WO2013081237A1 - (meta) acryloyl iminophosphazene compound, method for manufacturing same, and copolymer comprising same - Google Patents

(meta) acryloyl iminophosphazene compound, method for manufacturing same, and copolymer comprising same Download PDF

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WO2013081237A1
WO2013081237A1 PCT/KR2011/009991 KR2011009991W WO2013081237A1 WO 2013081237 A1 WO2013081237 A1 WO 2013081237A1 KR 2011009991 W KR2011009991 W KR 2011009991W WO 2013081237 A1 WO2013081237 A1 WO 2013081237A1
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carbon atoms
meth
copolymer
acryloyl
iminophosphazene
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PCT/KR2011/009991
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French (fr)
Korean (ko)
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이명렬
김만석
홍상현
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제일모직 주식회사
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Publication of WO2013081237A1 publication Critical patent/WO2013081237A1/en

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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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C247/00—Compounds containing azido groups
    • C07C247/02—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C247/12—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being further substituted by carboxyl groups
    • 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
    • C07F9/657154—Cyclic esteramides of oxyacids of phosphorus
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/062—Organo-phosphoranes without P-C bonds
    • C07F9/065—Phosphoranes containing the structure P=N-
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • 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
    • 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
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F24/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus

Definitions

  • the present invention provides a (meth) acryloyl diminophosphazene compound, a preparation method thereof, and a co-polymer including the same. More specifically, the present invention is to provide a (meth) acryloyl iminophosphazene compound having excellent heat resistance and flame retardancy, a preparation method thereof, and a copolymer including the same.
  • the flame retardant is a lot of building. This type of flame retardant can generally be obtained a certain flame retardant effect only when a large amount of flame retardant is added. If such a large amount of flame retardant is added, an additive crab such as a flame retardant may leak from the product.
  • An object of the present invention is to take over a new turnover that can improve the flame resistance and heat resistance at the same time. It is to provide a polymerizable compound and a preparation method thereof.
  • Another object of the present invention is to provide a novel (meth) acryloyl iminophosphazene-based ' compound that can be easily polymerized with other polymerizable monomers and can improve flame retardancy and heat resistance. It is for providing the manufacturing method.
  • a further object of the present "invention is stable as it is for handling and the service are already a well-established SPA jengye compound and a method of manufacturing easy to new (meth) acrylate.
  • Still another object of the present invention is to provide a copolymer having excellent flame retardancy and heat resistance by applying the new compound.
  • the (meth) acryloyl iminophosphazene compound has a structure of Formula 1 below:
  • R 2 and R 3 are each independently hydrogen, alkyl group of 1 to 6 carbon atoms, aryl group of 6 to 12 carbon atoms, alkylene group of 1 to 6 carbon atoms or 6 to 12 carbon atoms).
  • Arylene group, R 4 is hydrogen, alkyl group of 1 to 6 carbon atoms or aryl group of 6 to 12 carbon atoms, R 5 is linear or branched alkylene of 1 to 6 carbon atoms, or arylene of 6 to 12 carbon atoms, n is An integer of 0 or 1).
  • n 0, and R2, R3 and R4 may be the same.
  • Another aspect of the invention relates to a process for the preparation of an already well-established SPA jengye compound to the (meth) acrylate.
  • the method includes reacting a phosphite-based compound represented by the following Chemical Formula 3 on an azido (meth) acrylate represented by the following Chemical Formula 2:
  • 3 ⁇ 4 is hydrogen or methyl group
  • R 2 and R 3 are each independently hydrogen, alkyl group of 1 to 6 carbon atoms, aryl group of 6 to 12 carbon atoms, alkylene group of 1 to 6 carbon atoms or of 6 to 12 carbon atoms
  • R 4 is hydrogen, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms
  • R 5 is a linear or branched alkylene having 1 to 6 carbon atoms, or arylene having 6 to 12 carbon atoms
  • n is An integer of 0 or 1).
  • the method comprises reacting sodium azai H and (meth) acryloyl chloride to prepare an azido (meth) acrylate represented by Formula 2, and adding the azido (meth) acrylate to Formula 3
  • the phosphite compound represented by can be reacted in-situ /
  • Another aspect of the present invention relates to a copolymer including the (meth) acryloyl iminophosphazene compound.
  • the copolymer may be a copolymer obtained by copolymerizing the (meth) acryloyl miminophosphazene compound with a monofunctional unsaturated monomer.
  • the copolymer may include about 1 to about 50% by weight of the (meth) acryloyl iminophosphazene compound.
  • the monofunctional unsaturated monomer may be a (meth) acrylate monomer, an aromatic vinyl monomer, a vinyl cyanide monomer, an unsaturated carboxylic acid, an acid anhydride, or the like. These may be used alone or in combination of two or more thereof.
  • the copolymer may be a copolymer of a (meth) acryloyl iminophosphazene compound, an aromatic vinyl monomer and a vinyl cyanide monomer.
  • the copolymer may be a copolymer of a (meth) acryloyl ' iminophosphazene compound and a (meth) acrylate monomer.
  • the present invention can improve the flame retardancy and heat resistance at the same time, can be easily polymerized with other polymerizable monomers, can improve the flame retardancy and heat resistance, and easy to handle (meth) acryloyl iminophosphazene-based compound and a method of manufacturing the same And by applying the (meth) acryloyl iminophosphazene-based compound has the effect of the invention to provide a co-polymer excellent in flame retardancy and heat resistance.
  • Example 1 is an NMR photograph of propenoyl iminotrimethyl phospha- ⁇ 5 -gen prepared in Example 1 of the present invention. . '
  • Example 2 is an NMR photograph of 2-methylpropenoyl iminotrimethyl phospha- ⁇ 5 -gen prepared in Example 2 of the present invention.
  • Figure 3 is an NMR picture of the methyl methacrylate and propenoyl iminotrimethyl phospha - ⁇ 5 zen copolymer prepared in Example 4 of the present invention.
  • Example 4 is an NMR photograph of a copolymer of methyl methacrylate and 2-methylpropenyl iminotrimethyl phospha- ⁇ 5 -gen prepared in Example 5 of the present invention.
  • Example 5 is an NMR photograph of a copolymer of styrene-acrylonitrile-propenoyl iminotrimethyl phospha- ⁇ 5 -gen prepared in Example 6 of the present invention.
  • FIG. 6 is an NMR photograph of a copolymer of styrene-acrylonitrile-2-methylpropenyl iminotrimethyl phospha- ⁇ 5 -gen prepared in Example 7 of the present invention.
  • FIG. 6 is an NMR photograph of a copolymer of styrene-acrylonitrile-2-methylpropenyl iminotrimethyl phospha- ⁇ 5 -gen prepared in Example 7 of the present invention.
  • the (meth) acryloyl iminophosphazene compound of the present invention is represented by the following general formula (1):
  • Ri is hydrogen or methyl group
  • R2 and are each independently hydrogen, alkyl group of 1 to 6 carbon atoms, aryl group of 6 to 12 carbon atoms, alkylene group of 1 to 6 carbon atoms, arylene group of 6 to 12 carbon atoms
  • R 4 is hydrogen, an alkyl group of 1 to 6 carbon atoms or an aryl group of 6 to 12 carbon atoms
  • R 5 is a linear or branched alkylene of 1 to 6 carbon atoms, or arylene of 6 to 12 carbon atoms
  • n is 0 or 1 Is an integer of).
  • alkyl and aryl include both substituted or unsubstituted, R 2 and silver when 1 is 1, alkylene having 1 to 6 carbon atoms or arylene having 6 to 12 carbon atoms.
  • the R 5 may be an alkylene or arylene group, and in the case of the alkylene, R 5 may include both a linear or branched structure.
  • n 0, and R2, R3 and R4 may be the same.
  • the (meth) acryloyl iminophosphazene-based compound of the present invention has a conjugation effect as follows. Therefore, the copolymer in which the (meth) acryloyl iminophosphazene compound is polymerized decreases the fluidity of the phosphorus compound and thus inhibits plasticity, thereby improving heat resistance and flame retardancy of the copolymer.
  • It can be prepared by reacting a phosphite compound with (meth) acrylate.
  • the azido (meth) acrylate may be represented by the following formula (2):
  • the phosphite-based compound may be represented by the following formula:
  • R 2 and R 3 are each independently hydrogen, an alkyl group of 1 to 6 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkylene group of 1 to 6 carbon atoms or an arylene group of .6 12, R 4 is hydrogen , An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 5 is a linear or branched alkylene having 1 to 6 carbon atoms, or an arylene having 6 to 12 carbon atoms, n is 0 or an integer of 1) . '
  • the azido (meth) acrylate and the phosphite-based compound may prepare a (meth) acryloyl iminophosphazene-based compound through a Staudinger reaction.
  • the reaction solvent was dichloromethane (CH 2 C1 2 ), chloroform (CHC1 3 ), dichloroethane (C 2 H 4 C1 2 ), ether ((C 2 H 5 ) 2 0), acetone ((CH 3 ) 2 CO), tetrahydrofuran (C 4 H 8 0), toluene (C 6 H 5 CH 3 ), etc. may be used, and preferably, toluene may be used.
  • the reaction temperature may be about 0 ⁇ 40 ° C and preferably about 10 ⁇ 25 ° C. ⁇
  • the reaction weight is about 1.0 equivalent of azido acrylate and about 1.0-3. 0 equivalents of phosphite-based may be used, and preferably about 1.0 1.5 equivalents.
  • the azido (meth) acrylate may be prepared by reacting sodium azide and (meth) acryloyl chloride as shown in the following reaction formula 1 below.
  • the reaction temperature may be about 0 ⁇ 40 ° C and preferably about 10 ⁇ 25 ° C, the reaction pressure may be atmospheric pressure.
  • the reaction amount may be about 1.0-3.0 equivalents of sodium azide in about 1.0 equivalent of (meth) acryloyl ⁇ chloride, and preferably about 1.0-1.5 equivalents.
  • the synthesis of the azido (meth) acrylate and the synthesis of the (meth) acryloyl iminophosphazene-based compound may be performed in-situ reaction.
  • the boiling point of the (meth) acryloyl iminophosphazene compound is about 60 200 ° C. in the ltorr.
  • the (meth) acryloyl iminophosphazene compound of the present invention can contain phosphorus in the molecule to improve flame retardancy, and can reduce the fluidity of the phosphorus due to conjugation, thereby preventing a decrease in heat resistance. Therefore, as a result, the heat resistance, flame retardancy, and Tg of the copolymer can be increased.
  • Another aspect of the present invention relates to a copolymer including the (meth) acryloyl imanophosphazene compound represented by Chemical Formula 1.
  • the copolymer is a copolymer of the (meth) acryloyl iminophosphazene compound and a monofunctional unsaturated monomer.
  • a (meth) acrylate monomer an aromatic vinyl monomer, a cyanide monomer, an unsaturated carboxylic acid, an acid anhydride, or the like may be applied, but is not necessarily limited thereto. These alone or in combination of two or more . Can be used.
  • the copolymer comprises from about 1 to about 50 weight percent of the (meth) acryloyl diminophosphazene compound, preferably from about 1 to about 35 weight percent, more Preferably from about 3 to about 30 weight percent.
  • the copolymer may be prepared by conventional solvent polymerization reaction in the presence of a radical initiator.
  • the solvent may be an aromatic such as benzene, toluene, ethylbenzene, xylene, tetrahydrofuran, methyl ethyl ketone, ketone, ether or a combination thereof.
  • the solvent may be used in an amount of about 200 parts by weight or less, preferably about 80 to about 120 parts by weight, based on 100 parts by weight of the monomer mixture.
  • the polymerization reaction may be prepared by copolymerizing at about 60 to about 100 ° C. for about 3 hours to about 12 hours.
  • Initiators used in the polymerization reaction include benzoyl peroxide (BPO), dicumyl peroxide (DCP), di-tert-butylperoxide (DTBP),
  • ⁇ Radical initiators such as azobisisobutylonitrile (AIBN) and the like, but are not necessarily limited thereto.
  • the initiator may be used in an amount of about 0.005 to about 5 parts by weight, preferably about 0.05 to about 1 part by weight, based on 100 parts by weight of the monomer mixture.
  • a molecular weight regulator such as normaloctylmercaptan may be added to 100 parts by weight of the monomer mixture for molecular weight control.
  • the high heat-resistant phosphorus copolymer may be used in place of the existing arc 3 ⁇ 4- or styrene-based resin.
  • the high heat resistant phosphorus copolymer may be used alone or in combination with another resin such as polycarbonate in order to further improve the flame resistance of the high heat resistant phosphorus copolymer.
  • Sodium azide (10 g, 0.153 mol) was added to the reaction vessel and dissolved in 30 ml water.
  • 90 ml of acryloyl chloride (11. lg, 0.123 mol) was diluted in toluene, and then the solution of acryloyl chloride diluted in toluene was slowly added dropwise while stirring the sodium azide solution in a semi-quilter group.
  • the reaction temperature was adjusted using an ice bath so that the internal temperature of the reactor did not exceed 25 ° C.
  • the organic layer was separated using a separating funnel, and the aqueous layer was further extracted with 30 ml of luene.
  • the collected organic layer was dehydrated using magnesium sulfate, and magnesium sulfate was removed using a filter.
  • the filtrate filtered after the filter was an toluene solution containing azidoacrylate, yielding azido acrylate in almost quantitative yield.
  • the prepared azido acrylate was used to synthesize iminophosphazene acrylate without further purification or concentration.
  • Trimethyl phosphite (15.2 g, 0.123 mol) was slowly added dropwise for 30 minutes while stirring the azido acrylate toluene solution obtained in Preparation Example 1.
  • the reaction temperature was adjusted using an ice bath so that the internal silver of the reactor did not exceed 25 ° C.
  • the semi-aqueous solution was concentrated to remove toluene. The residue remaining after the removal of toluene was distilled under reduced pressure to give 16.6 g of 70% of propynolyl iminotrimethyl phospha- ⁇ 5 -gen. NMR results are shown in FIG. 1.
  • Example 2 Preparation of 2-methylpropenoyl iminotrimethyl phospha- ⁇ 5 -gen
  • Trimethyl phosphite (124 g, lOmol) was slowly added dropwise for 2 hours while stirring the azido methacrylate toluene solution obtained in Preparation Example 2.
  • the reaction temperature was adjusted by using water or an ice bath so that the internal temperature of the reaction vessel did not exceed 25 ° C.
  • the semi-aqueous solution was concentrated to remove toluene. The residue remaining after the removal of toluene was distilled under reduced pressure to obtain propenoyl iminotrimethyl phospha- ⁇ 5 -gen in a yield of 18, 87%. NMR results are shown in FIG. 2.
  • Example 3 Preparation of 2-methylpropenoyl iminomethyl neopentyl phospha ⁇ 5 -gen
  • Methyl neopentyl phosphite (8.2 g, 0.05 mol) toluene solution was slowly added dropwise for 30 minutes while stirring the azido methacrylate (0.05 mol) toluene solution obtained through Preparation Example 2.
  • the reaction temperature was adjusted using a water or ice bath so that the internal temperature of the reactor did not exceed 25 ° C.
  • the semi-aqueous solution was concentrated to remove toluene. The residue remaining after the removal of toluene was distilled under reduced pressure to obtain 2-methylpropenoyl iminomethyl neopentyl phospha- ⁇ 5 -gen in a yield of 8.6 g, 70%.
  • Glass Transition Temperature Tg ( ° C): The glass transition temperature was measured by using a Differential Scanning Calorimeter (DSC) while raising the temperature of the sample to 10 ° C / min from 25 to 200 ° C.
  • DSC Differential Scanning Calorimeter

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Abstract

The present invention provides a (meta) acryloyl iminophosphazene compound represented by chemical formula 1, a method for manufacturing same, and a copolymer and a composition comprising same. The (meta) acryloyl iminophosphazene compound can simultaneously enhance heat resistance and flame retardancy.

Description

【명세서】 . 【Specification】 .
【발명 의 명 칭】 [Name of invention]
(메타)아크릴로일 이미노포스파젠계 화합물， 그 제조방법 및 이를 포함한 공중합체  (Meth) acryloyl iminophosphazene compounds, preparation methods thereof and copolymers containing the same
[기술분야】 [Technical Field]
본 발명은 (메타)아크릴로일 이 미노포스파젠계 화합물， 그 제조방법 및 이를 포함한 공증합체을 제공한다. 보다 구체적으로， 본 발명은 내열성 및 난연성 이 우수한 (메타)아크릴로일 이 미노포스파젠계 화합물， 그 제조방법 및 이를 포함한 공중합체를 제공하는 것 이다.  The present invention provides a (meth) acryloyl diminophosphazene compound, a preparation method thereof, and a co-polymer including the same. More specifically, the present invention is to provide a (meth) acryloyl iminophosphazene compound having excellent heat resistance and flame retardancy, a preparation method thereof, and a copolymer including the same.
[배경 기술】 [Background technology]
인계 ' 난연제를 첨가하는 수지 의 난연화는 많이 구축되어 있다. 이와 같은 첨가형 난연화는 일반적으로 많은 양의 난연제가 첨가되어 야만 소정의 난연 효과를 얻을 수 있다. 이처 럼 많은 양의 난연제가 첨가될 경우 제품으로부터 난연제와 같은 첨가게가 누출될 수 있는 단점 이 있다. Of taking over "the resin to add a flame retardant the flame retardant is a lot of building. This type of flame retardant can generally be obtained a certain flame retardant effect only when a large amount of flame retardant is added. If such a large amount of flame retardant is added, an additive crab such as a flame retardant may leak from the product.
이에 따라 인이 포함된 단량체를 공중합에 참여시 켜 고분자의 주쇄에 인계화합물을 도입하려는 연구가 수행되 었다.  Accordingly, a study was conducted to introduce phosphorus-based compounds into the polymer main chain by participating in monomers containing phosphorus.
Polymer Degration and Stability (2000(69), Ebdon, JR. et al) 및 Polymer Degration and Stability (2000(70), Ebdon, JR. et al)지에 게재된 논문에서는 다양한 올레핀기를 갖는 인계 단량체를 합성하고 이를 중합에 참여시켜 난연성을 높이는 기술이 개시되고 있다. 그러나， 이들 단량체들은 인이 포함된 작용기의 가소 작용에 의해， 수지의 내열성 이. 급격히 저하되는 문제가 있다. 【발명의 상세한 설명】 The papers published in Polymer Degration and Stability (2000 (69), Ebdon, JR. Et al) and Polymer Degration and Stability (2000 (70), Ebdon, JR. Et al) have synthesized phosphorus monomers with various olefin groups and A technique for increasing flame retardancy by participating in polymerization has been disclosed. However, these monomers, due to the plasticization of the functional group containing phosphorus, have a low heat resistance of the resin . There is a problem that is sharply lowered. [Detailed Description of the Invention]
【기술적 과제】 [Technical problem]
본 발명 의 목적은 난연성과 내열성을 동시에 향상시 킬 수 있는 새로운 인계 . 중합성 화합물 및 그 제조방법을 제공하기 위 한 것이다.  An object of the present invention is to take over a new turnover that can improve the flame resistance and heat resistance at the same time. It is to provide a polymerizable compound and a preparation method thereof.
본 발명 의 다른 목적은 다른 중합성 모노머와 중합이 용이하며 난연성 및 내열성을 개선할 수 있는 새로운 (메타)아크릴로일 이미노포스파젠계 '화합물 및 그 제조방법을 제공하기 위한 것이다. Another object of the present invention is to provide a novel (meth) acryloyl iminophosphazene-based ' compound that can be easily polymerized with other polymerizable monomers and can improve flame retardancy and heat resistance. It is for providing the manufacturing method.
본 " 발명의 또 다른 목적은 안정적이어서 취급이 용이한 새로운 (메타)아크릴로일 이미노포스파젠계 화합물 및 그 제조방법을 제공하가 위한 것이다. A further object of the present "invention is stable as it is for handling and the service are already a well-established SPA jengye compound and a method of manufacturing easy to new (meth) acrylate.
본 발명의 또 다른 목적은 상기 새로운 화합물을 적용하여 난연성 및 내열성이 우수한 공중합체를 제공하기 위한 것이다.  Still another object of the present invention is to provide a copolymer having excellent flame retardancy and heat resistance by applying the new compound.
【기술적 해결방법】 Technical Solution
본 발명의 한 관점은 새로운 (메타)아크릴로일 이미노포스파젠계 화합물에 관한 것이다. 상기 (메타)아크릴로일 이미노포스파젠계 화합물은 하기 화학식 1의 구조를 갖는다:  One aspect of the invention relates to novel (meth) acryloyl iminophosphazene compounds. The (meth) acryloyl iminophosphazene compound has a structure of Formula 1 below:
[화학식 1:] ' [Formula 1:] '
Figure imgf000003_0001
Figure imgf000003_0001
(상기에서， ¾은 수소 또는 메틸기이고， R2 및 R3 는 각각 독립적으로 수소， 탄소수 1~6의 알킬기， 탄소수 6~12의 아릴기， 탄소수 1~6의 알킬렌기 또는 탄소수 6~12의 아릴렌기， R4는 수소， 탄소수 1~6의 알킬기 또는 탄소수 6~12의 아릴기， R5는 탄소수 1~6의 선형 또는 분지형 알킬렌， 또는 탄소수 6~12의 아릴렌이고， n은 0또는 1의 정수임). (Wherein ¾ is hydrogen or methyl group, R 2 and R 3 are each independently hydrogen, alkyl group of 1 to 6 carbon atoms, aryl group of 6 to 12 carbon atoms, alkylene group of 1 to 6 carbon atoms or 6 to 12 carbon atoms). Arylene group, R 4 is hydrogen, alkyl group of 1 to 6 carbon atoms or aryl group of 6 to 12 carbon atoms, R 5 is linear or branched alkylene of 1 to 6 carbon atoms, or arylene of 6 to 12 carbon atoms, n is An integer of 0 or 1).
구체예에서， 상기 n은 0 이며, 상기 R2,R3 및 R4는 동일할 수 있다. ' 본 발명의 다른 관점은 상기 (메타)아크릴로일 이미노포스파젠계 화합물의 제조방법에 관한 것이다. 상기 방법은 하기 화학식 2로 표시되는 아지도 (메타)아크릴레이트에 하기 화학식 3으로 표시되는 포스파이트계 화합물을 반웅시키는 단계를 포함한다: In embodiments, n is 0, and R2, R3 and R4 may be the same. "Another aspect of the invention relates to a process for the preparation of an already well-established SPA jengye compound to the (meth) acrylate. The method includes reacting a phosphite-based compound represented by the following Chemical Formula 3 on an azido (meth) acrylate represented by the following Chemical Formula 2:
[화학식 2]
Figure imgf000004_0001
[Formula 2]
Figure imgf000004_0001
(상기에서, ¾은 수소 또는 메틸기이고， R2 및 R3 는 각각 독립적으로 수소， 탄소수 1~6의 알킬기， 탄소수 6~12의 아릴기， 탄소수 1~6의 알킬렌기 또는 탄소수 6~12의 아릴렌기, R4는 수소， 탄소수 1~6의 알킬기 또는 탄소수 6~12의 아릴기， R5는 탄소수 1~6의 선형 또는 분지형 알킬렌, 또는 탄소수 6~12의 아릴렌이고 , n은 0또는 1의 정수임). (In the above, ¾ is hydrogen or methyl group, R 2 and R 3 are each independently hydrogen, alkyl group of 1 to 6 carbon atoms, aryl group of 6 to 12 carbon atoms, alkylene group of 1 to 6 carbon atoms or of 6 to 12 carbon atoms An arylene group, R 4 is hydrogen, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 5 is a linear or branched alkylene having 1 to 6 carbon atoms, or arylene having 6 to 12 carbon atoms, and n is An integer of 0 or 1).
한 구체예에서는 상기 방법은 소디움 아자이 H와 (메타)아크릴로일 클로라이드를 반웅시켜 상기 화학식 2로 표시되는 아지도 (메타)아크릴레이트를 제조하고， 상기 아지도 (메타)아크릴레이트에 상기 화학식 3으로 표시되는 포스파이트계 화합물을 인시츄 (in-situ) 반웅시킬 수 있다/ 본 발명의 또 다른 관점은 상기 (메타)아크릴로일 이미노포스파젠계 화합물을 포함하는 공중합체에 관한 것이다. 상기 공중합체는 상기 (메타)아크릴로일 미미노포스파젠계 화합물과 단관능상 불포화 단량체를 공중합한 공중합체일 수 있다. ,  In one embodiment, the method comprises reacting sodium azai H and (meth) acryloyl chloride to prepare an azido (meth) acrylate represented by Formula 2, and adding the azido (meth) acrylate to Formula 3 The phosphite compound represented by can be reacted in-situ / Another aspect of the present invention relates to a copolymer including the (meth) acryloyl iminophosphazene compound. The copolymer may be a copolymer obtained by copolymerizing the (meth) acryloyl miminophosphazene compound with a monofunctional unsaturated monomer. ,
구체예에서는 상기 공중합체는 (메타》아크뮐로일 이미노포스파젠계 화합물을 약 1 내지 약 50 중량 % 포함할 수 있다. '  In embodiments, the copolymer may include about 1 to about 50% by weight of the (meth) acryloyl iminophosphazene compound.
상기 단관능성 불포화 단량체는 (메타)아크릴레이트계 단량체, 방향족 비닐계 단량체， 시안화비닐계 단량체, 불포화 카르복실산, 산 무수물 등이 적용될 수 있다. 이들은 단독 또는 2종 이상 조합하여 사용될 수 있다.  The monofunctional unsaturated monomer may be a (meth) acrylate monomer, an aromatic vinyl monomer, a vinyl cyanide monomer, an unsaturated carboxylic acid, an acid anhydride, or the like. These may be used alone or in combination of two or more thereof.
한 구체예에서는， 상기 공중합체는 (메타)아크릴로일 이미노포스파젠계 화합물， 방향족 비닐계 단량체 및 시안화 비닐계 단량체의 공중합체일 수 있다. ' 다른 구체예에서는 상기 공중합체는 (메타)아크릴로일 ' 이미노포스파젠계 화합물과 (메타)아크릴레이트계 단량체의 공중합체일 수 있다. In one embodiment, the copolymer may be a copolymer of a (meth) acryloyl iminophosphazene compound, an aromatic vinyl monomer and a vinyl cyanide monomer. ' In another embodiment, the copolymer may be a copolymer of a (meth) acryloyl ' iminophosphazene compound and a (meth) acrylate monomer.
【유리한 효과】 Advantageous Effects
본 발명은 난연성과 내열성을 동시에 향상시킬 수 있으며， 다른 중합성 모노머와 중합이 용이하며 난연성 및 내열성을 개선할 수 있고， 취급이 용이한 (메타)아크릴로일 이미노포스파젠계 화합물 및 그 제조방법과 상기 (메타)아크릴로일 이미노포스파젠계 화합물을 적용하여 난연성 및 내열성이 우수한 공증합체를 제공하는 발명의 효과를 갖는다.  The present invention can improve the flame retardancy and heat resistance at the same time, can be easily polymerized with other polymerizable monomers, can improve the flame retardancy and heat resistance, and easy to handle (meth) acryloyl iminophosphazene-based compound and a method of manufacturing the same And by applying the (meth) acryloyl iminophosphazene-based compound has the effect of the invention to provide a co-polymer excellent in flame retardancy and heat resistance.
【도면의 간단한 설명] [Brief Description of Drawings]
도 1은 본 발명의 실시예 1에서 제조된 프로페노일 이미노트라이메틸 포스파 -λ 5-젠의 NMR사진이다. .' 1 is an NMR photograph of propenoyl iminotrimethyl phospha-λ 5 -gen prepared in Example 1 of the present invention. . '
도 2는 본 발명의 실시예 2에서 제조된 2-메틸프로페노일 이미노트라이메틸 포스파 -λ 5-젠의 NMR사진이다. 2 is an NMR photograph of 2-methylpropenoyl iminotrimethyl phospha-λ 5 -gen prepared in Example 2 of the present invention.
도 3은 본 발명의 실시예 4에서 제조된 메틸메타아크릴레이트와 프로페노일 이미노트라이메틸 포스파 -λ 5 젠꾀 공중합체의 NMR사진이다. Figure 3 is an NMR picture of the methyl methacrylate and propenoyl iminotrimethyl phospha -λ 5 zen copolymer prepared in Example 4 of the present invention.
도 4는 본 발명의 실사예 5에서 제조된 메틸메타아크릴레이트와 2-메틸프로페노일 이미노트라이메틸 포스파 -λ 5-젠의 공중합체의 NMR 사진이다. 4 is an NMR photograph of a copolymer of methyl methacrylate and 2-methylpropenyl iminotrimethyl phospha-λ 5 -gen prepared in Example 5 of the present invention.
도 5는 본 발명의 실시예 6에서 제조된 스티렌-아크릴로 니트릴 -프로페노일 이미노트라이메틸 포스파 -λ 5-젠의 공중합체의 NMR사진이다. 5 is an NMR photograph of a copolymer of styrene-acrylonitrile-propenoyl iminotrimethyl phospha-λ 5 -gen prepared in Example 6 of the present invention.
도 6은 본 발명의 실시예 7에서 제조된 스티렌-아크릴로 니트릴 -2-메틸프로페노일 이미노트라이메틸 포스파 -λ 5-젠의 공중합체의 NMR사진이다. FIG. 6 is an NMR photograph of a copolymer of styrene-acrylonitrile-2-methylpropenyl iminotrimethyl phospha-λ 5 -gen prepared in Example 7 of the present invention. FIG.
[발명의 실시를 위한 최선의 형태】 Best Mode for Carrying Out the Invention]
본 발명의 (메타)아크릴로일 이미노포스파젠계 화합물은 하기 화학식 1로 표시된다:  The (meth) acryloyl iminophosphazene compound of the present invention is represented by the following general formula (1):
. [화학식 1]
Figure imgf000006_0001
. [Formula 1]
Figure imgf000006_0001
(상기에서， Ri은 수소 또는 메틸기이고， R2 및 는 각각 독립적으로 수소， 탄소수 1~6의 알킬기, 탄소수 6~12의 아릴기， 탄소수 1~6의 알킬렌기 또는 탄소수 6~12의 아릴렌기， R4는 수소， 탄소수 1~6의 알킬기 또는 탄소수 6~12의 아릴기， R5는 탄소수 1~6의 선형 또는 분지형 알킬렌， 또는 탄소수 6~12의 아릴렌이고， n은 0또는 1의 정수임). (In the above, Ri is hydrogen or methyl group, R2 and are each independently hydrogen, alkyl group of 1 to 6 carbon atoms, aryl group of 6 to 12 carbon atoms, alkylene group of 1 to 6 carbon atoms, arylene group of 6 to 12 carbon atoms, R 4 is hydrogen, an alkyl group of 1 to 6 carbon atoms or an aryl group of 6 to 12 carbon atoms, R 5 is a linear or branched alkylene of 1 to 6 carbon atoms, or arylene of 6 to 12 carbon atoms, n is 0 or 1 Is an integer of).
본 발명에서 알킬 및 아릴은 치환 또는 비치환된 경우까지 모두 포함한다， 상기 R2 및 은 n이 1일 경우, 탄소수 1~6의 알킬렌 또는 탄소수 6~12의 아릴렌이다. In the present invention, alkyl and aryl include both substituted or unsubstituted, R 2 and silver when 1 is 1, alkylene having 1 to 6 carbon atoms or arylene having 6 to 12 carbon atoms.
상기 R5는 알킬렌, 아릴렌기일 수 있으며, 상기 알킬렌일 경우 선형 혹은 분지형 구조까지 모두 포함할 수 있다. The R 5 may be an alkylene or arylene group, and in the case of the alkylene, R 5 may include both a linear or branched structure.
구체예에서， 상기 n은 0 이며， 상기 R2, R3 및 R4는 동일할 수 있다. In embodiments, n is 0, and R2, R3 and R4 may be the same.
본 발명의 (메타)아크릴로일 이미노포스파젠계 화합물은 하기와 같이 컨쥬게이션 효과를 갖는다. 따라서， 상기 (메타)아크릴로일 이미노포스파젠계 화합물이 중합된 공중합체는 인화합물의 유동성을 줄여 가소성을 저해하므로 결과적으로 공중합체의 내열성 및 난연성을 향상시킬 수 있는 것이다. The (meth) acryloyl iminophosphazene-based compound of the present invention has a conjugation effect as follows. Therefore, the copolymer in which the (meth) acryloyl iminophosphazene compound is polymerized decreases the fluidity of the phosphorus compound and thus inhibits plasticity, thereby improving heat resistance and flame retardancy of the copolymer.
Figure imgf000006_0002
상기 (메타)아크릴로일 이미노포스파젠계 화합물은
Figure imgf000006_0003
Figure imgf000006_0002
The (meth) acryloyl iminophosphazene compound
Figure imgf000006_0003
(메타)아크릴레이트에 포스파이트계 화합물을 반웅시켜 제조될 수 있다. It can be prepared by reacting a phosphite compound with (meth) acrylate.
상기 아지도 (메타)아크릴레이트는 하기 화학식 2로 표시될 수 있다: The azido (meth) acrylate may be represented by the following formula (2):
[화학식 2]
Figure imgf000007_0001
[Formula 2]
Figure imgf000007_0001
(상기에서， ¾은 수소 또는 메틸기 임 ).  (Wherein ¾ is hydrogen or methyl group).
상기 포스파이트계 화합물은 하기 회:학식 3으로 표시될 수 있다: The phosphite-based compound may be represented by the following formula:
[화학식 ' 3 ] [Formula "3;
Figure imgf000007_0002
Figure imgf000007_0002
(상기에서， R2 및 R3 는 각각 독립적으로 수소， 탄소수 1~6의 알킬기， 탄소수 6~12의 아릴기， 탄소수 1~6의 알킬렌기 또는 탄소수 .6 12의 아릴렌기， R4는 수소， 탄소수 1~6의 알킬기 또는 탄소수 6~12의 아릴기， R5는 탄소수 1~6의 선형 또는 분지 형 알킬렌， 또는 탄소수 6~ 12의 아릴렌이고， n 은 0 .또는 1의 정수임 ). ' (In the above, R 2 and R 3 are each independently hydrogen, an alkyl group of 1 to 6 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkylene group of 1 to 6 carbon atoms or an arylene group of .6 12, R 4 is hydrogen , An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 5 is a linear or branched alkylene having 1 to 6 carbon atoms, or an arylene having 6 to 12 carbon atoms, n is 0 or an integer of 1) . '
상기 아지도 (메타)아크릴레이트와 상기 포스파이트계 화합물은 스타우딩거 반웅 (staudinger reaction)을 통해 (메타)아크릴로일 이 미 노포스파젠계 화합물을 제조할 수 있다. The azido (meth) acrylate and the phosphite-based compound may prepare a (meth) acryloyl iminophosphazene-based compound through a Staudinger reaction.
상기 반웅 용매는 다이클를로 메탄 (CH2C12), 클로로포름 (CHC13), 다이클로로에탄 (C2H4C12), 에 테르 ((C2H5)20), 아세톤 ((CH3)2CO), 테트라하이드로 퓨란 (C4H80), 를루엔 (C6H5CH3) 등이 사용될 수 있으며 바람직하게는 를루엔이 사용될 수 있다. The reaction solvent was dichloromethane (CH 2 C1 2 ), chloroform (CHC1 3 ), dichloroethane (C 2 H 4 C1 2 ), ether ((C 2 H 5 ) 2 0), acetone ((CH 3 ) 2 CO), tetrahydrofuran (C 4 H 8 0), toluene (C 6 H 5 CH 3 ), etc. may be used, and preferably, toluene may be used.
상기 반웅 온도는 약 0~40 °C 일 수 있으며 바람직하게는 약 10~25 °C 일 수 있다. ᅳ The reaction temperature may be about 0 ~ 40 ° C and preferably about 10 ~ 25 ° C. ᅳ
반웅 당량은 아지도 아크릴레이트 약 1.0당량에 포스파이트계 약 1.0~3.ᄋ 당량이 사용될 수 있으며 바람직하게는 약 1.0 1.5 당량이 사용될 수 있다. 또한， 상기 아지도 (메타)아크릴레 이트는 하기 반웅식 1과 같이 소디움 아자이드와 (메타)아크릴로일 클로라이드를 반웅시 켜 제조될 수 있다. The reaction weight is about 1.0 equivalent of azido acrylate and about 1.0-3. 0 equivalents of phosphite-based may be used, and preferably about 1.0 1.5 equivalents. In addition, the azido (meth) acrylate may be prepared by reacting sodium azide and (meth) acryloyl chloride as shown in the following reaction formula 1 below.
[반웅식 1 ]
Figure imgf000008_0001
(C6H6), 를루엔 (C6H5CH3), 크실렌 (( 0-， in-, or p-CH3)C6H4CH3)등이 사용될 수 있으며 바람직하게는 를루엔이 사용될 수 있다. [Banungsik 1]
Figure imgf000008_0001
(C 6 H 6 ), toluene (C 6 H 5 CH 3 ), xylene ((0-, in-, or p-CH 3 ) C 6 H 4 CH 3 ) and the like can be used, preferably toluene This can be used.
상기 반웅 온도는 약 0~40 °C 일 수 있으며 바람직하게는 약 10~25 °C 일 수 있으며 , 반웅 압력은 상압일 수 있다. The reaction temperature may be about 0 ~ 40 ° C and preferably about 10 ~ 25 ° C, the reaction pressure may be atmospheric pressure.
반웅 당량은 (메타)아크릴로일 ᅵ클로라이드 약 1.0당량에 소디움 아자이드 약 1.0-3.0 당량이 사용될 수 있으며 바람직하게는 약 1.0~ 1.5 당량이 사용될 수 있다. The reaction amount may be about 1.0-3.0 equivalents of sodium azide in about 1.0 equivalent of (meth) acryloyl ᅵ chloride, and preferably about 1.0-1.5 equivalents.
구체예에서는 상기 아지도 (메타)아크릴레이트의 합성과 (메타)아크릴로일 이미노포스파젠계 화합물의 합성은 인시츄 (in-situ) 반웅으로 진행될 수 있다. 상기 (메타)아크릴로일 이미노포스파젠계 화합물의 boiling point는 ltorr에서 약 60 200 °C 이다. In an embodiment, the synthesis of the azido (meth) acrylate and the synthesis of the (meth) acryloyl iminophosphazene-based compound may be performed in-situ reaction. The boiling point of the (meth) acryloyl iminophosphazene compound is about 60 200 ° C. in the ltorr.
본 발명 의 (메타)아크릴로일 이미노포스파젠계 화합물은 분자내에 인을 함유하여 난연성을 향상시 킬 수 있으며， 컨쥬게이션으로 인해 인의 유동성을 줄여 내열성 저하를 방지할 수 있다. 따라서 결과적으로 공중합체의 내열성과 난연성 및 Tg 가 상승될 수 있는 것 이다. The (meth) acryloyl iminophosphazene compound of the present invention can contain phosphorus in the molecule to improve flame retardancy, and can reduce the fluidity of the phosphorus due to conjugation, thereby preventing a decrease in heat resistance. Therefore, as a result, the heat resistance, flame retardancy, and Tg of the copolymer can be increased.
본 발명 의 다른 관점은 상기 화학식 1로 표시된 (메타)아크릴로일 이마노포스파젠계 화합물를 포함한 공중합체에 관한 것이다. Another aspect of the present invention relates to a copolymer including the (meth) acryloyl imanophosphazene compound represented by Chemical Formula 1.
구체 예에서 상기 공중합체는 상기 (메타)아크릴로일 이미노포스파젠계 화합물과 단관능성 불포화 단량체를 공중합한 것 이다. In a specific embodiment, the copolymer is a copolymer of the (meth) acryloyl iminophosphazene compound and a monofunctional unsaturated monomer.
상기 단관능성 불포화 단량체는 (메타)아크릴레이트계 단량체， 방향족 비 닐계 단량체， 시 안화비 닐계 단량체， 불포화 카르복실산， 산 무수물 등이 적용될 수 있으며， 반드시 이 에 제한되는 것은 아니다. 이들은 단독 또는 2종 이상 조합하여 .사용될 수 있다. As the monofunctional unsaturated monomer, a (meth) acrylate monomer, an aromatic vinyl monomer, a cyanide monomer, an unsaturated carboxylic acid, an acid anhydride, or the like may be applied, but is not necessarily limited thereto. These alone or in combination of two or more . Can be used.
구체 예에서， 상기 공중합체는 (메타)아크릴로일 이 미노포스파젠계 화합물을 약 1 내지 약 50 중량 바람직하게는 약 1 내지 약 35 중량 %， 더욱 바람직하게는 약 3 내지 약 30 중량 % 로 포함할 수 있다. In embodiments, the copolymer comprises from about 1 to about 50 weight percent of the (meth) acryloyl diminophosphazene compound, preferably from about 1 to about 35 weight percent, more Preferably from about 3 to about 30 weight percent.
상기 공중합체는 라디칼 개시제 존재 하에서 통상의 용매중합반웅으로 제조될 수 있다. 용매로는 벤젠， 를루엔， 에틸벤젠， 자일렌， 테트라하이드로퓨란， 메틸 에틸 케톤 등 방향족， 케톤， 에테르 또는 이들의 흔합일 수 있다. 상기 용매는 단량체 흔합물 100 중량부에 대하여 약 200 중량부 이하ᅳ 바람직하게는 약 80 내지 약 120 중량부의 범위로 사용할 수 있다. 중합반웅은 약 60 내지 약 100 °C에서 약 3시간 내지 약 12시간 동안 공중합하여 제조될 수 있다. The copolymer may be prepared by conventional solvent polymerization reaction in the presence of a radical initiator. The solvent may be an aromatic such as benzene, toluene, ethylbenzene, xylene, tetrahydrofuran, methyl ethyl ketone, ketone, ether or a combination thereof. The solvent may be used in an amount of about 200 parts by weight or less, preferably about 80 to about 120 parts by weight, based on 100 parts by weight of the monomer mixture. The polymerization reaction may be prepared by copolymerizing at about 60 to about 100 ° C. for about 3 hours to about 12 hours.
중합 반응에서 사용되는 개시제로는 벤조일퍼옥사이드 (BPO), 디큐밀퍼옥사이드 (DCP), 디 -tert-부틸퍼옥사이드 (DTBP), Initiators used in the polymerization reaction include benzoyl peroxide (BPO), dicumyl peroxide (DCP), di-tert-butylperoxide (DTBP),
^ 아조비스이소부틸로니트릴 (AIBN) 등과 같은 라디칼 개시제 둥이 있으며 반드시 이에 제한되는 것은 아니다. 상기 개시제는 단량체 흔합물 100 중량부에 대하여 약 0.005 내지 약 5 중량부， 바람직하게는 약 0.05 내지 약 1 중량부로 사용될 수 있다. 필요에 따라 분자량 조절을 위해 노말옥틸머캡탄 등의 분자량 조절제가 단량체 흔합물 100 중량부에 대하여 약 Q.1-2 중량부 첨가될 수도 있다. ^ Radical initiators such as azobisisobutylonitrile (AIBN) and the like, but are not necessarily limited thereto. The initiator may be used in an amount of about 0.005 to about 5 parts by weight, preferably about 0.05 to about 1 part by weight, based on 100 parts by weight of the monomer mixture. If necessary, about Q.1-2 parts by weight of a molecular weight regulator such as normaloctylmercaptan may be added to 100 parts by weight of the monomer mixture for molecular weight control.
상기 고내열성 인계 공중합체는 기존의 아크 ¾계 혹은 스티렌계 수지를 대체하여 사용될 수 았다. 예컨대， 상기 고내열성 인계 공중합체를 단독으로 사용하거나， 상기 고내열성 인계 공중합체의 난연성을 더욱 향상시키기 위해 폴리카보네이트 등 다른 수지와 블렌드하여 사용할 수 있다. 이하， 본 발명의 바람직한 실시예를 통해 본 발명의 구성 및 작용을 더욱 상세히 설명하기로 한다. 다만， 이는 본 발명와 바람직한 예시로 제시된 것이며 어떠한 의미로도 이에 의해 본 발명이 제한되는 것으로 해석될 수는 없다/ 여기에 기재되지 않은 내용은 이 기술 분야에서 숙련된 자이면 충분히 기술적으로 유추할 수 있는 것이므로 그 설명을 생략하기로 한다.  The high heat-resistant phosphorus copolymer may be used in place of the existing arc ¾- or styrene-based resin. For example, the high heat resistant phosphorus copolymer may be used alone or in combination with another resin such as polycarbonate in order to further improve the flame resistance of the high heat resistant phosphorus copolymer. Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, these are presented as the present invention and preferred examples and in no sense are to be construed as limiting the present invention / contents not described herein may be sufficiently technically inferred by those skilled in the art. The description thereof will be omitted.
【발명의 실시를 위한 형태】 [Form for implementation of invention]
실시예  EXAMPLE
제조예 1： 아지도아크릴레이트와제조  Production Example 1: Preparation with azido acrylate
반응 용기에 소디움 아자이드 (10g, 0.153mol)을 넣고 30ml 물로 용해시켰다. 아크릴로일 클로라이드 (11. lg, 0.123mol)를 90ml 를루엔에 묽힌 후 반웅용기의 소디움 아자이드 용액을 교반하면서 를루엔에 묽힌 아크릴로일 클로라이드 용액을 천천히 적가하였다. 아크릴로일 클로라이드 용액을 적가시 에는 반응기의 내부 온도가 25 °C를 넘지 않도록 얼음배쓰를 이용하여 반웅기 온도를 조절하였다. 3시간 교반후 분별 깔데기를 이용하여 유기층을 분리하고 추가로 수층을 30ml 를루엔으로 추출하였다. 모아진 유기층은 마그네슘 썰페이트를 이용하여 탈수한 후 마그네슘 썰페 이트는 필터를 이용하여 제거하였다. 필터 후 걸러진 여 액은 아지도아크릴레이트를 포함하는 를루엔 용액으로서 거의 정량적 인 수율로 아지도 아크릴레이트가 얻어졌다. 제조된 아지도 아크릴레이트는 추가적 인 정 제 과정 이나 농축없이 이미노포스파젠 아크릴레이트를 합성하는데 사용하였다. Sodium azide (10 g, 0.153 mol) was added to the reaction vessel and dissolved in 30 ml water. 90 ml of acryloyl chloride (11. lg, 0.123 mol) was diluted in toluene, and then the solution of acryloyl chloride diluted in toluene was slowly added dropwise while stirring the sodium azide solution in a semi-quilter group. When the acryloyl chloride solution was added dropwise, the reaction temperature was adjusted using an ice bath so that the internal temperature of the reactor did not exceed 25 ° C. After stirring for 3 hours, the organic layer was separated using a separating funnel, and the aqueous layer was further extracted with 30 ml of luene. The collected organic layer was dehydrated using magnesium sulfate, and magnesium sulfate was removed using a filter. The filtrate filtered after the filter was an toluene solution containing azidoacrylate, yielding azido acrylate in almost quantitative yield. The prepared azido acrylate was used to synthesize iminophosphazene acrylate without further purification or concentration.
Figure imgf000010_0001
제조예 2： 아지도 메타크릴레이트의 제조
Figure imgf000010_0001
Production Example 2 Preparation of Azido Methacrylate
반웅 용기 에 소디움 아자이드 (lOOg, 1.53mol)을 넣고 300ml 물로 용해시 켰다. 메타크릴로일 클로라이드 (104.5g, l.Omol)를 900ml 를루엔에 묽힌 후 반웅용기 의 . 소디움 아자이드 용액을 교반하면서 를루엔에 묽힌 메타크릴로일 클로라이드 용액을 천천하 적가하였다. 메타크릴로일 클로라이드 용액을 적가시에는 반웅기 의 내부 온도가 25 °C를 넘지 않도록 물또는 얼음배쓰를 이용하여 반웅기 온도를 조절하였다. 4시 간 교반후 분별 깔데기를 이용하여 유기층을 분리하고 추가로 수층을 300ml, 를루엔으로 추출하였다. 모아진 유기층은 마그네슴 썰페이트를 이용하여 탈수한 후 마그네슘 썰페 이트는 필터를 이용하여 제거하였다. 필터 후 걸러진 여 액은 아자도메타크릴레이트를 포함하는 를루엔 용액으로서 거 의 정량적 인 수율로 아지도 메타크릴레이트가 얻어졌다. 제조된 아지도 메타크릴레 이트는 추가적 인 정제 과정 이나 농축없이 이미노포스파젠 메타크릴레 이트를 합성하는데 사용하였다.
Figure imgf000011_0001
실시 예 1：프로페노일 이미노트라이메틸 포스파 -λ 5-젠 제조 Sodium azide (100 g, 1.53 mol) was added to the reaction vessel and dissolved in 300 ml of water. After diluting 900 ml of methacryloyl chloride (104.5 g, l.Omol) in luene, the reaction mixture of the semi-quilter group was dissolved. The solution of methacryloyl chloride diluted in toluene was slowly added dropwise while stirring the sodium azide solution. When the methacryloyl chloride solution was added dropwise, the reaction temperature was adjusted by using water or an ice bath so that the internal temperature of the reaction device did not exceed 25 ° C. After stirring for 4 hours, the organic layer was separated using a separating funnel, and the aqueous layer was further extracted with 300 ml and toluene. The collected organic layer was dehydrated using magnesium sulphate, and then magnesium sulphate was removed using a filter. The filtrate filtered after the filter was an toluene solution containing azadomethacrylate, yielding azido methacrylate in almost quantitative yield. The prepared azido methacrylate was used to synthesize iminophosphazene methacrylate without further purification or concentration.
Figure imgf000011_0001
Example 1: Preparation of propenoyl iminotrimethyl phospha-λ 5 -gen
제조예 1을 통해서 얻은 아지도 아크릴레이트 를루엔 용액을 교반하면서 트라이 메틸 포스파이트 (15.2g, 0.123mol)를 천천히 30분동안 적가하였다. 트라이 메틸 포스파이트 적가시 에는 반응기의 내부 은도가 25 °C를 넘지 않도록 얼음배쓰를 이용하여 반웅기 온도를 조절하였다. 6시 간 동안 교반 후 반웅용액을 농축하여 를루엔을 제거하였다. 를루엔 제거 후 남은 잔류물을 감압증류하여 프로쩨노일 이미노트라이 메틸 포스파 -λ 5-젠을 16.6g, 70%의 수율로 얻었다 . NMR 결과를 도 1에 나타내었다. 실시예 2： 2-메틸프로페노일 이미노트라이메틸 포스파 -λ 5-젠 제조 Trimethyl phosphite (15.2 g, 0.123 mol) was slowly added dropwise for 30 minutes while stirring the azido acrylate toluene solution obtained in Preparation Example 1. When trimethyl phosphite was added dropwise, the reaction temperature was adjusted using an ice bath so that the internal silver of the reactor did not exceed 25 ° C. After stirring for 6 hours, the semi-aqueous solution was concentrated to remove toluene. The residue remaining after the removal of toluene was distilled under reduced pressure to give 16.6 g of 70% of propynolyl iminotrimethyl phospha-λ 5 -gen. NMR results are shown in FIG. 1. Example 2 Preparation of 2-methylpropenoyl iminotrimethyl phospha-λ 5 -gen
제조예 2를 통해서 얻은 아지도 메타크릴레이트 를루엔 용액을 교반하면서 트라이 메틸 포스파이트 (124g, l.Omol)를 천천히 2시간 동안 적가하였다. 트라이 메틸 포스파이트 적가시에는 반웅기의 내부 온도가 25 °C를 넘지 않도록 물또는 얼음배쓰를 이용하여 반웅기 온도를 조절하였다. 20시간 동안 교반 후 반웅용액을 농축하여 를루엔을 제거하였다. 를루엔 제거 후 남은 잔류물을 감압증류하여 프로페노일 이미노트라이 메틸 포스파 -λ 5-젠을 18 ， 87%의 수율로 얻었다 . NMR 결과를 도 2에 나타내었다. 실시 예 3： 2-메틸프로페노일 이미노메틸네오펜틸 포스파 λ 5-젠 제조 Trimethyl phosphite (124 g, lOmol) was slowly added dropwise for 2 hours while stirring the azido methacrylate toluene solution obtained in Preparation Example 2. When trimethyl phosphite was added dropwise, the reaction temperature was adjusted by using water or an ice bath so that the internal temperature of the reaction vessel did not exceed 25 ° C. After stirring for 20 hours, the semi-aqueous solution was concentrated to remove toluene. The residue remaining after the removal of toluene was distilled under reduced pressure to obtain propenoyl iminotrimethyl phospha-λ 5 -gen in a yield of 18, 87%. NMR results are shown in FIG. 2. Example 3: Preparation of 2-methylpropenoyl iminomethyl neopentyl phospha λ 5 -gen
제조예 2를 통해서 얻은 아지도 메타크릴레이트 (0.05 mol) 를루엔 용액을 교반하면서 메틸네오펜틸 포스파이트 (8.2 g, 0.05 mol) 를루엔 용액를 천천히 30분 동안 적가하였다. 메틸네오¾틸 포스파이트 (8.2 g, 0.05 mol) 를루엔 용액을 적가시에는 반응기 의 내부 온도가 25 °C를 넘지 않도록 물또는 얼음배쓰를 이용하여 반웅기 온도를 조절하였다. 20시 간 동안 교반 후 반웅용액을 농축하여 를루엔을 제거하였다. 를루엔 제거 후 남은 잔류물을 감압증류하여 2-메틸프로페노일 이미노메틸네오펜틸 포스파 -λ 5-젠을 8.6g, 70%의 수율로 얻었다.
Figure imgf000012_0001
Methyl neopentyl phosphite (8.2 g, 0.05 mol) toluene solution was slowly added dropwise for 30 minutes while stirring the azido methacrylate (0.05 mol) toluene solution obtained through Preparation Example 2. When the methylneothibutyl phosphite (8.2 g, 0.05 mol) toluene solution was added dropwise, the reaction temperature was adjusted using a water or ice bath so that the internal temperature of the reactor did not exceed 25 ° C. After stirring for 20 hours, the semi-aqueous solution was concentrated to remove toluene. The residue remaining after the removal of toluene was distilled under reduced pressure to obtain 2-methylpropenoyl iminomethyl neopentyl phospha-λ 5 -gen in a yield of 8.6 g, 70%.
Figure imgf000012_0001
실시예 4 ： 메틸메타아크릴레이트와 프로페노일 이미노트라이메틸 포스파 -λ 5-젠의 공중합체 제조 Example 4 Preparation of Copolymer of Methyl methacrylate with Propenoyl Iminotrimethyl Phospa-λ 5 -Gen
메틸메타아크릴레이트 3g 과 프로페노일 이미노트라이메틸 포스파 -λ5—젠 0.9g을 를루엔 에 녹인 후 개시제로 AIBN(15mg)/BPO(15mg)을 넣고 90 °C에서 12시간 동안 중합을 진행하였다. 중합 후 폴리머를 클로로포름으로 회석시킨 후 과량의 헥산에 천천히 적가하여 고형물로 침전하고 진공오븐에서 12시간 건조하여 공중합체를 85% 수율로 얻었다. NMR 결과를 도 3에 나타내었다. 3 g of methyl methacrylate and 0.9 g of propenoyl iminotrimethyl phospha-λ 5 -gen were dissolved in toluene, and then AIBN (15 mg) / BPO (15 mg) was added as an initiator, and polymerization was performed at 90 ° C. for 12 hours. Proceeded. After polymerization, the polymer was distilled with chloroform, slowly added dropwise into excess hexane, precipitated as a solid, and dried in a vacuum oven for 12 hours to obtain a copolymer in 85% yield. NMR results are shown in FIG. 3.
Figure imgf000012_0002
실시예 5 ： 메틸메타아크릴레이트와 2—메틸프로페노일 이미노트라이메틸 포스파 -λ5—젠의 공중합체 제조
Figure imgf000012_0002
Example 5 Preparation of Copolymer of Methyl Methacrylate and 2—Methylpropenoyl Iminotrimethyl Phospa-λ 5 —Gen
메틸메타아크릴레이트 3g 과 2—메틸프로페노일 이미노트라이메틸 포스파 -λ 5-젠 0.9g을 를루엔 3g에 녹인 후 개시제로 AIBN(15mg)/BPO(15mg)을 넣고 90 °C에서 12시간 동안 중합을 진행하였다. 중합 후 폴리머를 클로로포름으로 희석시킨 후 과량의 핵산에 천천히 적가하예 고형물로 침전하고 진공오본에서 12시간 건조하여 공중합체를 89% 수율로 얻었다 · NMR결과를 도 4에 나타내었다. cr、ᄋ
Figure imgf000013_0001
Dissolve 3 g of methyl methacrylate and 0.9 g of 2-methylpropenoyl iminotrimethyl phospha-λ 5 -gen in 3 g of toluene, add AIBN (15 mg) / BPO (15 mg) as an initiator, and then add the residue at 90 ° C. The polymerization proceeded for a time. After the polymerization, the polymer was diluted with chloroform, slowly added dropwise to the excess nucleic acid, precipitated as a solid, and dried for 12 hours in a vacuum oven to obtain a copolymer in 89% yield. The NMR results are shown in FIG. 4. cr 、 ᄋ
Figure imgf000013_0001
비교예 1： 폴리메틸메타아크릴레이트 제조 Comparative Example 1: Polymethyl methacrylate
메틸메타아크릴레이트 3.9g 를루엔 3.9g에 녹인 후 개시 제로 AIBN(15mg)/BPO(15mg)을 넣고 90 °C에서 12시간 동안 중합을 진행하였다. 중합 후 폴리머를 클로롤포름으로 묽힌 후 과량의 핵산에 천천히 적가하여 고형물로 침전하고 진공오븐에서 12시 간 건조하여 중합체를 90% 수율로 얻었다. After dissolving 3.9 g of methyl methacrylate in 3.9 g of luene, AIBN (15 mg) / BPO (15 mg) was added as an initiator, and polymerization was performed at 90 ° C. for 12 hours. After the polymerization, the polymer was diluted with chloroform and slowly added dropwise to the excess nucleic acid to precipitate as a solid, and dried in a vacuum oven for 12 hours to obtain the polymer in 90% yield.
[표 1 ] TABLE 1
Figure imgf000013_0002
Figure imgf000013_0002
(1) 유리 전이온도 Tg( °C ) ： Differential Scanning Calorimeter(DSC)를 이용하여 시료를 25 ~ 200 °C 까지 10 °C/min 으로 승온하면서 유리 전이온도를 측정하였다. (1) Glass transition temperature Tg (° C): Differential Scanning while the sample temperature was raised to 10 ° C / min up to 25 ~ 200 ° C by using a Calorimeter (DSC) The glass transition temperature was measured.
(2) 난연성 ： UL-94 규정에 준하여 2.0mm 두께 시편을 이용하여 평가하였다. 실시예 6 ： 스티렌-아크릴로 니트릴—프로페노일 이미노트라이메틸 포스파 -λ 5-젠의 공중합체 제조 (2) Flame retardant: The evaluation was carried out using a 2.0 mm thick specimen in accordance with UL-94. Example 6 Preparation of Copolymer of Styrene-Acrylonitrile—propenoyl iminotrimethyl phospha-λ 5 -gen
스티 렌 2.13g, 아크릴로 니트릴 0.87g과 제조예 1에서 제조된 프로페노일 이미노트라이 메틸 포스파 -λ 5-젠 Q.9g을 를루엔 3g에 녹인 후 개시 제로 AIBN(15mg)/BPO(15mg)을 넣고 90°C에서 12시간 동안 중합을 진행하였다. 중합 후 플리머를 클로로포름으로 묽힌 후 과량의 핵산에 천천히 적가하여 고형물로 침 전하고 진공오본에서 12시간. 건조하여 공중합체를 69% 수율로 얻었다. NMR 결과를 도 5에 나타내었다. 2.13 g of styrene, 0.87 g of acrylonitrile, and Q.9 g of propenoyl iminotri methyl phospha-λ 5 -gen prepared in Preparation Example 1 were dissolved in 3 g of toluene, and then AIBN (15 mg) / BPO (Initiator) was used. 15 mg) was added and polymerization was performed at 90 ° C. for 12 hours. After polymerization, the polymer was diluted with chloroform and slowly added dropwise to the excess nucleic acid to settle as a solid, followed by 12 hours in a vacuum oven. Dried to give the copolymer in 69% yield. Got it. NMR results are shown in FIG. 5.
Figure imgf000014_0001
Figure imgf000014_0001
실시예 7 ： 스티렌-아크릴로 니트릴 -2-메틸프로페노일 이미노트라이메틸 포스파 -λ 5-젠의 공중합체 제조 Example 7 Preparation of Copolymer of Styrene-Acrylonitrile-2-methylpropenoyl iminotrimethyl phospha-λ 5 -gen
스티 렌 2.13g, 아크릴로 니트릴 0.87g과 제조예 2에서 제조된 2-메틸프로페노일 이미노트라이 메틸 포스파 -λ 5-젠 0.9g을 를루엔 3g에 녹인 후 개시 제로 AIBN(15mg)/BPO(15mg)을 넣고 90°C에서 12시간 동안 중합을 진행한다. 중합 후 폴리 머를 클로로포름으로 묽힌 후 과량의 핵산에 천천히 적가하여 고형물로 침 전하고 진공오븐에서 12시 간 건조하여 공중합체를 77% 수율로 얻었다. NMR 결과를 도 6에 나타내었다. ' 2.13 g of styrene, 0.87 g of acrylonitrile and 0.9 g of 2-methylpropenoyl iminotri methyl phospha-λ 5 -gen prepared in Preparation Example 2 were dissolved in 3 g of toluene, and then AIBN (15 mg) / Add BPO (15mg) and proceed with polymerization at 90 ° C for 12 hours. After the polymerization, the polymer was diluted with chloroform, slowly added dropwise to the excess nucleic acid, precipitated with solids, and dried in a vacuum oven for 12 hours to obtain a copolymer in 77% yield. NMR results are shown in FIG. 6. '
Figure imgf000014_0002
Figure imgf000014_0002
비교예 2：스티렌-아크릴로 니트릴 공중합체 제조 Comparative Example 2: Preparation of Styrene-Acrylonitrile Copolymer
스티 렌 2.13g, 아크릴로 니트릴 0.87g을 를루엔 3g에 녹인 후 개시 제로 AIBN(15mg)/BPO(15mg)을 넣고 90oC에서 12시간 동안 중합을 진행한다. 중합 후 폴리머를 클로로포름으로 묽힌 후 과량의 핵산에 천천히 적가하여 고형물로 침전하고 진공오본에서 12시간 건조하여 공중합체를 80% 수율로 얻었다. 2.13 g of styrene and 0.87 g of acrylonitrile were dissolved in 3 g of toluene, and then AIBN (15 mg) / BPO (15 mg) was added as an initiator, and polymerization was performed at 90 ° C. for 12 hours. After the polymerization, the polymer was diluted with chloroform, slowly added dropwise to the excess nucleic acid, precipitated as a solid, and dried in a vacuum oven for 12 hours to obtain a copolymer in 80% yield.
[표 2] . TABLE 2
Figure imgf000015_0001
Figure imgf000015_0001
(1) . 유리전이온도 Tg( °C) ： Differential Scanning Calorimeter(DSC)를 이용하여 시료를 25 ~ 200 °C 까지 10°C/min 으로 승온하면서 유리전이온도를 측정하였다. (1) . Glass Transition Temperature Tg ( ° C): The glass transition temperature was measured by using a Differential Scanning Calorimeter (DSC) while raising the temperature of the sample to 10 ° C / min from 25 to 200 ° C.
(2) 난연성 ： UL-94 규정에 준하여 2.0mm두께 시편을 이용하여 평가하였다. 상기 표 1 및 2에 나타난 바와 같이, (메타)아크릴로일 이미노포스파젠계 화합물이 공중합되지 않은 공중합체와 비교하여 내열도 및 난연성이 우수하다는 것을 알 수 있다. 이상 본 발명의 실시예들을 설명하였으나, 본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야 한다.  (2) Flame retardant: The evaluation was carried out using a 2.0 mm thick specimen in accordance with UL-94. As shown in Tables 1 and 2, it can be seen that the (meth) acryloyl iminophosphazene compound is superior in heat resistance and flame retardancy compared to the copolymer which is not copolymerized. Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments and can be manufactured in various forms, and a person of ordinary skill in the art to which the present invention pertains has the technical idea of the present invention. However, it will be understood that other specific forms may be practiced without changing the essential features. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims

【청구의 범위 ] [Claim]
1. 하기 화학식 1로 표시되는 (메타)아크릴로일 이미노포스파젠계 화합물:  1. (meth) acryloyl iminophosphazene compound represented by the following general formula (1):
[화학식 1 ]  [Formula 1]
Figure imgf000016_0001
Figure imgf000016_0001
(상기 에서， ¾은 수소 또는 메틸기 이고， R2 및 R3 는 각각 독립적으로 수소， 탄소수 1~6의 알킬기， 탄소수 6~12의 아릴기， 탄소수 1~6의 알킬렌기 또는 탄소수 6~12의 아릴렌기， R4는 수소, 탄소수 1~6의 알킬기 또는 탄소수 6~12의 아릴기， R5는 탄소수 1~6의 선형 또는 분지 형 알킬렌， 또는 탄소수 6~12의 아릴렌이고， n 은 0 또는 1의 정수임 ). (Wherein, ¾ is hydrogen or methyl group, R 2 and R 3 are each independently hydrogen, alkyl group of 1 to 6 carbon atoms, aryl group of 6 to 12 carbon atoms, alkylene group of 1 to 6 carbon atoms or of 6 to 12 carbon atoms) Arylene group, R 4 is hydrogen, alkyl group of 1 to 6 carbon atoms or aryl group of 6 to 12 carbon atoms, R 5 is linear or branched alkylene of 1 to 6 carbon atoms, or arylene of 6 to 12 carbon atoms, n is Is an integer of 0 or 1).
2. 게 1항에 있어서， 상기 n은 0 이며， 상기 R2, R3 및 R4는 동일한 것을 특징으로 하는 (메타)아크릴로일 이미노포스파젠계 화합물. 2. The (meth) acryloyl iminophosphazene compound according to item 1, wherein n is 0 and R 2, R 3 and R 4 are the same.
3. 하기 화학식 2로 표시되는 아지도 (메타)아크릴레이트에 3. To azido (meth) acrylate represented by the following formula (2)
표시되는 포스파이트계 화합물을 반응시 키 는 단계를 포함하는Reacting the displayed phosphite-based compound
Figure imgf000016_0002
Figure imgf000016_0002
표시되는 (메타)아크릴로일 이미노포스파젠계 화합물의 제조방법 : Method for preparing the (meth) acryloyl iminophosphazene compound represented:
[화학식 1 ] [Formula 1]
Figure imgf000016_0003
Figure imgf000016_0003
[화학식 2]
Figure imgf000017_0001
[Formula 2]
Figure imgf000017_0001
[화학식 3]
Figure imgf000017_0002
[Formula 3]
Figure imgf000017_0002
(상기 화학식 1， 2 및 3에서， ¾은 수소 또는 메틸기이고, R2 및 R3 는 각각 독립적으로 수소， 탄소수 1~6의 알킬기， 탄소수 6~12의 아릴기， 탄소수 1~6의 알킬렌기 또는 탄소수 6~12의 아릴렌기， R4는 수소， 탄소수 1~6의 알킬기 또는 탄소수 6~12의 아릴기, R5는 탄소수 1~6의 선형 또는 분지형 알킬렌， 또는 탄소수 6~12의 아릴렌이고， n은 0또는 1의 정수임). (In the above Chemical Formulas 1, 2 and 3, ¾ is hydrogen or a methyl group, R 2 and R 3 are each independently hydrogen, an alkyl group of 1 to 6 carbon atoms, an aryl group of 6 to 12 carbon atoms, an alkylene group of 1 to 6 carbon atoms) Or an arylene group having 6 to 12 carbon atoms, R 4 is hydrogen, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 5 is a linear or branched alkylene having 1 to 6 carbon atoms, or having 6 to 12 carbon atoms Arylene, n is an integer of 0 or 1).
4. 게 3항에 있어서， 소디움 아자이드와 (메타)아크릴로일 클로라이드를 반웅시켜 상기 화학식 2로 표시되는 아지도 (메타)아크릴레이트를 제조하고, 4. According to item 3, sodium azide and (meth) acryloyl chloride are reacted to prepare an azido (meth) acrylate represented by the formula (2),
상기 아지도 (메타)아크릴레이트에 상기 화학식 3으로 표시되는 포스파이트계 화합물을 인시츄 (in—situ) 반웅시키는 것을 특징으로 하는 방법.  And in situ reacting the phosphite compound represented by Chemical Formula 3 on the azido (meth) acrylate.
5. 제 1항의 (메타)아크릴로일 이미노포스파젠계 화합물과 단관능성 불포화 단량체를 공중합한 공중합체. 5. A copolymer obtained by copolymerizing the (meth) acryloyl iminophosphazene compound of claim 1 with a monofunctional unsaturated monomer.
6. 게 5항에 있어서， 상기 공중합체는 (메타)아크릴로일 이미노포스파젠계 화합물을 약 1 내지 약 50중량 % 포함하는 것을 특징으로 하는 공중합체. 6. The copolymer according to claim 5, wherein the copolymer comprises about 1 to about 50% by weight of a (meth) acryloyl iminophosphazene compound.
7.제 5항에 있어서，상기 단관능성 불포화 단량체는 (메타)아크릴레이트계 단량체， 방향족 비닐계 단량체， 시안화비닐계 단량체， 불포화 카르복실산, 산 무수물로 이루어지는 군으로부터 하나 이상 포함하는 갓을 특징으로 하는 공중합체. 7.The method according to claim 5, wherein the monofunctional unsaturated monomer is one comprising at least one from the group consisting of a (meth) acrylate monomer, an aromatic vinyl monomer, a vinyl cyanide monomer, an unsaturated carboxylic acid, and an acid anhydride. Copolymer.
8. 제 7항에 있어서， 상기 공중합체는 (메타)아크릴로일 이미노포스파젠계 화합물， 방향족 비닐계 단량체 및 시안화 비닐계 단량체을 공중합한 공중합체. 8. The copolymer according to claim 7, wherein the copolymer is a copolymer of a (meth) acryloyl iminophosphazene compound, an aromatic vinyl monomer, and a vinyl cyanide monomer.
9. 제 7항에 있어서， 상기 공중합체는 (메타)아크릴로일 이미노포스파젠계 화합물과 (메타)아크릴레이트계 단량체를 공중합한 공중합체. 9. The copolymer according to claim 7, wherein the copolymer is a copolymer of a (meth) acryloyl iminophosphazene compound and a (meth) acrylate monomer.
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