KR101829868B1 - Non-phosphorus type flame retardant resin having good storage-stability and Manufacturing method thereof - Google Patents
Non-phosphorus type flame retardant resin having good storage-stability and Manufacturing method thereof Download PDFInfo
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Abstract
Description
본 발명은 난연수지에 관한 것으로서, 알코올 용제에 대한 용해성이 우수하여 장기간 보관시 난연수지의 석출이 없어서 저장안정성이 우수한 비인계 난연수지 및 미반응 모노머를 최소화하여 이를 제조하는 방법에 관한 것이다.The present invention relates to a flame retardant resin, and more particularly, to a non-phosphorus flame retardant resin excellent in storage stability because of its excellent solubility in an alcohol solvent and having no precipitation of a flame retardant resin during long-term storage, and a method for minimizing unreacted monomer.
최근 플라스틱의 용도가 건축용, 자동차용, 전기제품, 항공기, 선박 등으로 광범위하게 확대됨에 따라 화재 발생시 안전을 고려한 난연화 필요성이 지속적으로 증대되고 있다.Recently, as the use of plastics has expanded widely to architectural, automotive, electric products, aircraft, ships, etc., the necessity of flame retardation taking safety into consideration is continuously increasing.
플라스틱에 널리 사용되고 있는 난연제는 크게 첨가형과 반응형으로 나뉘고 첨가형은 다시 유기와 무기 난연제로 구분된다. 첨가형은 물리적으로 플라스틱에 난연제를 첨가해서 난연성을 향상시키지만, 반응형은 플라스틱을 제조할 때 일부에 난연제를 첨가해서 화학반응을 시키고 난연성을 향상시키는 방법이다. Flame retardants widely used in plastics are divided into additive type and reactive type, and addition type is divided into organic and inorganic flame retardant. The addition type physically improves the flame retardancy by adding a flame retardant to the plastic, but the reaction type is a method of adding a flame retardant to a part of the plastic to make a chemical reaction and improve the flame retardancy.
그리고, 난연제는 구성성분에 따라서는 유기계와 무기계로 분류되는데, 유기계는 주로 인계, 브롬계, 염소계 등으로 분류되고 무기계는 수산화알루미늄, 안티몬계 제품, 수산화마그네슘으로 분류된다.The flame retardant is classified into an organic and an inorganic type depending on the constituent components. The organic type is mainly classified into phosphorus, bromine and chlorine. The inorganic type is classified into aluminum hydroxide, antimony type product and magnesium hydroxide.
할로겐계 난연제는 사출시 가스발생과 소각시 다이옥신 발생으로 인체 및 환경에 유하함으로 이를 대체할수 있는 난연제 개발의 요구가 증가함에 따라 인계, 무기계와 더불어 질소계 난연제 개발이 증가하고 있다. Halogen based flame retardants are increasingly being developed in addition to phosphorus and inorganic flame retardants, as the development of flame retardants that can replace them due to the generation of gases and the incineration of dioxins occurs in the human body and the environment.
첨가형 질소계 난연제로는 멜라민시아누레이트(MC), 멜라민포스페이트(MP), 멜라민파이로포스페이트(MPP), 멜라민폴리포스페이트(MPP), 멜라민보레이트(MB), 멜라민설페이트 등이 있으나, 상업적으로 사용되고 있는 난연제는 멜라민시아누레트와 멜라민폴리포스페이트가 있다. 이런 난연제는 열안정성이 우수하고, 독성이 없는 반면에 물 또는 알코올에 대한 용해성이 없어 컴파운딩 또는 몰딩용 제품에 한정적으로 첨가 사용되는 단점이 있다. Examples of the additive type nitrogen flame retardant include melamine cyanurate (MC), melamine phosphate (MP), melamine pyrophosphate (MPP), melamine polyphosphate (MPP), melamine borate (MB), melamine sulfate and the like, The flame retardants are melamine cyanurate and melamine polyphosphate. Such a flame retardant has a disadvantage that it is excellent in thermal stability and does not have toxicity, but is insoluble in water or alcohol and is added to a compounding or molding product in a limited manner.
또한 첨가형 질소계 난연제들은 혼합 후 장기 사용 시 용출현상이 발생하여 인체 및 환경에 영향을 주고 있어 문제가 되고 있다.In addition, the additive type nitrogen flame retardants are problematic due to the leaching phenomenon during long-term use after mixing and affecting the human body and the environment.
본 발명은 첨가형 난연제가 알코올 용제에 녹지 않아 사용 용도가 제한되는 단점과, 다단계 중합을 통해 미반응 모노머의 함량을 1% 미만으로 하여 질소계 모노머의 용출을 방지하고, 알코올 용제 상에서도 석출 또는 침전이 없는 저장안정성을 확보한 비인계형 난연 수지 및 이를 다단계 중합법으로 제조하는데 그 목적이 있다.The present invention is based on the disadvantage that the additive type flame retardant is not dissolved in an alcohol solvent and its use is limited, and that the content of unreacted monomers is less than 1% by multistage polymerization to prevent the elution of the nitrogen-based monomer and precipitation or precipitation Free flame-retardant resin having a high storage stability and a multistage polymerization method.
상기 과제를 해결하기 위한 본 발명은 비인계 난연수지는 하기 화학식 1로 표시되는 반복단위를 포함하는 질소화합물을 포함한다.In order to solve the above problems, the present invention provides a non-phosphorous flame retardant comprising a nitrogen compound containing a repeating unit represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
화학식 1에서, R1 및 R4 각각은 서로 독립적인 것으로서, 수소원자, C1 ~ C5의 직쇄형 알킬기, C3 ~ C5의 분쇄형 알킬기, 페닐기 또는 알킬페닐기이며, R5는 -CN 또는 -CH2CN이고, n은 중합체의 중량평균분자량 200 ~ 1,500을 만족시키는 유리수이다.Each of R 1 and R 4 is independently a hydrogen atom, a straight-chain alkyl group of C 1 to C 5, a branched alkyl group of C 3 to C 5, a phenyl group or an alkylphenyl group, R 5 is -CN or -CH 2 CN, and n is a rational number satisfying a weight average molecular weight of the polymer of 200 to 1,500.
본 발명의 바람직한 일실시예로서, 본 발명의 비인계 난연수지는 -5℃에서 방치시, 12일 이전에 상기 질소화합물(비인계 난연수지) 및/또는 하기 화학식 2로 표시되는 화합물이 석출되지 않을 수 있다.In one preferred embodiment of the present invention, the non-phosphorus hard weather resistant sheet of the present invention is a sheet having a non-phosphorous flame retardant resin and / or a compound represented by the following formula (2) precipitated .
본 발명의 바람직한 일실시예로서, 본 발명의 비인계 난연수지는 10℃에서 방치시, 15일 이전에 상기 질소화합물(비인계 난연수지) 및/또는 하기 화학식 2로 표시되는 화합물이 석출되지 않을 수 있다.In one preferred embodiment of the present invention, the non-phosphorous flame retardant resin of the present invention is such that when the flame retardant is left at 10 DEG C, the nitrogen compound (non-phosphorus flame retardant resin) and / or the compound represented by the following formula .
본 발명의 바람직한 일실시예로서, 본 발명의 비인계 난연수지는 25℃에서 방치시, 20일 이전에 상기 질소화합물(비인계 난연수지) 및/또는 하기 화학식 2로 표시되는 화합물이 석출되지 않을 수 있다.In one preferred embodiment of the present invention, the non-phosphorous flame retardant of the present invention is a flame-retardant resin composition wherein the nitrogen compound (non-phosphorous flame retardant resin) and / or a compound represented by the following formula 2 is not precipitated .
[화학식 2](2)
화학식 2에서, R1 내지 R4 각각은 독립적인 것으로서, 수소원자, C1 ~ C5의 직쇄형 알킬기, C3 ~ C5의 분쇄형 알킬기, 페닐기 또는 알킬페닐기이며, R5는 -CN 또는 -CH2CN 이다.In formula (2), each of R 1 to R 4 is independently a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a phenyl group or an alkylphenyl group, R 5 is -CN or -CH 2 CN to be.
본 발명의 바람직한 일실시예로서, 본 발명의 비인계 난연수지는 고형분을 40 중량% 이상으로 포함할 수 있다.In one preferred embodiment of the present invention, the non-phosphorus hard weather resistant sheet of the present invention may contain a solid content of 40 wt% or more.
본 발명의 다른 목적은 앞서 설명한 비인계 난연수지를 제조하는 방법에 관한 것으로서, 상기 화학식 2로 표시되는 화합물 및 하기 화학식 3으로 표시되는 알데하이드를 1 : 0.6 ~ 0.95 몰비로 중합시켜 제조하여 상기 화학식 1로 표시되는 질소화합물을 제조할 수 있다.Another object of the present invention is to provide a method for producing the above-described non-phosphorus flame retardant resin, which comprises polymerizing the compound represented by Formula 2 and the aldehyde represented by Formula 3 in a molar ratio of 1: 0.6-0.95, Can be produced.
[화학식 3] (3)
화학식 3에서, R1 및 R2 각각은 독립적인 것으로서, 수소원자, C1 ~ C3의 직쇄형 알킬기 또는 페닐기이다.In Formula (3), each of R 1 and R 2 is independently a hydrogen atom, a straight-chain alkyl group having 1 to 3 carbon atoms, or a phenyl group.
본 발명의 바람직한 일실시예로서, 본 발명의 비인계 난연수지의 제조방법은 상기 화학식 2로 표시되는 화합물, 상기 화학식 3으로 표시되는 알데하이드 및 용매를 혼합한 용액을 교반한 후, 38 ~ 45℃까지 승온시키는 1단계; 승온된 용액에 촉매를 투입한 후, 58 ~ 65℃까지 승온시킨 후, 2시간 30분 ~ 3시간 30분 동안 1차 정시반응을 수행하는 2단계; 1차 정시반응시킨 용액에 상기 알데하이드 및 촉매를 투입한 후, 68 ~ 75℃로 승온시킨 후, 환류(reflux)시키면서 2시간 30분 ~ 3시간 30분 동안 2차 정시반응을 수행하는 3단계; 및 1℃ ~ 5℃로 냉각 및 필터링하는 4단계;를 포함하는 공정을 수행하여 비인계 난연수지를 제조할 수 있다.In one preferred embodiment of the present invention, the method for producing a non-phosphorus flame retardant resin of the present invention comprises stirring the solution of the compound represented by Formula 2, the aldehyde represented by Formula 3 and a solvent, 1 < / RTI > A step of adding a catalyst to the heated solution, raising the temperature to 58 to 65 ° C, and then carrying out a first-order reaction for 2 to 30 minutes to 3 hours and 30 minutes; A third step in which the aldehyde and the catalyst are added to the first-order reaction solution, the temperature is raised to 68 to 75 ° C, and the second-order reaction is performed for 2 to 30 minutes to 3 hours and 30 minutes while refluxing; And 4 stages of cooling and filtering at 1 to 5 占 폚 to obtain a non-phosphorus flame retardant resin.
본 발명의 바람직한 일실시예로서, 1단계의 용액은 화학식 2로 표시되는 화합물 100 중량부에 대하여 상기 알데하이드 18 ~ 32 중량부 및 용매 110 ~ 180 중량부를 혼합하여 제조할 수 있다.In one preferred embodiment of the present invention, the solution of Step 1 may be prepared by mixing 18 to 32 parts by weight of the aldehyde and 110 to 180 parts by weight of the solvent with respect to 100 parts by weight of the compound represented by Formula 2.
본 발명의 바람직한 일실시예로서, 3단계의 알데하이드는 화학식 2로 표시되는 화합물 100 중량부에 대하여 4 ~ 12 중량부를 1차 정시반응시킨 용액에 투입할 수 있다.In one preferred embodiment of the present invention, the aldehyde in three stages may be added to a solution prepared by reacting 4 to 12 parts by weight with respect to 100 parts by weight of the compound represented by the general formula (2).
본 발명의 바람직한 일실시예로서, 2단계 및 3단계의 촉매는 디에틸렌아민, 트리에틸아민, 디에탄올아민 및 트리에탄올 아민 중에서 선택된 1종 이상을 포함하는 아민계 촉매를 포함할 수 있다.In one preferred embodiment of the present invention, the catalysts of the second and third stages may include amine catalysts containing at least one member selected from diethylenamine, triethylamine, diethanolamine and triethanolamine.
본 발명의 바람직한 일실시예로서, 2단계의 촉매는 화학식 2로 표시되는 화합물 100 중량부에 대하여, 0.15 ~ 0.50 중량부를 투입할 수 있다.In one preferred embodiment of the present invention, the catalyst of the second stage may be added in an amount of 0.15 to 0.50 parts by weight based on 100 parts by weight of the compound represented by the general formula (2).
본 발명의 바람직한 일실시예로서, 3단계의 촉매는 화학식 2로 표시되는 화합물 100 중량부에 대하여, 0.04 ~ 0.1 중량부를 투입할 수 있다.In one preferred embodiment of the present invention, the catalyst of the third step may be added in an amount of 0.04 to 0.1 part by weight based on 100 parts by weight of the compound represented by the general formula (2).
본 발명의 바람직한 일실시예로서, 상기 방법으로 제조한 비인계 난연수지를 메탄올에 100 ppm 농도로 용해시켰을 때, 비인계 난연수지 내 미반응 화합물인 상기 화학식 2로 표시되는 화합물의 검출량이 1중량% 이하일 수 있다.In one preferred embodiment of the present invention, when the non-phosphorus flame retardant resin prepared by the above method is dissolved in methanol at a concentration of 100 ppm, the amount of the unreacted compound represented by the above formula (2) in the non- % ≪ / RTI >
본 발명의 바람직한 일실시예로서, 상기 방법으로 메탄올 수용액에 제조한 비인계 난연수지 5g을 용해시킨 pH 3.5의 용액에 10부피% 하이드록실아민클로라이드 수용액을 투입한 후, 0.1 mol/L의 수산화나트륨 용액을 pH 3.5가 될 때까지 적정한 용액 내 잔류 알데하이드 양을 하기 수학식 1에 의거하여 측정시, 잔류 알데하이드가 검출양이 0.05% 이하일 수 있다.In one preferred embodiment of the present invention, 10 vol% hydroxylamine chloride aqueous solution was added to a solution of pH 3.5 in which 5 g of the non-phosphorous flame retardant resin prepared in the methanol aqueous solution was dissolved by the above method, and 0.1 mol / L sodium hydroxide The amount of residual aldehyde in the appropriate solution until pH of the solution reaches pH 3.5 can be less than or equal to 0.05% when measured according to the following equation (1).
[수학식 1][Equation 1]
잔류 알데하이드 검출량(%)= 3c(V1-Vo)/m × 100Residual aldehyde detection amount (%) = 3c (V1-Vo) / m x 100
수학식 1에서, c는 사용한 수산화나트륨 용액의 실제 몰농도(g/L), VO은 수산화나트륨 용액 적정 전의 수산화나트륨 용액의 부피(ml)이며, V1은 적정 후 수산화나트륨 용액의 부피(ml)이고, m은 계량한 난연수지의 질량(g)이다.In Equation 1, c is the actual molar concentration (g / L), V O is the volume (ml) of sodium hydroxide solution before titration of sodium hydroxide solution of sodium hydroxide with the solution, V 1 is the volume of sodium hydroxide and then titrated ( ml), and m is the mass (g) of the flame retardant resin measured.
본 발명의 비인계 난연수지는 미반응 모노머의 함량이 1% 미만인 바, 미반응 모노머의 용출을 방지하여 인체 및 환경에 무해하여 친환경적인 난연수지를 제공할 수 있으며, 또한, 알코올 용제상에서도 석출 또는 침전을 최소화 및/또는 방지되어 저장안정성이 매우 우수하여 난연수지를 제공할 수 있다.The non-phosphorous hard weather resistant resin of the present invention has an unreacted monomer content of less than 1%, thereby preventing the elution of unreacted monomers and providing an environmentally friendly flame retardant resin harmless to the human body and the environment. Also, It is possible to minimize and / or prevent precipitation and thus to provide a flame retardant resin with excellent storage stability.
이하 본 발명을 더 구체적으로 설명한다.Hereinafter, the present invention will be described more specifically.
본 발명의 저장안정성이 우수한 비인계 난연수지는 화학식 1로 표시되는 반복단위를 포함하는 질소화합물을 포함한다.The non-phosphorous flame retardant having excellent storage stability of the present invention comprises a nitrogen compound containing a repeating unit represented by the formula (1).
[화학식 1][Chemical Formula 1]
화학식 1에서, R1 및 R4 각각은 서로 독립적인 것으로서, 수소원자, C1 ~ C5의 직쇄형 알킬기, C3 ~ C5의 분쇄형 알킬기, 페닐기 또는 알킬페닐기이며, 바람직하게는 수소원자 또는 C1 ~ C5의 직쇄형 알킬기이고, 더욱 바람직하게는 수소원자 또는 C1 ~ C2의 알킬기이다. 그리고, 화학식 1의 R5는 -CN 또는 -CH2CN 이고, 바람직하게는 -CN이다. 또한, 화학식 1의 n은 중합체의 중량평균분자량 200 ~ 1,500을 만족시키는 유리수이며, 바람직하게는 중량평균분자량 200 ~ 900, 더욱 바람직하게는 중량평균분자량 400 ~ 900을 만족시키는 유리수이다.In formula (1), each of R 1 and R 4 is independent of each other and is a hydrogen atom, a straight-chain alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a phenyl group or an alkylphenyl group, More preferably a hydrogen atom or a C1 to C2 alkyl group. R 5 in the formula (1) is -CN or -CH 2 CN, preferably -CN. The n in the formula (1) is a rational number satisfying the weight average molecular weight of the polymer of 200 to 1,500, preferably a weight average molecular weight of 200 to 900, more preferably a weight average molecular weight of 400 to 900.
이러한 본 발명의 비인계 난연수지는 하기 화학식 2로 표시되는 화합물 및 하기 화학식 3으로 표시되는 알데하이드를 1 : 0.6 ~ 0.95 몰비로, 바람직하게는 1 : 0.7 ~ 0.92 몰비로 중합시켜 제조하여 상기 화학식 1로 표시되는 질소화합물을 제조할 수 있다. 이때, 알데하이드가 0.6 몰비 미만이면 제조된 비인계 난연수지에 화학식 2로 표현되는 물질이 잔류하여 수지의 저장안정을 떨어트리는 문제가 있을 수 있고, 0.95 몰비를 초과하면 제조된 비인계 난연수지 내에 화학식 3으로 표현되는 물질이 잔류하고 수지가 과중합되어 용제인 메탄올에 용해되지 않는 문제가 있을 수 있다.The non-phosphorous flame retardant of the present invention is prepared by polymerizing a compound represented by the following general formula (2) and an aldehyde represented by the following general formula (3) in a molar ratio of 1: 0.6-0.95, preferably 1: 0.7-0.92, Can be produced. If the aldehyde content is less than 0.6 mol, the material represented by the general formula (2) may remain in the prepared non-phosphorus flame retardant resin to deteriorate the storage stability of the resin. If the molar ratio exceeds 0.95, 3 may remain and the resin may be over-polymerized and not dissolved in the solvent methanol.
[화학식 2](2)
화학식 2에서, R1 내지 R4 각각은 독립적인 것으로서, 수소원자, C1 ~ C5의 직쇄형 알킬기, C3 ~ C5의 분쇄형 알킬기, 페닐기 또는 알킬페닐기이며, 바람직하게는 수소원자 또는 C1 ~ C5의 직쇄형 알킬기이고, 더욱 바람직하게는 수소원자 또는 C1 ~ C2의 알킬기이다. 그리고, 화학식 2의 R5는 -CN 또는 -CH2CN 이고, 바람직하게는 -CN이다In formula (2), each of R 1 to R 4 is independently a hydrogen atom, a straight-chain alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a phenyl group or an alkylphenyl group, More preferably a hydrogen atom or a C1 to C2 alkyl group. And R 5 of formula (2) is -CN or -CH 2 CN, preferably -CN
[화학식 3] (3)
화학식 3에서, R1 및 R2 각각은 독립적인 것으로서, 수소원자, C1 ~ C3의 직쇄형 알킬기 또는 페닐기이고, 바람직하게는 수소원자 또는 C1 ~ C2의 직쇄형 알킬기이다.In formula (3), each of R 1 and R 2 is independently a hydrogen atom, a straight-chain alkyl group of C1-C3 or a phenyl group, preferably a hydrogen atom or a straight-chain alkyl group of C1-C2.
이러한, 본 발명의 비인계 난연수지를 제조하는 방법을 단계별로 더욱 구체적으로 설명하면, 상기 화학식 1로 표시되는 질소화합물은 상기 화학식 2로 표시되는 화합물, 상기 화학식 3으로 표시되는 알데하이드 및 용매를 혼합한 용액을 교반한 후, 38 ~ 45℃까지 승온시키는 1단계; 승온된 용액에 촉매를 투입한 후, 58 ~ 65℃까지 승온시킨 후, 2시간 30분 ~ 3시간 30분 동안 1차 정시반응을 수행하는 2단계; 1차 정시반응시킨 용액에 상기 알데하이드 및 촉매를 투입한 후, 68 ~ 75℃로 승온시킨 후, 환류(reflux)시키면서 2시간 30분 ~ 3시간 30분 동안 2차 정시반응을 수행하는 3단계; 및 냉각 및 필터링하는 4단계;를 포함하는 공정을 수행하여 제조할 수 있다.The method for producing the non-phosphorus flame retardant resin of the present invention will be described in more detail step by step. The nitrogen compound represented by Formula 1 is prepared by mixing the compound represented by Formula 2, the aldehyde represented by Formula 3, Stirring one solution and then raising the temperature to 38 to 45 ° C; A step of adding a catalyst to the heated solution, raising the temperature to 58 to 65 ° C, and then carrying out a first-order reaction for 2 to 30 minutes to 3 hours and 30 minutes; A third step in which the aldehyde and the catalyst are added to the first-order reaction solution, the temperature is raised to 68 to 75 ° C, and the second-order reaction is performed for 2 to 30 minutes to 3 hours and 30 minutes while refluxing; And four steps of cooling and filtering.
1단계에서 상기 용액은 화학식 2로 표시되는 화합물 100 중량부에 대하여 상기 알데하이드 18 ~ 32 중량부 및 용매 110 ~ 180 중량부를, 바람직하게는 화학식 2로 표시되는 화합물 100 중량부에 대하여 상기 알데하이드 21 ~ 30 중량부 및 용매 120 ~ 170 중량부를, 더욱 바람직하게는 화학식 2로 표시되는 화합물 100 중량부에 대하여 상기 알데하이드 23 ~ 29 중량부 및 용매 125 ~ 165 중량부를 혼합하여 제조한다. 이때, 알데하이드 사용량이 18 중량부 미만이면 제조된 비인계 난연수지 내에 화학식 2로 표현되는 물질이 잔류하여 수지의 저장안정성을 떨어트리는 문제가 있을 수 있고, 알데하이드 사용량이 32 중량부를 초과하면 제조된 비인계 난연수지 내에 화학식 3으로 표현되는 물질이 잔류하고 수지가 과중합되어 용제인 메탄올에 용해되지 않는 문제가 있을 수 있으므로, 상기 범위 내로 사용하는 것이 좋다. 그리고, 용매 사용량이 110 중량부 미만이면 용매 사용량이 너무 적어서 제품의 외관이 불투명하게 변하는 하는 문제가 있을 수 있고, 용매 사용량이 180 중량부를 초과하면 그 사용량이 너무 많아서 반응물질의 반응성을 억제시키고 미반응 원료들이 제조된 비인계 난연수지 내에 잔존하는 문제가 있을 수 있으므로 상기 범위 내로 사용하는 것이 좋다.In the first step, the solution contains 18 to 32 parts by weight of the aldehyde and 110 to 180 parts by weight of the solvent, preferably 100 to 200 parts by weight of the aldehyde, based on 100 parts by weight of the compound represented by the formula (2) 30 to 40 parts by weight of the aldehyde and 125 to 165 parts by weight of the solvent are mixed with 100 parts by weight of the compound represented by the general formula (2), more preferably 120 to 170 parts by weight of the solvent. If the amount of the aldehyde is less than 18 parts by weight, the material represented by the general formula (2) may remain in the prepared non-phosphorus flame retardant resin to deteriorate the storage stability of the resin. If the amount of the aldehyde exceeds 32 parts by weight, There may be a problem that the substance represented by the general formula (3) remains in the phosphorus-based flame retardant resin and the resin is over-polymerized and is not dissolved in methanol as a solvent. If the amount of the solvent used is less than 110 parts by weight, there may be a problem that the amount of the solvent used is too small to make the appearance of the product opaque. If the amount of the solvent is more than 180 parts by weight, There may be a problem that the reaction raw materials remain in the produced non-phosphorus flame retardant resin.
이렇게 혼합된 상기 용매를 38 ~ 45℃까지, 바람직하게는 40 ~ 45℃까지 서서히 승온시킨 후, 승온된 용액에 촉매를 투입한다. 이때, 38 ~ 45℃까지 승온시키는 이유는 투입된 반응물질들이 용제에 완벽히 용해시키기 위한 것이다. 그리고, 2단계의 촉매는 상기 화학식 2로 표시되는 화합물 100 중량부에 대하여, 0.15 ~ 0.50 중량부를, 바람직하게는 0.19 ~ 0.25 중량부를 사용하는 것이 좋으며, 촉매 사용량이 0.15 중량부 미만이면 촉매량이 너무 적어 투입된 반응물질들이 반응하지 않고 제조된 비인계 난연수지 내에 잔존하는 문제가 있을 수 있고, 0.50 중량부를 초과하면 발열 제어가 어렵고 제조된 비인계 난연수지가 과중합되어 용제인 메탄올에 용해되지 않는 문제가 있을 수 있다.The mixed solvent is gradually heated to 38 to 45 ° C, preferably to 40 to 45 ° C, and then the catalyst is added to the heated solution. The reason for raising the temperature to 38 to 45 ° C is to completely dissolve the reactants in the solvent. The catalyst of the second stage is preferably used in an amount of 0.15 to 0.50 parts by weight, preferably 0.19 to 0.25 parts by weight, based on 100 parts by weight of the compound represented by the general formula (2). When the amount of the catalyst is less than 0.15 parts by weight, There may be a problem that the reacted materials, which have been put in small amounts, remain in the produced non-phosphorus flame retardant resin. If the amount exceeds 0.50 parts by weight, heat control is difficult and the produced non-phosphorus flame retardant resin is over- .
다음으로, 촉매를 투입한 용액을 다시 58 ~ 65℃까지, 바람직하게는 60 ~ 65℃까지 승온시킨 후, 2시간 30분 ~ 3시간 30분 동안 1차 정시반응을 수행한다. 1차 정시반응시 온도가 58℃ 미만이면 반응온도가 낮아 제조된 비인계 난연수지 내에 화학식 2로 표현되는 물질이 잔류하여 수지의 저장성을 떨어트리는 문제가 있을 수 있고, 65℃를 초과하면 제조된 비인계 난연수지가 과중합되어 메탄올에 용해되지 않는 문제가 있을 수 있으므로 상기 온도까지 승온시킨 후, 1차 정시반응을 수행하는 것이 좋다.Next, the solution containing the catalyst is heated again to 58 to 65 ° C, preferably 60 to 65 ° C, and then subjected to a first-order reaction for 2 to 30 minutes to 3 hours and 30 minutes. If the temperature is lower than 58 캜 in the first-order reaction, the reaction temperature is low, and the material represented by the general formula (2) may remain in the produced non-phosphorus flame retardant resin to deteriorate the storage stability of the resin. There may be a problem that the non-phosphorus flame-retardant resin is over-polymerized and is not dissolved in methanol. Therefore, it is preferable to perform the first-order reaction after raising the temperature to the above temperature.
3단계는 1차 정시반응된 반응생성물과 알데하이드를 2차적으로 정시반응을 수행하는 단계로서, 1차 정시반응시킨 용액에 상기 알데하이드 및 촉매를 투입한 후, 68 ~ 75℃로, 바람직하게는 70 ~ 75℃로 승온시킨 후, 환류(reflux)시키면서 2시간 30분 ~ 3시간 30분 동안 2차 정시반응을 수행한다. Step 3 is a step of carrying out a second-order periodic reaction between the first-order reaction product and the aldehyde. The aldehyde and the catalyst are added to the first-order reaction solution, and then the mixture is heated to 68-75 ° C, preferably 70 The temperature is raised to -75 ° C, and the reaction is carried out for 2 hours 30 minutes to 3 hours 30 minutes while refluxing.
3단계의 2차 정시반응시 상기 알데하이드 사용량은 1단계의 상기 화학식 2로 표시되는 화합물 100 중량부에 대하여 4 ~ 12 중량부를, 바람직하게는 6 ~ 12 중량부를 사용하는 것이 좋으며, 2차 정시반응시 알데하이드 사용량이 4 중량부 미만이면 미만이면 제조된 비인계 난연수지 내에 화학식 2로 표현되는 물질이 잔류하여 수지의 저장안정성을 떨어트리는 문제가 있을 수 있고, 12 중량부를 초과하면 제조된 비인계 난연수지 내 미반응 알데하이드 모노머 잔량이 증가할 수 있으므로 상기 범위 내로 사용하는 것이 좋다. The amount of the aldehyde to be used in the second step of the three-step reaction is preferably 4 to 12 parts by weight, preferably 6 to 12 parts by weight, per 100 parts by weight of the compound represented by the formula (2) If the amount of cyhaldehyde is less than 4 parts by weight, the material represented by the general formula (2) may remain in the produced non-phosphorus flame retardant resin to deteriorate the storage stability of the resin. If the amount is more than 12 parts by weight, The remaining amount of the unreacted aldehyde monomer in the resin may increase, so that it is preferable to use within the above range.
또한, 촉매의 사용량은 상기 화학식 2로 표시되는 화합물 100 중량부에 대하여 0.02 ~ 0.2 중량부를, 바람직하게는 0.04 ~ 0.10 중량부를 사용하는 것이 적절하다.The amount of the catalyst to be used is suitably 0.02 to 0.2 part by weight, preferably 0.04 to 0.10 part by weight based on 100 parts by weight of the compound represented by the formula (2).
그리고, 3단계의 2차 정시반응시 온도가 68℃ 미만이면 미만이면 반응온도가 낮아 제조된 비인계 난연수지 내에 화학식 2로 표현되는 물질이 잔류하여 수지의 저장안정성을 떨어트리는 하는 문제가 있을 수 있고, 75℃를 초과하면 반응용제가 휘발되어 제조된 비인계 난연수지가 과중합되어 메탄올에 용해되지 않는 문제가 있을 수 있으므로 상기 온도까지 승온시킨 후, 2차 정시반응을 수행하는 것이 좋다.If the temperature is lower than 68 ° C in the second-stage reaction of Step 3, the reaction temperature is low, and the material represented by Formula 2 may remain in the prepared non-phosphorus flame retardant resin, thereby deteriorating the storage stability of the resin If the temperature is higher than 75 ° C, there is a problem that the non-phosphorus flame retardant resin produced by volatilizing the reaction solvent volatilizes and is not dissolved in methanol. Therefore, it is preferable to raise the temperature to the above-mentioned temperature and then carry out the second-
또한, 2단계 및 3단계의 촉매는 디에틸렌아민, 트리에틸아민, 디에탄올아민 및 트리에탄올 아민 중에서 선택된 1종 이상을 포함하는 아민계 촉매를 사용하는 것이 좋으며, 바람직하게는 디에틸렌아민 및 트리에틸아민 중에서 선택된 1종 이상을 포함하는 아민계 촉매를 사용하는 것이 좋다.The catalysts of the second and third stages are preferably amine catalysts containing at least one member selected from diethylenamine, triethylamine, diethanolamine and triethanolamine, preferably diethylenamine and triethylamine, Amines, and the like.
다음으로, 3단계에서 2차 정시반응된 용액을 당업계에서 사용하는 일반적인 방법으로 냉각 및 필터링을 수행하여 상기 화학식 1로 표시되는 질소화합물을 얻을 수 있다.Next, the solution of the second periodically reacted in Step 3 may be cooled and filtered by a general method used in the art to obtain the nitrogen compound represented by Formula 1 above.
본 발명의 비인계 난연수지는 앞서 설명한 방법으로 제조한 화학식 1로 표시되는 질소화합물을 포함하며, 이러한, 본 발명의 난연수지는 저장안정성이 매우 우수하며, 미반응 모노머 함량이 매우 극소량 또는 없을 수 있다. 그리고, 제조된 본 발명의 비인계 난연수지는 고형분 함량이 40 중량% 이상일 수 있고, 바람직하게는 40 ~ 42 중량%일 수 있다.The non-phosphorous flame retardant of the present invention comprises the nitrogen compound represented by the formula (1) prepared by the above-mentioned method. The flame retardant of the present invention is excellent in storage stability, and the content of unreacted monomer is very small or absent have. The prepared non-phosphorous hard weather resistant paper of the present invention may have a solid content of 40 wt% or more, and preferably 40 to 42 wt%.
좀 더 구체적으로 설명하면 본 발명의 비인계 난연수지를 -5℃에서 방치시, 12일 이전에, 바람직하게는 15일 이전에, 더욱 바람직하게는 17일 이전에 비인계 난연수지 및/또는 화학식 2로 표시되는 화합물이 석출되지 않을 수 있다.More specifically, when the non-phosphorus flame retardant resin of the present invention is allowed to stand at -5 占 폚, the non-phosphorus flame retardant resin and / or the non-phosphorus flame retardant resin before the 12th, preferably after 15th, 2 may not be precipitated.
또한, 본 발명의 비인계 난연수지를 10℃에서 방치시, 15일 이전에, 바람직하게는 18일 이전에, 더욱 바람직하게는 20일 이전에 비인계 난연수지 및/또는 화학식 2로 표시되는 화합물이 석출되지 않을 수 있다.In addition, when the non-phosphorus flame retardant resin of the present invention is allowed to stand at 10 占 폚, the non-phosphorus flame retardant resin and / or the compound represented by the general formula (2) may be added before 15 days, preferably before 18 days, May not be precipitated.
또한, 본 발명의 비인계 난연수지를 25℃에서 방치시, 20일 이전에, 바람직하게는 23일 이전에, 더욱 바람직하게는 25일 이전에 비인계 난연수지 및/또는 화학식 2로 표시되는 화합물이 석출되지 않을 수 있다.In addition, when the non-phosphorus flame retardant resin of the present invention is allowed to stand at 25 占 폚, the non-phosphorus flame retardant resin and / or the compound represented by the general formula (2) may be added before 20 days, preferably before 23 days, more preferably after 25 days, May not be precipitated.
또한, 본 발명의 비인계 난연수지를 50℃에서 방치시, 25일 이전에, 바람직하게는 26일 이전에, 더욱 바람직하게는 28일 이전에 비인계 난연수지 및/또는 화학식 2로 표시되는 화합물이 석출되지 않을 수 있다.When the non-phosphorus-based flame retardant resin of the present invention is allowed to stand at 50 캜, the non-phosphorus flame retardant resin and / or the compound represented by the general formula (2) may be added before 25 days, preferably before 26 days, May not be precipitated.
나아가, 본 발명의 비인계 난연수지를 메탄올에 100 ppm 농도로 용해시켰을 때, 비인계 난연수지 내 미반응 모노머인 화학식 2로 표시되는 화합물의 검출량이 1중량% 이하일 수 있으며, 바람직하게는 0.9 중량% 이하, 더욱 바람직하게는 0.8 중량% 이하일 수 있다.Further, when the non-phosphorus flame retardant resin of the present invention is dissolved in methanol at a concentration of 100 ppm, the detection amount of the compound represented by the general formula (2) as the unreacted monomer in the non-phosphorus flame retardant resin may be 1% by weight or less, % Or less, more preferably 0.8 wt% or less.
또한, 본 발명의 비인계 난연수지를 5g 용해시킨 pH 3.5의 용액에 10부피% 하이드록실아민클로라이드 수용액을 투입한 후, 0.1 mol/L의 수산화나트륨 용액을 pH 3.5가 될 때까지 적정한 용액 내 잔류 화학식 3으로 표시되는 알데하이드 양을 하기 수학식 1에 의거하여 측정시, 잔류 알데하이드가 검출양이 0.05% 이하, 바람직하게는 0.03% 이하, 더욱 바람직하게는 0.001% 이하일 수 있다.In addition, 10 vol% hydroxylamine chloride aqueous solution was added to a solution of pH 3.5 in which 5 g of the non-phosphorus flame retardant resin of the present invention had been dissolved, then 0.1 mol / L sodium hydroxide solution was added to the solution When the amount of the aldehyde represented by the formula (3) is measured according to the following formula (1), the residual amount of the residual aldehyde may be 0.05% or less, preferably 0.03% or less, more preferably 0.001% or less.
[수학식 1][Equation 1]
잔류 알데하이드 검출량(%)= 3c(V1-Vo)/m × 100Residual aldehyde detection amount (%) = 3c (V1-Vo) / m x 100
수학식 1에서, c는 사용한 수산화나트륨 용액의 실제 몰농도(g/L), VO은 수산화나트륨 용액 적정 전의 수산화나트륨 용액의 부피(ml)이며, V1은 적정 후 수산화나트륨 용액의 부피(ml)이고, m은 계량한 난연수지의 질량(g)이다.In Equation 1, c is the actual molar concentration (g / L), V O is the volume (ml) of sodium hydroxide solution before titration of sodium hydroxide solution of sodium hydroxide with the solution, V 1 is the volume of sodium hydroxide and then titrated ( ml), and m is the mass (g) of the flame retardant resin measured.
이와 같이 본 발명의 비인계 난연수지는 다양한 온도 범위에서 장기간 석출되지 않기 때문에 저장안정성이 매우 우수하며, 특정 조건에서 다단계로 반응시켜 제조함으로써, 난연수지 내 미반응 모노머 함량을 최소화할 수 있는 바, 미반응 모노머의 용출을 방지하여 인체 및 환경에 무해하여 친환경적인 난연수지를 제공할 수 있다.As described above, the non-phosphorous flame retardant of the present invention is excellent in storage stability because it can not be precipitated for a long period of time under various temperature ranges, and can be reacted in multiple stages under specific conditions to minimize unreacted monomer content in the flame retardant resin. It is possible to prevent the elution of unreacted monomer and to provide an environmentally friendly flame retardant resin which is harmless to the human body and the environment.
이하 본 발명을 실시예에 의거하여 더욱 자세하게 설명을 한다. 그러나, 하기 실시예에 의해서 본 발명의 권리범위가 한정하여 해석해서는 안된다.Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention should not be construed to be limited by the following examples.
[[ 실시예Example ]]
실시예Example 1 One
온도계, 냉각관, 교반기를 장착한 케틀에 메탄올(Methanol) 280g과 하기 화학식 2-1로 표시되는 화합물 200g, 92% 농도의 화학식 3-1로 표시되는 알데하이드 55.90g을 투입하고 교반을 실시하며 40℃로 승온시켰다. To a kettle equipped with a thermometer, a cooling tube and a stirrer, 280 g of methanol, 200 g of the compound represented by the following formula (2-1) and 55.90 g of the aldehyde represented by the formula (3-1) in a concentration of 92% Lt; 0 > C.
40℃ 도달한 후, 촉매인 디에틸아민(Diethylamine) 0.44g을 투입하고 60℃ 승온하여 3시간 동안 1차 정시반응을 실시했다. 3시간 반응이 완료 후 하기 화학식 3으로 표시되는 알데하이드 13.98g, 촉매인 디에틸아민 0.11g을 투입하고 환류(Reflux) 온도 약 70℃로 승온시켰다. After reaching 40 캜, 0.44 g of diethylamine as a catalyst was added, and the temperature was raised to 60 캜 and the reaction was performed for a first time period for 3 hours. After the completion of the reaction for 3 hours, 13.98 g of an aldehyde represented by the following formula (3) and 0.11 g of diethylamine as a catalyst were charged and the temperature was raised to about 70 째 C with reflux.
환류가 시작되면 환류를 유지하며 3시간 동안 2차 정시반응을 실시하였다.When the reflux started, reflux was maintained and a second order reaction was performed for 3 hours.
정시반응 완료되면 반응 용액을 3 ~ 5℃로 냉각을 실시시키고 케틀 내부에 결정질로 석출된 염을 필터링하여, 고형분 40.3 중량%의 하기 화학식 1-1로 표시되는 비인계 난연수지를 얻었다(하기 표 1 참조).After completion of the reaction at the completion of the reaction, the reaction solution was cooled to 3 to 5 DEG C and the crystals precipitated as crystals in the kettle were filtered to obtain a non-phosphorus flame retardant resin having a solid content of 40.3 wt% 1).
[화학식 2-1] [Formula 2-1]
화학식 2-1에서, R1 내지 R4은 모두 수소원자이고, R5는 -CN이다.In Formula (2-1), R 1 to R 4 are all hydrogen atoms, and R 5 is -CN.
[화학식 3-1][Formula 3-1]
화학식 3-1에서, R1 및 R2은 모두 수소원자이다.In Formula (3-1), R 1 and R 2 are both hydrogen atoms.
[화학식 1-1][Formula 1-1]
화학식 1-1에서, R1 및 R4은 수소원자이고, R5는 -CN이며, n은 중합체의 중량평균분자량 800 ~ 900을 만족시키는 유리수이다.In Formula 1-1, R 1 and R 4 are hydrogen atoms, R 5 is -CN, and n is a rational number satisfying the weight average molecular weight of the polymer of 800 to 900.
실시예Example 2 2
온도계, 냉각관, 교반기를 장착한 케틀에 메탄올 280g과 실시예 1의 화학식 2-1로 표시되는 화합물 200g, 92% 농도의 화학식 3-1로 표시되는 알데하이드 48.92g을 투입하고 교반을 실시하며 40℃로 승온시켰다. 280 g of methanol, 200 g of the compound represented by the formula (2-1) of Example 1 and 48.92 g of the aldehyde represented by the formula (3-1) in a concentration of 92% were added to a kettle equipped with a thermometer, a cooling tube and a stirrer, Lt; 0 > C.
40℃ 도달한 후, 촉매인 디에틸아민(Diethylamine) 0.39g을 투입하고 60℃ 승온하여 3시간 동안 1차 정시반응을 실시했다. 3시간 반응이 완료 후 상기 화학식 3-1로 표시되는 알데하이드 20.96g, 디에틸아민 0.16g, 을 투입하고 환류(Reflux) 온도 약 70℃로 승온시켰다. After the temperature reached 40 ° C, 0.39 g of diethylamine as a catalyst was charged, and the temperature was raised to 60 ° C. and the first-order reaction was carried out for 3 hours. After completion of the reaction for 3 hours, 20.96 g of the aldehyde represented by the above formula (3-1) and 0.16 g of diethylamine were added and the temperature was raised to about 70 째 C with reflux.
환류가 시작되면 환류를 유지하며 3시간 동안 2차 정시반응을 실시하였다.When the reflux started, reflux was maintained and a second order reaction was performed for 3 hours.
정시반응 완료되면 반응 용액을 3 ~ 5℃로 냉각을 실시시키고 케틀 내부에 결정질로 석출된 염을 필터링하여, 고형분 40.1 중량%의 하기 화학식 1-2로 표시되는 비인계 난연수지를 얻었다.When the reaction was completed on time, the reaction solution was cooled to 3 to 5 DEG C, and the crystals precipitated as crystals in the kettle were filtered to obtain a non-phosphorus flame retardant resin having a solid content of 40.1 wt% represented by the following Formula 1-2.
[화학식 1-2][Formula 1-2]
화학식 1-2에서, R1 및 R4은 수소원자이고, R5는 -CN이며, n은 중합체의 중량평균분자량 700 ~ 800을 만족시키는 유리수이다.In the general formula (1-2), R 1 and R 4 are hydrogen atoms, R 5 is -CN, and n is a rational number satisfying the weight average molecular weight of the polymer of 700 to 800.
실시예Example 3 3
온도계, 냉각관, 교반기를 장착한 케틀에 메탄올(Methanol) 280g과 상기 화학식 2-1로 표시되는 화합물 200g, 92% 농도의 상기 화학식 3-1로 표시되는 알데하이드 43.48g을 투입하고 교반을 실시하며 40℃로 승온시켰다. 280 g of methanol, 200 g of the compound represented by the formula (2-1) and 43.48 g of the aldehyde represented by the formula (3-1) in a concentration of 92% were added to a kettle equipped with a thermometer, a cooling tube and a stirrer and stirred The temperature was raised to 40 占 폚.
40℃ 도달한 후, 촉매인 디에틸아민(Diethylamine) 0.44g을 투입하고 60℃ 승온하여 3시간 동안 1차 정시반응을 실시했다. 3시간 반응이 완료 후 하기 화학식 3으로 표시되는 알데하이드 10.87g, 촉매인 디에틸아민 0.11g, 을 투입하고 환류(Reflux) 온도 약 70℃로 승온시켰다. After reaching 40 캜, 0.44 g of diethylamine as a catalyst was added, and the temperature was raised to 60 캜 and the reaction was performed for a first time period for 3 hours. After completion of the reaction for 3 hours, 10.87 g of an aldehyde represented by the following formula (3) and 0.11 g of diethylamine as a catalyst were added and the temperature was raised to about 70 째 C with reflux.
환류가 시작되면 환류를 유지하며 3시간 동안 2차 정시반응을 실시하였다.When the reflux started, reflux was maintained and a second order reaction was performed for 3 hours.
정시반응 완료되면 반응 용액을 3 ~ 5℃로 냉각을 실시시키고 케틀 내부에 결정질로 석출된 염을 필터링하여, 고형분 40.8 중량%의 하기 화학식 1-3으로 표시되는 비인계 난연수지를 얻었다.When the reaction was completed on time, the reaction solution was cooled to 3 to 5 DEG C, and the crystals precipitated as crystals in the kettle were filtered to obtain a non-phosphorus flame retardant resin represented by the following Formula 1-3 having a solid content of 40.8 wt%.
[화학식 1-3][Formula 1-3]
화학식 1-3에서, R1 및 R4은 수소원자이고, R5는 -CN이며, n은 중합체의 중량평균분자량 200 ~ 300을 만족시키는 유리수이다.In the general formula 1-3, R 1 and R 4 are hydrogen atoms, R 5 is -CN, and n is a rational number satisfying the weight average molecular weight of the polymer of 200-300.
실시예Example 4 4
온도계, 냉각관, 교반기를 장착한 케틀에 메탄올(Methanol) 280g과 상기 화학식 2-1로 표시되는 화합물 200g, 92% 농도의 상기 화학식 3-1로 표시되는 알데하이드 38.05g을 투입하고 교반을 실시하며 40℃로 승온시켰다. To a kettle equipped with a thermometer, a cooling tube and a stirrer, 280 g of methanol, 200 g of the compound represented by the formula (2-1) and 38.05 g of the aldehyde represented by the formula (3-1) in a concentration of 92% The temperature was raised to 40 占 폚.
40℃ 도달한 후, 촉매인 디에틸아민(Diethylamine) 0.39g을 투입하고 60℃ 승온하여 3시간 동안 1차 정시반응을 실시했다. 3시간 반응이 완료 후 하기 화학식 3으로 표시되는 알데하이드 16.30g, 촉매인 디에틸아민 0.16g을 투입하고 환류(Reflux) 온도 약 70℃로 승온시켰다. After the temperature reached 40 ° C, 0.39 g of diethylamine as a catalyst was charged, and the temperature was raised to 60 ° C. and the first-order reaction was carried out for 3 hours. After completion of the reaction for 3 hours, 16.30 g of an aldehyde represented by the following formula (3) and 0.16 g of diethylamine as a catalyst were charged and the temperature was raised to about 70 째 C with reflux.
환류가 시작되면 환류를 유지하며 3시간 동안 2차 정시반응을 실시하였다.When the reflux started, reflux was maintained and a second order reaction was performed for 3 hours.
정시반응 완료되면 반응 용액을 3 ~ 5℃로 냉각을 실시시키고 케틀 내부에 결정질로 석출된 염을 필터링하여, 고형분 40.2 중량%의 하기 화학식 1-4로 표시되는 비인계 난연수지를 얻었다.When the reaction was completed on time, the reaction solution was cooled to 3 to 5 DEG C, and the crystals precipitated as crystals in the kettle were filtered to obtain a non-phosphorus flame retardant resin having a solid content of 40.2 wt% represented by the following Formula 1-4.
[화학식 1-4][Formula 1-4]
화학식 1-4에서, R1 및 R4은 수소원자이고, R5는 -CN이며, n은 중합체의 중량평균분자량 300 ~ 400을 만족시키는 유리수이다.In Formula 1-4, R 1 and R 4 are hydrogen atoms, R 5 is -CN, and n is a rational number satisfying the weight average molecular weight of the polymer of 300 to 400.
비교예Comparative Example 1 One
온도계, 냉각관, 교반기를 장착한 케틀에 메탄올 280g과 실시예 1의 화학식 2-1로 표시되는 화합물를 200g, 92% 농도의 화학식 3-1로 표시되는 알데하이드 69.88g을 투입하고 교반을 실시하며 40℃로 승온시켰다. To a kettle equipped with a thermometer, a cooling tube and a stirrer, 280 g of methanol, 200 g of the compound represented by the general formula (2-1) of Example 1, and 69.88 g of the aldehyde represented by the general formula (3-1) Lt; 0 > C.
40℃ 도달하면 촉매인 디에틸아민(Diethylamine) 0.55g을 투입하고 60℃ 승온하여 3시간 동안 정시반응을 실시했다. When the temperature reached 40 ° C., 0.55 g of diethylamine as a catalyst was added, and the temperature was raised to 60 ° C. and the reaction was carried out for 3 hours.
정시반응 완료 후 3~5℃로 냉각을 실시하고 케틀 내부에 결정질로 석출된 염을 필터링하여, 고형분 40.3 중량%의 하기 화학식 1-5로 표시되는 비인계 난연수지를 얻었다.After completing the reaction in time, the mixture was cooled to 3 to 5 DEG C, and the crystals precipitated as crystals in the kettle were filtered to obtain a non-phosphorus flame retardant resin having a solid content of 40.3 wt% represented by the following formula 1-5.
[화학식 1-5][Formula 1-5]
화학식 1-5에서, R1 및 R4은 수소원자이고, R5는 -CN이며, n은 중합체의 중량평균분자량 900 ~ 1,000을 만족시키는 유리수이다.In the general formula (1-5), R 1 and R 4 are hydrogen atoms, R 5 is -CN, and n is a rational number satisfying the weight average molecular weight of the polymer of 900-1,000.
비교예Comparative Example 2 2
온도계, 냉각관, 교반기를 장착한 케틀에 메탄올 280g과 실시예 1의 화학식 2-1로 표시되는 화합물를 200g, 92% 농도의 상기 화학식 3-1로 표시되는 알데하이드 54.35g을 투입하고 교반을 실시하며 40℃로 승온시켰다.To a kettle equipped with a thermometer, a cooling tube and a stirrer, 280 g of methanol, 200 g of the compound represented by the formula (2-1) of Example 1, and 54.35 g of the aldehyde represented by the above formula (3-1) in a concentration of 92% The temperature was raised to 40 占 폚.
40℃ 도달하면 촉매인 디에틸아민(Diethylamine) 0.55g을 투입하고 60℃ 승온하여 3시간 동안 정시반응을 실시했다. When the temperature reached 40 ° C., 0.55 g of diethylamine as a catalyst was added, and the temperature was raised to 60 ° C. and the reaction was carried out for 3 hours.
정시반응 완료 후 3~5℃로 냉각을 실시하고, 케틀 내부에 결정질로 석출된 염을 필터링하여, 고형분 40.5%의 하기 화학식 1-4로 표시되는 비인계 난연수지를 얻었다.After completion of the reaction on time, cooling was carried out at 3 to 5 ° C, and the crystals precipitated as crystals in the kettle were filtered to obtain a non-phosphorus flame retardant resin represented by the following Chemical Formula 1-4 having a solid content of 40.5%.
[화학식 1-6][Chemical Formula 1-6]
화학식 1-6에서, R1 및 R4은 수소원자이고, R5는 -CN이며, n은 중합체의 중량평균분자량 400 ~ 500을 만족시키는 유리수이다.In Formula 1-6, R 1 and R 4 are hydrogen atoms, R 5 is -CN, and n is a rational number satisfying a weight average molecular weight of 400 to 500 of the polymer.
비교예Comparative Example 3 3
상기 실시예 1과 동일한 방법으로 비인계 난연수지를 제조하되, 1차 정시반응을 73 ~ 74℃로 승온시킨 후, 이 온도에서 3시간 동안 수행한 후, 2차 정시반응, 냉각, 필터링하여 비인계 난연수지를 제조하였다.The non-phosphorus flame retardant resin was prepared in the same manner as in Example 1 except that the first-order reaction was performed at a temperature of 73 to 74 ° C for 3 hours, followed by a second-order reaction, cooling, Flame retardant resin was prepared.
비교예Comparative Example 4 4
상기 실시예 1과 동일한 방법으로 비인계 난연수지를 제조하되, 1차 정시반응을 52 ~ 53℃로 승온시킨 후, 이 온도에서 3시간 동안 수행한 후, 2차 정시반응, 냉각, 필터링하여 비인계 난연수지를 제조하였다.The non-phosphorus flame retardant resin was prepared in the same manner as in Example 1 except that the first-order reaction was heated to 52 to 53 ° C, followed by 3 hours at this temperature, followed by second- Flame retardant resin was prepared.
비교예Comparative Example 5 5
상기 실시예 1과 동일한 방법으로 비인계 난연수지를 제조하되, 2차 정시반응을 82 ~ 83℃로 승온시킨 후, 이 온도에서 3시간 동안 수행한 후, 냉각, 필터링하여 비인계 난연수지를 제조하였다.The non-phosphorus flame retardant resin was prepared in the same manner as in Example 1 except that the second periodic reaction was carried out at 82 to 83 ° C for 3 hours and then cooled and filtered to prepare a non- Respectively.
비교예Comparative Example 6 6
상기 실시예 1과 동일한 방법으로 비인계 난연수지를 제조하되, 2차 정시반응을 64 ~ 65℃로 승온시킨 후, 이 온도에서 3시간 동안 수행한 후, 냉각, 필터링하여 비인계 난연수지를 제조하였다.The non-phosphorus flame retardant resin was prepared in the same manner as in Example 1 except that the secondary reaction was performed at a temperature of 64 to 65 ° C for 3 hours, followed by cooling and filtering to prepare a non- Respectively.
비교예Comparative Example 7 7
상기 실시예 1과 동일한 방법으로 비인계 난연수지를 제조하되, 메탄올 280g과 화학식 2-1로 표시되는 화합물 200g, 92% 농도의 화학식 3-1로 표시되는 알데하이드 70g을 투입하여 혼합 용액을 제조한 후, 이를 1차 정시반응, 2차 정시반응, 냉각, 필터링하여 비인계 난연수지를 제조하였다.A non-phosphorus flame retardant resin was prepared in the same manner as in Example 1 except that 280 g of methanol, 200 g of the compound represented by Chemical Formula 2-1 and 70 g of the aldehyde represented by Chemical Formula 3-1 at a concentration of 92% Then, the non-phosphorous flame retardant resin was prepared by first order reaction, second order reaction, cooling, and filtering.
비교예Comparative Example 8 8
상기 실시예 1과 동일한 방법으로 비인계 난연수지를 제조하되, 메탄올 280g과 화학식 2-1로 표시되는 화합물 200g, 92% 농도의 화학식 3-1로 표시되는 알데하이드 30g을 투입하여 혼합 용액을 제조한 후, 이를 1차 정시반응, 2차 정시반응, 냉각, 필터링하여 비인계 난연수지를 제조하였다.A non-phosphorus flame retardant resin was prepared in the same manner as in Example 1 except that 280 g of methanol, 200 g of the compound represented by Chemical Formula 2-1 and 30 g of the aldehyde represented by Chemical Formula 3-1 at a concentration of 92% Then, the non-phosphorous flame retardant resin was prepared by first order reaction, second order reaction, cooling, and filtering.
비교예Comparative Example 9 9
상기 실시예 1과 동일한 방법으로 비인계 난연수지를 제조하되, 2차 정시반응시, 화학식 3-1로 표시되는 알데하이드를 28g을 투입한 후, 2차 정시반응, 냉각 및 필터링하여 비인계 난연수지를 제조하였다.The non-phosphorus flame retardant resin was prepared in the same manner as in Example 1 except that 28 g of the aldehyde represented by the general formula (3-1) was added during the second round of reaction, followed by a second order reaction, cooling, .
비교예Comparative Example 10 10
상기 실시예 1과 동일한 방법으로 비인계 난연수지를 제조하되, 2차 정시반응시, 화학식 3-1로 표시되는 알데하이드를 6g만 투입한 후, 2차 정시반응, 냉각 및 필터링하여 비인계 난연수지를 제조하였다.The non-phosphorus flame retardant resin was prepared in the same manner as in Example 1 except that 6 g of the aldehyde represented by the general formula (3-1) was added during the second periodic reaction and then subjected to the second periodic reaction, cooling, .
(g)The compound represented by the formula (2)
(g)
(g)The aldehyde represented by the formula (3)
(g)
정시반응Secondary
On-time response
(g)catalyst
(g)
아민Diethyl
Amine
정시반응Secondary
On-time response
3Comparative Example
3
4Comparative Example
4
5Comparative Example
5
6Comparative Example
6
7Comparative Example
7
8Comparative Example
8
9Comparative Example
9
10Comparative Example
10
(g)The aldehyde represented by the formula (3)
(g)
정시반응Secondary
On-time response
(g)catalyst
(g)
아민Diethyl
Amine
정시반응Secondary
On-time response
실험예Experimental Example
(1) 고형분 함량 테스트(1) Solid content test
실시예 및 비교예에서 제조된 수지를 평박의 반경 30.5mm, 깊이 30mm의 알루미늄(Al)은박지에 수지를 1.0±0.1g을 계량하고, 135℃로 미리 셋팅되어 있는 열풍오븐에 1시간동안 건조시킨 후 불휘발 물질의 함량을 분석하였고 그 결과를 하기 표 3 및 표 4에 나타내었다.The resin prepared in Examples and Comparative Examples was weighed 1.0 ± 0.1 g of resin into an aluminum (Al) foil having a flat radius of 30.5 mm and a depth of 30 mm and dried in a hot air oven preset at 135 ° C. for 1 hour And the results are shown in Tables 3 and 4 below.
(2) 미반응 잔류 화학식 2로 표시되는 화합물 검출량 테스트(2) Unreacted residual compound The compound of the formula (2)
HPLC(High Performance Liquid Chromatography)에 측정하는 중합체는 100ppm의 농도가 되도록 메탄올(Methanol)에 용해시켜 HPLC에 20㎕를 직접 주입시켰다. HPLC의 이동상은 ACN(Acetonitrile)과 물(Water)를 사용하였고, ACN:Water=95:5인 등용리 조건을 수행하였다. 0.6ml/분의 유속으로 유입하였으며, 분석은 35℃에서 수행하였다. 컬럼은 Unison UK-Amino(3㎛) 1개를 사용하였다. 검출기로는 UV-vis Detector를 이용하였다.The polymer to be measured by HPLC (High Performance Liquid Chromatography) was dissolved in methanol so as to have a concentration of 100 ppm, and 20 μl was directly injected into HPLC. The mobile phases of HPLC were ACN (Acetonitrile) and water (Water) and ACN: Water = 95: 5. At a flow rate of 0.6 ml / min, and the analysis was carried out at 35 ° C. One column of Unison UK-Amino (3 탆) was used. A UV-vis detector was used as the detector.
(3) 미반응 잔류 (3) unreacted residues 알데하이드Aldehyde 검출량 테스트 Detection amount test
실시예 및 비교예에서 제조된 수지를 250ml의 비이커에 5g을 계량한 후 메탄올 37.5mL, 증류수 12.5mL를 투입하고 0.1mol/L의 염산으로 pH 3.5로 조절한다. 조절된 용액에 미리 제조된 pH 3.5의 10% Hydroxylamine Chloride를 25mL 투입 후 10분간 교반한다. 10분간 교반한 용액에 0.1mol/L의 NaOH 용액으로 pH 3.5까지 적정한 후 적정된 용액의 양을 기록한다. 해당용액의 Free Formaldehyde는 다음과 같은 식으로 계산한다.After measuring 5 g of the resin prepared in Examples and Comparative Examples in a 250 ml beaker, 37.5 ml of methanol and 12.5 ml of distilled water are added, and the pH is adjusted to 3.5 with 0.1 mol / L hydrochloric acid. Add 25 mL of 10% Hydroxylamine Chloride, pH 3.5, previously prepared to the adjusted solution, and stir for 10 minutes. After stirring for 10 minutes, titrate to pH 3.5 with 0.1 mol / L NaOH solution and record the amount of titrated solution. Free Formaldehyde of the solution is calculated as follows.
[수학식 1][Equation 1]
잔류 알데하이드 검출량(%)= 3c(V1-Vo)/m × 100Residual aldehyde detection amount (%) = 3c (V1-Vo) / m x 100
수학식 1에서, c는 사용한 수산화나트륨 용액의 실제 몰농도(g/L), VO은 수산화나트륨 용액 적정 전의 수산화나트륨 용액의 부피(ml)이며, V1은 적정 후 수산화나트륨 용액의 부피(ml)이고, m은 계량한 난연수지의 질량(g)이다.In Equation 1, c is the actual molar concentration (g / L), V O is the volume (ml) of sodium hydroxide solution before titration of sodium hydroxide solution of sodium hydroxide with the solution, V 1 is the volume of sodium hydroxide and then titrated ( ml), and m is the mass (g) of the flame retardant resin measured.
(4) 저장안정성 테스트(4) Storage stability test
실시예 및 비교예에서 제조된 수지를 이용하여 -5~50℃ 각 특정 온도별 30일 저장 테스트를 실시하였다. 이후 보관된 용기 바닥에 수지의 석출 여부 및 그 기간을 확인하였다.Using the resins prepared in Examples and Comparative Examples, a storage test was carried out at a specific temperature of -5 to 50 ° C for 30 days. Thereafter, the presence or absence of deposition of the resin and the period of time were confirmed on the bottom of the container.
(5) 화학식 2로 표시되는 화합물 용출실험(5) Compound elution experiment represented by formula (2)
실시예 및 비교예에서 제조된 수지 3g을 평박에 계량하고 열풍오븐을 이용하여 135℃에서 1시간 동안 건조하였다. 건조된 수지를 메탄올을 이용하여 1시간 용출시킨 후 용출시킨 용액을 아미노 컬럼이 장착된 HPLC를 통해 모노머인 화학식 2로 표시되는 화합물 용출 여부를 분석하였다.3 g of the resin prepared in Examples and Comparative Examples were weighed on a flat scale and dried at 135 ° C for 1 hour using a hot air oven. The dried resin was eluted with methanol for 1 hour and then eluted, and the elution of the compound represented by the formula (2) as a monomer was analyzed by HPLC equipped with an amino column.
(중량%)Solids
(weight%)
화학식 2 화합물
(중량%)Unreacted residue
Compound (2)
(weight%)
(%)Unreacted residual aldehyde
(%)
(30일)clear
(30 days)
(30일)clear
(30 days)
(30일)clear
(30 days)
(30일)clear
(30 days)
(30일)clear
(30 days)
(30일)clear
(30 days)
(30일)clear
(30 days)
안됨Dissolution
no
안됨Dissolution
no
안됨Dissolution
no
안됨Dissolution
no
3Comparative Example
3
4Comparative Example
4
5Comparative Example
5
6Comparative Example
6
7Comparative Example
7
8Comparative Example
8
9Comparative Example
9
10Comparative Example
10
(중량%)Solids
(weight%)
화학식 2 화합물
(중량%)Unreacted residue
Compound (2)
(weight%)
(%)Unreacted residual aldehyde
(%)
상기 표 3 및 표 4의 실험결과를 살펴보면, 실시예 1 ~ 4의 경우, 미반응 잔류 알데하이드가 없으면서 난연수지 내 잔류 화학식 2로 표시되는 화합물이 0.85 중량% 이하로 매우 적을 뿐만 아니라, 난연수지를 건조시킨 후, 메탄올에 용출시켰을 때, 화학식 2로 표시되는 화합물이 용출되지 않았다. 또한, 다양한 온도 범위에서 저장안정성이 매우 뛰어난 결과를 보였다. The results of Tables 3 and 4 show that in the case of Examples 1 to 4, the amount of the compound represented by Formula 2 remaining in the flame retardant resin is very small at 0.85% by weight or less without any unreacted residual aldehyde, After drying and eluting with methanol, the compound represented by formula (2) was not eluted. In addition, the storage stability was excellent in various temperature ranges.
이에 반해, 다단중합이 아닌 일반적인 방법으로 합성한 비교예 1의 난연수지 및 비교예 2의 난연수지는 미반응 잔류 모노머가 다량 존재하고, 난연수지의 저장안정성이 좋지 않은 문제점이 있었다.On the other hand, the flame retardant resin of Comparative Example 1 and the flame retardant resin of Comparative Example 2, which were synthesized by a general method other than the multistage polymerization, existed in a large amount of unreacted residual monomers, and the storage stability of the flame retardant resin was poor.
또한, 1차 정시반응을 65℃ 초과한 조건에서 수행한 비교예 3 및 2차 정시반응을 75℃ 초과한 조건에서 수행한 비교예 5의 경우, 미반응 잔류 모노머는 거의 없으나, 과중합에 의해 난연수지가 불투명해지고, 메탄올 용해성이 떨어지며 비인계 난연수지가 석출되어 저장안정성이 매우 좋지 않은 문제점을 보였다.In the case of Comparative Example 3 in which the first order reaction was performed at a temperature exceeding 65 ° C and Comparative Example 5 in which the second order reaction was performed at a temperature higher than 75 ° C, there was almost no unreacted residual monomer, The flame retardant resin became opaque, the methanol solubility was poor, and the non-phosphorus flame retardant resin was precipitated, resulting in a problem that the storage stability was not very good.
그리고, 1차 정시반응을 58℃ 미만인 조건에서 수행한 비교예 4 및 2차 정시반응을 68℃ 미만인 조건에서 수행한 비교예 6의 경우, 미반응 잔류 모노머가 많이 발생하는 문제가 있었다.In the case of Comparative Example 4 in which the first order reaction was performed at a temperature lower than 58 ° C. and Comparative Example 6 in which the second order reaction was conducted at a temperature lower than 68 ° C., there was a problem that unreacted residual monomers were generated in a large amount.
또한, 1차 정시반응시 알데하이드 사용량이 32 중량부 초과한 비교예 7 및 2차 정시반응시 알데하이드 사용량이 12 중량부 초과한 비교예 9의 경우, 실시예와 비교할 때, 미반응 잔류 모노머인 알데하이드 함량이 크게 증가하는 문제가 있었다.In the case of Comparative Example 7 in which the amount of aldehyde used was more than 32 parts by weight in the first order reaction and Comparative Example 9 in which the amount of aldehyde used was more than 12 parts by weight in the second order reaction, the aldehyde as the unreacted residual monomer There was a problem that the content was greatly increased.
그리고, 또한, 1차 정시반응시 알데하이드 사용량이 18 중량부 미만인 비교예 8 및 2차 정시반응시 알데하이드 사용량이 4 중량부 미만이었던 비교예 10의 경우,실시예와 비교할 때, 비인계 난연수지가 빠른 시일 내에 석출되어 저장안정성이 크게 떨어지는 문제가 있었다.In addition, in Comparative Example 8 in which the amount of aldehyde used was less than 18 parts by weight in the first order reaction and Comparative Example 10 in which the amount of aldehyde used was less than 4 parts by weight in the second order reaction, the non-phosphorus- There is a problem in that the storage stability is greatly deteriorated due to precipitation within a short period of time.
상기 실시예 및 실험예를 통하여, 본 발명이 제시하는 방법으로 제조한 비인계 난연수지가 미반응 모노머의 함량을 방지 및/또는 최소화하여 이의 용출을 방지함으로써, 친환경적인 난연수지 제품을 제공할 수 있을 뿐만 아니라, 코올 용제상에서도 석출 또는 침전을 최소화 및/또는 방지되어 저장안정성이 매우 우수하여 난연수지를 제공할 수 있음을 확인할 수 있었다.Through the above Examples and Experimental Examples, the non-phosphorus flame retardant resin produced by the method proposed by the present invention can prevent and / or minimize the unreacted monomer content to thereby prevent its elution, thereby providing an environmentally friendly flame retardant resin product It is possible to provide a flame retardant resin because it has excellent storage stability and is minimized and / or prevented from precipitation or precipitation even in a co-solvent.
Claims (12)
하기 화학식 2로 표시되는 화합물, 하기 화학식 3으로 표시되는 알데하이드 및 용매를 혼합한 용액을 교반한 후, 38 ~ 45℃까지 승온시키는 1단계;
승온된 용액에 촉매를 투입한 후, 58 ~ 65℃까지 승온시킨 후, 2시간 30분 ~ 3시간 30분 동안 1차 정시반응을 수행하는 2단계;
1차 정시반응시킨 용액에 상기 알데하이드 및 촉매를 투입한 후, 68 ~ 75℃로 승온시킨 후, 환류(reflux)시키면서 2시간 30분 ~ 3시간 30분 동안 2차 정시반응을 수행하는 3단계; 및
1℃ ~ 5℃로 냉각 및 필터링하는 4단계;를 포함하는 공정을 수행하여,
하기 화학식 1로 표시되는 반복단위를 포함하는 질소화합물을 제조하는 것을 특징으로 하는 저장안정성이 우수한 비인계 난연수지의 제조방법;
[화학식 1]
화학식 1에서, R1 및 R4 각각은 서로 독립적인 것으로서, 수소원자, C1 ~ C5의 직쇄형 알킬기, C3 ~ C5의 분쇄형 알킬기, 페닐기 또는 알킬페닐기이며, R5는 -CN 또는 -CH2CN 이고, n은 중합체의 중량평균분자량 200 ~ 1,500을 만족시키는 유리수이며,
[화학식 2]
화학식 2에서, R1 내지 R4 각각은 독립적인 것으로서, 수소원자, C1 ~ C5의 직쇄형 알킬기, C3 ~ C5의 분쇄형 알킬기, 페닐기 또는 알킬페닐기이며, R5는 -CN 또는 -CH2CN 이고,
[화학식 3]
화학식 3에서, R1 및 R2 각각은 독립적인 것으로서, 수소원자, C1 ~ C3의 직쇄형 알킬기 또는 페닐기이다.
A method for producing a nitrogen compound comprising a repeating unit represented by the following formula (1) by polymerizing a compound represented by the following formula (2) and an aldehyde represented by the following formula (3) in a molar ratio of 1: 0.6-0.95,
A step of stirring a solution of a compound represented by the following formula (2), an aldehyde represented by the following formula (3) and a solvent, and then raising the temperature to 38 to 45 ° C;
A step of adding a catalyst to the heated solution, raising the temperature to 58 to 65 ° C, and then carrying out a first-order reaction for 2 to 30 minutes to 3 hours and 30 minutes;
A third step in which the aldehyde and the catalyst are added to the first-order reaction solution, the temperature is raised to 68 to 75 ° C, and the second-order reaction is performed for 2 to 30 minutes to 3 hours and 30 minutes while refluxing; And
And cooling and filtering the solution to 1 DEG C to 5 DEG C,
A process for producing a non-phosphorus flame retardant resin having excellent storage stability, which comprises preparing a nitrogen compound containing a repeating unit represented by the following formula (1):
[Chemical Formula 1]
Each of R 1 and R 4 is independently a hydrogen atom, a straight-chain alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a phenyl group or an alkylphenyl group, R 5 is -CN or -CH 2 CN, and n is a rational number satisfying a weight average molecular weight of the polymer of 200 to 1,500,
(2)
In formula (2), each of R 1 to R 4 is independently a hydrogen atom, a straight-chain alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a phenyl group or an alkylphenyl group, R 5 is -CN or -CH 2 CN ego,
(3)
In Formula (3), each of R 1 and R 2 is independently a hydrogen atom, a straight-chain alkyl group having 1 to 3 carbon atoms, or a phenyl group.
7. The method according to claim 6, wherein the solution of step 1 is prepared by mixing 18 to 32 parts by weight of the aldehyde and 110 to 180 parts by weight of a solvent with respect to 100 parts by weight of the compound represented by the formula (2) A method for producing a flame retardant resin.
[7] The method according to claim 6, wherein the aldehyde in Step 3 is added to a solution of 4 to 12 parts by weight based on 100 parts by weight of the compound represented by Formula 2, Way.
[Claim 7] The method according to claim 6, wherein the catalysts of the second and third stages are amine-based catalysts containing at least one member selected from the group consisting of diethyleneamine, triethylamine, diethanolamine and triethanolamine. A method for producing a flame retardant resin.
3단계의 촉매는 상기 화학식 2로 표시되는 화합물 100 중량부에 대하여, 0.04 ~ 0.1 중량부를 투입하는 것을 특징으로 하는 저장안정성이 우수한 비인계 난연수지의 제조방법.
7. The method according to claim 6, wherein 0.15 to 0.50 parts by weight of the catalyst of the second stage is added to 100 parts by weight of the compound represented by the general formula (2)
Wherein the catalyst of the third stage is fed in an amount of 0.04 to 0.1 part by weight based on 100 parts by weight of the compound represented by the general formula (2).
[화학식 2]
화학식 2에서, R1 내지 R4 각각은 독립적인 것으로서, 수소원자, C1 ~ C5의 직쇄형 알킬기, C3 ~ C5의 분쇄형 알킬기, 페닐기 또는 알킬페닐기이며, R5는 -CN 또는 -CH2CN이다.
The flame retardant resin composition according to any one of claims 6 to 10, wherein, when the prepared non-phosphorus flame retardant resin is dissolved in methanol at a concentration of 100 ppm, the amount of the unreacted compound represented by the general formula (2) % Or less of the total amount of the flame retardant resin.
(2)
In formula (2), each of R 1 to R 4 is independently a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a phenyl group or an alkylphenyl group, R 5 is -CN or -CH 2 CN to be.
[수학식 1]
잔류 알데하이드 검출량(%)= 3c(V1-Vo)/m × 100
수학식 1에서, c는 사용한 수산화나트륨 용액의 실제 몰농도(g/L), VO은 수산화나트륨 용액 적정 전의 수산화나트륨 용액의 부피(ml)이며, V1은 적정 후 수산화나트륨 용액의 부피(ml)이고, m은 계량한 난연수지의 질량(g)이다.10. The method according to any one of claims 6 to 10, wherein 10 vol% hydroxylamine chloride aqueous solution is added to a solution of pH 3.5 in which 5 g of the non-phosphorus flame retardant resin is dissolved, and then 0.1 mol / L sodium hydroxide solution a method for producing a non-phosphorus-based flame retardant resin having excellent storage stability, characterized in that the amount of residual aldehyde in an appropriate solution until pH is 3.5 is determined by the following equation (1), wherein the amount of residual aldehyde is 0.05% or less.
[Equation 1]
Residual aldehyde detection amount (%) = 3c (V1-Vo) / m x 100
In Equation 1, c is the actual molar concentration (g / L), V O is the volume (ml) of sodium hydroxide solution before titration of sodium hydroxide solution of sodium hydroxide with the solution, V 1 is the volume of sodium hydroxide and then titrated ( ml), and m is the mass (g) of the flame retardant resin measured.
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