季戊四醇下游产品的开发研究
|
摘要
结合山西省煤化工产业结构调整,为扩大煤化工产业链,对季戊四醇高附加值的下游产品开发进行了两方面的应用研究:
1、由季戊四醇制备双季戊四醇:探讨了在现有季戊四醇间歇生产工艺的反应体系中添加季戊四醇制备双季戊四醇的工艺条件,实验考察了10个方面的影响因素,筛选出了较佳工艺条件:
(1)原料投料比为:n(季戊四醇):n(氢氧化钠):n(甲醛):n(乙醛)=1:1.2:4.1:1,采用无碱底液法,底液由季戊四醇、水及整体投料甲醛的25%组成,其中m(季戊四醇):m(水)=1:2。
(2)采用二级控温生产,第一阶段反应控温于20℃,将氢氧化钠、甲醛和乙醛混合液同时分别注入,投料时间75 min。第二阶段反应控温于80℃,反应时间2h。
该工艺在较低浓度甲醛(31%)和乙醛(40%)的条件下,单程季戊四醇收率为41.14%,双季戊四醇收率为37.26%,与国内近期最佳研究结果相比,季戊四醇消耗量减少1/6,降低了生产成本,有较好的经济效益。
2、以季戊四醇为中心核的紫外光固化水性超支化聚酯的合成及性能研究
由季戊四醇与2,2-二羟甲基丙酸反应制备了8个端羟基的多元醇,并用丁二酸酐进行羧基封端,再用甲基丙烯酸缩水甘油酯与部分羧基反应接枝,最后用三乙醇胺中和其余羧基。通过调整紫外光固化和亲水性基团的比例,合成了三种紫外光固化水性超支化聚酯,并考察了这三种聚酯的相关性质。结果表明:所得聚酯水溶液具有固含量高、粘度低、易涂布的特点,而且储存稳定性良好,光固化时间短,耐溶剂性好,具有潜在应用价值。
In view of the coal chemical industrial restructuring in Shanxi province, two kinds of downstream products of pentaerythritol with the high added value was explored for expending coal chemical industry chains:
1.Preparation of dipentaerythritol from pentaerythritol
One systhetic process for dipentaerythritol,in which pentaerythritol was added into the reaction system of the present intermittent production of pentaerythritol,was proposed.The ten factors were studied and the optimal conditions were obtained:
The molar ratio of raw materials:n(pentaerythritol):n(sodium hydroxide):n(formaldehyde):n(aldehyde) = 1:1.2:4.1:1.The substrate which was alkali-free consisted of pentaerythritol,water and 25%in the overall formaldehyde,and the mass ratio of pentaerythritol to water was one second.
The reaction was carried out successively in two-level temperature. The temperature for the first stage was keeped at 20℃.Sodium hydroxide, and the mixture of formaldehyde and acetaldehyde was added simultaneous -ly within 75 min.The temperature for the second stage raised up to80℃and was maintained for 2 h.
41.14%of one-way yield of pentaerythritol and 37.26%of one-way yield of dipentaerythritol could be obtained using the developed process under the conditions of low concentrations of formaldehyde(31%) and acetaldehyde(40%).Compared with the recent domestic results,the consumption of pentaerythritol was reduced by one sixth reduction.Thus, the cost of production was lowered.Therefore,those findings could bring about better cost-effectiveness and was really meaningful to small and medium-sized manufacturers.
2.Study on synthesis and performance of UV-curable waterborne hyperbranched polyester using pentaerythritol as core
Hydroxy-terminated 8-polyols was prepared by reaction of pentaeryth -ritol and 2,2-dimethylolpropionic acid.And the polyols was end-capped with succinic anhydride,and then the resulting carboxy groups partially reacted with glycidyl methacrylate.Finally,the rest of carboxy groups were neutralized by triethanolamine.By adjusting the molar ratio of UV-curable and hydrophilic groups,three kinds of UV-curable hyperbran -ched waterborne polyester were synthesized,and their properties were investigated.The results showed that the aqueous solution of obtained polyester had the properties of a high solid content,low viscosity, easy-coating,and had good storage stability,short UV-curable time and good solvent resistance,which had potential application value.
1、由季戊四醇制备双季戊四醇:探讨了在现有季戊四醇间歇生产工艺的反应体系中添加季戊四醇制备双季戊四醇的工艺条件,实验考察了10个方面的影响因素,筛选出了较佳工艺条件:
(1)原料投料比为:n(季戊四醇):n(氢氧化钠):n(甲醛):n(乙醛)=1:1.2:4.1:1,采用无碱底液法,底液由季戊四醇、水及整体投料甲醛的25%组成,其中m(季戊四醇):m(水)=1:2。
(2)采用二级控温生产,第一阶段反应控温于20℃,将氢氧化钠、甲醛和乙醛混合液同时分别注入,投料时间75 min。第二阶段反应控温于80℃,反应时间2h。
该工艺在较低浓度甲醛(31%)和乙醛(40%)的条件下,单程季戊四醇收率为41.14%,双季戊四醇收率为37.26%,与国内近期最佳研究结果相比,季戊四醇消耗量减少1/6,降低了生产成本,有较好的经济效益。
2、以季戊四醇为中心核的紫外光固化水性超支化聚酯的合成及性能研究
由季戊四醇与2,2-二羟甲基丙酸反应制备了8个端羟基的多元醇,并用丁二酸酐进行羧基封端,再用甲基丙烯酸缩水甘油酯与部分羧基反应接枝,最后用三乙醇胺中和其余羧基。通过调整紫外光固化和亲水性基团的比例,合成了三种紫外光固化水性超支化聚酯,并考察了这三种聚酯的相关性质。结果表明:所得聚酯水溶液具有固含量高、粘度低、易涂布的特点,而且储存稳定性良好,光固化时间短,耐溶剂性好,具有潜在应用价值。
In view of the coal chemical industrial restructuring in Shanxi province, two kinds of downstream products of pentaerythritol with the high added value was explored for expending coal chemical industry chains:
1.Preparation of dipentaerythritol from pentaerythritol
One systhetic process for dipentaerythritol,in which pentaerythritol was added into the reaction system of the present intermittent production of pentaerythritol,was proposed.The ten factors were studied and the optimal conditions were obtained:
The molar ratio of raw materials:n(pentaerythritol):n(sodium hydroxide):n(formaldehyde):n(aldehyde) = 1:1.2:4.1:1.The substrate which was alkali-free consisted of pentaerythritol,water and 25%in the overall formaldehyde,and the mass ratio of pentaerythritol to water was one second.
The reaction was carried out successively in two-level temperature. The temperature for the first stage was keeped at 20℃.Sodium hydroxide, and the mixture of formaldehyde and acetaldehyde was added simultaneous -ly within 75 min.The temperature for the second stage raised up to80℃and was maintained for 2 h.
41.14%of one-way yield of pentaerythritol and 37.26%of one-way yield of dipentaerythritol could be obtained using the developed process under the conditions of low concentrations of formaldehyde(31%) and acetaldehyde(40%).Compared with the recent domestic results,the consumption of pentaerythritol was reduced by one sixth reduction.Thus, the cost of production was lowered.Therefore,those findings could bring about better cost-effectiveness and was really meaningful to small and medium-sized manufacturers.
2.Study on synthesis and performance of UV-curable waterborne hyperbranched polyester using pentaerythritol as core
Hydroxy-terminated 8-polyols was prepared by reaction of pentaeryth -ritol and 2,2-dimethylolpropionic acid.And the polyols was end-capped with succinic anhydride,and then the resulting carboxy groups partially reacted with glycidyl methacrylate.Finally,the rest of carboxy groups were neutralized by triethanolamine.By adjusting the molar ratio of UV-curable and hydrophilic groups,three kinds of UV-curable hyperbran -ched waterborne polyester were synthesized,and their properties were investigated.The results showed that the aqueous solution of obtained polyester had the properties of a high solid content,low viscosity, easy-coating,and had good storage stability,short UV-curable time and good solvent resistance,which had potential application value.
引文
[1]李峰,朱铨寿.甲醛及其衍生物[M].北京:化学工业出版社2006 p38-39
[2]国家标准GB/T 7815-1995工业用季戊四醇[S].
[3]李峰,朱铨寿.甲醛及其衍生物[M].北京:化学工业出版社[M].2006 p47
[4]梁建新,陈建锋C03-1各色醇酸调和漆的研制[J].广西化工1993,22(4):13-14
[5]陈启明,郭嘉,陈金芳等.油酸季戊四醇酯的合成及性能研究[J].2007,29(3):4-7
[6]朱永进,曹扩.合成润滑剂的现状及发展合成润滑材料[J].合成润滑材料2003,30(2):41-44
[7]陈洪波.国内外季戊四醇市场前景预测[J].化工技术经济2003,21(7):29-32
[8]洪仲苓主编.化工有机原料深加工[M].北京:化学工业出版社,1997:p261
[9]罗金岳,郑巧铃,安鑫南.浅色145~#松香季戊四醇酯合成工艺的研究[J]林产化学与工业2005,25(增刊)99-101
[10]戴洪义,王少君等.用于辐射固化的特种丙烯酸酯单体及其发展动向[J].山东化工,2000,(1):25-27
[11]李安梅.多元醇丙烯酸酯的制备和紫外光固化反应的研究[D].东南大学硕士硕士毕业论文.2006
[12]欧育湘.太安[M].北京:兵器工业出版社1993 p2
[13]任特生.硝铵及硝酸酯炸药化学与工艺学[M].北京:兵器工业出版社1994. p400-401
[14]金秋.季戊四醇产能和需求市场[J].精细化工原料及中间体2005,(2):11-13
[15]董延茂,鲍治宇.季戊四醇在膨胀型阻燃体系中的研究与应用进展[J].化学世界2005,9(3):177-180
[16]高明,李桂芬,杨荣杰.含季戊四醇二磷酸酯三聚氰胺-尿醛树脂盐环氧树脂的阻燃性能[J]过程工程学报,2008,8(1):182-186
[17]许晶晶,邓敏,郝惠军,等.磷酸季戊四醇酯缩合物的合成及阻燃性能研究[J].胶体与聚合物,2006,24(1):23-24
[18]金闪,刘俊康,倪忠斌等.季戊四醇磷酸酯蜜胺盐阻燃剂的合成及其在聚乙烯中的应用[J].江南大学学报,2006,5(3):341-348
[19]李到,胡静平,秦艳等.磷酸酯双三聚氰胺盐阻燃环氧树脂的燃烧性能和阻燃机理[J]功能高分子学报,2007,20(1):81-86
[20]Berlow E.,Barth R.H.and Snow J.E..The pentaerythritol[M],New York,Reinhold Publishing Co.1958,p4-7
[21]魏文德.有机化工原料大全(第二卷)[M].北京:化学工业出版社1989:p154-155
[22]Jeffrey S.S.,Oakdale B.Manufacture of neopentyl glycol[P].US5146012,1992
[23]Aiken,John E.Manufacture of neopentyl[P].EP0522368,1993
[24]Nimomiya,Teruyuki.Process for producing polhydric alcohol[P].EP0708073,1996.
[25]王永军.钙法生产季戊四醇[P].CN1651373,2005
[26]胡兵,龙化云,孙凤兰等.季戊四醇合成新工艺研究[J].湖北工学院学报2003,18(5):4-6,10
[27]魏文德.有机化工原料大全,(第二卷)[M].北京:化学工业出版社,1989:p134,157
[28]Mchenry M.A,Carr D.D,Hutter J.A.High temperature lubricant omposition[P].CA2449778.2002
[29]NCH Corporation.Multifunctional lubricants formed therefrom[P].US58859421999
[30]Exxon Chemical Patents Inc.Biodegradable branched synthetic ester base stocks and lubricants formed therefrom.[P].US5817607,1998
[31]Douglas R.Synthetic lubricant based on enhanced performance of synthetic ester fluids.[P].US573528,1998
[32]Cardis A.B.,Ardito S.Biodegradable non-toxic gear oil.[P].US6649574.2003
[33]Kitamura T.,Kanezaki,Hiroyuki.Preparation of diprentaerythritol hexa(meth)acrylate[P].JP 03234957,1989
[34]Toray Industries Inc.Scratch and weather-resistant transparent multiplayer films for safety glass.[P].JP11115107,1999
[35]Yokashima,Minora.UV-curable di-or tri(meth) acrylate ester compositions[P].JP11124515.,1999
[36]吴宇明,胡辉.Synthesis of dipentaerythritol hexaacrylate and UV-curable abrasion resistancecoaing[J].长沙电力学院学报(自然科学版),1998,13(2):178-181
[37]Toyo Ink Co Ltd.Rosin-modified phenolic resin and printing ink with improved missing abrasion resistance and dryablity[P].JP09249726,1997
[38]Nation Starch and Chemical Investment Holding Co,Vehicle system for thick film inks[P].US5622547,1997
[39]Vrsula B.,Thomas F,Klaus H.Sheer-fed offset-printing ink with cow migration,oder and swalling[P].DE19653828,1998
[40]Konica C.Ink-jet Ink compositions for color filters[P].JP20003443,2000
[41]王永强.阻燃材料及应用技术[M].北京:化学工业出版社,2003.p45.
[42]王雪峰,孙春梅,吴荣梁等.膨胀型环状类磷酸酯蜜胺盐阻燃剂的合成及阻燃聚丙烯的结构与性能[J].功能高分子学报.2005,18(4):474-478
[43]王雪峰,吴荣梁,孙春梅等.膨胀型类磷酸酯蜜胺盐阻燃剂的合成及应用研究[J].功能高分子学报2004,17(4):630-634
[44]高瑜,姜志国,华健华等.增效膨胀型阻燃双季戊四醇的性能研究[J].北京化工大学学报2000,27(4):52-55
[45]Mikimoto Seiyalu Co.Ltd.Nail Lacquers containing dipentaerythriol fatty acid esters and pearloyster shell sterols.[P].JP04346910,1992
[46]Kobayashi kose Co Ltd.Aqueous skin and hair preps,containing polyoxyethylene castor oil derivatives and oils[P].JP0338508,1991
[47]Higuchi T,Yamamoto H,et al.Transparent coated molden article and its production[P].JP1107787,1999
[48]Kondo S.,Higuchi T.,Yamamoto H.Transparent coated moldingan manufacture thereof[P].JP0108005.1999
[49]Ah K.K.,Kun S.B.Method for preparing biodegradable polyester and itself prepared thereby[P].WO02072663,2002
[50]Hatton K.B.,Liz X.Highly functional polymer[P].US0082734,2004
[51]Berlow.E,Barth R.H and.Snow.J.E.The pentaerythritol.[M]New York,Rein -hold Publishing Co.1958,p4-7
[52]岳宏君.双季戊四醇合成工艺研究[D].华东理工大学硕士毕业论文2003.
[53]王强,刘启东,邓胜民,等.单、双、叁季戊四醇的制备方法及其设备[P].CN1097004,1995
[54]吴海霞,张又文.反应条件的改变对季戊四醇生产中复产双季戊四醇的影响[J]化学工程师,1992,(7):4-7
[55]张又文,吴海霞.高比率双季戊四醇的合成研究[J]精细石油化工,1993,(6):22-25
[56]张又文,吴海霞.反应条件的改变对季戊四醇生产中副产双季戊四醇的影响[J].化学工程师,1992,(5):4-7
[57]张又文,吴海霞.双季戊四醇收率与反应条件依赖关系研究[J].化学工程师,1995,23(2):31-33
[58]贺楚华,李珊,肖志海等.单、双、三季戊四醇的合成[J].化工时刊,2005,19(1):11-13
[59]张健伟,赫广田.单、双季戊四醇的合成工艺研究[J]天然气化工,2007,32(5):40-42,46
[60]蒋远华,杨晓勤,卞平官等.一种单、双季戊四醇的制备方法[P].CN1092330,2007
[61]王永军.双季戊四醇和/或三季戊四醇生产工艺[P].CN 1012156,2007
[62]John P.R,Metuchene N.J.and Philip I.B.Manufacture of polypentaerythritols.[P].US2441597,1948
[63]Otaki,Yasushi,Fukuda,et al.Preparation of dipentaerythritol from monopentaerythritol,formaldehyde,and acetaldehyde.[P]JP09301908,1997
[64]岳宏君,王幸宜,李春香等.双季戊四醇的合成方法[P].CN1390817,2003
[65]阳永荣,刘芳,贺鑫平.一种生产双季戊四醇的方法[P].CN1522998,2004
[66]Fukuda,Takashi,Otaki,et al.Preparation of dipentaerythritol from monopent- aerythritol,formaldehyde,and acetaldehyde.[P]JP09301909,1997
[67]王幸宜,岳宏君.双季戊四醇的合成方法[P].CN1380278,2002
[68]岳宏君,王幸宜,李春香.用原位红外光谱研究氧化镁上甲醛与乙醛合成双季戊四醇反应的机理[J].催化学报,2002,23(3):276-280
[69]王幸宜,李到,杨彩平.双季戊四醇的合成方法[P].CN1016232,2007
[70]Inomata,Masasane,Ishii,Seiichi.Preparation of dipentaerythritol from acetaldehyde,formaldehyde,and acrolein[P].JP 08176048,1996
[71]Kambara,Yoshihiko,Idemoto,et al.Process for producing dipentaerythritol[P].WO9110633,1991
[72]Yamamoto,Toshio,Katsura,Akio.Preparation of dipentaerythritol[P].JP04208242,1992
[73]Watabe,Yasuyoshi,Hazama,et al.Preparation of dipentaerythritol[P].JP06016585,1994
[74]Lianshun Li,Yuichi K.,Toshio O.Catalytic dehydration of pentaerythritol to dipentaerythritol over heteropoly compounds.Applied CatalysisA:General 2003,(253):29-32
[75]Suzuki,Toshiaki,Watabe,et al.Preparation of dipentaerythritol[P].JP 07076541,1995
[76]Watabe,Yasuyoshi,Suzuki,etal.Preparation of dipentaerythritol[P].JP07165651,1995
[77]Watabe,Yasuyoshi,Suzuki,et al.Preparation of dipentaerythritol from erythritol and urea using tin catalysts[P].JP 07165653,1995
[78]Suzuki,Toshiaki,Watabe,et al.Preparation of dipentaerythritol[P].JP07258139,1995
[79]Suzuki,Toshiaki,Watabe,etal.Preparation of dipentaerythritol[P].JP07188086,1995
[80]Watabe,Yasuyoshi,Suzuki,Toshiaki.Preparation of dipentaerythritol with high efficiency[P].JP07157450,1995
[81]Watabe,Yasuyoshi,Suzuki,Toshiaki.Preparation of dipentaerythritol from 3,3-bis (hydroxymethyl)oxetane and pentaerythritol[P].JP 07165652,1995
[82]Doi,Kenji,et al.Preparation of dipentaerythritol from polypentaerythritol[P] JP09059199,1997
[83]陈用烈,曾兆华,杨建文.辐射固化材料及其应用[M].北京:化学工业出版社,2003:p354-356
[84]李红强,曾幸荣.紫外光固化水性涂料的研究进展[J].中国涂料.2007,2(5):28-33
[85]Jan S.J.Water soluble,self-emulsifying polyester resins[J].European Coating Journal,1996,(11):810-812
[86]Dvorchak M.J.,Riberi B.H.Water-reducible unsaturated polymers as binders and clear coatings for UV-curable furniture coatings[J].Journal of Coating Technology,1992,43(64):808-815
[87]Lewarchi K.Ronald J.UV-stablewater-borne polyester compositions[P].US5484842,1996
[88]Park N.H.,Suh K.D.,Kim J.Y.Preparation of UV-curable PEG-modified urethane acrylate emulsions and their coating properties.Ⅱ.Effect of chain length of polyoxyethylene[J].Journal of Applied Polymer Science,1997,64(13):2657-2664
[89]胡飞,唐黎明,李易等.紫外光固化水性聚氨酯涂料研究[J].化学世界,2002,(4):189-191
[90]白湘云,刘磊,金养智.紫外线固化水性聚氨酯丙烯酸树脂的研究[J].影像技术,2000,(3):33-36
[91]沈效峰,郁建华.光交联型水性聚氨酯乳液的研究[J].聚氨酯工业,1998,13(2):9-12
[92]韩仕甸,金养智,王菲.水性紫外光固化体系中光固化速度的影响因素[J].北京化工大学学报,2002,29(1):30-32
[93]韩飞雁,杨小毛,杨建文.紫外光固化水性涂料[J].胶体与聚合物,2001,19(2):23-26
[94]Ishida H.Study on UV curable resins with quatemary ammonium groups[C].Procee -dings ofRad.Tech.Asia97,Tokyo,Japan:1997,539-542
[95]Wuertz C.,Bismarck A.,Springer J.E.Kinetic and mechanical characterization of UV in duced crossinked acrylic copolymers[J].Progress in Organic Coatings,1999,37(3-4):117-129
[96]Wood K.A.European polymers[J].Paint and Colour Journal,1993,18(12):34-37
[97]Schlarb,Rau M.G.,Haremza S.Hydroresin dispersions:new emulsifier free binders for aqueous coatings[J].Progress in Organic Coatings,1995,26(2-4):207-215
[98]杨小毛,杨建文,陈用烈等.光固化聚氨酯改性丙烯酸系水性涂料[J].功能高分子学报,1999,12(3):285-288
[99]Loutz J.M,Peters S,Lindekens L.Radiationcurable water-borne systems[J].Journal of Coated Fbrics,1993(22):298-307
[100]Overbeek A.,Buckmann E,Martin E.New generation decorative paint technology [J].Progress in Organic Coatings,2003,48(2-4):125-139
[101]张洁,张可达.紫外光固化水溶性聚酯丙烯酸酯的合成与感光性能[J].苏州大学学报(自然科学版),2000,16(2):66-71
[102]谭惠民,罗运军.超支化聚合物[M].北京:化学工业出版,2005:p221-223
[103]Asif A.,Shi W.F.Synthesis and properties of UV curable waterborne hyperbranched aliphatic polyester[J].European Polymer Journal,2003,39(5):933-938
[104]Asif A,Huang C Y,Shi W F,et al.Structure property study of aterborne,polyurethane acrylate dispersions based on hyperbranched aliphaticpolyester for UV-curable coating[J].Colloid Polymer Science,2004,283(2):200-208
[105]Asif A,Shi W.F.UV curable waterborne polyurethane acrylate dispersions based on hyperbranched aliphatic polyester:Effect of molecular structure on physical and thermal properties[J].Polymer for Advanced Technologies,2004,1(11):669-675
[106]苏琳,蒋浩,罗凯等.UV固化水性高支化聚酯[J].热固性树脂,2004,19(2):17-20
[107]陈梦茹,龙宇,金养智等.含光敏基团的光固化水性超支化聚酯的合成与性能研究[J].影像技术,2003,(2):18-21.
[1]John P.R.,Metuchene N.J.,Philip I.B.Manufacture of polypentaerythritols[P].US 2441597,1948.
[2]Otaki Y.,Fukuda T.,Noguchi T.,et al.Preparation of dipentaerythritol from monopentaerythritol,formaldehyde and acetaldehyde[P].JP 09301908,1997.
[3]Fukuda T.,Otaki Y.,Noguchi,T.,et al.Preparation of dipentaerythritol from monopentaerythritol,formaldehyde,and acetaldehyde[P].JP 09301909,1997.
[4]王幸宜,岳宏君.双季戊四醇合成方法[P].CN 1380278,2002.
[5]岳宏君,王幸宜,李春香等.双季戊四醇合成方法[P].CN 1390817,2003.
[6]王强,刘启东,邓胜民等.单、双、三季戊四醇的制备方法及其设备[P].CN 1097004.1995.
[7]贺楚华,李珊,肖志海等.单、双、三季戊四醇的合成[J].化工时刊,2005,19(1):11-13.
[8]国家标准.GB/T 7815-1995工业用季戊四醇[S].1996
[9]Suchanec R.R.Gas chromatographic separation and determination of pentareythritol system by methylsilyl ether derivatives[J].Analytical Chemistry,1965,37(11):1361-1365.
[10]杨昀,刘玉林.季戊四醇和双季戊四醇气相色谱分析方法研究[J].理化检验-化学分册.2006,42(7):557-559
[11]国药集团上海化学试剂公司.试剂手册(第三版)[M].上海:上海科学技术出版社,2002:p807
[12]魏文德.有机化工原料大全(第二卷)[M].北京:化学工业出版社,1989:p152
[13]魏文德.有机化工原料大全(第二卷)[M].北京:化学工业出版社,1989:p134
[14]Berlow E.,Barth R.H and Snow.J.E.The Pentaerythritol.[M]New York:Reinhold Publishing Co,1958:p4-7
[15]Salkind M,Ahern H.F.and Albert A.A.Peataerythritol[J].Industrial and Engineering Chemistry.1958,50(8):1106-1114.
[16]岳宏君.双季戊四醇合成工艺研究[D].华东理工大学硕士学位论文,2003.p37-40
[17]李峰,朱铨寿.甲醛及其衍生物[M].北京:化学工业出版社,2006:p41.
[18]胡宏纹.有机化学[M].北京:高等教育出版社(上册),1990:p360.
[19]滕冬成.双季戊四醇重结晶新工艺的研究[J].精细化工中间体,2004,34(2):53-55.
[20]魏文德.有机化工原料大全(第二卷)[M].北京:化学工业出版社,1989:p281
[21]胡宏纹.有机化学[M].北京:高等教育出版社(上册),1990:p339.
[22]胡宏纹.有机化学[M].北京:高等教育出版社(上册),1990:p274.
[23]Bried E.A.Acetaldehyde-formaldehyde condensation product[P].US 2325589,1943.
[24]Peters M.S.and Cupit C.R.,Kinetics of pentaerythritol-production reactions[J].Chemical Engineering Science,1959,10:57-67
[25]Joseph A.W.and Edwin A.W.,Double compound of pentaerythritol and dipentaerythritol [P].US2251236,1941
[26]Joseph A.W.and Allentown P.,Process of obtaining dipentaerythritol from mixtures containing the same[P].US2448566,1948
[1]李红强,曾幸荣.紫外光固化水性涂料的研究进展[J].中国涂料,2007,2(5):28-33
[2]Dzunuzovic E.,Tasic S.UV-curable hyperbranched urethaneacrylate oligomers containing soybean fatty acids[J].Progress in Organic Coatings,2005,(52):136-143
[3]Gao C.,Yan D.Hyperbranched polymers:From synthesis to applications[J].Progress in Polymer Science.2004,(29):183-275
[4]童身毅,王黎.超支化聚酯聚酯在涂料中的应用[J].涂料工业,2007,37(1):39-42
[5]陈梦茹,龙宇,金养智.含光敏基团的光固化水性超支化聚酯的合成与性能研究[J].影像技术,2003,(2):18-21.
[6]Anila A.,Shi W.F.Synthesis and properties of UV curable waterborne hyperbranched aliphatic polyester[J].European Polymer Journal.2003,39:933-938
[7]国家标准HG/T2708-1995聚酯多元醇中酸值的测定[S].
[8]国家标准HG/T2709-1995聚酯多元醇中羟值的测定[S].
[9]陈用烈,曾兆华,杨建文.辐射固化材料及其应用[M].北京:化学工业出版社,2003:p38
[10]国家标准GB/T6739-1996涂膜硬度铅笔测定法[S]
[11]刘宏文.超分枝多元醇的合成及其在紫外光固化体系中的应用[J].南昌大学学报(理科版),2002,26(2):135-137
[12]Hult A.and Malmstrom E.Kinetics of formation of hyperbranched polyesters based on 2,2-bis(methylol)propionic acid[J]Macromolecules.1996,29:1222-1228
[13]孟令芝,龚淑玲,何永炳.有机波谱分析(第二版)[M].武汉:武汉大学出版社,2003:213-225
[14]孙彦璞,方琪,程国平.聚酯多元醇羟值测定方法的改进[J].宁夏工程技术,2007,6(2):141-143
[15]谭惠民,罗运军.超支化聚合物[M].北京:化学工业出版社,2005:p154
[16]Bohdanecky M.,Kovor J.,Viscosity of polymer solutions[M].Amsterdam:Elsevier Scientific Publishing Company,1982:p20-30
[17]徐敏,谭克,周鸿君等.端基超支化高分子性质影响的研究[J].功能高分子学报,2003,16(3):299-303
[18]谭惠民,罗运军.超支化聚合物[M].北京:化学工业出版社,2005:p98
[2]国家标准GB/T 7815-1995工业用季戊四醇[S].
[3]李峰,朱铨寿.甲醛及其衍生物[M].北京:化学工业出版社[M].2006 p47
[4]梁建新,陈建锋C03-1各色醇酸调和漆的研制[J].广西化工1993,22(4):13-14
[5]陈启明,郭嘉,陈金芳等.油酸季戊四醇酯的合成及性能研究[J].2007,29(3):4-7
[6]朱永进,曹扩.合成润滑剂的现状及发展合成润滑材料[J].合成润滑材料2003,30(2):41-44
[7]陈洪波.国内外季戊四醇市场前景预测[J].化工技术经济2003,21(7):29-32
[8]洪仲苓主编.化工有机原料深加工[M].北京:化学工业出版社,1997:p261
[9]罗金岳,郑巧铃,安鑫南.浅色145~#松香季戊四醇酯合成工艺的研究[J]林产化学与工业2005,25(增刊)99-101
[10]戴洪义,王少君等.用于辐射固化的特种丙烯酸酯单体及其发展动向[J].山东化工,2000,(1):25-27
[11]李安梅.多元醇丙烯酸酯的制备和紫外光固化反应的研究[D].东南大学硕士硕士毕业论文.2006
[12]欧育湘.太安[M].北京:兵器工业出版社1993 p2
[13]任特生.硝铵及硝酸酯炸药化学与工艺学[M].北京:兵器工业出版社1994. p400-401
[14]金秋.季戊四醇产能和需求市场[J].精细化工原料及中间体2005,(2):11-13
[15]董延茂,鲍治宇.季戊四醇在膨胀型阻燃体系中的研究与应用进展[J].化学世界2005,9(3):177-180
[16]高明,李桂芬,杨荣杰.含季戊四醇二磷酸酯三聚氰胺-尿醛树脂盐环氧树脂的阻燃性能[J]过程工程学报,2008,8(1):182-186
[17]许晶晶,邓敏,郝惠军,等.磷酸季戊四醇酯缩合物的合成及阻燃性能研究[J].胶体与聚合物,2006,24(1):23-24
[18]金闪,刘俊康,倪忠斌等.季戊四醇磷酸酯蜜胺盐阻燃剂的合成及其在聚乙烯中的应用[J].江南大学学报,2006,5(3):341-348
[19]李到,胡静平,秦艳等.磷酸酯双三聚氰胺盐阻燃环氧树脂的燃烧性能和阻燃机理[J]功能高分子学报,2007,20(1):81-86
[20]Berlow E.,Barth R.H.and Snow J.E..The pentaerythritol[M],New York,Reinhold Publishing Co.1958,p4-7
[21]魏文德.有机化工原料大全(第二卷)[M].北京:化学工业出版社1989:p154-155
[22]Jeffrey S.S.,Oakdale B.Manufacture of neopentyl glycol[P].US5146012,1992
[23]Aiken,John E.Manufacture of neopentyl[P].EP0522368,1993
[24]Nimomiya,Teruyuki.Process for producing polhydric alcohol[P].EP0708073,1996.
[25]王永军.钙法生产季戊四醇[P].CN1651373,2005
[26]胡兵,龙化云,孙凤兰等.季戊四醇合成新工艺研究[J].湖北工学院学报2003,18(5):4-6,10
[27]魏文德.有机化工原料大全,(第二卷)[M].北京:化学工业出版社,1989:p134,157
[28]Mchenry M.A,Carr D.D,Hutter J.A.High temperature lubricant omposition[P].CA2449778.2002
[29]NCH Corporation.Multifunctional lubricants formed therefrom[P].US58859421999
[30]Exxon Chemical Patents Inc.Biodegradable branched synthetic ester base stocks and lubricants formed therefrom.[P].US5817607,1998
[31]Douglas R.Synthetic lubricant based on enhanced performance of synthetic ester fluids.[P].US573528,1998
[32]Cardis A.B.,Ardito S.Biodegradable non-toxic gear oil.[P].US6649574.2003
[33]Kitamura T.,Kanezaki,Hiroyuki.Preparation of diprentaerythritol hexa(meth)acrylate[P].JP 03234957,1989
[34]Toray Industries Inc.Scratch and weather-resistant transparent multiplayer films for safety glass.[P].JP11115107,1999
[35]Yokashima,Minora.UV-curable di-or tri(meth) acrylate ester compositions[P].JP11124515.,1999
[36]吴宇明,胡辉.Synthesis of dipentaerythritol hexaacrylate and UV-curable abrasion resistancecoaing[J].长沙电力学院学报(自然科学版),1998,13(2):178-181
[37]Toyo Ink Co Ltd.Rosin-modified phenolic resin and printing ink with improved missing abrasion resistance and dryablity[P].JP09249726,1997
[38]Nation Starch and Chemical Investment Holding Co,Vehicle system for thick film inks[P].US5622547,1997
[39]Vrsula B.,Thomas F,Klaus H.Sheer-fed offset-printing ink with cow migration,oder and swalling[P].DE19653828,1998
[40]Konica C.Ink-jet Ink compositions for color filters[P].JP20003443,2000
[41]王永强.阻燃材料及应用技术[M].北京:化学工业出版社,2003.p45.
[42]王雪峰,孙春梅,吴荣梁等.膨胀型环状类磷酸酯蜜胺盐阻燃剂的合成及阻燃聚丙烯的结构与性能[J].功能高分子学报.2005,18(4):474-478
[43]王雪峰,吴荣梁,孙春梅等.膨胀型类磷酸酯蜜胺盐阻燃剂的合成及应用研究[J].功能高分子学报2004,17(4):630-634
[44]高瑜,姜志国,华健华等.增效膨胀型阻燃双季戊四醇的性能研究[J].北京化工大学学报2000,27(4):52-55
[45]Mikimoto Seiyalu Co.Ltd.Nail Lacquers containing dipentaerythriol fatty acid esters and pearloyster shell sterols.[P].JP04346910,1992
[46]Kobayashi kose Co Ltd.Aqueous skin and hair preps,containing polyoxyethylene castor oil derivatives and oils[P].JP0338508,1991
[47]Higuchi T,Yamamoto H,et al.Transparent coated molden article and its production[P].JP1107787,1999
[48]Kondo S.,Higuchi T.,Yamamoto H.Transparent coated moldingan manufacture thereof[P].JP0108005.1999
[49]Ah K.K.,Kun S.B.Method for preparing biodegradable polyester and itself prepared thereby[P].WO02072663,2002
[50]Hatton K.B.,Liz X.Highly functional polymer[P].US0082734,2004
[51]Berlow.E,Barth R.H and.Snow.J.E.The pentaerythritol.[M]New York,Rein -hold Publishing Co.1958,p4-7
[52]岳宏君.双季戊四醇合成工艺研究[D].华东理工大学硕士毕业论文2003.
[53]王强,刘启东,邓胜民,等.单、双、叁季戊四醇的制备方法及其设备[P].CN1097004,1995
[54]吴海霞,张又文.反应条件的改变对季戊四醇生产中复产双季戊四醇的影响[J]化学工程师,1992,(7):4-7
[55]张又文,吴海霞.高比率双季戊四醇的合成研究[J]精细石油化工,1993,(6):22-25
[56]张又文,吴海霞.反应条件的改变对季戊四醇生产中副产双季戊四醇的影响[J].化学工程师,1992,(5):4-7
[57]张又文,吴海霞.双季戊四醇收率与反应条件依赖关系研究[J].化学工程师,1995,23(2):31-33
[58]贺楚华,李珊,肖志海等.单、双、三季戊四醇的合成[J].化工时刊,2005,19(1):11-13
[59]张健伟,赫广田.单、双季戊四醇的合成工艺研究[J]天然气化工,2007,32(5):40-42,46
[60]蒋远华,杨晓勤,卞平官等.一种单、双季戊四醇的制备方法[P].CN1092330,2007
[61]王永军.双季戊四醇和/或三季戊四醇生产工艺[P].CN 1012156,2007
[62]John P.R,Metuchene N.J.and Philip I.B.Manufacture of polypentaerythritols.[P].US2441597,1948
[63]Otaki,Yasushi,Fukuda,et al.Preparation of dipentaerythritol from monopentaerythritol,formaldehyde,and acetaldehyde.[P]JP09301908,1997
[64]岳宏君,王幸宜,李春香等.双季戊四醇的合成方法[P].CN1390817,2003
[65]阳永荣,刘芳,贺鑫平.一种生产双季戊四醇的方法[P].CN1522998,2004
[66]Fukuda,Takashi,Otaki,et al.Preparation of dipentaerythritol from monopent- aerythritol,formaldehyde,and acetaldehyde.[P]JP09301909,1997
[67]王幸宜,岳宏君.双季戊四醇的合成方法[P].CN1380278,2002
[68]岳宏君,王幸宜,李春香.用原位红外光谱研究氧化镁上甲醛与乙醛合成双季戊四醇反应的机理[J].催化学报,2002,23(3):276-280
[69]王幸宜,李到,杨彩平.双季戊四醇的合成方法[P].CN1016232,2007
[70]Inomata,Masasane,Ishii,Seiichi.Preparation of dipentaerythritol from acetaldehyde,formaldehyde,and acrolein[P].JP 08176048,1996
[71]Kambara,Yoshihiko,Idemoto,et al.Process for producing dipentaerythritol[P].WO9110633,1991
[72]Yamamoto,Toshio,Katsura,Akio.Preparation of dipentaerythritol[P].JP04208242,1992
[73]Watabe,Yasuyoshi,Hazama,et al.Preparation of dipentaerythritol[P].JP06016585,1994
[74]Lianshun Li,Yuichi K.,Toshio O.Catalytic dehydration of pentaerythritol to dipentaerythritol over heteropoly compounds.Applied CatalysisA:General 2003,(253):29-32
[75]Suzuki,Toshiaki,Watabe,et al.Preparation of dipentaerythritol[P].JP 07076541,1995
[76]Watabe,Yasuyoshi,Suzuki,etal.Preparation of dipentaerythritol[P].JP07165651,1995
[77]Watabe,Yasuyoshi,Suzuki,et al.Preparation of dipentaerythritol from erythritol and urea using tin catalysts[P].JP 07165653,1995
[78]Suzuki,Toshiaki,Watabe,et al.Preparation of dipentaerythritol[P].JP07258139,1995
[79]Suzuki,Toshiaki,Watabe,etal.Preparation of dipentaerythritol[P].JP07188086,1995
[80]Watabe,Yasuyoshi,Suzuki,Toshiaki.Preparation of dipentaerythritol with high efficiency[P].JP07157450,1995
[81]Watabe,Yasuyoshi,Suzuki,Toshiaki.Preparation of dipentaerythritol from 3,3-bis (hydroxymethyl)oxetane and pentaerythritol[P].JP 07165652,1995
[82]Doi,Kenji,et al.Preparation of dipentaerythritol from polypentaerythritol[P] JP09059199,1997
[83]陈用烈,曾兆华,杨建文.辐射固化材料及其应用[M].北京:化学工业出版社,2003:p354-356
[84]李红强,曾幸荣.紫外光固化水性涂料的研究进展[J].中国涂料.2007,2(5):28-33
[85]Jan S.J.Water soluble,self-emulsifying polyester resins[J].European Coating Journal,1996,(11):810-812
[86]Dvorchak M.J.,Riberi B.H.Water-reducible unsaturated polymers as binders and clear coatings for UV-curable furniture coatings[J].Journal of Coating Technology,1992,43(64):808-815
[87]Lewarchi K.Ronald J.UV-stablewater-borne polyester compositions[P].US5484842,1996
[88]Park N.H.,Suh K.D.,Kim J.Y.Preparation of UV-curable PEG-modified urethane acrylate emulsions and their coating properties.Ⅱ.Effect of chain length of polyoxyethylene[J].Journal of Applied Polymer Science,1997,64(13):2657-2664
[89]胡飞,唐黎明,李易等.紫外光固化水性聚氨酯涂料研究[J].化学世界,2002,(4):189-191
[90]白湘云,刘磊,金养智.紫外线固化水性聚氨酯丙烯酸树脂的研究[J].影像技术,2000,(3):33-36
[91]沈效峰,郁建华.光交联型水性聚氨酯乳液的研究[J].聚氨酯工业,1998,13(2):9-12
[92]韩仕甸,金养智,王菲.水性紫外光固化体系中光固化速度的影响因素[J].北京化工大学学报,2002,29(1):30-32
[93]韩飞雁,杨小毛,杨建文.紫外光固化水性涂料[J].胶体与聚合物,2001,19(2):23-26
[94]Ishida H.Study on UV curable resins with quatemary ammonium groups[C].Procee -dings ofRad.Tech.Asia97,Tokyo,Japan:1997,539-542
[95]Wuertz C.,Bismarck A.,Springer J.E.Kinetic and mechanical characterization of UV in duced crossinked acrylic copolymers[J].Progress in Organic Coatings,1999,37(3-4):117-129
[96]Wood K.A.European polymers[J].Paint and Colour Journal,1993,18(12):34-37
[97]Schlarb,Rau M.G.,Haremza S.Hydroresin dispersions:new emulsifier free binders for aqueous coatings[J].Progress in Organic Coatings,1995,26(2-4):207-215
[98]杨小毛,杨建文,陈用烈等.光固化聚氨酯改性丙烯酸系水性涂料[J].功能高分子学报,1999,12(3):285-288
[99]Loutz J.M,Peters S,Lindekens L.Radiationcurable water-borne systems[J].Journal of Coated Fbrics,1993(22):298-307
[100]Overbeek A.,Buckmann E,Martin E.New generation decorative paint technology [J].Progress in Organic Coatings,2003,48(2-4):125-139
[101]张洁,张可达.紫外光固化水溶性聚酯丙烯酸酯的合成与感光性能[J].苏州大学学报(自然科学版),2000,16(2):66-71
[102]谭惠民,罗运军.超支化聚合物[M].北京:化学工业出版,2005:p221-223
[103]Asif A.,Shi W.F.Synthesis and properties of UV curable waterborne hyperbranched aliphatic polyester[J].European Polymer Journal,2003,39(5):933-938
[104]Asif A,Huang C Y,Shi W F,et al.Structure property study of aterborne,polyurethane acrylate dispersions based on hyperbranched aliphaticpolyester for UV-curable coating[J].Colloid Polymer Science,2004,283(2):200-208
[105]Asif A,Shi W.F.UV curable waterborne polyurethane acrylate dispersions based on hyperbranched aliphatic polyester:Effect of molecular structure on physical and thermal properties[J].Polymer for Advanced Technologies,2004,1(11):669-675
[106]苏琳,蒋浩,罗凯等.UV固化水性高支化聚酯[J].热固性树脂,2004,19(2):17-20
[107]陈梦茹,龙宇,金养智等.含光敏基团的光固化水性超支化聚酯的合成与性能研究[J].影像技术,2003,(2):18-21.
[1]John P.R.,Metuchene N.J.,Philip I.B.Manufacture of polypentaerythritols[P].US 2441597,1948.
[2]Otaki Y.,Fukuda T.,Noguchi T.,et al.Preparation of dipentaerythritol from monopentaerythritol,formaldehyde and acetaldehyde[P].JP 09301908,1997.
[3]Fukuda T.,Otaki Y.,Noguchi,T.,et al.Preparation of dipentaerythritol from monopentaerythritol,formaldehyde,and acetaldehyde[P].JP 09301909,1997.
[4]王幸宜,岳宏君.双季戊四醇合成方法[P].CN 1380278,2002.
[5]岳宏君,王幸宜,李春香等.双季戊四醇合成方法[P].CN 1390817,2003.
[6]王强,刘启东,邓胜民等.单、双、三季戊四醇的制备方法及其设备[P].CN 1097004.1995.
[7]贺楚华,李珊,肖志海等.单、双、三季戊四醇的合成[J].化工时刊,2005,19(1):11-13.
[8]国家标准.GB/T 7815-1995工业用季戊四醇[S].1996
[9]Suchanec R.R.Gas chromatographic separation and determination of pentareythritol system by methylsilyl ether derivatives[J].Analytical Chemistry,1965,37(11):1361-1365.
[10]杨昀,刘玉林.季戊四醇和双季戊四醇气相色谱分析方法研究[J].理化检验-化学分册.2006,42(7):557-559
[11]国药集团上海化学试剂公司.试剂手册(第三版)[M].上海:上海科学技术出版社,2002:p807
[12]魏文德.有机化工原料大全(第二卷)[M].北京:化学工业出版社,1989:p152
[13]魏文德.有机化工原料大全(第二卷)[M].北京:化学工业出版社,1989:p134
[14]Berlow E.,Barth R.H and Snow.J.E.The Pentaerythritol.[M]New York:Reinhold Publishing Co,1958:p4-7
[15]Salkind M,Ahern H.F.and Albert A.A.Peataerythritol[J].Industrial and Engineering Chemistry.1958,50(8):1106-1114.
[16]岳宏君.双季戊四醇合成工艺研究[D].华东理工大学硕士学位论文,2003.p37-40
[17]李峰,朱铨寿.甲醛及其衍生物[M].北京:化学工业出版社,2006:p41.
[18]胡宏纹.有机化学[M].北京:高等教育出版社(上册),1990:p360.
[19]滕冬成.双季戊四醇重结晶新工艺的研究[J].精细化工中间体,2004,34(2):53-55.
[20]魏文德.有机化工原料大全(第二卷)[M].北京:化学工业出版社,1989:p281
[21]胡宏纹.有机化学[M].北京:高等教育出版社(上册),1990:p339.
[22]胡宏纹.有机化学[M].北京:高等教育出版社(上册),1990:p274.
[23]Bried E.A.Acetaldehyde-formaldehyde condensation product[P].US 2325589,1943.
[24]Peters M.S.and Cupit C.R.,Kinetics of pentaerythritol-production reactions[J].Chemical Engineering Science,1959,10:57-67
[25]Joseph A.W.and Edwin A.W.,Double compound of pentaerythritol and dipentaerythritol [P].US2251236,1941
[26]Joseph A.W.and Allentown P.,Process of obtaining dipentaerythritol from mixtures containing the same[P].US2448566,1948
[1]李红强,曾幸荣.紫外光固化水性涂料的研究进展[J].中国涂料,2007,2(5):28-33
[2]Dzunuzovic E.,Tasic S.UV-curable hyperbranched urethaneacrylate oligomers containing soybean fatty acids[J].Progress in Organic Coatings,2005,(52):136-143
[3]Gao C.,Yan D.Hyperbranched polymers:From synthesis to applications[J].Progress in Polymer Science.2004,(29):183-275
[4]童身毅,王黎.超支化聚酯聚酯在涂料中的应用[J].涂料工业,2007,37(1):39-42
[5]陈梦茹,龙宇,金养智.含光敏基团的光固化水性超支化聚酯的合成与性能研究[J].影像技术,2003,(2):18-21.
[6]Anila A.,Shi W.F.Synthesis and properties of UV curable waterborne hyperbranched aliphatic polyester[J].European Polymer Journal.2003,39:933-938
[7]国家标准HG/T2708-1995聚酯多元醇中酸值的测定[S].
[8]国家标准HG/T2709-1995聚酯多元醇中羟值的测定[S].
[9]陈用烈,曾兆华,杨建文.辐射固化材料及其应用[M].北京:化学工业出版社,2003:p38
[10]国家标准GB/T6739-1996涂膜硬度铅笔测定法[S]
[11]刘宏文.超分枝多元醇的合成及其在紫外光固化体系中的应用[J].南昌大学学报(理科版),2002,26(2):135-137
[12]Hult A.and Malmstrom E.Kinetics of formation of hyperbranched polyesters based on 2,2-bis(methylol)propionic acid[J]Macromolecules.1996,29:1222-1228
[13]孟令芝,龚淑玲,何永炳.有机波谱分析(第二版)[M].武汉:武汉大学出版社,2003:213-225
[14]孙彦璞,方琪,程国平.聚酯多元醇羟值测定方法的改进[J].宁夏工程技术,2007,6(2):141-143
[15]谭惠民,罗运军.超支化聚合物[M].北京:化学工业出版社,2005:p154
[16]Bohdanecky M.,Kovor J.,Viscosity of polymer solutions[M].Amsterdam:Elsevier Scientific Publishing Company,1982:p20-30
[17]徐敏,谭克,周鸿君等.端基超支化高分子性质影响的研究[J].功能高分子学报,2003,16(3):299-303
[18]谭惠民,罗运军.超支化聚合物[M].北京:化学工业出版社,2005:p98