KR100963277B1 - Acrylic Polymer and manufacture method - Google Patents
Acrylic Polymer and manufacture method Download PDFInfo
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- KR100963277B1 KR100963277B1 KR1020080106226A KR20080106226A KR100963277B1 KR 100963277 B1 KR100963277 B1 KR 100963277B1 KR 1020080106226 A KR1020080106226 A KR 1020080106226A KR 20080106226 A KR20080106226 A KR 20080106226A KR 100963277 B1 KR100963277 B1 KR 100963277B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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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
- C04B26/26—Bituminous materials, e.g. tar, pitch
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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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- C08F4/00—Polymerisation catalysts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/20—Mixtures of bitumen and aggregate defined by their production temperatures, e.g. production of asphalt for road or pavement applications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
- C08L2555/50—Inorganic non-macromolecular ingredients
- C08L2555/52—Aggregate, e.g. crushed stone, sand, gravel or cement
Abstract
본 발명은 포장용 아스팔트 콘크리트에 사용되는 수성아크릴폴리머에 관한 것으로서, MMA(methylmethacrylate) 모노머(monomer) 100중량부와, BAM(buthylacrylate monomer) 100~150중량부와, 물 100~150중량부와, 유화제인 알킬설폰산염 0.3~0.5중량부와, 촉매인 과황산암모늄과 중아황산소다 0.05~0.2중량부로 구성된다.The present invention relates to an aqueous acrylic polymer used in asphalt concrete for pavement, comprising 100 parts by weight of MMA (methylmethacrylate) monomer, 100 to 150 parts by weight of BAM (buthylacrylate monomer), 100 to 150 parts by weight of water, and an emulsifier. It is comprised from 0.3-0.5 weight part of phosphorus alkyl sulfonates, 0.05-0.2 weight part of ammonium persulfate and sodium bisulfite which are catalysts.
또한, 본 발명은 상기와 같이 구성되는 수성아크릴폴리머의 제조방법에 관한 것으로서, 물에 유화제인 알킬설폰산염을 녹이는 유화제 용해단계와; 상기 알킬설폰산염이 용해된 용액에 MMA(methylmethacrylate) 모노머(monomer)와, BAM(buthylacrylate monomer)을 혼합하는 모노머 용해단계와; 상기 모노머 용해단계에서 생성된 용액에 주촉매인 과황산암모늄을 혼합하는 주촉매 혼합단계와; 상기 과황산암모늄이 혼합된 용액에 부촉매인 중아황산소다를 혼합하는 부촉매 혼합단계와; 상기 부촉매 혼합단계에서 생성된 용액을 냉각 및 여과시키는 냉각/여과단계로 구성된다.In addition, the present invention relates to a method for producing an aqueous acrylic polymer, which is configured as described above, comprising: an emulsifier dissolving step of dissolving an alkyl sulfonate as an emulsifier in water; A monomer dissolving step of mixing an MMA (methylmethacrylate) monomer and a BAM (buthylacrylate monomer) in a solution in which the alkyl sulfonate is dissolved; A main catalyst mixing step of mixing ammonium persulfate as a main catalyst in the solution produced in the monomer dissolving step; A subcatalyst mixing step of mixing sodium bisulfite, which is a subcatalyst, into the solution in which the ammonium persulfate is mixed; It consists of a cooling / filtration step of cooling and filtering the solution produced in the subcatalyst mixing step.
이로써, 본 발명에 의한 수성아크릴폴리머는 골재와 골재 사이에서 망상구조를 형성하여 공극을 채우고 접착력과 인장강도를 증가시켜 도로를 포장한 후에 도로의 표면을 보호하고 마모를 낮출 수 있는 이점이 있다.Thus, the aqueous acrylic polymer according to the present invention has the advantage of forming a network structure between the aggregate and the aggregate to fill the voids and increase the adhesion and tensile strength to protect the surface of the road after paving the road and lower wear.
아스팔트 콘크리트, 순환골재, MMA, BAM Asphalt Concrete, Recycled Aggregate, MMA, BAM
Description
본 발명은 포장용 아스팔트 콘크리트에 사용되는 수성아크릴폴리머와 이의 제조방법에 관한 것으로서, 특히 아스팔트 콘크리트를 구성하는 골재 사이의 적정 공극률을 유지할 수 있을 뿐만 아니라 아스팔트 콘크리트의 강도를 증진하고 탄력성을 유지할 수 있는 수성아크릴폴리머와 이의 제조방법에 관한 것이다.The present invention relates to an aqueous acrylic polymer used for pavement asphalt concrete and a method of manufacturing the same, in particular, can maintain the proper porosity between the aggregates constituting the asphalt concrete, as well as to improve the strength and elasticity of the asphalt concrete It relates to an acrylic polymer and a preparation method thereof.
일반적으로 도로 등을 포장하는 포장재로는 아스팔트와 골재의 가열 혼합물인 아스팔트 콘크리트가 주원료로 사용된다. 아스팔트 콘크리트는 주행성과 탄력성이 우수하며 부분절개 등의 보수가 용이한 장점이 있어 주로 사용되지만, 중교통량에 대한 내구성 및 소성변형이 약하고 콘크리트 포장에 비해 비용이 비싼 문제가 있다.In general, asphalt pavement, which is a heating mixture of asphalt and aggregate, is used as a main material for paving roads. Asphalt concrete is mainly used because of its excellent running properties and elasticity and easy repair, such as partial incision, but has a problem in that durability and plastic deformation for heavy traffic are weak and expensive compared to concrete pavement.
이러한 문제를 해결하기 위해 최근에는 폐아스팔트와 폐콘크리트를 활용함으로써 폐기물 처리비용을 절약함과 동시에 친환경적인 아스팔트 콘크리트를 생산하 려는 움직임이 증가되고 있다.In order to solve these problems, recently, waste asphalt and waste concrete have been used to reduce waste disposal costs and to produce eco-friendly asphalt concrete.
그러나, 이러한 재활용 방법에 의해 생산된 아스팔트 콘크리트는 입자간의 결합력이 크지 않고 소성변형이 생기며, 포장초기에는 강도가 높지만 그 강도값이 오래 지속되지 않아 조기에 균열이 발생하거나 파괴되는 문제가 있다. However, the asphalt concrete produced by this recycling method does not have a large bonding strength between the particles and plastic deformation occurs, the strength of the early pavement, but the strength value is not long lasting, there is a problem that early cracking or destruction occurs.
또한, 아스콘 순환골재와, 콘크리트 순환골재의 입자의 분포가 커서 아스팔트 혼합물 품질 기준에 따른 공극률의 기준값을 만족하기 어렵고, 아스콘 순환골재와, 콘크리트 순환골재의 배합을 위해 다량의 유화아스팔트와 시멘트를 소비하게 되는 문제가 있다.In addition, it is difficult to meet the standard value of porosity according to the asphalt mixture quality standards because of the large distribution of particles of asphalt concrete and concrete recycle aggregate, and it consumes a large amount of emulsified asphalt and cement for mixing asphalt concrete and concrete recycle aggregate. There is a problem done.
본 발명은 상기한 종래 기술의 문제점을 해결하기 위하여 안출된 것으로서, 포장용 아스팔트 콘크리트를 구성하는 각종 골재간의 결합력을 향상시키고 골재 사이의 적정 공극률을 유지시키며 소성변형을 방지할 수 있을 뿐만 아니라 아스팔트 콘크리트의 강도를 증진하고 탄력성을 유지시킬 수 있는 수성아크릴폴리머와 이의 제조방법을 제공하는데 그 목적이 있다.The present invention has been made to solve the above problems of the prior art, it is possible to improve the bonding strength between the various aggregates constituting the paving asphalt concrete, to maintain the proper porosity between the aggregates and to prevent plastic deformation as well as the An object of the present invention is to provide an aqueous acrylic polymer capable of improving strength and maintaining elasticity and a method of preparing the same.
상기한 과제를 해결하기 위한 본 발명에 의한 수성아크릴폴리머는 신골재 또는 폐콘크리트 순환골재와, 폐아스콘 순환골재와, 시멘트 및 음이온계 유화아스팔트와 함께 사용되어 포장용 아스팔트 콘크리트를 구성하는 것으로서, MMA(methylmethacrylate) 모노머(monomer) 100중량부와, BAM(buthylacrylate monmer) 100~150중량부와, 물 100~150중량부와, 유화제인 알킬설폰산염 0.3~0.5중량부와, 촉매인 과황산암모늄과 중아황산소다 0.05~0.2중량부로 구성된다.The aqueous acrylic polymer according to the present invention for solving the above problems is used together with new aggregates or recycled concrete recycled aggregates, waste ascone recycled aggregates, cement and anionic emulsion asphalt to form asphalt concrete for pavement, MMA ( 100 parts by weight of methylmethacrylate) monomer, 100 to 150 parts by weight of BAM (buthylacrylate monmer), 100 to 150 parts by weight of water, 0.3 to 0.5 parts by weight of alkyl sulfonate as an emulsifier, ammonium persulfate Sodium sulfate is composed of 0.05 to 0.2 parts by weight.
또한, 상기와 같이 구성되는 본 발명에 의한 포장용 아스팔트 콘크리트에 사용되는 수성아크릴폴리머의 제조방법은 물에 유화제인 알킬설폰산염을 녹이는 유화제 용해단계와; 상기 알킬설폰산염이 용해된 용액에 MMA(methylmethacrylate) 모노머(monomer)와, BAM(buthylacrylate monomer)을 혼합하는 모노머 용해단계와; 상기 모노머 용해단계에서 생성된 용액에 주촉매인 과황산암모늄을 혼합하는 주촉매 혼 합단계와; 상기 과황산암모늄이 혼합된 용액에 부촉매인 중아황산소다를 혼합하는 부촉매 혼합단계와; 상기 부촉매 혼합단계에서 생성된 용액을 냉각 및 여과시키는 냉각/여과단계로 구성된다.In addition, the manufacturing method of the aqueous acrylic polymer used in the asphalt concrete for paving according to the present invention configured as described above is an emulsifier dissolving step of dissolving alkyl sulfonate which is an emulsifier in water; A monomer dissolving step of mixing an MMA (methylmethacrylate) monomer and a BAM (buthylacrylate monomer) in a solution in which the alkyl sulfonate is dissolved; A main catalyst mixing step of mixing ammonium persulfate as a main catalyst in the solution produced in the monomer dissolving step; A subcatalyst mixing step of mixing sodium bisulfite, which is a subcatalyst, into the solution in which the ammonium persulfate is mixed; It consists of a cooling / filtration step of cooling and filtering the solution produced in the subcatalyst mixing step.
상기와 같이 구성되는 본 발명에 의한 수성아크릴폴리머는 폐아스콘 순환골재로부터 발생되는 
이하, 본 발명에 의한 수성아크릴폴리머와 이의 제조방법의 실시 예를 상세히 설명한다.Hereinafter, embodiments of the aqueous acrylic polymer and a method for preparing the same according to the present invention will be described in detail.
본 발명에 의한 수성아크릴폴리머는 포장용 아스팔트 콘크리트를 제조하기 위하여 사용되는 것으로, 상기 포장용 아스팔트 콘크리트에는 수성아크릴폴리머 외에 신골재 또는 폐콘크리트 순환골재와, 폐아스콘 순환골재와, 시멘트 및 음이온계 유화아스팔트 등을 포함하여 구성된다.The aqueous acrylic polymer according to the present invention is used to manufacture pavement asphalt concrete, and the pavement asphalt concrete includes new aggregate or waste concrete circulating aggregate, waste ascon circulating aggregate, cement and anionic emulsion asphalt, etc., in addition to the aqueous acrylic polymer. It is configured to include.
상기 수성아크릴폴리머는 포장용 아스팔트 콘크리트를 구성하는 골재 사이의 공극률을 적정하게 유지하고 아스팔트 콘크리트의 강도를 증가시키며, 그 탄력성을 유지할 수 있도록 하는 기능을 하는 것으로, MMA(Methylmethacrylate) 모노머(Monomer) 100중량부와, BAM(buthylacrylate monomer) 100~150중량부와, 물 100~150중량부와, 유화제 0.3~0.5중량부와, 촉매 0.05~0.2중량부로 구성된다.The aqueous acrylic polymer is to maintain the porosity between the aggregates constituting the asphalt concrete for pavement, increase the strength of the asphalt concrete, and maintain its elasticity, MMA (Methylmethacrylate) monomer (Monomer) 100 weight And 100 to 150 parts by weight of BAM (buthylacrylate monomer), 100 to 150 parts by weight of water, 0.3 to 0.5 parts by weight of emulsifier, and 0.05 to 0.2 parts by weight of catalyst.
상기 MMA(Methylmethacrylate)는 염소이온 및 차량용 유류를 포함한 각종 화학물질에 대하여 탁월한 내구성을 갖고 있는 물질로서, 화학관련 업계에서는 주지의 물질이므로 여기에서는 이에 대한 자세한 설명을 생략한다.The MMA (Methylmethacrylate) is a material having excellent durability against various chemicals including chlorine ions and vehicle oils, and thus, a detailed description thereof will be omitted here.
상기 유화제는 알킬설폰산염을 사용한다. 물론 상기 유화제는 알킬설폰산염에 한정되는 것은 아니고 카르복시산염, 도데실벤젠설폰산염, 수지산나트륨염 등이 사용될 수도 있다.The emulsifiers use alkylsulfonates. Of course, the emulsifier is not limited to alkylsulfonates, carboxylates, dodecylbenzenesulfonates, sodium resin salts and the like may be used.
상기 촉매는 상기 MMA 100중량부에 대하여 0.05~0.2중량부를 혼합하는 것이 바람직하다. 이러한 촉매는 주촉매와 부촉매로 구분할 수 있는데, 주촉매로는 과황산암모늄을 사용하고 부촉매로는 중아황산소다를 사용한다.It is preferable that the said catalyst mixes 0.05-0.2 weight part with respect to 100 weight part of said MMA. These catalysts can be classified into a main catalyst and a subcatalyst. As the main catalyst, ammonium persulfate is used, and sodium bisulfite is used as the subcatalyst.
그리고, 상기 촉매는 과황산암모늄 100중량부와, 중아황산소다 30~60중량부의 혼합으로 이루어진다.The catalyst is composed of 100 parts by weight of ammonium persulfate and 30 to 60 parts by weight of sodium bisulfite.
이하에서는 상기와 같이 구성되는 포장용 아스팔트 콘크리트에 사용되는 수성아크릴폴리머의 제조방법을 살펴보도록 한다.Hereinafter, look at the manufacturing method of the aqueous acrylic polymer used in the asphalt concrete for pavement configured as described above.
본 발명에 의한 수성아크릴폴리머 제조방법은 유화제 용해단계와, 모노머 용 해단계와, 주촉매 혼합단계와, 부촉매 혼합단계 및 냉각/여과단계를 포함하여 구성된다.The aqueous acrylic polymer production method according to the present invention comprises an emulsifier dissolving step, a monomer dissolving step, a main catalyst mixing step, a subcatalyst mixing step and a cooling / filtration step.
상기 유화제 용해단계는 유화제인 알킬설폰산염을 물에 녹이는 공정이다. 즉, 반응기에 물과 알킬설폰산염을 투입한 후 반응기 내부를 약 45℃의 온도에서 30~40분 정도 유지하여 상기 알킬설폰산염이 물에 완전히 용해될 수 있도록 한다. 이렇게 알킬설폰산염이 물에 용해되면 이 용액을 혼합탱크에 이송한다.The emulsifier dissolving step is a step of dissolving the alkyl sulfonate as an emulsifier in water. That is, after the water and the alkyl sulfonate is added to the reactor, the inside of the reactor is maintained for about 30 to 40 minutes at a temperature of about 45 ℃ so that the alkyl sulfonate can be completely dissolved in water. When the alkyl sulfonate is dissolved in water, the solution is transferred to the mixing tank.
상기 모노머(Monomer) 용해단계는 혼합탱크로 이송된 알킬설폰산염이 용해된 물에 MMA(methylmethacrylate) 모노머(monomer)와, BAM(buthylacrylate monmer)을 혼합하는 공정이다. 이때는 MMA와 BAM이 좀 더 잘 용해될 수 있도록 교반작업을 수행한다. 그리고 모노머를 혼합한 이후에는 물과 유화제인 알킬설폰산염을 추가하여 최적의 수성아크릴폴리머가 제조될 수 있도록 구성성분의 비율을 조정하는 과정이 더 추가될 수도 있다.The monomer dissolution step is a process of mixing MMA (methylmethacrylate) monomer (BM) and BAM (buthylacrylate monmer) in water in which the alkyl sulfonate transferred to the mixing tank is dissolved. At this time, stirring is performed so that MMA and BAM can be dissolved more. After mixing the monomers, a process of adjusting the proportion of the constituents may be further added to add water and an alkylsulfonate as an emulsifier so that an optimal aqueous acrylic polymer may be prepared.
상기 주촉매 혼합단계는 상기 모노머 용해단계에서 생성된 용액에 주촉매인 과황산암모늄을 혼합하고 촉매반응이 일어나도록 30~40분정도 그 상태를 유지하는 공정이다.The main catalyst mixing step is a process of mixing the ammonium persulfate as the main catalyst with the solution produced in the monomer dissolution step and maintaining the state for about 30 to 40 minutes so that a catalytic reaction occurs.
상기 부촉매 혼합단계는 주촉매인 상기 과황산암모늄이 혼합된 용액에 부촉매인 중아황산소다를 혼합하고 촉매반응이 일어나도록 30~40분정도 그 상태를 유지하는 공정이다.The subcatalyst mixing step is a process of mixing sodium bisulfite as a subcatalyst in a solution in which the ammonium persulfate as the main catalyst is mixed and maintaining the state for about 30 to 40 minutes so that a catalytic reaction occurs.
상기와 같이 주촉매와 부촉매 혼합단계가 완료된 이후에는 약 60~70℃의 온도에서 6시간정도 가열하면서 교반을 한다. 이 과정을 통하여 단분자들인 MMA(methylmethacrylate)와 BAM(Buthylacrylate monomer)은 촉매들에 의하여 개시반응(initiation reaction)과 성장반응(propagation reaction) 및 종결반응(termination reaction)을 거쳐 고분자인 아크릴폴리머로 생성되는 것이다. After the main catalyst and subcatalyst mixing step is completed as described above, the mixture is stirred while heating for about 6 hours at a temperature of about 60 ~ 70 ℃. Through this process, MMA (methylmethacrylate) and BAM (Buthylacrylate monomer), which are single molecules, are formed into an acrylic polymer as a polymer through an initiation reaction, a growth reaction, and a termination reaction by catalysts. Will be.
상기 냉각/여과단계는 부촉매 혼합단계에서 생성된 용액을 45℃ 이하로 냉각시킨 후 아크릴폴리머에 혼재된 고형분을 여과시키는 여과시키는 공정이다.The cooling / filtration step is a process of filtering the solids mixed in the acrylic polymer after cooling the solution produced in the subcatalyst mixing step to 45 ° C. or less.
여기서, 상기와 같은 과정을 거쳐 생성된 수성아크릴폴리머의 분자식은 
한편, 상기와 같은 제조방법에 의하여 제조된 수성아크릴폴리머에는 미량의 알킬설폰산염과 촉매가 잔류하지만, 이것을 사용하여 포장용 아스팔트 콘크리트를 제조하면 상기 알킬설폰산염은 음이온계 유화아스팔트에 포함되는 작용을 하게 되고, 상기 촉매는 촉매자체의 특성상 반응속도만을 변화시키므로 수성아크릴폴리머의 작용에는 별다른 영향을 미치지 않는다.On the other hand, a small amount of alkyl sulfonate and a catalyst remain in the aqueous acrylic polymer prepared by the above-described manufacturing method. However, when the asphalt concrete for pavement is prepared using this, the alkyl sulfonate may be included in the anionic emulsion asphalt. In addition, since the catalyst only changes the reaction rate due to the characteristics of the catalyst itself, it does not affect the action of the aqueous acrylic polymer.
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