WO2013100290A1 - Phosphinate-based flame-retarding agent and production method therefor - Google Patents

Phosphinate-based flame-retarding agent and production method therefor Download PDF

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WO2013100290A1
WO2013100290A1 PCT/KR2012/005268 KR2012005268W WO2013100290A1 WO 2013100290 A1 WO2013100290 A1 WO 2013100290A1 KR 2012005268 W KR2012005268 W KR 2012005268W WO 2013100290 A1 WO2013100290 A1 WO 2013100290A1
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phosphinate
flame retardant
formula
meth
reaction
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PCT/KR2012/005268
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French (fr)
Korean (ko)
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강용희
김만석
이은주
안성희
홍상현
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제일모직주식회사
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus

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  • the present invention relates to a phosphinate flame retardant and a method for producing the same. More specifically, the present invention relates to a method for producing a high purity phosphinate flame retardant with a high yield by reacting (meth) acrylic anhydride with a phosphinate alcohol compound, and to a phosphinide flame retardant prepared by the method. will be.
  • the present invention relates in particular to phosphinate flame retardants which can be used in methacrylic resins.
  • Methacrylic resins have excellent scratch resistance due to excellent transparency, weather resistance, and excellent rigidity. Due to these properties, methacryl-based resins are not only used for general molded products, but also variously used as materials for electric and electronic products, display materials, optical materials, building materials, automobile articles, and the like, and the amount thereof is increasing. However, since methacryl-type resin is flammable, the use is restrict
  • a method of blending an antimony compound, a halogen compound, a phosphorus compound, or a compound including nitrogen to impart flame retardancy in order to overcome flammability disadvantages of the resin is known and used.
  • halogen-based flame retardants are most widely used because they impart high flame retardancy in a relatively small amount.
  • a halogen-based flame retardant there is a disadvantage in generating a corrosive gas during processing to cause corrosion of the processing equipment, and also generates a toxic gas such as dioxin or hydrogen halide gas during combustion.
  • the phosphorus-based flame retardant has a disadvantage in that the inherent physical properties of the resin are lowered due to the large amount of the flame retardant.
  • the flame retardants are limited to resins containing polycarbonate and polyphenylene ether, and thus are almost impossible to apply to methacrylic resins. Therefore, it is difficult to maintain transparency and scratch resistance which are inherent advantages of methacrylic resin.
  • Japanese Laid-Open Patent Publication No. 2009-109425 discloses an example of copolymerization using an acrylic monomer containing a phosphinate group, but in a method of synthesizing the monomer, an excess of methacrylic acid is directly added at a high temperature using a strong acid catalyst such as sulfuric acid. There is a method of carrying out the esterification reaction.
  • the direct esterification reaction is not suitable for industrial production due to the low conversion rate, and even if the reaction temperature is increased to increase the reaction conversion rate, it is difficult to obtain a product with high yield due to the polymerization reaction of (meth) acrylic acid as a raw material. Rather, it causes serious problems in the machinery used for the reaction, causing problems such as deterioration of the color of the product.
  • the present invention is to provide a high refractive acrylic phosphorus-based monomer flame retardant having a high refractive index, high flame retardancy, heat resistance can be achieved by applying to methacrylic resin at the same time (physical properties) including flame retardancy, high refractive index, heat resistance performance .
  • the present invention has led to the development of a method for synthesizing a phosphorus monomer having a specific structure and containing a (meth) acryl group by a new method.
  • An object of the present invention is to provide a high purity phosphinate-based flame retardant and a method for producing the same.
  • Still another object of the present invention is to provide a method for preparing a colorless phosphinate flame retardant.
  • the (meth) acrylic acid anhydride and the phosphinate alcohol represented by the following formula (1) is esterified for 2 to 12 hours at a conversion rate of 90 to 100% at 0 to 100 °C It provides a method for producing a phosphinate-based flame retardant represented by the following formula (2).
  • R1 is a C1-C4 saturated or unsaturated hydrocarbon group.
  • R1 is a C1-C4 saturated or unsaturated hydrocarbon group
  • R2 is H or methyl group.
  • the molar ratio of the phosphinate alcohol: the (meth) acrylic anhydride is 1: 1.0 to 1: 1.5.
  • reaction is carried out in the presence of an organic solvent selected from the group consisting of benzene, toluene, xylene, n-hexane, cyclohexane, n-heptane, n-octane, ethyl ether, acetonitrile, methylene chloride or mixtures thereof. It is done.
  • an organic solvent selected from the group consisting of benzene, toluene, xylene, n-hexane, cyclohexane, n-heptane, n-octane, ethyl ether, acetonitrile, methylene chloride or mixtures thereof. It is done.
  • the reaction may be reacted in the presence of at least one catalyst selected from the group consisting of alkali metal salts, amine compounds or organic acids, wherein the catalyst is 0.01 to a weight of (meth) acrylic anhydride. It may be added at -5.0% by weight.
  • at least one catalyst selected from the group consisting of alkali metal salts, amine compounds or organic acids, wherein the catalyst is 0.01 to a weight of (meth) acrylic anhydride. It may be added at -5.0% by weight.
  • reaction may be performed by adding at least one polymerization inhibitor selected from the group consisting of butylated hydroxytoluene (BHT), hydroquinone, p-benzoquinone and the like.
  • BHT butylated hydroxytoluene
  • hydroquinone hydroquinone
  • p-benzoquinone p-benzoquinone
  • the method may further include distilling and recovering the (meth) acrylic acid produced after the reaction is terminated at a pressure of 5 to 100 mmHg and a temperature of 30 to 100 ° C.
  • the reaction product may further comprise a step of purification through an alkali washing, concentration and filtration process.
  • the phosphinate-based flame retardant prepared by the above production method preferably has a purity of 90% or more and a yield of 85% or more.
  • the phosphinate-based flame retardant prepared by the above production method preferably has an APHA Color value of A-10 to A-50 based on ASTM D1209.
  • the phosphinate flame retardant manufacturing method of the present invention is excellent in synthetic yield, the phosphinate flame retardant prepared by the production method is excellent in purity and colorability.
  • 1 is a diagram showing a 1 H-NMR peak of the phosphinate alcohol used in the present invention.
  • FIG. 2 is a diagram showing a 1 H-NMR peak of the phosphinate flame retardant of the present invention.
  • the phosphinate flame retardant of the present invention is prepared by reacting (meth) acrylic anhydride and phosphinate alcohol as a reactant.
  • the phosphinate alcohol used in the present invention is characterized by represented by the following formula (1)
  • the phosphinate-based flame retardant is a product of the present invention is represented by the formula (2).
  • R1 is a C1-C4 saturated or unsaturated hydrocarbon group.
  • R1 is a C1-C4 saturated or unsaturated hydrocarbon group
  • R2 is H or methyl group.
  • the phosphinate-based alcohol may be prepared by reacting 9,10-dihydro-9-oxy-10-hospapenantorene-10-oxide and paraformaldehyde.
  • the paraformaldehyde used in the present invention may be used in a molar ratio of 0.9 to 2.0 with respect to 9,10-dihydro-9-oxy-10-hospphenanthrene-10-oxide, more preferably 0.9 to 1.1. Can be used as a ratio.
  • the reaction proceeds without a catalyst, the reaction temperature may be 50 ⁇ 110 °C, more preferably at 70 ⁇ 90 °C.
  • the production of the phosphinate alcohol can be confirmed through the 1 H-NMR peak of FIG.
  • the (meth) acrylic acid anhydride may be prepared by a method of reacting (meth) acrylic acid halide with (meth) acrylic acid (method 1), and a method of reacting (meth) acrylic acid with acetic anhydride (method 2). .
  • method 1 Since method 1 has a problem in that handling of (meth) acrylic acid halide is not easy and reaction stability is inferior, it is preferable that (meth) acrylic anhydride is produced by method 2.
  • the catalyst may be used in an amount of 0.01 to 3.0%, preferably 0.1 to 1.0% based on the weight of the (meth) acrylic acid.
  • the molar ratio of the (meth) acrylic acid: acetic anhydride may be 1: 0.2 to 1: 0.5, for example, 1: 0.45 to 1: 0.5.
  • polymerization inhibitors chosen from the group which consists of butylated hydroxy toluene (BHT), p-benzoquinone, etc. can further be included.
  • the molar ratio of the phosphinate-based alcohol: (meth) acrylic anhydride used in the present invention can be reacted with 1: 0.5 to 1: 1.5, more preferably 1: 0.9 to 1: 1.1.
  • the solvent used in the present invention may be an organic solvent selected from the group consisting of toluene, xylene, n-hexane, cyclohexane, n-heptane, n-octane, ethyl ether, acetonitrile, methylene chloride or mixtures thereof.
  • the reaction temperature of the present invention can be carried out at 0 ⁇ 100 °C, more preferably at 40 ⁇ 90 °C. If the reaction temperature is lower than 0 °C, the reaction rate is excessively lowered and is not effective. If the reaction temperature exceeds 100 °C, even if a polymerization inhibitor is used, polymerization of (meth) acrylic anhydride or phosphinate flame retardant may occur. to be. Therefore, the present invention can produce a high-purity phosphinate-based flame retardant by not increasing the reaction temperature to a temperature at which side reactions can occur.
  • reaction time of the present invention can be made for 2 to 12 hours until the reaction conversion rate is 85 to 100%, more preferably carried out for 5 to 10 hours.
  • the reaction can be carried out even under the non-catalyst condition during the reaction, but it is more preferable to use a catalyst used in a conventional esterification reaction.
  • the catalyst include alkali metal salts such as lithium acetate, sodium acetate, and potassium propionate, amine compounds such as pyridine, triethylamine, and triethyldiamine, sulfuric acid, boric acid, and methane.
  • Organic acids, such as sulfonic acid and p-toluenesulfonic acid, etc. are mentioned. It is preferable to use the said catalyst at 0.001 to 3.0 weight% with respect to (meth) crylic acid anhydride. More preferably, 0.1 to 1.0 weight% can be used.
  • the catalyst is added to (meth) acrylic anhydride with phosphinate alcohol, or to phosphinate alcohol with (meth) acrylic anhydride, or (meth) acrylic anhydride, phosphinate alcohol, and
  • the catalysts may be added in any order, but are not limited to these.
  • At least one polymerization inhibitor selected from the group consisting of butylated hydroxytoluene (BHT), hydroquinone, p-benzoquinone and the like may be added to prevent polymerization that may occur during the reaction.
  • the polymerization inhibitor may be included in an amount of 0.01 to 0.5% based on the weight of the phosphinate-based flame retardant.
  • (meth) acrylic acid is produced from (meth) acrylic acid anhydride
  • the (meth) acrylic acid can be recovered through distillation.
  • the pressure condition required for distillation is 5-100 mmHg, More preferably, it is 5-20 mmHg.
  • Temperature conditions are 30-100 degreeC, More preferably, it is 50-80 degreeC.
  • the (meth) acrylic acid recovered at this time can be used to prepare (meth) acrylic anhydride.
  • the phosphinate-based flame retardant of the present invention can be purified using a process of alkali washing with water, concentration and filtration.
  • the phosphinate-based flame retardant prepared by the above process can be confirmed by analyzing the 1 H-NMR peak of FIG.
  • the phosphinate-based flame retardant prepared through the above process is preferably color close to colorless.
  • the chromaticity may be APHA Color (Hazen Color) measured by the Pt-Co measurement method according to ASTM D 1209. In the measurement method, the chromaticity ranges from 0 to 500, the chromaticity of Platinum-Cobalt Stock Solution becomes APHA 500, and the chromaticity of ultrapure water (D.I water) used as a diluent corresponds to APHA 0. At this time, depending on the degree of dilution is classified quantitatively in steps of 1 to 500.
  • the phosphinate flame retardant of the present invention preferably has an APHA Color value of A-10 to A-50.
  • the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was reacted at 40 ° C. for 12 hours.
  • the reaction was carried out in the same manner as in Comparative Example 1 except that the reaction temperature was reacted at 120 ° C. or higher using xylene.

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Abstract

The present invention relates to a phosphinate-based flame-retarding agent represented by chemical formula 2, and to a production method therefor, wherein a (meth)acrylic anhydride and a phosphinate-based alcohol represented by chemical formula 1 undergo an esterification reaction at between 0 and 100°C for between 2 and 12 hours until the conversion rate reaches between 85 and 100%. With the production method for the phosphinate-based flame-retarding agent of the present invention, the synthesis yield is outstanding, and the phosphinate-based flame-retarding agent which is produced has outstanding purity and colourability.

Description

포스피네이트계 난연제 및 그 제조방법Phosphate flame retardant and its manufacturing method
본 발명은 포스피네이트계 난연제 및 그 제조 방법에 관한 것이다. 보다 구체적으로, 본 발명은 (메타)아크릴산 무수물과 포스피네이트계 알코올 화합물을 반응시켜 높은 수율로 고순도의 포스피네이트계 난연제를 제조하는 방법 및 그 방법에 의하여 제조된 포스피네이드계 난연제에 관한 것이다.The present invention relates to a phosphinate flame retardant and a method for producing the same. More specifically, the present invention relates to a method for producing a high purity phosphinate flame retardant with a high yield by reacting (meth) acrylic anhydride with a phosphinate alcohol compound, and to a phosphinide flame retardant prepared by the method. will be.
본 발명은 특히 메타크릴계 수지에 사용될 수 있는 포스피네이트계(phosphinate) 난연제에 관한 것이다. 메타크릴계 수지는 우수한 투명성, 내후성, 그리고 우수한 강성에 기인한 뛰어난 내스크래치성을 갖는다. 이러한 특성으로 인하여 메타크릴계 수지는 일반 성형품 뿐만 아니라, 전기 전자 제품의 소재, 디스플레이 재료, 광학 재료, 건축재료, 자동차 용품 등의 소재로 다양하게 사용되고 있고, 그 양이 증가하는 추세에 있다. 하지만 메타크릴계 수지는 가연성이 있기 때문에 그 용도가 제한되고 있다.The present invention relates in particular to phosphinate flame retardants which can be used in methacrylic resins. Methacrylic resins have excellent scratch resistance due to excellent transparency, weather resistance, and excellent rigidity. Due to these properties, methacryl-based resins are not only used for general molded products, but also variously used as materials for electric and electronic products, display materials, optical materials, building materials, automobile articles, and the like, and the amount thereof is increasing. However, since methacryl-type resin is flammable, the use is restrict | limited.
일반적으로 수지가 가지는 가연성의 단점을 극복하기 위해 안티몬계 화합물, 할로겐계 화합물, 인계 화합물, 또는 질소를 포함한 화합물을 블렌드하여 난연성을 부여하는 방법이 공지의 기술로 알려져 사용되고 있다. 이 중 할로겐계 난연제가 비교적 적은 양으로 높은 난연성을 부여하므로 가장 널리 사용되고 있다. 그러나 할로겐계 난연제를 사용할 경우, 가공시 부식성 가스를 발생하여 가공기기의 부식을 유발하고, 또한 연소시에는 다이옥신이나 할로겐화 수소 가스 등 유독성 가스를 발생시키는 단점이 있다. 따라서 전 세계적으로 그 사용의 제한을 점차 확대하는 추세에 있고, 이로 인해 할로겐계 난연제를 함유하지 않은 수지에 대한 수요가 최근 급격히 확대되고 있다. 할로겐계 난연제를 대체하는 난연제로 현재 가장 많은 연구가 되어 있고 보편적으로 사용되고 있는 것은 인계 난연제이다. 인계 난연제는 할로겐계 난연제보다 부식성과 독성 측면에 그 우위에 있다. 그러나 인계 난연제는 난연 성능이 할로겐계에 비해 떨어지며 이로 인해 다량의 난연제를 투입하고도 목적하고자 하는 수준의 난연성을 얻기 어렵다. 또한 인계 난연제는 다량의 난연제로 인해 수지가 가지고 있던 고유의 물성이 저하되는 단점이 있다. 무엇보다 상기 난연제들은 폴리카보네이트 및 폴리페닐렌에테르를 함유한 수지에 제한되어 메타크릴계 수지에는 적용이 거의 불가능하다. 따라서 메타크릴계 수지가 갖는 고유의 장점인 투명성이나 내스크래치성을 유지하기 어렵다.In general, a method of blending an antimony compound, a halogen compound, a phosphorus compound, or a compound including nitrogen to impart flame retardancy in order to overcome flammability disadvantages of the resin is known and used. Of these, halogen-based flame retardants are most widely used because they impart high flame retardancy in a relatively small amount. However, when using a halogen-based flame retardant, there is a disadvantage in generating a corrosive gas during processing to cause corrosion of the processing equipment, and also generates a toxic gas such as dioxin or hydrogen halide gas during combustion. Therefore, there is a tendency to gradually increase the restriction of its use all over the world, which has led to a sharp increase in the demand for resins containing no halogen-based flame retardant in recent years. Flame retardants replace halogen-based flame retardants. Currently, the most researched and commonly used phosphorus-based flame retardants. Phosphorus-based flame retardants have the advantage of corrosion and toxicity over halogen-based flame retardants. However, phosphorus-based flame retardants are inferior in flame retardancy compared to halogen-based flame retardants, and thus, even when a large amount of flame retardants are added, it is difficult to obtain a desired level of flame retardancy. In addition, the phosphorus-based flame retardant has a disadvantage in that the inherent physical properties of the resin are lowered due to the large amount of the flame retardant. Above all, the flame retardants are limited to resins containing polycarbonate and polyphenylene ether, and thus are almost impossible to apply to methacrylic resins. Therefore, it is difficult to maintain transparency and scratch resistance which are inherent advantages of methacrylic resin.
일본공개특허 제2009-109425호에서는 포스피네이트기를 포함한 아크릴계 단량체를 이용하여 공중합한 예를 제시하고 있으나 단량체를 합성하는 제조 방법에서 과량의 메타아크릴산을 황산과 같은 강산 촉매를 사용하여 높은 온도에서 직접 에스테르화 반응을 진행하는 방법이 있다. 그러나 직접 에스테르화 반응은 전환율이 낮아서 산업용 제조방법으로서는 적합하지 않으며, 또한 반응 전환율을 높이고자 반응온도를 상승시키더라도, 원료인 (메타)아크릴산의 중합반응이 발생하여 높은 수율로 제품을 얻기 어려울 뿐만 아니라 반응에 사용하는 기계장치에 심각한 문제를 발생시키며, 생성물의 색상이 악화되는 등의 문제를 야기시킨다.Japanese Laid-Open Patent Publication No. 2009-109425 discloses an example of copolymerization using an acrylic monomer containing a phosphinate group, but in a method of synthesizing the monomer, an excess of methacrylic acid is directly added at a high temperature using a strong acid catalyst such as sulfuric acid. There is a method of carrying out the esterification reaction. However, the direct esterification reaction is not suitable for industrial production due to the low conversion rate, and even if the reaction temperature is increased to increase the reaction conversion rate, it is difficult to obtain a product with high yield due to the polymerization reaction of (meth) acrylic acid as a raw material. Rather, it causes serious problems in the machinery used for the reaction, causing problems such as deterioration of the color of the product.
본 발명은 메타크릴계 수지에 적용하여 난연성, 고굴절률, 내열성 성능을 포함한 물질특성(Physical properties)을 동시에 달성할 수 있는 굴절률이 높고, 난연성, 내열성이 높은 고굴절 아크릴 인계 단량체 난연제를 제공하기 위한 것이다. 본 발명은 특정 구조를 갖고 (메타)아크릴기를 함유하고 있는 인계 단량체를 새로운 방법으로 합성하는 방법을 개발하기에 이른 것이다.The present invention is to provide a high refractive acrylic phosphorus-based monomer flame retardant having a high refractive index, high flame retardancy, heat resistance can be achieved by applying to methacrylic resin at the same time (physical properties) including flame retardancy, high refractive index, heat resistance performance . The present invention has led to the development of a method for synthesizing a phosphorus monomer having a specific structure and containing a (meth) acryl group by a new method.
본 발명의 목적은 고순도의 포스피네이트계 난연제 및 그 제조방법을 제공하는 것이다.An object of the present invention is to provide a high purity phosphinate-based flame retardant and a method for producing the same.
본 발명의 다른 목적은 고순도의 포스피네이트계 난연제를 고수율로 제조하는 방법을 제공하는 것이다.It is another object of the present invention to provide a method for producing a high purity phosphinate flame retardant.
본 발명의 또 다른 목적은 무색의 포스피네이트계 난연제를 제조하는 방법을 제공하는 것이다.Still another object of the present invention is to provide a method for preparing a colorless phosphinate flame retardant.
본 발명의 구체예에 따르면, (메타)아크릴산 무수물 및 하기 화학식 1로 표시되는 포스피네이트계 알코올을 0∼100 ℃에서 전환율이 90∼100%가 될 때까지 2∼12시간 동안 에스테르 반응되는 것을 특징으로 하는 하기 화학식 2로 표시되는 포스피네이트계 난연제의 제조 방법을 제공한다.According to an embodiment of the present invention, the (meth) acrylic acid anhydride and the phosphinate alcohol represented by the following formula (1) is esterified for 2 to 12 hours at a conversion rate of 90 to 100% at 0 to 100 ℃ It provides a method for producing a phosphinate-based flame retardant represented by the following formula (2).
[화학식 1][Formula 1]
Figure PCTKR2012005268-appb-I000001
Figure PCTKR2012005268-appb-I000001
(상기 화학식 1에서 R1은 C1-C4의 포화 또는 불포화 탄화수소기임.)(In Formula 1, R1 is a C1-C4 saturated or unsaturated hydrocarbon group.)
[화학식 2][Formula 2]
(상기 화학식 2에서 R1은 C1-C4의 포화 또는 불포화 탄화수소기이고, R2는 H 또는 메틸기임.)(In Formula 2, R1 is a C1-C4 saturated or unsaturated hydrocarbon group, R2 is H or methyl group.)
상기 포스피네이트계 알코올 : 상기 (메타)아크릴산 무수물의 몰비는 1 : 1.0∼1 : 1.5인 것을 특징으로 한다.The molar ratio of the phosphinate alcohol: the (meth) acrylic anhydride is 1: 1.0 to 1: 1.5.
또한, 상기 반응은 벤젠, 톨루엔, 크실렌, n-헥산, 사이클로헥산, n-헵탄, n-옥탄, 에틸 에테르, 아세토니트릴, 메틸렌클로라이드 또는 그 혼합물로 이루어진 군으로부터 선택되는 유기용매 존재 하에서 이루어지는 것을 특징으로 한다.In addition, the reaction is carried out in the presence of an organic solvent selected from the group consisting of benzene, toluene, xylene, n-hexane, cyclohexane, n-heptane, n-octane, ethyl ether, acetonitrile, methylene chloride or mixtures thereof. It is done.
본 발명의 구체예에 따르면, 상기 반응은 알칼리 금속염, 아민계 화합물 또는 유기산으로 이루어진 군으로부터 선택되는 1종 이상의 촉매의 존재 하에 반응할 수 있으며, 상기 촉매는 (메타)아크릴산 무수물의 중량에 대하여 0.01∼5.0 중량%로 가해질 수 있다.According to an embodiment of the present invention, the reaction may be reacted in the presence of at least one catalyst selected from the group consisting of alkali metal salts, amine compounds or organic acids, wherein the catalyst is 0.01 to a weight of (meth) acrylic anhydride. It may be added at -5.0% by weight.
또한, 상기 반응은 부틸레이티드하이드록시톨루엔(BHT), 하이드로퀴논, p-벤조퀴논 등으로 이루어진 군으로부터 선택되는 1종 이상의 중합 방지제를 첨가하여 이루어질 수 있다.In addition, the reaction may be performed by adding at least one polymerization inhibitor selected from the group consisting of butylated hydroxytoluene (BHT), hydroquinone, p-benzoquinone and the like.
본 발명의 다른 구체예에 따르면, 상기 반응이 종결된 이후 생성된 (메타)아크릴산을 5∼100 mmHg 압력 및 30∼100 ℃ 온도로 증류하여 회수하는 단계를 더 포함할 수 있다.According to another embodiment of the present invention, the method may further include distilling and recovering the (meth) acrylic acid produced after the reaction is terminated at a pressure of 5 to 100 mmHg and a temperature of 30 to 100 ° C.
본 발명의 또 다른 구체예에 따르면, 상기 (메타)아크릴산 회수 단계 종료 후 반응생성물은 알칼리 세정, 농축 및 여과 공정을 거쳐 정제하는 단계를 더 포함할 수 있다.According to another embodiment of the present invention, after completion of the (meth) acrylic acid recovery step, the reaction product may further comprise a step of purification through an alkali washing, concentration and filtration process.
상기 제조방법으로 제조된 포스피네이트계 난연제는 순도가 90% 이상, 수율이 85% 이상인 것이 바람직하다.The phosphinate-based flame retardant prepared by the above production method preferably has a purity of 90% or more and a yield of 85% or more.
또한, 상기 제조방법으로 제조된 포스피네이트계 난연제는 ASTM D1209 규정에 의거한 APHA Color 값이 A-10∼A-50인 것이 바람직하다.In addition, the phosphinate-based flame retardant prepared by the above production method preferably has an APHA Color value of A-10 to A-50 based on ASTM D1209.
본 발명의 포스피네이트계 난연제 제조방법은 합성수율이 우수하고, 상기 제조방법으로 제조된 포스피네이트계 난연제는 순도 및 착색성이 우수하다.The phosphinate flame retardant manufacturing method of the present invention is excellent in synthetic yield, the phosphinate flame retardant prepared by the production method is excellent in purity and colorability.
도 1은 본 발명에서 사용되는 포스피네이트계 알코올의 1H-NMR 피크를 나타낸 도면이다.1 is a diagram showing a 1 H-NMR peak of the phosphinate alcohol used in the present invention.
도 2는 본 발명의 포스피네이트계 난연제의 1H-NMR 피크를 나타낸 도면이다.2 is a diagram showing a 1 H-NMR peak of the phosphinate flame retardant of the present invention.
이하, 본 발명을 구체적으로 설명하기로 한다.Hereinafter, the present invention will be described in detail.
포스피네이트계 난연제 제조방법Phosphate flame retardant manufacturing method
본 발명의 포스피네이트계 난연제는 반응물질로서 (메타)아크릴산 무수물 및 포스피네이트계 알코올을 반응시켜 제조된다.The phosphinate flame retardant of the present invention is prepared by reacting (meth) acrylic anhydride and phosphinate alcohol as a reactant.
본 발명에서 사용되는 포스피네이트계 알코올은 하기 화학식 1로 표시되는 것을 특징으로 하며, 본 발명의 생성물인 포스피네이트계 난연제는 하기 화학식 2로 표시된다.The phosphinate alcohol used in the present invention is characterized by represented by the following formula (1), the phosphinate-based flame retardant is a product of the present invention is represented by the formula (2).
[화학식 1][Formula 1]
Figure PCTKR2012005268-appb-I000003
Figure PCTKR2012005268-appb-I000003
(상기 화학식 1에서 R1은 C1-C4의 포화 또는 불포화 탄화수소기임.)(In Formula 1, R1 is a C1-C4 saturated or unsaturated hydrocarbon group.)
[화학식 2][Formula 2]
Figure PCTKR2012005268-appb-I000004
Figure PCTKR2012005268-appb-I000004
(상기 화학식 2에서 R1은 C1-C4의 포화 또는 불포화 탄화수소기이고, R2는 H 또는 메틸기임.)(In Formula 2, R1 is a C1-C4 saturated or unsaturated hydrocarbon group, R2 is H or methyl group.)
상기 포스피네이트계 알코올은 9,10-디하이드로-9-옥시-10-호스파페난토렌-10-옥사이드 및 파라포르알데히드를 반응시켜 제조할 수 있다. 본 발명에 사용하는 파라포름알데히드는 9,10-디하이드로-9-옥시-10-호스파페난토렌-10-옥사이드에 대하여 0.9∼2.0의 몰비로 사용할 수 있으며, 더욱 바람직하게는 0.9∼1.1의 비율로 사용할 수 있다. 상기 반응은 무촉매로 진행하며, 반응온도는 50∼110 ℃일 수 있으나, 보다 바람직하게는 70∼90 ℃에서 진행된다. 상기 포스피네이트계 알코올의 생성여부는 도 1의 1H-NMR 피크를 통하여 확인할 수 있다.The phosphinate-based alcohol may be prepared by reacting 9,10-dihydro-9-oxy-10-hospapenantorene-10-oxide and paraformaldehyde. The paraformaldehyde used in the present invention may be used in a molar ratio of 0.9 to 2.0 with respect to 9,10-dihydro-9-oxy-10-hospphenanthrene-10-oxide, more preferably 0.9 to 1.1. Can be used as a ratio. The reaction proceeds without a catalyst, the reaction temperature may be 50 ~ 110 ℃, more preferably at 70 ~ 90 ℃. The production of the phosphinate alcohol can be confirmed through the 1 H-NMR peak of FIG.
본 발명에서 상기 (메타)아크릴산 무수물은 (메타)아크릴산 할라이드를 (메타)아크릴산과 반응시키는 방법(방법 1), (메타)아크릴산과 무수 초산을 반응시키는 방법(방법 2)에 의해 제조될 수 있다.In the present invention, the (meth) acrylic acid anhydride may be prepared by a method of reacting (meth) acrylic acid halide with (meth) acrylic acid (method 1), and a method of reacting (meth) acrylic acid with acetic anhydride (method 2). .
방법 1은 (메타)아크릴산 할라이드의 취급이 용이하지 않고 반응 안정성이 떨어지는 문제점이 있으므로 (메타)아크릴산 무수물은 방법 2에 의해 제조되는 것이 바람직하다.Since method 1 has a problem in that handling of (meth) acrylic acid halide is not easy and reaction stability is inferior, it is preferable that (meth) acrylic anhydride is produced by method 2.
특히, 방법 2에 의할 경우, 본 발명에서 사용된 촉매 존재 하에 수행할 수 있으므로, 촉매를 추가로 사용하거나 정제할 필요가 없다는 효과를 갖고 있다. 상기 촉매는 상기 (메타)아크릴산의 중량에 대하여 0.01∼3.0%, 바람직하게는 0.1∼1.0%로 사용할 수 있다.In particular, in the case of method 2, since it can be carried out in the presence of the catalyst used in the present invention, it has the effect that there is no need to further use or purify the catalyst. The catalyst may be used in an amount of 0.01 to 3.0%, preferably 0.1 to 1.0% based on the weight of the (meth) acrylic acid.
또한, 상기 방법 2에서, 상기 (메타)아크릴산 : 상기 무수 초산의 몰비는 1 : 0.2∼1 : 0.5, 예를 들면 1 : 0.45∼1 : 0.5가 될 수 있다.In addition, in the method 2, the molar ratio of the (meth) acrylic acid: acetic anhydride may be 1: 0.2 to 1: 0.5, for example, 1: 0.45 to 1: 0.5.
또한, 상기 방법 2에서는, 부틸레이티드하이드록시 톨루엔(BHT), p-벤조퀴논 등으로 이루어지는 군으로부터 선택되는 1종 이상의 중합 방지제를 추가로 포함할 수 있다.Moreover, in the said method 2, 1 or more types of polymerization inhibitors chosen from the group which consists of butylated hydroxy toluene (BHT), p-benzoquinone, etc. can further be included.
본 발명에 사용되는 상기 포스피네이트계 알코올 : 상기 (메타)아크릴산 무수물의 몰비는 1 : 0.5∼1 : 1.5로 반응할 수 있으며, 1 : 0.9∼1 : 1.1인 것이 보다 바람직하다.The molar ratio of the phosphinate-based alcohol: (meth) acrylic anhydride used in the present invention can be reacted with 1: 0.5 to 1: 1.5, more preferably 1: 0.9 to 1: 1.1.
본 발명에서 사용되는 용매는 톨루엔, 크실렌, n-헥산, 사이클로헥산, n-헵탄, n-옥탄, 에틸 에테르, 아세토니트릴, 메틸렌클로라이드 또는 그 혼합물로 이루어진 군으로부터 선택되는 유기용매를 사용할 수 있다.The solvent used in the present invention may be an organic solvent selected from the group consisting of toluene, xylene, n-hexane, cyclohexane, n-heptane, n-octane, ethyl ether, acetonitrile, methylene chloride or mixtures thereof.
본 발명의 반응온도는 0∼100 ℃에서 수행할 수 있으며, 40∼90 ℃에서 수행하는 것이 보다 바람직하다. 반응온도가 0 ℃ 미만이면 반응속도가 과도하게 저하되어 효과적이지 못하며, 반응온도가 100 ℃를 초과하면 중합방지제를 사용하더라도 (메타)아크릴산 무수물 또는 포스피네이트계 난연제의 중합반응이 발생할 수 있기 때문이다. 따라서 본 발명은 부반응이 일어날 수 있는 온도까지 반응온도를 높이지 않음으로써 고순도의 포스피네이트계 난연제를 고수율로 제조할 수 있다.The reaction temperature of the present invention can be carried out at 0 ~ 100 ℃, more preferably at 40 ~ 90 ℃. If the reaction temperature is lower than 0 ℃, the reaction rate is excessively lowered and is not effective. If the reaction temperature exceeds 100 ℃, even if a polymerization inhibitor is used, polymerization of (meth) acrylic anhydride or phosphinate flame retardant may occur. to be. Therefore, the present invention can produce a high-purity phosphinate-based flame retardant by not increasing the reaction temperature to a temperature at which side reactions can occur.
또한, 본 발명의 반응시간은 반응전환율이 85∼100%가 될 때까지 2∼12시간 동안 이루어질 수 있으며, 5∼10시간 동안 수행하는 것이 보다 바람직하다.In addition, the reaction time of the present invention can be made for 2 to 12 hours until the reaction conversion rate is 85 to 100%, more preferably carried out for 5 to 10 hours.
본 발명에 있어서, 상기 반응시 무촉매 조건에서도 반응이 가능하지만, 통상의 에스테르화 반응에 사용되는 촉매를 사용하는 것이 보다 바람직하다. 상기 촉매의 예로서 초산리튬(lithium acetate), 초산나트륨(sodium acetate), 프로피온산칼륨(calcium propionate) 등의 알칼리금속염, 피리딘, 트리에틸아민, 트리에틸다이아민 등의 아민 화합물, 황산, 붕산, 메탄술폰산, p-톨루엔술폰산 등의 유기산 등을 들 수 있다. 상기 촉매는 (메타)크릴산 무수물에 대하여 0.001∼3.0 중량%로 사용하는 것이 바람직하다. 더욱 바람직하게는 0.1∼1.0 중량%를 사용할 수 있다.In the present invention, the reaction can be carried out even under the non-catalyst condition during the reaction, but it is more preferable to use a catalyst used in a conventional esterification reaction. Examples of the catalyst include alkali metal salts such as lithium acetate, sodium acetate, and potassium propionate, amine compounds such as pyridine, triethylamine, and triethyldiamine, sulfuric acid, boric acid, and methane. Organic acids, such as sulfonic acid and p-toluenesulfonic acid, etc. are mentioned. It is preferable to use the said catalyst at 0.001 to 3.0 weight% with respect to (meth) crylic acid anhydride. More preferably, 0.1 to 1.0 weight% can be used.
상기 촉매는 포스피네이트계 알코올과 함께 (메타)아크릴산 무수물에 첨가되거나, 또는 (메타)아크릴산 무수물과 함께 포스피네이트계 알코올에 첨가되거나, 또는 (메타)아크릴산 무수물, 포스피네이트계 알코올, 및 촉매의 임의의 순서대로 첨가될 수 있지만, 이들에 제한되는 것은 아니다.The catalyst is added to (meth) acrylic anhydride with phosphinate alcohol, or to phosphinate alcohol with (meth) acrylic anhydride, or (meth) acrylic anhydride, phosphinate alcohol, and The catalysts may be added in any order, but are not limited to these.
본 발명에 있어서, 상기 반응시 발생할 수 있는 중합을 방지하기 위하여 부틸레이티드하이드록시톨루엔(BHT), 하이드로퀴논, p-벤조퀴논 등으로 이루어진 군으로부터 선택되는 1종 이상의 중합 방지제를 첨가할 수 있다. 상기 중합 방지제는 포스피네이트계 난연제의 중량을 기준으로 0.01∼0.5%로 포함될 수 있다.In the present invention, at least one polymerization inhibitor selected from the group consisting of butylated hydroxytoluene (BHT), hydroquinone, p-benzoquinone and the like may be added to prevent polymerization that may occur during the reaction. . The polymerization inhibitor may be included in an amount of 0.01 to 0.5% based on the weight of the phosphinate-based flame retardant.
상기 반응이 종료된 후 (메타)아크릴산 무수물로부터 (메타)아크릴산이 생성되며, 상기 (메타)아크릴산은 증류를 통하여 회수할 수 있다. 증류에 필요한 압력조건은 5∼100 mmHg이며, 보다 바람직하게는 5∼20 mmHg이다. 온도조건은 30∼100 ℃이며, 보다 바람직하게는 50∼80 ℃이다. 이때 회수한 (메타)아크릴산은 (메타)아크릴산 무수물을 제조하는데 사용 할 수 있다.After the reaction is completed (meth) acrylic acid is produced from (meth) acrylic acid anhydride, the (meth) acrylic acid can be recovered through distillation. The pressure condition required for distillation is 5-100 mmHg, More preferably, it is 5-20 mmHg. Temperature conditions are 30-100 degreeC, More preferably, it is 50-80 degreeC. The (meth) acrylic acid recovered at this time can be used to prepare (meth) acrylic anhydride.
상기 (메타)아크릴산 제거 후 본 발명의 포스피네이트계 난연제를 알칼리 수세, 농축 및 여과의 공정을 이용하여 정제할 수 있다.After removing the (meth) acrylic acid, the phosphinate-based flame retardant of the present invention can be purified using a process of alkali washing with water, concentration and filtration.
상기의 공정을 통하여 제조된 포스피네이트계 난연제는 도 2의 1H-NMR 피크를 분석하여 확인할 수 있으며, 순도는 90% 이상, 수율은 85% 이상으로 제조될 수 있다.The phosphinate-based flame retardant prepared by the above process can be confirmed by analyzing the 1 H-NMR peak of FIG.
또한, 상기 공정을 통하여 제조된 포스피네이트계 난연제는 색상이 무색에 가까운 것이 바람직하다. 본 발명에서 색도는 ASTM D 1209에 의거한 Pt-Co 측정법에 의하여 측정되는 APHA Color(Hazen Color)가 될 수 있다. 상기 측정법은 색도의 범위가 0 내지 500으로서, Platinum-Cobalt Stock Solution의 색도가 APHA 500이 되며, 희석제로 사용되는 초순수(D.I water)의 색도가 APHA 0에 해당된다. 이때 희석된 정도에 따라 1∼500의 단계로 정량적으로 분류된다. 본 발명의 포스피네이트계 난연제는 APHA Color 값이 A-10∼A-50인 것이 바람직하다.In addition, the phosphinate-based flame retardant prepared through the above process is preferably color close to colorless. In the present invention, the chromaticity may be APHA Color (Hazen Color) measured by the Pt-Co measurement method according to ASTM D 1209. In the measurement method, the chromaticity ranges from 0 to 500, the chromaticity of Platinum-Cobalt Stock Solution becomes APHA 500, and the chromaticity of ultrapure water (D.I water) used as a diluent corresponds to APHA 0. At this time, depending on the degree of dilution is classified quantitatively in steps of 1 to 500. The phosphinate flame retardant of the present invention preferably has an APHA Color value of A-10 to A-50.
이하, 본 발명의 바람직한 실시예를 기재한다. 다만, 하기의 실시예는 본 발명의 바람직한 일 실시예일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.
실시예EXAMPLE
제조예(포스피네이트계 알코올)Production example (phosphinate alcohol)
교반기, 온도계, 콘덴서를 구비한 반응기에 9,10-디하이드로-9-옥시-10-호스파페난토렌-10-옥사이드 216.2 g(1.0 mol)과 톨루엔 216.2 g을 넣고 70∼90 ℃로 승온하며 교반한다. 여기에 파라포름알데히드 30.03 g을 서서히 투입한다. 투입 후 약 4시간 동안 70∼90 ℃에서 반응 후 가스 크로마토그래피(gas chromatography) 분석하여 확인한다. 반응이 종결되면 상온으로 냉각하여 여과한다. 여과 후 녹는점이 170∼171 ℃의 백색 결정물 246.2 g을 얻었다. 생성물은 수율 100%, 순도 99%이었다.Into a reactor equipped with a stirrer, a thermometer, and a condenser, 216.2 g (1.0 mol) of 9,10-dihydro-9-oxy-10-hosphenanthrene-10-oxide and 216.2 g of toluene were added thereto, and the temperature was raised to 70-90 ° C. Stir. Slowly add 30.03 g of paraformaldehyde. After the reaction, the reaction was carried out at 70 to 90 ° C. for about 4 hours, followed by gas chromatography analysis. After the reaction is completed, the mixture is cooled to room temperature and filtered. After filtration, 246.2 g of a white crystal having a melting point of 170 to 171 캜 was obtained. The product was 100% yield, 99% purity.
실시예 1Example 1
제조예에서 얻은 백색 결정물 246.2 g(1.0 mol), 메타크릴산 무수물 154.17 g(1.0 mol), 초산 나트륨 0.8 g, 부틸레이티드하이드록시톨루엔 0.02 g을 넣고, 90 ℃에서 3시간 반응한다. 반응 후 가스 크로마토그래피(gas chromatography)로 분석하여 확인한다. 얻어진 반응액을 10% 탄산나트륨 수용액으로 중화하고, 20% 식염수로 1회 세정한 후 톨루엔을 감압 증류시켜 고점도의 맑은 액상의 포스피네이트기를 함유한 생성물을 얻었다.246.2 g (1.0 mol) of white crystals obtained in the preparation example, 154.17 g (1.0 mol) of methacrylic anhydride, 0.8 g of sodium acetate, 0.02 g of butylated hydroxytoluene were added and reacted at 90 ° C for 3 hours. After the reaction, it is confirmed by analyzing by gas chromatography. The obtained reaction solution was neutralized with an aqueous 10% sodium carbonate solution, washed once with 20% brine, and then toluene was distilled off under reduced pressure to obtain a product containing a high viscosity clear liquid phosphinate group.
실시예 2Example 2
반응온도를 40 ℃에서 12시간 반응한 것을 제외하고는 실시예 1과 동일한 방법으로 반응을 진행하였다.The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was reacted at 40 ° C. for 12 hours.
비교예 1Comparative Example 1
제조예에서 얻은 백색 결정물 246.2 g(1.0 mol), 메타크릴산 172 g(2.0 mol), 톨루엔 500 g, 하이드로퀴논 1.7 g, p-톨루엔 술폰산 17 g을 넣고 100∼120 ℃로 16시간 탈수 반응한다. 반응 후 가스 크로마토그래피(gas chromatography)로 분석하여 확인한다. 여기서 얻어진 반응액을 10% 탄산나트륨 수용액으로 2회, 20%식염수로 1회 세척 후 톨루엔을 감압 증류하여 담황색의 고점도 화합물을 얻었다.246.2 g (1.0 mol) of white crystals obtained in the preparation example, 172 g (2.0 mol) of methacrylic acid, 500 g of toluene, 1.7 g of hydroquinone, and 17 g of p-toluene sulfonic acid were added and dehydrated at 100 to 120 ° C for 16 hours. do. After the reaction, it is confirmed by analyzing by gas chromatography. The reaction solution obtained here was washed twice with 10% aqueous sodium carbonate solution and once with 20% brine, and then toluene was distilled off under reduced pressure to obtain a pale yellow high viscosity compound.
비교예 2Comparative Example 2
자일렌을 사용하여 반응온도를 120 ℃ 이상에서 반응시킨 것을 제외하고는 상기 비교예 1과 동일한 방법으로 반응 진행하였다.The reaction was carried out in the same manner as in Comparative Example 1 except that the reaction temperature was reacted at 120 ° C. or higher using xylene.
물성 측정 방법Property measurement method
(1) 수율 : (생성물의 실제 몰수/이론상 몰수)*100의 식을 이용하여 측정하였다.(1) Yield: measured using a formula of (the actual mole number / theoretical mole number of the product) * 100.
(2) 순도 : GC 분석결과를 통하여 순도를 측정하였다.(2) Purity: Purity was measured through GC analysis.
(3) APHA Color 값 : ASTM D 1209에 의거한 Pt-Co 측정법에 의하여 측정하였다.(3) APHA Color value: measured by Pt-Co measurement method according to ASTM D 1209.
표 1
Figure PCTKR2012005268-appb-T000001
 Table 1
Figure PCTKR2012005268-appb-T000001
상기 표 1에서 나타난 바와 같이, 본 발명의 제조방법은 실시예 1 내지 2의 결과를 보면, 고순도 및 고수율로 무색의 포스피네이트계 난연제를 제조할 수 있음을 확인할 수 있다.As shown in Table 1, the production method of the present invention can be seen that the colorless phosphinate-based flame retardant with high purity and high yield can be seen in the results of Examples 1 to 2.
반면, 통상의 산촉매 에스테르화 반응을 통한 제조방법으로는 수율 및 순도가 저하되고 색상 역시 담황색 등으로 우수하지 못함을 알 수 있다. 또한, 100 ℃를 초과하여 반응시킨 비교예 2의 경우 일부 중합현상으로 인한 수율 저하가 확인되었다.On the other hand, it can be seen that the production method through a conventional acid catalyst esterification reaction yields and purity is lower and the color is also not excellent such as pale yellow. In addition, in the case of Comparative Example 2 reacted in excess of 100 ° C, a decrease in yield due to some polymerization phenomenon was confirmed.

Claims (12)

  1. (메타)아크릴산 무수물 및 하기 화학식 1로 표시되는 포스피네이트계 알코올을 0∼100 ℃에서 전환율이 85∼100%가 될 때까지 2∼12시간 동안 에스테르 반응되는 것을 특징으로 하는 하기 화학식 2로 표시되는 포스피네이트계 난연제의 제조 방법.(Meth) acrylic anhydride and the phosphinate alcohol represented by the following formula (1) is esterified for 2 to 12 hours at 0 to 100 ℃ until the conversion rate is 85 to 100% represented by the formula (2) Method for producing a phosphinate-based flame retardant.
    [화학식 1][Formula 1]
    Figure PCTKR2012005268-appb-I000005
    Figure PCTKR2012005268-appb-I000005
    (상기 화학식 1에서 R1은 C1-C4의 포화 또는 불포화 탄화수소기임.)(In Formula 1, R1 is a C1-C4 saturated or unsaturated hydrocarbon group.)
    [화학식 2][Formula 2]
    Figure PCTKR2012005268-appb-I000006
    Figure PCTKR2012005268-appb-I000006
    (상기 화학식 2에서 R1은 C1-C4의 포화 또는 불포화 탄화수소기이고, R2는 H 또는 메틸기임.)(In Formula 2, R1 is a C1-C4 saturated or unsaturated hydrocarbon group, R2 is H or methyl group.)
  2. 제1항에 있어서, 상기 포스피네이트계 알코올 : 상기 (메타)아크릴산 무수물의 몰비는 1 : 0.5∼1 : 1.5인 것을 특징으로 하는 포스피네이트계 난연제의 제조 방법.The method for producing a phosphinate flame retardant according to claim 1, wherein the molar ratio of the phosphinate alcohol: the (meth) acrylic anhydride is 1: 0.5 to 1: 1.5.
  3. 제1항에 있어서, 상기 반응은 벤젠, 톨루엔, 크실렌, n-헥산, 사이클로헥산, n-헵탄, n-옥탄, 에틸 에테르, 아세토니트릴, 메틸렌클로라이드 또는 그 혼합물로 이루어진 군으로부터 선택되는 유기용매 존재 하에서 이루어지는 것을 특징으로 하는 포스피네이트계 난연제의 제조 방법.The organic solvent of claim 1, wherein the reaction is selected from the group consisting of benzene, toluene, xylene, n-hexane, cyclohexane, n-heptane, n-octane, ethyl ether, acetonitrile, methylene chloride or mixtures thereof. A process for producing a phosphinate-based flame retardant, characterized by the following.
  4. 제1항에 있어서, 상기 반응은 알칼리 금속염, 아민계 화합물 또는 유기산으로 이루어진 군으로부터 선택되는 1종 이상의 촉매의 존재 하에 반응하는 것을 특징으로 하는 포스피네이트계 난연제의 제조 방법.The method of claim 1, wherein the reaction is performed in the presence of at least one catalyst selected from the group consisting of alkali metal salts, amine compounds or organic acids.
  5. 제4항에 있어서, 상기 촉매는 (메타)아크릴산 무수물의 중량에 대하여 0.01∼3.0 중량%로 가해지는 것을 특징으로 하는 포스피네이트계 난연제의 제조 방법.The method for producing a phosphinate flame retardant according to claim 4, wherein the catalyst is added at 0.01 to 3.0% by weight based on the weight of the (meth) acrylic anhydride.
  6. 제1항에 있어서, 상기 반응은 부틸레이티드하이드록시톨루엔(BHT), 하이드로퀴논, p-벤조퀴논으로 이루어진 군으로부터 선택되는 1종 이상의 중합 방지제를 첨가하여 이루어지는 것을 특징으로 하는 포스피네이트계 난연제의 제조 방법.The phosphinate flame retardant according to claim 1, wherein the reaction is performed by adding at least one polymerization inhibitor selected from the group consisting of butylated hydroxytoluene (BHT), hydroquinone and p-benzoquinone. Method of preparation.
  7. 제1항에 있어서, 상기 반응이 종결된 이후 생성된 (메타)아크릴산을 5∼100 mmHg 압력 및 30∼100 ℃ 온도로 증류하여 회수하는 단계를 더 포함하는 것을 특징으로 하는 포스피네이트계 난연제의 제조 방법.The phosphinate-based flame retardant of claim 1, further comprising distilling and recovering the (meth) acrylic acid produced after completion of the reaction at a pressure of 5 to 100 mmHg and a temperature of 30 to 100 ° C. Manufacturing method.
  8. 제7항에 있어서, 상기 (메타)아크릴산 회수 단계 종료 후 반응생성물은 알칼리 세정, 농축 및 여과 공정을 거쳐 정제하는 단계를 더 포함하는 것을 특징으로 하는 포스피네이트계 난연제의 제조 방법.The method of claim 7, wherein after completion of the (meth) acrylic acid recovery step, the reaction product further comprises purifying through an alkali washing, concentration, and filtration process.
  9. 제1항에 있어서, 상기 제조된 포스피네이트계 난연제는 순도가 90% 이상, 수율이 85% 이상인 것을 특징으로 하는 포스피네이트계 난연제의 제조 방법.The method of claim 1, wherein the prepared phosphinate flame retardant is at least 90% pure, yield is at least 85%.
  10. 제1항에 있어서, 상기 제조된 포스피네이트계 난연제는 ASTM D 1209에 의거한 APHA Color 값이 A-10∼A-50인 것을 특징으로 하는 포스피네이트계 난연제의 제조 방법.The method of claim 1, wherein the phosphinate flame retardant prepared according to ASTM D 1209 has an APHA Color value of A-10 to A-50.
  11. 제1항 내지 제10항에 따른 제조 방법에 의하여 제조되는 포스피네이트계 난연제.A phosphinate flame retardant prepared by the production method according to claim 1.
  12. 하기 화학식 2로 표시되고, ASTM D 1209에 의거한 APHA Color 값이 A-10∼A-50인 것을 특징으로 하는 포스피네이트계 화합물:A phosphinate compound represented by the following Chemical Formula 2, wherein the APHA Color value according to ASTM D 1209 is A-10 to A-50:
    [화학식 2][Formula 2]
    Figure PCTKR2012005268-appb-I000007
    Figure PCTKR2012005268-appb-I000007
    상기 화학식 2에서 R1은 C1-C4의 포화 또는 불포화 탄화수소기이고, R2는 H 또는 메틸기임.In Formula 2, R1 is a C1-C4 saturated or unsaturated hydrocarbon group, R2 is H or a methyl group.
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KR20090100258A (en) * 2008-03-18 2009-09-23 닛뽄 가야쿠 가부시키가이샤 Active energy beam-curable resin composition using reactive compound having flame retardancy, process for producing cured product, and multilayer material having layer of the same
JP2010254906A (en) * 2009-04-28 2010-11-11 Nippon Kayaku Co Ltd Thermosetting resin composition containing compound having flame retardancy, and cured product thereof
JP2011039417A (en) * 2009-08-18 2011-02-24 Kyocera Chemical Corp Photosensitive resin composition, and photosensitive film and photosensitive resist using the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3540000A1 (en) 2018-03-16 2019-09-18 Stutz, Felix Benjamin Flame retardant polyamide 6 master batch and fibers made thereof
WO2019175421A1 (en) 2018-03-16 2019-09-19 Stutz Felix Benjamin Flame retardant master batch for polyamide 6 and fibers made thereof

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KR101447456B1 (en) 2014-10-06

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