KR100491098B1 - Method for preparing high purity methacrylate quaternary ammonium salt - Google Patents
Method for preparing high purity methacrylate quaternary ammonium salt Download PDFInfo
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- KR100491098B1 KR100491098B1 KR1019970052732A KR19970052732A KR100491098B1 KR 100491098 B1 KR100491098 B1 KR 100491098B1 KR 1019970052732 A KR1019970052732 A KR 1019970052732A KR 19970052732 A KR19970052732 A KR 19970052732A KR 100491098 B1 KR100491098 B1 KR 100491098B1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/20—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated
Abstract
본 발명은 고순도 메타아크릴레이트 4급 암모늄염의 제조방법에 관한 것으로서, 더욱 상세하게는 메타아크릴레이트 3급 아민과 할로겐화물을 반응시켜 메타아크릴레이트 4급 암모늄염을 제조하는 공지방법에서 반응용매로는 유일하게 물만을 사용하므로 반응완료후 용매제거를 위한 복잡한 공정과 계면활성제를 추가로 주입하는 공정이 필요없고, 반응기 내부로의 물 용매의 주입 속도를 메타아크릴레이트 4급 암모늄염의 생성속도에 비례하여 조절하여 메타아크릴레이트 3급 아민의 가수분해를 방지하며, 종래 방법이 할로겐화물을 기상(氣相)주입하여 반응시간 지연과 유리산 생성의 증가를 초래한 대신에 액상(液相)주입법을 채택하여 반응열을 효율적으로 제어함으로써 상기와 같은 문제를 해결하였으며, 또한 반응완료후에는 에어블리딩(air bleeding)에 의한 간단한 정제방법으로 미반응 할로겐화물과 저비점 화합물을 제거하고 생성된 메타아크릴레이트 4급 암모늄염의 가교결합을 방지하게 되는 고순도의 메타아크릴레이트 4급 암모늄염의 제조방법에 관한 것이다.The present invention relates to a method for producing a high-purity methacrylate quaternary ammonium salt, and more particularly, the reaction solvent in the known method for producing a methacrylate quaternary ammonium salt by reacting a methacrylate tertiary amine with a halide. Since only water is used, there is no need for complicated process for removing solvent and additional injection of surfactant after completion of reaction, and the rate of injection of water solvent into reactor is controlled in proportion to the production rate of methacrylate quaternary ammonium salt. Hydrolysis of methacrylate tertiary amines is prevented, and the conventional method adopts liquid phase injection instead of gas phase injection of halides, resulting in increased reaction time and increased free acid formation. The above problem was solved by efficiently controlling the heat of reaction, and after the reaction was completed, air bleeding The present invention relates to a method for preparing a high purity methacrylate quaternary ammonium salt which removes unreacted halides and low boiling point compounds by ing) and prevents crosslinking of the resulting methacrylate quaternary ammonium salt.
Description
본 발명은 고순도 메타아크릴레이트 4급 암모늄염의 제조방법에 관한 것으로서, 더욱 상세하게는 메타아크릴레이트 3급 아민과 할로겐화물을 반응시켜 메타아크릴레이트 4급 암모늄염을 제조하는 공지방법에서 반응용매로는 유일하게 물만을 사용하므로 반응완료후 용매제거를 위한 복잡한 공정과 계면활성제를 추가로 주입하는 공정이 필요없고, 반응기 내부로의 물 용매의 주입 속도를 메타아크릴레이트 4급 암모늄염의 생성속도에 비례하여 조절하여 메타아크릴레이트 3급 아민의 가수분해를 방지하며, 종래 방법이 할로겐화물을 기상(氣相)주입하여 반응시간 지연과 유리산 생성의 증가를 초래한 대신에 액상(液相)주입법을 채택하여 반응열을 효율적으로 제어함으로써 상기와 같은 문제를 해결하였으며, 또한 반응완료후에는 에어블리딩(air bleeding)에 의한 간단한 정제방법으로 미반응 할로겐화물과 저비점 화합물을 제거하고 생성된 메타아크릴레이트 4급 암모늄염의 가교결합을 방지하게 되는 고순도의 메타아크릴레이트 4급 암모늄염의 제조방법에 관한 것이다.The present invention relates to a method for producing a high-purity methacrylate quaternary ammonium salt, and more particularly, the reaction solvent in the known method for producing a methacrylate quaternary ammonium salt by reacting a methacrylate tertiary amine with a halide. Since only water is used, there is no need for complicated process for removing solvent and additional injection of surfactant after completion of reaction, and the rate of injection of water solvent into reactor is controlled in proportion to the production rate of methacrylate quaternary ammonium salt. Hydrolysis of methacrylate tertiary amines is prevented, and the conventional method adopts liquid phase injection instead of gas phase injection of halides, resulting in increased reaction time and increased free acid formation. The above problem was solved by efficiently controlling the heat of reaction, and after the reaction was completed, air bleeding The present invention relates to a method for preparing a high purity methacrylate quaternary ammonium salt which removes unreacted halides and low boiling point compounds by ing) and prevents crosslinking of the resulting methacrylate quaternary ammonium salt.
메타아크릴레이트 4급 암모늄염은 수처리 고분자응집제의 원료로 널리 사용되고 있으며, 이의 제조방법에 대한 다각적인 연구가 진행되어 왔다.Methacrylate quaternary ammonium salt is widely used as a raw material of the water treatment polymer coagulant, and various studies have been conducted on its preparation method.
예를 들면, 4급 암모늄염을 유기용매에 직접 석출시켜 제조한 후 용매를 여과하고 건조시켜 회수하는 방법[일본특허공개 소 52-27712 호]과, 물을 용매로 사용하여 합성된 암모늄염을 용해시켜 수용액상으로 제조하는 방법[일본특허공개 소 52-31016 호]등이 개시되어 있다. 또한, 4급 암모늄염 합성반응을 고농도하에서 개시하고 4급염의 농도가 포화량을 넘을 때 물을 주입하는 방법[일본특허공개 소 59-101914 호]과, 물과 혼합성을 갖는 저비점 유기용매의 존재하에서 반응하는 방법[일본특허공개 소 52-27712 호]등이 개시되어 있으나, 반응시간이 6 ∼ 10시간으로 비교적 장시간이 소요되는 문제점이 있다. 좀더 개선된 방법으로서 반응용매인 물과 저비점 유기용매인 아세톤을 혼합하여 반응시키고 미반응 3급 아민을 염산으로 중화시킨 후, 아세톤을 감압하에 제거하여 4급 암모늄염을 얻는 방법[일본특허공개 평 2-129156 호]이 있으나, 이 방법은 전체적인 반응시간을 단축시키는 효과는 있지만 미반응 3급 아민을 염산으로 중화반응시켜 제거해야 하는 문제점이 있다.For example, quaternary ammonium salts are prepared by directly depositing them in an organic solvent, and then the solvent is filtered and dried to recover the solution (Japanese Patent Publication No. 52-27712), and water is used as a solvent to dissolve the synthesized ammonium salt. Japanese Patent Laid-Open No. 52-31016, and the like, which are prepared in an aqueous phase, are disclosed. In addition, a method of initiating quaternary ammonium salt synthesis reaction under high concentration and injecting water when the concentration of the quaternary salt exceeds the saturation amount (Japanese Patent Laid-Open No. 59-101914), and the presence of a low boiling organic solvent having a miscibility with water Although the method of reacting under Japanese Patent Application Laid-Open No. 52-27712 is disclosed, there is a problem that the reaction time is 6 to 10 hours and takes a relatively long time. As a further improved method, a reaction mixture of water, a reaction solvent, and acetone, a low boiling point organic solvent, is neutralized with hydrochloric acid, and then acetone is removed under reduced pressure to obtain a quaternary ammonium salt. -129156], but this method has the effect of shortening the overall reaction time, but there is a problem to remove the unreacted tertiary amine by neutralization with hydrochloric acid.
상기에서 설명한 바와 같은 종래의 4급 암모늄염의 제조방법은 반응계가 불균일 상태로 유지되기 때문에 반응시간이 길고, 반응 도중에 반응의 점도가 증가하여 교반의 부하가 매우 크게 되며, 반응 완료후에 용제 제거를 위한 복잡한 조작이 추가되어야 하는 번거로움이 있다.The conventional quaternary ammonium salt manufacturing method as described above has a long reaction time because the reaction system is maintained in a non-uniform state, the viscosity of the reaction increases during the reaction, the load of agitation is very large, and the solvent is removed for completion of the reaction. There is a hassle that complicated operations need to be added.
또한, 반응시간을 단축하기 위해 안정제와 계면활성제를 1.5 중량% 주입한 후 할로겐화물을 부가시켜 4급 암모늄염을 제조하는 방법[일본특허공개 평 1-249729 호]이 개시되어 있으나, 계면활성제의 추가주입으로 인한 제품의 첨가물 증가를 초래하고, 미반응 3급 아민의 잔류량(0.5%)이 많은 문제가 있다.In addition, a method of preparing a quaternary ammonium salt by injecting a stabilizer and a surfactant in an amount of 1.5% by weight and then adding a halide to shorten the reaction time is disclosed. The injection results in an increase in the additives of the product, and the residual amount of unreacted tertiary amine (0.5%) is problematic.
반응액을 균일상태로 유도하고 반응시간을 단축하기 위한 보다 개선된 방법으로서, 합성 도중에 물 용매를 여러번 분할 주입하고 할로겐화물을 기상으로 주입하여 기액반응시키는 방법[대한민국특허출원 제 95-3603 호]이 개시되어 있으나, 기액반응에 의한 반응열이 유발되고 이로 인하여 반응시간이 지연되고 유리산의 생산을 초래하게 된다.As a further improved method for inducing the reaction solution to a uniform state and shortening the reaction time, a method of gas-liquid reaction by injecting a water solvent several times during the synthesis and injecting a halide into the gas phase [Korea Patent Application No. 95-3603] Although it is disclosed, the heat of reaction caused by the gas-liquid reaction is induced, which leads to a delay in the reaction time and the production of free acid.
또한, 반응 생성 혼합물로부터 고순도 4급 암모늄염을 회수하기 위하여 일반적으로 장시간에 걸친 진공법을 채택하고 있으나, 이는 생성된 4급 암모늄염의 가교결합을 유발하는 문제점이 있다.In addition, in order to recover the high-purity quaternary ammonium salt from the reaction product mixture generally employs a vacuum method for a long time, which has a problem of causing cross-linking of the quaternary ammonium salt produced.
본 발명자들은 3급 아민과 할로겐화물을 반응시켜 4급 암모늄염을 제조하는 공지 제조방법상의 문제점을 개선하고자 연구 노력하였다. 그 결과, 본 발명은 물을 용매로 사용하여 계면활성제 및 기타 첨가물을 주입하지 않고도 단일공정으로 4급 암모늄염을 제조할 수 있으며, 반응속도에 비례한 물 용매 주입법으로 가수분해를 최대한 억제할 수 있고, 할로겐화물의 액상 주입법을 도입하여 반응열 제어가 가능하며 또한, 에어 블리딩(air bleeding)에 의한 정제방법에 의해 안정한 고품질의 메타아크릴레이트 4급 암모늄염을 제조하는 방법을 제공하는데 그 목적이 있다.The present inventors have tried to improve the problems in the known production method for producing a quaternary ammonium salt by reacting a tertiary amine with a halide. As a result, the present invention can produce quaternary ammonium salt in a single process without using a water and a solvent injecting surfactants and other additives, it is possible to suppress the hydrolysis as much as possible by the injection of water solvent proportional to the reaction rate It is an object of the present invention to provide a method for preparing a stable high-quality methacrylate quaternary ammonium salt by introducing a liquid injection method of a halide and controlling reaction heat, and by a purification method by air bleeding.
본 발명은 다음 화학식 1로 표시되는 메타아크릴레이트 3급 아민과 다음 화학식 2로 표시되는 할로겐화물을 반응시켜 다음 화학식 3으로 표시되는 메타아크릴레이트 4급 암모늄염을 제조하는 방법에 있어서,The present invention provides a method for preparing a methacrylate quaternary ammonium salt represented by the following formula (3) by reacting a methacrylate tertiary amine represented by the following formula (1) with a halide represented by the following formula (2),
반응용매인 물은 합성반응전에 일정량 주입하고 나머지 잔여분은 액상(액상)의 할로겐화물 부가반응 속도에 비례한 주입속도로 반응물중 균일하게 주입하여 반응시키는 것을 그 특징으로 한다.Water as a reaction solvent is injected into a predetermined amount before the synthesis reaction, and the remainder is characterized in that the reaction is uniformly injected in the reaction at an injection rate proportional to the rate of the halide addition reaction of the liquid (liquid).
상기 화학식들에서: R1 및 R2는 각각 수소원자 또는 탄소수 1 ∼ 3의 알킬기를 나타내고; R3는 탄소수 1 ∼ 3의 알킬기, 페닐기 또는 벤질기를 나타내고; X는 할로겐 원자를 나타낸다.In the above formulas: R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R 3 represents an alkyl group having 1 to 3 carbon atoms, a phenyl group or a benzyl group; X represents a halogen atom.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명은 메타아크릴레이트 3급 아민과 할로겐화물의 반응에서 반응용매로 는 오로지 물만을 사용하고 기타 다른 첨가제의 첨가없이 단일공정으로 수행되며 할로겐화물을 액상 주입하여 반응열을 효과적으로 제어하는 메타아크릴레이트 4급 암모늄염의 제조방법에 관한 것이다.The present invention uses only water as a reaction solvent in the reaction of methacrylate tertiary amines with halides and is carried out in a single process without the addition of other additives. It relates to a method for producing a class ammonium salt.
본 발명에 따른 메타아크릴레이트 4급 암모늄염의 제조반응을 간략히 나타내면 다음 반응식 1과 같다.Briefly showing the reaction of the methacrylate quaternary ammonium salt according to the present invention as shown in Scheme 1.
상기 반응식 1에서: R1 및 R2는 각각 수소원자 또는 탄소수 1 ∼ 3의 알킬기를 나타내고; R3는 탄소수 1 ∼ 3의 알킬기, 페닐기 또는 벤질기를 나타내고; X는 할로겐 원자를 나타낸다.In Reaction Scheme 1, R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R 3 represents an alkyl group having 1 to 3 carbon atoms, a phenyl group or a benzyl group; X represents a halogen atom.
본 발명에 따른 제조방법에서는 반응초기에는 메타아크릴레이트 3급 아민을 소량의 물용매에서 1 ∼ 2시간 정도 반응시킨 후, 4급 암모늄염의 생성속도 다시 말하면 할로겐화물 부가반응 속도에 비례한 주입속도로 나머지 물용매를 주입하면서 반응시킨다. 반응초기에 투입되는 물의 양은 메타아크릴레이트 3급 아민 1몰에 대하여 1 ∼ 2 몰비가 바람직하고, 반응도중에 투입되는 물의 양은 메타아크릴레이트 4급 암모늄염 생성량 1몰에 대하여 2 ∼ 3 몰비 범위내에서 0.4 ∼ 0.6 ㎖/min의 유속으로 연속적으로 흘려준다. 상기에서 설명한 바와 같은 조건하에서 반응초기에 소량의 물용매를 사용하여 과량의 물에 의한 메타아크릴레이트 3급 아민의 가수분해를 방지하고, 반응 도중에 물을 일정 주입속도로 주입하여 생성된 메타아크릴레이트 4급 암모늄염의 고형화를 막을 수 있게 된다.In the preparation method according to the present invention, after the reaction of the methacrylate tertiary amine in a small amount of water for 1 to 2 hours at the beginning of the reaction, the rate of formation of the quaternary ammonium salt, that is, in proportion to the rate of halide addition reaction, React while injecting the remaining water solvent. The amount of water added at the beginning of the reaction is preferably 1 to 2 moles per 1 mole of methacrylate tertiary amine, and the amount of water to be added during the reaction is 0.4 to 2 moles to 1 mole of methacrylate quaternary ammonium salt produced. It is continuously flowed at a flow rate of ˜0.6 ml / min. Under the conditions as described above, a small amount of water solvent is used at the beginning of the reaction to prevent hydrolysis of the methacrylate tertiary amine by excess water, and methacrylate formed by injecting water at a constant injection rate during the reaction. The solidification of the quaternary ammonium salt can be prevented.
또한, 본 발명은 할로겐화물을 액상(액상)으로 주입하는 방법에도 그 특징이 있다. 할로겐화물을 액상으로 주입함으로써 증발잠열로 반응액을 냉각시켜 반응열을 제거할 수 있어 반응액의 온도제어가 용이하고 반응속도를 증가시켜 반응시칸을 단축할 수 있고, 또한 반응속도는 액체 할로겐화물의 주입량으로도 쉽게 조절이 가능하다. 액체 할로겐화물은 메타아크릴레이트 3급 아민 1몰에 대하여 1 ∼ 1.5 몰비 범위내에서 1 ∼ 2시간동안 균일하게 주입하며, 이로써 빠른 반응속도를 유지할 수 있어 전반적인 반응시간을 단축시킬 수 있다. 이때, 액체 할로겐화물을 20% 과잉 주입하여 반응기내의 압력을 2 ∼ 8 ㎏/㎠으로 유지할 수 있게 하며, 반응 후 미반응 할로겐화물은 회수하여 재사용한다.Moreover, this invention also has the characteristics in the method of injecting a halide in liquid form (liquid phase). By injecting the halide into the liquid phase, it is possible to remove the heat of reaction by cooling the reaction liquid with the latent heat of evaporation, so that the temperature of the reaction liquid can be easily controlled, and the reaction rate can be shortened by increasing the reaction speed. It can be easily adjusted with the injection amount of. The liquid halide is uniformly injected for 1 to 2 hours in the range of 1 to 1.5 molar ratio with respect to 1 mole of methacrylate tertiary amine, thereby maintaining a fast reaction rate and shortening the overall reaction time. At this time, by injecting 20% excess of the liquid halide to maintain the pressure in the reactor to 2 ~ 8 kg / ㎠, unreacted halide after the reaction is recovered and reused.
종래 4급 암모늄염의 합성방법이 기액반응으로 수행되므로 많은 반응열을 발출하였고, 반응속도를 높이기 위하여 발생되는 많은 반응열을 신속히 제거해야만 하였다. 그러나, 본 발명에서는 반응열을 효율적으로 제거하기 위해 기초원료로 투입되는 할로겐화물을 액상으로 부가반응시키므로 반응중에 발생되는 반응열은 증발잠열로 상쇄되어 반응초기에 발생되는 급격한 발열을 제어할 수 있다.Since the conventional method of synthesizing quaternary ammonium salt is carried out by gas-liquid reaction, a lot of heat of reaction is extracted, and much heat of reaction generated in order to increase the reaction rate has to be removed quickly. However, in the present invention, since the halide introduced as a base material is added to the liquid phase in order to efficiently remove the reaction heat, the reaction heat generated during the reaction is offset by latent heat of evaporation, thereby controlling the rapid exotherm generated at the beginning of the reaction.
상기에서 설명한 바와 같은 메타아크릴레이트 3급 아민에의 할로겐화물의 부가반응은 10 ∼ 80℃, 바람직하기로는 20 ∼ 60℃의 온도범위에서 수행된다. 만일, 반응온도가 10℃ 미만이면 할로겐화물의 부가반응 속도가 느려 용매로 주입된 물로 인한 가수분해 현상이 일어나고, 80℃를 초과하면 아크릴레이트 화합물이 폴리머를 형성하거나 가교결합을 일으키게 된다.The addition reaction of the halides to the methacrylate tertiary amines as described above is carried out at a temperature range of 10 to 80 ° C., preferably 20 to 60 ° C. If the reaction temperature is less than 10 ° C, the addition reaction rate of the halide is slow and hydrolysis due to water injected into the solvent occurs. If the reaction temperature exceeds 80 ° C, the acrylate compound forms a polymer or causes crosslinking.
이와 같이 액체 할로겐화물을 주입함으로써 합성반응초기의 압력은 상승하지 않지만 반응이 1 ∼ 2시간 경과한 후에는 그 압력이 1 ∼ 6 ㎏/㎠까지 상승하게 되므로 반응압력은 2 ∼ 10 ㎏/㎠, 바람직하기로는 3 ∼ 6 ㎏/㎠의 범위가 좋다. 이러한 반응들은 상압에서 수행하기 어려우므로 반응기 내무가 외부와 차단되어야 하고, 또한 내부에 발생되는 열은 외부로 손쉽게 배출될 수 있도록 자켓타입 고압 반응기(autoclave)를 사용한다.By injecting the liquid halide as described above, the pressure of the initial stage of the synthesis reaction does not increase, but after 1 to 2 hours, the pressure rises to 1 to 6 kg / cm 2, so the reaction pressure is 2 to 10 kg / cm 2, Preferably, the range of 3-6 kg / cm <2> is good. Since these reactions are difficult to perform at atmospheric pressure, the inside of the reactor should be shut off from the outside, and heat generated inside the jacket type autoclave is used so that it can be easily discharged to the outside.
또한, 본 발명은 반응완료후 반응 생성물 혼합물로부터 고순도 메타아크릴레이트 4급 암모늄염을 회수하는 방법에도 또다른 특징이 있다.In addition, the present invention also has another feature in the method of recovering high-purity methacrylate quaternary ammonium salt from the reaction product mixture after completion of the reaction.
반응 종료시 반응하지 않고 남은 할로겐화물을 제거하기 위해 종래에는 진공펌프를 작동시켜 제거하였으나, 본 발명에서는 반응기내에 순도 99.995의 고순도 건조공기를 2 ∼ 3 ℓ/min 유속으로 1 ∼ 2시간 불어넣어 반응액중에 반응하지 않고 남아 있는 미반응 할로겐화물 및 저비점 화합물 등의 불순물을 제거하여 안정화된 메타아크릴레이트 4급 암모늄염을 수용액상으로 제조할 수 있다.Conventionally, a vacuum pump was operated to remove the halides remaining unreacted at the end of the reaction. However, in the present invention, high purity dry air having a purity of 99.995 is blown into the reactor at a flow rate of 2 to 3 l / min for 1 to 2 hours. Impurities such as unreacted halides and low-boiling compounds that remain unreacted in the water may be removed to prepare a stabilized methacrylate quaternary ammonium salt in the form of an aqueous solution.
그리고, 제조후 제품에서 안정제를 별도로 분리하지 않아도 되도록 폴리머 제조시 통상적으로 사용되는 안정제를 선택하여 주입할 수도 있다. 안정제의 사용량은 메타아크릴레이트 3급 아민에 대하여 0.1 ∼ 0.5 중량%, 바람직하기로는 0.15 ∼ 0.3 중량%를 사용하는 것이다.In addition, a stabilizer commonly used in polymer production may be selected and injected so as not to separate the stabilizer from the product after manufacture. The amount of stabilizer to be used is 0.1 to 0.5% by weight, preferably 0.15 to 0.3% by weight based on the methacrylate tertiary amine.
이와 같은 본 발명에 따른 메타아크릴레이트 4급 암모늄염의 제조방법은 용매로서 물만 사용하므로 4급 암모늄염을 폴리머 원료로 사용할 때 용매를 제거하거나 교체할 필요 없이 희석하여 사용할 수 있으므로 경제적이다. 그리고, 본 발명의 제조방법에 따라 제조된 4급 암모늄염의 농도를 65 ∼ 80%로하여 제품을 단일공정에서 농축이나 희석과정 없이 제조할 수 있으나 통상적으로 75%의 제품을 제조하여 사용한다.Such a method for producing the methacrylate quaternary ammonium salt according to the present invention is economical because only water is used as the solvent, so that when the quaternary ammonium salt is used as a polymer raw material, it can be used without diluting or removing the solvent. And, the concentration of the quaternary ammonium salt prepared according to the production method of the present invention to 65 to 80% can be produced without concentration or dilution in a single process, but is usually used to prepare a product of 75%.
이와 같은 본 발명을 실시예에 의거하여 상세하게 설명하겠는 바, 본 발명이 실시예에 한정되는 것은 아니다. 다음의 실시예와 비교예에서는 특정 원료 물질만을 사용한 예를 기재하고 있지만, 이와 유사한 구조의 3급 아민이나 할로겐화물을 사용하여도 동일한 효과를 얻을 수 있다.Although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example. In the following examples and comparative examples, examples using only specific raw materials are described, but similar effects can be obtained by using tertiary amines or halides having similar structures.
또한, 다음의 실시예 및 비교예에서의 반응하지 않고 남은 할로겐화물은 20℃의 온도를 유지하는 항온조에서 증발되는 기체를 기체 크로마토그래피로 분석하거나 또는 디메틸 클로라이드로 추출한 후 기체 크로마토그래피로 분석하였고, 3급 아민은 0.1N 염산으로 자동적정기기에서 산염기 적정하여 아민값(total amine value)으로 확인하였으며, 가수분해 정도는 0.1N 수산화칼륨 수용액으로 적정하여 산가(acid value)를 측정하였다.In addition, the halides left unreacted in the following examples and comparative examples were analyzed by gas chromatography after gas evaporation in a thermostat maintained at a temperature of 20 ° C. or by extraction with dimethyl chloride, and gas chromatography. The tertiary amine was titrated with 0.1 N hydrochloric acid in an automatic titrator to confirm the amine value, and the degree of hydrolysis was titrated with 0.1 N aqueous potassium hydroxide solution to determine the acid value.
실시예 1Example 1
유효 용량이 500 ㎖인 자켓 타입의 유리 고압반응기(glass autoclave)에 온도를 확인할 수 있는 온도측정기와 물을 일정유속으로 주입할 수 있는 미니펌프와 액체 메틸 클로라이드를 주입할 수 있는 장치를 설치하였다.A jacket-type glass autoclave with an effective capacity of 500 ml was installed with a temperature meter to check the temperature, a minipump to inject water at a constant flow rate, and a device to inject liquid methyl chloride.
준비된 반응기에 디메틸아미노에틸메타아크릴레이트(이하 "DMAEM"라 함) 157.2g, 물 27.9g 및 하이드로퀴논모노메틸에테르(이하 "HQME"라 함) 0.24g을 넣고 반응액의 온도를 40℃로 유지하며 메틸 클로라이드를 액체상태로 주입하여 부가반응시켰다. 이때, 반응압력은 메틸 클로라이드로 4 ㎏/㎠를 유지할 수 있게 하고, 41.3g의 초순수를 추가로 준비하였다.157.2 g of dimethylaminoethyl methacrylate (hereinafter referred to as "DMAEM"), 27.9 g of water and 0.24 g of hydroquinone monomethyl ether (hereinafter referred to as "HQME") were added to the prepared reactor, and the temperature of the reaction solution was maintained at 40 ° C. Methyl chloride was injected into the liquid state and reacted by addition. At this time, the reaction pressure was able to maintain 4 kg / ㎠ with methyl chloride, 41.3g of ultrapure water was further prepared.
1시간 동안 부가반응 시킨후 3급 아민이 4급 암모늄염으로 전환되는 속도에 비례하여 추가로 준비된 물을 0.48 ㎖/min 속도로 1시간 25분 동안 주입하며 반응시키고, 물 주입 종료후 30분 동안 반응압력을 유지하면서 계속 교반시킨후 반응을 종료하였다. 반응후 반응하지 않고 남은 메틸 클로라이드는 회수하여 재사용하고 반응액에 잔류한 메틸 클로라이드는 고순도 공기를 불어 넣어 제거하였다.After 1 hour of addition reaction, the prepared water is reacted with an additional rate of 0.48 ml / min for 1 hour and 25 minutes in proportion to the rate at which the tertiary amine is converted to the quaternary ammonium salt. After the stirring was continued while maintaining the pressure, the reaction was terminated. After the reaction, methyl chloride remaining without reaction was recovered and reused, and methyl chloride remaining in the reaction solution was removed by blowing high purity air.
이때, 메타아크릴로일옥시에틸트리메틸암모늄클로라이드(4급 암모늄염)의 수율은 99.7%, 반응하지 않고 남은 DMAEM은 0.01%, 유리산은 0.01% 이었고 클로로메탄은 흔적량 정도로 거의 존재하지 않았다.At this time, the yield of methacryloyloxyethyltrimethylammonium chloride (quaternary ammonium salt) was 99.7%, DMAEM remaining unreacted was 0.01%, free acid was 0.01% and chloromethane was hardly present in trace amounts.
실시예 2Example 2
상기 실시예 1과 동일한 방법으로 하되, 메틸 클로라이드를 기체상태로 주입하여 반응시켰다. 이때, 4급 암모늄염의 수율은 99.2%, 반응하지 않고 남은 DMAEM은 0.05%, 유리산은 0.04% 이었고 반응하지 않고 남은 메틸 클로라이드는 없었으나 전반적인 반응속도가 느려져 반응시간이 4시간으로 늘어났고, 반응시 많은 열이 발생하였다.In the same manner as in Example 1, methyl chloride was injected into a gaseous state for reaction. At this time, the yield of quaternary ammonium salt was 99.2%, DMAEM remaining unreacted was 0.05%, free acid was 0.04%, and there was no methyl chloride left unreacted, but the overall reaction rate was slowed to increase the reaction time to 4 hours. A lot of heat was generated.
실시예 3Example 3
상기 실시예 1과 동일한 방법으로 하되, 액상의 메틸 클로라이드를 반응전에 일시 주입한 후 부가반응시켰다. 이때, 4급 암모늄염의 수율은 98.9%, 반응하지 않고 남은 DMAEM은 0.01%, 유리산은 0.07% 이었으나 초기 반응열이 급격히 증가하였다.In the same manner as in Example 1, the liquid methyl chloride was temporarily injected before the reaction, followed by addition reaction. At this time, the yield of quaternary ammonium salt was 98.9%, DMAEM remaining unreacted was 0.01%, free acid was 0.07%, but the initial heat of reaction increased rapidly.
실시예 4Example 4
상기 실시예 1과 동일한 방법으로 하되, 반응전에 물을 전량(69.2g) 주입한 후 합성하여 반응시켰다. 이때, 4급 암모늄염의 수율은 263.9g(98.4%), 반응하지 않고 남은 DMAEM은 0.03%, 유리산은 0.06% 이었다.In the same manner as in Example 1, before the reaction was injected a total amount of water (69.2g) and then synthesized and reacted. At this time, the yield of the quaternary ammonium salt was 263.9g (98.4%), DMAEM remaining unreacted was 0.03%, free acid was 0.06%.
실시예 5Example 5
상기 실시예 1과 동일한 방법으로 하되, DMAEM 157.2g, HQME 0.24g을 반응기에 넣고 물 27.9g과 아세톤 48g을 주입한 후 40℃의 반응온도에서 메틸 클로라이드를 액상으로 주입하며 부가반응시킨 후 아세톤을 진공제거하였다. 이때, 4급 암모늄염의 수율은 97.7%, 반응하지 않고 남은 DMAEM은 0.48%, 유리산은 0.06% 이었다.In the same manner as in Example 1, DMAEM 157.2g, HQME 0.24g into the reactor, 27.9g of water and 48g of acetone were injected, methyl chloride was injected into the liquid phase at a reaction temperature of 40 ℃ and the addition reaction after acetone Vacuum removed. At this time, the yield of the quaternary ammonium salt was 97.7%, the remaining DMAEM without reaction was 0.48%, the free acid was 0.06%.
실시예 6Example 6
상기 실시예 1과 동일한 방법으로 하되, 물을 초기주입(합성반응전 주입)하지 않고 실시하였다. DMAEM 157.2g, HQME 0.24g을 주입한후 물의 69.2g을 3시간 30분간 0.33 ㎖/min 속도로 주입하며 메틸 클로라이드로 부가반응시켰다. 이때, 4급 암모늄염의 수율은 273.4g(98.8%), 반응하지 않고 남은 DMAEM은 0.3%, 유리산은 0.05% 이었다.In the same manner as in Example 1, it was carried out without the initial injection of water (injection before the synthesis reaction). After injecting 157.2 g of DMAEM and 0.24 g of HQME, 69.2 g of water was injected at a rate of 0.33 ml / min for 3 hours and 30 minutes, followed by addition reaction with methyl chloride. At this time, the yield of quaternary ammonium salt was 273.4g (98.8%), DMAEM remaining unreacted was 0.3%, free acid was 0.05%.
비교예 1Comparative Example 1
상기 실시예 1과 동일한 방법으로 하되, 기상 메틸 클로라이드를 반응전에 전량 주입한후 합성하였다. 이때, 4급 암모늄염의 수율은 260.12g(94%), 반응하지 않고 남은 DMAEM은 1.52%, 유리산은 3.6% 이었다.Synthesis was carried out in the same manner as in Example 1, after the total amount of gaseous methyl chloride was injected before the reaction. At this time, the yield of the quaternary ammonium salt was 260.12g (94%), DMAEM remaining unreacted was 1.52%, free acid was 3.6%.
비교예 2Comparative Example 2
상기 실시예 1과 동일한 방법으로 하되, 반응온도를 90℃로 승온하고 액체 메틸 클로라이드를 주입하여 합성반응을 실시하였다. 이때, 회수 반응액은 248.5g(89.8%), 반응하지 않고 남은 메틸 클로라이드를 제거시 폴리머의 시드가 생성되었다.In the same manner as in Example 1, the reaction temperature was raised to 90 ℃ and the liquid methyl chloride was injected to carry out the synthesis reaction. At this time, the recovered reaction solution was 248.5g (89.8%), the seed of the polymer was produced when removing the methyl chloride remaining without reacting.
비교예 3Comparative Example 3
상기 실시예 1과 동일한 방법으로 하되, 메틸 클로라이드의 주입압력을 상압으로 실시하였다. 이때, 4급 암모늄염의 수율은 226.9g(82%)이었다.In the same manner as in Example 1, the injection pressure of methyl chloride was carried out at normal pressure. At this time, the yield of the quaternary ammonium salt was 226.9g (82%).
상술한 바와 같이, 본 발명은 단일용매를 사용한 고순도 메타아크릴레이트 4급 암모늄염을 제조하는데 반응열을 최소화시키고, 반응시간을 단축시켜 부반응을 최대한 억제하고, 미반응 할로겐화물과 저비점 화합물의 효율적 제거로 안정성 높은 고농도의 메타아크릴레이트 4급 암모늄염을 제조할 수 있음을 알 수 있다.As described above, the present invention is to prepare a high-purity methacrylate quaternary ammonium salt using a single solvent, to minimize the heat of reaction, to shorten the reaction time to suppress side reactions as much as possible, the stability of the unreacted halides and low-boiling compounds efficiently It can be seen that a high concentration of methacrylate quaternary ammonium salt can be prepared.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4180519A (en) * | 1974-06-13 | 1979-12-25 | Rhone-Poulenc Industries | Process for obtaining and product acrylic monomers useful in the preparation of cationic flocculants |
| JPS57126452A (en) * | 1981-01-28 | 1982-08-06 | Sanyo Chem Ind Ltd | Preparation of quaternary ammonium salt |
| US4745214A (en) * | 1986-06-20 | 1988-05-17 | Norsolor | Process for the preparation of an aqueous solution of unsaturated quaternary ammonium salts |
| KR19980059283A (en) * | 1996-12-31 | 1998-10-07 | 박영구 | Method for preparing acrylate quaternary ammonium salt |
| KR100367906B1 (en) * | 1995-10-20 | 2003-03-04 | 삼성정밀화학 주식회사 | Preparation method of alkyl acrylate quaternary ammonium salt |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4180519A (en) * | 1974-06-13 | 1979-12-25 | Rhone-Poulenc Industries | Process for obtaining and product acrylic monomers useful in the preparation of cationic flocculants |
| JPS57126452A (en) * | 1981-01-28 | 1982-08-06 | Sanyo Chem Ind Ltd | Preparation of quaternary ammonium salt |
| US4745214A (en) * | 1986-06-20 | 1988-05-17 | Norsolor | Process for the preparation of an aqueous solution of unsaturated quaternary ammonium salts |
| KR100367906B1 (en) * | 1995-10-20 | 2003-03-04 | 삼성정밀화학 주식회사 | Preparation method of alkyl acrylate quaternary ammonium salt |
| KR19980059283A (en) * | 1996-12-31 | 1998-10-07 | 박영구 | Method for preparing acrylate quaternary ammonium salt |
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