CN102140019A - Polycarboxylic acid water reducing agent and preparation method thereof - Google Patents

Polycarboxylic acid water reducing agent and preparation method thereof Download PDF

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CN102140019A
CN102140019A CN 201010557733 CN201010557733A CN102140019A CN 102140019 A CN102140019 A CN 102140019A CN 201010557733 CN201010557733 CN 201010557733 CN 201010557733 A CN201010557733 A CN 201010557733A CN 102140019 A CN102140019 A CN 102140019A
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superplasticizer
monomer
reducing agent
formula
concrete
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CN102140019B (en
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仲崇纲
侯光
刘兆滨
周立明
朱建民
田威
董振鹏
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吉林奥克新材料有限公司
广东奥克化学有限公司
辽宁奥克化学股份有限公司
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Abstract

The invention provides a concrete polycarboxylic acid water reducing agent, structure of which is shown in the following formula (1), wherein R1, R2, R4 and R6 are H or alkyl groups with 1 to 3 carbon atom(s); R3 is an alkylidene group with 1 to 20 carbon atom(s); R5 is H or -COOM and M is H, Na or K; R is an alkylidene group or arylidene with 1 to 10 carbon atom(s); Y represents COOH or -SO3H; BO is -C2H4O<->, -C3H6O<-> or -C4H8O<->, or an ordered block or an disorder hybrid block formed among -C2H4O<->, -C3H6O<-> or -C4H8O<->; m is a positive integer from 10 to 120; and n, x, y and z are all positive numbers. The water reducing agent can endow good working performance to concrete, increase the early-period dispersion performance and later-period slump maintaining performance of concrete and improve the adaptability of polycarboxylic acid water reducing agent. The invention also provides a preparation method for the water reducing agent.

Description

一种聚羧酸系减水剂及其制备方法 A carboxylic acid and preparation method superplasticizer poly

技术领域 FIELD

[0001] 本发明涉及一种混凝土外加剂,具体涉及一种混凝土聚羧酸系减水剂,及其制备方法。 [0001] The present invention relates to a concrete admixture, particularly to a concrete superplasticizer, and a preparation method.

背景技术 Background technique

[0002] 随着中国建筑规模越来越大,高速铁路、高速公路、重大基础设施、超高层建筑及核电站等工程,对混凝土的施工性能和综合性能要求也越来越高。 [0002] With the increasing scale of Chinese architecture, high-speed railways, highways, major infrastructure, high-rise buildings and nuclear power plants and other projects, are increasingly high workability of concrete and comprehensive performance requirements. 在混凝土中掺加外加剂是提高混凝土施工性能和综合性能的有效手段。 Adding admixtures in the concrete construction is an effective means to improve the performance of concrete and overall performance. 减水剂作为混凝土外加剂中最主要的一种,可以在极低掺量下大幅较少拌合用水量,改善混凝土性能。 Superplasticizer concrete admixture as the most important one, can be significantly less mixing water at a very low dosage, improve concrete performance. 目前国内外都在从第一代、 第二代等减水剂向聚羧酸系减水剂转移,因为聚羧酸系减水剂“环保、节能、降耗”,性能高, 符合社会及经济发展的大趋势,但是,聚羧酸系减水剂现有技术还不完善,如在拌制混凝土时的坍落度损失快。 Superplasticizer at home and abroad are transferred from the first-generation, second generation and so on to the polycarboxylic acid water reducing agent, superplasticizer as "environmental protection, energy conservation, energy", high performance, and socially economic development trend, however, superplasticizer existing technology is not perfect, as fast slump loss when the concrete mixing. 建筑业的迅猛发展,一方面要求混凝土的性能更优异,另一方面造成砂石等这些混凝土必备的原料资源的过度开采,使混凝土的骨料质量逐步恶化,这些都将对减水剂的性能提出更高的要求,当前迫切需求能有效改善新拌混凝土工作性能的,尤其是改善坍落度保持性能的,性能更优异的聚羧酸系减水剂。 The rapid development of the construction industry, on the one hand requires superior performance of concrete, on the other hand caused by over-exploitation of raw material resources necessary concrete these sand, so that the gradual deterioration of the quality of concrete aggregate, these will water reducer demanding higher performance, can effectively improve the current urgent need for workability of fresh concrete, in particular to improve slump retention performance, superior performance polycarboxylate superplasticizer.

[0003] 专利US7691921中通过控制物料的滴加方式获得一种聚羧酸系减水剂,在混凝土的减水与坍落度保持方面体现出一定的效果,但这种方法在操作上控制困难,并且制得的聚羧酸系减水剂未能达到良好效果。 [0003] Patent US7691921 by controlling dropwise materials to obtain a superplasticizer, showing some aspects of the holding effect of water reduction and slump of concrete, but this method is difficult to control in operation , and the resulting superplasticizer failed to achieve good results.

[0004] 专利CN101708973中采用保水保塑型的大单体与小单体共聚获得一种保水保塑型的聚羧酸系减水剂,在解决泌水离析和坍落度损失快的问题等方面取得一定的效果,但是其保水保塑的大单体是由酯类大单体和醚类大单体混合而成,单体组成复杂,各种单体的反应活性存在差异,往往使得聚合反应控制不好,造成产品性能不稳定。 [0004] Patent CN101708973 used to retain water and small plastic macromer monomer superplasticizer obtained to retain water and one kind of plastic, the problem is solved in the water separating bleeding quickly and slump loss, etc. achieved a certain effect, but which retain water plasticized macromer is a mixture of esters and ethers macromonomer from macromers, monomers complex, there is a difference of reactivity of various monomers, the polymerization tends to make reaction control is not good, resulting in unstable performance.

[0005] 专利CN101774779中以苯乙烯磺酸钠和烯丙基磺酸钠为小单体制备了一种聚羧酸保塑剂,该聚羧酸保塑剂可以实现坍落度在7〜9cm的小坍落度混凝土的良好保塑性。 [0005] Patent CN101774779 to sodium styrene sulfonate and allyl monomers a small PLASTICIZER polycarboxylate, polycarboxylic acid which may be implemented PLASTICIZER slump in preparation 7~9cm good plasticity of small slump concrete. 但是其减水率不高,使其应用受到限制。 However, a water reducing ratio is not high, its application is limited.

[0006] 综上所述,以往的发明不是存在工艺难以控制,就是产品性能不近理想等各种问题,本发明在考虑了以往发明所存在的问题的基础上,提出了一种新的聚羧酸系减水剂及其制备方法,在产品性能上得以改善和提高,特别是在混凝土坍落度保持性能方面取得明显的效果。 [0006] In summary, the present invention does not conventional process is difficult to control, it is the product performance is not nearly over other problems, the present invention in consideration of the conventional problem of the invention is proposed based on a novel poly superplasticizer and its preparation method, improved performance and improved product, especially to obtain significant results in terms of concrete slump retention performance.

发明内容 SUMMARY

[0007] 本发明的一个目的是:提供一种新的混凝土聚羧酸系减水剂,能够有效地提高新拌混凝土的工作性能。 An object of the [0007] present invention are: to provide a new concrete superplasticizer, can be effectively improved workability of fresh concrete.

[0008] 本发明的另一个目的是:提供所述减水剂的制备方法,能够有效调节所述减水剂聚合单体之间的聚合比例,从而充分提高各个单体的转化率,得到有效成份高的减水剂。 [0008] Another object of the present invention are: to provide a method of the superplasticizer, the superplasticizer can be effective to modulate the ratio between the polymerization of the polymerizable monomer, thereby sufficiently improve the conversion rate of the individual monomers, effectively high water reducer ingredients.

[0009] 本发明是上述目的是通过以下技术方案实现的:[0010] 提供一种混凝土聚羧酸系减水剂,其结构如下式(1)所示,其中,礼、1?2、1?4和1?6 是H或碳原子数为1〜3的烷基;R3是碳原子数为1〜20的亚烷基成是H或-COOM且M是H、Na或K等;R是碳原子数为1〜10的亚烷基或亚芳基;Y代表-COOH或-SO3H ;BO 是-C2H40-、-C3H6O-或-C4H8O-,或是它们之间形成的有序嵌段或无序杂嵌段;m是10〜120 的正整数;n、x、y和ζ均为正数。 [0009] The present invention is the above object is achieved by the following technical solution: [0010] to provide a concrete superplasticizer, the structure of the following formula (1), wherein Li, 2, 1? ?? 16 and 4 are H or an alkyl group of 1~3 carbon atoms; R3 is 1~20 carbon atoms as the alkylene group -COOM and M is H or the like is H, Na or K; R is 1~10 carbon atoms, alkylene group or an arylene group; Y Representative -COOH or -SO3H; BO is -C2H40 -, - C3H6O- or -C4H8O-, ordered or block formed therebetween or random block heteroaryl; m is a positive integer of 10~120; n, x, y and ζ are positive.

[0011] [0011]

Figure CN102140019AD00051

[0012] 优选的所述减水剂的结构中,χ、y和ζ之间满足以下关系:x : y = 1 : 1〜10, 且ζ : (x+y) =1 : 10 〜100。 [0012] Preferably the water-reducing agent structure, satisfied between χ, y [zeta], and the following relationship: x: y = 1: 1~10, and ζ: (x + y) = 1: 10 ~100.

[0013] 所述减水剂由结构如式(2)所示的单体A、结构如式(3)所示的单体B以及结构如式(4)所示的单体C——马来酰胺酸共聚而成 [0013] The water-reducing agent as monomers A by the structural formula (2), the structure as shown in (3) and the structure of formula B monomers monomers C-- Ma as shown in (4) of the formula copolymerization of acid to amide

[0014] [0014]

Figure CN102140019AD00052

[0015] 式(2)中,礼、R2和R4是H或碳原子数为1〜3的烷基;R3是碳原子数为1〜20 的亚烷基;BO是-C2H40-、-C3H60-或-C4H8O-,或是它们中的一种或两种以上形成的有序嵌段或无序杂嵌段;m是10〜120的正整数; [0015] Formula (2), Li, R2 and R4 are H or an alkyl group of 1~3 carbon atoms; R3 is an alkylene group having a carbon number of 1~20; BO is -C2H40 -, - C3H60 - or -C4H8O-, ordered or block them form one or two or more blocks or disordered heteroaryl; m is a positive integer of 10~120;

[0016] 式(3)中,Ii5是!1或-COOM^SH或碳原子数为1〜3的烷基;M是H、Na或K等; [0016] Formula (3), Ii5 -COOM ^ SH or a number of 1 ~ 3 carbon atoms or an alkyl group;! M is other H, Na or K;

[0017] 式中,R是碳原子数为1〜10的亚烷基或亚芳基;Y代表-COOH或_S03H。 [0017] In the formula, R is an alkylene group having a carbon number 1~10 or an arylene group; Y Representative -COOH or _S03H.

[0018] 所述的单体A、B和C均为市售的产品。 [0018] The monomers A, B and C are commercially available products.

[0019] 所述的减水剂重均分子量5000〜70000,优选10000〜30000。 Superplasticizer weight [0019] The average molecular weight 5000~70000, preferably 10000~30000.

[0020] 所述的单体A优选由环氧乙烷(EO)和环氧丙烷(PO)嵌段得到的烯丙醇醚、甲基丙烯醇醚、丁烯醇醚或甲基丁烯醇醚中的一种或几种的混合物。 [0020] A is preferably a monomer of the ethylene oxide (EO) and propylene oxide (PO) block obtained allyl ethers, methyl ethers of propylene, butene-methylbut-enol ethers or or a mixture of several ether. [0021] 所述的EO和PO嵌段可以是规嵌或杂嵌等各种方式的嵌段。 [0021] The EO and the PO block may be a block or heteroaryl Regulation insert embedded in various other ways.

[0022] 所述的单体B优选丙烯酸、甲基丙烯酸或它们的盐类中的一种或几种的混合物。 [0022] The monomers B preferably acrylic acid, methacrylic acid or a mixture of one or more of the salts thereof.

[0023] 所述的单体C可以看作是第三种聚合小单体,优选马来酰胺乙酸、马来酰胺己酸或马来酰胺苯磺酸等。 [0023] The C monomer can be seen as a small third polymerizable monomer, preferably maleic acid amide, maleic acid amide or maleic acid, hexanoic acid and the like amides.

[0024] 本发明还提供所述减水剂的制备方法,具体包括以下工艺步骤: [0024] The present invention also provides a method of preparing the water-reducing agent, comprises the following process steps:

[0025] 1)将单体A和去离子水投于反应器中,制成质量浓度为40〜70%的水溶液,缓慢升温到50-90°C的反应温度; [0025] 1) A monomer cast and deionized water in the reactor to produce a concentration of 40~70% by mass aqueous solution was slowly warmed to the reaction temperature of 50-90 ° C;

[0026] 2)将单体B、单体C制成总质量浓度为30〜50%的溶液作为1#料,另以总质量浓度为0. 7〜8%的还原剂溶液作为2#料,当步骤1)的反应器中的单体A水溶液温度到达50〜90°C的反应温度时,开始向其中一次性加入质量浓度为30%的双氧水溶液,待温度回到先前的反应温度后,开始同时向其中滴加1#料和2#料,1#料2. 0〜3. Oh加完,2#料2. 5〜4h加完,使单体A、B和C之间的摩尔比符合式(1)中χ、y和ζ之间的关系,加入的双氧水和还原剂的摩尔重均为单体A、单体B、单体C摩尔数之和的2% -10%, 1#和2#加完后,保温反应1〜浊; [0026] 2) The monomers B, from C having a total monomer concentration of 30 ~ 50% by mass was used as material # 1, the total concentration of the other 7~8 0.5% solution as a reducing agent feed # 2 after the monomer a when the temperature of the aqueous solution of step 1) in the reactor reaches a temperature of 50~90 ° C the reaction began to which was added in one mass concentration of 30% hydrogen peroxide solution, until the temperature back to the previous reaction temperature start dropwise thereto while feed # 1 and # 2 feed, feed # 1 2. 0~3. Oh completion of the addition, feed # 2 2. 5~4h addition was complete, between the monomers a, B and C the relationship between the χ, y and ζ molar ratio according to formula (1), the added hydrogen peroxide and the reducing agent are the molar weight of monomer a, monomers B, from the number of moles of monomer C is 2-10% , # 1 and # 2 addition was complete, the reaction was kept 1 ~ turbidity;

[0027] 3)步骤2)保温结束后,将反应器中的物料降温到30°C以下,再用30%的NaOH溶液调节PH到6〜8,即获得所述的混凝土聚羧酸系减水剂。 [0027] 3) Step 2) After completion of incubation, the material in the reactor was cooled to below 30 ° C, then 30% NaOH solution was adjusted to PH 6 ~ 8, i.e., to obtain the polycarboxylate concrete Save agent.

[0028] 步骤幻所述的还原剂选自L-抗坏血酸、亚硫酸氢钠、巯基乙酸或巯基丙酸中的一种或几种的混合物。 [0028] Step phantom said reducing agent is selected L- ascorbic acid, or a mixture of several sodium hydrogen sulfite, thioglycolic acid or mercaptopropionic acid of one.

[0029] 与现有技术相比,本发明的减水剂对新拌混凝土具有更好的坍落度保持性能。 [0029] Compared with the prior art, the present invention has better water-reducing agent slump retention performance of the fresh concrete.

[0030] 本发明将具有可聚合活性的聚醚——单体A和含有双键结构的羧酸或盐——单体B以及马来酰胺酸共聚后,得到了一种新的含有马来酰胺酸结构单元的混凝土聚羧酸系减水剂。 [0030] The present invention is a polyether having polymerizable activity - monomer A contains a double bond and a carboxylic acid or a salt of structure - and B monomers copolymerized maleic acid amides, to give a new maleic comprising acid amide concrete structural unit polycarboxylate superplasticizer. 通过将马来酰胺酸引入到减水剂分子结构中,利用马来酰胺酸的双羧基,提高了减水剂对混凝土的吸附效果,同时可以有效调节分子主链长度与侧链密度的分配,达到了减水剂坍落度保持性好的效果。 By maleamic acid water reducing agent is introduced into the molecular structure, using two carboxyl maleamic acid improves the adsorption of concrete superplasticizer, and can effectively regulate the molecular main chain length distribution density of the side chain, superplasticizer slump retention achieved good results.

[0031] 同时,与现有技术相比,本发明的减水剂制备方法具有以下有益效果: [0031] Meanwhile, compared to the prior art, the present invention superplasticizer production method has the following advantages:

[0032] 1)本发明涉及的聚合单体和羧酸范围广泛,现有可以用于减水剂生产的醚类单体都可以应用此工艺。 [0032] 1) a polymerizable monomer and a carboxylic acid broad scope of the present invention, the conventional water reducing agent may be used ether-based monomer can be applied in this production process.

[0033] 2)本减水剂使用的聚合单体马来酰胺酸亲水性强,适用于水溶液体系的聚合,既有利于工业化生产,又能保证生产及使用中的安全和环境友好,且原料易购。 [0033] 2) The water-reducing agent used in the polymerizable monomer more hydrophilic maleic acid amides, suitable for the polymerization of aqueous systems, not only industrially advantageous, but also to ensure the production and use of environmentally friendly and safe, and easy to purchase raw materials.

[0034] 3)马来酰胺酸活性适中,用量低,可以调节醚类单体与羧酸类单体之间的竞聚率, 有效提高了单体的转化率。 [0034] 3) moderate activity maleamic acid, low dose can be adjusted between ether monomer reactivity with a carboxylic acid monomer ratio, improve the conversion of the monomers.

[0035] 4)本发明的制备方法中,只是将马来酰胺酸类物质添加到聚合的羧酸溶液中,操作上并不繁琐,并可以直接应用于现有减水剂的工艺生产。 [0035] 4) Preparation method of the present invention, just add to the polymerization of maleamic acids in the acid solution, the operation is not complicated, and the production process can be directly applied to conventional water reducer.

具体实施方式 Detailed ways

[0036] 下面结合实施例对本发明做进一步的详细描述,但本发明的实施不限于此。 [0036] The following embodiments in conjunction with embodiments of the present invention will be further described in detail, but the present invention is not limited to this embodiment.

[0037] 为了简化表述,特使用以下符号代替相应中文通用名称: [0037] In order to simplify the notation, the following notation instead of the corresponding Japanese Chinese common name:

[0038] 用AL表示“丙烯醇聚氧乙烯醚”; [0038] AL expressed by "allyl alcohol polyoxyethylene ethers";

[0039] 用MAL表示“甲基丙烯醇聚氧乙烯醚”;用BL表示“丁烯醇聚氧乙烯醚”; 用MBL表示“甲基丙烯醇聚氧乙烯聚氧丙烯醚”; 用Cl表示“马来酰胺乙酸”; 用c2表示“马来酰胺己酸”; 用c3表示“马来酰胺苯磺酸钠”; 用MA表示“马来酸酐”; 用AA表示“丙烯酸”; 用MPA表示“巯基丙酸”; 用Vc表示“L-抗坏血酸”; 用APS表示“过硫酸铵”。 [0039] represented by MAL "methacryl alcohol polyoxyethylene ethers"; represents "butenol polyoxyethylene ethers" as used BL; with MBL represents "methacryl alcohol polyoxyethylene ether, polyoxypropylene"; represented by Cl "maleamic acid"; c2 represents a "maleic hexanoic acid amide"; denotes "maleic amide benzene sulfonate" as used C3; denotes "maleic anhydride" as used MA; represents "acrylic acid" as used AA; represented by MPA "mercaptopropionic acid"; Vc represented by "L-ascorbic acid"; represents "ammonium persulfate" as used APS. 实施例一 Example a

将240克AL (重均分子量M00)和水147克,加入反应釜,开启搅拌器,缓慢升温, 升温到50°C,加入质量浓度为30%的双氧水溶液12. 60克,待温度回升到50°C稳定后,滴加含有2. 0680克Vc和3. 7366克MPA的2#水溶液48. 2g ;待2#溶液滴加^iin后,开始滴加含有19. 6克MA和0. 92克cl的1#水溶液39. 2克,滴加时间为3小时。 The AL 240 g (weight average molecular weight M00) and 147 g of water, adding to the reactor, the stirrer was gradually raised, and warmed to 50 ° C, added to a concentration of 30 mass% hydrogen peroxide solution 12.60 g, until the temperature rose to after the 50 ° C stability, # 2 aqueous solution containing 2.0680 g and 3.7366 g MPA Vc of 48. 2g; ^ was added dropwise until the solution # 2 after Iin, dropwise addition of 19.6 g containing 0 and MA. an aqueous solution of 39.92 g # cl 2 g was added dropwise for 3 hours. 1#、2#水溶液加完之后于50°C保持1小时。 # 1, # 2 After completion of the aqueous solution held at 50 ° C 1 hour. 然后降温至30°C以下,再用30%氢氧化钠溶液中和至pH值为7,即得到本发明的一种聚羧酸减水剂产品,其结构式如式(¾所示:对应的重均分子量: 15000 〜30000。 Then cooled to below 30 ° C, 30% sodium hydroxide solution and then neutralized to pH 7, i.e., the present invention is to obtain a product polycarboxylate superplasticizer, the structural formula as shown in Formula (¾: corresponding a weight average molecular weight: 15,000 ~30000.

[0052] [0052]

Figure CN102140019AD00071

[0053]其中,χ : y = 1 : 1. 5 〜2. 5,ζ : (x+y) = 1 : 45 〜55,η 取值范围为6 〜10, m取值范围为52〜57。 [0053] wherein, χ: y = 1:. 1. 5 ~2 5, ζ: (x + y) = 1: 45 ~55, η in the range of 6 ~10, m in the range of 52~57 .

[0054] 实施例二 [0054] Second Embodiment

[0055] 将240克MAL (重均分子量M00)和水147克,加入反应釜,开启搅拌器,缓慢升温, 升温至60°C,加入质量浓度为30%的双氧水溶液10. 95克,待温度回升到60°C稳定后,滴加含有1. 7972克Vc和3. 2473克MPA的2#水溶液48. 2g ;滴加时间为3. 5小时。 [0055] The 240 g of MAL (M00 weight average molecular weight) and 147 g of water, adding to the reactor, the stirrer was gradually raised, and warmed to 60 ° C, added to a concentration of 30 mass% hydrogen peroxide solution 10.95 g, be # 2 aqueous solution temperature rises to 60 ° C stability, Vc solution containing 1.7972 grams and 3.2473 grams of MPA 48. 2g; dropwise over 3.5 hours. 待2#滴加2min后,开始滴加含有19. 6克AA和4. 15克c2的1#水溶液39. 2克,滴加时间为3小时。 After the dropwise addition # 2 2min, start solution containing 19.6 g of AA and 4.15 g aqueous 1 # c2 are 39.2 g was added dropwise for 3 hours. 1#、姊水溶液加完之后于60°C保持1小时。 # 1, percent aqueous After completion held at 60 ° C 1 hour. 然后降温至30°C以下,再用30%氢氧化钠溶液中和至PH值为7,即得到本发明的一种聚羧酸减水剂产品,其结构如式(6)所示:对应的重均分子量:20000〜35000。 Then cooled to below 30 ° C, and then 30% sodium hydroxide solution to a PH value of 7, i.e., to obtain a product of polycarboxylate superplasticizer of the present invention, the structure of formula (6): corresponding to the weight average molecular weight: 20000~35000.

[0056] [0056]

Figure CN102140019AD00081

[0057]其中,χ : y = 1 : 2 〜3,z : (x+y) =1 : 15 〜25,n 取值范围为8 〜12,m 取值范围为52〜57。 [0057] wherein, χ: y = 1: 2 ~3, z: (x + y) = 1: 15 ~25, n ranges from 8 ~12, m in the range of 52~57.

[0058] 实施例三 [0058] Example three

[0059] 将240克MAL (重均分子量M00)和水147克,加入反应釜,开启搅拌器,缓慢升温, 升温至60°C,加入质量浓度为30%的双氧水溶液10. 95克,待温度回升到60°C稳定后,滴加含有1. 7972克Vc和3. 2473克MPA的2#水溶液48. 2g ;滴加时间为3. 5小时。 [0059] The 240 g of MAL (M00 weight average molecular weight) and 147 g of water, adding to the reactor, the stirrer was gradually raised, and warmed to 60 ° C, added to a concentration of 30 mass% hydrogen peroxide solution 10.95 g, be # 2 aqueous solution temperature rises to 60 ° C stability, Vc solution containing 1.7972 grams and 3.2473 grams of MPA 48. 2g; dropwise over 3.5 hours. 待2#滴加2min后,开始滴加含有19. 6克AA和2. 82克c3的1#水溶液39. 2克,滴加时间为3小时。 After the dropwise addition # 2 2min, start solution containing 19.6 g AA and 2.82 g aqueous 1 # c3, 39.2 g was added dropwise for 3 hours. 1#、姊水溶液加完之后于60°C保持1小时,然后降温至30°C以下,再用30%氢氧化钠溶液中和至PH值为7,即得到本发明的一种聚羧酸减水剂产品,其结构如式(7)所示:对应的重均分子量:20000〜35000。 # 1, percent aqueous After completion held at 60 ° C 1 hour and then cooled to below 30 ° C, and then 30% sodium hydroxide solution to a PH value of 7, i.e., the present invention is to obtain a polycarboxylic acid superplasticizer products, such as the structure of formula (7): corresponding to a weight average molecular weight: 20000~35000.

[0060] [0060]

Figure CN102140019AD00082

[0061]其中,χ : y = 1 : 2 〜3,z : (x+y) =1 : 35 〜40,n 取值范围为8 〜12,m 取值范围为52〜57。 [0061] wherein, χ: y = 1: 2 ~3, z: (x + y) = 1: 35 ~40, n ranges from 8 ~12, m in the range of 52~57.

[0062] 实施例四 [0062] Fourth Embodiment

[0063] 将240克MBL (重均分子量M00)和水147克,加入反应釜,开启搅拌器,缓慢升温, 升温至60°C,加入质量浓度为30%的双氧水溶液10. 95克,待温度回升到60°C稳定后,滴加含有1. 7972克Vc和3. 2473克MPA的2#水溶液48. 2g ;滴加时间为3. 5小时。 [0063] The 240 g of MBL (M00 weight average molecular weight) and 147 g of water, adding to the reactor, the stirrer was gradually raised, and warmed to 60 ° C, added to a concentration of 30 mass% hydrogen peroxide solution 10.95 g, be # 2 aqueous solution temperature rises to 60 ° C stability, Vc solution containing 1.7972 grams and 3.2473 grams of MPA 48. 2g; dropwise over 3.5 hours. 待2#滴加2min后,开始滴加含有19. 6克AA和2. 82克c3的1#水溶液39. 2克,滴加时间为3小时。 After the dropwise addition # 2 2min, start solution containing 19.6 g AA and 2.82 g aqueous 1 # c3, 39.2 g was added dropwise for 3 hours. 1#、姊水溶液加完之后于60°C保持1小时。 # 1, percent aqueous After completion held at 60 ° C 1 hour. 然后降温至30°C以下,再用30%氢氧化钠溶液中和至PH值为7,即得到本发明的一种聚羧酸减水剂产品,其结构如式(8)所示:对应的重均分子量:20000〜35000。 Then cooled to below 30 ° C, and then 30% sodium hydroxide solution to a PH value of 7, i.e., to obtain a product of polycarboxylate superplasticizer of the present invention, such as the structure of formula (8): the corresponding the weight average molecular weight: 20000~35000.

[0064] [0064]

Figure CN102140019AD00091

[0065]其中,χ : y = 1 : 1. 5 〜2. 5,ζ : (x+y) =1 : 35 〜40,η 取值范围为8 〜12, ml取值范围为18〜22,m2取值范围为3〜5,m3取值范围为28〜32。 [0065] wherein, χ: y = 1:. 1. 5 ~2 5, ζ: (x + y) = 1: 35 ~40, η in the range of 8 ~12, ml in the range of 18~22 , m2 in the range of 3~5, m3 in the range of 28~32.

[0066] 实施例五 [0066] Embodiment V

[0067] 将165克MAL (重均分子量3300)和水110克,加入反应釜,开启搅拌器,缓慢升温, 升温至65°C,加入质量浓度为30%的双氧水溶液5. 48克,待温度回升到65°C稳定后,滴加含有0. 8986克Vc和1. 6236克MPA的2#水溶液24. Ig ;滴加时间为3. 5小时。 [0067] The 165 g of MAL (average molecular weight 3300) and 110 g of water, adding to the reactor, the stirrer was gradually raised, and warmed to 65 ° C, added to a concentration of 30 mass% hydrogen peroxide solution 5.48 grams, to be # 2 aqueous solution temperature rises to 65 ° C stability, Vc solution containing 0.8986 grams and 1.6236 grams of MPA 24. Ig; dropwise over 3.5 hours. 待2#滴加2min后,开始滴加含有14. 4克AA和1. 67克c2的1#水溶液28. 8克,滴加时间为3小时。 After the dropwise addition # 2 to be 2min, start solution containing 14.4 g AA and 1.67 g aqueous 1 # c2 of 28.8 g was added dropwise for 3 hours. 1#、姊水溶液加完之后于65°C保持1小时。 # 1, percent aqueous After completion held at 65 ° C 1 hour. 然后降温至30°C以下,再用30%氢氧化钠溶液中和至PH值为7,即得到本发明的一种聚羧酸减水剂产品,其结构如式(9)所示:对应的重均分子量:30000〜45000。 Then cooled to below 30 ° C, and then 30% sodium hydroxide solution to a PH value of 7, i.e., to obtain a product of polycarboxylate superplasticizer of the present invention, the structure of formula (9): the corresponding the weight average molecular weight: 30000~45000.

[0068] [0068]

Figure CN102140019AD00092

[0069]其中,χ : y = 1 : 3 〜5,z : (x+y) = 1 : 60 〜65,n 取值范围为8 〜12,m 取值范围为72〜78。 [0069] wherein, χ: y = 1: 3 ~5, z: (x + y) = 1: 60 ~65, n ranges from 8 ~12, m in the range of 72~78.

[0070] 实施例六 [0070] Sixth Embodiment

[0071] 将120克BL (重均分子量1200)和水73. 5克,加入反应釜,开启搅拌器,缓慢升温,升温至65°C,加入质量浓度为30%的双氧水溶液10. 95克,待温度回升到65°C稳定后, 滴加含有1. 7972克Vc和3. 2473克MPA的2#水溶液48. 2g ;滴加时间为3. 5小时。 [0071] A 120 g BL (weight average molecular weight 1200) and 73.5 g of water, adding to the reactor, the stirrer was gradually raised, and warmed to 65 ° C, added to a concentration of 30 mass% hydrogen peroxide solution of 10.95 g # 2 aqueous solution, until the temperature rose to 65 ° C stability, Vc solution containing 1.7972 grams and 3.2473 grams of MPA 48. 2g; dropwise over 3.5 hours. 待2# 滴加aiiin后,开始滴加含有21. 6克AA和3. 036克c3的1#水溶液43. 2克,滴加时间为3 小时。 After the dropwise addition # 2 aiiin, start solution containing 21.6 g of AA and 3.036 g aqueous 1 # c3, 43.2 g was added dropwise for 3 hours. 1#、姊水溶液加完之后于65°C保持1小时。 # 1, percent aqueous After completion held at 65 ° C 1 hour. 然后降温至30°C以下,再用30%氢氧化钠溶液中和至PH值为7,即得到本发明的一种聚羧酸减水剂产品,其结构如式(10)所示: 对应的重均分子量:10000〜20000。 Then cooled to below 30 ° C, and then 30% sodium hydroxide solution to a PH value of 7, i.e., to obtain a product of polycarboxylate superplasticizer of the present invention, the structure of formula (10): the corresponding the weight average molecular weight: 10000~20000.

[0072] [0072]

Figure CN102140019AD00101

[0073]其中,χ : y = 1 : 2 〜4,ζ : (x+y) =1 : 35 〜45,η 取值范围为10 〜12,m 取值范围为26〜观。 [0073] wherein, χ: y = 1: 2 ~4, ζ: (x + y) = 1: 35 ~45, η in the range of 10 ~12, m in the range of 26~ concept.

[0074] 比较例一 [0074] Comparative Example a

[0075] 将240克AL (重均分子量M00)和水147克,加入反应釜,开启搅拌器,缓慢升温, 升温到50°C,加入质量浓度为30%的双氧水溶液10. 95克,待温度回升到50°C稳定后,滴加含有1. 7972克Vc和3. 2473克MPA的2#水溶液48. 2g ;待2#溶液滴加2min后,开始滴加含有19. 6克MA的1#水溶液39. 2克,滴加时间为3小时。 [0075] A 240 g AL (M00 weight average molecular weight) and 147 g of water, adding to the reactor, the stirrer was gradually raised, and warmed to 50 ° C, added to a concentration of 30 mass% hydrogen peroxide solution 10.95 g, be after the temperature rose to 50 ° C a stable, aqueous solution containing 2 # 1.7972 g and 3.2473 g MPA Vc of 48. 2g; # 2 after the solution was dropwise 2min, start solution containing 19.6 g of MA # 1 solution 39.2 g was added dropwise for 3 hours. 1#、2#水溶液加完之后于50°C 保持1小时。 # 1, # 2 After completion of the aqueous solution held at 50 ° C 1 hour. 然后降温至30°C以下,再用30%氢氧化钠溶液中和至pH值为7,即为一种不含有马来酰胺酸结构单元的聚羧酸减水剂产品。 Then cooled to below 30 ° C, 30% sodium hydroxide solution and then neutralized to pH 7, that is, containing no polycarboxylate superplasticizer product maleamic acid structural units.

[0076] 比较例二 [0076] Comparative Example Two

[0077] 将240克MBL (重均分子量2400)和水147克,加入反应釜,开启搅拌器,缓慢升温, 升温至60°C,加入质量浓度为30%的双氧水溶液10. 95克,待温度回升到60°C稳定后,滴加含有1. 7972克Vc和3. 2473克MPA的2#水溶液48. 2g ;滴加时间为3. 5小时。 [0077] The 240 g of MBL (weight average molecular weight 2400) and 147 g of water, adding to the reactor, the stirrer was gradually raised, and warmed to 60 ° C, added to a concentration of 30 mass% hydrogen peroxide solution 10.95 g, be # 2 aqueous solution temperature rises to 60 ° C stability, Vc solution containing 1.7972 grams and 3.2473 grams of MPA 48. 2g; dropwise over 3.5 hours. 待2#滴加2min后,开始滴加含有19. 6克AA的1#水溶液39. 2克,滴加时间为3小时。 After the dropwise addition # 2 2min, dropwise addition of an aqueous solution containing 19.6 g 1 # AA, 39.2 g was added dropwise for 3 hours. 1#、2#水溶液加完之后于60°C保持1小时。 # 1, # 2 After completion of the aqueous solution held at 60 ° C 1 hour. 然后降温至30°C以下,再用30%氢氧化钠溶液中和至pH值为7,即为又一种不含有马来酰胺酸结构单元的聚羧酸减水剂产品。 Then cooled to below 30 ° C, 30% sodium hydroxide solution and then neutralized to pH 7, and that is containing no polycarboxylate superplasticizer product maleamic acid structural units.

[0078] 将实施例一到例六及比较例一和比较例二所制得的聚羧酸系减水剂应用到P. 042. 5水泥,测定其含气量、混凝土坍落度、扩展度及其1小时后的坍落度、扩展度。 [0078] The first embodiment to Example VI and Comparative Examples and a Comparative Example obtained in two superplasticizer cement applied to P. 042. 5, measured air content, slump concrete, expansion of and slump after 1 hour the degree of expansion. (掺量折固为水泥的0.3% )。 (0.3% solid dosage off cement).

[0079] 各实例的混凝土坍落度、扩展度和含气量列于表1 : [0079] each instance of concrete slump, air content and the degree of expansion shown in Table 1:

[0080] 表1混凝土性能比较表 [0080] Table 1 Performance comparison table Concrete

[0081] [0081]

Figure CN102140019AD00111

[0082] 从表1中可以看出,本发明的含有马来酰胺酸结构的减水剂的坍落度保持效果明显好于不含有马来酰胺酸结构的减水剂。 [0082] As can be seen from Table 1, the slump superplasticizer comprising maleamic acid structure of the present invention maintains significantly better than water-reducing agent containing no maleamic acid structure. 本发明实施例的减水剂1小时坍落度保持率都在90%以上,而未加入马来酰胺酸结构的对比例减水剂的坍落度损失则比较多,保持率一般在70-80%。 Superplasticizer embodiment of the present invention 1 hour slump retention rate above 90%, whereas the addition of amides of maleic slump loss ratio is more superplasticizer acid structure, retention rate is generally 70 80%. 加入马来酰胺酸的种类和对聚醚单体的要求则没有限制,制备出的减水剂在减水率、坍落度保持及28天的抗压强度比等性能方面都有明显提高。 Maleic acid amide type and requirements of the polyether monomer is not limited superplasticizer prepared in water reduction, slump retention performance and compressive strength than the other 28 days are significantly improved.

Claims (12)

1. 一种混凝土聚羧酸系减水剂,其结构如下式(1)所示,其中,队、1?2、1?4和1?6是H或碳原子数为1〜3的烷基;R3是碳原子数为1〜20的亚烷基;R5是!1或-COOM且M是H、Na或K ;R是碳原子数为1〜10的亚烷基或亚芳基;Y代表-COOH或-SO3H ;BO 是-C2H40-、-C3H6O-或-C4H8O-,或是它们之间形成的有序嵌段或无序杂嵌段;m是10〜120 的正整数;n、x、y和ζ均为正数 A concrete superplasticizer, the structure of the following formula (1), wherein, team, 1? 2, 1? 4 and 1? 6 is H or an alkyl having a carbon number of 1 ~ 3 group; R3 is an alkylene group having a carbon number of 1~20; R5 is 1 or -COOM and M is H, Na or K;! R 1~10 carbon atoms as the alkylene group or an arylene group; Y represents -COOH or -SO3H; BO is -C2H40 -, - C3H6O- or -C4H8O-, ordered or block or random block formed therebetween heteroaryl; m is a positive integer of 10~120; n- , x, y and ζ are positive
Figure CN102140019AC00021
2.权利要求1所述的聚羧酸系减水剂,其特征在于:所述的χ、y和ζ之间满足以下关系:x : y = 1 : 1 〜10,且ζ : (x+y) =1 : 10 〜100。 Superplasticizer according to claim 1, wherein: said satisfies the following relationship between χ, y and ζ: x: y = 1: 1 ~10, and ζ: (x + y) = 1: 10 ~100.
3.权利要求1所述的聚羧酸系减水剂,其特征在于:所述的减水剂重均分子量为5000 〜70000。 Superplasticizer according to claim 1, wherein: said weight-average molecular weight of 5,000 superplasticizer ~70000.
4.权利要求3所述的聚羧酸系减水剂,其特征在于:所述的减水剂重均分子量为10000 〜30000。 Superplasticizer claimed in claim 3, wherein: said water-reducing agent having a weight average molecular weight of 10,000 ~30000.
5.权利要求1所述的聚羧酸系减水剂,其特征在于:所述减水剂由结构如式(2)所示的单体A、结构如式(3)所示的单体B以及结构如式(4)所示的单体C——马来酰胺酸共聚而成 Superplasticizer according to claim 1, wherein: said monomer A superplasticizer by the structural formula (2) as a formula, a monomer structure as shown in (3) of the formula B and structural formula (4) C-- maleamic acid monomer copolymerized shown
Figure CN102140019AC00022
式(2)中,礼、R2和R4是H或碳原子数为1〜3的烷基;R3是碳原子数为1〜20的亚烷基;BO是-C2H40-、-C3H60-或-C4H8O-,或是它们中的一种或两种以上形成的有序嵌段或无序杂嵌段;m是10〜120的正整数;式(3)中,R5是H或-COOM ;R6为H或碳原子数为1〜3的烷基;M是H、Na或K等; 式(4)中,R是碳原子数为1〜10的亚烷基或亚芳基;Y代表-COOH或-S03H。 Formula (2), Li, R2 and R4 are H or an alkyl group of 1~3 carbon atoms; R3 is an alkylene group having a carbon number of 1~20; BO is -C2H40 -, - C3H60- or - C4H8O-, ordered or block or random block heteroatom one or two of them formed above; m is a positive integer of 10~120; of formula (3), R5 is H or -COOM; R6 It is H or an alkyl group of 1~3 carbon atoms; M is other H, Na or K; of formula (4), R is the number of carbon atoms of 1~10 alkylene group or an arylene group; Y represents - COOH or -S03H.
6.权利要求5所述的聚羧酸系减水剂,其特征在于:所述的单体A是由环氧乙烷和环氧丙烷嵌段得到的烯丙醇醚、甲基丙烯醇醚、丁烯醇醚或甲基丁烯醇醚中的一种或几种的混合物。 6. A superplasticizer according to claim 5, wherein: said A monomer is allyl ethers, methyl ethers of propylene obtained from ethylene oxide and propylene oxide block , a mixture of one or more of butylene ether or methyl ether of butene.
7.权利要求6所述的聚羧酸系减水剂,其特征在于:所述的环氧乙烷和环氧丙烷嵌段是有规嵌段。 The superplasticizer according to claim 6, characterized in that: said ethylene oxide and propylene oxide block is random block.
8.权利要求6所述的聚羧酸系减水剂,其特征在于:所述的环氧乙烷和环氧丙烷嵌段是无规杂嵌。 Superplasticizer of claim 6, wherein: said ethylene oxide and propylene oxide block is embedded in a random heteroaryl.
9.权利要求5所述的聚羧酸系减水剂,其特征在于:所述的单体B选自丙烯酸、甲基丙烯酸或它们的盐类中的一种或几种的混合物。 9. A superplasticizer according to claim 5, wherein: said monomer B selected from acrylic acid, methacrylic acid or a mixture of one or more of the salts thereof.
10.权利要求5所述的聚羧酸系减水剂,其特征在于:所述的单体C选自马来酰胺乙酸、马来酰胺己酸或马来酰胺苯磺酸。 10. A superplasticizer according to claim 5, wherein: said C monomer selected from maleic acid amide, maleic acid amide or maleic acid, hexanoic acid amide.
11.权利要求5所述的聚羧酸系减水剂的制备方法,具体包括以下工艺步骤:1)将单体A和去离子水投于反应器中,制成质量浓度为40〜70%的水溶液,缓慢升温到50-90°C的反应温度;2)将单体B、单体C制成总质量浓度为30〜50%的溶液作为1#料,另以总质量浓度为0. 7〜8%的还原剂溶液作为2#料,当步骤1)的反应器中的单体A水溶液温度到达50〜 90°C的反应温度时,开始向其中一次性加入质量浓度为30%的双氧水溶液,待温度回到先前的反应温度后,开始同时向其中滴加1#料和2#料,1#料2. 0〜3. Oh加完,2#料2. 5〜 4h加完,使单体A、B和C之间的摩尔比符合式(1)中x、y和ζ之间的关系,加入的双氧水和还原剂的摩尔重均为单体A、单体B、单体C摩尔数之和的2% -10%,1#和2#加完后,保温反应1〜2h ;3)步骤2)保温结束后,将反应器中的物料降温到30°C以下,再用30%的NaOH溶液调节pH到6 Preparation 11. superplasticizer according to claim 5, comprises the following process steps: 1) A monomer cast and deionized water in the reactor to produce a concentration of 40~70 mass% the aqueous solution was slowly warmed to the reaction temperature of 50-90 ° C; 2) made of monomers B, from the total concentration of monomer C 30 ~ 50% was used as material # 1, based on the total mass concentration of the other 0. 7~8% of the reducing agent solution as material # 2, when the temperature of the aqueous solution of step 1 a) monomer in a reactor reaches a reaction temperature of 50~ 90 ° C, the start-time concentration was added thereto 30% hydrogen peroxide solution, when the temperature of the reaction back to the previous temperature, was added dropwise thereto while the start material 1 # 2 # and a feed, feed # 1 2. 0~3. Oh addition is complete, # 2 feed addition was complete 2. 5~ 4h , monomer a, the relationship between the x, y and ζ molar ratio between B and C according to formula (1), the molar hydrogen peroxide and a reducing agent are added to the weight of monomer a, monomer B, single 2% -10%, and the number of moles of the body C, # 1 and # 2 addition was complete, the reaction was kept 1~2h; 3) step 2) after completion of incubation, the material in the reactor was cooled to below 30 ° C, then a 30% NaOH solution pH was adjusted to 6 8,即获得所述的混凝土聚羧酸系减水剂。 8, i.e., to obtain a concrete superplasticizer.
12.权利要求11所述的制备方法,其特征在于:步骤2)所述的还原剂选自L-抗坏血酸、亚硫酸氢钠、巯基乙酸或巯基丙酸中的一种或两种以上的混合物。 12. The production method according to claim 11, wherein: the reducing agent of step 2) is selected from L- ascorbic acid, a mixture of sodium hydrogen sulfite, thioglycolic acid or mercaptopropionic acid of one or more of .
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CN103787608A (en) * 2012-10-30 2014-05-14 辽宁奥克化学股份有限公司 Polycarboxylic acid water reducer used for high mud concrete and synthetic method
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