9572, and polydispersity index is 1.23.
Embodiment 9
Implementation step is with embodiment 5, and different is that catalyzer is an 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(ν，cm-1)：1738(COO)。This solid is poly-ethoxy carbonyl Cabbeen.The GPC test result shows that its weight-average molecular weight is 9736, and polydispersity index is 1.25.
Claims (3)
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, and its weight-average molecular weight is 2763-12063.
2. method for preparing the polymkeric substance of 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 50-100 ℃ again and react, polymerisate separation, extraction are promptly got polyhydrocarbon oxygen carbonyl carbene.
3. method according to claim 2 is characterized in that described diazonium acetate is diazonium allyl acetate, ethyl diazoacetate or diazoacetic acid methyl esters.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102977364A (en) * | 2012-11-30 | 2013-03-20 | 武汉大学 | Diazoacetate-ethoxycarbonyl carbene copolymer 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 |
| CN103319709B (en) * | 2013-07-04 | 2015-06-10 | 武汉大学 | Terpolymer of carbene-diazo compound-acraldehyde and preparation method thereof |
| CN104193970B (en) * | 2014-09-22 | 2016-09-14 | 武汉大学 | A kind of stereospecificity poly-(alcoxyl carbonyl Cabbeen) and its preparation method and application |
| 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 |
| US20230323593A1 (en) * | 2020-09-09 | 2023-10-12 | Soochow University | Water-repellent fabric and preparation method therefor |
| CN113061340B (en) * | 2021-06-04 | 2021-08-20 | 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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