CN1042427C - 2－羟基－2膦酸基乙酸的合成方法 - Google Patents
2－羟基－2膦酸基乙酸的合成方法 Download PDFInfo
- Publication number
- CN1042427C CN1042427C CN94110195A CN94110195A CN1042427C CN 1042427 C CN1042427 C CN 1042427C CN 94110195 A CN94110195 A CN 94110195A CN 94110195 A CN94110195 A CN 94110195A CN 1042427 C CN1042427 C CN 1042427C
- Authority
- CN
- China
- Prior art keywords
- hydroxy
- acid
- reaction
- products
- phosphorus compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- UTCHNZLBVKHYKC-UHFFFAOYSA-N 2-hydroxy-2-phosphonoacetic acid Chemical compound OC(=O)C(O)P(O)(O)=O UTCHNZLBVKHYKC-UHFFFAOYSA-N 0.000 title claims description 11
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- -1 radical acetate Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 239000003112 inhibitor Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 238000005272 metallurgy Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YXNNSWYDFRWCBQ-UHFFFAOYSA-N C(C)(=O)O.P(O)(O)=O Chemical compound C(C)(=O)O.P(O)(O)=O YXNNSWYDFRWCBQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 2
- DEBRGDVXKPMWQZ-UHFFFAOYSA-N Formylphosphonate Chemical class OP(O)(=O)C=O DEBRGDVXKPMWQZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- IQEKRNXJPCBUAT-UHFFFAOYSA-N 2-[hydroperoxy(hydroxy)phosphoryl]acetic acid Chemical compound OOP(O)(=O)CC(O)=O IQEKRNXJPCBUAT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- IZQZNLBFNMTRMF-UHFFFAOYSA-N acetic acid;phosphoric acid Chemical compound CC(O)=O.OP(O)(O)=O IZQZNLBFNMTRMF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- OOSPDKSZPPFOBR-UHFFFAOYSA-N butyl dihydrogen phosphite Chemical compound CCCCOP(O)O OOSPDKSZPPFOBR-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- VWCFCFOIUSKKSC-UHFFFAOYSA-N ethane-1,2-diamine;2-hydroxy-1,3,2$l^{5}-dioxaphosphepane 2-oxide Chemical compound NCCN.OP1(=O)OCCCCO1 VWCFCFOIUSKKSC-UHFFFAOYSA-N 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
Abstract
本发明公开了一种2-羟基-2-膦酸基乙酸的合成方法。将乙醛酸与含磷化合物进行缩合反应，反应时间为1-30小时，温度为25℃-150℃，去除掉不需要的醇和水，即可得到产品HPA高效缓蚀剂。该合成反应工艺条件易控制，合成路线简单，无三废、无污染，产品在化工、电力、冶金等行业的工业循环水***中得以广泛应用。反应式为：
HCOCOOH+(RO)nP(OH)3-n+nH2O
→(HO)2POCHOHCOOH+nROH
Description
本发明属于一种用于工业循环水的阻垢缓蚀剂2-羟基-2膦酸基乙酸的合成。
目前，我国化工、电力、冶金等部门都广泛应用工业循环水***，而循环水***的主要设备如贮水槽、锅炉、热交换器等存在严重的腐蚀阻垢问题。为解决这一问题，实践中通常要使用缓蚀剂。进口缓蚀剂效果好，但价格昂贵，合成工艺路线复杂；国内缓蚀剂品种少，不能满足应用的要求。2-羟基-2膦酸基乙酸，又称HPA缓蚀剂，是一种新型缓蚀剂。其结构式为：
它具有如下的特点：(1)缓蚀性能好，其缓蚀性能比国内常用的羟基乙叉二膦酸(HEDP)和乙二胺四甲叉磷酸(EDTMP)高5～8倍；(2)低浓度高效性，常以PPM级使用；(3)化学稳定性好，不易水解，不易被酸或碱所破坏；(4)使用安全可靠、无毒、无污染；(5)水溶性好。HPA新型缓蚀剂作为一种理想的缓蚀剂，可广泛应用于铜、钢、铝、锡及其合金制品的贮水槽、锅炉、热交换器和循环水设备的防腐阻垢。现在国内尚无生产HPA新型缓蚀剂的厂家，国外已有类似产品的生产，其典型代表是Ciba-Geigy公司的商品Belcor-575。合成HPA新型缓蚀剂的有效成份羟基膦酸基乙酸的路线有两个：(1)专利文献Eur.Pat.Appl.EP.50792报道的合成路线是先用二烷基亚磷酸酯与原甲酸酯反应，再水解得到膦酸基甲醛的盐，将其与氢氰酸作用可得羟基膦酸基乙腈，把腈进行酸性水解得到产品；(2)专利文献Ger.Offen.2941384(1979)报道的合成路线是由二烷基亚磷酸酯与乙醛酸酯反应，生成羟基膦酸酯基乙酸酯，再经过适当的水解得到产品。此两种方法均需多步反应完成，且方法(1)中涉及到使用剧毒的氰化物，易造成危害，且分离产品尚需一定的复杂技术，方法(2)中涉及的各化合物基本无毒，但技术难度较大，主要是要在较高的真空下蒸馏得到羟基膦酸基乙酯。
本发明的目的是寻找一条新的合成路线，合成方法简单，收率高，无污染，不涉及剧毒物，克服现有技术中的不足与缺陷。
本发明的技术方案是：一种以含ROOCCHO结构化合物和磷化合物反应，合成2-羟基-2膦酸基乙酸的方法，本发明的特殊之处是乙醛酸与磷化合物(RO)nP(OH)3-n进行反应，摩尔比为1.0∶0.5-2，反应温度为25℃-150℃，反应时间为1-30小时，得到生成物，将生成物蒸馏得到2-羟基-2膦酸基乙酸。
乙醛酸是纯固体或浓度为5-50％的水溶液。
磷化合物(RO)nP(OH)3-n中n可以是0,2或3,R可以是具有碳数为1-10的烷基或芳烷基。
蒸馏生成物是在25℃-100℃，常压或133-95000Pa压力下进行的。
该反应式为：
反应式中的磷化合物的R代表烷基或芳烷基，其碳数为1-10，特别是C1-C4的烷基，如亚磷酸甲酯，亚磷酸丁酯等。其中的n可以是0,2或3，当n为0时，即为亚磷酸；n为2时，即为亚磷酸二烷酯或二芳烷酯；n为3时，即为亚磷酸三烷酯或三芳烷酯。反应的时间依照反应物乙醛酸的浓度和磷化合物的浓度的不同以及反应温度的不同而为1-30小时。
根据本发明得到的产品经红外光谱、核磁共振和液相色谱分析等证明与国外产品一样，为同一化合物2-羟基-2膦酸基乙酸。用亚磷酸二甲酯和乙醛酸、亚磷酸和乙醛酸可直接合成2-羟基-2膦酸基乙酸，这两个新反应在国内外均未见文献报导。本发明反应收率高，通常可达到80％以上，不涉及剧毒物的产生，无污染、无三废，工艺条件易控制，合成方法简单，成本较低。
以下结合实施例，对本发明做进一步的阐述。
实施例1。在反应器中加入16.4克亚磷酸和29.6克50％的乙醛酸溶液，装上回流冷凝装置，用沸水浴加热，当反应物温度临近100℃时，反应放热明显，反应物温度可自行上升到104℃左右，经过约半小时后，反应物料温度回落到约100℃，用沸水浴维持加热5-6小时后，停止加热，得到2-羟基-2膦酸基乙酸的水溶液。将此水溶液在25-100℃内，常压蒸馏，除去醇及部分水，可得到2-羟基-2膦酸基乙酸。
实施例2。在反应器中加入25克亚磷酸二甲酯和29克50％的乙醛酸溶液，混合后反应液乳浊，先在25℃下反应2小时，再用水浴缓缓加热至沸腾并保持2-4小时。然后将反应液在25℃-100℃，减压至133-95000Pa下进行蒸馏，蒸除去水和甲醇，得到2-羟基-2膦酸基乙酸。
Claims (3)
1．一种以含ROOCCHO结构化合物和磷化合物反应，合成2-羟基-2膦酸基乙酸的方法，其特征是乙醛酸与磷化合物(RO)nP(OH)3-n进行反应，摩尔比为1.0∶0.5-2，反应温度为25℃-150℃，反应时间为1-30小时，得到生成物，将生成物蒸馏得到2-羟基-2膦酸基乙酸，磷化合物(RO)nP(OH)3-n中的n可以是0,2或3,R可以是具有碳数为1-10的烷基或芳烷基。
2．根据权利要求1所述的2-羟基-2膦酸基乙酸的合成方法，其特征是乙醛酸是纯固体或浓度为5-50％的水溶液。
3．根据权利要求2所述的2-羟基-2膦酸基乙酸的合成方法，其特征是蒸馏生成物是在25-100℃，常压或133-95000Pa压力下进行的。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110195A CN1042427C (zh) | 1994-04-15 | 1994-04-15 | 2－羟基－2膦酸基乙酸的合成方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110195A CN1042427C (zh) | 1994-04-15 | 1994-04-15 | 2－羟基－2膦酸基乙酸的合成方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1110277A CN1110277A (zh) | 1995-10-18 |
| CN1042427C true CN1042427C (zh) | 1999-03-10 |
Family
ID=5034181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94110195A Expired - Fee Related CN1042427C (zh) | 1994-04-15 | 1994-04-15 | 2－羟基－2膦酸基乙酸的合成方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1042427C (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102363538B (zh) * | 2010-12-07 | 2013-04-03 | 新疆德蓝股份有限公司 | 一种用于低硬度循环冷却水的复合缓蚀阻垢剂的制备 |
| CN103087099B (zh) * | 2013-01-15 | 2015-11-18 | 湖北兴发化工集团股份有限公司 | 一种2-羟基膦酰基乙酸的制备方法 |
| CN103435644B (zh) * | 2013-09-09 | 2015-07-08 | 山东省泰和水处理有限公司 | 一种低氯2-羟基膦酰基乙酸的制备方法 |
| CN104528962A (zh) * | 2014-10-24 | 2015-04-22 | 中国海洋石油总公司 | 一种新型采暖***停炉保护液的制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2941384A1 (de) * | 1979-10-12 | 1981-04-23 | Bayer Ag, 5090 Leverkusen | Phosphono-hydroxy-essigsaeure, verfahren zu ihrer herstellung sowie ihre verwendung als arzneimittel |
| EP0050792A1 (de) * | 1980-10-23 | 1982-05-05 | Bayer Ag | Verfahren zur Herstellung von Phosphonohydroxyacetonitril |
-
1994
- 1994-04-15 CN CN94110195A patent/CN1042427C/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2941384A1 (de) * | 1979-10-12 | 1981-04-23 | Bayer Ag, 5090 Leverkusen | Phosphono-hydroxy-essigsaeure, verfahren zu ihrer herstellung sowie ihre verwendung als arzneimittel |
| EP0050792A1 (de) * | 1980-10-23 | 1982-05-05 | Bayer Ag | Verfahren zur Herstellung von Phosphonohydroxyacetonitril |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1110277A (zh) | 1995-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7884248B2 (en) | Process for the manufacture of aminopolyalkylenephosphonic acid compounds | |
| CA2022392C (en) | 4-phosphonomethyl-2-hydroxy-2-oxo-1,4,2-oxazaphosphorinane n-oxide and water-soluble salts thereof | |
| EP0178168A2 (en) | Process for purification of methacrylic acid | |
| JP2014185150A (ja) | ジ（２−エチルヘキシル）テレフタレートの製造方法 | |
| CN1042427C (zh) | 2－羟基－2膦酸基乙酸的合成方法 | |
| US6166232A (en) | Process for producing ester quats | |
| FI91873B (fi) | Menetelmä 2-fosfonobutaani-1,2,4-trikarboksyylihapon ja sen alkalimetallisuolojen valmistamiseksi jatkuvatoimisesti | |
| CN105714302A (zh) | 一种防锈缓蚀多功能制剂 | |
| US4260422A (en) | Novel phosphonocarboxylic acid compounds | |
| WO2006069113A2 (en) | Method to produce a carboxylic acid ester from a carboxylic acid ammonium salt by alcoholysis | |
| CA1063616A (en) | Quaternary aminoalkylene phosphonic acids and method of preparation | |
| CN1288009A (zh) | N－膦酰基甲氨基羧酸的制备方法 | |
| US5430183A (en) | Para-hydroxyalkylation of hydroxylated aromatic compounds | |
| USRE32250E (en) | Stabilization of silicates using salts of substituted nitrogen or sulfur containing siliconates | |
| Mikroyannidis | Hydroxy and/or carboxy substituted phosphonic and bisphosphonic acids usable as corrosion and scale inhibitors | |
| CN103087099B (zh) | 一种2-羟基膦酰基乙酸的制备方法 | |
| KR101375753B1 (ko) | 식관용 강판에 사용하는 방청유용 디옥틸 세바케이트의 제조방법 | |
| US5639909A (en) | Production of 2-phosphonobutane-1,2,4-tricarboxylic acid and the alkali metal salts thereof | |
| EP1810975B1 (en) | Method for producing phosphonates having an alcoholic hydroxy group | |
| JPS5912799A (ja) | スケ−ル防止剤 | |
| CN104211192A (zh) | 一种膦酰基丁烷三羧酸复配阻垢剂的制备方法 | |
| US4911887A (en) | Phosphonic acid compounds and the preparation and use thereof | |
| EP0199525B1 (en) | Phosphorous acid catalyzed phenol esterification | |
| EP0463676A1 (en) | Process for the synthesis of alpha-hydroxy-esters | |
| CN1048988C (zh) | 一种2－膦酸丁烷－1,2,4－三羧酸的合成方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |