CN109206450A - 一种绿色催化剂催化合成十二烷基磷酸酯 - Google Patents
一种绿色催化剂催化合成十二烷基磷酸酯 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- QZRMKGRPCTVXBS-UHFFFAOYSA-N 2,6,8-trimethylnonan-4-yl dihydrogen phosphate Chemical compound CC(C)CC(C)CC(CC(C)C)OP(O)(O)=O QZRMKGRPCTVXBS-UHFFFAOYSA-N 0.000 title claims abstract description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 230000007246 mechanism Effects 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims 2
- 238000004679 31P NMR spectroscopy Methods 0.000 claims 1
- IIVCYFSRDZBYCV-UHFFFAOYSA-N C(CCCCCCCCCCC)[P] Chemical compound C(CCCCCCCCCCC)[P] IIVCYFSRDZBYCV-UHFFFAOYSA-N 0.000 claims 1
- 239000011949 solid catalyst Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 5
- 239000012153 distilled water Substances 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 description 32
- 239000010452 phosphate Substances 0.000 description 32
- -1 alkyl phosphate Chemical compound 0.000 description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 15
- 239000004094 surface-active agent Substances 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07F9/02—Phosphorus compounds
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- B01J2229/10—After treatment, characterised by the effect to be obtained
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Abstract
本发明涉及一种绿色催化剂催化合成十二烷基磷酸酯,通过这种方法可以显著提高产物中单十二烷基磷酸酯含量。本方法以十二醇和五氧化二磷为原料,利用单因素实验研究法考察催化剂用量、催化剂的负载量、反应时间、加入蒸馏水量、温度对反应产物中单酯含量的影响,从而找到提高单酯含量的最佳合成工艺条件。本发明制备的十二烷基磷酸酯单酯含量高,制备方法工艺简单,成本低。
Description
技术领域
本发明涉及一种绿色催化剂合成十二烷基磷酸酯技术,旨在提高反应物中单十二烷基磷酸酯的含量。
背景技术
磷酸酯类表面活性剂性能温和、拥有良好的生物降性,刺激性很低,另外还具备润湿、净洗、增溶、乳化、润滑、防锈、缓蚀、分散、螯合、抗静电等多种优良的性能,但随着磷酸酯类表面活性剂中所含的单酯、双酯和三酯三者的比例不同,磷酸酯类表面活性剂表现出的性能有很大的差别。磷酸酯类表面活性剂主要有三类:第一类为磷酸三酯,它属于非离子型表面活性剂具有良好的阻燃和增塑性能,在高分子材料生产工艺中有广泛的应用;第二类为磷酸双酯,它属于离子型表面活性剂在平滑方面具有优异的表现,另外它可以很好的减小被处理物的摩擦系数,常常被用作平滑剂;第三类为磷酸单酯,它属于离子型表面活性剂,由于单酯中含有较多的亲水基使其具备优异亲水性能,因而在其具有良好的溶解能力的同时拥有良好的抗静电性、乳化性、束集性和抗锈性,并且与烷基硫酸盐和烷基磺酸盐等阴离子表面活性剂相比对皮肤刺激性更小,因此,单酯常常作为乳化剂应用于洗涤类和化妆品类等产品中,在皮肤的清洗和护理、香波、口腔护理中具有广阔的应用前景。磷酸酯在日化、轻化、精细化工等行业的应用愈来愈广,成为一类不可或缺的表面活性剂。高比例烷基磷酸单酯是指烷基磷酸单酯在单烷基磷酸酯和烷基磷酸双酯中的质量分数含量大于90%的磷酸酯。国内市售磷酸酯的烷基磷酸单酯含量大多都在35%-65%之间,随着磷酸酯中烷基磷酸双酯含量增加,磷酸酯的泡沫性、溶解性都有不同程度的降低。我国使用的高比例烷基磷酸单酯主要从国外进口。国外磷酸酯类表面活性剂的研究开始于19世纪初,自八十年代开始报导数量逐渐增加。1990年美国磷酸酯消耗量达2.7万吨、西欧磷酸酯消耗量达0.6万吨、日本磷酸酯消耗量达2.2万吨,而我国在1993年磷酸酯年产量产量只有0.21万吨。Henkel公司、 Kao Corp公司、Rhodia(US)公司等对烷基磷酸单酯的合成技术做了大量的研究工作,掌握了较为成熟的烷基磷酸单酯合成工艺技术,在很大程度推动了烷基磷酸单酯的应用,迄今为止烷基磷酸单酯在欧美等国众多领域广泛使用。我国对于磷酸酯类表面活性剂的研究开始于 19世纪60年代末,在最近十多年磷酸酯类表面活性剂的研究活动有了很大的成就,已有五氧化二磷法、磷酰氯和三氯化磷法、磷酸法和聚磷酸法等合成磷酸酯的方法,尤其最近几年,随着对表面活性剂在降解性和皮肤刺激性等方面要求的提高,磷酸酯类表面活性剂越来越受到关注,但高比例烷基磷酸单酯主要还是依赖进口,国内的磷酸酯至今为止还是只有少数几个大类,几十个品种,磷酸单酯比例只在80%上下浮动,而游离磷酸则在10%左右,与国外的磷酸酯类表面活性剂相比还有较大差距。为使我国磷酸酯类表面活性剂有更加广阔的发展,开展磷酸酯合成工艺研究提高磷酸单酯的比例,用以满足我国各个生产领域对磷酸酯类表面活性剂的需要是非常必要的。
发明内容
本发明采用浸渍法将磷钨酸负载到HMCM-22分子筛上得到绿色催化剂PW/HMCM-22。
本发明涉及一种绿色催化剂PW/HMCM-22催化合成十二烷基磷酸酯,通过这种方法可以提高十二烷基磷酸单酯含量。
本发明以十二醇,五氧化二磷为原料,PW/HMCM-22为催化剂。采用单因素实验研究法考察催化剂用量、催化剂的负载量、反应时间、加入蒸馏水量、温度对反应产物中单酯含量的影响,从而找到提高单酯含量的最佳合成条件。
本发明在反应结束后采用电位滴定法检测产物的酸值和单酯值及双酯值。
具体实施方式
步骤一:先配置所需浓度的磷钨酸溶液,然后取一定质量的HMCM-22将二者置于烧瓶中在90℃下混合搅拌3h,然后将其取出置于150℃烘箱中烘4h,即得到负载型HMCM-22 催化剂,记为PW/HMCM-22,x为H3PO4.12WO3占HMCM-22分子筛的质量百分数。
步骤二:将十二醇(0.5mol)加入装有搅拌装置的烧瓶(250m L)中,然后依次加入一定量的蒸馏水和催化剂,最后将五氧化二磷(0.25mol)分批次加入烧杯中控制投料时温度在 60℃以下,投料完成后将温度控制在指定温度开始反应,反应指定的小时后得到反应产物,取样用电位滴定法分析产物中单双酯和磷酸的含量。
步骤三:利用单因素实验研究法考察催化剂用量、催化剂的负载量、反应时间、加入蒸馏水量、温度对反应产物中单酯含量的影响,从而找到提高单酯含量的最佳合成工艺条件。
一种绿色催化剂催化合成十二烷基磷酸酯,反应机理如下:
(1)本反应的催化剂为制备的绿色催化剂,醇为十二醇;
(2)本反应的物料比为十二醇∶五氧化二磷=2∶1;
(3)本反应的反应投料温度为20-60℃,反应温度为60℃-150℃;
(4)本反应的反应时间为1-12小时;
(5)本反应的催化剂用量为反应物总质量的0-5%;
(6)本反应的水与反应物中十二醇的摩尔比为2∶1-3。
Claims (5)
1.一种绿色催化剂催化合成十二烷基磷酸酯,其方法为:制备绿色催化剂,以十二醇与五氧化二磷为原料,在水和绿色催化剂条件下反应得到十二烷基磷酸酯。
2.根据权利要求1所述有十二醇、五氧化二磷、水、绿色催化剂。
3.根据权利要求1所述反应机理第一步为制备绿色催化剂的制备,其特征为:
(1)先配制所需浓度的磷钨酸溶液;
(2)取一定质量的HMCM-22和配制好的磷钨酸溶液将二者置于烧瓶中在90℃下混合搅拌3h;
(3)将固体催化剂取出置于150℃烘箱中烘4h,即得到负载型HMCM-22催化剂,记为PW/HMCM-22,x为H3PO4.12WO3占HMCM-22分子筛的质量百分数。
4.根据权利要求1所述反应机理第二步为十二烷基磷酸酯的合成,其特征为:
(1)物料比为十二醇∶五氧化二磷=2∶1;
(2)反应投料温度为20-60℃,反应温度为60℃-150℃;
(3)反应时间为1-12小时;
(4)催化剂用量为反应物总质量的0-5%;
(5)水与反应物中十二醇的摩尔比为2∶1-3。
5.根据权利要求1中制备的绿色催化剂用XRD、SEM、FT-IR进行表征,合成的十二烷基磷酸酯用31P-NMR,FT-IR进行表征。
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