WO2014059765A1 - Super plasticizer for precast concrete component - Google Patents

Super plasticizer for precast concrete component Download PDF

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Publication number
WO2014059765A1
WO2014059765A1 PCT/CN2013/073683 CN2013073683W WO2014059765A1 WO 2014059765 A1 WO2014059765 A1 WO 2014059765A1 CN 2013073683 W CN2013073683 W CN 2013073683W WO 2014059765 A1 WO2014059765 A1 WO 2014059765A1
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WO
WIPO (PCT)
Prior art keywords
monomer
superplasticizer
concrete
general formula
chloride
Prior art date
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PCT/CN2013/073683
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French (fr)
Chinese (zh)
Inventor
冉千平
刘金芝
刘加平
周栋梁
杨勇
张建纲
Original Assignee
江苏博特新材料有限公司
江苏苏博特新材料股份有限公司
江苏省建筑科学研究院有限公司
姜堰市博特新材料有限公司
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Application filed by 江苏博特新材料有限公司, 江苏苏博特新材料股份有限公司, 江苏省建筑科学研究院有限公司, 姜堰市博特新材料有限公司 filed Critical 江苏博特新材料有限公司
Publication of WO2014059765A1 publication Critical patent/WO2014059765A1/en

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Classifications

    • 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
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • 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
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
    • 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
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688—Copolymers containing at least three different monomers
    • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
    • 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
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/32—Superplasticisers

Definitions

  • the invention relates to an ultra-early-strength superplasticizer suitable for concrete precast members.
  • the superplasticizer can not only significantly improve the early strength of the concrete, but also has excellent performance without delaying the cement setting time.
  • the slump retention ability belongs to the technical field of concrete admixtures. Background technique
  • Concrete prefabricated components are the key products for the development of the 12th Five-Year Development Plan of the Building Materials Industry.
  • the output of traditional prefabricated components such as concrete precast piles, drain pipes, pressure pipes and electric poles maintained a rapid growth.
  • a large number of infrastructure construction projects in the country have higher and higher technical requirements and quality requirements for concrete products, which promoted the rapid development of new technologies and new products in the concrete and cement products industry, such as the construction of urban subways and river tunnels.
  • precast concrete shows obvious advantages compared with cast-in-place concrete in terms of production standardization and construction greening, it also faces great pressure in energy saving, emission reduction and durability.
  • the common feature of concrete prefabricated components is that the concrete is high-strength and early-strength.
  • the main technical approaches at home and abroad mainly include changes in cement composition or fineness, addition of early strength admixtures, and thermal curing systems, but At present, these technologies have more or less different defects.
  • the finer the fineness of the cement the faster the early hydration speed and the higher the early strength, but the concrete has poor construction performance, large shrinkage and easy cracking.
  • the Beijing-Tianjin Passenger Dedicated Line used the German technical scheme of high-grade superfine cement (specific surface area up to 600m 2 /kg) to produce plate-type ballastless track plates. This technology has the defects of poor construction performance, low production efficiency and high cost, and it is difficult to adapt to China. The need for high-speed railway construction.
  • special cements such as fast hard Portland cement, sulphoaluminate super early strength cement and fluoroaluminate fast setting fast hard cement can be produced by adjusting the composition of cement mineral phase to improve early strength, but early hydration heat is high.
  • high-pressure steam curing accounts for more than 90% of total conservation energy consumption, and each production is 1M.
  • 3 PHC pipe piles are used for curing up to 40kg of standard coal and 30kg of carbon dioxide.
  • the steam-contained concrete members not only deteriorate in later mechanical properties, but also reduce the durability of the members.
  • Ultra-early strength technology based on molecular structure regulation of graft copolymers. Recent studies have confirmed that graft copolymer admixtures can impart high initial fluidity and high workability to fresh concrete, and can also be used to impart ultra-early strength and low shrinkage of hardened concrete by modern molecular cutting technology, and even meet the requirements of hydration control.
  • the research object of the present invention is to develop a superplasticizer for a concrete precast member which can overcome the disadvantages described in the background art, has a relatively simple production technique, and has a high water-reducing rate, a good early reinforcing effect, and a strong fluidity retaining ability.
  • the length of the side chain of the graft copolymer is the main influencing factor of cement hydration speed.
  • R 2 is H or an alkyl group having 1 to 4 carbon atoms
  • AO is an oxyalkylene group having 2 to 4 carbon atoms or two or more such oxyalkylene groups are optional. a mixture of ratios
  • n is the average addition mole number of AO, which is an integer of 100 to 300
  • (AO) n is a homopolymerized, random copolymer, diblock or multi-block copolymer structure;
  • R 3 is H or methyl
  • R 4 is H or -C-OM
  • M is H, an alkali metal ion, an alkaline earth metal ion, an ammonium ion or an organic amine group
  • the monomer c is a cationic monomer, and the substance represented by the general formula (3) is used:
  • R 5 is H or methyl
  • R 6 , R 7 and R 8 each independently represent 15 or ⁇ .
  • A is O or NH
  • P is a positive integer of 1 to 3;
  • the monomer d is a hydroxyester monomer, and the substance represented by the formula (4) is used:
  • the monomer a represented by the formula (1) in the present invention is a polyalkylene glycol mono(meth)acrylate monomer, it is composed of an alkoxy polyalkylene glycol and (meth)acrylic acid or An esterified composition of (meth)acrylic anhydride; or an adduct of at least one of hydroxyalkyl (meth) acrylate and ethylene oxide, propylene oxide, butylene oxide, these monomers It can be used singly or in the form of a mixture of two or more components in any ratio.
  • the monomer b represented by the formula (2) in the present invention is an unsaturated carboxylic acid, and includes acrylic acid, methacrylic acid, maleic acid, or a monovalent metal salt, a divalent metal salt, an ammonium salt or an organic of these unsaturated carboxylic acids.
  • Amine salts, these monomers are used singly or in the form of a mixture of two or more components.
  • the typical ion which can be regarded as the cationic monomer c represented by the general formula (3) in the present invention is methacryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyldimethylbenzyl chloride.
  • Ammonium methacryloxypropyltrimethylammonium chloride, methacryloxypropyldimethylbenzylammonium chloride, acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyl Dimethylbenzylammonium chloride, acrylamidopropyltrimethylammonium chloride, acrylamidopropyldimethylbenzylammonium chloride, methacrylamidopropyltrimethylammonium chloride, A Acrylamide propyldimethylbenzylammonium chloride, these monomers are used singly or in the form of a mixture of two or more components.
  • the monomer d represented by the formula (4) in the invention is a hydroxyalkyl (meth) acrylate, and includes hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate.
  • the monomers are used singly or in the form of a mixture of two or more components.
  • the monomer a represented by the formula (1) is copolymerized into the main chain, and the long-chain branching thereof mainly provides a steric hindrance effect, thereby imparting excellent dispersibility to the graft copolymer. If the monomer a ratio is too low, the copolymer produced will have a low early strength. If the ratio is too high, the copolymer dispersion is weak.
  • n is an average addition mole number of AO, which is an integer of 100 to 300.
  • n is too small, the synthesized copolymer has low early strength; if n is too large, the copolymerization activity is poor, The low bulk conversion rate not only does not improve the early strength, but also the dispersion properties of the synthesized copolymer are also poor.
  • monomer b (formula 2) is necessary, the carboxylic acid group provides adsorption point and electrical repulsive force in the copolymer, the monomer b content is too low, and the synthesized copolymer cannot be sufficiently adsorbed to the cement. On the particles, therefore, the dispersion cannot be exerted. If the content is too high, the copolymer produced will have a low early strength.
  • the cationic monomer c represented by the formula (3) is necessary, and the cationic group thereof not only increases the adsorption point in the copolymer, but also improves the early hydration behavior of the cement. If the content of monomer c is too low, the amphoteric characteristics of the synthesized copolymer are not obvious, and it cannot be sufficiently adsorbed onto the cement particles, and the early hydration of the cement and the ability to maintain fluidity can not be significantly improved. If the content is too high, the dispersion properties of the produced copolymer are deteriorated.
  • the hydroxyester monomer d represented by the formula (4) is necessary and copolymerized into the main chain.
  • the main dynamic regulation of the adsorption behavior of the copolymer thereby improving the fluidity retention ability of the copolymer. If the content of the monomer d is too low, the effect of dynamically controlling the adsorption behavior of the copolymer is not obtained, and the fluidity retaining ability of the copolymer is lowered. If the content is too high, the early dispersion properties of the produced copolymer and the early strength of the concrete may also be deteriorated.
  • the radical copolymerization reaction itself is not critical, and it can be carried out according to a usual method using a known radical initiator without any difficulty.
  • the water-soluble initiator suitable for the present invention is a conventional free radical water-soluble initiator, and a water-soluble ammonium persulfate, potassium persulfate, sodium persulfate or hydrogen peroxide or a mixture of two or more thereof may be used. All of the initiator added to the reaction mixture accounts for 1.0 to 6.0% of the total moles of the monomer (a+b+c+d) added. It is generally known to those skilled in the art that there is a relationship between the actual amount of initiator added in the copolymerization reaction and the type of initiator employed.
  • the molecular weight of the copolymer can be controlled by a polymeric chain transfer agent such as mercaptopropionic acid, thioglycolic acid, mercaptoethanol, and dodecyl mercaptan.
  • the amount of the polymeric chain transfer agent used in the copolymerization process is from 1.0 to 5.0% of the total mole of the monomer (a + b + c + d).
  • the total mass concentration of the copolymerization monomer is preferably controlled at 25 to 50%, and the reaction time is controlled at 5 to 10 hours.
  • the monomer and the initiator solution are separately and simultaneously added to control the uniformity of the copolymer chain distribution and the stability of the copolymerization reaction itself, and the monomer mixture liquid and the initiator dropping time are preferably controlled at 2.0 to 6.0 hours.
  • the co-polymerization temperature is preferably carried out at 60 to 100 ° C, which is mainly related to the decomposition temperature of the initiator used.
  • a basic compound is added to the reaction product to adjust the pH value to 6.0 to 10.0, and the basic compound is selected from ammonia water, ammonium hydrogencarbonate, organic amine, monovalent metal or divalent metal hydroxide or carbon thereof. Acid salt.
  • the pH is too low or too high, the storage stability of the copolymer is not good.
  • the weight average molecular weight of the comb-shaped graft copolymer using the concrete superplasticizer is not particularly limited, and is generally from 20,000 to 100,000. If the molecular weight is too small and too large, the water reducing property is deteriorated.
  • the conventional superplasticizer of the present invention is conventionally added in an amount of 0.1% to 0.4% by mass of the total gum, and the optimum amount is 0.15 to 0.3%. If the amount added is less than 0.10%, the dispersion property and the reinforcing effect are unsatisfactory. On the contrary, if the amount added exceeds 0.4%, the excessive addition proves to be only an economic waste because it does not bring about a corresponding increase in effect.
  • the concrete superplasticizer of the present invention may also be combined with at least one selected from the group consisting of sulfamic acid-based water reducing agents, lignin-based ordinary water reducing agents, and existing polycarboxylic acid-based superplasticizers. Mixed.
  • an air entraining agent a swelling agent, a retarder, an early strength agent, a tackifier, a shrinkage reducing agent, an antifoaming agent, and the like may be added thereto.
  • the superplasticizer for the prefabricated member of the present invention has the following characteristics as compared with the conventional superplasticizer: (1)
  • the invention introduces a long side chain polyether and a cationic monomer, which can obviously improve the early hydration of the cement and improve the compressive strength of the concrete, especially the early strength;
  • the invention introduces a hydroxy ester monomer, which can greatly improve the slump loss caused by the long side chain of the polyether, improve the concrete retaining ability, and can meet the requirements of the pumped pipe pile concrete. Save a lot of labor costs;
  • the superplasticizer for prefabricated members prepared in the present invention exhibits outstanding dispersibility, dispersion retention, and reinforcing effect at low dosage, especially early reinforcement.
  • the effect is remarkable, and the enhancement effect is very significant both at normal temperature and low temperature, and the strength is also stable in the middle and late stages, which is beneficial to speed up the template turnover and improve the construction progress.
  • the monomers a, monomers b, c and monomer d described in Table 1 are all commercial products and are commercially available.
  • the weight average molecular weight of the polymer was measured by a Wyatt technology corporation gel permeation chromatograph.
  • gel column Shodex SB806+803 two columns in series; eluent: 0.1M NaN0 3 solution; mobile phase velocity: 1.0 ml/min; injection: 20 ⁇ 0.5% aqueous solution; detector: Shodex RI-71 Refractive Index Detector; Standard: Polyethylene glycol GPC standard (Sigma-Aldrich, molecular weight 1010000, 478000, 263000, 118000, 44700, 18600, 6690, 1960, 628, 232).
  • the cement used is Onoda 525R.R II cement
  • the stone is continuous grade with particle size of 5 ⁇ 20mm. Crushed stone.
  • the cement mortar fluidity test is carried out according to the GB/T8077-2000 standard.
  • the mortar expansion is measured on the flat glass.
  • the determination of the setting time is carried out according to the GB/T1346-2001 standard.
  • the dropping time is about 5 h.
  • the reaction is kept for 2 h.
  • 40 parts of an initiator solution containing 1.5 g of sodium persulfate is added to the reaction bottle, and the mixture is kept for 1 hour, and cooled to room temperature, and alkali is adjusted to adjust the pH to 7.5.
  • Solid content 39.5 % brown transparent liquid, molecular weight 68,000 (PE-2) o Synthesis Example 3
  • the addition time is about 6 h. After the addition, the reaction is kept for 2 h. Then, 40 parts of an initiator solution containing 2.5 g of ammonium persulfate is added to the reaction bottle, and the mixture is kept for 1 hour. The mixture is cooled to room temperature and alkali is adjusted to pH 9.0. The solid content is 48.8 % brown transparent liquid, and the molecular weight is 81,400 (PE-3) o Synthesis Example 4
  • Table 4 lists the effects of various copolymers on concrete water reduction rate, gas content and compressive strength.
  • the test results show that the polycarboxylate concrete superplasticizer of the present invention has excellent dispersing properties and can be remarkable.
  • the 3d compressive strength is increased by 160 ⁇ 200% relative to the standard, the compressive strength of 28d can be increased by 50 ⁇ 65%, and the reinforcing effect is remarkable in low temperature environment, at 5°C low temperature environment.
  • Id compressive strength increased by 270 ⁇ 350%, it can be seen that the compressive strength of the concrete mixed with the polycarboxylate concrete superplasticizer of the invention not only has a relatively high early strength, but also has a large increase in late strength, and Constantly growing steadily.
  • PE-2 0.20 27.8 2.3 6.4 65.8 87.8 PE-3 0.20 28.0 2.5 7.2 70.5 89.2
  • the production process of prefabricated components puts forward the requirements of pumping, and requires the production of large fluid concrete in the case where the existing pipe pile mix ratio is basically unchanged.
  • the relatively mature steam curing system is adopted to improve the early strength of the components.
  • the concrete exit is required to be greater than 180mm, the expansion is greater than 450mm, and the working performance must be at least 30min.
  • the steaming strength refers to the demolding strength after curing at 80-90 °C for 4 hours, and the compressive strength is under the pressure of IMPa, and the compressive strength is maintained for 4 hours.
  • the test results are shown in Table 5.
  • the polycarboxylate concrete superplasticizer of the present invention can significantly improve the slump retention ability of the concrete, can meet the pumping requirements, and can improve the compressive strength of the concrete under steam curing and steaming conditions.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The present invention relates to a super plasticizer for a precast concrete component, and the super plasticizer is prepared by carrying out a free radical copolymerization reaction on monomer a, monomer b, monomer c and monomer d in an aqueous medium, and adding an alkali compound into the reaction product for neutralization, wherein a molar ratio among the monomer a, the monomer b, the monomer c and the monomer d is 1.0:(5.0-16.0):(1.0-4.0):(2.0-6.0). Through comparison between the super plasticizer for a precast concrete component of the present invention and a conventional high efficiency water reducing agent, the admixture has the characteristics that: (1) the super plasticizer can obviously improve early hydration of cement, compression strength of concrete, and especially the early strength; (2) the super plasticizer can greatly alleviate the problem of slump loss caused by polyether long side chain, so as to enhance the slump loss resistance of concrete and satisfy the requirement of pumping pipe pile concrete; and (3) under the condition of a low amount of admixture, the super plasticizer has remarkable dispersing performance, slump-retaining capability and enhancement effect, wherein the early enhancement effect is especially remarkable no matter at the room temperature or low temperature, and later strength increment is also stable, which facilitates turnover of templates and accelerates the construction progress.

Description

混凝土预制构件用超塑化剂 技术领域  Superplasticizer for concrete prefabricated components
本发明涉及一种适用于混凝土预制构件用的超早强型超塑化剂， 这种超塑化剂 在不延缓水泥凝结时间的前提下， 不但能能够显著提高混凝土早期强度， 而且具有 优异的坍落度保持能力， 属混凝土外加剂技术领域。 背景技术  The invention relates to an ultra-early-strength superplasticizer suitable for concrete precast members. The superplasticizer can not only significantly improve the early strength of the concrete, but also has excellent performance without delaying the cement setting time. The slump retention ability belongs to the technical field of concrete admixtures. Background technique
混凝土预制构件是 《建材工业 "十二五"发展规划》 发展的重点产品。 十一五 期间， 我国混凝土预制桩、 排水管、 压力管和电杆等传统预制构件产量保持了较快 增长。 与此同时国家一大批基础设施建设工程对混凝土制品技术水平和质量要求越 来越高， 促进了混凝土与水泥制品行业新技术、 新产品的快速发展， 例如用于城市 地铁和过江隧道建设的关键部件混凝土盾构管片、 直径达 4米的高工压大口径钢筒 混凝土输水管 （PCCP)、 强度等级达到 C80以上的高强预应力 （PHC) 管桩、 高速 客运专线取代轨枕的混凝土无砟道板、 大型预制混凝土梁， 体现建筑文化与生态和 谐的各种装饰混凝土及制品等。随着住宅产业化的持续升温， 预制混凝土装配整体 式结构施工技术由于其绿色、 环保施工方式逐渐受到青睐， 已经被住房与城乡建设 部列入了建筑业 10项新技术之一。可以预见，未来几年混凝土预制构件领域必将迎 来新一轮的发展热潮。 预制混凝土虽然在生产的标准化、施工绿色化等方面同现浇 混凝土相比显示出了明显的优势， 但在节能减排、 耐久性等方面也面临着很大的压 力。 混凝土预制构件的共同特点是混凝土高强、 早强， 为了提高预制混凝土的早期 强度， 国内外的主要技术途径主要有改变水泥组成或细度、 外加早强外加剂、 以及 热养护制度等方法， 但目前这些技术都或多或少存在着不同的缺陷。 1 )基于水泥组 成或细度调控的早强技术： 目前为了提高混凝土早期强度， 制造商不得不采用超细 水泥和改变水泥矿物组成。水泥的细度越细， 其早期水化速度越快， 早期强度越高， 但混凝土施工性能差、 收縮大、 易开裂。 京津客运专线曾采用高标号超细水泥 (比表 面积达到 600m2/kg)的德国技术方案生产板式无磴轨道板， 该技术存在施工性能差、 生产效率低、 成本高的缺陷， 难以适应我国高速铁路建设的需要。 此外， 还可通过 调整水泥矿物相组成生产快硬硅酸盐水泥、 硫铝酸盐超早强水泥以及氟铝酸盐快凝 快硬水泥等特种水泥来提高早期强度， 但早期水化热高、 早期干縮率大， 且后期强 度及性能呈现下降； 2)基于外加早强剂的早强技术： 早强外加剂在建材领域已经有 多年的应用历史， 其应用技术也较全面， 但仍有一些技术问题难于解决。 无机早强 剂虽然早强效果较好， 但掺量较高， 并且混凝土后期强度倒縮严重， 混凝土干燥收 縮大，不利于混凝土耐久性，碱金属盐类早强剂还会增大混凝土碱 -集料反应的风险, 其使用越来越受制约。 相对而言有机类早强剂使用起来比较安全可靠， 但其掺加量 难以控制， 使用不当容易造成混凝土严重缓凝和混凝土强度下降， 而且其高昂的价 格影响了其在混凝土行业的应用； 3)基于养护工艺调控的早强技术： 预制构件生产 中广泛采用热养护工艺提高早期强度， 加快模板周转速度。 C50以上的地铁管片、 混凝土预制梁、 混凝土管等预制构件主要采用 40-6CTC下的蒸汽养护， 蒸汽养护是 这一类预制构件的主要能耗环节。 C80 以上高强预应力混凝土管桩或管片 (PHC， PCCP)主要采用常压与高压蒸汽养护结合的两段养护工艺， 该工艺中高压蒸汽养护 占据总养护能耗的 90%以上， 每生产 1M3PHC管桩用于养护所消耗的标准煤达到 40kg, 同时排放二氧化碳 30kg。 蒸汽养护的混凝土构件不但后期力学性能下降， 而 且构件的耐久性降低。 4)基于接枝共聚物分子结构调控的超早强技术。最新研究证 实接枝共聚物外加剂除可以赋予新拌混凝土高初始流动性和高工作性保持外， 还可 以采用现代分子裁剪技术赋予硬化混凝土超早强、 低收縮， 甚至满足水化控制的要 求等多种功能， 水泥基材料超早强技术的发展开辟了新的途径。 发明专利 (EP1547986、 US723287、 EP2128110 、 ZL200710024394.4, ZL200710024392.5) 采用超长侧链聚醚的技术途径， 发明了提高混凝土早期强度的超早强型外加剂， 虽 然大幅度提高了混凝土早期强度， 但聚醚侧链长度的增加， 加快了水泥早期水化， 从而加剧了新拌混凝土早期的坍落度损失。 随着劳动力成本的增加， 预制混凝土不 但对早期强度有很高的要求， 同时也要求混凝土实行泵送。 Concrete prefabricated components are the key products for the development of the 12th Five-Year Development Plan of the Building Materials Industry. During the 11th Five-Year Plan period, the output of traditional prefabricated components such as concrete precast piles, drain pipes, pressure pipes and electric poles maintained a rapid growth. At the same time, a large number of infrastructure construction projects in the country have higher and higher technical requirements and quality requirements for concrete products, which promoted the rapid development of new technologies and new products in the concrete and cement products industry, such as the construction of urban subways and river tunnels. Key components concrete shield segments, high-pressure large-diameter steel cylinder concrete water pipes (PCCP) with a diameter of 4 meters, high-strength prestressed (PHC) pipe piles with a strength class above C80, and high-speed passenger lines replace the concrete for the sleepers. Ramp plates, large precast concrete beams, various decorative concrete and products that reflect the harmony of architectural culture and ecology. As the industrialization of housing continues to heat up, the prefabricated concrete assembly integral structure construction technology has gradually been favored by its green and environmentally friendly construction methods, and has been included in the construction industry as one of the 10 new technologies. It is foreseeable that the field of concrete prefabricated components will surely usher in a new round of development boom in the next few years. Although precast concrete shows obvious advantages compared with cast-in-place concrete in terms of production standardization and construction greening, it also faces great pressure in energy saving, emission reduction and durability. The common feature of concrete prefabricated components is that the concrete is high-strength and early-strength. In order to improve the early strength of precast concrete, the main technical approaches at home and abroad mainly include changes in cement composition or fineness, addition of early strength admixtures, and thermal curing systems, but At present, these technologies have more or less different defects. 1) Early strength technology based on cement composition or fineness control: At present, in order to improve the early strength of concrete, manufacturers have to use ultra-fine cement and change the composition of cement minerals. The finer the fineness of the cement, the faster the early hydration speed and the higher the early strength, but the concrete has poor construction performance, large shrinkage and easy cracking. The Beijing-Tianjin Passenger Dedicated Line used the German technical scheme of high-grade superfine cement (specific surface area up to 600m 2 /kg) to produce plate-type ballastless track plates. This technology has the defects of poor construction performance, low production efficiency and high cost, and it is difficult to adapt to China. The need for high-speed railway construction. In addition, special cements such as fast hard Portland cement, sulphoaluminate super early strength cement and fluoroaluminate fast setting fast hard cement can be produced by adjusting the composition of cement mineral phase to improve early strength, but early hydration heat is high. , early shrinkage rate is large, and late strong Degree and performance are declining; 2) Early strength technology based on external early strength agent: Early strength admixture has been used for many years in the field of building materials, and its application technology is also comprehensive, but there are still some technical problems that are difficult to solve. Although the early strength agent of inorganic early strength is better, the dosage is higher, and the strength of the concrete is severely reversed. The dry shrinkage of the concrete is large, which is not conducive to the durability of the concrete. The alkali metal salt early strengthening agent will also increase the concrete alkali- The risk of aggregate reactions is increasingly restricted. Relatively speaking, organic early strength agents are safer and more reliable to use, but their dosage is difficult to control. Improper use can cause serious retardation of concrete and decrease of concrete strength, and its high price affects its application in the concrete industry; Early-strength technology based on maintenance process regulation: The heat curing process is widely used in the production of prefabricated components to improve the early strength and speed up the template turnover. The prefabricated components such as subway segments, concrete precast beams and concrete pipes above C50 mainly adopt steam curing under 40-6CTC. Steam curing is the main energy consumption link of this type of prefabricated components. High-strength prestressed concrete pipe piles or segments (PHC, PCCP) above C80 mainly adopt two-stage curing technology combining atmospheric pressure and high-pressure steam curing. In this process, high-pressure steam curing accounts for more than 90% of total conservation energy consumption, and each production is 1M. 3 PHC pipe piles are used for curing up to 40kg of standard coal and 30kg of carbon dioxide. The steam-contained concrete members not only deteriorate in later mechanical properties, but also reduce the durability of the members. 4) Ultra-early strength technology based on molecular structure regulation of graft copolymers. Recent studies have confirmed that graft copolymer admixtures can impart high initial fluidity and high workability to fresh concrete, and can also be used to impart ultra-early strength and low shrinkage of hardened concrete by modern molecular cutting technology, and even meet the requirements of hydration control. With a variety of functions, the development of cement-based materials super early strength technology has opened up new avenues. Invention patents (EP1547986, US723287, EP2128110, ZL200710024394.4, ZL200710024392.5) The use of ultra-long side chain polyether technology, invented a super early strength admixture to improve the early strength of concrete, although greatly improved the early strength of concrete However, the increase in the length of the polyether side chain accelerates the early hydration of the cement, thereby exacerbating the early slump loss of the fresh concrete. As labor costs increase, precast concrete not only has high requirements for early strength, but also requires concrete to be pumped.
综上所述， 采用传统无机盐或有机早强剂提高混凝土早期强度是不能令人满意 的， 其掺量高， 降低了混凝土后期强度； 传统水泥组成或细度调控的早强技术易收 縮、 开裂， 混凝土耐久性不高； 传统高温、 高压蒸汽养护耗能高， 不利于混凝土耐 久性。这些传统早强技术不能有效解决早强和高耐久的矛盾，不能满足建筑业"节能、 低碳、减排"的发展需求。而新型超早强型外加剂的早强效果令人满意， 但坍落度损 失却非常大。 而采用复配保坍型外加剂或缓凝剂来提高其流动性保持性能， 又劣化 了混凝土早期强度的发展。 发明内容 本发明的研究目的是研制能克服背景技术所述的那些缺点， 生产技术相对简单 以及具有减水率高、 早期增强效果好、 流动性保持能力强的混凝土预制构件用超塑 化剂。 In summary, the use of traditional inorganic salts or organic early strength agents to improve the early strength of concrete is unsatisfactory, its high content, reducing the late strength of concrete; traditional cement composition or fineness control of early strength technology is easy to shrink, Cracking, concrete durability is not high; traditional high temperature, high pressure steam curing energy consumption is high, which is not conducive to concrete durability. These traditional early-strength technologies cannot effectively solve the contradiction between early strength and high durability, and cannot meet the development needs of the construction industry for "energy saving, low carbon, and emission reduction." The early strength of the new super-early strong admixture is satisfactory, but the slump loss is very large. The use of a compound-type admixture admixture or retarder to improve its fluidity retention performance degrades the development of early strength of concrete. Summary of the invention The research object of the present invention is to develop a superplasticizer for a concrete precast member which can overcome the disadvantages described in the background art, has a relatively simple production technique, and has a high water-reducing rate, a good early reinforcing effect, and a strong fluidity retaining ability.
申请人经研究发现， 接枝共聚物侧链长度是水泥水化速度的主要影响因素。 侧链越 长， 水泥水化越快， 且长支链由于其强的空间位阻效应导致共聚物优异的分散性， 也加快了水泥的水化， 有利于混凝土早期强度的提高。 Applicants have found that the length of the side chain of the graft copolymer is the main influencing factor of cement hydration speed. The longer the side chain, the faster the hydration of the cement, and the long-chain branching has excellent dispersibility of the copolymer due to its strong steric hindrance effect, which also accelerates the hydration of the cement and is beneficial to the early strength of the concrete.
申请人经研究惊奇地发现， 通过在主链上引入阳离子基团， 改善共聚物吸附行 为， 不但可以加快水泥早期水化， 而且还可大幅度提升混凝土流动性保持能力。  Applicants have surprisingly discovered through research that by introducing a cationic group into the main chain, the adsorption behavior of the copolymer is improved, which not only accelerates the early hydration of the cement, but also greatly improves the fluidity retention ability of the concrete.
申请人经研究还发现， 通过在主链上引入对水泥强碱性环境具有响应的羟基酯 类共聚单体， 可进一步提升新拌混凝土流动性保持能力。  Applicants have also found through research that by introducing a hydroxy ester comonomer which is responsive to the strong alkaline environment of the cement in the main chain, the fluidity retention ability of the fresh concrete can be further improved.
基于上述研究， 本发明所述羧酸类接枝共聚物超塑化剂由单体 a、单体 b、单体 c和单体 d在水性介质中发生自由基共聚反应后加碱性化合物中和制备而成， 其中 单体 a: 单体 b: 单体 c: 单体 d的摩尔比 =1.0:5.0~16.0:1.0~4.0:2.0~6.0； Based on the above research, the carboxylic acid graft copolymer superplasticizer of the present invention is obtained by adding a basic compound to the radical compound after the monomer a, the monomer b, the monomer c and the monomer d are subjected to a free radical copolymerization reaction in an aqueous medium. And prepared, wherein monomer a: monomer b: monomer c: monomer d molar ratio = 1.0: 5.0 ~ 16.0: 1.0 ~ 4.0: 2.0 ~ 6.0;
上述单体 a用通式 （1 ) 表示：  The above monomer a is represented by the general formula (1):
Ri  Ri
H2〇 C (1) H 2〇C (1)
c=o  c=o
O— (AO)nR2 O—(AO)nR 2
通式 （1 ) 中 为11或甲基， R2是 H或 1~4个碳原子的烷基； AO为 2-4个碳 原子的氧化烯基或两种以上的这种氧化烯基任意比例的混合物； n为 AO的平均加 成摩尔数， 是 100〜300的整数； （AO) n是均聚、 无规共聚、 二嵌段或多嵌段共聚 结构； In the formula (1), 11 or a methyl group, R 2 is H or an alkyl group having 1 to 4 carbon atoms; AO is an oxyalkylene group having 2 to 4 carbon atoms or two or more such oxyalkylene groups are optional. a mixture of ratios; n is the average addition mole number of AO, which is an integer of 100 to 300; (AO) n is a homopolymerized, random copolymer, diblock or multi-block copolymer structure;
上述单体 b用通式 （2) 表示：  The above monomer b is represented by the formula (2):
Figure imgf000005_0001
Figure imgf000005_0001
0  0
通式 （2) 中 R3是 H或甲基， R4是 H或- C-OM， M为 H、 碱金属离子、 碱土 金属离子、 铵离子或有机胺基团； In the formula (2), R 3 is H or methyl, R 4 is H or -C-OM, M is H, an alkali metal ion, an alkaline earth metal ion, an ammonium ion or an organic amine group;
单体 c是阳离子单体， 采用由通式 （3) 所表示物质：
Figure imgf000006_0001
The monomer c is a cationic monomer, and the substance represented by the general formula (3) is used:
Figure imgf000006_0001
其中： R5为 H或甲基， R6、 R7、 R8均独立代表 15或 ~ 。的烷基； Wherein: R 5 is H or methyl, and R 6 , R 7 and R 8 each independently represent 15 or ~. Alkyl
X F、 Cl、 Br或 I;  X F, Cl, Br or I;
A为 O或 NH;  A is O or NH;
P是 1〜3的正整数；  P is a positive integer of 1 to 3;
单体 d是羟基酯类单体， 采用由通式 （4) 所表示物质：  The monomer d is a hydroxyester monomer, and the substance represented by the formula (4) is used:
Ri  Ri
H2C^=C—— COORg 4) 通式 （4) 中！^同通式 （1)， R9表示为 -(CH2)xOH， x=2〜10的正整数。 H 2 C^=C——COORg 4) In the formula (4)! ^ is a normal integer of the formula (1), and R 9 is represented by -(CH 2 ) xOH, x = 2 to 10.
本发明中通式 （1 ) 表示的单体 a为聚亚烷基二醇单 （甲基） 丙烯酸酯单体时， 是由烷氧基聚亚烷基二醇与 （甲基） 丙烯酸或与 （甲基） 丙烯酸酐的酯化合成物； 或为 （甲基） 丙烯酸羟烷基酯与环氧乙烷、 环氧丙烷、 环氧丁烷中至少一种物质的 加成物， 这些单体单独使用或以两种以上成份以任意比例的混合物形式使用。  When the monomer a represented by the formula (1) in the present invention is a polyalkylene glycol mono(meth)acrylate monomer, it is composed of an alkoxy polyalkylene glycol and (meth)acrylic acid or An esterified composition of (meth)acrylic anhydride; or an adduct of at least one of hydroxyalkyl (meth) acrylate and ethylene oxide, propylene oxide, butylene oxide, these monomers It can be used singly or in the form of a mixture of two or more components in any ratio.
可以作为大单体 a的聚亚烷基二醇单 （甲基） 丙烯酸酯单体的具体例子包括： 聚乙二醇单（甲基）丙烯酸酯、 聚丙二醇单 （甲基）丙烯酸酯、 聚丁二醇单（甲基） 丙烯酸酯、 聚乙二醇聚丙二醇单 （甲基） 丙烯酸酯、 聚乙二醇聚丁二醇单 （甲基） 丙烯酸酯、 聚丙二醇聚丁二醇单 （甲基） 丙烯酸酯、 聚乙二醇聚丙二醇聚丁二醇单 Specific examples of the polyalkylene glycol mono(meth)acrylate monomer which can be used as the macromonomer a include: polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, poly Butanediol mono(meth) acrylate, polyethylene glycol polypropylene glycol mono(meth) acrylate, polyethylene glycol polybutylene glycol mono (meth) acrylate, polypropylene glycol polybutylene glycol single (a) Acrylate, polyethylene glycol polypropylene glycol polybutylene glycol single
(甲基） 丙烯酸酯、 甲氧基聚乙二醇单 （甲基） 丙烯酸酯、 甲氧基聚丙二醇单 （甲 基） 丙烯酸酯、 甲氧基聚丁二醇单 （甲基） 丙烯酸酯、 甲氧基聚乙二醇聚丙二醇单(meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, methoxy polypropylene glycol mono (meth) acrylate, methoxy polybutylene glycol mono (meth) acrylate, Methoxy polyethylene glycol polypropylene glycol single
(甲基） 丙烯酸酯、 甲氧基聚乙二醇聚丁二醇单 （甲基） 丙烯酸酯、 甲氧基聚丙二 醇聚丁二醇单 （甲基） 丙烯酸酯、 甲氧基聚乙二醇聚丙二醇聚丁二醇单 （甲基） 丙 烯酸酯、 乙氧基聚乙二醇单 （甲基） 丙烯酸酯、 乙氧基聚丙二醇单 （甲基） 丙烯酸 酯、 乙氧基聚丁二醇单 （甲基） 丙烯酸酯、 乙氧基聚乙二醇聚丙二醇单 （甲基） 丙 烯酸酯、 乙氧基聚乙二醇聚丁二醇单 （甲基） 丙烯酸酯、 乙氧基聚丙二醇聚丁二醇 单 （甲基） 丙烯酸酯、 乙氧基聚乙二醇聚丙二醇聚丁二醇单 （甲基） 丙烯酸酯、 丙 氧基聚乙二醇单 （甲基） 丙烯酸酯、 丙氧基聚丙二醇单 （甲基） 丙烯酸酯、 丙氧基 聚丁二醇单 （甲基） 丙烯酸酯、 丙氧基聚乙二醇聚丙二醇单 （甲基） 丙烯酸酯、 丙 氧基聚乙二醇聚丁二醇单 （甲基） 丙烯酸酯、 丙氧基聚丙二醇聚丁二醇单 （甲基） 丙烯酸酯、 丙氧基聚乙二醇聚丙二醇聚丁二醇单 （甲基） 丙烯酸酯、 丁氧基聚乙二 醇单 （甲基） 丙烯酸酯、 丁氧基丙氧基聚丙二醇单 （甲基） 丙烯酸酯、 丁氧基聚丁 二醇单 （甲基） 丙烯酸酯、 丁氧基聚乙二醇聚丙二醇单 （甲基） 丙烯酸酯、 丁氧基 聚乙二醇聚丁二醇单 （甲基） 丙烯酸酯、 丁氧基聚丙二醇聚丁二醇单 （甲基） 丙烯 酸酯、 丁氧基聚乙二醇聚丙二醇聚丁二醇单 （甲基） 丙烯酸酯。 它们是已知的， 它 们或者可商购， 或者可按照公开的文献或专利中所述的方法制备。 (Meth) acrylate, methoxy polyethylene glycol polybutylene glycol mono(meth) acrylate, methoxy polypropylene glycol polybutylene glycol mono(meth) acrylate, methoxy polyethylene glycol Polypropylene glycol polybutylene glycol mono(meth) acrylate, ethoxypolyethylene glycol mono(meth) acrylate, ethoxylated polypropylene glycol mono(meth) acrylate, ethoxylated polybutylene glycol single (Meth) acrylate, ethoxypolyethylene glycol polypropylene glycol mono(meth) acrylate, ethoxypolyethylene glycol polybutylene glycol mono(meth) acrylate, ethoxylated polypropylene glycol polybutylene Glycol mono(meth) acrylate, ethoxypoly polyethylene glycol polypropylene glycol polybutylene glycol mono(meth) acrylate, propoxy polyethylene glycol mono(meth) acrylate, propoxy poly Propylene glycol mono(meth) acrylate, propoxy polybutanediol mono(meth) acrylate, propoxy polyethylene glycol polypropylene glycol mono(meth) acrylate, propoxy polyethylene glycol polybutylene Glycol mono (meth) acrylate, propoxy polypropylene glycol polybutylene glycol mono (methyl Acrylate, propoxylated polyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylate, butoxy polyethylene glycol Alcohol mono (meth) acrylate, butoxy propoxy polypropylene glycol mono (meth) acrylate, butoxy polybutylene glycol mono (meth) acrylate, butoxy polyethylene glycol polypropylene glycol single (Meth) acrylate, butoxy polyethylene glycol polybutylene glycol mono(meth) acrylate, butoxy polypropylene polypropylene glycol polybutylene glycol mono (meth) acrylate, butoxy polyethylene glycol Polypropylene glycol polybutylene glycol mono(meth) acrylate. They are known, they are either commercially available or can be prepared according to the methods described in the published literature or patents.
本发明中通式（2)表示的单体 b为不饱和羧酸， 包括丙烯酸、 甲基丙烯酸、 马 来酸， 或这些不饱和羧酸的单价金属盐、 二价金属盐、 铵盐或有机胺盐， 这些单体 单独使用或以两种以上成份的混合物形式使用。  The monomer b represented by the formula (2) in the present invention is an unsaturated carboxylic acid, and includes acrylic acid, methacrylic acid, maleic acid, or a monovalent metal salt, a divalent metal salt, an ammonium salt or an organic of these unsaturated carboxylic acids. Amine salts, these monomers are used singly or in the form of a mixture of two or more components.
本发明中通式（3 )表示的可以作为阳离子单体 c的典型离子列举出的是甲基丙 烯酰氧乙基三甲基氯化铵， 甲基丙烯酰氧乙基二甲基苄基氯化铵， 甲基丙烯酰氧丙 基三甲基氯化铵， 甲基丙烯酰氧丙基二甲基苄基氯化铵， 丙烯酰氧乙基三甲基氯化 铵， 丙烯酰氧乙基二甲基苄基氯化铵， 丙烯酰胺基丙基三甲基氯化铵， 丙烯酰胺基 丙基二甲基苄基氯化铵， 甲基丙烯酰胺基丙基三甲基氯化铵， 甲基丙烯酰胺基丙基 二甲基苄基氯化铵，这些单体单独使用或以两种或两种以上成份的混合物形式使用。  The typical ion which can be regarded as the cationic monomer c represented by the general formula (3) in the present invention is methacryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyldimethylbenzyl chloride. Ammonium, methacryloxypropyltrimethylammonium chloride, methacryloxypropyldimethylbenzylammonium chloride, acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyl Dimethylbenzylammonium chloride, acrylamidopropyltrimethylammonium chloride, acrylamidopropyldimethylbenzylammonium chloride, methacrylamidopropyltrimethylammonium chloride, A Acrylamide propyldimethylbenzylammonium chloride, these monomers are used singly or in the form of a mixture of two or more components.
本发明中通式（4)表示的单体 d是（甲基）丙烯酸羟烷基酯， 包括丙烯酸羟乙 酯、 甲基丙烯酸羟乙酯、 丙烯酸羟丙酯或甲基丙烯酸羟丙酯， 这些单体单独使用或 以两种或两种以上成份的混合物形式使用。  The monomer d represented by the formula (4) in the invention is a hydroxyalkyl (meth) acrylate, and includes hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate. The monomers are used singly or in the form of a mixture of two or more components.
本发明中通式（1 )表示的单体 a共聚到主链中， 其长支链主要提供空间位阻效 应， 从而赋予接枝共聚物优异的分散性能。 如果单体 a比例过低， 则所生产的共聚 物早期强度较低。 如果比例过高， 则合成的共聚物分散作用较弱。 通式 （1 ) 中 n 为 AO的平均加成摩尔数， 其为 100〜300的整数， 如果 n太小， 则合成的共聚物早 期强度低； 如果 n太大， 则其共聚活性差， 单体转化率低， 不但不能提高早期强度， 而且合成的共聚物分散性能也差。  In the present invention, the monomer a represented by the formula (1) is copolymerized into the main chain, and the long-chain branching thereof mainly provides a steric hindrance effect, thereby imparting excellent dispersibility to the graft copolymer. If the monomer a ratio is too low, the copolymer produced will have a low early strength. If the ratio is too high, the copolymer dispersion is weak. In the formula (1), n is an average addition mole number of AO, which is an integer of 100 to 300. If n is too small, the synthesized copolymer has low early strength; if n is too large, the copolymerization activity is poor, The low bulk conversion rate not only does not improve the early strength, but also the dispersion properties of the synthesized copolymer are also poor.
在本发明范围内， 单体 b (通式 2)是必须的， 其羧酸基团在共聚物中提供吸附 点和电斥力， 单体 b含量过低， 合成的共聚物不能充分吸附到水泥粒子上， 因此不 能发挥分散作用。 如果含量过高， 则所生产的共聚物早期强度较低。  Within the scope of the present invention, monomer b (formula 2) is necessary, the carboxylic acid group provides adsorption point and electrical repulsive force in the copolymer, the monomer b content is too low, and the synthesized copolymer cannot be sufficiently adsorbed to the cement. On the particles, therefore, the dispersion cannot be exerted. If the content is too high, the copolymer produced will have a low early strength.
在本发明范围内， 通式（3 )所表示的阳离子单体 c是必须的， 其阳离子基团在 共聚物中不但提高吸附点， 也改善了水泥早期水化行为。 单体 c含量过低， 则合成 的共聚物的两性特征不明显， 不能充分吸附到水泥颗粒上， 也不能明显改善水泥的 早期水化和提升流动性保持能力。 如果含量过高， 则生产的共聚物分散性能变差。  Within the scope of the present invention, the cationic monomer c represented by the formula (3) is necessary, and the cationic group thereof not only increases the adsorption point in the copolymer, but also improves the early hydration behavior of the cement. If the content of monomer c is too low, the amphoteric characteristics of the synthesized copolymer are not obvious, and it cannot be sufficiently adsorbed onto the cement particles, and the early hydration of the cement and the ability to maintain fluidity can not be significantly improved. If the content is too high, the dispersion properties of the produced copolymer are deteriorated.
在本发明范围内， 通式（4)所表示的羟基酯类单体 d是必须的， 共聚到主链中 主要动态调控共聚物的吸附行为， 从而提升共聚物的流动性保持能力。 单体 d含量 过低， 则起不到动态调控共聚物吸附行为的作用， 共聚物的流动性保持能力降低。 如果含量过高， 则生产的共聚物早期分散性能和混凝土早期强度也会变差。 Within the scope of the present invention, the hydroxyester monomer d represented by the formula (4) is necessary and copolymerized into the main chain. The main dynamic regulation of the adsorption behavior of the copolymer, thereby improving the fluidity retention ability of the copolymer. If the content of the monomer d is too low, the effect of dynamically controlling the adsorption behavior of the copolymer is not obtained, and the fluidity retaining ability of the copolymer is lowered. If the content is too high, the early dispersion properties of the produced copolymer and the early strength of the concrete may also be deteriorated.
自由基共聚反应本身来说并不重要， 它可根据通常的方法， 用已知的自由基引 发剂在毫不困难的情况下进行。 适宜于本发明的水溶性引发剂是常规的自由基水溶 性引发剂， 可选用水溶性过硫酸铵、 过硫酸钾、 过硫酸钠或过氧化氢或其中两种以 上任意比例的混合物。 加入到反应混合物中的全部引发剂占所加入单体 (a+b+c+d) 总摩尔数的 1.0〜6.0 %。 本技术领域熟练的技术人员普遍知悉共聚反应中引发剂实 际加入量和所采用的引发剂种类有一定的关系。  The radical copolymerization reaction itself is not critical, and it can be carried out according to a usual method using a known radical initiator without any difficulty. The water-soluble initiator suitable for the present invention is a conventional free radical water-soluble initiator, and a water-soluble ammonium persulfate, potassium persulfate, sodium persulfate or hydrogen peroxide or a mixture of two or more thereof may be used. All of the initiator added to the reaction mixture accounts for 1.0 to 6.0% of the total moles of the monomer (a+b+c+d) added. It is generally known to those skilled in the art that there is a relationship between the actual amount of initiator added in the copolymerization reaction and the type of initiator employed.
共聚物的分子量可利用聚合链转移剂选择控制， 如巯基丙酸， 巯基乙酸， 巯基 乙醇以及十二硫醇。 聚合链转移剂在共聚过程中的用量为单体 (a+b+c+d)总摩尔的 1·0〜5·0 %。  The molecular weight of the copolymer can be controlled by a polymeric chain transfer agent such as mercaptopropionic acid, thioglycolic acid, mercaptoethanol, and dodecyl mercaptan. The amount of the polymeric chain transfer agent used in the copolymerization process is from 1.0 to 5.0% of the total mole of the monomer (a + b + c + d).
共聚反应单体总质量浓度以控制在 25〜50 %为宜，反应时间控制在 5〜10小时。 单体和引发剂溶液采取分开同时滴加的方式来控制共聚物链节分布的均匀性和共聚 反应本身的稳定性， 单体混合液和引发剂滴加时间以控制在 2.0〜6.0小时为宜。 共 聚作用温度好在 60〜100°C下进行， 它主要与所用的引发剂的分解温度有关。  The total mass concentration of the copolymerization monomer is preferably controlled at 25 to 50%, and the reaction time is controlled at 5 to 10 hours. The monomer and the initiator solution are separately and simultaneously added to control the uniformity of the copolymer chain distribution and the stability of the copolymerization reaction itself, and the monomer mixture liquid and the initiator dropping time are preferably controlled at 2.0 to 6.0 hours. . The co-polymerization temperature is preferably carried out at 60 to 100 ° C, which is mainly related to the decomposition temperature of the initiator used.
共聚反应结束后， 向反应产物中加入碱性化合物调整 pH值为 6.0〜10.0， 所述 的碱性化合物选择氨水、 碳酸氢氨、 有机胺、 单价金属或二价金属的氢氧化物或其 碳酸盐。 pH值过低和过高， 则共聚物的贮存稳定性都不好。  After the completion of the copolymerization reaction, a basic compound is added to the reaction product to adjust the pH value to 6.0 to 10.0, and the basic compound is selected from ammonia water, ammonium hydrogencarbonate, organic amine, monovalent metal or divalent metal hydroxide or carbon thereof. Acid salt. When the pH is too low or too high, the storage stability of the copolymer is not good.
在本发明中， 用着混凝土超塑化剂的梳形接枝共聚物的重均分子量没有特别限 制， 一般在 20,000— 100,000， 如果分子量太小和太大， 减水性能都会劣化。  In the present invention, the weight average molecular weight of the comb-shaped graft copolymer using the concrete superplasticizer is not particularly limited, and is generally from 20,000 to 100,000. If the molecular weight is too small and too large, the water reducing property is deteriorated.
使用时， 本发明的混凝土超塑化剂常规掺量在总胶材质量的 0.1 %〜0.4%， 最 优掺量为 0.15〜0.3 %。如果添加量小于 0.10 %， 那么其分散性能和增强效果是不能 令人满意的。相反如果添加量超过 0.4%， 则过量添加证明仅仅是经济上的浪费， 因 为并没有带来效果上的相应增长。  When used, the conventional superplasticizer of the present invention is conventionally added in an amount of 0.1% to 0.4% by mass of the total gum, and the optimum amount is 0.15 to 0.3%. If the amount added is less than 0.10%, the dispersion property and the reinforcing effect are unsatisfactory. On the contrary, if the amount added exceeds 0.4%, the excessive addition proves to be only an economic waste because it does not bring about a corresponding increase in effect.
当然， 本发明的混凝土超塑化剂也可以与至少一种选自现有技术中已知氨基磺酸系 减水剂、 木质素系普通减水剂以及现有聚羧酸系超塑化剂相混合。 Of course, the concrete superplasticizer of the present invention may also be combined with at least one selected from the group consisting of sulfamic acid-based water reducing agents, lignin-based ordinary water reducing agents, and existing polycarboxylic acid-based superplasticizers. Mixed.
另外， 除上面提到的已知混凝土减水剂外， 自其中也可以加入引气剂、膨胀剂、 缓凝剂、 早强剂、 增粘剂、 减縮剂和消泡剂等。  Further, in addition to the known concrete water reducing agent mentioned above, an air entraining agent, a swelling agent, a retarder, an early strength agent, a tackifier, a shrinkage reducing agent, an antifoaming agent, and the like may be added thereto.
本发明的预制构件用超塑化剂， 与传统的高效减水剂相比， 该外加剂具有如下 特点： (1) 本发明引入了长侧链聚醚以及阳离子单体， 能明显改善水泥的早期水化， 提高混凝土的抗压强度， 尤其是早期强度； The superplasticizer for the prefabricated member of the present invention has the following characteristics as compared with the conventional superplasticizer: (1) The invention introduces a long side chain polyether and a cationic monomer, which can obviously improve the early hydration of the cement and improve the compressive strength of the concrete, especially the early strength;
(2) 本发明引入了羟基酯类单体， 能够极大的改善聚醚长侧链带来的坍落度损 失问题， 提高了混凝土的保坍能力， 能够满足泵送管桩混凝土的要求， 节省大量的 人力成本；  (2) The invention introduces a hydroxy ester monomer, which can greatly improve the slump loss caused by the long side chain of the polyether, improve the concrete retaining ability, and can meet the requirements of the pumped pipe pile concrete. Save a lot of labor costs;
(3) 本发明中所制备的预制构件用超塑化剂与常规混凝土超塑化剂相比， 在低 掺量下表现出了突出的分散性能、 分散保持能力以及增强效果， 尤其是早期增强效 果显著， 且无论是在常温或低温早期增强效果都十分显著， 并中后期强度也增长稳 定， 有利于加快模板周转， 提高施工进度。 具体实施方式  (3) Compared with the conventional concrete superplasticizer, the superplasticizer for prefabricated members prepared in the present invention exhibits outstanding dispersibility, dispersion retention, and reinforcing effect at low dosage, especially early reinforcement. The effect is remarkable, and the enhancement effect is very significant both at normal temperature and low temperature, and the strength is also stable in the middle and late stages, which is beneficial to speed up the template turnover and improve the construction progress. detailed description
以下实施例更详细的描述了根据本发明的方法制备聚合产物的过程， 并且这些 实施例以说明的方式给出， 其目的在于让熟悉此项技术的人士能够了解本发明的内 容并据以实施， 但这些实施例绝不限制本发明的范围。 凡根据本发明精神实质所作 的等效变化或修饰，都应涵盖在本发明的保护范围之内。如果没有另外规定， "份数" 是指"重量份"。在如下实施例中所用的单体如表 1所示， 合成的羧酸类预制构件用 混凝土超塑化剂简记为 PE。  The following examples describe in more detail the process of preparing a polymeric product in accordance with the process of the present invention, and these examples are given by way of illustration, the purpose of which is to enable those skilled in the art to understand and practice the present invention. However, these examples in no way limit the scope of the invention. Equivalent variations or modifications made in accordance with the spirit of the invention are intended to be included within the scope of the invention. If not otherwise specified, "parts" means "parts by weight". The monomers used in the following examples are shown in Table 1, and the concrete superplasticizer for the synthetic carboxylic acid prefabricated member is abbreviated as PE.
a) 本发明实施中， 表 1所述的单体 a、 单体 b、 c和单体 d都为商业化产品， 可 以市场上购买。  a) In the practice of the present invention, the monomers a, monomers b, c and monomer d described in Table 1 are all commercial products and are commercially available.
b) 本发明实施例中， 聚合物的重均分子量采用 Wyatt technology corporation凝 胶渗透色谱仪测定。 （凝胶柱： Shodex SB806+803 两根色谱柱串联； 洗提液： 0.1M NaN03溶液；流动相速度： 1.0 ml/min;注射： 20 μΐ 0.5%水溶液；检测器： Shodex RI-71 型示差折光检测器； 标准物： 聚乙二醇 GPC标样（Sigma-Aldrich, 分子量 1010000, 478000, 263000, 118000, 44700, 18600, 6690, 1960, 628, 232)。 b) In the examples of the present invention, the weight average molecular weight of the polymer was measured by a Wyatt technology corporation gel permeation chromatograph. (gel column: Shodex SB806+803 two columns in series; eluent: 0.1M NaN0 3 solution; mobile phase velocity: 1.0 ml/min; injection: 20 μΐ 0.5% aqueous solution; detector: Shodex RI-71 Refractive Index Detector; Standard: Polyethylene glycol GPC standard (Sigma-Aldrich, molecular weight 1010000, 478000, 263000, 118000, 44700, 18600, 6690, 1960, 628, 232).
c) 本发明应用实施例中， 除特别说明， 所采用的水泥均为小野田 525R.R II水 泥， 砂为细度模数 Mx=2.6的中砂， 石子为粒径为 5〜20mm连续级配的碎石。  c) In the application examples of the present invention, unless otherwise specified, the cement used is Onoda 525R.R II cement, the sand is medium sand with fineness modulus Mx=2.6, and the stone is continuous grade with particle size of 5~20mm. Crushed stone.
d) 水泥砂浆流动度测试参照 GB/T8077-2000标准进行， 在平板玻璃上测定砂 浆扩展度， 凝结时间的测定参照 GB/T1346-2001标准进行。  d) The cement mortar fluidity test is carried out according to the GB/T8077-2000 standard. The mortar expansion is measured on the flat glass. The determination of the setting time is carried out according to the GB/T1346-2001 standard.
e) 减水率、 含气量试验方法参照 GB8076-2008《混凝土外加剂》 的相关规定执 行。 坍落度及坍落度损失参照 JC473-2001 《混凝土泵送剂》相关规定执行。 混凝土 抗压强度参照 GB/T50081-2002《普通混凝土力学性能试验方法标准》的相关规定执 表 1 实施例中所用单体 e) The test method for water reduction rate and gas content shall be carried out in accordance with the relevant provisions of GB8076-2008 “Concrete admixture”. The slump and slump loss shall be implemented in accordance with the relevant provisions of JC473-2001 Concrete Pumping Agent. Refer to GB/T50081-2002 "Standards for Testing Methods of Mechanical Properties of Ordinary Concrete" for the concrete compressive strength. Table 1 monomers used in the examples
Figure imgf000010_0001
合成实施例 1
Figure imgf000010_0001
Synthesis Example 1
在装有温度计、搅拌器、滴液漏斗、氮气导入管和回流冷凝器的玻璃反应器中， 加入 300ml去离子水， 边搅拌边用氮气吹扫反应容器， 并升温至 95°C， 然后将含有 333.6g(a-l , 0.05mol)、 28.8g(b-l , 0.4mol)、 14.5g ( c-1 , 0.075mol)、 16.25g (d-1 , 0.125mol)、 水 300份和 3.4g巯基丙酸相混， 搅拌制成均匀的单体水溶液， 将其滴 加入反应器， 滴加时间为 4h， 并同时滴加 100份含有 1.3 g过硫酸钾的引发剂溶液， 滴加时间约 4 h， 滴加完毕后保温反应 2h， 再向反应瓶内补加 30份含有 0.5 g过硫 酸钾的引发剂溶液， 并继续保温 lh， 冷却至室温加入碱溶液调节 pH值 8.2， 固含量 为 34.8 %棕色透明液体， 分子量为 52,600 (PE-1 )。 合成实施例 2  In a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, 300 ml of deionized water was added, and the reaction vessel was purged with nitrogen while stirring, and the temperature was raised to 95 ° C, and then Containing 333.6 g (al, 0.05 mol), 28.8 g (bl, 0.4 mol), 14.5 g (c-1, 0.075 mol), 16.25 g (d-1, 0.125 mol), 300 parts of water and 3.4 g of mercaptopropionic acid Mix, stir to make a uniform aqueous monomer solution, drop it into the reactor, add dropwise for 4h, and simultaneously add 100 parts of initiator solution containing 1.3 g of potassium persulfate, add about 4 h, drop After the addition was completed, the reaction was kept for 2 h, and then 30 parts of an initiator solution containing 0.5 g of potassium persulfate was added to the reaction flask, and the mixture was further kept for 1 hour. The mixture was cooled to room temperature, and an alkali solution was added to adjust the pH value of 8.2. The solid content was 34.8% brown transparent. The liquid has a molecular weight of 52,600 (PE-1). Synthesis Example 2
在装有温度计、搅拌器、滴液漏斗、氮气导入管和回流冷凝器的玻璃反应器中， 加入 300ml去离子水， 边搅拌边用氮气吹扫反应容器， 并升温至 75°C， 然后将含有 411.3g(a-2, 0.05mol)、51.6g(b-2， 0.6mol)、 25.8g (c-2， 0.125mol)、 23.2g (d-2, 0.2mol)、 水 300份和 2.0g巯基乙酸相混， 搅拌制成均匀的单体水溶液， 将其滴加入反应器， 滴加时间为 5h，并同时滴加 120份含有 9.5 g过硫酸钠的引发剂溶液，滴加时间约 5 h， 滴加完毕后保温反应 2h， 再向反应瓶内补加 40份含有 1.5 g过硫酸钠的引发剂 溶液， 并继续保温 lh， 冷却至室温加碱调节 pH值 7.5， 固含量为 39.5 %棕色透明液 体， 分子量为 68,000 (PE-2) o 合成实施例 3 In a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, 300 ml of deionized water was added, and the reaction vessel was purged with nitrogen while stirring, and the temperature was raised to 75 ° C, and then Containing 411.3 g (a-2, 0.05 mol), 51.6 g (b-2, 0.6 mol), 25.8 g (c-2, 0.125 mol), 23.2 g (d-2, 0.2 mol), 300 parts of water and 2.0 g of thioglycolic acid were mixed, stirred to prepare a uniform aqueous monomer solution, which was added dropwise to the reactor, and the dropping time was 5 h, and 120 parts of an initiator solution containing 9.5 g of sodium persulfate was added dropwise at the same time. The dropping time is about 5 h. After the completion of the dropwise addition, the reaction is kept for 2 h. Then, 40 parts of an initiator solution containing 1.5 g of sodium persulfate is added to the reaction bottle, and the mixture is kept for 1 hour, and cooled to room temperature, and alkali is adjusted to adjust the pH to 7.5. Solid content: 39.5 % brown transparent liquid, molecular weight 68,000 (PE-2) o Synthesis Example 3
在装有温度计、搅拌器、滴液漏斗、氮气导入管和回流冷凝器的玻璃反应器中， 加入 200ml去离子水， 边搅拌边用氮气吹扫反应容器， 并升温至 65°C， 然后将含有 445.7g(a-3, 0.04mol)、 46.1g(b-l , 0.64mol)、 24.9g c-2、 8.3g c-3 (共 0.16mol)、 31.2g (d-3, 0.24mol)、 水 200份和 4.0g巯基丙酸相混， 搅拌制成均匀的单体水溶液， 将 其滴加入反应器，滴加时间为 6h， 并同时滴加 110份含有 11 g过硫酸铵的引发剂溶 液， 滴加时间约 6 h， 滴加完毕后保温反应 2h， 再向反应瓶内补加 40份含有 2.5 g 过硫酸铵的引发剂溶液， 并继续保温 lh， 冷却至室温加碱调节 pH值 9.0， 固含量为 48.8 %棕色透明液体， 分子量为 81,400 (PE-3 ) o 合成实施例 4  In a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, 200 ml of deionized water was added, and the reaction vessel was purged with nitrogen while stirring, and the temperature was raised to 65 ° C, and then Containing 445.7 g (a-3, 0.04 mol), 46.1 g (bl, 0.64 mol), 24.9 g c-2, 8.3 g c-3 (total 0.16 mol), 31.2 g (d-3, 0.24 mol), water 200 parts and 4.0 g of mercaptopropionic acid were mixed, stirred to prepare a uniform aqueous monomer solution, and dropped into the reactor for 6 h, and 110 parts of an initiator solution containing 11 g of ammonium persulfate was added dropwise. The addition time is about 6 h. After the addition, the reaction is kept for 2 h. Then, 40 parts of an initiator solution containing 2.5 g of ammonium persulfate is added to the reaction bottle, and the mixture is kept for 1 hour. The mixture is cooled to room temperature and alkali is adjusted to pH 9.0. The solid content is 48.8 % brown transparent liquid, and the molecular weight is 81,400 (PE-3) o Synthesis Example 4
在装有温度计、搅拌器、滴液漏斗、氮气导入管和回流冷凝器的玻璃反应器中， 加入 400ml去离子水， 边搅拌边用氮气吹扫反应容器， 并升温至 80°C， 然后将含有 308.8g(a-4, 0.06mol)、 34.8g(b-3, 0.3mol)、 11.6g (c-l , 0.06mol)、 11.6g d-2、 2.6g d-l(共 0.12mol)、 水 400份和 0.6g巯基丙酸相混， 搅拌制成均匀的单体水溶液， 将其滴加 入反应器， 滴加时间为 2.5h， 并同时滴加 150份含有 2.0 g过硫酸钠的引发剂溶液， 滴加时间约 2.5 h，滴加完毕后保温反应 2h，再向反应瓶内补加 50份含有 0.6 g过硫 酸钠的引发剂溶液， 并继续保温 lh， 冷却至室温加碱溶液调节 pH值 6.7， 固含量为 27.6 %棕色透明液体， 分子量为 43,000 (PE-4) o 合成实施例 5  In a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, 400 ml of deionized water was added, and the reaction vessel was purged with nitrogen while stirring, and the temperature was raised to 80 ° C, and then Containing 308.8 g (a-4, 0.06 mol), 34.8 g (b-3, 0.3 mol), 11.6 g (cl, 0.06 mol), 11.6 g d-2, 2.6 g dl (total 0.12 mol), 400 parts of water Mix with 0.6g mercaptopropionic acid, stir to make a uniform aqueous monomer solution, drop it into the reactor, add dropwise for 2.5h, and add 150 parts of initiator solution containing 2.0 g of sodium persulfate at the same time, drop Adding time is about 2.5 h, after the completion of the addition, the reaction is kept for 2 h, and then 50 parts of an initiator solution containing 0.6 g of sodium persulfate is added to the reaction bottle, and the mixture is kept for 1 hour, cooled to room temperature, and alkali solution is adjusted to adjust the pH value of 6.7. Solid content: 27.6% brown transparent liquid, molecular weight 43,000 (PE-4) o Synthesis Example 5
在装有温度计、搅拌器、滴液漏斗、氮气导入管和回流冷凝器的玻璃反应器中， 加入 300ml去离子水， 边搅拌边用氮气吹扫反应容器， 并升温至 85°C， 然后将含有 267.4g a-l , 51.5g a-4 (共 0.05mol)、28.8g b-l，4.3g b-2(共 0.45mol)、20.6g(c-3， 0.1mol)、 20.3g (d-2, 0.175mol)、 水 300份和 2.5g巯基丙酸相混， 搅拌制成均匀的单体水溶 液， 将其滴加入反应器， 滴加时间为 4h， 并同时滴加 90份含有 4.5 g过硫酸钠的引 发剂溶液， 滴加时间约 4 h， 滴加完毕后保温反应 2h， 再向反应瓶内补加 30份含有 l.Og过硫酸钠的引发剂溶液， 并继续保温 lh， 冷却至室温加碱溶液调节 pH值 7.2， 固含量为 34.5 %棕色透明液体， 分子量为 35,500 (PE-5)。 比较例 1 In a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, 300 ml of deionized water was added, and the reaction vessel was purged with nitrogen while stirring, and the temperature was raised to 85 ° C, and then Contains 267.4 g al, 51.5 g a-4 (0.05 mol total), 28.8 g bl, 4.3 g b-2 (0.45 mol total), 20.6 g (c-3, 0.1 mol), 20.3 g (d-2, 0.175) Mol), 300 parts of water and 2.5g of mercaptopropionic acid mixed, stirred to make a uniform monomer water soluble The solution was added dropwise to the reactor, and the dropping time was 4 h. At the same time, 90 parts of an initiator solution containing 4.5 g of sodium persulfate was added dropwise, and the dropping time was about 4 h. After the completion of the dropwise addition, the reaction was kept for 2 hours, and then the reaction was further carried out. Add 30 parts of initiator solution containing 1.0 g of sodium persulfate to the bottle, and keep it for 1 h. Cool to room temperature and add alkali solution to adjust pH 7.2. Solid content is 34.5 % brown transparent liquid, molecular weight is 35,500 (PE-5 ). Comparative example 1
在装有温度计、搅拌器、滴液漏斗、氮气导入管和回流冷凝器的玻璃反应器中， 加入 300ml去离子水， 边搅拌边用氮气吹扫反应容器， 并升温至 95°C， 然后将含有 333.6g(a-l , 0.05mol)、 28.8g(b-l , 0.4mol)、 14.5g (c-l， 0.075mol)、水 300份和 3.4g 巯基丙酸相混， 搅拌制成均匀的单体水溶液， 将其滴加入反应器， 滴加时间为 4h， 并同时滴加 100份含有 1.3 g过硫酸钾的引发剂溶液， 滴加时间约 4 h，  In a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, 300 ml of deionized water was added, and the reaction vessel was purged with nitrogen while stirring, and the temperature was raised to 95 ° C, and then Containing 333.6 g (al, 0.05 mol), 28.8 g (bl, 0.4 mol), 14.5 g (cl, 0.075 mol), 300 parts of water and 3.4 g of mercaptopropionic acid, and stirred to form a uniform aqueous monomer solution, The dropping solution was added to the reactor, and the dropping time was 4 hours, and 100 parts of an initiator solution containing 1.3 g of potassium persulfate was added dropwise at the same time, and the dropping time was about 4 h.
滴加完毕后保温反应 2h，再向反应瓶内补加 30份含有 0.5 g过硫酸钾的引发剂溶液， 并继续保温 lh， 冷却至室温加入 NaOH溶液调节 pH值 8.2， 固含量为 32.5 %棕色 透明液体， 分子量为 45,600 (CP-1)。 比较例 2 After the completion of the dropwise addition, the reaction was kept for 2 hours, and then 30 parts of an initiator solution containing 0.5 g of potassium persulfate was added to the reaction flask, and the mixture was further kept for 1 hour, cooled to room temperature, and added with a NaOH solution to adjust the pH value of 8.2, and the solid content was 32.5 % brown. Transparent liquid with a molecular weight of 45,600 (CP-1). Comparative example 2
在装有温度计、搅拌器、滴液漏斗、氮气导入管和回流冷凝器的玻璃反应器中， 加入 300ml去离子水， 边搅拌边用氮气吹扫反应容器， 并升温至 95°C， 然后将含有 333.6g(a-l , 0.05mol)、 28.8g(b-l , 0.4mol)、 16.25g (d-1 , 0.125mol)、水 300份和 3.4g 巯基丙酸相混， 搅拌制成均匀的单体水溶液， 将其滴加入反应器， 滴加时间为 4h， 并同时滴加 100份含有 1.3 g过硫酸钾的引发剂溶液， 滴加时间约 4 h， 滴加完毕后 保温反应 2h， 再向反应瓶内补加 30份含有 0.5 g过硫酸钾的引发剂溶液， 并继续保 温 lh， 冷却至室温加碱溶液调节 pH值为 8.2， 固含量为 33.2%棕色透明液体， 分子 量为 48,000 (CP-2) o 比较例 3  In a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, 300 ml of deionized water was added, and the reaction vessel was purged with nitrogen while stirring, and the temperature was raised to 95 ° C, and then It contains 333.6g (al, 0.05mol), 28.8g (bl, 0.4mol), 16.25g (d-1, 0.125mol), 300 parts of water and 3.4g of mercaptopropionic acid, and is stirred to form a uniform aqueous monomer solution. , dropping it into the reactor, adding time to 4h, and simultaneously adding 100 parts of initiator solution containing 1.3 g of potassium persulfate, adding time for about 4 h, after the completion of the addition, the reaction was kept for 2 h, and then the reaction bottle was further Add 30 parts of initiator solution containing 0.5 g of potassium persulfate, continue to keep for 1 h, cool to room temperature, add alkali solution to adjust pH 8.2, solid content is 33.2% brown transparent liquid, molecular weight is 48,000 (CP-2) o Comparative Example 3
在装有温度计、搅拌器、滴液漏斗、氮气导入管和回流冷凝器的玻璃反应器中， 加入 100ml去离子水， 边搅拌边用氮气吹扫反应容器， 并升温至 95°C， 然后将含有 104g(a-5，0.05mol)、28.8g(b-l，0.4mol)、14.5g(c-l，0.075mol)、16.25g (d-l， 0.125mol)、 水 200份和 3.4g巯基丙酸相混， 搅拌制成均匀的单体水溶液， 将其滴加入反应器， 滴加时间为 4h，并同时滴加 100份含有 1.3 g过硫酸钾的引发剂溶液，滴加时间约 4 h， 滴加完毕后保温反应 2h， 再向反应瓶内补加 30份含有 0.5 g过硫酸钾的引发剂 溶液， 并继续保温 lh， 冷却至室温加碱调节 pH值为 8.2， 固含量为 27.5 %棕色透明 液体， 分子量为 31,000 (CP-3) o 表 2 In a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, 100 ml of deionized water was added, and the reaction vessel was purged with nitrogen while stirring, and the temperature was raised to 95 ° C, and then Containing 104g (a-5, 0.05mol), 28.8g (bl, 0.4mol), 14.5g (cl, 0.075mol), 16.25g (dl, 0.125mol), 200 parts of water and 3.4g of mercaptopropionic acid, Stir to make a uniform aqueous monomer solution, drop it into the reactor, add dropwise for 4h, and simultaneously add 100 parts of initiator solution containing 1.3 g of potassium persulfate, add about 4 times. h, after the completion of the addition, the reaction was kept for 2 h, and then 30 parts of an initiator solution containing 0.5 g of potassium persulfate was added to the reaction flask, and the mixture was further kept for 1 hour, cooled to room temperature, and alkali was added to adjust the pH to 8.2, and the solid content was 27.5. % brown transparent liquid, molecular weight 31,000 (CP-3) o Table 2
Figure imgf000013_0001
应用例 1
Figure imgf000013_0001
Application example 1
采用小野田 525R.R II水泥， 砂为标准砂， 配合比水泥 450g， 标准砂 1350g， 水 180g。表 3中列出了各种共聚物对水泥砂浆的流动度保持能力、凝结时间和胶砂 强度的影响， 由表 3可见， 本发明的聚羧酸类混凝土超塑化剂的不仅提高了砂浆的 流动度保持能力， 同时促进了水泥早期水化， 提高了水泥基材料的早期力学性能。 相比之下， 短链聚合物如 CP-3以及未添加阳离子单体的聚合物 CP-2的早期强度 偏低， 而未使用羟基酯类单体的 CP-1 的保坍能力比较差， 难以满足混凝土的泵送 的要求。 Use Onoda 525R.R II cement, sand as standard sand, blending ratio 450g, standard sand 1350g, water 180g. Table 3 lists the effects of various copolymers on the fluidity retention ability, the setting time and the strength of the cement mortar. As can be seen from Table 3, the polycarboxylate concrete superplasticizer of the present invention not only improves the mortar. of The fluidity retention ability promotes the early hydration of cement and improves the early mechanical properties of cement-based materials. In contrast, the early strength of short-chain polymers such as CP-3 and polymer CP-2 without added cationic monomer is low, while CP-1 without hydroxyester monomer has poor retention ability. It is difficult to meet the pumping requirements of concrete.
表 3  table 3
水泥凝结时间  Cement setting time
紗浆流动度匪 24h 抗压 ¾  Yarn fluidity 匪 24h Compression 3⁄4
羅 /%  Luo /%
度 /MPa  Degree / MPa
初始 30ϋ«ίϊ - Initial 30ϋ«ίϊ -
ΡΕ-1 0.20 210 203 3; ί2 4:36 41.2 ΡΕ-1 0.20 210 203 3; ί2 4:36 41.2
FE-2 0.20 202 2i0 3; ί8 4:40 40,2  FE-2 0.20 202 2i0 3; ί8 4:40 40,2
ΡΕ~3 0,20 200 20 ί 3:02 4:2S 2.S  ΡΕ~3 0,20 200 20 ί 3:02 4:2S 2.S
ΡΕ-4 0.20 198 190 3:15 4-35 39.S  ΡΕ-4 0.20 198 190 3:15 4-35 39.S
ΡΕ-5 0.20 1 S "iSS 3: 10 4 0 38.5  ΡΕ-5 0.20 1 S "iSS 3: 10 4 0 38.5
CP- 1 0,20 18? 132 3；20 4:45 36,4  CP-1 0,20 18? 132 3;20 4:45 36,4
CP-2 0.20 1S5 175 4；25 5；25 29 5  CP-2 0.20 1S5 175 4;25 5;25 29 5
CP-3 0、20 220 4:38 52 26. S 应用例 2  CP-3 0, 20 220 4:38 52 26. S Application 2
表 4列出了各种共聚物对混凝土减水率、 含气量以及抗压强度的影响， 试验结 果表明， 本发明的聚羧酸类混凝土超塑化剂具有优异的分散性能， 且可以显著的提 高混凝土的早期强度， 根据试验结果， 3d抗压强度相对基准提高 160〜200%， 28d 的抗压强度可增加 50〜65%， 同时在低温环境下增强效果显著， 在 5°C低温环境下， Id抗压强度提高 270〜350%， 可见， 掺本发明的聚羧酸类混凝土超塑化剂的混凝土 的抗压强度不仅具有相当高的早期强度， 其后期强度亦有大幅度提高， 且不断稳定 增长。  Table 4 lists the effects of various copolymers on concrete water reduction rate, gas content and compressive strength. The test results show that the polycarboxylate concrete superplasticizer of the present invention has excellent dispersing properties and can be remarkable. According to the test results, the 3d compressive strength is increased by 160~200% relative to the standard, the compressive strength of 28d can be increased by 50~65%, and the reinforcing effect is remarkable in low temperature environment, at 5°C low temperature environment. , Id compressive strength increased by 270~350%, it can be seen that the compressive strength of the concrete mixed with the polycarboxylate concrete superplasticizer of the invention not only has a relatively high early strength, but also has a large increase in late strength, and Constantly growing steadily.
表 4  Table 4
_m.  _m.
里 ： 减水率 /
Figure imgf000014_0001
運 ： 抗压强度 （MPa) Lane: Water reduction rate /
Figure imgf000014_0001
Transportation: Compressive strength (MPa)
编号  Numbering
/ % / ld (5°C) 3d(20°C) 28d(20°C) 基准 - 2.0 1.6 23.5 54.1  / % / ld (5°C) 3d (20°C) 28d (20°C) Benchmark - 2.0 1.6 23.5 54.1
PE-1 0.20 29.5 2.2 6.8 67.7 85.4  PE-1 0.20 29.5 2.2 6.8 67.7 85.4
PE-2 0.20 27.8 2.3 6.4 65.8 87.8 PE-3 0.20 28.0 2.5 7.2 70.5 89.2 PE-2 0.20 27.8 2.3 6.4 65.8 87.8 PE-3 0.20 28.0 2.5 7.2 70.5 89.2
PE-4 0.20 27.1 2.2 5.9 60.6 81.2  PE-4 0.20 27.1 2.2 5.9 60.6 81.2
PE-5 0.20 26.5 2.5 6.5 68.5 86.0  PE-5 0.20 26.5 2.5 6.5 68.5 86.0
CP-2 0.20 25.0 2.4 3.9 40.2 73.8  CP-2 0.20 25.0 2.4 3.9 40.2 73.8
CP-3 0.20 29.2 3.0 3.2 38.6 70.2  CP-3 0.20 29.2 3.0 3.2 38.6 70.2
应用例 3 Application example 3
预制构件的生产过程提出了泵送的要求， 要求在现有管桩配合比基本不变的情 况下实现大流态混凝土的生产， 同时采用比较成熟的蒸汽养护制度提高构件的早期 强度。 试验配合比水泥： 水： 砂： 石 =440:135:646:1100。 要求混凝土出机坍落度大 于 180mm，扩张度大于 450mm，且工作性能至少要保持 30min。蒸养强度是指 80-90 °C养护 4h后的脱模强度， 压蒸强度为 IMPa压力下， 养护 4h的抗压强度。  The production process of prefabricated components puts forward the requirements of pumping, and requires the production of large fluid concrete in the case where the existing pipe pile mix ratio is basically unchanged. At the same time, the relatively mature steam curing system is adopted to improve the early strength of the components. Test mix ratio cement: Water: Sand: Stone = 440: 135: 646: 1100. The concrete exit is required to be greater than 180mm, the expansion is greater than 450mm, and the working performance must be at least 30min. The steaming strength refers to the demolding strength after curing at 80-90 °C for 4 hours, and the compressive strength is under the pressure of IMPa, and the compressive strength is maintained for 4 hours.
试验结果见表 5,本发明的聚羧酸类混凝土超塑化剂可以显著提高混凝土的坍落度保 持能力， 能够满足泵送的要求， 且能够提高蒸汽养护和压蒸条件下混凝土的抗压强 度， CP-1中没有羟基酯类共聚单体， 使 The test results are shown in Table 5. The polycarboxylate concrete superplasticizer of the present invention can significantly improve the slump retention ability of the concrete, can meet the pumping requirements, and can improve the compressive strength of the concrete under steam curing and steaming conditions. Strength, no hydroxyl ester comonomer in CP-1,
得混凝土的保坍能力严重不足， CP-2中没有引入阳离子基团， 混凝土的抗压强度明 显降低， 而 CP-3 采用较短侧链聚醚共聚物， 混凝土的蒸养和压蒸强度都远低于采 用长侧链的共聚物。 The concrete retaining capacity is seriously insufficient. No cationic groups are introduced in CP-2, and the compressive strength of concrete is significantly reduced. CP-3 uses a shorter side chain polyether copolymer, and the steaming and steaming strength of concrete are both Far less than copolymers with long side chains.
表 5  table 5
坍藩度 /扩展度《«« 抗压强度 MPa  坍藩 degree / expansion "«« compressive strength MPa
编号  Numbering
初始 30inia 蒸养 压蒸  Initial 30inia steaming
PE- 1 0.25 2, 1 200/459 195/460 46.8 SS.5  PE- 1 0.25 2, 1 200/459 195/460 46.8 SS.5
0.26 2,3 195/460 203//46S 47.2 89.3  0.26 2,3 195/460 203//46S 47.2 89.3
PE-3 O 25 - ! 92/455 19iV456 50.S 90.8  PE-3 O 25 - ! 92/455 19iV456 50.S 90.8
FE- 0.26 2. 188/456 193/460 45.9 87.1  FE- 0.26 2. 188/456 193/460 45.9 87.1
PE-5 0,27 2.4 205/470 200 465 S. 90,4  PE-5 0,27 2.4 205/470 200 465 S. 90,4
CP-1 190/465 i4 3 44.5 82,3  CP-1 190/465 i4 3 44.5 82,3
CP-2 0^2 2.6 195/472 185/438 38 '2 70.5  CP-2 0^2 2.6 195/472 185/438 38 '2 70.5
CP-3 <K25 2,8 205/462 200/460 32.5 68,6  CP-3 <K25 2,8 205/462 200/460 32.5 68,6

Claims

权利要求书 claims
1、 一种混凝土预制构件用超塑化剂， 其特征在于由单体 a、 单体 b、 单体 c 和单体 d在水性介质中发生自由基共聚反应后加碱性化合物中和制备而成，单体 a:单体 b:单体 c:单体 d的摩尔比为 1.0:5.0-16.0: 1.0-4.0:2.0-6.0； 1. A superplasticizer for precast concrete components, which is characterized in that it is prepared by neutralizing monomer a, monomer b, monomer c and monomer d through free radical copolymerization in an aqueous medium and then adding an alkaline compound. into, the molar ratio of monomer a:monomer b:monomer c:monomer d is 1.0:5.0-16.0:1.0-4.0:2.0-6.0;
上述单体 a用通式 （1 ) 表示： The above monomer a is represented by the general formula (1):
Ri Ri
H2〇 C (1) H 20C (1)
c=o c=o
O— (AO)nR2 O—(AO)nR 2
通式 （1 ) 中！^为 H或甲基， R2是 H或 1~4个碳原子的烷基； AO为 2-4 个碳原子的氧化烯基或两种以上的这种氧化烯基任意比例的混合物； n为 AO的 平均加成摩尔数， 是 100〜300的整数； （AO) n是均聚、 无规共聚、 二嵌段或 多嵌段共聚结构； In general formula (1)! ^ is H or methyl, R 2 is H or an alkyl group of 1 to 4 carbon atoms; AO is an oxyalkylene group of 2 to 4 carbon atoms or a mixture of two or more such oxyalkylene groups in any proportion; n is the average number of added moles of AO, which is an integer from 100 to 300; (AO) n is a homopolymer, random copolymer, diblock or multi-block copolymer structure;
上述单体 b用通式 （2) 表示： The above monomer b is represented by the general formula (2):
Figure imgf000016_0001
Figure imgf000016_0001
0 0
通式 （2) 中 R3是 H或甲基， R4是 H氢原子或- C-OM， M为 H、 碱金属离 子、 碱土金属离子、 铵离子或有机胺基团； In general formula (2), R3 is H or methyl, R4 is H hydrogen atom or -C-OM, M is H, alkali metal ion, alkaline earth metal ion, ammonium ion or organic amine group;
单体 c是阳离子单体， 采用由通式 （3 ) 所表示物质：
Figure imgf000016_0002
 Monomer c is a cationic monomer, and a substance represented by general formula (3) is used:
Figure imgf000016_0002
其中： R5为 H或甲基， R6、 R7、 R8均独立代表 15或 ~ 。的烷基； Among them: R 5 is H or methyl, R 6 , R 7 , R 8 all independently represent 15 or ~. of alkyl;
X F、 Cl、 Br或 I; X F, Cl, Br or I;
A为 O或 NH; A is O or NH;
P是 1〜3的正整数； P is a positive integer from 1 to 3;
单体 d是羟基酯类单体， 采用由通式 （4) 所表示物质： Monomer d is a hydroxyester monomer, which is represented by the general formula (4):
Ri Ri
H2C^=C—— COOR9 ( 4) 通式 （4) 中！^同通式 （1)， R9表示为 -(CH2)xOH， x=2〜10的正整数。 H 2 C^=C—— COOR 9 (4) In general formula (4)! ^Same as general formula (1), R 9 is expressed as -(CH 2 ) x OH, x=a positive integer from 2 to 10.
2、 如权利要求 1所述的混凝土预制构件用超塑化剂， 其特征在于通式 （1 ) 表示的单体 a为聚亚烷基二醇单（甲基）丙烯酸酯单体时， 是由烷氧基聚亚烷基 二醇与 （甲基） 丙烯酸或与 （甲基）丙烯酸酐的酯化合成物； 或为 （甲基）丙烯 酸羟烷基酯与环氧乙烷、环氧丙烷、环氧丁烷至少一种物质的加成物， 这些单体 单独使用或以两种以上成份以任意比例的混合物形式使用。 2. The superplasticizer for precast concrete components according to claim 1, characterized in that when the monomer a represented by the general formula (1) is a polyalkylene glycol mono(meth)acrylate monomer, it is Esterification synthesis of alkoxypolyalkylene glycol and (meth)acrylic acid or (meth)acrylic anhydride; or hydroxyalkyl (meth)acrylate and ethylene oxide or propylene oxide , the adduct of at least one substance butylene oxide, these monomers are used alone or in the form of a mixture of two or more components in any proportion.
3、 如权利要求 1所述的混凝土预制构件用超塑化剂， 其特征在于通式 （2) 表示的单体 b为不饱和羧酸， 选自丙烯酸、 甲基丙烯酸、 马来酸， 或这些不饱和 羧酸的单价金属盐、 二价金属盐、铵盐或有机胺盐， 这些单体单独使用或以两种 以上任意比例的混合物形式使用。 3. The superplasticizer for precast concrete components according to claim 1, characterized in that the monomer b represented by the general formula (2) is an unsaturated carboxylic acid, selected from acrylic acid, methacrylic acid, maleic acid, or These monovalent metal salts, divalent metal salts, ammonium salts or organic amine salts of unsaturated carboxylic acids can be used alone or in a mixture of two or more types in any proportion.
4、 如权利要求 1所述的混凝土预制构件用超塑化剂， 其特征在于通式 （3 ) 表示的阳离子单体 c选自甲基丙烯酰氧乙基三甲基氯化铵，甲基丙烯酰氧乙基二 甲基苄基氯化铵， 甲基丙烯酰氧丙基三甲基氯化铵， 甲基丙烯酰氧丙基二甲基苄 基氯化铵， 丙烯酰氧乙基三甲基氯化铵， 丙烯酰氧乙基二甲基苄基氯化铵， 丙烯 酰胺基丙基三甲基氯化铵， 丙烯酰胺基丙基二甲基苄基氯化铵， 甲基丙烯酰胺基 丙基三甲基氯化铵或甲基丙烯酰胺基丙基二甲基苄基氯化铵，这些单体单独使用 或以两种以上任意比例的混合物形式使用。 4. The superplasticizer for precast concrete components according to claim 1, characterized in that the cationic monomer c represented by the general formula (3) is selected from the group consisting of methacryloyloxyethyltrimethylammonium chloride, methyl Acryloyloxyethyldimethylbenzylammonium chloride, Methacryloyloxypropyltrimethylammonium chloride, Methacryloyloxypropyldimethylbenzylammonium chloride, Acryloyloxyethyltrimonium chloride Methyl ammonium chloride, acryloyloxyethyldimethylbenzyl ammonium chloride, acrylamidopropyltrimonium chloride, acrylamidopropyldimethylbenzyl ammonium chloride, methacrylamide Propyltrimethylammonium chloride or methacrylamidopropyldimethylbenzylammonium chloride, these monomers are used alone or in the form of a mixture of two or more in any proportion.
5、 如权利要求 1所述的混凝土预制构件用超塑化剂， 其特征在于通式 （4) 表示的羟基酯类单体 d是（甲基）丙烯酸羟烷基酯， 选自丙烯酸羟乙酯、 甲基丙 烯酸羟乙酯、丙烯酸羟丙酯或甲基丙烯酸羟丙酯， 这些单体单独使用或以两种以 上任意比例的混合物形式使用。 5. The superplasticizer for precast concrete components according to claim 1, characterized in that the hydroxyester monomer d represented by the general formula (4) is hydroxyalkyl (meth)acrylate, selected from hydroxyethyl acrylate. Ester, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate, these monomers are used alone or in a mixture of two or more in any proportion.
6、 如权利要求 1所述的混凝土预制构件用超塑化剂， 其特征在于采用自由 基水溶性引发剂引发自由基共聚反应， 引发剂选自水溶性过硫酸铵、 过硫酸钾、 过硫酸钠或过氧化氢， 或其中两种以上任意比例的混合物， 其用量是&、 b、 c、 d四种单体总摩尔数的 1.0〜6.0 %。 6. The superplasticizer for precast concrete components according to claim 1, characterized in that a free radical water-soluble initiator is used to initiate the free radical copolymerization reaction, and the initiator is selected from water-soluble ammonium persulfate, potassium persulfate, and persulfate. Sodium or hydrogen peroxide, or a mixture of two or more of them in any proportion, the dosage is 1.0 to 6.0% of the total moles of the four monomers b, b, c, and d.
7、 如权利要求 1所述的混凝土预制构件用超塑化剂， 其特征在于利用聚合 链转移剂选择控制共聚反应形成的共聚物的分子量，聚合链转移剂在共聚过程中 的用量 a、 b、 c、 d四种单体总摩尔的 1.0〜5.0 %。 7. The superplasticizer for concrete prefabricated components according to claim 1, characterized in that a polymer chain transfer agent is used to selectively control the molecular weight of the copolymer formed by the copolymerization reaction, and the dosage of the polymer chain transfer agent in the copolymerization process is a and b. , 1.0~5.0% of the total mole of the four monomers c and d.
8、 如权利要求 1所述的混凝土预制构件用超塑化剂， 其特征在于共聚反应 时单体总质量浓度控制在 25〜50 %， 反应时间控制在 5〜10小时。 8. The superplasticizer for concrete prefabricated components as claimed in claim 1, characterized in that during the copolymerization reaction, the total mass concentration of monomers is controlled at 25 to 50%, and the reaction time is controlled at 5 to 10 hours.
9、 如权利要求 1所述的混凝土预制构件用超塑化剂， 其特征在于单体和引 发剂溶液采取分开同时滴加的方式， 单体混合液和引发剂滴加时间控制在 2.0〜 6.0小时， 共聚反应在 60〜100°C下进行。 9. The superplasticizer for concrete prefabricated components according to claim 1, characterized in that the monomer and initiator solutions are dropped separately and simultaneously, and the monomer mixture and initiator dripping time are controlled at 2.0~ 6.0 hours, the copolymerization reaction is carried out at 60~100°C.
10、如权利要求 1所述的混凝土预制构件用超塑化剂， 其特征在于共聚反应 结束后， 向反应产物中加入碱性化合物调整 pH值为 6.0〜10.0， 所述的碱性化合 物选择氨水、 碳酸氢氨、 有机胺、 单价金属或二价金属的氢氧化物或其碳酸盐。 10. The superplasticizer for precast concrete components according to claim 1, characterized in that after the copolymerization reaction is completed, an alkaline compound is added to the reaction product to adjust the pH value to 6.0~10.0, and ammonia water is selected as the alkaline compound. , ammonia bicarbonate, organic amines, hydroxides of monovalent metals or divalent metals or their carbonates.
11、如权利要求 1所述的混凝土预制构件用超塑化剂， 其特征在于其重均分 子量在 20,000— 100,000。 11. The superplasticizer for precast concrete components according to claim 1, characterized in that its weight average molecular weight is between 20,000 and 100,000.
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