WO2013113152A1 - Emulsion de copolymère d'acétate de vinyle-éthylène et composition de polymère-ciment imperméable à l'eau à base de celle-ci - Google Patents

Emulsion de copolymère d'acétate de vinyle-éthylène et composition de polymère-ciment imperméable à l'eau à base de celle-ci Download PDF

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Publication number
WO2013113152A1
WO2013113152A1 PCT/CN2012/070794 CN2012070794W WO2013113152A1 WO 2013113152 A1 WO2013113152 A1 WO 2013113152A1 CN 2012070794 W CN2012070794 W CN 2012070794W WO 2013113152 A1 WO2013113152 A1 WO 2013113152A1
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Prior art keywords
vinyl acetate
polymer cement
emulsion
cement waterproof
ethylene
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PCT/CN2012/070794
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English (en)
Inventor
Linlin MIAO
Xiaodong Zhao
Meixiang ZHANG
Yifang SHI
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Celanese International Corporation
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Filing date
Publication date
Application filed by Celanese International Corporation filed Critical Celanese International Corporation
Priority to CN201280068605.3A priority Critical patent/CN104093679A/zh
Priority to PCT/CN2012/070794 priority patent/WO2013113152A1/fr
Publication of WO2013113152A1 publication Critical patent/WO2013113152A1/fr

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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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials

Definitions

  • Vinyl acetate-ethylene copolymer emulsion and polymer cement waterproof composition based on the same
  • the present invention relates to a vinyl acetate-ethylene copolymer emulsion and a polymer cement waterproof composition based on the same. More specifically, the present invention relates to a vinyl acetate-ethylene copolymer emulsion based cement waterproof composition with high filler loading. The present invention also relates to processes for preparing the vinyl acetate-ethylene copolymer emulsion and the polymer cement waterproof composition, and uses thereof.
  • Polymer cement waterproof composition is flexible waterproof slurry which is prepared by using cement and fine aggregate as main components, polymer and additives etc. as modifiers in suitable ratio.
  • the polymer cement waterproof composition should have a relative high weight ratio of solid part to liquid part, normally about 2.7:1 to 4:1 .
  • Anti-water permeability and bonding strength of a polymer cement waterproof composition are the main factors for the end users when choosing suitable polymer cement waterproof composition.
  • the polymer cement waterproof composition is dominated by styrene acrylic emulsion.
  • the waterproof slurry thus obtained is odorous, while a more environmentally friendly and easily applied product is required by the market;
  • the storage life of waterproof slurry obtained by mixing styrene acrylic emulsion with cement is short, typically less than about 45 minutes, while a longer storage life product is required in the on-site application;
  • the price of styrene acrylic emulsion is increasing in the last two years for the reason that the cost of raw materials increases and the supply of raw materials is unstable. Therefore the manufactures are seeking for a cheaper alternative for the styrene acrylic emulsion.
  • CN19981 1 1098 discloses a waterproof glue.
  • said waterproof glue has a lower solid/liquid weight ratio of about 1 :1 , which is far less than 2.7:1 to 4:1 as required in waterproof slurry field.
  • CN200610015818 discloses a two components water-proof paint for roofing which is based on polyacrylic emulsion and vinyl acetate-ethylene emulsion.
  • the two components water-proof paint is not targeted for mixing with cement, and uses polyacrylic emulsion as essential component.
  • CN200610165204 discloses a vinyl acetate-ethylene copolymer emulsion.
  • the vinyl acetate-ethylene copolymer emulsion is used as adhesive for wood processing and package, not for waterproof application during construction by mixing with cement.
  • KR200928065A discloses a polymer-modified mortar composition used for waterproof coating during construction which is based on ethylene vinyl acetate copolymer and/or styrene acrylic copolymer.
  • the polymer-modified mortar composition has a low solid/liquid weight ratio, and is not used for mixing with cement.
  • the polymer cement waterproof composition of the present invention has excellent anti-permissive pressure, bonding strength, workability and long-time storage stability, while the preparation cost thereof is decreased as compared to traditional styrene acrylic emulsion based cement composition.
  • the inventive vinyl acetate-ethylene copolymer emulsion has the following advantages: high filler loading, low production cost, unodorous smell, good workability, high bonding strength and long-time storage stability.
  • one object of the present invention is to provide a vinyl acetate-ethylene copolymer emulsion.
  • Another object of the present invention is to provide a process for preparing said vinyl acetate-ethylene copolymer emulsion.
  • Still another object of the present invention is to provide a use of the vinyl acetate-ethylene copolymer emulsion for polymer cement waterproof composition.
  • one object of the present invention is to provide a high filler loaded polymer cement waterproof composition.
  • Another object of the present invention is to provide a process for preparing said high filler loaded polymer cement waterproof composition.
  • Still another object of the present invention is to provide a use of the high filler loaded polymer cement waterproof composition.
  • a vinyl acetate-ethylene copolymer-based emulsion for polymer cement waterproof composition wherein the copolymer comprises, based on the total weight of the copolymer:
  • copolymer-based emulsion is formed by emulsion polymerization of the monomers in the presence of about 1 -5pphm of a surfactant and about 0-3pphm of a polymeric protective colloid as emulsifier / protective colloid.
  • the monomers used in emulsion polymerization can be composed of about 70-95pphm of vinyl acetate, about 5-30pphm of ethylene and about 0-10pphm of other comonomers or functional monomers.
  • examples of other comonomers or functional monomers suitable for the present invention include, but not limited to, one or more selected from the group of: vinyl esters of polyacid; acrylates; methacrylates; maleate
  • each of Ri and R2 is hydrogen or alkyl group, provided that the total carbon atom number of Ri and R2 is from 0 to
  • R 3 is hydrogen or alkyl group with 1 to 16 carbon atom(s);
  • R 4 is hydrogen or alkyl group with 1 to 16 carbon atom(s);
  • each of R5 and R6 is alkyl group with 1 to 16 carbon atom(s); acrylic acid; methacrylic acid; maleic acid; maleic anhydride; fumaric acid; crotonic acid; itaconic acid; sodium vinylsulfonate; mono-sodium 2-methyl-2-[(1 -oxo-2-propenyl)amino]-1 -propylsulfonate; methacrylate ethyl trimethyl ammonium chloride; acrylamide; hydroxymethylacrylamide; hydroxyethylacrylamide; hydroxypropylacrylamide ; vinyltrimethoxysilane; vinyltriethoxysilane; vinyltri(2-methoxyethoxy)silane; methylacryloxypropyltrimethoxysilane; ethylene glycol acrylate; propylene glycol acrylate; glycidyl acrylate; diallyl maleate; diallyl phthalate; triallyl cyanurate; allyl me
  • anionic surfactants suitable for the present invention include, but not limited to: alkylsulfates, alkylsulfonates, alkyl benzenesulfonates, alkyl polyoxyethylene ether sulfates, alkylpolyoxyethylene-propylene ether sulfates, sodium fatty alcohol succinic acid mono ester sulfonates, disodium fatty alcohol polyoxyethylene ether sulfosuccinates, disodium fatty alcohol polyoxyethylene-propylene ether sulfosuccinates, alkylpolyoxyethylene phosphates, alkylpolyoxyethylene-propylene phosphates and alkali metal salts of fatty acids.
  • anionic surfactants suitable for the present invention include, but not limited to: sodium dodecylbenzene sulfonate, sodium dodecylsulfonate, sodium dodecylsulfate, disodium dodecyldiphenylether sulfonate, octadecyl sulfosuccinic acid and sodium dioctylsulfosuccinate.
  • nonionic surfactants suitable for the present invention include, but not limited to: linear alkyl alcohol polyoxyethylene ethers, linear alkyl alcohol polyoxyethylene-propylene ethers, branched alkyl alcohol polyoxyethylene ethers, branched alkyl alcohol polyoxyethylene-propylene ethers, fatty acid polyoxyethylenemonoesters, fatty acid polyoxyethylene-propylenemonoesters.
  • nonionic surfactants suitable for the present invention include, but not limited to: isometric tridecyl alcohol polyoxyethylene monoether, cetyl alcohol polyoxyethylenemonoether, octadecyl alcohol polyoxyethylenemonoether a-lauroyl-w-Hydroxylpolyoxyethylene, etc., wherein the EO numbers of polyoxyethylene section are chosen according to the desired HLB value of the surfactant, typically in the range of about 20 to 40.
  • the surfactant can be used in an amount of about 1 -5 pphm, preferably about 2-5 pphm, more preferably about 2-4 pphm.
  • the said polymeric protective colloid can be selected from partially hydrolyzed polyvinyl alcohols, cellulose ethers and polyvinyl pyrrolidone.
  • polymeric protective colloids suitable for the present invention include, but not limited to: polyvinyl alcohols having a degree of alcoholysis of about 75 to 95% and a degree of polymerization of about 200 to 4000, most preferably polyvinyl alcohols having a degree of alcoholysis of about 80 to 90% and a degree of polymerization of about 200 to 4000.
  • Cellulose ethers as polymeric protective colloid suitable for the present invention include, but not limited to, hydroxymethyl cellulose ether, hydroxyl ethylcellulose ether and hydroxypropyl cellulose ether.
  • the polymeric protective colloid can be used in an amount of about 0-3 pphm, preferably about 0-1 pphm.
  • copolymer-based emulsion is formed by emulsion polymerization of the monomers in the presence of about 1 -5pphm of a surfactant and about 0-3pphm of a polymeric protective colloid as emulsifier / protective colloid,
  • the vinyl acetate-ethylene copolymer emulsion based cement waterproof composition comprises the liquid part and the solid part.
  • the weight ratio of solid part to liquid part is about 2.7:1 to 4:1 , preferably about 2.7:1 to 3.3:1 .
  • the liquid part mainly comprises about 30 to 70% by weight of a vinyl acetate-ethylene copolymer-based emulsion and other common additives, such as wetting dispersing agents, preservatives, defoamers, etc..
  • wetting dispersing agents suitable for the present invention may include, but not limited to, sodium, potassium and ammonium salts-based dispersing agents containing acrylic group(s), or mixtures thereof.
  • wetting dispersing agents commercially available under trade name Hydropalat 5040, SN5027, SN5029, SN5468, Hypropalat3204, Hydropalat3275, can be mentioned.
  • wetting dispersing agents such as Hydropalat5040 can be added in an amount of about 0 to 1 %, preferably about 0.2 to 0.4%, based on the total weight of the composition.
  • preservatives suitable for the present invention may include, but not limited to MIT, BIT, CMIT, bronopol, or mixtures thereof.
  • preservatives commercially available under trade name Rocima 562, ATICIDE MBS, ATICIDE RS, Kathlon LXE, Rocima 523 can be mentioned.
  • preservatives such as Kathlon LXE can be added in an amount of about 0 to 1 %, preferably about 0.1 to 0.2%, based on the total weight of the composition.
  • defoamers suitable for the present invention may include, but not limited to mineral oil, silicon based oil, or mixtures thereof.
  • defoamers commercially available under trade name Foamaster 1 1 1 , Foamaster NXZ, SN470, SN1370, SN1390 can be mentioned.
  • defoamers such as SN1370 can be added in an amount of about 0 to 1 %, preferably about 0.1 to 0.3%, based on the total weight of the composition.
  • additional water may be added to the liquid part of the inventive cement waterproof composition.
  • the said additional water may be added in an amount of about 30 to 70%, preferably about 40 to 60%, based on the total weight of liquid part.
  • the liquid part essentially consists of vinyl acetate-ethylene copolymer-based emulsion, additional water and other common additives. In some non-limiting embodiments of the present invention, the liquid part does not comprise other polymers.
  • the solid part mainly comprises hydraulic cement, filler and regular powder additives.
  • cements suitable for the present invention may include, but not limited to various kinds of portland cements, aluminate cements, sulphoaluminate cements, ferroaluminate cements, fluoaluminate cements, cements having volcanic ash, potential hydraulic materials or other active materials as the main components, or mixtures thereof.
  • portland cement 42.5 can be added in an amount of about 30 to 60%, preferably about 40 to 60%, based on the total weight of the composition.
  • fillers suitable for the present invention may include, but not limited to: particulate fillers prepared by mining and processing of natural minerals as raw materials, such as river (sea) sands, silica, silicates, carbonates and carbides; or some kinds of industrial active fillers commonly used in cement products, such fly ash, slag, volcanic ash, mineral powder, silica fume, etc..
  • particulate fillers prepared by mining and processing of natural minerals as raw materials, such as river (sea) sands, silica, silicates, carbonates and carbides
  • industrial active fillers commonly used in cement products, such fly ash, slag, volcanic ash, mineral powder, silica fume, etc.
  • 70-40 mesh quartz sand can be added in an amount of about 30 to 70%, preferably about 40 to 60%, based on the total weight of the solid part.
  • powder additives suitable for the present invention may include, but not limited to those commonly used in cement products, such as defoamers, water reducing agents, etch.. In some non-limiting embodiments of the present invention, the powder additives can be added in an amount of about 0 to 2%, based on the total weight of the composition.
  • the conventional additives added to the aqueous phase include those known in the art which are useful in the emulsion polymerization system or improve the stability or pot life of the final emulsion. For example, those additives can be redox reaction promoter, pH adjusting agents, defoamers, fungicides, chelating agents, and the like.
  • the emulsion polymerization is conducted in the presence of a redox initiator.
  • the oxidizing agent and reducing agent used to make up of the redox initiator include, but not limited to water soluble oxidizing agents and reducing agents known in the art.
  • oxidizing agents and reducing agents suitable for the present invention may include, but not limited to, ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl peroxide, sodium formaldehyde-sulfoxylate, disodium 2-hydroxyl-2-sulfinatoacetate, ascorbic acid, erythorbic acid, sodium bisulfite, sodium sulfite, sodium metabisulfite, etc..
  • the oxidizing agent and reducing agent can be each added in an amount of about 0.05 to 5 pphm.
  • a process for preparing the vinyl acetate-ethylene copolymer-based emulsion comprises emulsion polymerizing a monomeric composition comprising:
  • a process for preparing the polymer cement waterproof composition comprises
  • the vinyl acetate-ethylene copolymer-based emulsion can be obtained by emulsion polymerization of vinyl acetate, ethylene and other comonomers or functional monomers, in the presence of a surfactant and a polymeric protective colloid as emulsion system.
  • the emulsion generally can have a solid content of about 40 to 70%.
  • the emulsion polymerization process is well known in the art.
  • the emulsion may be obtained by the following steps: forming an aqueous phase by adding surfactant and protective colloid, as emulsifier, and other conventional additives into water; feeding the aqueous phase to a reactor under slow stirring; evacuating the reactor under vacuum and purging with nitrogen at least three times for removing any air; raising the temperature of the reactor to about 40-70°C, then increasing the speed of stirring, adding to the reactor part of the vinyl acetate monomer or mixture of the vinyl acetate monomer and the other comonomers or functional monomers, together with part of ethylene gas; after the pressure of the reactor becomes constant, adding dropwise oxidizing agent and reducing agent, as redox initiator, so that polymerization takes place, with increasing of temperature; adding remaining monomers when the temperature of the reactor reaches a predetermined value, about 50-90°C, until the consumption of the monomers.
  • the temperature of the reactor was controlled at about 50-90°C during the emulsion polymerization process. After completion of polymerization, the reactor is cooled to selected temperature, about 50-70°C, and the polymerization product therein was transferred to a post-treatment reactor, while the unreacted ethylene gas was discharged as exhaust gas. Subsequently, certain amount of oxidizing agent and reducing agent were added to the post-treatment reactor, to reduce the amount of residual monomers by further initiating the polymerization of residual monomers. Alternatively, the amount of residual monomers can be further reduced by extraction of water vapor. Finally, the emulsion parameters of the copolymer-based emulsion thus obtained can be adjusted by feeding with additional water and/or other conventional additives. The emulsion thus obtained can have a solid content of about 40 to 70%, most commonly about 50 to 60%.
  • a vinyl acetate-ethylene copolymer-based emulsion was obtained according to the above mentioned formulation and process, and the vinyl acetate-ethylene copolymer-based emulsion thus obtained can be used to formulate the polymer cement waterproof composition.
  • the polymer cement waterproof composition may be obtained by the following steps: forming an liquid part by adding required additives, including defoamers, preservatives and dispersing agent etc., and then the polymer emulsion to certain amount of water under a stirring rate of about 300rpm for about 5 minutes; forming a solid part by mixing certain amount of cement, filler and some additives under stirring until a uniform mixture was obtained; mixing the liquid part and solid part in specific ratio under stirring to get a homogeneous polymer cement waterproof composition.
  • required additives including defoamers, preservatives and dispersing agent etc.
  • the anti-water permeability of the inventive polymer cement waterproof composition was tested according to anti water permeability test of Chinese Standard GB 23440-2009 after curing 7 days.
  • the anti-water permeability test cannot be carried out on the polymer cement waterproof composition which was prepared by conventional vinyl acetate-ethylene copolymer-based emulsion in similar weight ratio of liquid part to liquid part, since such polymer cement waterproof composition has a high consistency, therefore cannot be applied and tested.
  • the bonding strength of the inventive polymer cement waterproof composition was tested according to Part 7.6.3.1 of Chinese Standard GB23445-2009 after curing 7 days.
  • the bonding strength test cannot be carried out on the polymer cement waterproof composition which was prepared by conventional vinyl acetate-ethylene copolymer-based emulsion in similar weight ratio of liquid part to liquid part, since such polymer cement waterproof composition has a high consistency, therefore cannot be applied and tested.
  • the required anti-permissive pressure and bonding strength of the polymer cement waterproof composition can be varied according to specific application. Typically, the required anti-permissive pressure of the polymer cement waterproof composition is equal to or greater than 0.5MPa, and the required bonding strength of the polymer cement waterproof composition is equal to or greater than 0.7MPa.
  • the anti-water permeability of the inventive polymer cement waterproof composition was tested according to anti water permeability test of Chinese Standard GB 23440-2009 after curing 7 days.
  • a vinyl acetate-ethylene copolymer-based emulsion (Emulsion 1 ) was prepared using the following formulation.
  • Disponil A3065 (Cognis, a.i. 65%) 238.47 g
  • the post-treatment reactor was stirred at a speed of 200 rpm. The solution of sodium metabisulfite was added within 15 mins. Then, the solution of i-butyl peroxide was added within 10 mins. The post-treatment reactor was cooled to 40 °C.
  • the obtained vinyl acetate-ethylene copolymer-based emulsion (Emulsion 1 ) has the following properties:
  • Example 2 A vinyl acetate-ethylene copolymer-based emulsion (Emulsion 2) was prepared using the following formulation.
  • Disponil AFX 3070 (a.i. 70%) 222.42 g
  • the temperature of the reactor reached 52 °C
  • the remaining mixture of vinyl acetate, vinyl silane and glycidyl acrylate was added.
  • the reactor was maintained for 240 mins.
  • the temperature of the reactor was adjusted to 65 °C within 15 mins.
  • the reaction temperature was controlled at 65 °C during the whole polymerization process.
  • the temperature of the reactor reached 60°C
  • the remaining ethylene gas was fed within 150 mins and maintained the maximum pressure of the reactor below 55 bar.
  • the reactor was then cooled from 65 °C to 55 °C.
  • the obtained emulsion was transferred to post-treatment reactor.
  • the post-treatment reactor was stirred at a speed of 200 rpm, and the temperature was set to 50 °C.
  • the solution of sodium metabisulfite was added within 10 mins.
  • the solution of i-butyl peroxide was added within 10 mins.
  • the post-treatment reactor was stirred at a speed of 200 rpm for another 30mins at a temperature of 50°C.
  • the obtained vinyl acetate-ethylene copolymer-based emulsion (Emulsion 2) has the following properties:
  • a vinyl acetate-ethylene copolymer-based emulsion (Emulsion 3) was prepared using the following formulation.
  • Disponil A3065 (Cognis, a.i. 65%) 238.47 g
  • the post-treatment reactor was stirred at a speed of 200 rpm. The solution of sodium metabisulfite was added within 15 mins. Then, the solution of i-butyl peroxide was added within 10 mins. The post-treatment reactor was cooled to 40 °C. [0068] The obtained vinyl acetate-ethylene copolymer-based emulsion (Emulsion 3) has the following properties:
  • a vinyl acetate-ethylene copolymer-based emulsion (Emulsion 4) was prepared using the following formulation.
  • Disponil A3065 (Cognis, a.i. 65%) 238.47 g polyvinyl alcohol (Celvol 504 from Sekisui
  • the post-treatment reactor was stirred at a speed of 200 rpm. The solution of sodium metabisulfite was added within 15 mins. Then, the solution of i-butyl peroxide was added within 10 mins. The post-treatment reactor was cooled to 40 °C.
  • the obtained vinyl acetate-ethylene copolymer-based emulsion (Emulsion 4) has the following properties:
  • 0.2 g SN1370 defoamers and 0.1 g Kathon LXE were added in 59.7g water to get a solution which was stirred at a speed of 400rpm for 2mins.
  • 40g commercially available vinyl acetate-ethylene copolymer-based emulsion (Comparative Emulsion 1 , containing 4.5 pphm polymeric protective colloid and 0.4 pphm surfactant) was added in the solution, which was then stirred at a speed of 400rpm for 5mins. A homogeneous liquid part for polymer cement waterproof composition was obtained.
  • Comparative Example 1 The data of Comparative Example 1 shows that the polymer cement composition prepared by commercially available vinyl acetate-ethylene copolymer-based emulsion (i.e. Comparative Emulsion 1 ) cannot be stirred or coated, therefore cannot be applied in practice.

Abstract

La présente invention porte sur une émulsion de copolymère d'acétate de vinyle-éthylène et sur une composition de polymère-ciment imperméable à l'eau à base de celle-ci. Plus précisément, la présente invention porte sur une composition de ciment imperméable à l'eau à base d'émulsion de copolymère d'acétate de vinyle-éthylène à haute teneur en matière de charge. La présente invention porte également sur des procédés pour la préparation de l'émulsion de copolymère d'acétate de vinyle-éthylène et de la composition de polymère-ciment imperméable à l'eau et sur leurs utilisations.
PCT/CN2012/070794 2012-01-31 2012-01-31 Emulsion de copolymère d'acétate de vinyle-éthylène et composition de polymère-ciment imperméable à l'eau à base de celle-ci WO2013113152A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201280068605.3A CN104093679A (zh) 2012-01-31 2012-01-31 醋酸乙烯酯-乙烯共聚物乳液和基于醋酸乙烯酯-乙烯共聚物乳液的聚合物水泥防水组合物
PCT/CN2012/070794 WO2013113152A1 (fr) 2012-01-31 2012-01-31 Emulsion de copolymère d'acétate de vinyle-éthylène et composition de polymère-ciment imperméable à l'eau à base de celle-ci

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PCT/CN2012/070794 WO2013113152A1 (fr) 2012-01-31 2012-01-31 Emulsion de copolymère d'acétate de vinyle-éthylène et composition de polymère-ciment imperméable à l'eau à base de celle-ci

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CN112961521A (zh) * 2021-02-02 2021-06-15 黄生旺 一种地下通道用高耐腐蚀性加固涂料
CN114456658A (zh) * 2022-02-21 2022-05-10 广州市白云化工实业有限公司 密封胶底涂液及其制备方法
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CN107793517A (zh) * 2016-09-07 2018-03-13 中国石油化工股份有限公司 一种制备eva弹性体微乳液的方法
CN111689750B (zh) * 2019-03-13 2021-11-16 唐山东方雨虹防水技术有限责任公司 一种快凝堵漏材料及其制备方法
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CN102173728A (zh) * 2010-12-22 2011-09-07 北京东方雨虹防水技术股份有限公司 一种自愈合型聚合物水泥防水涂料及其制备工艺
CN102167551A (zh) * 2011-01-26 2011-08-31 蔡海军 一种快干强力型有机水硬性粘结料

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WO2018162399A1 (fr) * 2017-03-06 2018-09-13 L. Brüggemann Gmbh & Co. Kg Composition active de façon synergique
KR20190122705A (ko) * 2017-03-06 2019-10-30 엘. 브뤼그만 게엠베하 운트 코 카게 상승작용적으로 활성인 조성물
KR102573741B1 (ko) 2017-03-06 2023-09-01 엘. 브뤼그만 게엠베하 운트 코 카게 상승작용적으로 활성인 조성물
US11753526B2 (en) 2017-03-06 2023-09-12 L. Brüggemann Gmbh & Co. Kg Synergistically active composition
CN111875734A (zh) * 2019-05-02 2020-11-03 大连化学工业股份有限公司 硅改质的乙酸乙烯酯乙烯共聚物
US20200346977A1 (en) * 2019-05-02 2020-11-05 Dairen Chemical Corporation Silicon modified vinyl acetate ethylene copolymers
US20210114930A1 (en) * 2019-05-02 2021-04-22 Dairen Chemical Corporation Silicon modified vinyl acetate ethylene copolymers
CN112961521A (zh) * 2021-02-02 2021-06-15 黄生旺 一种地下通道用高耐腐蚀性加固涂料
CN114456658A (zh) * 2022-02-21 2022-05-10 广州市白云化工实业有限公司 密封胶底涂液及其制备方法
CN114456658B (zh) * 2022-02-21 2023-03-31 广州市白云化工实业有限公司 密封胶底涂液及其制备方法
CN116655329A (zh) * 2023-06-13 2023-08-29 德州科顺建筑材料有限公司 用于制备防水砂浆的组合物、防水砂浆及其制备方法和应用
CN116655329B (zh) * 2023-06-13 2024-02-02 德州科顺建筑材料有限公司 用于制备防水砂浆的组合物、防水砂浆及其制备方法和应用

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