KR930000374B1 - Process for producing aromatic polyisocyanate - Google Patents

Process for producing aromatic polyisocyanate Download PDF

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KR930000374B1
KR930000374B1 KR1019890002889A KR890002889A KR930000374B1 KR 930000374 B1 KR930000374 B1 KR 930000374B1 KR 1019890002889 A KR1019890002889 A KR 1019890002889A KR 890002889 A KR890002889 A KR 890002889A KR 930000374 B1 KR930000374 B1 KR 930000374B1
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aromatic
aromatic polyisocyanate
polyisocyanate
phosgene
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KR890014594A (en
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기요시 시까이
류지 하세야마
고우조오 하야시
가쯔요시 사사가와
아끼히로 야마구찌
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미쯔이도오아쯔가가꾸 가부시기가이샤
머지마 마사요시
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F18/00Homopolymers 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/77Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78Nitrogen
    • C08G18/79Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates

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Abstract

내용 없음.No content.

Description

방향족 폴리이소시아네이트 및 그 제조방법Aromatic Polyisocyanate and Manufacturing Method Thereof

제1도는 실시예 1에서 얻은 폴리파라크실릴렌-폴리페닐-폴리이소시아네이트의 IR 스펙트럼.1 is an IR spectrum of the polyparaxylylene-polyphenyl-polyisocyanate obtained in Example 1. FIG.

제2도는 실시예 2에서 얻은 파라크실릴렌 디페닐이소시아네이트의 IR 스펙트럼.2 is an IR spectrum of paraxylylene diphenylisocyanate obtained in Example 2. FIG.

본 발명은 방향족 폴리이소시아네이트 및 그 제조방법에 관한 것이다.The present invention relates to an aromatic polyisocyanate and a method for producing the same.

본 발명의 폴리이소시아네이트는 신규의 구조를 지니는 폴리이소시아네이트로서 발포체, 탄성체, 합성피혁, 접착제 및 필림과 같은 다방면에 폴리우레탄수지 및 폴리우레아수지의 원료로서 사용된다.The polyisocyanate of the present invention is a polyisocyanate having a novel structure and is used as a raw material of polyurethane resins and polyurea resins in various fields such as foams, elastomers, synthetic leathers, adhesives and films.

종래에 공지된 방향족 폴리이소시아네이트중에서, 다음의 일반식,Among the aromatic polyisocyanates conventionally known, the following general formula

Figure kpo00001
Figure kpo00001

로 표현된 폴리페닐메탄-폴리이소시아네이트(이하, P-MDI라 한다)가 잘 알려져 있으며, 폴리우레탄수지 및 폴리우레아수지의 원료로서 다방면에 사용되고 있다.Polyphenylmethane-polyisocyanate (hereinafter referred to as P-MDI) represented by is well known, and is widely used as a raw material for polyurethane resins and polyurea resins.

본 발명의 첫째목적은 P-MDI와는 구조가 완전히 다르고 폴리우레탄수지 및 폴리우레아수지의 원료로서 새로운 용도가 기대되는 신규의 방향족 폴리이소시아네이트를 제공한다.The first object of the present invention is to provide a novel aromatic polyisocyanate which is completely different from P-MDI and is expected to be used as a raw material for polyurethane resins and polyurea resins.

본 발명의 둘째목적은 상기 폴리이소시아네이트의 신규의 제조방법을 제공한다.A second object of the present invention is to provide a novel process for preparing the polyisocyanate.

상기 목적을 달성하기 위하여 본 발명자들의 광범위한 연구결과 본 발명의 목적은 특정의 구조를 지니는 방향족 아민수지 또는 이들의 염을 포스겐과 반응시켜서 달성될 수 있음이 발견되었고 본 발명은 이 발견을 기본으로 하여 달성된다.In order to achieve the above object, extensive research by the present inventors has found that the object of the present invention can be achieved by reacting an aromatic amine resin having a specific structure or a salt thereof with phosgene, and the present invention is based on this finding. Is achieved.

특히, 본 발명의 신규의 폴리이소시아네이트는 일반식,In particular, the novel polyisocyanates of the present invention are of the general formula,

Figure kpo00002
Figure kpo00002

(식중, A는 페닐렌기, 알킬렌기, 알킬치환페닐렌기, 디페닐렌기, 디페닐에테르기 또는 나프틸렌일기를 표시하며 R1은 할로겐원자, 탄소수 4이하인 저급알콕시기 또는 탄소수 5이하인 저급알킬기로서 R1은 서로 같거나 다를 수 있으며 고리를 형성할 수 있고

Figure kpo00003
은 1 또는 2, m은 0~3의 정수이고 n은 0~300의 정수를 나타낸다)로 표현되는 방향족 폴리이소시아네이트의 혼합물을 포함하는 폴리이소시아네이트이다.(Wherein A represents a phenylene group, an alkylene group, an alkyl-substituted phenylene group, a diphenylene group, a diphenylether group or a naphthyleneyl group, and R 1 is a halogen atom, a lower alkoxy group having 4 or less carbon atoms or a lower alkyl group having 5 or less carbon atoms) R 1 may be the same or different from each other and may form a ring
Figure kpo00003
Is 1 or 2, m is an integer of 0-3, n represents an integer of 0-300), and is a polyisocyanate containing the mixture of aromatic polyisocyanate represented by).

또한, 본 발명의 신규의 제조방법은 일반식(a)로 표현된 방향족 폴리이소시아네이트의 혼합물을 포함하는 폴리이소시아네이트의 제조방법으로, 이 방법은 일반식Further, the novel production method of the present invention is a method for producing a polyisocyanate comprising a mixture of aromatic polyisocyanates represented by the general formula (a), which method is a general formula

Figure kpo00004
Figure kpo00004

(식중 A,R1,l,m 및 n은 일반식(a)와, 동일하다)로 표현된 방향족 아민화합물의 혼합물을 포함하는 방향족 아민수지 또는 이들의 염을 포스겐과 반응시키는 것을 포함한다.Reacting an amine with an amine, or an aromatic amine resin comprising a mixture of aromatic amine compounds represented by formula (A, R 1 , 1, m, and n are the same as in general formula (a)).

일반식(b)로 표현된 방향족 아민수지는 최근에 개발된 신규의 화합물로 이들의 성질 및 제조방법은 일본 특허출원 제 252517/1987 및 282048/1987에 상세히 기재되어 있다.The aromatic amine resin represented by formula (b) is a novel compound recently developed and its properties and preparation methods are described in detail in Japanese Patent Application Nos. 252517/1987 and 282048/1987.

본 발명의 방향족 폴리이소시아네이트는 전술한 일반식(b)로 표현된 방향족 아민수지를 포스겐과 직접반응시켜 제조하거나, 또는 방향족 아민수지의 염산염과 같은 염을 미리 합성하고 그 염을 불활성용매에 현탁시켜서 포스겐과 반응시켜 제조한다.The aromatic polyisocyanate of the present invention is prepared by directly reacting the aromatic amine resin represented by the general formula (b) with phosgene or by synthesizing a salt such as a hydrochloride salt of the aromatic amine resin in advance and suspending the salt in an inert solvent. Prepared by reaction with phosgene.

전자의 방법을 ″냉열 2단계 포스겐화″라고 하며 반응의 실시양태는 특별히 제한되지 않으나, 일반식으로 반응계가 완전히 교반될 수 있고, 포스겐 가스도입관이 구비된 반응기에서 반응계의 온도를 0~5℃로 냉각하면서 불활성용매속에 포스겐가스를 도입시킨다. 즉, 용매에 대한 포스겐의 용해도가 거의 포화되도록 불활성용매내에 포스겐을 용해한 다음, 이것에 불활성 용매에 상기 기술한 아민수지를 용해시켜 따로이 형성된 용액을 화학량적으로 1~2배의 포스겐가스를 도입하면서 첨가한다. 중간쯤에 반응액의 온도를 15℃로 유지하고, 이때 발생된 염화수소와 과잉의 포스겐을 환류응축기를 통해 계의 외부로 방출시킨다. 반응기내의 내용물은 슬러리를 형성하며, 주반응은 카르바밀 클로라이드와 아민염산염의 생성이다. 아민용액을 첨가한 후 반응을 30분~2시간 진행시킨다. 상기 기술한 방법을 냉포스겐화라고 한다.The former method is called ″ cold heat two-stage phosgenation ″ and the embodiment of the reaction is not particularly limited, but in general, the reaction system may be completely stirred, and the temperature of the reaction system in a reactor equipped with a phosgene gas introduction tube is 0-5. The phosgene gas is introduced into the inert solvent while cooling to 캜. That is, the phosgene is dissolved in an inert solvent so that the solubility of the phosgene in the solvent is almost saturated, and then the amine resin described above is dissolved in the inert solvent, and a solution formed separately is introduced into the stoichiometric amount of phosgene 1-2 times. Add. About halfway, the temperature of the reaction solution is maintained at 15 ° C., and hydrogen chloride and excess phosgene generated are released to the outside of the system through a reflux condenser. The contents in the reactor form a slurry and the main reaction is the production of carbamyl chloride and amine hydrochloride. After adding the amine solution, the reaction proceeds for 30 minutes to 2 hours. The method described above is called cold phosgenation.

다음, 반응계를 130℃~160℃의 온도에서 30분~3시간 가열한다. 온도를 상승시키면, 용매에 용해된 포스겐이 기화되어 거품을 만들기 쉬우므로, 냉포스겐화의 경우와는 반대로 이론양에 대한 포스겐의 흐름비를 감소시키는데 바람직하다. 온도를 상승시킨후에 반응을 1~3시간 진행한다. 슬러리가 완전히 용해되면 반응이 완결된 것으로 한다. 상기 방법을 열포스겐화라고 하며 열포스겐화의 주반응은 이소시아네이트로의 카르바밀클로라이드의 분해와 이소시아네이트로의 아민염산염의 포스겐화이다.Next, the reaction system is heated at a temperature of 130 ° C to 160 ° C for 30 minutes to 3 hours. Increasing the temperature is preferable to reduce the flow ratio of phosgene to the theoretical amount as opposed to the case of cold phosgenation, since phosgene dissolved in the solvent tends to vaporize to foam. After raising the temperature, the reaction proceeds for 1 to 3 hours. When the slurry is completely dissolved, the reaction is considered complete. This method is called thermophosphogenation and the main reactions of thermophosphogenation are the decomposition of carbamyl chloride to isocyanate and phosgenation of amine hydrochloride to isocyanate.

열포스겐화를 완결한 후, 반응계를 150~180℃온도로 가열하고 적당비율(즉, 200ml/분 ; 이 값은 반응규모에 의존하여 변동)로 반응계에 질소가스를 불어넣어 용해된 가스성분을 제거하고 미 반응의 카르바밀클로라이드를 충분히 분해한다. 다음, 냉각후, 감압하에 불활성용매를 증류 제거하여 방향족 폴리이소시아네이트를 얻는다.After the completion of thermal phosgenation, the reaction system is heated to a temperature of 150 to 180 ° C., and nitrogen gas is blown into the reaction system at an appropriate ratio (ie, 200 ml / min; this value varies depending on the reaction scale) to dissolve the dissolved gas component. Remove and sufficiently decompose the unreacted carbamylchloride. Next, after cooling, the inert solvent is distilled off under reduced pressure to obtain an aromatic polyisocyanate.

후자의 방법은 ″아민 염산염의 포스겐화″라고 하며, 상기 기술한 방향족 아민수지의 염산염은 미리 합성한다. 염산염의 합성은 방향족 아민수지를 염화수소 또는 진한 염산으로 처리하는 공지된 방법으로 쉽게 실행된다. 이렇게 형성된, 충분히 건조되고 미분쇄된 방향족 아민 염산염을 상기 기술한 ″냉열 2단계 포스겐화″방법에서 사용된 것과 동일한 반응기에서 불활성용매에 분산시키고 반응계를 80~160℃온도로 유지하며, 계에 포스겐가스를 3~10시간 도입시켜 전체 포스겐 도입량이 화학량적으로 2~10배로 되게 하여 이소시아네이트를 합성한다. 반응의 진행은 발생된 염화수소가스량과, 원료물질로서 사용되고 불활성용매에 불용인 방향족 아민 염산염의 소실 및 반응액의 투명성, 균일성에 의해 추측할 수 있다. 발생된 염화수소와 과잉의 포스겐은 환류응축기를 통하여 반응계의 외부로 방출된다. 반응이 완결된 후에 질소가스를 반응용매에 도입시켜 용해된 포스겐을 제거하고, 냉각하고 여과한 다음 불활성용매를 감압하에 증류시켜 방향족 폴리이소시아네이트를 얻는다.The latter method is called "phosgenation of amine hydrochloride", and the hydrochloride of the aromatic amine resin described above is synthesized in advance. The synthesis of the hydrochloride is easily carried out by known methods in which the aromatic amine resin is treated with hydrogen chloride or concentrated hydrochloric acid. The sufficiently dried and pulverized aromatic amine hydrochloride thus formed is dispersed in an inert solvent in the same reactor as used in the ″ cold heat two stage phosgenation ″ process described above and the reaction system is maintained at a temperature of 80-160 ° C. and the phosgene in the system Gas is introduced for 3 to 10 hours to make the total phosgene introduction amount 2 to 10 times stoichiometrically to synthesize isocyanate. The progress of the reaction can be estimated by the amount of generated hydrogen chloride gas, the loss of aromatic amine hydrochloride used as a raw material, and insoluble in an inert solvent, and the transparency and uniformity of the reaction solution. The generated hydrogen chloride and excess phosgene are released out of the reaction system through the reflux condenser. After the reaction was completed, nitrogen gas was introduced into the reaction solvent to remove dissolved phosgene, cooled and filtered, and the inert solvent was distilled off under reduced pressure to obtain an aromatic polyisocyanate.

도입하는 포스겐의 양은 ″냉열 2단계 포스겐화″와 ″아민염산염의 포스겐화″의 방법에서 화학량적으로 2~10배면 충분하다, 불활성 용매로서는 방향족 탄화수소, 지방산에스테르 및 염소화 방향족 탄화수소가 있으며 이들중에서 오르토디클로로벤젠이 적당하다.The amount of phosgene to be introduced is two to ten times stoichiometrically by means of ″ cold heat two-stage phosgenation ″ and ″ phosgenation of amine hydrochloride ″. Inert solvents include aromatic hydrocarbons, fatty acid esters and chlorinated aromatic hydrocarbons. Dichlorobenzene is suitable.

본 발명을 다음의 실시예와 관련하여 설명한다. 이들 실시예는 본 발명을 설명하는 것으로 본 발명의 범위를 한정하는 것은 아니다. 실시예는 일반식(a)에 있어서 A가 P-페닐렌기, m은 0,

Figure kpo00005
은 1의 화합물인 다음의 일반식(C)The present invention is explained in connection with the following examples. These examples illustrate the invention and do not limit the scope of the invention. In the formula (a), A is a P-phenylene group, m is 0,
Figure kpo00005
Is the compound of formula (1)

Figure kpo00006
Figure kpo00006

인 폴리파라크실릴렌-폴리페닐-폴리이소시아네이트에 대해서 설명한다.Phosphorus polyparaxylylene-polyphenyl-polyisocyanate is demonstrated.

[실시예 1]Example 1

일반식General formula

Figure kpo00007
Figure kpo00007

로 표현된 폴리파라크실릴렌-폴리아닐린을 포스겐화의 원료로 사용한다. 폴리아닐린 수지의 분자량 분포를 GPC컬럼을 사용하여 고속액체크로마토그라피로 분석한다. 분석결과분포를 보면, 일반식(b')의 화합물에 대해서 n=0일때 76.3wt%, n=1일때 18.7wt%, n=2일때 4.3wt%, n=3이상일때 0.7wt%이며, 평균분자량은 대략 350이고 과염소산-빙상의 아세트산 방법에 따른 수지의 아민당량은 0.653eq/100g이다.Polyparaxylylene-polyaniline represented by is used as a raw material for phosgenation. The molecular weight distribution of the polyaniline resin is analyzed by high performance liquid chromatography using a GPC column. As a result of analysis, the compound of general formula (b ') is 76.3 wt% when n = 0, 18.7wt% when n = 1, 4.3wt% when n = 2, and 0.7wt% when n = 3 or more. The average molecular weight is approximately 350 and the amine equivalent of the resin according to the acetic acid method of perchloric acid-ice phase is 0.653 eq / 100 g.

교반기, 온도계, 포스겐도입관, 냉각관, 적하깔대기가 부착된 2ℓ 반응플라스크에 오르토디클로로벤젠(ODCB) 682g을 장입한다. 반응플라스크를 교반하에 얼음물통에 놓아두어 플라스크의 내부온도를 1~2℃로 유지한다. 다음, 이곳에 100g/시간의 비율로 포스겐가스를 2시간동안 도입하고, 704g의 오르토디클로로벤젠내 상기 기술한 폴리아닐린 수지의 100g 용액을 45분 동안 적하한다. 또한 적하시 100g/시간의 비율로 포스겐가스를 도입시킨다. 이때의 온도는 2~8℃이다. 다음, 포스겐가스를 100g/시간의 비율로 도입하면서 4~5℃에서 30분간 냉포스겐화를 실행한다. 냉포스겐화는 카르바밀클로라이드와 아민염산염의 형성에 기인하여 반응플라스크에 황록색의 슬러리를 생성한다. 반응플라스크를 멘틀히터로 가열시켜 대략 45분이상 140℃로 상승시킨다. 온도상승동안 포스겐가스를 100g/시간의 비율로 장입한다. 온도를 상승시키는 과정에 슬러리는 염화수소가스를 심하게 방출하면서 오르토디클로로벤젠에 완전히 용해된다. 다음 열포스겐화를 100g/시간의 비율로 포스겐가스를 도입하면서 140℃에서 75분간 진행시킨다. 냉열 2단계 포스겐화에 의해 도입된 포스겐가스는 젠체 525g으로 이양은 이론치의 8.1배와 동량이다. 다음은, 반응액을 160℃의 온도로 상승시키고 그곳에 500ml/분의 비율로 2시간동안 질소가스를 도입시켜 용해된 가스성분을 제거하고 미반응의 카르바밀 클로라이드를 완전분해시킨다. 냉각후, 소량의 불용물을 여과하고 감압(대략 1mmHg)하에 증류하여 반응액에서 오르토디클로로벤젠을 제거시킨다. 즉, 119.8g의 폴리파라크실릴렌-폴리페닐-폴리이소시아네이트를 얻는다. 분석결과 NCO%는 23.5중량%(이론치 : 23.5중량%)이고, 가수분해성 염소함량은 0.28중량%이며, 산함량은 0.063중량%, 잔존 ODCB함량은 47중량 ppm이다.682 g of orthodichlorobenzene (ODCB) is charged to a 2 L reaction flask equipped with a stirrer, thermometer, phosgene introduction tube, cooling tube, and dropping funnel. The reaction flask is placed in an ice bucket with stirring to maintain the internal temperature of the flask at 1-2 ° C. Next, phosgene gas was introduced thereto for 2 hours at a rate of 100 g / hour, and a 100 g solution of the polyaniline resin described above in 704 g of orthodichlorobenzene was added dropwise for 45 minutes. In addition, phosgene gas is introduced at a rate of 100 g / hour upon dropping. The temperature at this time is 2-8 degreeC. Next, cold phosgenation is performed at 4-5 ° C. for 30 minutes while introducing phosgene gas at a rate of 100 g / hour. Cold phosgenation results in the formation of a yellowish green slurry in the reaction flask due to the formation of carbamyl chloride and amine hydrochloride. The reaction flask is heated to 140 ° C. for at least 45 minutes by heating with a mantle heater. Charge phosgene gas at a rate of 100 g / hour during the temperature rise. In the course of raising the temperature, the slurry dissolves completely in orthodichlorobenzene with severe release of hydrogen chloride gas. The heat phosgenation is then performed at 140 ° C. for 75 minutes while introducing phosgene gas at a rate of 100 g / hour. The phosgene gas introduced by cold-heat two-stage phosgenation is 525 g of porcine, which is equivalent to 8.1 times of theoretical value. Next, the reaction solution was raised to a temperature of 160 ° C. and nitrogen gas was introduced therein at a rate of 500 ml / min for 2 hours to remove dissolved gas components and to completely decompose unreacted carbamyl chloride. After cooling, a small amount of insolubles is filtered off and distilled under reduced pressure (approximately 1 mmHg) to remove orthodichlorobenzene from the reaction solution. That is, 119.8 g of polyparaxylylene-polyphenyl-polyisocyanate is obtained. As a result, NCO% was 23.5 wt% (theoretical value: 23.5 wt%), hydrolyzable chlorine content was 0.28 wt%, acid content was 0.063 wt%, and residual ODCB content was 47 wt ppm.

방향족 폴리이소시아네이트의 IR스펙트럼은 제1도에 나타내었다.The IR spectrum of the aromatic polyisocyanate is shown in FIG.

[실시예 2]Example 2

진공증류를 하여 실시예 1에서 얻은 방향족 폴리이소시아네이트 30g을 정제한다. 끊는 점 210~220℃ 10.2mmHg, 증류플라스크용 기름통온도를 220~240℃로 한 상태하에 대략 20g의 황색투명액을 얻는다. 액체생성물을 신속하게 고형화하여 녹는점 45~48℃의 결정으로 만든다. 이하 기술된 분석에 의한 결과 액체 생성물은 파라크실릴렌디페닐 이소시아네이트이며, 이것은 실시예 1에서 얻은 방향족 폴리이소시아네이트를 표현하는 일반식(C)에서 n=0인 일반식(C)로 표현된 화합물이다.Vacuum distillation purifies 30 g of the aromatic polyisocyanate obtained in Example 1. Break point Approximately 20 g of yellow transparent liquid is obtained under the condition of 210-220 ° C 10.2mmHg and the distillation flask sump temperature of 220-240 ° C. Rapidly solidify the liquid product to form crystals with a melting point of 45-48 ° C. The resultant liquid product by the analysis described below is paraxylylenediphenyl isocyanate, which is a compound represented by formula (C) with n = 0 in Formula (C) representing the aromatic polyisocyanate obtained in Example 1 .

Figure kpo00008
원소분석(C22H16N2O2) :
Figure kpo00008
Elemental Analysis (C 22 H 16 N 2 O 2 ):

계산치(%) : C ; 77.63, H ; 4.74, N : 8.23.Calculated (%): C; 77.63, H; 4.74, N: 8.23.

분석치(%) : C ; 77.86, H ; 4.35, N : 8.25.Analytical Value (%): C; 77.86, H; 4.35, N: 8.25.

Figure kpo00009
NCO중량% : 분석치 24.65%(계산치 24.69%)
Figure kpo00009
NCO weight%: Analytical value 24.65% (calculated 24.69%)

Figure kpo00010
IR스펙트럼 : 제2도
Figure kpo00010
IR Spectrum: 2nd

Figure kpo00011
H-NMR(CDCl3, TMS)ppm
Figure kpo00011
H-NMR (CDCl 3 , TMS) ppm

δ 3.92(4H-CH2-×2), 7.10(12H PH-H4×3)δ 3.92 (4H-CH 2- × 2), 7.10 (12H PH-H 4 × 3)

[실시예 3]Example 3

원료로서 화학식(b')로 표현된 폴리파라크실릴렌-폴리아닐린을 사용하여 실시예 1과 동일방법으로 포스겐화를 진행한다. 원료로서 사용된 폴리아닐린 수지의 분자량분포를 실시예 1과 동일한 분석방법에 따라 분석한다. 분석결과 분포를 보면 n=0일때 화학식(b')의 화합물은 56.5wt%, n=1일때 화합물은 26.5wt%, n=2일때 화합물은 10.1wt%, n=3일때 화합물은 5.6wt%, n

Figure kpo00012
4일때 화합물은 1.3wt%이다. 평균분자량은 대략 423이며 과염소산-빙상의 아세트산 방법에 따른 수지의 아민당량은 0.633eg/100g이다.The phosgenation is carried out in the same manner as in Example 1 using polyparaxylylene-polyaniline represented by the formula (b ') as a raw material. The molecular weight distribution of the polyaniline resin used as a raw material is analyzed according to the same analysis method as in Example 1. The analysis results show that the compound of formula (b ') is 56.5 wt% when n = 0, the compound is 26.5 wt% when n = 1, the compound is 10.1 wt% when n = 2, and the compound is 5.6 wt% when n = 3 , n
Figure kpo00012
When 4, the compound is 1.3 wt%. The average molecular weight is approximately 423 and the amine equivalent of the resin according to the acetic acid method of perchloric acid-ice phase is 0.633eg / 100g.

704g의 오르토디클로로벤젠에 100g의 폴리아닐린 수지를 용해하고 실시예 1과 동일한 방법으로 포스겐화를 진행한다. 냉열 2단계 포스겐화에 도입된 전체 포스겐가스는 400g이며 이양은 이론치의 6.4배에 상당한다. 연속하여, 반응액에서 용해된 가스성분을 제거하고 카르바밀 클로라이드를 완전히 분해한다. 냉각 및 여과를 행하고, 감압하에 증류하여 오르토디클로로벤젠을 제거하여 103.5g의 폴리파라크실릴렌-폴리페닐-폴리이소시아네이트를 얻는다. 분석결과 NCO%는 23.1중량%이고, 가용성 염소함량은 0.41중량%이며 산함량은 0.10중량%이다.100 g of polyaniline resin was dissolved in 704 g of orthodichlorobenzene and phosgenation was carried out in the same manner as in Example 1. The total phosgene gas introduced in the cold heat two-stage phosgenation is 400 g, which is equivalent to 6.4 times theoretical. Subsequently, dissolved gaseous components are removed from the reaction solution and carbamyl chloride is completely decomposed. After cooling and filtration, distillation under reduced pressure removes orthodichlorobenzene to obtain 103.5 g of polyparaxylylene-polyphenyl-polyisocyanate. The analysis shows that the NCO% is 23.1% by weight, the soluble chlorine content is 0.41% by weight and the acid content is 0.10% by weight.

본 발명의 방법에 따라 얻은 방향족 폴리이소시아네이트는 종래에 공지되지 않았던 전혀 새로운 화합물이므로 폴리우레탄수지 및 폴리우레아수지에 대한 원료로서 새로운 용도를 지니는 것으로 기대된다. 더우기, 방향족 폴리이소시아네이트에서 고진공 증류등의 방법으로 비교적 저분자 방향족 폴리이소시아네이트, 즉, 일반식(a)에 있어서 A는 P-페닐렌기, m은 0,

Figure kpo00013
은 1, n은 0(즉, 방향족 디이소시아네이트)인 화합물을 얻으며 이들은 완전히 새로운 화합물로 신규의 용도를 지닐 것으로 기대된다.The aromatic polyisocyanate obtained according to the method of the present invention is an entirely new compound that has not been known in the past, and thus is expected to have new use as a raw material for polyurethane resins and polyurea resins. Moreover, in the aromatic polyisocyanate, a relatively low molecular weight aromatic polyisocyanate, i.e., in general formula (a), is a P-phenylene group, m is 0,
Figure kpo00013
Silver 1, n is 0 (ie aromatic diisocyanate) compounds are obtained which are expected to have new uses as a completely new compound.

Claims (8)

일반식General formula
Figure kpo00014
Figure kpo00014
(식중 A는 페닐렌기, 알킬렌기, 알킬치환페닐렌기, 디페닐렌기, 디페닐에테르기 또는 나프틸렌일기를 표시하며 R1은 할로겐원자, 탄소수 4이하의 저급알콕시기 또는 탄소수 5이하의 저급알킬기로 R1은 서로 같거나 다를 수 있으며 고리를 형성할 수 있고,
Figure kpo00015
은 1 또는 2, m은 0~3의 정수, n은 0~300의 정수를 표시한다)로 표현된 방향족 폴리이소시아네이트의 혼합물을 포함하는 폴리이소시아네이트인 것을 특징으로 하는 방향족 폴리이소시아네이트.
(Wherein A represents a phenylene group, an alkylene group, an alkyl substituted phenylene group, a diphenylene group, a diphenyl ether group or a naphthyleneyl group, and R 1 represents a halogen atom, a lower alkoxy group having 4 or less carbon atoms or a lower alkyl group having 5 or less carbon atoms) R 1 may be the same as or different from each other and may form a ring,
Figure kpo00015
Is 1 or 2, m is an integer of 0 to 3, n represents an integer of 0 to 300), an aromatic polyisocyanate comprising a mixture of aromatic polyisocyanates represented by.
제1항에 있어서,
Figure kpo00016
은 1이고 m은 0인 것을 특징으로 하는 방향족 폴리이소시아네이트.
The method of claim 1,
Figure kpo00016
Is 1 and m is 0. 9.
제2항에 있어서, n은 0,1,2,3 또는 4인 방향족 폴리이소시아네이트의 혼합물을 포함하는 폴리이소시아네이트인 것을 특징으로 하는 방향족 폴리이소시아네이트.3. The aromatic polyisocyanate of claim 2 wherein n is a polyisocyanate comprising a mixture of aromatic polyisocyanates of 0,1,2,3 or 4. 제3항에 있어서, A는 페닐렌기인 것을 특징으로 하는 방향족 폴리이소시아네이트.The aromatic polyisocyanate according to claim 3, wherein A is a phenylene group. 제1항에 있어서, A는 페닐렌기인 것을 특징으로 하는 방향족 폴리이소시아네이트.The aromatic polyisocyanate according to claim 1, wherein A is a phenylene group. 제5항에 있어서,
Figure kpo00017
는 1이고 m은 0인 것을 특징으로 하는 방향족 폴리이소시아네이트.
The method of claim 5,
Figure kpo00017
Is 1 and m is 0.
제1항에 있어서, m은 2 또는 3이며 R1기의 2개는 측사슬을 지닐 수 있는 5~6개의 지방족고리를 형성하도록 결합되는 것을 특징으로 하는 방향족 폴리이소시아네이트.The aromatic polyisocyanate of claim 1, wherein m is 2 or 3 and two of the R 1 groups are bonded to form 5 to 6 aliphatic rings which may have side chains. 제5항에 있어서, A는 P-페닐렌기이며 n은 0인 것을 특징으로 하는 방향족 폴리이소시아네이트.The aromatic polyisocyanate according to claim 5, wherein A is a P-phenylene group and n is 0.
KR1019890002889A 1988-03-10 1989-03-09 Process for producing aromatic polyisocyanate KR930000374B1 (en)

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