WO2017101608A1 - 一种新型钢筋阻锈剂及其应用 - Google Patents

一种新型钢筋阻锈剂及其应用 Download PDF

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WO2017101608A1
WO2017101608A1 PCT/CN2016/104955 CN2016104955W WO2017101608A1 WO 2017101608 A1 WO2017101608 A1 WO 2017101608A1 CN 2016104955 W CN2016104955 W CN 2016104955W WO 2017101608 A1 WO2017101608 A1 WO 2017101608A1
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rust inhibitor
steel bar
carboxylic acid
organic
organic carboxylic
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PCT/CN2016/104955
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English (en)
French (fr)
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刘加平
蔡景顺
赵旦
刘建忠
石亮
沙建芳
姜骞
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江苏苏博特新材料股份有限公司
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Priority to MYPI2018000905A priority Critical patent/MY184429A/en
Publication of WO2017101608A1 publication Critical patent/WO2017101608A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/61—Corrosion inhibitors

Definitions

  • the invention relates to a novel steel bar rust inhibitor, in particular to a hydroxyamide compound, and a combination thereof with an organic carboxylic acid or an organic carboxylate as a steel bar rust inhibitor, belonging to the technical field of building materials.
  • Steel bar rust inhibitors are mainly classified into inorganic rust inhibitors and organic rust inhibitors.
  • Inorganic rust inhibitors mainly include nitrites, chromates, etc., and the more mature products are mainly nitrite-based steel bar rust inhibitors. It has been reported in the patents US 6,340,438 and US 5,527,388 that nitrite has a significant corrosion inhibiting effect. However, the substances themselves are toxic and the corrosion may accelerate due to improper use. Most countries in Europe have explicitly prohibited their use as rust inhibitors in infrastructure and offshore engineering construction.
  • Organic rust inhibitors mainly include organic amines, alcohol amines, organic acids or esters. Due to their own environmental protection, high efficiency and strong structural design, they have become a hot research topic at home and abroad, and are gradually becoming an alternative to nitrite. New rust inhibitor.
  • organic amines or alcohol amines with inorganic or organic acid reactants into cement-based materials is taught in the patents US Pat. No. 5,916, 836 and EP 34,807, and it is confirmed that it has a good rust-preventing effect.
  • Such organic substances are mainly adsorbed on the surface of the steel by N, O hetero atom groups, and the adsorbed chloride ions are eliminated, thereby preventing rust.
  • ZL20081010234924.2 reports an alkali-free non-nitrite concrete bar rust inhibitor, mainly zinc gluconate, lithium silicate and a mixture of ammonium benzoate and low molecular weight (alcohol) amines.
  • the simple mixing of these substances does not It has a significant enhancement to its respective adsorption capacity.
  • the rust inhibitors currently used have a certain inhibitory effect on chloride ion corrosion, and have a weak effect on the corrosion of steel bars caused by carbonization.
  • the object of the present invention is to provide a new type of steel bar rust inhibitor, which can effectively resist the damage of the high-concentration aggressive ions (Cl - etc.) on the passivation film of the steel bar when applied to the reinforced concrete structure, and can also effectively resist Corrosion of steel bars by acidic media such as CO 2 .
  • it solves the problems of weak adsorption capacity and high volatility of low molecular weight alcoholamines, effectively improves the rust inhibition efficiency and ionic corrosion resistance of the rust inhibitor, and expands the application range of the rust inhibitor.
  • the novel steel bar rust inhibitor of the present invention comprises an organic compound having a hydroxyamide structure, and a combination thereof with an organic carboxylic acid or an organic carboxylic acid salt.
  • hydroxyamide has become a research hotspot of metal corrosion resistance against CO 2 , acid or salt due to its environmentally friendly, strong acid or strong alkali environment and stable structure and strong designability.
  • the suppression of corrosion of steel bars in such concrete systems has not been studied and reported.
  • the amide organic compound having a polyhydroxy structure has a polyhydroxyl group and a barrier layer structure, which can form a dense adsorption film on the surface of the steel bar, and greatly improve the corrosion resistance of the steel bar under different corrosive environments.
  • the molecular weight and physical properties of the organic substances are greatly adjustable, and can effectively solve the disadvantages of low molecular alcohol amine adsorption capacity and high volatility.
  • polyhydroxyamide compounds are more environmentally friendly, more efficient, and have a wider range of applications than existing organophosphorus, highly volatile organic alkanolamines.
  • the invention provides a novel steel bar rust inhibitor which is a compound having a hydroxyamide structure, and the hydroxyamide structure conforms to the following formula:
  • R 1 is an integer from 0 to 7; when R 1 and R 2 are the same, R 1 may be selected from methyl, ethyl, propyl, butyl, hydroxyethyl; when R 1 is H, ethyl
  • R 2 is a hydroxyethyl group or an alkyl group or an aryl group having from 4 to 18 carbon atoms, and R 2 is not only a linear alkyl group and an aryl group, but may also have a branch.
  • R 3 is an alkyl group or an aryl group having H, a hydroxyl group or a C atom number of from 1 to 18.
  • the steel bar rust inhibitor of the present invention is a composition of a compound having a hydroxyamide structure of the formula (I) and an organic carboxylic acid or an organic carboxylic acid salt, and the structure of the organic carboxylic acid conforms to the following formula:
  • m is an integer from 0 to 7;
  • R 3 is H, a hydroxyl group or an alkyl or aryl group having from 1 to 18 C atoms;
  • the organic carboxylate is a salt formed by reacting an organic carboxylic acid of the formula (II) with at least one or any two of an inorganic base, an organic amine, and an organic alcohol amine;
  • the ratio of the hydroxyamide compound to the organic carboxylic acid or the organic carboxylic acid salt in the composition is: hydroxyl amide accounts for 2% to 35% of the total mass fraction, and the organic carboxylic acid or salt accounts for the total mass.
  • the score is 0% to 45%, and the balance is water.
  • the ratio of the hydroxyamide compound to the organic carboxylic acid or the organic carboxylic acid salt in the composition is: hydroxyl amide accounts for 2% to 25% of the total mass fraction, and organic carboxylic acid or salt accounts for 1% to 25%.
  • the balance is water.
  • m is 0, 1, 4 or 5.
  • R 1 and R 2 are the same, it is further preferred that the group is a methyl group or a hydroxyethyl group.
  • R 1 is H
  • a further preferred group of R 2 is hydroxyethyl, phenyl, cyclohexyl, octyl or lauryl.
  • Further preferred groups for R 3 are H, methyl or hydroxy.
  • the inorganic base includes NaOH, KOH, Ca(OH) 2 , Zn(OH) 2 , Ce(OH) 3 , a further preferred inorganic base is NaOH, KOH or Ce(OH) 3 ;
  • the organic amine includes C An aliphatic and aromatic organic amine having an atomic number of from 0 to 18, further preferably an aliphatic organic amine having from 0 to 12 carbon atoms; an organic alcohol amine of HOCH 2 CH 2 NH 2 , (HOCH 2 CH 2 ) 2 NH (HOCH 2 CH 2 ) 3 N, HOCH 2 CH 2 (CH 3 ) 2 N, HOCH 2 (CH 3 ) 2 CNH 2 .
  • the rust inhibitor of the present invention is convenient to implement, and the prepared hydroxyamide compound, and the combination thereof with the organic carboxylic acid or the organic carboxylic acid salt are environmentally friendly, have a wide application range, and have excellent effects. It can be used as a blending type rust inhibitor or as a surface coating type rust inhibitor. Among them, as the incorporation type application, there is no significant negative impact on the concrete performance, and the mass fraction of the rust inhibitor is 0.05% to 4% relative to the cementitious material. It is used as a surface coating type rust inhibitor and has excellent permeation performance, and the surface coating amount of concrete is 2 to 6 m 2 /kg.
  • the invention has the advantages that the novel hydroxyl amide molecule is used as the main component of the steel bar rust inhibitor, and the designed molecule has a plurality of hetero atom groups such as a hydroxyl group, a carbonyl group and an amino group, thereby increasing the number of molecular adsorption centers and, on the other hand, increasing the number of molecular adsorption centers.
  • Good adsorption on the surface of the steel bar improve the electric double layer resistance and capacitance of the steel surface, reduce the transfer of surface electrons, and thus effectively inhibit the redox reaction of corrosion on the steel surface.
  • the non-polar hydrophobic groups in the fatty acid can be adjusted by adjusting the size of the non-polar groups in the fatty acid, a dense barrier layer can be formed, and the hydrophobic ability of the adsorbed molecules on the surface of the steel bar can be improved.
  • the non-polar hydrophobic groups are staggered over the surface of the steel bar to reduce the penetration of harmful ions into the surface of the steel bar, thereby improving the corrosion resistance of the steel bar.
  • the structural formula A is formulated into a 20% aqueous solution to obtain the hydroxyamide-based novel steel bar rust inhibitor, which is designated as S1.
  • N-phenylglucose amide is mixed with benzoic acid to give a composition of a hydroxyamide and an organic carboxylic acid. The proportion of the mass fraction of each component is 15% for N-phenylglucoseamide and 15% for benzoic acid, the rest is water, and the resulting rust inhibitor is labeled as S2.
  • a novel steel bar rust inhibitor which is a composition of a compound having a hydroxyamide structure and an organic carboxylate, comprising the following components and ratio: N-phenylglucose amide accounts for 15% of the mass fraction The organic carboxylate formed by gluconic acid and ethanolamine accounts for 5% of the total mass fraction, the balance is water, and the resulting rust inhibitor is labeled S3.
  • a novel steel bar rust inhibitor which is a composition of a compound having a hydroxyamide structure and an organic carboxylate, comprising the following components and ratio: N, N-dimethyl glucosamide as a mass fraction
  • N, N-dimethyl glucosamide as a mass fraction
  • the 18% organic carboxylic acid salt formed by lactic acid and sodium hydroxide accounts for 8% of the total mass fraction, the balance is water, and the resulting rust inhibitor is labeled S4.
  • a novel steel bar rust inhibitor which is a composition of a compound having a hydroxyamide structure and an organic carboxylate, comprising the following components and ratio: N-phenylglucose amide accounts for 14% of the mass fraction The organic carboxylate formed by caprylic acid and cyclohexylamine accounts for 8% of the total mass fraction, the balance is water, and the resulting rust inhibitor is labeled as S5.
  • Control rust inhibitor numbers Ref.1 and Ref.2 are 30% aqueous solutions of calcium nitrite and dimethylethanolamine, respectively. These two substances were selected for comparison because calcium nitrite and dimethylethanolamine are commercially available. The main components of common inorganic and organic rust inhibitors.
  • An example having a mass fraction of 2% was added to the comparative solution as a solution system for the corrosion resistance test of the steel bar.
  • the test was carried out using a three-electrode system. Cylindrical Q 235 steel bar is used, surrounded by epoxy resin, leaving 1cm 2 working area, polished and polished with 600#, 1000#, 2000# sandpaper, then soaked in acetone for 15min, dried and used as working electrode The platinum electrode is used as the counter electrode and the saturated calomel electrode is used as the reference electrode.
  • R p is the polarization resistance and B is the constant associated with the anode and cathode Tafel slopes, where 26 mV is taken uniformly.
  • the rust-removing efficiency is above 95% after 7 days, and it is obviously higher than the common organic rust inhibitor amino alcohol, and is better than The traditional nitrite inorganic rust inhibitor exhibits excellent rust resistance.
  • Cylindrical Q 235 steel bar is used, surrounded by epoxy resin, leaving 1cm 2 working area, polished and polished with 600#, 1000#, 2000# sandpaper, then soaked in acetone for 15min, dried and used as working electrode
  • the platinum electrode is used as the counter electrode and the saturated calomel electrode is used as the reference electrode.
  • R p is the polarization resistance
  • B is the constant associated with the anode and cathode Tafel slopes, and the B value is taken to be 26 mV.
  • the rust-resistance efficiency after 7 days is above 87.6%, and it is significantly higher than the common organic rust inhibitor amino alcohol, and is superior.
  • the traditional nitrite inorganic rust inhibitor exhibits excellent corrosion resistance.
  • the results in Table 5 show that the rust inhibitor of the present invention is used as an inner-doped steel bar rust inhibitor, and has no significant effect on concrete workability.
  • the slump shows that the rust inhibitor of the present invention slightly enhances the slump and is advantageous for concrete mixing. Nitrite significantly reduces concrete slump and affects concrete performance.
  • the strength results show that the rust inhibitor of the present invention slightly improves the concrete strength, and the comparative amino alcohol rust inhibitor slightly reduces the compressive strength of the concrete and affects the mechanical properties of the concrete.
  • the comprehensive results show that the rust inhibitor of the present invention is used as an internal blending, and has good improvement on the working performance and mechanical properties of the concrete.
  • the migration and diffusion properties of surface-coated rust inhibitors are the key to determining the performance of rust inhibitors. For this reason, their properties are characterized by surface migration performance tests.
  • the raw materials and mix ratios used in the test are shown in Table 6. After molding, a sample of 3 m 2 /kg of the sample was applied to the concrete surface, and then sealed with a plastic wrap to reduce the outward diffusion of the rust inhibitor. Then, the migration depth of the rust inhibitor was measured at 3, 7, and 28 d, respectively. Table 7 shows.
  • the rust inhibitor of the present invention has a penetration depth of more than 50 mm after being coated for 28 days on the concrete surface, and the nitrite-based rust inhibitor has a very limited migration ability in concrete.
  • the alcohol amine rust inhibitor has good migration and permeability in concrete, its rust resistance is relatively weak.
  • the comprehensive results show that the rust inhibitor of the invention not only has a good rust-preventing effect, but also exhibits a strong migration and penetration ability, and has a remarkable effect as a coating-type rust inhibitor.

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

一种钢筋阻锈剂及其应用，所述钢筋阻锈剂包括一种具有羟基酰胺结构的化合物、及其与有机羧酸或有机羧酸盐的组合物，所述有机羧酸盐为所述有机羧酸与无机碱、有机胺、有机醇胺中至少一种或任意两种反应所成的盐，所述的组合物中羟基酰胺化合物与有机羧酸或有机羧酸盐的配比为：羟基酰胺占总质量分数的2％～35％，有机羧酸或盐占总质量分数的0％～45％，余量为水；所述钢筋阻锈剂可以作为掺入型阻锈剂使用，也可以作为表面涂覆型阻锈剂使用。该新型钢筋阻锈剂适用于高氯盐、以及氯盐与碳化耦合环境下混凝土结构中钢筋的腐蚀防护与修复。

Description

一种新型钢筋阻锈剂及其应用 技术领域
本发明涉及一种新型钢筋阻锈剂，具体包括一种羟基酰胺类化合物、及其与有机羧酸或有机羧酸盐的组合物作为钢筋阻锈剂的应用，属于建筑材料技术领域。
背景技术
钢筋混凝土作为最主要的土木工程结构，建设规模越来越大。然而，随着全球气候变化以及混凝土服役环境的日趋恶劣，混凝土结构的腐蚀破坏将给国民经济带来巨大的损失。这其中钢筋锈蚀作为混凝土结构腐蚀破坏的主要原因，已经受到国内外科技工作者的广泛关注。而钢筋阻锈剂被认为是解决这一问题有效，经济且方便的方法之一。
钢筋阻锈剂主要分为无机阻锈和有机阻锈剂。无机阻锈剂主要包括亚硝酸盐、铬酸盐等，形成较为成熟产品的主要是亚硝酸盐类钢筋阻锈剂。专利US 6340438和US 5527388中曾报道亚硝酸盐具有明显的腐蚀抑制效果。但该类物质本身具有毒性以及使用不当可能导致的腐蚀加速等缺陷，欧洲大部分国家已明确禁止其在基础设施和海洋工程建设中作为阻锈剂使用。
有机阻锈剂主要包括有机胺、醇胺、有机酸或酯等，由于其自身具有的环保、高效以及结构设计性强等优势，目前已成为国内外研究的热点，正逐步成为替代亚硝酸盐的新型阻锈剂。如专利US5916483和EP34807中提到将有机胺或醇胺与无机或有机酸的反应物掺入到水泥基材料应用，并证实了其具有较好的阻锈效果。此类有机物主要通过N、O杂原子基团在钢筋表面吸附，排除吸附的氯离子，从而起到阻锈作用。然而，这类分子通常具有较高的饱和蒸汽压，极易挥发，使用过程中有效利用率低。ZL20081010234924.2报道了一种无碱非亚硝酸盐混凝土钢筋阻锈剂，主要为葡萄糖酸锌、硅酸锂以及苯甲酸铵和低分子量(醇)胺类混合物，这些物质的简单混合并不会对其各自的吸附能力有明显的增强作用。此外，目前使用的阻锈剂多对氯离子腐蚀具有一定的抑制作用，对于受碳化引起的钢筋锈蚀作用效果较弱。我们的研究也发现，目前通用的醇胺型阻锈剂分子不仅对临界氯离子浓度提升效果不够明显，同时很难有效抑制碳化对钢筋的腐蚀加速。有必要研究和开发一种新型钢筋阻锈剂，不仅能明显抑制氯盐导致的钢筋锈蚀，提升临界氯离子浓度；同时还能有效预防碳化或碳化和氯盐耦合导致的钢 筋锈蚀加速。
发明内容
本发明的目的是提供一种新型钢筋阻锈剂，使其应用于钢筋混凝土结构中时，不仅能够有效抵御高浓度侵蚀性离子(Cl-等)对钢筋钝化膜的破坏，也能有效抵御CO2等酸性介质对钢筋的锈蚀。同时解决低分子量醇胺存在的吸附能力弱及挥发性大等问题，有效提升阻锈剂的阻锈效率和抗离子腐蚀能力、扩大阻锈剂的应用范围。
本发明的新型钢筋阻锈剂，包括一种具有羟基酰胺结构的有机化合物、及其与有机羧酸或有机羧酸盐的组合物。
其中的羟基酰胺，因其绿色环保、强酸或强碱环境下结构稳定和可设计性强等优点，目前已成为金属抗CO2、酸或盐腐蚀的研究热点。但该类物质在混凝土体系中对钢筋腐蚀的抑制还未见相关研究和报道。我们通过对该类分子结构的设计和调控，惊奇的发现无论其在碱性氯盐或碳化环境下均具有非常明显的抑制钢筋的腐蚀。尤其是具有多羟基结构的酰胺类有机物，其自身具有的多羟基及阻挡层结构，能够更好的在钢筋表面形成致密吸附膜，大大提升不同腐蚀环境下钢筋的耐腐蚀性能。同时，该类有机物的分子量及物理性能可调性大，能够有效解决低分子醇胺吸附能力弱、挥发性大等弊端。此外，多羟基酰胺化合物相比于现有的有机磷、高挥发性的有机醇胺更加环保、高效，应用范围更广。
本发明提供了一种新型钢筋阻锈剂，所述钢筋阻锈剂为具有羟基酰胺结构的化合物，所述的羟基酰胺结构符合下述通式：
Figure PCTCN2016104955-appb-000001
其中，m是0到7的整数；当R1与R2基团相同时，R1可以选自甲基、乙基、丙基、丁基、羟乙基；当R1为H、乙基羧基或乙基磺酸基时，R2是羟乙基或C原子数从4到18的烷基或芳基，并且R2不仅仅是直链烷基及芳基，也可以是带有支链的烷基，烷芳基或芳烷基；R3是H、羟基或C原子数从1到18的烷基或芳基。
本发明所述钢筋阻锈剂为具有通式(I)所述羟基酰胺结构的化合物与有机羧酸或有机羧酸盐的组合物，所述有机羧酸的结构符合下述通式：
Figure PCTCN2016104955-appb-000002
其中，m是0到7的整数；R3是H、羟基或C原子数从1到18的烷基或芳基；
所述有机羧酸盐为符合结构式(II)的有机羧酸与无机碱、有机胺、有机醇胺中至少一种或任意两种反应所成的盐；
同时通过研究也发现，所述的组合物中羟基酰胺化合物与有机羧酸或有机羧酸盐的配比为：羟基酰胺占总质量分数的2％～35％，有机羧酸或盐占总质量分数的0％～45％，余量为水。
优选地，所述的组合物中羟基酰胺化合物与有机羧酸或有机羧酸盐的配比为：羟基酰胺占总质量分数的2％～25％，有机羧酸或盐占1％～25％，余量为水。
更进一步的优选，m为0、1、4或5。通过合适的羟基数量与结构中其他基团的调控，能够很好的增强阻锈剂在钢筋表面的吸附。在此基础上，调节R1和R2基团，能够更好的增强吸附膜的致密性和稳定性。
其中，R1与R2相同时，进一步优选基团为甲基或羟乙基。
R1为H时，R2进一步的优选基团为羟乙基、苯基、环己基、辛基或月桂基。而R3进一步的优选基团为H、甲基或羟基。
此外，我们通过大量的电化学试验研究，也发现具有羟基酰胺结构的化合物主要通过强吸附作用，抑制钢筋表面阴极区电化学反应，而当其与具有一定阳极抑制作用的有机羧酸或有机羧酸盐组合时，阻锈剂的阻锈效率还能够显著的提升，起到很好的协同提升效果。
所述无机碱包括NaOH、KOH、Ca(OH)2、Zn(OH)2、Ce(OH)3，进一步优选的的无机碱为NaOH，KOH或Ce(OH)3；所述有机胺包括C原子数从0到18的脂肪族和芳香族有机胺，进一步优选的碳原子数为0到12的脂肪族有机胺；有机醇胺为HOCH2CH2NH2，(HOCH2CH2)2NH，(HOCH2CH2)3N，HOCH2CH2(CH3)2N，HOCH2(CH3)2CNH2。
本发明的阻锈剂实施方便，且制备的羟基酰胺类化合物、及其与有机羧酸或有机羧酸盐的组合物绿色环保、应用范围广，作用效果优异等优点。既可以作为掺入型阻锈剂使用，也可以作为表面涂覆型阻锈剂应用。其中，作为掺入型应用，对混凝土性能无明显负面影响，阻锈剂掺量相对胶凝材料的质量分数为0.05％～4％。作为表面涂覆型阻锈剂使用，渗透性能优异，混凝土表面涂覆量为2～6m2/kg。
本发明的优点在于：采用全新的羟基酰胺分子作为钢筋阻锈剂主要成分使用，所设计的分子中带有多个羟基、羰基以及氨基等杂原子基团，一方面增加分子吸附中心数，更好的在钢筋表面形成吸附，提高钢筋表面双电层电阻及电容，降低表面电子的转移，从而有效抑制钢筋表面发生腐蚀的氧化还原反应。此外，通过调节脂肪酸中非极性基团的大小，可以形成致密阻挡层，提高吸附分子在钢筋表面的疏水能力。分子结构中极性基团吸附于钢筋表面后，非极性疏水基团交错覆盖于钢筋表面，减少环境中有害离子向钢筋表面的渗透，从而提高钢筋的耐腐蚀性能。
具体实施例方式
表1分子结构
Figure PCTCN2016104955-appb-000003
为了更充分的解释本发明的实施，提供下述羟基酰胺类钢筋阻锈剂及相关制备实施例。这些实施例仅仅是解释，而不是限制本发明的范围。
实施例1
一种新型钢筋阻锈剂，所述钢筋阻锈剂为具有羟基酰胺结构的化合物，结构于表1中A(N,N-二甲基葡糖糖酰胺)所示，对应于结构式(I)中R3为羟基，m＝4，R1与R2均为甲基。将结构式A配制成20％水溶液后得到所述的羟基酰胺类新型钢筋阻锈剂，标记为S1。
实施例2
一种新型钢筋阻锈剂，所述钢筋阻锈剂为具有羟基酰胺结构的化合物与有机羧酸的组合物，其中羟基酰胺为N-苯基葡萄糖酰胺，结构于表1中B所示，对应于结构为式(I)中R3为羟基，m＝4，R1为H，R2为苯基。将N-苯基葡萄糖酰胺与苯甲酸混合，得到羟基酰胺与有机羧酸的组合物。各组分所占质量分数比例为N-苯基葡萄糖酰胺占15％，苯甲酸所占比例15％，其余是水，所得阻锈剂标记为S2。
实施例3
一种新型钢筋阻锈剂，所述钢筋阻锈剂为具有羟基酰胺结构的化合物与有机羧酸盐的组合物，包括如下组分及配比：N-苯基葡萄糖酰胺占质量分数的15％，葡萄糖酸和乙醇胺形成的有机羧酸盐占总体质量分数的5％，余量是水，所得阻锈剂标记为S3。
实施例4
一种新型钢筋阻锈剂，所述钢筋阻锈剂为具有羟基酰胺结构的化合物与有机羧酸盐的组合物，包括如下组分及配比：N，N-二甲基葡萄糖酰胺占质量分数的18％，乳酸和氢氧化钠形成的有机羧酸盐占总体质量分数的8％，余量是水，所得阻锈剂标记为S4。
实施例5
一种新型钢筋阻锈剂，所述钢筋阻锈剂为具有羟基酰胺结构的化合物与有机羧酸盐的组合物，包括如下组分及配比：N-苯基葡萄糖酰胺占质量分数的14％，辛酸和环己胺形成的有机羧酸盐占总体质量分数的8％，余量是水，所得阻锈剂标记为S5。
对照阻锈剂编号Ref.1和Ref.2分别为30％的亚硝酸钙和二甲基乙醇胺的水溶液，选择这两种物质作为对比是因为亚硝酸钙和二甲基乙醇胺为市售两种常用无机和有机阻锈剂的主要成分。
性能测试
1、阻锈性能测试
配制饱和氢氧化钙溶液，向其中加入3.5％wt.NaCl(pH＝12.5)作为对比溶液。分别向对比溶液中添加质量分数为2％的实施例作为钢筋耐腐蚀性能测试的溶液体系。采用三电极体系进行测试。选用圆柱状Q 235钢筋，周围用环氧树脂包封，留1cm2工作面积，用600#，1000#，2000#砂纸打磨并抛光，之后泡于丙酮中超声15min，吹干后用作工作电极，铂电极作对电极，饱和甘汞电极作参比电极。测试对比溶液及含不同阻锈剂的溶液中工作电极的线性极化电阻随时间变化，分别记为Rp、Rp'，根据Stern-Geary方程计算钢筋腐蚀电流密度：
icorr＝B/Rp
其中，Rp是极化电阻，B是阳极和阴极Tafel斜率相关的常数，在这里统一取26mV。
Figure PCTCN2016104955-appb-000004
计算浸泡7天后阻锈剂的缓蚀效率，测试结果见表2。
表2高氯盐环境下阻锈剂对钢筋腐蚀抑制效果
Figure PCTCN2016104955-appb-000005
结果显示，实施例阻锈剂在高浓度氯盐环境中均具有非常好的阻锈效果，7d后阻锈效率均在95％以上，而且明显高于常用有机阻锈剂氨基醇，且优于传统亚硝酸盐类无机阻锈剂，表现出非常优异的阻锈性能。
同时研究了该类阻锈剂在碳化和氯盐耦合腐蚀环境下的阻锈性能。首先配制饱和氢氧化钙溶液，向其中加入1.15％wt.NaCl，通过通入气体CO2降低溶液pH至9作为对比溶液。分别向对比溶液中添加质量分数为2％的实施例作为钢筋耐腐蚀性能测试的溶液体系。同样采用三电极体系进行测试。选用圆柱状Q 235钢筋，周围用环氧树脂包封，留1cm2工作面积，用600#，1000#，2000#砂纸打磨并抛光，之后泡于丙酮中超声15min，吹干后用作工作电极，铂电极作对电极，饱和甘汞电极作参比电极。测试对比溶液及含不同阻锈剂的溶液中工作电极的线性极化电阻随时间变化，分别记为Rp、Rp'，根据Stern-Geary方程计算钢筋腐蚀电流密度：
icorr＝B/Rp
其中，Rp是极化电阻，B是阳极和阴极Tafel斜率相关的常数，B值统一取26mV。
Figure PCTCN2016104955-appb-000006
计算浸泡7天后阻锈剂的缓蚀效率，测试结果见表3。
表3碳化和氯盐耦合环境下阻锈剂对钢筋腐蚀抑制效果
Figure PCTCN2016104955-appb-000007
结果显示，实施例阻锈剂在氯盐和碳化环境中同样具有非常好的阻锈效果，7d后阻锈效率均在87.6％以上，而且明显高于常用有机阻锈剂氨基醇，且优于传统亚硝酸盐类无机阻锈剂，表现出非常优异的耐蚀性能。
2、混凝土性能测试
此外，还考察了实施例有机阻锈剂内掺混凝土中对混凝土工作性能的影响，试验所用配合比为现有工程常用混凝土配合比，所用材料均为市售常用材料，具体配合比及实验结果见表4和表5所示。
表4原材料组成及配合比：kg/m3
Figure PCTCN2016104955-appb-000008
表5阻锈剂对新拌混凝土性能影响
Figure PCTCN2016104955-appb-000009
表5的结果显示，本发明的阻锈剂作为内掺型钢筋阻锈剂使用，对混凝土工作性能没有明显影响。坍落度显示，本发明阻锈剂稍微增强坍落度，有利于混凝土拌合。而亚硝酸盐明显降低混凝土坍落度，影响混凝土工作性能。此外，强度结果显示，本发明阻锈剂对混凝土强度略有提升，而作为对比的氨基醇类阻锈剂会略微降低混凝土抗压强度，影响混凝土力学性能。综合结果显示，本发明阻锈剂作为内掺使用，对混凝土工作性能及力学性能均具有较好改善。
3、阻锈剂迁移性能测试
表面涂覆型阻锈剂迁移扩散性能是决定阻锈剂性能的关键，为此通过表面迁移性能测试对其性能进行表征。试验所用原材料及配合比见表6所示。成型后涂覆3m2/kg的实 施例样品于混凝土表面，之后用保鲜膜密封，减少阻锈剂的向外扩散，之后分别在3、7、28d检测阻锈剂的迁移深度，所得结果见表7所示。
表6原材料组成及配合比：kg/m3
Figure PCTCN2016104955-appb-000010
表7阻锈剂在混凝土中迁移深度
Figure PCTCN2016104955-appb-000011
结果显示，本发明阻锈剂在混凝土表面涂覆28d后渗透深度均大于50mm，而亚硝酸盐类阻锈剂在混凝土中迁移能力非常有限。尽管醇胺类阻锈剂在混凝土中也均有较好的迁移渗透能力，但其阻锈性相对较弱。综合结果显示，本发明阻锈剂不仅具有较好的阻锈效果，同时也表现出较强的迁移渗透能力，作为涂覆型阻锈剂使用具有显著的作用效果。

Claims (9)

  1. 一种新型钢筋阻锈剂，其特征在于，所述钢筋阻锈剂为具有羟基酰胺结构的化合物，所述的羟基酰胺结构符合下述通式：
    Figure PCTCN2016104955-appb-100001
    其中，m是0到7的整数；当R1与R2基团相同时，R1可以选自甲基、乙基、丙基、丁基、羟乙基；当R1为H、乙基羧基或乙基磺酸基时，R2是羟乙基或C原子数从4到18的烷基或芳基，并且R2不仅仅是直链烷基及芳基，也可以是带有支链的烷基，烷芳基或芳烷基；R3是H、羟基或C原子数从1到18的烷基或芳基。
  2. 根据权利要求1所述的一种新型钢筋阻锈剂，其特征在于，所述钢筋阻锈剂为具有通式(I)所述羟基酰胺结构的化合物与有机羧酸或有机羧酸盐的组合物，所述有机羧酸的结构符合下述通式：
    Figure PCTCN2016104955-appb-100002
    其中，m是0到7的整数；R3是H、羟基或C原子数从1到18的烷基或芳基；
    所述有机羧酸盐为符合结构式(II)的有机羧酸与无机碱、有机胺、有机醇胺中至少一种或任意两种反应所成的盐；
    所述的组合物中羟基酰胺化合物与有机羧酸或有机羧酸盐的配比为：羟基酰胺占总质量分数的2％～35％，有机羧酸或盐占总质量分数的0％～45％，余量为水。
  3. 根据权利要求2所述的一种新型钢筋阻锈剂，其特征在于，所述的组合物中羟基酰胺化合物与有机羧酸或有机羧酸盐的配比为：羟基酰胺占总质量分数的2％～25％，有机羧酸或盐占1％～25％，余量为水。
  4. 根据权利要求2所述的一种新型钢筋阻锈剂，其特征在于，m为0、1、4或5。
  5. 根据权利要求4所述的一种新型钢筋阻锈剂，其特征在于，R1与R2相同时，R1与R2为甲基或羟乙基。
  6. 根据权利要求5所述的一种新型钢筋阻锈剂，其特征在于，R1为H时，R2为羟乙基、苯基、环己基、辛基或月桂基；R3为H、甲基或羟基。
  7. 根据权利要求2所述的一种新型钢筋阻锈剂，其特征在于，所述无机碱包括NaOH、KOH、Ca(OH)2、Zn(OH)2、Ce(OH)3，所述有机胺包括C原子数从0到18的脂肪族和芳香族有机胺，有机醇胺为HOCH2CH2NH2，(HOCH2CH2)2NH，(HOCH2CH2)3N，HOCH2CH2(CH3)2N，HOCH2(CH3)2CNH2。
  8. 根据权利要求7所述的一种新型钢筋阻锈剂，其特征在于，所述无机碱为NaOH，KOH或Ce(OH)3；所述有机胺包括碳原子数为0到12的脂肪族有机胺。
  9. 权利要求1或2所述的一种新型钢筋阻锈剂的应用方法，其特征在于，所述钢筋阻锈剂作为掺入型应用，阻锈剂掺量2～16kg/m3；作为表面涂覆型阻锈剂使用，混凝土表面涂覆量为2～6m2/kg。
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CN102503237A (zh) * 2011-11-09 2012-06-20 上海大学 一种新型钢筋阻锈剂的制备方法
CN103513514A (zh) * 2012-06-25 2014-01-15 罗门哈斯电子材料有限公司 包含酰胺组分的光致抗蚀剂
CN103666427A (zh) * 2013-11-15 2014-03-26 西安石油大学 油田用多功能羟基酰胺的制备方法及其应用
CN103755584A (zh) * 2014-01-21 2014-04-30 安徽师范大学 一种α-羟基酰胺类化合物的合成方法
CN105601150A (zh) * 2015-12-17 2016-05-25 江苏苏博特新材料股份有限公司 一种新型钢筋阻锈剂及其应用

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CN110964196A (zh) * 2018-09-30 2020-04-07 镇江苏博特新材料有限公司 一种混凝土侵蚀介质传输抑制剂及其制备方法
CN112979201A (zh) * 2021-02-19 2021-06-18 江苏奥莱特新材料股份有限公司 一种防腐阻锈剂的制备方法

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