CN102199158A - Synthesis method for 2-decyl-2-dihydroxymethyl propylene spiro-orthocarbonate monomer - Google Patents
Synthesis method for 2-decyl-2-dihydroxymethyl propylene spiro-orthocarbonate monomer Download PDFInfo
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- CN102199158A CN102199158A CN2011100945407A CN201110094540A CN102199158A CN 102199158 A CN102199158 A CN 102199158A CN 2011100945407 A CN2011100945407 A CN 2011100945407A CN 201110094540 A CN201110094540 A CN 201110094540A CN 102199158 A CN102199158 A CN 102199158A
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Abstract
The invention relates to a synthesis method for a 2-decyl-2-dihydroxymethyl propylene spiro-orthocarbonate monomer, which comprises the following steps: adding a trihydric alcohol and di-n-butyl tin oxide together into a single-mouth flask, and adding toluene; reducing the temperature of oil bath to room temperature; adding CS2 into a funnel, slowly and dropwisely adding into a reaction flask, heating the oil bath under reflux, cooling to room temperature, and carrying out vacuum distillation while depressurizing to remove toluene; washing with n-hexane multiple times while stirring to obtain an oily viscous liquid monomer which is a pure monomer at the bottom, adding toluene, heating for dissolving, cooling to room temperature, placing into a refrigerator for crystallizing, filtering, and drying to obtain the product. The volume change of the monomer during polymerization process is tracked by an dilatometer; a copolymerization reaction is carried out on an expansion monomer and a prepolymer thereof and epoxy resin, thus reducing or even eliminating the internal stress caused by volume shrinkage, improving the conversion rate of the epoxy group, improving the strength of the epoxy resin, and acquiring an epoxy resin-based composite material and adhesive with higher performance.
Description
Technical field
The present invention relates to the monomeric synthetic method of a kind of spiro orthocarbonate, particularly relate to a kind of 2-decyl-monomeric synthetic method of 2-dihydroxymethyl propylene glycol spiro orthocarbonate.
Background technology
When macromolecular material is found from it, just be subject to people's attention, and obtained using widely with its special and excellent performance.The widespread use of macromolecular material has promoted the development of theoretical investigation, and the help people have solved the problem in many reality.Along with further developing and more deep application of industrial and agricultural production, have higher requirement to macromolecular material.In polymerization process, produce volumetric shrinkage without any exception as the commodity polymer material, for example: the photopolymerization system that general monomer and photosensitizers are formed, producing the volumetric shrinkage discomfort during owing to polymerization uses and sensitive materials with plate-making, the matrix material of internal stress free for another example, accurate casting mold anti-ballistic materials, high-strength structureal adhesives and filling tooth material etc. all require not take place volume change or slightly volumetric expansion in polymerization process.Promptly, reduced the intensity of material, brought certain restriction for their practical application owing to the generation of string stress.Thereby, development of new macromolecular material and original macromolecular material carried out modification, just become polymer science urgently generation the problem that solves.
Macromolecular material can too much or less produce volumetric shrinkage in polymerization process, the volumetric shrinkage during curing has certain influence to the performance of macromolecular material.To produce certain unrelieved stress inevitably because of volumetric shrinkage during as widely used epoxy resin cure, unrelieved stress in the resin is a kind of potential destructive factor, it makes between resin and the fiber interface or adhesively bonded joint just is subjected to appreciable stress when not having outer year, thereby cause strength degradation, even can cause the coming unstuck etc. of cracking, size instability or adhesively bonded joint of matrix material.Experiment shows, Expanding Monomer and performed polymer thereof and Resins, epoxy copolymerization, can reduce even eliminate the internal stress that causes because of volumetric shrinkage, its adding has improved the transformation efficiency of epoxide group, improved Resins, epoxy intensity, near and we can obtain the matrix material and the tackiness agent of more high performance epoxy resin-matrix.
Summary of the invention
The object of the present invention is to provide a kind of 2-decyl-monomeric synthetic method of 2-dihydroxymethyl propylene glycol spiro orthocarbonate; new volution monomer: 3; the 9---dihydroxymethyl---3; the 9---didecyl---1; 5; 7; 11---four oxa-volutions [5; 5] undecane; under the effect of boron trifluoride diethyl etherate catalyzer, can carry out the positively charged ion ring-opening polymerization, and because the substituting group increase on 3,9; volution monomer and polymerization mechanism are had a significant impact, and the increase of substitution in ring base can increase monomeric cubical expansivity usually.
The objective of the invention is to be achieved through the following technical solutions:
A kind of 2-decyl-monomeric the synthetic method of 2-dihydroxymethyl propylene glycol spiro orthocarbonate comprises that synthesis step is: add lauryl aldehyde in there-necked flask, formalin, methyl alcohol, install reflux condensing tube, stir temperature control, drip the NaOH aqueous solution, between the control PH=10-11, reaction; After having reacted, drip acetic acid aqueous solution and be neutralized to PH=6, dewater and excessive formaldehyde with underpressure distillation; With ethyl acetate gradation extraction, combining extraction liquid also washs with less water; Add anhydrous magnesium sulfate drying, remove by filter sal epsom, to remove ethyl acetate, decompression is steamed to slip and is promptly got pure product again with the filtrate distillation; Get trivalent alcohol, di-n-butyl stannic oxide adds in the single port bottle in the lump, adds toluene, stirs control oil bath temperature, reaction; Oil bath temperature is reduced to room temperature, remove water trap, load onto constant pressure funnel and reflux, and on reflux condensing tube, the CaCl2 drying tube is installed; In funnel, add CS2, slowly be added dropwise in the reaction flask, and, reflux oil bath heating, reduce to room temperature after, vacuum decompression distills out toluene; With normal hexane gradation washing, remove n-Bu2SnS, continue in the washing process to stir, the oily thick liquid of bottom is purer monomer, adds toluene, and heating makes its dissolving, after being cooled to room temperature, put into refrigerator and make its crystallization, filtration drying is 3, the 9--dihydroxymethyl--and 3,9--didecyl-1,5, the undecanoic product of 7,11-four oxa-volutions [5,5].
The described a kind of 2-decyl-monomeric synthetic method of 2-dihydroxymethyl propylene glycol spiro orthocarbonate, 150 ℃ of described control oil bath temperatures react about 12hr.
The described a kind of 2-decyl-monomeric synthetic method of 2-dihydroxymethyl propylene glycol spiro orthocarbonate, described oil bath is heated to 100 ℃, backflow 12hr.
Advantage of the present invention and effect are:
The present invention has synthesized a kind of new spiro orthocarbonate monomer 3,9--dihydroxymethyl--and 3,9--didecyl-1,5,7,11-four oxa-volution [5,5] undecanes utilize dilatometer to follow the tracks of the volume change of monomer in polymerization process; Expanding Monomer and performed polymer thereof and Resins, epoxy copolymerization, can reduce even eliminate the internal stress that causes because of volumetric shrinkage, its adding has improved the transformation efficiency of epoxide group, has improved Resins, epoxy intensity, closely can obtain the matrix material and the tackiness agent of more high performance epoxy resin-matrix.
Description of drawings
Fig. 1 is the INFRARED SPECTRUM of the present invention's 2-decyl-2-dihydroxymethyl propylene glycol;
Fig. 2 is the present invention 3,9--dihydroxymethyl--3,9--didecyl-1,5,7, and the undecanoic infrared spectrum of 11-four oxa-volutions [5,5];
Fig. 3 is the present invention 3,9--dihydroxymethyl--3,9--didecyl-1,5,7, and the undecanoic 1H-NMR spectrogram of 11-four oxa-volutions [5,5].
Annotate: Fig. 1-Fig. 3 of the present invention is the analysis synoptic diagram of product state, the unintelligible understanding that does not influence technical solution of the present invention of literal or image among the figure.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
A kind of 2-decyl of the present invention-monomeric synthetic method of 2-dihydroxymethyl propylene glycol spiro orthocarbonate, its synthesis step comprised for two steps, be Synthetic 2-decyl-2-dihydroxymethyl propylene glycol and 3,9--dihydroxymethyl--3,9--didecyl-1,5,7,11-four oxa-volutions [5,5] are undecanoic synthetic.
The synthetic route of 2-decyl-2-dihydroxymethyl propylene glycol is:
Its step:
In there-necked flask, add the 0.3mol lauryl aldehyde, the 1.2mol formalin, 15 ml methyl alcohol install reflux condensing tube, interpolation thermometer and dropping funnel, induction stirring, controlled temperature is 58 ℃, drip the NaOH aqueous solution of 30 ml 40%, between the control PH=10-11, reacted 2 hours.After having reacted, the acetic acid aqueous solution of dropping 36% is neutralized to PH=6, removes most of water and excessive formaldehyde with the vacuum pump underpressure distillation.Divide 5 extractions with 100 ml ethyl acetate, combining extraction liquid and with less water washing 1 time.Add anhydrous magnesium sulfate drying and spend the night, remove by filter sal epsom, filtrate is distilled to remove ethyl acetate.Decompression is steamed to slip and is promptly got product again.Product utilization is infrared, and means such as nuclear-magnetism characterize.
From the infrared spectrum of 2-decyl shown in Figure 1-2-dihydroxymethyl propylene glycol as can be seen, strong-OH absorption peak is arranged at the 3354cm-1 place, and this absorption peak broad, the generation of polyvalent alcohol proved.
3,9--dihydroxymethyl--3,9--didecyl-1,5,7,11-four oxa-volution [5,5] undecane synthetic routes:
Its step:
Take by weighing trivalent alcohol 0.1 mol, di-n-butyl stannic oxide 0.1 mol, add in the lump in the 250 ml single port bottles, add toluene 150 ml, load onto water trap and reflux, induction stirring, 150 ℃ of control oil bath temperatures, react about 12hr, can response estimator whether complete by the water yield that reads collection in the water trap.Oil bath temperature is reduced to room temperature, remove water trap, load onto constant pressure funnel and reflux, and on reflux condensing tube, the CaCl2 drying tube is installed.In funnel, add CS2 8ml, slowly be added dropwise in the reaction flask, and oil bath slowly is heated to 100 ℃, backflow 12hr, reduce to room temperature after, the underpressure distillation of water vacuum pump goes out toluene.Divide 5 washings with normal hexane 100ml, to remove n-Bu2SnS, continue in the washing process to stir, the oily thick liquid of bottom is purer monomer.Add toluene 50ml, heating makes its dissolving, be cooled to room temperature after, put into refrigerator and make its crystallization, filtration drying is product.
From shown in Figure 23,9--dihydroxymethyl--3,9--didecyl-1,5,7, the undecanoic infrared spectrum of 11-four oxa-volutions [5,5]; As can be seen, the volution characteristic peak occurs near 1189cm-1, near appearance-OH absorption peak 3460cm-1 illustrates that existing hydroxyl has volution to exist in the product, has proved the monomeric existence of volution.
From shown in Figure 33,9--dihydroxymethyl--3,9--didecyl-1,5,7, the undecanoic 1H-NMR spectrogram of 11-four oxa-volutions [5,5].As can be seen, δ 0.8-1.0 is-3 H on the CH3, δ 1.2-1.4 is 36 H on the methylene radical, δ 3.1 is-on the OH three H, δ 3.4 is the H on the CH2OH, and δ 3.8 is 8 H of methylene radical on the volution, and nuclear-magnetism has confirmed the monomeric generation of volution equally.
Claims (3)
1. 2-decyl-monomeric synthetic method of 2-dihydroxymethyl propylene glycol spiro orthocarbonate, it is characterized in that, comprise that synthesis step is: in there-necked flask, add lauryl aldehyde, formalin, methyl alcohol, install reflux condensing tube, stir, temperature control drips the NaOH aqueous solution, between the control PH=10-11, reaction; After having reacted, drip acetic acid aqueous solution and be neutralized to PH=6, dewater and excessive formaldehyde with underpressure distillation; With ethyl acetate gradation extraction, combining extraction liquid also washs with less water; Add anhydrous magnesium sulfate drying, remove by filter sal epsom, to remove ethyl acetate, decompression is steamed to slip and is promptly got pure product again with the filtrate distillation; Get trivalent alcohol, di-n-butyl stannic oxide adds in the single port bottle in the lump, adds toluene, stirs control oil bath temperature, reaction; Oil bath temperature is reduced to room temperature, remove water trap, load onto constant pressure funnel and reflux, and on reflux condensing tube, the CaCl2 drying tube is installed; In funnel, add CS2, slowly be added dropwise in the reaction flask, and, reflux oil bath heating, reduce to room temperature after, vacuum decompression distills out toluene; With normal hexane gradation washing, remove n-Bu2SnS, continue in the washing process to stir, the oily thick liquid of bottom is purer monomer, adds toluene, and heating makes its dissolving, after being cooled to room temperature, put into refrigerator and make its crystallization, filtration drying is 3, the 9--dihydroxymethyl--and 3,9--didecyl-1,5, the undecanoic product of 7,11-four oxa-volutions [5,5].
2. a kind of 2-decyl according to claim 1-monomeric synthetic method of 2-dihydroxymethyl propylene glycol spiro orthocarbonate is characterized in that 150 ℃ of described control oil bath temperatures react about 12hr.
3. according to the described a kind of 2-decyl of claim 1-monomeric synthetic method of 2-dihydroxymethyl propylene glycol spiro orthocarbonate, it is characterized in that described oil bath is heated to 100 ℃, backflow 12hr.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103408596A (en) * | 2013-07-19 | 2013-11-27 | 沈阳化工大学 | Phosphorus-containing spiro-compound and preparation method thereof |
| CN104356990A (en) * | 2014-11-23 | 2015-02-18 | 桂林理工大学 | Preparation method of adhesive for optical spare parts |
| CN112830934A (en) * | 2021-02-26 | 2021-05-25 | 汕头市骏码凯撒有限公司 | Unsaturated spiro orthocarbonate expansion monomer and synthesis method and application thereof |
| CN114989187A (en) * | 2021-11-03 | 2022-09-02 | 深圳市撒比斯科技有限公司 | Spiro-carbon ortho ester and preparation method thereof |
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2011
- 2011-04-15 CN CN2011100945407A patent/CN102199158A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103408596A (en) * | 2013-07-19 | 2013-11-27 | 沈阳化工大学 | Phosphorus-containing spiro-compound and preparation method thereof |
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| CN104356990A (en) * | 2014-11-23 | 2015-02-18 | 桂林理工大学 | Preparation method of adhesive for optical spare parts |
| CN112830934A (en) * | 2021-02-26 | 2021-05-25 | 汕头市骏码凯撒有限公司 | Unsaturated spiro orthocarbonate expansion monomer and synthesis method and application thereof |
| CN112830934B (en) * | 2021-02-26 | 2022-04-12 | 汕头市骏码凯撒有限公司 | Unsaturated spiro orthocarbonate expansion monomer and synthesis method and application thereof |
| CN114989187A (en) * | 2021-11-03 | 2022-09-02 | 深圳市撒比斯科技有限公司 | Spiro-carbon ortho ester and preparation method thereof |
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Application publication date: 20110928 |