维生素C聚磷酸酯及其镁盐合成工艺条件研究
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摘要
维生素C聚磷酸酯及其镁盐既性质稳定,又能很好的发挥维生素C的作用,被广泛应用于饲料添加剂,食品营养添加剂,化妆品美白添加剂,医药辅助制剂等。随着生活水平的提高,维生素C聚磷酸酯及其镁盐有着更加巨大的需求空间。结合维生素C聚磷酸酯现有的直接酰化法工艺技术路线,本文改进了工艺条件,提高收率;针对维生素C磷酸酯镁现有的后处理工艺,本文提出了在酸性条件下水解脱除保护基的低能耗的处理工序。
1.以维生素C为原料,三偏磷酸钠为磷酸化试剂,氯化钙为催化剂,在极性水溶液体系中发生酯化反应生成维生素C聚磷酸酯。通过单因素及正交实验,讨论了原料配比(维生素C与三偏磷酸钠),反应温度,催化剂用量和溶液pH值对产品维生素C聚磷酸酯收率的影响,获得了适宜的反应条件:
反应温度为35℃,维生素C与三偏磷酸钠的摩尔配比为1:1.3,维生素C与氯化钙的摩尔配比为1:0.15,反应溶液pH为9,在该反应条件下,维生素C聚磷酸酯收率为76.58%。
2.以维生素C为原料,采用基团保护法,先用丙酮对维生素C的5、6位羟基进行保护生成中间产物5,6-O-异丙叉维生素C,再以三氯氧磷为磷酸化试剂,吡啶为催化剂,在碱性条件下发生磷酰化反应,后在酸性条件下水解脱除保护基,再与碱中和得到维生素C磷酸酯镁。通过单因素实验,讨论了第一步反应中原料配比(维生素C与丙酮),反应温度,反应时间对中间产物收率的影响,第二步反应中原料配比(5,6-O-异丙叉维生素C与三氯氧磷),催化剂用量和溶液pH对产品维生素C磷酸酯镁收率的影响,获得了适宜的反应条件:
反应温度为25℃,反应时间4小时,维生素C与丙酮摩尔配比为15:1,在该反应条件下,5,6-O-异丙叉维生素C收率达到82.94%;5,6-O-异丙叉维生素C与三氯氧磷摩尔配比为1:1.4,5,6-O-异丙叉维生素与吡啶的摩尔配比为1:6,溶液pH为12时,在该反应条件下,维生素C磷酸酯镁的收率达到78.62%。
按饲料添加剂,食品添加剂行业标准,采用红外光谱,核磁共振谱等方法对产品进行了定性鉴定。
Ascorbyl polyphosphate and its magnesium salts are not only stable, but also good to play the role of ascorbic acid, so which are widely used in feed addivites, food nutrition additives, cosmetic whitening additives, medicine auxiliary preparation and so on.
Along with the enhancement of people's living standards, ascorbyl polyphosphate and its magnesium salts has even greater demand for space. In view of the existing post- processing techniques of ascorbic acid phospate magnesium, the low energy consumption process of hydrolysis removal of protecting group in the acidic conditions was proposed in the article.
1. Take ascorbic acid as raw material, sodium trimetaphosphat as phosphorylation agent, calcium chloride as catalyst, ascorbyl polyphosphate was prepared through esterifying reactions in polar solvement water system. Through single factor and orthogonal experiment, the ratio of raw materials (ascorbic acid to sodium trimetaphosphat), reaction temperature, amount of catalyst and pH of the solution on the yield of ascorbyl polyphosphate were discussed, and obtained the optimal reaction conditions:
The results showed that the reaction temperature was 35℃, the mole ratio of ascorbic acid and sodium trimetaphosphat was 1.0:1.3, the mole ratio of ascorbic acid and calcium chloride was 1:0.15, pH of the solution was 9, at which experimental conditions, the yield of ascorbyl polyphosphate could be up to 76.58%.
2. Take ascorbic acid as raw material, using the methods of group protection, frist reacting ascorbic acid with acetone to prepare 5,6-isopropylideneascorbic acid, then with phosphoryl chloride as phosphorylation agent, pyridine as catalyst, occurred phosphorylation reactions under alkaline conditions and removed protecting group through hydrolyzed in acidic conditions, then neutralized with alkali to prepare ascorbyl polyphosphate. Through single factor experiment, the ratio of raw materials (ascorbic acid to actone), reaction temperature and reaction time to the yield of intermediate product in the first step were investigated, the ratio of raw materials (5,6-isopropylideneascorbic acid to phosphoryl chloride), amount of catalyst and pH of the solution on the yield of ascorbyl polyphosphate in the second step were also discussed, and obtained a appropriate experimental conditions.
The results showed that the reaction temperature was 25℃, the mole ratio of ascorbic acid and actone was 15:1, the mole ratio of ascorbic acid and the reaction time was 4h, at which experimental conditions, the yield of 5,6-isopropylideneascorbic acid could be up to 82.94%; the mole ratio of 5,6-isopropylideneascorbic acid and phosphoryl chloride was 1:1.4, the mole ratio of 5,6-isopropylideneascorbic acid and pyridine was 1:6, pH of the solution was 12, at which experimental conditions, the yield of ascorbyl polyphosphate could be up to 78.62%.
According with the industry standards of feeding additives, the product was qualitative identified by way of infared (IR) spectrum and nuclear magnetic resonance (NMR).
1.以维生素C为原料,三偏磷酸钠为磷酸化试剂,氯化钙为催化剂,在极性水溶液体系中发生酯化反应生成维生素C聚磷酸酯。通过单因素及正交实验,讨论了原料配比(维生素C与三偏磷酸钠),反应温度,催化剂用量和溶液pH值对产品维生素C聚磷酸酯收率的影响,获得了适宜的反应条件:
反应温度为35℃,维生素C与三偏磷酸钠的摩尔配比为1:1.3,维生素C与氯化钙的摩尔配比为1:0.15,反应溶液pH为9,在该反应条件下,维生素C聚磷酸酯收率为76.58%。
2.以维生素C为原料,采用基团保护法,先用丙酮对维生素C的5、6位羟基进行保护生成中间产物5,6-O-异丙叉维生素C,再以三氯氧磷为磷酸化试剂,吡啶为催化剂,在碱性条件下发生磷酰化反应,后在酸性条件下水解脱除保护基,再与碱中和得到维生素C磷酸酯镁。通过单因素实验,讨论了第一步反应中原料配比(维生素C与丙酮),反应温度,反应时间对中间产物收率的影响,第二步反应中原料配比(5,6-O-异丙叉维生素C与三氯氧磷),催化剂用量和溶液pH对产品维生素C磷酸酯镁收率的影响,获得了适宜的反应条件:
反应温度为25℃,反应时间4小时,维生素C与丙酮摩尔配比为15:1,在该反应条件下,5,6-O-异丙叉维生素C收率达到82.94%;5,6-O-异丙叉维生素C与三氯氧磷摩尔配比为1:1.4,5,6-O-异丙叉维生素与吡啶的摩尔配比为1:6,溶液pH为12时,在该反应条件下,维生素C磷酸酯镁的收率达到78.62%。
按饲料添加剂,食品添加剂行业标准,采用红外光谱,核磁共振谱等方法对产品进行了定性鉴定。
Ascorbyl polyphosphate and its magnesium salts are not only stable, but also good to play the role of ascorbic acid, so which are widely used in feed addivites, food nutrition additives, cosmetic whitening additives, medicine auxiliary preparation and so on.
Along with the enhancement of people's living standards, ascorbyl polyphosphate and its magnesium salts has even greater demand for space. In view of the existing post- processing techniques of ascorbic acid phospate magnesium, the low energy consumption process of hydrolysis removal of protecting group in the acidic conditions was proposed in the article.
1. Take ascorbic acid as raw material, sodium trimetaphosphat as phosphorylation agent, calcium chloride as catalyst, ascorbyl polyphosphate was prepared through esterifying reactions in polar solvement water system. Through single factor and orthogonal experiment, the ratio of raw materials (ascorbic acid to sodium trimetaphosphat), reaction temperature, amount of catalyst and pH of the solution on the yield of ascorbyl polyphosphate were discussed, and obtained the optimal reaction conditions:
The results showed that the reaction temperature was 35℃, the mole ratio of ascorbic acid and sodium trimetaphosphat was 1.0:1.3, the mole ratio of ascorbic acid and calcium chloride was 1:0.15, pH of the solution was 9, at which experimental conditions, the yield of ascorbyl polyphosphate could be up to 76.58%.
2. Take ascorbic acid as raw material, using the methods of group protection, frist reacting ascorbic acid with acetone to prepare 5,6-isopropylideneascorbic acid, then with phosphoryl chloride as phosphorylation agent, pyridine as catalyst, occurred phosphorylation reactions under alkaline conditions and removed protecting group through hydrolyzed in acidic conditions, then neutralized with alkali to prepare ascorbyl polyphosphate. Through single factor experiment, the ratio of raw materials (ascorbic acid to actone), reaction temperature and reaction time to the yield of intermediate product in the first step were investigated, the ratio of raw materials (5,6-isopropylideneascorbic acid to phosphoryl chloride), amount of catalyst and pH of the solution on the yield of ascorbyl polyphosphate in the second step were also discussed, and obtained a appropriate experimental conditions.
The results showed that the reaction temperature was 25℃, the mole ratio of ascorbic acid and actone was 15:1, the mole ratio of ascorbic acid and the reaction time was 4h, at which experimental conditions, the yield of 5,6-isopropylideneascorbic acid could be up to 82.94%; the mole ratio of 5,6-isopropylideneascorbic acid and phosphoryl chloride was 1:1.4, the mole ratio of 5,6-isopropylideneascorbic acid and pyridine was 1:6, pH of the solution was 12, at which experimental conditions, the yield of ascorbyl polyphosphate could be up to 78.62%.
According with the industry standards of feeding additives, the product was qualitative identified by way of infared (IR) spectrum and nuclear magnetic resonance (NMR).
引文
[1]郭俊生.维生素C[J].科学世界,2007,7:40-43.
[2]李思健,李晓.维生素C的结构、性质以及在烹调中的变化[J].枣庄师专学报,2000,17(2):73-74.
[3]Prazeres DMF,Cabral JMS.Enzvmatic membrane bioreactorsand their applications.Enzyme Mierob.Technol.1994,16:738-750.
[4]鲍扬.维生素C与营养[J].肠与肠内营养,1998,5(3):168-172.
[5]Conner EM,Grisham MB.Inflammmion flee radicals,and antioxidants.Nutrition,1996,12:174.
[6]Jeng KCG,Yang CS,Siu WY,etal.Supplementation with Vitamin Cand E enhances eytokine production by peripheral blood mononuclearcells in healthy adults.Am.[J].Clin.Nutr,1996,64:960.
[7]Halliwell B.Ascorbie acid;hype,hoax,or healer Am.[J].Clin.Nutr,1997,65:1891.
[8]李越中.维生素C(“二步发酵法”第二步发酵混合菌的生理机制暨混合菌共固定化合成2-酮基-L古龙酸的研究.[博士后研究报告].沈阳:中科院沈阳应用生态所.
[9]王焕章.维生素C的生理作用及其在饲料中的应用[J].湖南饲料,2003,1:23-24.
[10]张伦.维生素C的应用、生产和市场以及我国产销对策[J].化工时刊,1997,11(3):33-35.
[11]Rosevear A.Immobilized biocatalysts-a critical review[J].Chem.Biotech.1984,34:127-150.
[12]Roche公司.生产2-酮基-L-古洛糖酸及其盐的方法[P].中国专利,971 10732.7,1992.
[13]李春艳,夏海平,蓝伟光.维生素C生产工艺进展[J].中国医药工业杂志,2001,30(1):38-41.
[14]杨萍,董家灿,刘士清.酵母细胞固定化新方法PVA包埋吸附[J].工业微生物,1992,22(6):12-15,19.
[15]Nishio N,Kayawake E,Nagai S.Rapjd methane production from formate or acetate in fixed bed bioreactors.[J].Ferm.Tech.1985,63:205-209.
[16]Van HJL,Bremaeker MD,Rouxhet PG.Immobilization of yeast by adhesion to support without use of chemical agent.Enzyme Mierob.Technol.1984,6:221-227.
[17]仪宏,张华蜂,曾远智,等.维生素C生产技术[J].中国食品添加剂,2003,6:76-81.
[18]张志峰,冯惠勇.维生素C产业现状于发展[J].中国食品添加剂,2004,2:45-48.
[19]王瑾,刘志敏.生素C生产及应用概况[J].辽宁化工,1995,5:17-19.
[20]李健,万宇,储怀付.新型稳定性VC源L-抗坏血酸-2-三聚磷酸酯(AsTP)[J].粮食与饲料工业,1997,2:29-32.
[21]杜亚威,杨文玲,刘红梅.维生素C磷酸酯钠的合成进展[J].精细与专用化学品,2006,14(21):4-7.
[22]王荣.维生素C营养的发展方向[J].食品与机械.2001,83(4)31-33.
[23]张玮,韩文爱.维生素C磷酸酯镁提纯方法的改进[J].河北化工,2008,31(3):39-40.
[24]薛福连.异维生素C钠应用开发[J].上海化工,2005,30(4).
[25]李诚让,朱元文.维生素C衍生物研究进展[J].临床皮肤科杂志,2005,34(7):487-488.
[26]王兴国,裘爱泳.抗坏血酸棕榈酸酯在不同油脂中的抗氧化性能研究[J].粮食与油脂,2000,25(3):52-55.
[27]曹栋,章立群.新型营养性抗氧剂L-抗坏血酸-6-棕榈酸酯抗氧化性研究[J].粮食与油脂,2002,1:3-4.
[28]杜亚威,杨文玲,刘红梅.维生素C磷酸酯衍生物的制备及其在化妆品中的应用[J].香精香料化妆品,2007,1:26-29.
[29]徐积恩.维生素C衍生物的开发和应用[J].食品饲料添加剂信息,1999,8:1-3.
[30]张彦玲,刘建峰,齐永斌.维生素C衍生物的现状与发展[J].河北化工,2005,3:18-21.
[31]张玮,王爱军,寇寅客.化妆品配方中维生素C衍生物的合成研究[J].石家庄职业技术学院学报,2008,20(2):11-13.
[32]依凡林(美).皮肤美白剂的比较[J].郑德芳译.日用化学品科学,1999,109(6):13-14.
[33]午荣富.食品强化剂Vc磷酸醣镁及人体效用[J].医药月刊,1991,(2):28-30.
[34]王荣耕.Vc单据磷酸酯镁[J].精细与专用化学品,2001,3(4):14..
[35]宋进美,龙广怀,张玉荣.不同剂型维生素C对罗非鱼生长的影响[J].中国饲料,1996,(14):29-31.
[36]卢雪娟,张会轻,王云霞.基团保护法合成维生素C磷酸酯镁[J].河北化工,2008,31(9):42-43.
[37]王三永,李晓光,李春荣,李韶雄.维生素C磷酸酯镁的合成研究[J].食品与机械,2001,82(2)34-35.
[38]Dziezak JD.Antioxidants[J].Food Technology,1984:40(9) 94-102.
[39]Paul.A.Seib Xiao Y.Wang Method of preparing 2-phosphorylated compound o f ascorbic acid[P]US 5110950.
[40]张越,李小云,侯钰,翟学良.L-抗坏血酸-2聚磷酸酯的合成[J].精细化工2005,5.
[41]刘毓林,石明孝,沈海峰.L-抗坏血酸-2-磷酸醣镁的合成[J].精细化工,1997,14(2):19-22.
[42]Paul A S,Liao M L.Ascorbate-2-polyphosphate esters and method of making same[P].US 4 647 672 263-264.
[43]Chen H Lee,et al,Carbohydr Res,67(1),127(1978).
[44]Paul A S,Wang X Y.M ethod of preparing 2-phosphorylated compounds of ascorbic acid[P].US 5 1 10 950.
[45]Cutolo E,et al,Gazz Chim Ital,91,964(1961).
[46]Chen H Lee,Paul A Seib,Yunt T Liang,etal.Chemical synethesis of several phosphoric esters of L—ascorbic acid[J].Carbohydr Res,1978.67(1):127-135.
[47]Dobler,Walter.Paust,et al.Preparation of ascorbic acid 2-phosphate and of 5,6-isopropylideneascorbic acid and potassium magnesium L-ascorbate 2-phosphate as an advantageous salt of L-ascorbic acid 2-phosphate[P].US:4 999 437,1991-3-2.
[48]Boettcher Andreas.Gurski Hans.Preparation of salts of ascorbyL-2-phosphoric esters[P].US:6121464,2000-9-19.
[49]田龙,刘亚伟.三偏磷酸钠制备小麦淀粉磷酸酯研究[J].粮食与饲料工业,2005,1:20-21.
[50]金显春,赵敏,王锦堂.六偏磷酸钠与Vc合成Vc多聚磷酸酯[J].化工时刊,2003,17(8):38-39.
[51]GB/T 19422-2003,饲料添加剂L-抗坏血酸-2-磷酸酯.
[52]夏志伟,钟振声.L-抗坏血酸-2-磷酸酯镁的合成与纯化[J].广东化工,2003,6:24-25.
[53]Kaiser Klaus,Balkenhohi Friedhelm,Paust Joachim.Preparation of calcium L-ascorbate 2-phosphate[P].US:5 420 302,1995-5-30.
[54]Ming Long Liao,PaulAS.Astable form of vitamin C:L-2-ascorbate-2-triphosphate.[J].Agric Food Chem,1990,38(2).
[55]郝确,范崇旺.Vc-磷酸酯锌的合成研究[J].郑州粮食学院学报,1994,15(2):46-49.
[56]Ichard L Koch Paul A Seb Carl hoseney Incorpanating Ascorbyl 6-palmitate in Bread and Its Shorening-Sparing and Anti-firing Effects Journal of Food Science[P].1987 524954-957.
[57]Himbo,etal.Process for purifying L-ascorbicacid 2-phosphate[P].US:4724 262,1988.
[58]DoberWalter.Preparationofascorbicacid2-phosphateandof 5,6-isopropylideneascorbic acid and potassium magnesiumL-ascorbic-2-phosphate[P].USPatent:4999437,1991.
[59]EnomotoK,MiyamoriT,SakimaeA,etal.Manufacture of ascorbic Acid Estersor Erythorbic Acid Esters with Esterase[P].JP:03259089,1991.
[60]Raymond C Cousins,etal,Journal of the American Oil Chemists,Society,Vol.54.309-310(1997).
[61]曾少行,孙勤.三氯氧磷及其衍生产品的生产及应用综述[J].氯碱工业,2002,2:28-31.
[62]中国食品添加剂生产应用工业协会,食品添加剂手册,北京,中国轻工业出版社,1996:193.
[63]食品添加剂,维生素C磷酸酯镁.中华人民共和国行业标准,YY0036-91.
[64]孙丽梅,陈志斌,张宪志,张现华.紫外分光光度法测定L-抗坏血酸多聚磷酸酯中有效维生素C含量[J].河北化工,2005,4:76-77.
[2]李思健,李晓.维生素C的结构、性质以及在烹调中的变化[J].枣庄师专学报,2000,17(2):73-74.
[3]Prazeres DMF,Cabral JMS.Enzvmatic membrane bioreactorsand their applications.Enzyme Mierob.Technol.1994,16:738-750.
[4]鲍扬.维生素C与营养[J].肠与肠内营养,1998,5(3):168-172.
[5]Conner EM,Grisham MB.Inflammmion flee radicals,and antioxidants.Nutrition,1996,12:174.
[6]Jeng KCG,Yang CS,Siu WY,etal.Supplementation with Vitamin Cand E enhances eytokine production by peripheral blood mononuclearcells in healthy adults.Am.[J].Clin.Nutr,1996,64:960.
[7]Halliwell B.Ascorbie acid;hype,hoax,or healer Am.[J].Clin.Nutr,1997,65:1891.
[8]李越中.维生素C(“二步发酵法”第二步发酵混合菌的生理机制暨混合菌共固定化合成2-酮基-L古龙酸的研究.[博士后研究报告].沈阳:中科院沈阳应用生态所.
[9]王焕章.维生素C的生理作用及其在饲料中的应用[J].湖南饲料,2003,1:23-24.
[10]张伦.维生素C的应用、生产和市场以及我国产销对策[J].化工时刊,1997,11(3):33-35.
[11]Rosevear A.Immobilized biocatalysts-a critical review[J].Chem.Biotech.1984,34:127-150.
[12]Roche公司.生产2-酮基-L-古洛糖酸及其盐的方法[P].中国专利,971 10732.7,1992.
[13]李春艳,夏海平,蓝伟光.维生素C生产工艺进展[J].中国医药工业杂志,2001,30(1):38-41.
[14]杨萍,董家灿,刘士清.酵母细胞固定化新方法PVA包埋吸附[J].工业微生物,1992,22(6):12-15,19.
[15]Nishio N,Kayawake E,Nagai S.Rapjd methane production from formate or acetate in fixed bed bioreactors.[J].Ferm.Tech.1985,63:205-209.
[16]Van HJL,Bremaeker MD,Rouxhet PG.Immobilization of yeast by adhesion to support without use of chemical agent.Enzyme Mierob.Technol.1984,6:221-227.
[17]仪宏,张华蜂,曾远智,等.维生素C生产技术[J].中国食品添加剂,2003,6:76-81.
[18]张志峰,冯惠勇.维生素C产业现状于发展[J].中国食品添加剂,2004,2:45-48.
[19]王瑾,刘志敏.生素C生产及应用概况[J].辽宁化工,1995,5:17-19.
[20]李健,万宇,储怀付.新型稳定性VC源L-抗坏血酸-2-三聚磷酸酯(AsTP)[J].粮食与饲料工业,1997,2:29-32.
[21]杜亚威,杨文玲,刘红梅.维生素C磷酸酯钠的合成进展[J].精细与专用化学品,2006,14(21):4-7.
[22]王荣.维生素C营养的发展方向[J].食品与机械.2001,83(4)31-33.
[23]张玮,韩文爱.维生素C磷酸酯镁提纯方法的改进[J].河北化工,2008,31(3):39-40.
[24]薛福连.异维生素C钠应用开发[J].上海化工,2005,30(4).
[25]李诚让,朱元文.维生素C衍生物研究进展[J].临床皮肤科杂志,2005,34(7):487-488.
[26]王兴国,裘爱泳.抗坏血酸棕榈酸酯在不同油脂中的抗氧化性能研究[J].粮食与油脂,2000,25(3):52-55.
[27]曹栋,章立群.新型营养性抗氧剂L-抗坏血酸-6-棕榈酸酯抗氧化性研究[J].粮食与油脂,2002,1:3-4.
[28]杜亚威,杨文玲,刘红梅.维生素C磷酸酯衍生物的制备及其在化妆品中的应用[J].香精香料化妆品,2007,1:26-29.
[29]徐积恩.维生素C衍生物的开发和应用[J].食品饲料添加剂信息,1999,8:1-3.
[30]张彦玲,刘建峰,齐永斌.维生素C衍生物的现状与发展[J].河北化工,2005,3:18-21.
[31]张玮,王爱军,寇寅客.化妆品配方中维生素C衍生物的合成研究[J].石家庄职业技术学院学报,2008,20(2):11-13.
[32]依凡林(美).皮肤美白剂的比较[J].郑德芳译.日用化学品科学,1999,109(6):13-14.
[33]午荣富.食品强化剂Vc磷酸醣镁及人体效用[J].医药月刊,1991,(2):28-30.
[34]王荣耕.Vc单据磷酸酯镁[J].精细与专用化学品,2001,3(4):14..
[35]宋进美,龙广怀,张玉荣.不同剂型维生素C对罗非鱼生长的影响[J].中国饲料,1996,(14):29-31.
[36]卢雪娟,张会轻,王云霞.基团保护法合成维生素C磷酸酯镁[J].河北化工,2008,31(9):42-43.
[37]王三永,李晓光,李春荣,李韶雄.维生素C磷酸酯镁的合成研究[J].食品与机械,2001,82(2)34-35.
[38]Dziezak JD.Antioxidants[J].Food Technology,1984:40(9) 94-102.
[39]Paul.A.Seib Xiao Y.Wang Method of preparing 2-phosphorylated compound o f ascorbic acid[P]US 5110950.
[40]张越,李小云,侯钰,翟学良.L-抗坏血酸-2聚磷酸酯的合成[J].精细化工2005,5.
[41]刘毓林,石明孝,沈海峰.L-抗坏血酸-2-磷酸醣镁的合成[J].精细化工,1997,14(2):19-22.
[42]Paul A S,Liao M L.Ascorbate-2-polyphosphate esters and method of making same[P].US 4 647 672 263-264.
[43]Chen H Lee,et al,Carbohydr Res,67(1),127(1978).
[44]Paul A S,Wang X Y.M ethod of preparing 2-phosphorylated compounds of ascorbic acid[P].US 5 1 10 950.
[45]Cutolo E,et al,Gazz Chim Ital,91,964(1961).
[46]Chen H Lee,Paul A Seib,Yunt T Liang,etal.Chemical synethesis of several phosphoric esters of L—ascorbic acid[J].Carbohydr Res,1978.67(1):127-135.
[47]Dobler,Walter.Paust,et al.Preparation of ascorbic acid 2-phosphate and of 5,6-isopropylideneascorbic acid and potassium magnesium L-ascorbate 2-phosphate as an advantageous salt of L-ascorbic acid 2-phosphate[P].US:4 999 437,1991-3-2.
[48]Boettcher Andreas.Gurski Hans.Preparation of salts of ascorbyL-2-phosphoric esters[P].US:6121464,2000-9-19.
[49]田龙,刘亚伟.三偏磷酸钠制备小麦淀粉磷酸酯研究[J].粮食与饲料工业,2005,1:20-21.
[50]金显春,赵敏,王锦堂.六偏磷酸钠与Vc合成Vc多聚磷酸酯[J].化工时刊,2003,17(8):38-39.
[51]GB/T 19422-2003,饲料添加剂L-抗坏血酸-2-磷酸酯.
[52]夏志伟,钟振声.L-抗坏血酸-2-磷酸酯镁的合成与纯化[J].广东化工,2003,6:24-25.
[53]Kaiser Klaus,Balkenhohi Friedhelm,Paust Joachim.Preparation of calcium L-ascorbate 2-phosphate[P].US:5 420 302,1995-5-30.
[54]Ming Long Liao,PaulAS.Astable form of vitamin C:L-2-ascorbate-2-triphosphate.[J].Agric Food Chem,1990,38(2).
[55]郝确,范崇旺.Vc-磷酸酯锌的合成研究[J].郑州粮食学院学报,1994,15(2):46-49.
[56]Ichard L Koch Paul A Seb Carl hoseney Incorpanating Ascorbyl 6-palmitate in Bread and Its Shorening-Sparing and Anti-firing Effects Journal of Food Science[P].1987 524954-957.
[57]Himbo,etal.Process for purifying L-ascorbicacid 2-phosphate[P].US:4724 262,1988.
[58]DoberWalter.Preparationofascorbicacid2-phosphateandof 5,6-isopropylideneascorbic acid and potassium magnesiumL-ascorbic-2-phosphate[P].USPatent:4999437,1991.
[59]EnomotoK,MiyamoriT,SakimaeA,etal.Manufacture of ascorbic Acid Estersor Erythorbic Acid Esters with Esterase[P].JP:03259089,1991.
[60]Raymond C Cousins,etal,Journal of the American Oil Chemists,Society,Vol.54.309-310(1997).
[61]曾少行,孙勤.三氯氧磷及其衍生产品的生产及应用综述[J].氯碱工业,2002,2:28-31.
[62]中国食品添加剂生产应用工业协会,食品添加剂手册,北京,中国轻工业出版社,1996:193.
[63]食品添加剂,维生素C磷酸酯镁.中华人民共和国行业标准,YY0036-91.
[64]孙丽梅,陈志斌,张宪志,张现华.紫外分光光度法测定L-抗坏血酸多聚磷酸酯中有效维生素C含量[J].河北化工,2005,4:76-77.