KR101115054B1 - Water Soluble Acrylic Polymer and Cement Mortar Quick Strength Admixture Using the Same - Google Patents
Water Soluble Acrylic Polymer and Cement Mortar Quick Strength Admixture Using the Same Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
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- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
Abstract
본 발명은 수용성 아크릴중합체 및 이를 이용한 시멘트몰탈 급결강도 혼화제에 관한 것으로, 보다 구체적으로는, 아크릴계 모노머와 관능성 모노머 및 공중합 가능한 모노머를 유화 중합하여 제조된 수용성 아크릴중합체와 이를 이용한 시멘트몰탈 급결강도 혼화재에 관한 것이다.The present invention relates to a water-soluble acrylic polymer and a cement mortar fastening strength admixture using the same, and more particularly, to a water-soluble acrylic polymer prepared by emulsion polymerization of an acrylic monomer, a functional monomer and a copolymerizable monomer, and a cement mortar quickening steel using the same. It also relates to a mixed material.
수용성 아크릴중합체, 아크릴계 모노머, 관능성 모노머, 시멘트 혼화제 Water Soluble Acrylic Polymer, Acrylic Monomer, Functional Monomer, Cement Admixture
Description
본 발명은 수용성 아크릴중합체 및 이를 이용한 시멘트몰탈 급결강도 혼화재에 관한 것으로, 보다 구체적으로는, 아크릴계 모노머와 관능성 모노머 및 공중합 가능한 모노머를 유화 중합하여 제조된 수용성 아크릴중합체와 이를 이용한 시멘트몰탈 급결강도 혼화재에 관한 것이다.The present invention relates to a water-soluble acrylic polymer and a cement mortar fastening strength admixture using the same, and more particularly, to a water-soluble acrylic polymer prepared by emulsion polymerization of an acrylic monomer, a functional monomer and a copolymerizable monomer, and a cement mortar quickening steel using the same. It also relates to a mixed material.
일반적으로 콘크리트는 시멘트에 모래, 자갈, 물 및 기타 혼화재료를 첨가하고 시멘트가 물과 반응하여 굳어지는 수화반응을 이용하여 제조되는 것으로서 댐이나 도로포장, 교량 등의 각종 토목공사나 건축용 구조재료의 중심이 되는 재료로서, 설계자나 시공자의 노력에도 불구하고 콘크리트는 시공 후에 균열이 발생하게 되고 이러한 미세균열을 통해 외부의 이산화탄소, 물, 염화물 등이 콘크리트 내부로 침투되면 콘크리트 내의 철근이 부식되어 콘크리트가 붕괴되는 심각한 문제가 발생할 수 있다.Generally, concrete is manufactured by adding sand, gravel, water, and other miscible materials to cement, and using a hydration reaction in which cement reacts with water, and is the center of various civil works such as dams, pavements, bridges, and structural materials for construction. As a material, despite the efforts of designers and builders, concrete is cracked after construction, and when external carbon dioxide, water, chloride, etc. penetrate into the concrete through such microcracks, the steel in the concrete is corroded and the concrete collapses. Serious problems can arise.
따라서, 콘크리트의 미세균열, 열화 등을 방지하기 위하여 시멘트에 물을 첨가한 시멘트 페이스트, 시멘트 페이스트에 쇄골재인 모래를 혼합한 몰타르, 몰타르에 조골재를 혼합한 콘크리트 등과 같은 시멘트 조성물에 내구성이나 강도를 향상시키는 것을 목적으로 하는 시멘트 혼화제가 첨가되며, 시멘트 혼화제는 시멘트 입자에 흡착하여 시멘트 입자가 응집하는 것을 억제하고, 시멘트 조성물의 사용시 분산성을 높이는 작용도 가지게 된다.Therefore, durability and strength are improved in cement compositions such as cement paste in which water is added to cement, mortar mixed with sand as crushed aggregate, and concrete mixed with coarse aggregate in mortar to prevent microcracks and degradation of concrete. A cement admixture for the purpose of adding is added, and the cement admixture has the effect of adsorbing on the cement particles to suppress the aggregation of the cement particles and increasing the dispersibility in the use of the cement composition.
상기 시멘트 혼화제로서는 예를 들어, 나프탈렌계의 시멘트 혼화제나 폴리카르본산계 시멘트 혼화제가 알려져 있는데, 예를 들어, 불포화 카르본산계 단량체와 불포화 폴리알킬렌글리콜에테르계 단량체를 공중합시켜 얻어지는 시멘트 혼화제용 공중합체가 알려져 있다. 이 시멘트 혼화제용 공중합체는 불포화 카르본산계 단량체에 유래하는 카르복실기가 시멘트 입자에 흡착하는 흡착기로 작용하며, 불포화 폴리알킬렌글리콜에테르계 단량체에 유래하는 폴리알킬렌글리콜 쇄가 시멘트 입자를 분산시키는 분산기로서 작용한다.As said cement admixture, the naphthalene cement admixture and the polycarboxylic acid cement admixture are known, for example, the air for cement admixtures obtained by copolymerizing an unsaturated carboxylic acid monomer and an unsaturated polyalkylene glycol ether monomer. Union is known. This copolymer for cement admixtures acts as an adsorber where carboxyl groups derived from unsaturated carboxylic acid monomers adsorb to cement particles, and polyalkylene glycol chains derived from unsaturated polyalkylene glycol ether monomers disperse the cement particles. Act as.
또한, 국제공개 WO 2006/011182에는 불포화기를 가지는 폴리아미드폴리아민알킬렌옥사이드 부가물, 2종 이상의 폴리알킬렌글리콜에스테르를 포함하는 수용성 양성형 공중합체로서, 콘크리트 조성물에 혼련했을 때 경시적으로 분산성능이 증가하고, 콘크리트 점성의 저감에 뛰어난 시멘트 혼화제 및 이 혼화제를 포함하는 콘 크리트 조성물이 공지되어 있다.In addition, WO 2006/011182 discloses a water-soluble amphoteric copolymer comprising a polyamide polyamine alkylene oxide adduct having an unsaturated group and two or more polyalkylene glycol esters, which has a dispersing performance over time when kneaded into a concrete composition. Cement admixtures and concrete compositions comprising these admixtures are known which increase and are excellent in reducing concrete viscosity.
또한, 폴리아미드폴리아민 또는 그 알킬렌옥사이드 부가물을 포함하는 공중합 화합물로서 일본특허 제3235002호, 일본특허 제3336456호에 개시된 콘크리트용 폴리카르복실산계 혼화제가 공지되어 있다.As the copolymer compound containing polyamide polyamine or an alkylene oxide adduct thereof, polycarboxylic acid-based admixtures for concrete disclosed in Japanese Patent Nos. 32,5002 and 3,36,456 are known.
그러나, 상기 문헌에 개시되어 있는 것과 같은 시멘트 혼화제용 공중합체는 불포화 폴리알킬렌글리콜에테르계 단량체에 유래하는 폴리알킬렌글리콜 쇄의 입체 반발에 따라, 어느 정도 높은 분산 성능을 발휘하는 시멘트 혼화제를 부여하지만, 고강도의 콘크리트를 얻거나, 콘크리트의 미세균열, 열화 등을 방지하기에는 한계가 있었다.However, copolymers for cement admixtures such as those disclosed in the literature give a cement admixture that exhibits a somewhat high dispersion performance in accordance with the steric repulsion of polyalkylene glycol chains derived from unsaturated polyalkylene glycol ether monomers. However, there was a limit in obtaining high strength concrete or preventing microcracks, deterioration, etc. of concrete.
한편, 상기 혼화제 뿐만 아니라, 콘크리트에 사용되는 첨가제 일종으로서 시멘트의 수화반응을 촉진시킴으로써 콘크리트의 응결시간(setting time)을 단축시키고 초기강도의 발현을 증진시키는 역할을 하는 급결강도 혼화제가 사용되고 있다.On the other hand, as well as the admixture, as a kind of additive used in the concrete is used to promote the hydration reaction of cement to shorten the setting time (concrete time) of concrete and to enhance the expression of the initial strength has been used.
기존의 액상 급결 혼화제들은 대부분 강알칼리성을 띄고 있어 이로 인한 부식성으로 인해 작업환경이 저해되고 침출수 또는 누출수로 인해 주위환경이 오염되는 등의 잠재적인 문제점이 있었으며, 또한, 수화반응 초기에 강알칼리성 환경을 제공하여 초기 응결은 상당히 빠르지만 장기 강도가 크게 저하되는 단점이 있었다.Conventional liquid quenching admixtures have strong alkalinity, so there is a potential problem such as impaired working environment due to corrosiveness and contamination of the surrounding environment due to leachate or leaking water, and also strong alkaline environment at the beginning of the hydration reaction. The initial condensation was considerably faster, but the long-term strength was significantly reduced.
이러한 문제점을 해결한 급결 혼화제가 개발되었는데, 이는 강알칼리 성분의 함량이 1% 이내로 매우 낮은 비알칼리성 급결 혼화제로서, 강알칼리 성분의 최소화에 따라 작업환경을 개선시키고 환경 오염의 위험성을 획기적으로 줄일 수 있는 장점을 가지며, 콘크리트 중의 골재와 알칼리 성분이 반응하여 콘크리트의 내구성을 열화시킬 수 있는 알칼리-골재 반응의 위험성을 현저하게 감소시켜 주는 장점이 있지만, 이러한 비알칼리성 급결 혼화제는 완전한 액상이 아닌 현탁액 혹은 슬러리 형태이기 때문에 콘크리트와의 균일한 혼합이 어렵고 또한 장기 보관시 상분리 현상에 의한 안정성 저하와 같은 문제점이 있었다.A quick admixture has been developed to solve these problems. It is a non-alkaline quick admixture with a very low alkali content of less than 1%, which can improve the working environment and minimize the risk of environmental pollution by minimizing the strong alkali. Although it has the advantage of significantly reducing the risk of alkali-aggregate reaction, which can degrade the durability of concrete by reacting aggregates and alkali components in concrete, these non-alkaline quenching admixtures are in the form of suspensions or slurries rather than complete liquid phases. Because of this, it is difficult to uniformly mix with concrete, and there are problems such as deterioration in stability due to phase separation during long-term storage.
본 발명은 상술한 바와 같은 종래의 문제점을 해결하기 위해서 안출된 것으로서, 우수한 응결 특성 및 초기 강도 특성을 가지고 상안정성이 우수하여 장기 보관이 가능하며 인체 및 환경에 무해한 시멘트 몰타르 급결강도 혼화재용 공중합체로서 아크릴계 모노머와 관능성 모노머 및 공중합 가능한 모노머를 유화 중합하여 제조된 수용성 아크릴중합체와 이를 이용한 시멘트 몰타르 급결강도 혼화재를 제공하는 것을 해결하고자 하는 과제로 한다.The present invention has been made to solve the conventional problems as described above, has excellent condensation properties and initial strength characteristics, excellent phase stability, long-term storage is possible, harmless to the human body and environment, cement mortar rapid strength admixtures An object of the present invention is to provide a water-soluble acrylic polymer prepared by emulsion polymerization of an acrylic monomer, a functional monomer, and a copolymerizable monomer as a copolymer, and a cement mortar rapid strength admixture using the same.
본 발명은 아크릴계 모노머와 관능성 모노머 및 공중합 가능한 모노머를 유화 중합하여 제조된 수용성 아크릴중합체 및 이를 이용한 시멘트 몰타르 급결강도 혼화재를 과제해결수단으로 한다.The present invention provides a water-soluble acrylic polymer prepared by emulsion polymerization of an acrylic monomer, a functional monomer, and a copolymerizable monomer, and a cement mortar rapid strength admixture using the same.
본 발명에 따른 수용성 아크릴중합체를 포함하는 시멘트 몰타르 급결강도 혼화재는 액상으로서 우수한 응결 특성 및 초기 강도 특성을 가지고 상안정성이 우수하며 장기 보관이 가능한 효과를 나타낸다.Cement mortar fastening strength admixture comprising a water-soluble acrylic polymer according to the present invention has an excellent coagulation characteristics and initial strength characteristics as a liquid phase, excellent in phase stability and exhibits the effect of long-term storage.
본 발명은 아크릴계 모노머와 관능성 모노머 및 공중합 가능한 모노머를 유화 중합하여 제조된 수용성 아크릴중합체와 이를 이용한 시멘트 몰타르 급결강도 혼화재를 기술구성의 특징으로 한다.The present invention is characterized by a water-soluble acrylic polymer prepared by emulsion polymerization of an acrylic monomer, a functional monomer, and a copolymerizable monomer, and a cement mortar rapid strength admixture using the same.
이하에서, 본 발명에 따른 수용성 아크릴중합체와 이를 이용한 시멘트 몰타르 급결강도 혼화재에 대해 상세하게 설명하기로 한다.Hereinafter, the water-soluble acrylic polymer and cement mortar fastening strength admixture using the same according to the present invention will be described in detail.
본 발명에 있어서 수용성 아크릴중합체 제조시 사용 가능한 아크릴계 모노머로서는, 아크릴계의 모노머로서 당업자에게 주지된 것이라면 특별히 한정되지 않으며, 아크릴계 모노머의 구체예로서는, 메틸아크릴레이트(Methylacrylate), 에틸아 크릴레이트(Ethylacrylate), 부틸아크릴레이트(Butylacrylate), 2-에틸헥실아크릴레이트(2-Ethyhexylacrylate), 시클로헥실아크릴레이트, 메틸메타크릴레이트, 에틸메타크릴레이트, 부틸메타크릴레이트, 옥틸메타크릴레이트 등과 같은 아크릴산또는 메타크릴산 알킬에스테르류를 들 수 있다. In the present invention, the acrylic monomer that can be used in the production of the water-soluble acrylic polymer is not particularly limited as long as it is well known to those skilled in the art as an acrylic monomer. Specific examples of the acrylic monomer include methyl acrylate, ethyl acrylate, and the like. Acrylic acid or methacrylic acid such as butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, etc. Alkyl esters are mentioned.
본 발명에 있어서, 아크릴계 모노머는, 폴리머를 구성하는 주성분이 되는 것으로, 그 사용량은, 180~220중량부인 것이 바람직하며, 사용량이 180중량부 보다 적으면 내수성이 및 내후성이 취약할 우려가 있고, 220중량부 이상 사용하는 경우는 유연성이 취약한 단점이 있게 된다.In the present invention, the acrylic monomer becomes a main component constituting the polymer, and the amount of the acrylic monomer is preferably 180 to 220 parts by weight, and when the amount is less than 180 parts by weight, the water resistance and weather resistance may be weak. When using more than 220 parts by weight there is a disadvantage that the flexibility is weak.
또한, 상기 아크릴계 모노머와 함께 유화 중합하는 것으로 관능성 모노머를 사용한다. 여기서 관능성 모노머는 글리시딜기 함유 모노머, 아릴기 함유 모노머, 가수분해성 실릴기 함유 모노머 등을 말하는데, 글리시딜기 함유 모노머의 구체예로서는, 글리시딜(메타)아크릴레이트(Glycidylmethacrylate), 글리시딜(메타)아릴에테르, 3,4-에폭시시클로헥실(메타)아크릴레이트 등을 들 수 있으며, 이 중에, 시멘트 몰타르 조성물의 물 습윤시의 접착성을 위하여는 글리시딜메타아크릴레이트가 바람직하다.Moreover, a functional monomer is used by emulsion-polymerizing with the said acryl-type monomer. The functional monomer refers to a glycidyl group-containing monomer, an aryl group-containing monomer, a hydrolyzable silyl group-containing monomer, and the like, and specific examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and glycidyl. (Meth) aryl ether, 3, 4- epoxycyclohexyl (meth) acrylate, etc. are mentioned, Among these, glycidyl methacrylate is preferable for the adhesiveness at the time of water wet of a cement mortar composition.
상기 관능성 모노머의 사용량은, 아크릴계 모노머와 같이 180~220중량부인 것이 바람직하며, 사용량이 180중량부 보다 적으면 내수성이나 내습윤 접착성이 불 충분하게 되고, 220중량부 이상 사용하는 경우는 분산성이 저하될 우려가 있다.It is preferable that the usage-amount of the said functional monomer is 180-220 weight part like an acryl-type monomer, and when the usage-amount is less than 180 weight part, water resistance or wet-wetting adhesiveness may become inadequate, and when using 220 weight part or more, There is a fear that the acidity is lowered.
또한, 아크릴계 모노머와 관능성 모노머 외에, 공중합 가능한 모노머를 사용하여 유화 중합하는데, 여기서, 공중합 가능한 모노머로서는, 통상의 유화 중합에 사용 가능한 것이라면, 특별한 제한은 없고, 예를 들면, 아크릴산, 메타크릴산, 말레인산, 인타콘산, 크로톤산 등의 에틸렌성 불포화 카르본산; 에틸렌 등의 올레핀계 단량체; 스틸렌, α-메틸스틸렌, 비닐톨루엔 등의 스틸렌계 단량체 등을 들 수 있다.Moreover, in addition to an acryl-type monomer and a functional monomer, it is emulsion-polymerizing using the monomer which can be copolymerized, If a copolymerizable monomer is what can be used for normal emulsion polymerization, there will be no restriction | limiting in particular, For example, acrylic acid and methacrylic acid Ethylenically unsaturated carboxylic acids such as maleic acid, intaconic acid and crotonic acid; Olefin monomers such as ethylene; Styrene-type monomers, such as styrene, (alpha) -methylstyrene and vinyltoluene, etc. are mentioned.
상기 공중합 가능한 모노머의 사용량은 30~50중량부인 것이 바람직하며, 사용량이 30중량부 보다 적으면 내후성 및 경도가 취약해질 우려가 있고, 50중량부 이상 사용하는 경우는 분산성이 취약하게 된다.It is preferable that the usage-amount of the said copolymerizable monomer is 30-50 weight part, and when the usage-amount is less than 30 weight part, there exists a possibility that weather resistance and hardness may become weak, and when using 50 weight part or more, dispersibility becomes weak.
본 발명에 의한 수용성 아크릴중합체의 유화중합에 있어서는, 상기의 아크릴계 모노머 및 관능성 모노머 등의 모노머 성분 이외에, 용매, 유화제, 중합개시제, 중합촉진제, 중화제 등이 사용된다.In the emulsion polymerization of the water-soluble acrylic polymer according to the present invention, solvents, emulsifiers, polymerization initiators, polymerization accelerators, neutralizing agents and the like are used in addition to the monomer components such as the acrylic monomers and the functional monomers.
본 발명의 수용성 아크릴중합체를 얻기 위한 제조방법은 유화중합으로서 이 때 사용되는 용매로서는 물, 알코올류: 메탄올, 에탄올, 이소프로판올 등, 방향족 혹은 지방족 탄화수소류; 벤젠, 톨루엔, 크실렌, 시클로헥산, n-헥산 등, 에스테르 또는 케톤 화합물류; 초산에틸, 아세톤, 메틸에틸케톤 등, 환상(環狀) 에테르 화합물류; 테트라히드로푸란, 디옥산 등을 들 수 있는데, 원료단량체 및 얻어지는 공중합체의 용해성으로부터 물 및 탄소수 1~4의 저급알코올로 이루어지는 군에서 선택된 적어도 1종을 사용하는 것이 바람직하고, 그 중에서도 물 바람직하게는 탈이온수 또는 증류수를 사용한다. 이렇게 물을 용제로 사용하면 제조과정에서 휘발성 유기화합물을 방출하지 않아 친환경적인 공정을 수행할 수 있는 장점을 제공한다.The production method for obtaining the water-soluble acrylic polymer of the present invention is emulsion polymerization, and the solvent used at this time includes water and alcohols: aromatic or aliphatic hydrocarbons such as methanol, ethanol and isopropanol; Esters or ketone compounds, such as benzene, toluene, xylene, cyclohexane, n-hexane; Cyclic ether compounds such as ethyl acetate, acetone and methyl ethyl ketone; Tetrahydrofuran, dioxane, etc. are mentioned, It is preferable to use at least 1 sort (s) chosen from the group which consists of water and the C1-C4 lower alcohol from the solubility of a raw material monomer and the copolymer obtained, and water is especially preferable. Use deionized or distilled water. The use of water as a solvent does not release volatile organic compounds in the manufacturing process, thus providing an advantage in performing environmentally friendly processes.
또한, 수용성 아크릴중합체 입자를 안정화시키고, 중합 안정성에 기여하는데 이용되는 유화제는 비이온성 유화제를 적용하는 것이 바람직하다. 바람직하게는 비이온성 유화제로서는 에톡시레이티드 노닐페놀(Ethoxylated nonylphenol), 폴리옥시에틸렌 이소옥틸페닐 에테르(Polyoxyethylene(10) isooctylphenyl ether)중 어느 하나를 사용한다.In addition, it is preferable to apply a nonionic emulsifier to the emulsifier used to stabilize the water-soluble acrylic polymer particles and contribute to the polymerization stability. Preferably, as the nonionic emulsifier, any one of ethoxylated nonylphenol and polyoxyethylene isoctylphenyl ether is used.
한편, 라디칼을 생성하여 중합반응을 개시하기 위한 용도로 사용되는 중합개 시제는 통상의 유화 중합에 사용할 수 있는 것이라면 특별한 제한 없이 사용할 수 있으며, 바람직한 수용성 중합개시제로서는 과황산염류; 과황산암모늄, 과황산나트륨, 과황산칼륨 등, 과산화수소, 아조아미딘 화합물류; 2,2'-아조비스-2-메틸프로피온아미딘염산염 등, 환상 아조아미딘 화합물류; 2,2'-아조비스-2-(2-이미다졸린-2-일)프로판염산염 등, 수용성 아조계류; 2-카바모일아조이소부티로니트릴(carbamoyl azoisobutyronitrile) 등의 아조니트릴 화합물 등이 사용되며, 이들 은 2종 이상을 병용하여도 좋다. 본 발명에 있어서는 이들 중에서 시멘트 몰타르 강도증강에 영향이 없고 중합이 용이한 점에서 과황산암모늄이 바람직하다.On the other hand, the polymerization initiator used for generating radicals to initiate the polymerization reaction can be used without particular limitation, as long as it can be used in the ordinary emulsion polymerization, and preferred water-soluble polymerization initiators include persulfates; Hydrogen peroxide and azoamidine compounds such as ammonium persulfate, sodium persulfate and potassium persulfate; Cyclic azoamidine compounds such as 2,2'-azobis-2-methylpropionamidine hydrochloride; Water-soluble azo compounds such as 2,2'-azobis-2- (2-imidazolin-2-yl) propane hydrochloride; Azonitrile compounds, such as 2-carbamoyl azoisobutyronitrile, etc. are used, These may use 2 or more types together. In this invention, ammonium persulfate is preferable at the point which does not affect cement mortar strength buildup and is easy to superpose | polymerize among these.
또한 상기 중합개시제와는 별도로 아황산수소나트륨 등의 알칼리금속 아황산염, 메타이아황산염, 차아인산(hypophosphorous acid) 나트륨, 히드록시메탄술폰산나트륨이수화물, 히드록실아민염류 등의 중합촉진제를 병용할 수도 있다.In addition to the polymerization initiator, a polymerization accelerator such as alkali metal sulfite such as sodium hydrogen sulfite, metasulfite, sodium hypophosphorous acid, sodium hydroxymethanesulfonate dihydrate, and hydroxylamine salts may be used in combination.
또한, 수용성 중합체의 용해를 돕고 안정화시키는데 이용되는 중화제는 암모니아(NH3), AMP(2-amino-2-methyl-1-propanol), 알킬아민(Alkylamine), 수산화나트룸(NaOH), 수산화 칼륨(KOH) 등이 사용될 수 있으나, 암모니아가 바람직하다.In addition, the neutralizers used to aid and stabilize the dissolution of the water-soluble polymer include ammonia (NH 3), AMP (2-amino-2-methyl-1-propanol), alkylamines (Alkylamine), sodium hydroxide (NaOH), potassium hydroxide ( KOH) and the like can be used, but ammonia is preferred.
한편, 본 발명에 따른 수용성 아크릴중합체의 제조방법은 아크릴계 모노머와 관능성 모노머 및 공중합 가능한 모노머를 비이온성 유화제 및 물에 유화시키는 단계와; 상기 유화된 유화물을 물, 비이온성 유화제와 중합개시제 및 중합촉진제에 적하 투입하여 수용성 아크릴중합체를 생성하는 단계;를 포함한다.On the other hand, the method for producing a water-soluble acrylic polymer according to the present invention comprises the steps of emulsifying the acrylic monomer, functional monomer and copolymerizable monomer in a nonionic emulsifier and water; And adding the emulsified emulsion dropwise to water, a nonionic emulsifier, a polymerization initiator, and a polymerization accelerator to produce a water-soluble acrylic polymer.
상기 아크릴계 모노머와 관능성 모노머 및 공중합 가능한 모노머를 물, 비이온성 유화제와 중합개시제로 유화중합하는 메카니즘을 모식도로 나타내면 다음과 같다.A mechanism of emulsion-polymerizing the acrylic monomer, the functional monomer and the copolymerizable monomer with water, a nonionic emulsifier and a polymerization initiator is shown as follows.
상기 수용성 아크릴중합체 제조방법을 상세히 설명하면, 용제로서 물 260~280중량부, 비이온성 유화제 1~6중량부, 아크릴계 모노머 180~220중량부, 관능성 모노머 180~220중량부 및 공중합 가능한 모노머 30~50중량부를 배합기내에서 배합, 교반하여 유화시키고, 반응기내에 질소가스를 주입하여 60 내지 70℃로 승온시킨다. When describing the water-soluble acrylic polymer manufacturing method in detail, 260 to 280 parts by weight of water, 1 to 6 parts by weight of nonionic emulsifier, 180 to 220 parts by weight of acrylic monomer, 180 to 220 parts by weight of functional monomer and copolymerizable monomer 30 ˜50 parts by weight of the mixture is mixed, stirred and emulsified, and nitrogen gas is injected into the reactor to raise the temperature to 60 to 70 ° C.
다음, 반응기내에 물 260~280중량부 및 비이온성 유화제 1~6중량부와 중합개시제 0.3~0.5중량부 및 중합촉진제 0.3~0.5중량부를 투입, 교반하면서 70 내지 80 ℃로 승온시킨 후, 중합온도 70 내지 80℃에서 배합기내의 유화물과 중합개시제 0.5~1중량부, 중합촉진제 0.5~1중량부를 반응기내에 drop방식으로 적하하면서 5~8시간 동안 중합시킨다.Subsequently, the mixture was heated to 260 to 280 parts by weight of water, 1 to 6 parts by weight of a nonionic emulsifier, 0.3 to 0.5 parts by weight of a polymerization initiator, and 0.3 to 0.5 parts by weight of a polymerization accelerator, and heated to 70 to 80 ° C while stirring, followed by polymerization temperature. At 70 to 80 ° C., the emulsion and the polymerization initiator in the blender, 0.5-1 part by weight, and polymerization initiator 0.5-1 part by weight are added dropwise into the reactor for 5-8 hours.
다음, 중합온도 70~80℃에서 2~3시간 숙성을 유지하면서 질소주입을 차단한 후 50~60℃로 냉각한 다음 중화제를 투입하고 중합을 완료하여 수용성 아크릴중합체를 생성한다.Next, the injection of nitrogen was blocked while maintaining the aging at a polymerization temperature of 70 to 80 ° C. for 2 to 3 hours, cooled to 50 to 60 ° C., and then a neutralizing agent was added to complete the polymerization to generate a water-soluble acrylic polymer.
상기 방법은 유화 중합을 진행시키는 데 필요한 배합기, 교반장치, 중합온도 조절수단, 예를 들어, 중합 반응기 내의 온도를 측정하여 그에 따라 중합 반응기를 가열량을 조절하는 온도 제어 장치가 구비된 스팀 자켓(steam jacket), 온수 자켓(hot water jacket), 전열장치(electric heating device), 기타 본 발명이 속하는 기술 분야에서 공지된 임의의 가열 수단, 응축기(condenser)가 구비되고, 중합 반응기 내의 분위기를 불활성 질소 분위기로 만들고 유지하기 위한 질소 퍼지(purge) 수단이 구비된 중합 반응기내에서 수행된다.The method comprises a steam jacket having a temperature control device for measuring a temperature in a blender, a stirring device, a polymerization temperature control means, for example, a polymerization reactor, and thus controlling the amount of heating according to the emulsion polymerization. steam jacket, hot water jacket, electric heating device, any heating means known in the art to which the present invention pertains, a condenser is provided, and the atmosphere in the polymerization reactor is inert nitrogen It is carried out in a polymerization reactor equipped with nitrogen purge means for bringing into and maintaining the atmosphere.
중합시간은 특별히 한정되지 않지만, 예를 들어, 5~8시간의 범위가 적당하며, 더욱 바람직하게는 약6시간의 범위가 좋다. 중합시간은 이 범위보다 너무 짧거나 너무 길면, 중합율의 저하나 생산성의 저하를 초래하여 바람직하지 못하다.Although polymerization time is not specifically limited, For example, the range of 5 to 8 hours is suitable, More preferably, the range of about 6 hours is good. If the polymerization time is too short or too long than this range, the polymerization rate is lowered or the productivity is lowered, which is not preferable.
본 발명의 다른 형태에 의하면, 시멘트 몰타르 급결강도 혼화제는, 본 발명에 의한 수용성 아크릴 중합체를 포함하게 된다. 시멘트 몰타르 급결강도 혼화제는, 보존제, 방청제, 증점제, 소포제, 유동화제, 경화지연제, 경화촉진제 등의 추가성분을 함유할 수 있다.According to another aspect of the present invention, the cement mortar fastening strength admixture includes the water-soluble acrylic polymer according to the present invention. The cement mortar rapid strength admixture may contain additional components such as preservatives, rust inhibitors, thickeners, defoamers, glidants, curing retardants, curing accelerators, and the like.
본 발명의 수용성 아크릴중합체로 이루어지는 시멘트 몰타르 혼화제는 시멘트 몰타르 재료에 그대로 혼합할 수 있으며, 그 이외의 재료도 첨가하여, 현장에서 물을 반죽하여 섞는 것만으로 사용할 수 있다. 본 발명에 의한 수용성 아크릴 중합체를 포함한 시멘트 몰타르 혼화제를 시멘트 몰타르 재료에 첨가하면, 보통 상태에서의 접착력의 향상 뿐만아니라, 습윤시의 접착력도 향상시킬 수 있다. The cement mortar admixture made of the water-soluble acrylic polymer of the present invention can be mixed with the cement mortar material as it is, and other materials can also be added and used by simply kneading water in the field. When the cement mortar admixture containing the water-soluble acrylic polymer according to the present invention is added to the cement mortar material, not only the adhesion in the normal state but also the adhesion in wet can be improved.
여기서, 시멘트 몰타르 재료로서는, 예를 들면, 포틀랜드 시멘트, 조강성 시멘트, 속경성 시멘트 등의 각종 시멘트계 재료, 무수석고, 반수석고, 소석고 등의 각종 석고계 재료, 고로 슬래그 등을 들 수 있으며, 또한 기타 별도의 재료를 포함할 수 있다. 이와 같은 별도의 재료로서는, 예를 들면, 규사, 비산회(fly ash), 석회석분, 수산화 칼슘, 소석회, 탄산칼슘 등을 들 수 있다.Here, examples of the cement mortar material include various cement materials such as portland cement, rough cement, and fast cement, various gypsum materials such as anhydrous gypsum, hemihydrate gypsum and calcined gypsum, and blast furnace slag. Other separate materials may be included. Examples of such another material include silica sand, fly ash, limestone powder, calcium hydroxide, calcined lime, calcium carbonate and the like.
시멘트 몰타르 조성물에 있어서 본 발명에 의한 수용성 아크릴중합체를 포함하는 시멘트 몰타르 급결강도 혼화재 함유량은, 시멘트 몰타르 재료 100중량부에 대해, 10~30 중량부 정도인 것이 바람직한데, 10중량부 보다 적으면 초기 응결이 불충분하게 될 수 있고, 30중량부 보다 많으면, 시멘트 몰타르 재료의 본래 성능이 발휘되지 못하는 경우가 있다.In the cement mortar composition, the cement mortar fastening strength admixture content containing the water-soluble acrylic polymer according to the present invention is preferably about 10 to 30 parts by weight with respect to 100 parts by weight of the cement mortar material, but is less than 10 parts by weight. Initial condensation may be insufficient, and if it is more than 30 parts by weight, the original performance of the cement mortar material may not be exhibited.
실시예Example 1 수용성 아크릴중합체 합성 1 Water Soluble Acrylic Polymer Synthesis
배합기내에 탈이온수 270.0g, 에톡시레이티드 노닐페놀(Ethoxylated nonylphenol) 7g, 2-에틸헥실아크릴레이트(2-Ethyhexylacrylate; 2-EHA) 200.0g, 글리시딜(메타)아크릴레이트(Glycidylmethacrylate; GMA) 210.0g, 메타크릴산(MAA) 40.0g을 투입하고 배합, 교반하여 유화시켰다.270.0 g of deionized water, 7 g of ethoxylated nonylphenol, 200.0 g of 2-Ethyhexylacrylate (2-EHA), glycidylmethacrylate (GMA) 210.0 g and 40.0 g of methacrylic acid (MAA) were added, blended, stirred and emulsified.
온도계, 교반기, 적하 로트, 질소 도입관 및 환류 냉각기를 구비한 유리제 반응 용기내를 질소 치환하고, 질소 분위기하에, 65℃로 승온시키고, 반응용기내에 탈이온수 280.0g 및 에톡시레이티드 노닐페놀(Ethoxylated nonylphenol) 3g과 과황산암모늄(Ammonium persulfate) 0.4g 및 메타이아황산나트륨(Sodium Metabissulfate) 0.35g 투입, 교반하면서 75℃로 승온시켰다.The glass reaction vessel equipped with a thermometer, a stirrer, a dropping lot, a nitrogen introduction tube and a reflux condenser was nitrogen-substituted, heated to 65 ° C. under a nitrogen atmosphere, and 280.0 g of deionized water and ethoxylated nonylphenol ( 3 g of ethoxylated nonylphenol, 0.4 g of ammonium persulfate and 0.35 g of sodium metabissulfate were added thereto, and the temperature was raised to 75 ° C. while stirring.
다음에, 중합온도 75℃에서 배합기내의 유화물과 과황산암모늄(Ammonium persulfate) 0.9g 및 메타이아황산나트륨(Sodium Metabissulfate) 0.9g을 반응기내에 drop방식으로 적하하면서 6시간 동안 중합시킨 후, 중합온도 75℃에서 2시간 숙성을 유지하면서 질소주입을 차단하고, 50℃로 냉각한 다음 암모니아를 투입하여 중화한 후 중합을 완료하여 수용성 아크릴중합체를 생성하였다.Next, the emulsion in the blender, 0.9 g of ammonium persulfate and 0.9 g of sodium metabissulfate were added dropwise into the reactor at a polymerization temperature of 75 ° C. for 6 hours, followed by polymerization at 75 ° C. Nitrogen injection was blocked while maintaining aging at 2 hours, cooled to 50 ° C., neutralized by addition of ammonia, and polymerization was completed to produce a water-soluble acrylic polymer.
상기 실시예 1의 수용성 아크릴중합체 제조에 사용된 원료 및 그 사용량은 다음과 같다.The raw materials used in the preparation of the water-soluble acrylic polymer of Example 1 and the amount thereof used are as follows.
실시예Example 2 시멘트 2 cement 몰타르Maltar 응결 시간 및 압축강도측정 Setting time and compressive strength measurement
상기 실시예 1에서 얻어진 수용성 아크릴중합체를 포함한 급결 혼화제의 응결특성을 평가하기 위하여 시멘트 200g, 물 50g의 시멘트 몰타르에 실시예 1에서 얻은 수용성 아크릴중합체를 포함한 급결 혼화제 50g을 투입한 후 길모아침을 사용하여 응결시간을 3회 측정한 후 그 평균값으로 응결시간을 결정하였다.In order to evaluate the coagulation characteristics of the quench admixture including the water-soluble acrylic polymer obtained in Example 1, 50 g of the quench admixture containing the water-soluble acrylic polymer obtained in Example 1 was added to cement mortar of 200 g of cement and 50 g of water. By measuring the setting time three times, the setting time was determined by the average value.
또한 비교를 위하여 종래의 비알칼리성 급결제인 실크로드시앤티 ROADCON-LF1000 (비교예 1) 및 강알칼리성 급결제인 실크로드 시앤티 ROADCON-LA(비교예 2)의 응결시간도 동일한 방법으로 측정하였다. 그 결과는 표 1에 나타내었다.In addition, for comparison, the solidification time of the conventional non-alkaline fastener, Silk Road C & T ROADCON-LF1000 (Comparative Example 1) and the strongly alkaline fastener, Silk Road C & T ROADCON-LA (Comparative Example 2), were also measured. . The results are shown in Table 1.
[표 1][Table 1]
또한, 본 발명에 따른 급결 혼화제의 압축강도를 평가하기 위하여 시멘트 500g, 표준모래 1200g, 물 240g을 배합한 몰타르에 실시예 1에서 얻은 수용성 아크릴중합체를 포함한 급결 혼화제 300g을 첨가한 후 이를 KS L 5015 "시멘트 몰타르의 압축강도 시험방법"에 준하여 압축강도를 측정하였으며, 비교를 위하여 종래의 비알칼리성 급결제인 실크로드시앤티 ROADCON-LF1000 (비교예 1), 강알칼리성 급결제인 실크로드시앤티 ROADCON-LA(비교예 2) 및 급결혼화제를 사용하지 않은 모르타르(비교예 3)의 압축강도도 동일한 방법으로 측정하였다. 그 결과는 표 2에 나타내었다.In addition, in order to evaluate the compressive strength of the quench admixture according to the present invention, 300 grams of the quench admixture including the water-soluble acrylic polymer obtained in Example 1 was added to a mortar containing 500 g of cement, 1200 g of standard sand, and 240 g of water, followed by KS L 5015. The compressive strength was measured according to the "Test Method for the Compressive Strength of Cement Maltar". The compressive strength of -LA (Comparative Example 2) and mortar (Comparative Example 3) without using a quick blending agent was also measured in the same manner. The results are shown in Table 2.
[표 2]TABLE 2
위의 결과로부터 알 수 있는 바와 같이, 본 발명에 따른 급결 강도 혼화제를 포함하는 시멘트 몰타르는 응결특성 및 압축강도 특성이 종래의 급결제 보다 우수할 뿐만 아니라 급결제를 사용하지 않는 동일 배합의 시멘트 몰타르와 비교하여도 높은 압축강도 특성을 나타내었다. As can be seen from the above results, the cement mortar including the fastening strength admixture according to the present invention not only has better coagulation characteristics and compressive strength characteristics than conventional fasteners, but also cement mortar of the same formulation without using a fastener. Compared with, it showed high compressive strength characteristics.
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| KR101732895B1 (en) | 2016-07-14 | 2017-05-08 | 일우토건(주) | polymer mortar compositon and repairing method of water permeable concrete road surface using the same |
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| KR102160080B1 (en) * | 2020-01-20 | 2020-09-28 | 김동춘 | A composite waterproofing sheet laminated with organic and inorganic hybrid water proofing material and non-woven fabric coated with cutoff film and the method of manufacturing thereof and the waterproofing method using thereof |
| WO2021194001A1 (en) * | 2020-03-25 | 2021-09-30 | 김동춘 | Composite waterproof sheet in which organic-inorganic hybrid waterproof material layer comprising organic-inorganic hybrid hollow nanoparticles and cutoff film-deposited non-woven fabric are laminated, and waterproof structure and waterproof construction method using same |
| KR20210119674A (en) * | 2020-03-25 | 2021-10-06 | 김동춘 | A composite waterproofing sheet laminated with organic and inorganic hybrid water proofing layer comprising organic and inorganic hybrid hollow nanoparticles and non-woven fabric coated with cutoff film and the waterproofing structure and the waterproofing method using thereof |
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