WO2013026252A1 - 一种多支化的曼尼希碱缓蚀剂及其制备方法 - Google Patents

一种多支化的曼尼希碱缓蚀剂及其制备方法 Download PDF

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WO2013026252A1
WO2013026252A1 PCT/CN2012/000567 CN2012000567W WO2013026252A1 WO 2013026252 A1 WO2013026252 A1 WO 2013026252A1 CN 2012000567 W CN2012000567 W CN 2012000567W WO 2013026252 A1 WO2013026252 A1 WO 2013026252A1
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ketone
group
branched
corrosion inhibitor
mannich base
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PCT/CN2012/000567
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English (en)
French (fr)
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马玲
李磊
孔祥军
地力拜·马克
甄新平
牛春革
白生军
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中国石油天然气股份有限公司
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Priority to CA2841020A priority Critical patent/CA2841020C/en
Priority to AP2014007352A priority patent/AP2014007352A0/xx
Priority to US14/234,854 priority patent/US9493399B2/en
Publication of WO2013026252A1 publication Critical patent/WO2013026252A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C225/04—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated
    • C07C225/06—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and acyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C225/04—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated
    • C07C225/08—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing rings
    • C07C225/10—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing rings with doubly-bound oxygen atoms bound to carbon atoms not being part of rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C225/04—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated
    • C07C225/08—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing rings
    • C07C225/12—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing rings with doubly-bound oxygen atoms bound to carbon atoms being part of rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C225/14—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated
    • C07C225/16—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds

Definitions

  • the invention relates to a multi-branched Mannich base corrosion inhibitor and a preparation method thereof.
  • Mannich Reaction also known as amine methylation
  • amine hydrochloride formaldehyde
  • C-H acid compounds especially with ketones.
  • the reaction components can be appropriately selected, and substances similar to alkaloids can be prepared.
  • Mannich School has published a large number of research reports, especially the reaction of fatty ketones, fatty ketones and alicyclic ketones as acid components, which laid the foundation for the Mannich reaction. Mannich base and its derivatives were originally applied as medicines.
  • Mannich base was used as a corrosion inhibitor in the 1970s and was originally used as a preservative in antifreeze solutions and later used to treat the inner wall of LPG storage.
  • Mannich base corrosion inhibitors With the increase in well depth in oil exploration and production, the widespread application of oil well acidification to increase crude oil technology, the demand for high temperature acidification inhibitors has led to the promotion of Mannich base corrosion inhibitors.
  • Mannich type corrosion inhibitors are mainly - Duan Xiaoyun
  • Li Pengjiang uses formaldehyde, cyclohexylamine and acetophenone as main raw materials to synthesize Mannich base corrosion inhibitors by Mannich reaction, and studied formaldehyde and ring. Effect of hexylamine and acetophenone on the corrosion inhibition performance of synthetic Mannich base corrosion inhibitors [DUAN Xiaoyun, LI Pengjiang. A synthesis of Mannich base corrosion inhibitors. Chemical Technology and Development.
  • Chinese patent CN 100577877C discloses a method for synthesizing Mannich base steel corrosion inhibitor mother liquor and a steel corrosion inhibitor mother liquor, which is a secondary amine, an aldehyde and a mercapto group, a cyclodecyl group, an aromatic group in an aqueous medium.
  • CN 101451242A "A high temperature acidification corrosion inhibitor for a Cr-containing oil pipe” discloses an acidizing corrosion inhibitor
  • the composition of the main agent A is: 25 parts to 35 parts of quinoline quaternary ammonium salt or quinoline derivative quaternary ammonium salt, 5 parts to 10 parts of potassium iodide and 40 parts to 60 parts of organic solvent methanol or formaldehyde.
  • CN 1761715A is a phenolic compound, formaldehyde and at least one polyamine synthesized by epoxy or polyurethane system Nich base type curing agent, in order to make the phenolic compound react as completely as possible without leaving the product to be environmentally friendly, an excess of amine is used in the patent; and the patent disclosed in CN 101182296A also reports an epoxy system or a polyurethane system.
  • the curing agent is synthesized by a Mannich reaction based on dicyclohexanone, formaldehyde and at least one polyamine, and also takes an excess of the raw material ratio of the amine.
  • the synthetic raw materials of the Mannich type corrosion inhibitor synthesized in the prior art mainly include: (1) ketones, mainly fatty ketones (such as acetone, butanone, pentanone, ketone, etc.), cyclohexanone (such as cyclohexyl) Ketone) and aromatic ketone (such as acetophenone); (2) aldehyde, usually formaldehyde, or polyoxymethylene.
  • ketones mainly fatty ketones (such as acetone, butanone, pentanone, ketone, etc.), cyclohexanone (such as cyclohexyl) Ketone) and aromatic ketone (such as acetophenone)
  • aldehyde usually formaldehyde, or polyoxymethylene.
  • Amines mainly fatty amines (such as diethanolamine, dimethylamine, diethylamine, ethylenediamine, fatty polyamines), cyclodecylamine (cyclohexylamine, morpholine, etc.), aromatic amines (such as aniline, Benzylamine, aromatic polyamine, etc.).
  • the ketone, aldehyde, amine (monoamine) in the prior art is 1:1:1 or the ketone, aldehyde, amine (diamine) is 2:2:1, and therefore, the obtained Mannich base is a linear structure. : ,0
  • the adsorption center is distributed at one end or both ends of the molecule.
  • the linear Mannich type corrosion inhibitor meets the metal wall surface, it exhibits end group adsorption.
  • the end containing the adsorption center forms chemical or physical adsorption with the metal, and the other end extends outward. Hydrophobic layer.
  • the defect of the linear structure Mannich type corrosion inhibitor on the metal surface is that the corrosion inhibitor and the metal wall have poor adhesion due to single point adsorption, low film strength, poor film density, especially in the case of being eroded or unclean.
  • the metal wall surface is difficult to form or form a film, and the etching ability is poor.
  • the object of the present invention is to provide a multi-branched space-shaped structure of Mannich base or chiral Mannich base corrosion inhibitor, which is a ketone, an aldehyde and contains three or more primary and/or secondary amines.
  • the two primary or secondary amine groups are respectively subjected to Mannich reaction with a ketone or an aldehyde, that is, the organic polyamine is used to carry out functional group grafting on a plurality of amine groups to obtain a multi-branched Mannich base corrosion inhibitor structure. :
  • ⁇ , , N x , N y , N m , N n are the nitrogen atoms on the carbon-nitrogen skeleton, x, y, m, n are their sequential numbers, 2 xmy nl, and 3 n 7;
  • R, R m and R n are substituents in which the active hydrogen on the carbon atom to which the carbonyl group is bonded in the starting ketone is substituted, and may be an aliphatic ketone group, an alicyclic ketone group or an aromatic ketone group, respectively.
  • the cycloketone group in the alicyclic ketone group includes a cyclohexanone group, a cyclopentanone group, an o-methylcyclohexanone group, a p-methylcyclohexanone group, a 2-methylcyclopentanone group, a 2-ethyl group.
  • Cyclopentanone, 3-ethylcyclopentanone; aliphatic ketone, aromatic ketone and other alicyclic ketone groups can be represented by the following formula -
  • R x , R y can be H, or z R'
  • R' is a substituent in which the active hydrogen on the carbon atom to which the carbonyl group is bonded in the raw material ketone is substituted, and may be an aliphatic ketone group, an alicyclic ketone group or an aromatic ketone group, respectively.
  • the cycloketone group in the alicyclic ketone group includes a cyclohexanone group, a cyclopentanone group, an o-methylcyclohexanone group, a p-methylcyclohexanone group, a 2-methylcyclopentanone group, a 2-ethyl group.
  • Cyclopentanone, 3-ethylcyclopentanone; aliphatic ketone, aromatic ketone and other alicyclic ketone groups can be represented by the following formula:
  • R a and R b each independently represent a C-C 6 fluorenyl group, a C 6 -C 9 linear or branched aromatic group, and a C 5 -C 9 linear or branched cyclic fluorenyl group;
  • Another object of the present invention is to provide a method for preparing a Mannich base corrosion inhibitor, which is a ketone (which may be a fatty ketone, an alicyclic ketone, an aromatic ketone), formaldehyde (or a compound which can dissociate formaldehyde). And an organic polyamine containing three or more primary and/or secondary amino groups as a raw material, which is obtained by a Mannich reaction.
  • the preparation process is simple, the reaction condition is mild, the raw materials are easy to obtain, and the energy consumption is small.
  • One of the technical solutions provided by the present invention is to provide a Mannich base corrosion inhibitor prepared by reacting 1 mole of organic polyamine with 3-7 moles of ketone and 3-7 moles of aldehyde by Mannich reaction.
  • the organic polyamine is an organic compound containing three or more primary and/or secondary amino groups, and is diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptaamine. One or any combination of two or more components.
  • the ketone is one of an aliphatic ketone, an alicyclic ketone, an aromatic ketone, or a combination of any two or more components.
  • Alicyclic ketone which includes cyclohexanone, cyclopentanone, cycloheptanone, o-methylcyclohexanone, p-methylcyclohexanone,
  • 2-methylcyclopentanone, 2-ethylcyclopentanone, 3-ethylcyclopentanone; fatty ketones, aromatic ketones and other alicyclic ketones can be expressed as:
  • R a and R b each independently represent a d-C 6 alkyl group, a C 6 -C 9 linear or branched aromatic group, and a C 5 -C 9 linear or branched cyclic fluorenyl group.
  • the aldehyde is formaldehyde or a compound polyoxymethylene which is capable of dissociating formaldehyde, preferably formaldehyde.
  • the second technical solution provided by the present invention provides a preparation method of a Mannich base corrosion inhibitor.
  • the preparation method comprises the following steps:: by adding an excess amount of a ketone or an aldehyde, at least three primary and/or secondary amino groups on the organic polyamine are respectively subjected to Mannich reaction with the ketone and aldehyde to form a multi-branched Mann. Nixi base corrosion inhibitor.
  • the specific preparation steps are as follows: (1) adding 3 to 7 moles of ketone and 3 to 7 moles of aldehyde to the reaction vessel, adjusting the pH to 2 to 6 with acid, controlling the temperature to 20 to 50 ° C, stirring 20 to 30 (2) Adding 1 mole of the organic polyamine to the reaction vessel under stirring, or adding the pH-adjusted ketone, aldehyde and organic solvent to the organic polyamine to control the temperature at 60-90 °C. The reaction time was 1 to 3 hours. After the reaction was completed, the system was heated to 110 ° C under a nitrogen atmosphere to remove the reaction water.
  • a more preferred preparation method is as follows: (1) adding 3 to 7 moles of ketone and 3 to 7 moles of aldehyde to the reaction vessel, adjusting the pH to 2 to 4 with acid, controlling the temperature to 30 to 40 Torr, stirring 20 ⁇ 30 minutes; (2) The 1 mol of the organic polyamine and the organic solvent are added to the reaction vessel under stirring conditions, the temperature is controlled at 70 to 85 ° C, and the reaction time is 1.5 to 2.5 hours. After the reaction is completed, the nitrogen gas is protected. The system was heated to 11 (TC, the reaction water was removed.
  • the organic solvent added during the reaction is an organic solvent in methanol, ethanol or petroleum ether, preferably the solvent is ethanol;
  • the acid used in the process of adjusting the pH is one of hydrochloric acid, formic acid and acetic acid, preferably hydrochloric acid.
  • the raw material is added by adding an organic polyamine to a ketone or an aldehyde, or adding a ketone or an aldehyde to an organic polyamine, but a preferred embodiment is to add an organic polyamine to a ketone or an aldehyde.
  • Reaction raw material molar ratio: Diethylenetriamine: cyclohexanone: formaldehyde 1: 2: 2
  • corrosion inhibitor rating increased by at least two grades; compared with pentaethylene hexamine: acetophenone: formaldehyde molar ratio of 1:1:1 synthetic corrosion inhibitor increased by 43.47%, corrosion inhibitor rating increased by two levels.
  • the corrosion assessment method is the oil and gas industry standard of the People's Republic of China SY/T 5405-1996 "Test method and evaluation index of corrosion inhibitor performance for acidification", using atmospheric pressure static weight loss method, corrosion system is 9 (TC, 15% HC1 , Corrosion time 4h, Mannich base corrosion inhibitor dosage is 1% (% by weight) of acid solution, corrosion coupon is N80 steel sheet. Corrosion rate calculation formula is:
  • the present invention adopts the above technical solutions, and has the following advantages compared with the prior art:
  • the amine component of the reaction raw material is an organic polyamine containing three or more primary and/or secondary amino groups, and at least three primary amino groups on the organic polyamine are reacted by reacting the organic polyamine with an excess of a ketone or an aldehyde.
  • And/or secondary amine groups are respectively subjected to Mannich reaction with ketones and aldehydes, and fully utilize organic polyamines to carry out functional group grafting on a plurality of amine groups to obtain a Mannich base corrosion inhibitor of a multi-branched space type,
  • the adsorption center of the obtained product can form a multi-point adsorption with the metal surface, and the formed adsorption film is stronger and more attractive than the Mannich corrosion inhibitor of the linear structure.
  • the molecular shape of the space shape Mannich base corrosion inhibitor is larger than that of the prior art linear Mannich base.
  • the space shape Mannich base appears to be bridging or more. Molecular winding bridging can show good corrosion inhibition effect. Therefore, in summary, the space shape of the Mannich base or chirality
  • the Mannich base corrosion inhibitor has strong adsorption force, high film strength, high film density, corrosion inhibition rate of at least 2%, and corrosion inhibitor rating of at least one level.
  • the utility model overcomes the defects that the corrosion inhibitor has less adsorption center, single adsorption group and weak adsorption force with the metal surface in the prior art.

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  • Engineering & Computer Science (AREA)
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Abstract

本发明涉及一种多支化的曼尼希碱缓蚀剂及其制备方法；（1）将3〜7摩尔酮、3〜7摩尔醛加入反应釜，用酸调节pH值至2~6，控制温度为20~50°C，搅拌20~30分钟；（2）搅拌条件下，将1摩尔有机多胺加入反应釜中，或者将调节好ρΗ值的酮、醛及有机溶剂加入有机多胺中，控制温度60~90°C，反应时间为1〜3小时，反应完毕后，在氮气保护下将体系加热至110°C，去除反应水；有机多胺为含有三个以上伯胺基和/或仲胺基的有机化合物；本缓蚀剂具有吸附力强、膜强度高、膜致密性高的特性，缓蚀率至少提高2%以上，克服了现有技术中缓蚀剂吸附中心少，吸附基团单一，与金属表面吸附力不强的缺点。

Description

一种多支化的曼尼希碱缓蚀剂及其制备方法
技术领域
本发明涉及一种多支化的曼尼希碱缓蚀剂及其制备方法。
背景技术
曼尼希反应 (Mannich Reaction)又称胺甲基化反应， 是从 20世纪初逐步发展起来 的一个重要的有机反应。 它是以德国化学家 Carl Ulvich Franz Mannch( 1877- 1947)的 名字命名的。 1917年曼尼希发现了胺类盐酸盐、 甲醛与 C-H酸化合物、 特别是与酮 的反应， 不仅能制备酮碱， 而且适当选择反应组分， 还可以制备出类似生物碱特性的 物质。此后， 曼尼希学派发表了大量的研究报告， 特别是对脂肪酮类、脂肪芳香酮类 及脂环酮作为酸组分的反应进行了详细研究，奠定了曼尼希反应的基础。曼尼希碱及 其衍生物最初是作为药物而得到应用的， 随着时间的推移， 该反应的产物几乎深入到 了人类生活资料生产的各个领域， 如在医药方面可用于合成镇静止痛药、杀菌剂、水 肿抑制药、 抗肿瘤药保肝药、 抗凝血药等， 另外， 在炸药及推进剂、 高分子絮凝剂、 防腐缓蚀剂、 硫化促进剂、 除莠剂、 分散剂、 抗氧化剂、 活性染料、 食物香料、 金属 螯合剂等方面都有很多产品和应用。
曼尼希碱作为缓蚀剂应用始于上世纪 70年代， 最初用作防冻溶液中的防腐剂， 后来用于处理石油气储存器内壁。随着石油勘探和开采中井深增加，油井酸化增产原 油技术的普遍应用， 对高温酸化缓蚀剂的需求使得曼尼希碱型缓蚀剂的应用得到推 广。
有关曼尼希型缓蚀剂的文献和专利报道主要有- 段晓云， 李朋江以甲醛、 环己胺、 苯乙酮为主要原料， 利用 Mannich 反应合成 Mannich碱类缓蚀剂， 研究了甲醛、 环己胺、 苯乙酮各原料配比对合成 Mannich碱类 缓蚀剂缓蚀性能的影响【段晓云，李朋江.一种 Mannich碱类缓蚀剂合成的研究.化工 技术与开发. 2008， 37 (9) : 11-12]； 文献 " YZ-1酸化缓蚀剂的合成及其性能"报道了 一种以甲醛、 丙酮和乙二胺为原料， 经过 Mannich 反应合成的曼尼希碱酸化缓蚀剂 YZ-1。在盐酸、氢氟酸和土酸中均有较好的缓蚀效果。其耐温性高达 15CTC【郑海洪， 李建波， 莫治兵， 等. YZ-1 酸化缓蚀剂的合成及其性能.石油化工腐蚀与防 护. 2008， 25 (4) : 8-10]； 西南石油大学田发国， 李建波，颜紫霖， 等以甲醛、苯乙酮、 乙二胺为主要原料，通过曼尼希反应制得曼尼希碱， 再与氯化苄进行季铵化得到曼尼 希碱季铵盐， 所得缓蚀剂产品酸溶性较好， 与其他酸化添加剂配伍性好， 无毒， 能抗 高温， 在不同酸液中均表现出了优良的缓蚀性能【田发国， 李建波， 颜紫霖， 等.一 种新型油井高温酸化缓蚀剂 SYB的制备及性能评价.石油与天然气化工. 2009, 38 (5)： 426-429 ]； "一种曼尼希碱型盐酸酸化缓蚀剂的研制"一文报道了利用环己胺研制的 一种低成本曼尼希碱。 该曼尼希碱可用作油气井酸化缓蚀剂的主剂， 腐蚀试验表明， 在 6(TC， 20%的工业盐酸中只需加入 0. 5 %， 即可满足石油天然气行业标准中酸化缓 蚀剂一级品的要求【王京光， 于洪江， 李谦定.一种曼尼希碱型盐酸酸化缓蚀剂的研 制.西安石油大学学报： 自然科学版. 2007， 22 (3)： 77 - 79】; 中国专利 CN 100577877C 公开一种合成曼尼希碱钢铁缓蚀剂母液的方法及钢铁缓蚀剂母液，该方法是在水介质 中通过仲胺、 醛和垸基、 环垸基、 芳香基或卤代垸基、 环垸基、 芳香基酮的曼尼希反 应， 制备钢铁缓蚀剂； CN 101451242A "—种用于含 Cr油管的高温酸化缓蚀剂"公开 了一种酸化缓蚀剂，其主剂 A组成为： 25份〜 35份喹啉季铵盐或喹啉衍生物季铵盐， 5份〜 10份碘化钾和 40份〜 60份有机溶剂甲醇或甲醛。 助剂 B组成为： 30份〜 50 份曼尼希碱， 15份〜 35份丙炔醇， 5份〜 15份氯化铬和 20份〜 35份甲醛。使用时 A： B = 2〜1. 5： 1 ; CN 1761715A以酚类化合物、 甲醛和至少一种多胺合成了环氧体系或 聚氨酯体系的曼尼希碱型固化剂，为使酚类化合物尽量完全反应而不残留致使产物环 境友好性差， 专利中采用过量的胺； CN 101182296A公开的专利也报道了一种用于环 氧体系或聚氨酯体系的固化剂，方法是基于二聚环己酮、 甲醛及至少一种多胺通过曼 尼希反应合成， 同样采取胺过量的原料配比。
现有技术中合成的曼尼希型缓蚀剂的合成原料主要有：（1 )酮，主要有脂肪酮（如 丙酮、 丁酮、 戊酮、 己酮等）、 环垸酮 （如环己酮） 和芳香酮 （如苯乙酮）； (2) 醛， 一般为甲醛， 或者聚甲醛。 （3 ) 胺， 主要有脂肪胺 （如二乙醇胺、 二甲胺、 二乙胺、 乙二胺， 脂肪多胺）、 环垸胺（环己胺、 吗啉等)、 芳香胺（如苯胺、 苄胺、 芳香多胺 等）。 现有技术方案中的酮、 醛、 胺 （单胺） 为 1 :1 :1或酮、 醛、 胺 （二胺） 为 2:2:1， 因此， 所得到的曼尼希碱为线形结构： ,0
： N— H + — C ~ H + Z—— C— H Z— C— C— N + H，0
Figure imgf000004_0001
或
I II III IV
I : 伯、 仲胺或氨
II： 甲醛或其他醛
III： 含有一个或多个活泼氢的化合物
IV： 曼尼希碱
Z: 吸电子基
其吸附中心分布于分子一端或两端， 当线形曼尼希型缓蚀剂遇见金属壁面时，表现为 端基吸附，含吸附中心的一端与金属形成化学或物理吸附， 另一端向外伸展形成疏水 层。线形结构曼尼希型缓蚀剂在金属表面成膜的缺陷在于：缓蚀剂与金属壁面因单点 吸附而结合力差、膜强度低、膜致密性差， 尤其在已被侵蚀或不光洁的金属壁面， 难 以成膜或无法成膜， 蚀能力差。
Figure imgf000004_0002
线形结构曼尼希型缓蚀剂在金属表面的吸附
发明内容
本发明的目的在于提供一种多支化的空间体形结构的曼尼希碱或称手性曼尼希 碱缓蚀剂， 是以酮、 醛和含有三个以上伯胺基和 /或仲胺基的有机多胺经曼尼希反应 制得， 且其原料摩尔比为： 酮:醛:多胺= X1 :X2 :1， 其中 >2、 X2>2, 使有机多胺上 至少两个伯胺基或仲胺基分别与酮、 醛进行曼尼希反应， 即充分利用有机多胺进 行多个胺基上的官能团接枝， 得到多支化的曼尼希碱缓蚀剂结构：
Figure imgf000004_0003
其中： Ν, , Nx， Ny， Nm， Nn为碳氮骨架上的氮原子， x， y， m， n 为其顺序编 号， 2 x m y n-l， 且 3 n 7;
R, , Rm， Rn为原料酮中与羰基相连的碳原子上的活泼氢被取代后的取代基， 可 以分别是脂肪酮基、 脂环酮基、 芳香酮基。 脂环酮基中的环内酮基包括环己酮基、环 戊酮基、 邻甲基环己酮基、 对甲基环己酮基、 2-甲基环戊酮基， 2-乙基环戊酮基， 3- 乙基环戊酮基； 脂肪酮基、 芳香酮基和其它脂环酮基可以表示为下式-
0
Rk Rb
H2
Rx、 Ry， 可以是 H， 或者 z R'
R'为原料酮中与羰基相连的碳原子上的活泼氢被取代后的取代基，可以分别是脂 肪酮基、 脂环酮基、 芳香酮基。 脂环酮基中的环内酮基包括环己酮基、 环戊酮基、 邻 甲基环己酮基、 对甲基环己酮基、 2-甲基环戊酮基， 2-乙基环戊酮基， 3-乙基环戊酮 基； 脂肪酮基、 芳香酮基和其它脂环酮基可以表示为下式：
Figure imgf000005_0001
上述 Ra和 Rb各自独立代表 C广 C6垸基， C6~C9直链或支链的芳香基， C5~C9 直链或支链的环垸基；
本发明的另一目的在于是提供一种曼尼希碱缓蚀剂的制备方法， 是以酮（可以是 脂肪酮、 脂环酮、 芳香酮）、 甲醛 （或可以解离出甲醛的化合物） 以及含有三个以上 伯胺基和（或）仲胺基的有机多胺为原料，经曼尼希反应制得。该工艺制备工艺简单， 反应条件温和， 原料易得， 能耗小。
本发明提供的技术方案之一是提供一种曼尼希碱缓蚀剂， 是以 1摩尔有机多胺 与 3~7摩尔酮、 3~7摩尔醛通过曼尼希反应制备而成。
所述的有机多胺为含有三个以上伯胺基和 /或仲胺基的有机化合物， 是二乙烯三 胺、 三乙烯四胺、 四乙烯五胺、 五乙烯六胺、 六乙烯七胺中的一种或任意两种以上组 分组合而成。
所述的酮是脂肪酮、 脂环酮、 芳香酮中的一种或任意两种以上组分组合而成。 脂环酮， 其环内酮包括环己酮， 环戊酮， 环庚酮， 邻甲基环己酮， 对甲基环己酮，
2-甲基环戊酮， 2-乙基环戊酮， 3-乙基环戊酮； 脂肪酮、 芳香酮和其它脂环酮可以表 示为下式：
Figure imgf000006_0001
其中 Ra和 Rb各自独立代表 d~C6烷基， C6~C9直链或支链的芳香基， C5〜C9 直链或支链的环垸基。
所述的醛是甲醛或者是可以解离出甲醛的化合物聚甲醛， 优选为甲醛。
本发明提供的技术方案之二是提供一种曼尼希碱缓蚀剂的制备方法。其制备方法 为： 通过加入过量的酮、 醛， 使有机多胺上的至少三个伯胺基和 /或仲胺基分别 与所述的酮、醛进行曼尼希反应形成多支化的曼尼希碱缓蚀剂。具体制备步骤是: ( 1 ) 将所述的 3〜7摩尔酮、 3~7摩尔醛加入反应釜， 用酸调节 pH值至 2〜6， 控制 温度为 20〜50°C， 搅拌 20〜30分钟； （2)搅拌条件下， 将所述的 1摩尔有机多胺加入 反应釜中，或者将调节好 pH值的酮、醛及有机溶剂加入有机多胺中，控制温度 60~90 °C， 反应时间为 1~3小时， 反应完毕后， 在氮气保护下将体系加热至 110°C， 去除反 应水。
更为优选的制备方法为： （1 ) 将所述的 3~7摩尔酮、 3~7摩尔醛加入反应釜， 用酸调节 pH值至 2〜4， 控制温度为 30〜40Ό， 搅拌 20〜30分钟； （2)搅拌条件下， 将所述的 1摩尔有机多胺及有机溶剂加入反应釜中， 控制温度 70〜85°C， 反应时间 为 1.5〜2.5小时， 反应完毕后， 在氮气保护下将体系加热至 11(TC， 去除反应水。
其反应过程中加入的有机溶剂是甲醇， 乙醇， 石油醚中的一种有机溶剂， 优选溶剂为乙醇； 调节 pH值过程所用的酸为盐酸、 甲酸、 乙酸中的一种， 优选为 盐酸。
以上制备方法中原料的加入方式是向酮、醛中加入有机多胺，或是向有机多胺中 加入酮、 醛， 但优选方式为向酮、 醛中加入有机多胺。
具体实施方式 曼尼希碱缓蚀剂制备及腐蚀评定的实施例:
Figure imgf000007_0001
对比实施例 1:
制备条件： pH值 =2、 反应温度 =80°C、 反应时间 =1.5h， 即实施例 1的反应工艺 条件。 反应原料摩尔比： 二乙烯三胺:环己酮：甲醛 =1 :2:2
腐蚀评定结果： 腐蚀速率 =6.21g/m2.h， 缓蚀率 =94.83%， 缓蚀剂评级： 三级 应原料摩尔比： 二乙烯三胺:环己酮:甲醛 =1 : 1 :1
腐蚀评定结果： 腐蚀速率 =14.13g/m2.h， 缓蚀率 =88.23%， 缓蚀剂评级： —— 结论：当反应原料摩尔比为实施例 1的投料比，即二乙烯三胺:环己酮：甲醛 =1 :3:3 时， 其缓蚀率较二乙烯三胺:环己酮:甲醛摩尔比为 1 :2:2合成的缓蚀剂提高 2%， 缓蚀 剂评级提高二个级别； 较二乙烯三胺：环己酮:甲醛摩尔比为 1 : 1 :1 合成的缓蚀剂提高
8.6%， 缓蚀剂评级提高至少三个级别。
对比实施例 2:
制备条件： pH值 =2、 反应温度 =85°C、 反应时间 =2h， 即实施例 2的反应工艺 条件。
反应原料摩尔比： 五乙烯六胺： 苯乙酮：甲醛 =1 :2:2
腐蚀评定结果： 腐蚀速率 =32.36g/m2.h， 缓蚀率 =73.06%， 缓蚀剂评级： —— 反应原料摩尔比： 五乙烯六胺： 苯乙酮：甲酵 =1 :1 :1
腐蚀评定结果： 腐蚀速率 =57.10/m2.h， 缓蚀率 =52.46%， 缓蚀剂评级： —— 结论： 当反应原料摩尔比为实施例 2 的投料比， 即五乙烯六胺： 苯乙酮：甲醛
=1 :6:6， 其缓蚀率较五乙烯六胺： 苯乙酮:甲醛摩尔比为 1 :2:2 合成的缓蚀剂提高
22.87%, 缓蚀剂评级提高至少二个级别； 较五乙烯六胺： 苯乙酮:甲醛摩尔比为 1 :1 :1 合成的缓蚀剂提高 43.47%， 缓蚀剂评级提高二个级别。
对比实施例 3:
制备条件： pH值 =3、 反应温度 =8(TC、 反应时间 =2h， 即实施例 3 的反应工艺 条件。
反应原料摩尔比： 四乙烯五胺： 环己酮：甲醛 =1:2:2
腐蚀评定结果： 腐蚀速率 =8.68g/m2.h， 缓蚀率 =92.77%， 缓蚀剂评级： 三级 反应原料摩尔比： 四乙烯五胺： 环己酮：甲醛 =1 :1 :1
腐蚀评定结果： 腐蚀速率 =21.01/m2.h， 缓蚀率 =82.51%， 缓蚀剂评级： —— 结论： 当反应原料摩尔比为实施例 3的投料比， 即四乙烯五胺： 环己酮:甲醛： 三 聚甲醛 (当量甲醛) =1 :5:2:3， 其缓蚀率较四乙烯五胺： 环己酮:甲醛摩尔比为 1 :2:2合成 的缓蚀剂 高 3.43%， 缓蚀剂评级提高一个级别； 较四乙烯五胺： 环己酮：甲醛摩尔比 为 1 :1 :1合成的缓蚀剂提高 13.69%， 缓蚀剂评级提高二个级别。 对比实施例 4:
制备条件： pH值 =5、 反应温度 =75 °C、 反应时间 =2h， 即实施例 4的反应工艺 条件。
反应原料摩尔比： 三乙烯四胺： 苯乙酮：甲醛 =1 :4:4
腐蚀评定结果： 腐蚀速率 =1.98g/m2.h， 缓蚀率 =98.35%， 缓蚀剂评级： 一级 反应原料摩尔比： 三乙烯四胺： 苯乙酮：甲醛 =1 :2:2
腐蚀评定结果： 腐蚀速率 1.44g/m2.h， 缓蚀率 =95.48%， 缓蚀剂评级： 三级 反应原料摩尔比： 三乙烯四胺： 苯乙酮：甲酸 =1 :1 :1
腐蚀评定结果： 腐蚀速率 =9.92 g /m2.h， 缓蚀率 =91.74%， 缓蚀剂评级： 三级 结论： 当反应原料摩尔比为实施例 4 的投料比， 即三乙烯四胺： 苯乙酮：甲醛 =1 :4:4 , 其缓蚀率较三乙烯四胺： 苯乙酮:甲醛摩尔比为 1 :2:2 合成的缓蚀剂提高 2.87%, 缓蚀剂评级提高二个级别； 较三乙烯四胺： 苯乙酮:甲醛摩尔比为 1:1 :1 合成 的缓蚀剂提高 6.61%， 缓蚀剂评级提高二个级别。
注： 腐蚀评定方法为中华人民共和国石油天然气行业标准 SY/ T 5405-1996 《酸 化用缓蚀剂性能试验方法及评价指标》， 采用常压静态失重法， 腐蚀体系为 9(TC， 15%HC1， 腐蚀时间 4h， 曼尼希碱缓蚀剂加量为酸液的 1% (重量百分比）， 腐蚀挂片为 N80钢片。 腐蚀速率计算公式为：
v= (腐蚀前试片重量-腐蚀后试片重量） I (试片表面积 X腐蚀时间）
以上技术特征构成了本发明的实施例， 其具有较强的适应性和较佳的实施效果， 可根据实际需要增减非必要的技术特征， 来满足不同情况的需求。
工业实用性
本发明采用以上技术方案， 与现有技术相比， 具有以下优点：
反应原料的胺组分采用含有三个以上伯胺基和 /或仲胺基的有机多胺， 通过将有 机多胺与过量的酮、 醛反应， 使有机多胺上的至少三个伯胺基和 （或） 仲胺基 分别与酮、 醛进行曼尼希反应， 充分利用有机多胺进行多个胺基上的官能团接枝， 得到多支化空间体型的曼尼希碱缓蚀剂， 增加了所得产物的吸附中心， 能够与金属 表面形成多点吸附，从而形成的吸附膜相对线形结构的曼尼希缓蚀剂更加牢固， 吸附 力更强。同时，空间体形曼尼希碱缓蚀剂分子链长度大于现有技术中的线形曼尼希碱， 当金属壁面已被侵蚀或金属壁面不光洁时，空间体形曼尼希碱表现为桥接或多分子缠 绕桥接， 能表现出良好的缓蚀效果。 因此， 综上所述， 空间体形的曼尼希碱或称手性 曼尼希碱缓蚀剂较现有技术中线形的曼尼希碱吸附力强、膜强度高、 膜致密性高， 缓 蚀率至少提高 2%以上， 缓蚀剂评级至少提高一个级别以上。 克服了现有技术中缓蚀 剂吸附中心少， 吸附基团单一， 与金属表面吸附力不强的缺点。

Claims

权利 要 求
-种多支化的曼尼希碱缓蚀剂， 其特征在于： 如下结构式所示：
†' R、
CH? H2C CH2
Rx Ry
其中： Nx， Ny， Nm， Nn为碳氮骨架上的氮原子， x， y， m， n为其顺序编 号， 2 x m y n-l， 且 3 n 7;
， Rm， R„为原料酮中与羰基相连的碳原子上的活泼氢被取代后的取代基， 分 别是脂肪酮基、 脂环酮基、 芳香酮基；
H2
Rx、 Ry， 是 H， 或者 Z R'
R'为原料酮中与羰基相连的碳原子上的活泼氢被取代后的取代基，分别是脂肪酮 基、 脂环酮基、 芳香酮基。
2.根据权利要求 1所述的多支化的曼尼希碱缓蚀剂， 其特征在于： Rm， R„ 选自脂环酮基中的环内酮基。
3. 根据权利要求 2所述的多支化的曼尼希碱缓蚀剂， 其特征在于： 环内酮基选 自环己酮基、 环戊酮基、 邻甲基环己酮基、 对甲基环己酮基、 2-甲基环戊酮基， 2-乙 基环戊酮基， 3-乙基环戊酮基； 或其它脂环酮基， 表示为下式：
Figure imgf000011_0001
上述 Ra和 Rb各自独立代表 d~C6垸基， C6~C9直链或支链的芳香基， C5~C9 直链或支链的环烷基。
4. 根据权利要求 1所述的多支化的曼尼希碱缓蚀剂， 其特征在于： R'选自脂 环酮基中的环内酮基。
5. 根据权利要求 4所述的多支化的曼尼希碱缓蚀剂， 其特征在于： 环内酮基选 自环己酮基、 环戊酮基、 邻甲基环己酮基、 对甲基环己酮基、 2-甲基环戊酮基， 2-乙 基环戊酮基， 3-乙基环戊酮基； 脂肪酮基、 芳香酮基和其它脂环酮基表示为下式-
0
H2
Z Rf Rb。
上述 Ra和 Rb各自独立代表 d~C6垸基， C6~C9直链或支链的芳香基， C5〜C9 直链或支链的环烷基。
6.—种权利要求 1所述的多支化的曼尼希碱缓蚀剂的制备方法， 其特征在于：
( 1 )将 3~7摩尔酮、 3~7摩尔醛加入反应釜， 用酸调节 pH值至 2~6， 控制温度 为 20~50°C， 搅拌 20~30分钟；
(2 ) 搅拌条件下， 将 1摩尔有机多胺加入反应釜中， 或者将调节好 pH值的酮、 醛及有机溶剂加入有机多胺中， 控制温度 60~90°C， 反应时间为 1~3小时， 反应完毕 后， 在氮气保护下将体系加热至 110°C , 去除反应水；
所述的有机多胺为含有三个以上伯胺基和 /或仲胺基的有机化合物；
所述的酮是脂肪酮、 脂环酮、 芳香酮中的一种或两种以上组分的组合。
7.根据权利要求 6所述的多支化的曼尼希碱缓蚀剂的制备方法， 其特征在于- 所述的有机多胺为二乙烯三胺、 三乙烯四胺、 四乙烯五胺、 五乙烯六胺、 六乙烯七 胺中的一种或两种以上组分组合而成。
8.根据权利要求 6所述的多支化的曼尼希碱缓蚀剂的制备方法， 其特征在于： 所述的脂环酮， 其环内酮为环己酮， 环戊酮， 环庚酮， 邻甲基环己酮， 对甲基环己 酮， 2-甲基环戊酮， 2-乙基环戊酮或 3-乙基环戊酮。
9.根据权利要求 6所述的多支化的曼尼希碱缓蚀剂的制备方法， 其特征在于： 所述的脂肪酮、 芳香酮或脂环酮为下式：
Figure imgf000012_0001
其中 Ra和 Rb各自独立代表 d~C6垸基， C6~C9直链或支链的芳香基， C5〜C9 直链或支链的环烷基。
10.根据权利要求 6所述的多支化的曼尼希碱缓蚀剂的制备方法，其特征在于： 所述的醛是甲醛或者是可以解离出甲醛的化合物聚甲醛。
11.根据权利要求 6所述的多支化的曼尼希碱缓蚀剂的制备方法，其特征在于： 反应过程中加入的有机溶剂是甲醇， 乙醇， 石油醚中的一种。
12. 根据权利要求 6 所述的多支化的曼尼希碱缓蚀剂的制备方法， 其特征在 于： 调节 pH值过程所用的酸为盐酸、 甲酸、 乙酸中的一种。
\1
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