CN102167765B - Polymerized vitamin C acrylic ester high molecular material and preparation method thereof - Google Patents
Polymerized vitamin C acrylic ester high molecular material and preparation method thereof Download PDFInfo
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- CN102167765B CN102167765B CN201110024166A CN201110024166A CN102167765B CN 102167765 B CN102167765 B CN 102167765B CN 201110024166 A CN201110024166 A CN 201110024166A CN 201110024166 A CN201110024166 A CN 201110024166A CN 102167765 B CN102167765 B CN 102167765B
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- YNKQCPNHMVAWHN-UHFFFAOYSA-N CC(CCC(O)=O)(C#N)SC(c1ccccc1)=S Chemical compound CC(CCC(O)=O)(C#N)SC(c1ccccc1)=S YNKQCPNHMVAWHN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a polymerized vitamin C acrylic ester high molecular material and a preparation method thereof and belongs to the technical field of high molecular materials. The chemical structure of the polymerized vitamin C acrylic ester is shown as the following general formula I. The preparation method comprises the following steps of: reacting vitamin C with benzyl bromide according to the molar ratio of the vitamin C to the benzyl bromide of 1:2 to obtain a compound II; reacting the compound II, triethylamine and acryloyl chloride to obtain a compound III; reacting bromobenzene, magnesium powder, carbon disulfide and azo bicyan valeric acid to prepare a compound IV; reacting the compound IV, the azo bicyan valeric acid and the compound III to obtain a compound V; and reacting the compound V with palladium carbon to obtain the compound I. The polymerized vitamin C has high heat stability and oxidation resistance. The polymerized vitamin C acrylic ester high molecular material has the characteristics of high water solubility and highly enriched reducibility. A redox system formed by the polymerized vitamin C acrylic ester high molecular material and hydrogen peroxide has high activity of initiating polymerization.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to gather vitamins C propenoate material and preparation method thereof.
Background technology
Vitamins C has another name called xitix, is to keep the necessary small molecules organic cpds of normal activities.Because its distinctive physiologically active and chemical structure characteristics, vitamins C all causes great concern in scientific research and industrial applications.As inhibitor, vitamins C can be participated in multiple anti-oxidant reaction in the body, has the enhancing body resistibility; Improve cardio cerebral function, antithrombotic, anti-ageing; Effect such as anticancer, so vitamins C is widely used in industries such as medicine, food, makeup, material, feeds.In addition, utilize that the enol form reductibility constructional feature on the prosposition carbon combines with hydrogen peroxide on the vitamins C chemical structure, can under gentle conditions such as normal temperature, normal pressure, produce radical fast, initiating methacrylates class monomer carries out redox radical polymerization.Since this kind produce the method for hydroxyl free radical have easy to operate, need not external stimulus; Only need reductive agent vitamins C and oxidants hydrogen peroxide to be in contact with one another the characteristics that can produce, so the redox initiation system of vitamins C and hydrogen peroxide composition have vast potential for future development in material engineering and industrial production.
Up to the present, most relevant ascorbic exploitations mainly concentrate on its oxidation-resistance, and the exploitation of redox-catalyst system that forms to ascorbic reductibility and with hydrogen peroxide and initiated polymerization ability is less relatively.Especially to still less by the application of highly enriched the gathering of the reductibility redox polymerization system that vitamins C and hydrogen peroxide form.The polymer form of molecule is compared with corresponding small molecules, has higher stability and slow degradation property.Replace corresponding small molecules can be applied to the field that small molecules can't use with polymer form.Vitamins C is prone to oxidized and thermal destruction, is the effective way that improves resistance to overturning through forming the vitamins C polymkeric substance.And highly enriched with vitamins C for repeating unitary polymer reduction property, the redox polymerization system that forms with hydrogen peroxide has stronger initiating activity.
Summary of the invention
The objective of the invention is to solve the deficiency that the small molecules vitamins C exists, provide a kind of reductibility highly enriched gather vitamins C acrylate polymeric material and preparation method thereof.Macromolecular material provided by the present invention is synthetic easy, and under mild conditions, the redox catalysed polymerization system that forms with hydrogen peroxide can be than efficient initiation Hydroxyethyl acrylate polymerization mild conditions under.
The highly enriched chemical structure of gathering the vitamins C propenoate of a kind of reductibility provided by the present invention is shown in general formula I:
In the formula, 20≤n≤200, n is an integer.
Reductibility provided by the present invention is highly enriched gathers vitamins C propenoate preparation methods, may further comprise the steps:
1) under nitrogen protection, with vitamins C and soda ash light in molar ratio 1: 2.0-3.0 is dissolved in N, in the dinethylformamide; After stirring 1-2 hour under 50-70 ℃, add cylite, cylite and ascorbic mol ratio are 2.0-3.0: 1; Continue to stir deionized water wash, drying 5-10 hour; Concentrate, column chromatography for separation gets compound I I;
2) 0 ℃ with nitrogen protection under; With compound I I and triethylamine be in molar ratio be dissolved in methylene dichloride at 1: 1.2 after; In reaction solution, drip the dichloromethane solution of acrylate chloride, the mol ratio of acrylate chloride and compound I I is 1.1: 1.0, reacts 8 hours after-filtration and concentrated; Column chromatography for separation gets compound III;
3) under 0 ℃, bromobenzene and magnesium powder in molar ratio 1: 1.0-2.0 stirred in tetrahydrofuran solution 6 hours, added dithiocarbonic anhydride, and the mol ratio of bromobenzene and dithiocarbonic anhydride is 1: 1.0-1.2, continued stirring after 10 hours; Hcl acidifying, extraction, drying concentrates; Add DMSO and ETHYLE ACETATE, room temperature reaction 10 hours adds azo dicyanogen methyl isophorone valeric acid, and the mol ratio of bromobenzene and azo dicyanogen methyl isophorone valeric acid is 1: 0.5-1.0; Refluxed 16 hours, and concentrated, column chromatography for separation gets compound IV;
4) under nitrogen protection; Initiator azo dicyanogen methyl isophorone valeric acid, chain transfer agents IV and compound III are 1 with mol ratio: 2-5: 100-400 is dissolved in the dioxane; Stirred 10-30 hour down at 60-90 ℃, liquid concentrator precipitates in the mixed solution of ether and normal hexane, gets polymkeric substance V;
In the formula, 20≤n≤200, n is an integer.
5) under atmosphere of hydrogen, be 1.0-1.3 with the weight ratio with polymkeric substance V and palladium carbon: 1 is dissolved in THF and the methanol mixed solution, and stirring at room 10-30 hour, filter, concentrate, deposition gets the highly enriched polymkeric substance I of reductibility,
In the formula, 20≤n≤200, n is an integer.
The present invention has following beneficial effect:
1) the vitamins C acrylate polymeric material molecule amount of gathering provided by the present invention reaches tens thousand ofly, compares with the small molecules vitamins C and to have thermostability and resistance of oxidation preferably.
2) the vitamins C acrylate polymeric that gathers provided by the present invention has good water-solubility and the highly enriched characteristics of reductibility; The redox system that forms with hydrogen peroxide shows the initiated polymerization activity stronger than small molecules vitamins C; Be more suitable for mild condition in the material engineering; Be swift in response the requirement that no molecule is residual.
Description of drawings
Fig. 1 embodiment of the invention 1 gather vitamins C acrylic ester polymer chemical structure nuclear-magnetism figure;
It is the Hydroxyethyl acrylate monomer polymerization of 2.0M that the redox system that Fig. 2 embodiment 1 and 2 resulting polymers form according to 1: 2 mol ratio with hydrogen peroxide respectively when vitamins C repeating unit concentration is 1.0mM and 2.0mM causes concentration; Conversion of monomer is the change curve graph of a relation in time; Wherein, AA: small molecules vitamins C; P-1: embodiment 1 resulting polymers I; P-2: embodiment 2 resulting polymers I.
Below in conjunction with embodiment the present invention is described further.
Embodiment
Embodiment 1
1) under nitrogen protection, in the 100mL there-necked flask, add successively vitamins C (10.5g, 60mmol), salt of wormwood (20.7g, 150mmol) and N; N '-N (40mL), 50 ℃ of down reactions after 2 hours, drip bromotoluene (23.9g, 140mmol) and N; The mixing solutions of N '-N (30mL) continues reaction 8 hours, and reaction solution is used deionized water wash, collects organic phase; Drying concentrates, and column chromatography for separation obtains product II;
2) 0 ℃ with nitrogen protection under, to fill compound I I (10.6g, 30mmol); Triethylamine (3.6g, 36mmol) and drip in 100 milliliters of there-necked flasks of anhydrous methylene chloride (50mL) acrylate chloride (3.0g, 33mmol) and methylene dichloride (20mL) mixing solutions; Reacted 8 hours, reaction solution is used deionized water wash, drying; Concentrate, column chromatography for separation gets compound III;
3) under nitrogen protection, in the 100mL there-necked flask, add the magnesium powder (2.0g, 83mmol) and 20mL THF and a small amount of iodine, add a spot of bromobenzene THF after, add thermal booster reaction; Slowly drip remaining bromobenzene (9.42g 60mmol) with THF (30mL) solution, at room temperature stirred 6 hours, dropping dithiocarbonic anhydride (4.6g, 60mmol); Continue reaction after 10 hours, add the 30mL deionized water, filter, in filtrating, drip the 20mL concentrated hydrochloric acid; Extracted with diethyl ether, drying is filtered, and concentrates; Under nitrogen protection, and adding DMSO (9.4g, 120mmol), stirring at room 10 hours, absolute ethyl alcohol recrystallization; (3.4g 12mmol) is dissolved in the 40mL ETHYLE ACETATE after 100mL single port bottle internal heating refluxed 16 hours, and column chromatography for separation obtains compound IV for crystallized product (2.5g, 8mmol) and azo dicyanogen methyl isophorone valeric acid;
4) under nitrogen protection, in the 25mL reaction flask, add successively azo dicyanogen methyl isophorone valeric acid (5.6mg, 0.02mmol); Compound IV (28mg, 0.1mmol), compound III (820mg; 2mmol) and dioxane (3mL); Reaction system places 80 ℃ of oil baths to stir after 9 hours, and reaction solution is concentrated in deposition in the anhydrous diethyl ether (100mL), obtains polymkeric substance V;
In the formula, n=20.
5) in 50 milliliters single port bottle, add polymkeric substance V (520mg) successively, palladium carbon (500mg), THF (10mL) and methyl alcohol (10mL), under atmosphere of hydrogen, stirring at room 10 hours is filtered, and concentrates, and deposition in anhydrous diethyl ether (100mL) gets polymkeric substance I;
In the formula, n=20.
1) with embodiment 1 step 1)
2) with embodiment 1 step 2)
3) with embodiment 1 step 3)
4) under nitrogen protection, in the 25mL reaction flask, add successively azo dicyanogen methyl isophorone valeric acid (14mg, 0.05mmol); Compound IV (70mg, 0.25mmol), compound III (1.6g; 4mmol) and dioxane (3mL); Reaction system places 80 ℃ of oil baths to stir after 20 hours, and reaction solution is concentrated in deposition in the anhydrous diethyl ether (100mL), obtains polymkeric substance V;
In the formula, n=90.
5) in 50 milliliters single port bottle, add polymkeric substance V (600mg) successively, palladium carbon (480mg), THF (10ml) methyl alcohol (10mL), under atmosphere of hydrogen, stirring at room 15 hours is filtered, and concentrates, and deposition obtains product I in anhydrous diethyl ether (100mL);
In the formula, n=90.
It is the Hydroxyethyl acrylate monomer polymerization of 2.0M that the redox system that embodiment 1 and 2 resulting polymers are formed according to 1: 2 mol ratio with hydrogen peroxide respectively when vitamins C repeating unit concentration is 1.0mM and 2.0mM causes concentration, and conversion of monomer is the change curve graph of a relation in time.
1) with embodiment 1 step 1)
2) with embodiment 1 step 2)
3) with embodiment 1 step 3)
4) under nitrogen protection, in the 25mL reaction flask, add successively azo dicyanogen methyl isophorone valeric acid (14mg, 0.05mmol); Compound IV (28mg, 0.1mmol), compound III (1.64g; 4mmol) and dioxane (3mL); Reaction system places 80 ℃ of oil baths to stir after 20 hours, and reaction solution is concentrated in deposition in the anhydrous diethyl ether (100mL), obtains polymkeric substance V;
In the formula, n=173.
5) in 50 milliliters single port bottle, add polymkeric substance V (500mg) successively, palladium carbon (400mg), THF (10ml) methyl alcohol (10mL), under atmosphere of hydrogen, stirring at room 20 hours is filtered, and concentrates, and deposition obtains product I in anhydrous diethyl ether (100mL);
In the formula, n=173.
Claims (2)
1. a reductibility is highly enriched gathers vitamins C acrylate polymeric material, it is characterized in that chemical structure is shown in general formula I:
In the formula, 20≤n≤200, n is an integer.
2. one kind prepares the highly enriched method of gathering vitamins C acrylate polymeric material of the described reductibility of claim 1, it is characterized in that, may further comprise the steps:
1) under nitrogen protection, with vitamins C and soda ash light in molar ratio 1: 2.0-3.0 is dissolved in N, in the dinethylformamide; After stirring 1-2 hour under 50-70 ℃, add cylite, cylite and ascorbic mol ratio are 2.0-3.0: 1; Continue to stir deionized water wash, drying 5-10 hour; Concentrate, column chromatography for separation gets compound ii;
2) 0 ℃ with nitrogen protection under; With compound I I and triethylamine be in molar ratio be dissolved in methylene dichloride at 1: 1.2 after; In reaction solution, drip the dichloromethane solution of acrylate chloride, the mol ratio of acrylate chloride and compound I I is 1.1: 1.0, reacts 8 hours after-filtration and concentrated; Column chromatography for separation gets compound III;
3) under 0 ℃, bromobenzene and magnesium powder in molar ratio 1: 1.0-2.0 stirred in tetrahydrofuran solution 6 hours, added dithiocarbonic anhydride, and the mol ratio of bromobenzene and dithiocarbonic anhydride is 1: 1.0-1.2, continued stirring after 10 hours; Hcl acidifying, extraction, drying concentrates; Add DMSO and ETHYLE ACETATE, room temperature reaction 10 hours adds azo dicyanogen methyl isophorone valeric acid, and the mol ratio of bromobenzene and azo dicyanogen methyl isophorone valeric acid is 1: 0.5-1.0; Refluxed 16 hours, and concentrated, column chromatography for separation gets compound IV;
4) under nitrogen protection; Initiator azo dicyanogen methyl isophorone valeric acid, chain transfer agents IV and compound III are 1 with mol ratio: 2-5: 100-400 is dissolved in the dioxane; Stirred 10-30 hour down at 60-90 ℃, liquid concentrator precipitates in the mixed solution of ether and normal hexane, gets polymkeric substance V;
In the formula, 20≤n≤200, n is an integer;
5) under atmosphere of hydrogen, be 1.0-1.3 with the weight ratio with polymkeric substance V and palladium carbon: 1 is dissolved in THF and the methanol mixed solution, and stirring at room 10-30 hour, filter, concentrate, deposition gets the highly enriched polymkeric substance I of reductibility;
In the formula, 20≤n≤200, n is an integer.
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| CN101701061A (en) * | 2009-10-30 | 2010-05-05 | 北京化工大学 | Drug delivering material taking Vitamin C as hydrophilic fragments and preparation method thereof |
| CN101857683A (en) * | 2010-06-09 | 2010-10-13 | 中国科学院青岛生物能源与过程研究所 | Different types of chitosan methacrylate and preparation method thereof |
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| CN101701061A (en) * | 2009-10-30 | 2010-05-05 | 北京化工大学 | Drug delivering material taking Vitamin C as hydrophilic fragments and preparation method thereof |
| CN101857683A (en) * | 2010-06-09 | 2010-10-13 | 中国科学院青岛生物能源与过程研究所 | Different types of chitosan methacrylate and preparation method thereof |
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