CN104496960A - Di(trimethylolpropane)-based biodegradable cycloacetal alkene monomer, and preparation method thereof - Google Patents
Di(trimethylolpropane)-based biodegradable cycloacetal alkene monomer, and preparation method thereof Download PDFInfo
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- CN104496960A CN104496960A CN201410681803.8A CN201410681803A CN104496960A CN 104496960 A CN104496960 A CN 104496960A CN 201410681803 A CN201410681803 A CN 201410681803A CN 104496960 A CN104496960 A CN 104496960A
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- trishydroxymethyl
- propane
- reaction
- cyclic ketal
- vinyl monomer
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
Abstract
The invention discloses a di(trimethylolpropane)-based biodegradable cycloacetal alkene monomer. The structure of the di(trimethylolpropane)-based biodegradable cycloacetal alkene monomer is represented by a formula in the invention, wherein R can be -COO-CH=CH2, -COO-C(CH3)=CH2, -COO-CH2-CH=CH2, -CO-CH=CH2, and -CH2-CH=CH2. A synthetic method of the di(trimethylolpropane)-based biodegradable cycloacetal alkene monomer comprises following steps: di(trimethylolpropane) and 2,2-dimethyl-3-hydroxy-propionaldehyde are dissolved in a solvent; aldol condensation is performed at a certain temperature so as to obtain an intermediate product; the intermediate product is reacted with an alkene compound so as to obtain the di(trimethylolpropane)-based biodegradable cycloacetal alkene monomer. The di(trimethylolpropane)-based biodegradable cycloacetal alkene monomer is of a double hexatomic ring structure, so that bond rotating in photopolymerization is prevented, molecule rigidity is increased, and glass-transition temperature after solidification is high.
Description
Technical field
The present invention relates to photosensitive macromolecular material and biologic bracket material field, particularly relate to a kind of based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane.
Background technology
Cyclic ketal biomaterial (CAB) is a kind of novel biomaterial, can be used in the equivalent material of hard and soft tissue.Be different from the biomaterials such as PLA and PCL, the degraded product of PLA and PCL is acid compounds, the acid that polymkeric substance produces on the one hand accelerates the degraded of PLA and PCL, the acid product of PLA and PCL degraded causes the inflammatory reaction of body on the other hand, and cyclic ketal material is by hydrolytic deterioration, the end product of degraded is alcohol and carbonyl.The degraded product of cyclic ketal material can not cause inflammation reaction.A lot of research is had to prove that cyclic ketal biomaterial can be applied to tissue engineering material recently.Cyclic ketal biomaterial performance can carry out the EH network of obtained very hydrophobic by changing various process parameters.But after traditional degraded of the cyclic ketal biomaterial containing acrylate, still produce vinylformic acid.The acid produced not only causes the inflammation of tissue, also accelerates the degradation rate of biomaterial further, result in degradation rate non-adjustable.This patent is intended to substitute vinylformic acid with other vinyl compounds, generation based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane.Its degraded product is not completely containing acid.
Summary of the invention
The invention provides a kind of based on biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane and preparation method thereof, the present invention, from Molecular Structure Design, synthesizes based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane.There is in this monomer cure process the features such as volumetric shrinkage reduces, and geometrical dimension is stablized, biodegradable.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane, its structural formula is as follows:
Wherein R can be-COO-CH=CH2 ,-COO-C (CH3)=CH2 ,-COO-CH2-CH=CH2 ,-CO-CH=CH2 ,-CH2-CH=CH2.
A kind of preparation method based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane, comprises the steps:
The first step: by 1.3 ~ 1.8 parts of two (trishydroxymethyl) propane, 2 part of 2,2-pentaldol is dissolved in toluene, add the catalyzer of 0.005 ~ 0.05 molar fraction, nitrogen protection, reacts at 105 ~ 115 DEG C, and the water that reaction generates is taken out of by toluene, stirring reaction 24h, after reaction terminates, respectively wash three times with saturated sodium bicarbonate and deionized water, spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation obtains intermediate product;
Second step: add in solvent by 1 part of the first step reaction product and 3 parts of acid binding agents and catalyzer, heated and stirred is dissolved.Slowly drip containing 3 parts of vinyl compounds and solvent liquid under ice bath or 65 DEG C of conditions, 3 ~ 4h is added dropwise to complete, and continues to stir 4h.After reaction terminates, filter the salt of generation, wash three times, spend the night with anhydrous sodium sulfate drying with deionized water, filter, underpressure distillation removes desolventizing and obtains based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane.
Particularly, in the described the first step, catalyzer used is selected from sulfuric acid, tosic acid or boron trifluoride.
Particularly, the vinyl compound that with hydroxyl affine replacement can occur in the reaction of described second step is selected from chloroformic acid vinyl acetate, allyl chlorocarbonate, the different propylene of chloroformic acid, allyl bromide 98, chlorallylene, acrylate chloride or methacrylic chloride.
Embodiment
Embodiment 1
The first step is reacted: by 1.3 parts of two (trishydroxymethyl) propane, 2 part of 2,2-pentaldol is dissolved in toluene; add the tosic acid of 0.005 molar fraction, nitrogen protection, react at 105 DEG C; the water that reaction generates is taken out of by toluene, stirring reaction 24h.After reaction terminates, respectively wash three times with saturated sodium bicarbonate and deionized water.Spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation obtains intermediate product.
Second step reacts: 1 part of the first step reaction product and 3 parts of triethylamines are dissolved in chloroform, and slowly drip the chloroform mixed solution containing 3 parts of chloroformic acid vinyl acetate under condition of ice bath, 3h is added dropwise to complete, and continues to stir 4h.After reaction terminates, filter the salt of generation, wash three times with deionized water.Spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation removes desolventizing and obtains based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane.
1H NMR(400MHz,CDCl
3)δ(ppm):0.90(6H,-CH2CH3)，0.99(12H,-C(CH
3)
2-)，1.69(4H,CH
3-CH
2-)，1.99(2H,CH＝CH-H)，3.85,3.60(8H,-C-CH
2-O)，3.79(4H,-O-CH
2-C)，4.07(4H,-C-CH
2-O)，4.67(2H,O-CH-O)，5.59-6.27(6H,-CH＝CH
2)
Embodiment 2
The first step is reacted: by 1.4 parts of two (trishydroxymethyl) propane, 2 part of 2,2-pentaldol is dissolved in toluene; add the tosic acid of 0.005 molar fraction, nitrogen protection, react at 110 DEG C; the water that reaction generates is taken out of by toluene, stirring reaction 24h.After reaction terminates, respectively wash three times with saturated sodium bicarbonate and deionized water.Spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation obtains intermediate product.
Second step reacts: 1 part of the first step reaction product and 3 parts of triethylamines are dissolved in chloroform, and slowly drip the chloroform mixed solution containing 3 parts of allyl chlorocarbonates under condition of ice bath, 4h is added dropwise to complete, and continues to stir 4h.After reaction terminates, filter the salt of generation, wash three times with deionized water.Spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation removes desolventizing and obtains based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane.
Embodiment 3
The first step is reacted: by 1.5 parts of two (trishydroxymethyl) propane, 2 part of 2,2-pentaldol is dissolved in toluene; add the sulfuric acid of 0.05 molar fraction, nitrogen protection, react at 105 DEG C; the water that reaction generates is taken out of by toluene, stirring reaction 24h.After reaction terminates, respectively wash three times with saturated sodium bicarbonate and deionized water.Spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation obtains intermediate product.
Second step reacts: 1 part of the first step reaction product and 3 parts of triethylamines are dissolved in chloroform, and slowly drip the chloroform mixed solution containing 3 parts of different propylenes of chloroformic acid under condition of ice bath, 3h is added dropwise to complete, and continues to stir 4h.After reaction terminates, filter the salt of generation, wash three times with deionized water.Spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation removes desolventizing and obtains based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane.
Embodiment 4
The first step is reacted: by 1.5 parts of two (trishydroxymethyl) propane, 2 part of 2,2-pentaldol is dissolved in toluene; add the sulfuric acid of 0.05 molar fraction, nitrogen protection, react at 110 DEG C; the water that reaction generates is taken out of by toluene, stirring reaction 24h.After reaction terminates, respectively wash three times with saturated sodium bicarbonate and deionized water.Spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation obtains intermediate product.
Second step reacts: by 1 part of the first step reaction product, the Tetrabutyl amonium bromide of 3 parts of sodium hydroxide and 0.05 molar fraction joins heated and stirred in tetrahydrofuran (THF) and dissolves, slowly drip the tetrahydrofuran (THF) mixed solution containing 3 parts of chlorallylenes at 65 DEG C, 3h is added dropwise to complete, and continues to stir 4h.After reaction terminates, filter the salt of generation, wash three times with deionized water.Spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation removes desolventizing and obtains based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane.
Embodiment 5
The first step is reacted: by 1.6 parts of two (trishydroxymethyl) propane, 2 part of 2,2-pentaldol is dissolved in toluene; add the boron trifluoride of 0.04 molar fraction, nitrogen protection, react at 115 DEG C; the water that reaction generates is taken out of by toluene, stirring reaction 24h.After reaction terminates, respectively wash three times with saturated sodium bicarbonate and deionized water.Spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation obtains intermediate product.
Second step reacts: by 1 part of the first step reaction product, the tetramethyl ammonium chloride of 3 parts of sodium hydroxide and 0.05 molar fraction joins heated and stirred in tetrahydrofuran (THF) and dissolves, slowly drip the tetrahydrofuran (THF) mixed solution containing 3 parts of chlorallylenes at 65 DEG C, 4h is added dropwise to complete, and continues to stir 4h.After reaction terminates, filter the salt of generation, wash three times with deionized water.Spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation removes desolventizing and obtains based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane.
Embodiment 6
The first step is reacted: by 1.8 parts of two (trishydroxymethyl) propane, 2 part of 2,2-pentaldol is dissolved in toluene; add the boron trifluoride of 0.04 molar fraction, nitrogen protection, react at 115 DEG C; the water that reaction generates is taken out of by toluene, stirring reaction 24h.After reaction terminates, respectively wash three times with saturated sodium bicarbonate and deionized water.Spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation obtains intermediate product.
Second step reacts: 1 part of the first step reaction product and 3 parts of triethylamines are dissolved in chloroform, and slowly drip the chloroform mixed solution containing 3 parts of methacrylic chlorides under condition of ice bath, 4h is added dropwise to complete, and continues to stir 4h.After reaction terminates, filter the salt of generation, wash three times with deionized water.Spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation removes desolventizing and obtains based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to right.
Claims (4)
1., based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane, its structural formula is as follows:
Wherein R can be-COO-CH=CH2 ,-COO-C (CH3)=CH2 ,-COO-CH2-CH=CH2 ,-CO-CH=CH2 ,-CH2-CH=CH2.
2., based on a preparation method for the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane, comprise the steps:
The first step: by 1.3 ~ 1.8 parts of two (trishydroxymethyl) propane, 2 part of 2,2-pentaldol is dissolved in toluene, add the catalyzer of 0.005 ~ 0.05 molar fraction, nitrogen protection, reacts at 105 ~ 115 DEG C, and the water that reaction generates is taken out of by toluene, stirring reaction 24h, after reaction terminates, respectively wash three times with saturated sodium bicarbonate and deionized water, spend the night with anhydrous sodium sulfate drying, filter, underpressure distillation obtains intermediate product;
Second step: add in solvent by 1 part of the first step reaction product and 3 parts of acid binding agents and catalyzer, heated and stirred is dissolved.Slowly drip containing 3 parts of vinyl compounds and solvent liquid under ice bath or 65 DEG C of conditions, 3 ~ 4h is added dropwise to complete, and continues to stir 4h.After reaction terminates, filter the salt of generation, wash three times, spend the night with anhydrous sodium sulfate drying with deionized water, filter, underpressure distillation removes desolventizing and obtains based on the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane.
3. one according to claim 2 is based on the preparation method of the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane, it is characterized in that: catalyzer used in the described the first step is selected from sulfuric acid, tosic acid or boron trifluoride.
4. one according to claim 2 is based on the preparation method of the biodegradable cyclic ketal vinyl monomer of two (trishydroxymethyl) propane, it is characterized in that: the vinyl compound that with hydroxyl affine replacement can occur in the reaction of described second step is selected from chloroformic acid vinyl acetate, allyl chlorocarbonate, the different propylene of chloroformic acid, allyl bromide 98, chlorallylene, acrylate chloride or methacrylic chloride.
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| CN201410681803.8A CN104496960A (en) | 2014-11-24 | 2014-11-24 | Di(trimethylolpropane)-based biodegradable cycloacetal alkene monomer, and preparation method thereof |
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| CN201410681803.8A CN104496960A (en) | 2014-11-24 | 2014-11-24 | Di(trimethylolpropane)-based biodegradable cycloacetal alkene monomer, and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115433334A (en) * | 2021-06-02 | 2022-12-06 | 北京化工大学 | Main chain type benzoxazine resin with di (trimethylolpropane) acetal structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3708502A (en) * | 1970-07-16 | 1973-01-02 | Quaker Oats Co | Terephthaldehyde acetals |
| JPS6032808A (en) * | 1983-08-02 | 1985-02-20 | Mitsubishi Gas Chem Co Inc | Molding composition |
| CN1911886A (en) * | 2006-08-24 | 2007-02-14 | 王强 | Production technology of bi-tribydroxy methyl propane and/or trihydroxy methyl propane methylal |
| CN103788054A (en) * | 2014-01-24 | 2014-05-14 | 北京化工大学常州先进材料研究院 | Photopolymerizable polyacetal acrylate and synthesis method thereof |
-
2014
- 2014-11-24 CN CN201410681803.8A patent/CN104496960A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3708502A (en) * | 1970-07-16 | 1973-01-02 | Quaker Oats Co | Terephthaldehyde acetals |
| JPS6032808A (en) * | 1983-08-02 | 1985-02-20 | Mitsubishi Gas Chem Co Inc | Molding composition |
| CN1911886A (en) * | 2006-08-24 | 2007-02-14 | 王强 | Production technology of bi-tribydroxy methyl propane and/or trihydroxy methyl propane methylal |
| CN103788054A (en) * | 2014-01-24 | 2014-05-14 | 北京化工大学常州先进材料研究院 | Photopolymerizable polyacetal acrylate and synthesis method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115433334A (en) * | 2021-06-02 | 2022-12-06 | 北京化工大学 | Main chain type benzoxazine resin with di (trimethylolpropane) acetal structure |
| CN115433334B (en) * | 2021-06-02 | 2023-12-15 | 北京化工大学 | Main chain type benzoxazine resin with bis (trimethylol) propane acetal structure |
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