JPH10158231A - Production of methylene cross-linked polyphenylene polyisocyanate containing diphenylmetane triisocyanate as main component - Google Patents
Production of methylene cross-linked polyphenylene polyisocyanate containing diphenylmetane triisocyanate as main componentInfo
- Publication number
- JPH10158231A JPH10158231A JP31919196A JP31919196A JPH10158231A JP H10158231 A JPH10158231 A JP H10158231A JP 31919196 A JP31919196 A JP 31919196A JP 31919196 A JP31919196 A JP 31919196A JP H10158231 A JPH10158231 A JP H10158231A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene polyisocyanate
- methylene
- triisocyanate
- diphenylmethane
- main component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 50
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 50
- -1 polyphenylene Polymers 0.000 title claims abstract description 42
- 229920000265 Polyparaphenylene Polymers 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 title abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 30
- ZNXHWPFMNPRKQA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C(C1=CC=CC=C1)C1=CC=CC=C1 Chemical class N=C=O.N=C=O.N=C=O.C(C1=CC=CC=C1)C1=CC=CC=C1 ZNXHWPFMNPRKQA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010409 thin film Substances 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 230000008020 evaporation Effects 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 16
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- GSJAIVTZOBRVKN-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C2C(C=CC=C3)=C3C3=CC=CC=C3C2=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C2C(C=CC=C3)=C3C3=CC=CC=C3C2=C1 GSJAIVTZOBRVKN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はジフェニルメタント
リイソシアネート類を含有するメチレン架橋ポリフェニ
レンポリイソシアネート混合物から特定の条件下での抽
出および薄膜型蒸発装置を用いた蒸発を組み合わせるこ
とによって、ジフェニルメタントリイソシアネート類を
主要成分とするメチレン架橋ポリフェニレンポリイソシ
アネートを分離する方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a process for extracting diphenylmethane triisocyanates from a methylene-bridged polyphenylene polyisocyanate mixture containing diphenylmethane triisocyanates by combining extraction under specific conditions and evaporation using a thin film type evaporator. The present invention relates to a method for separating a methylene-crosslinked polyphenylene polyisocyanate as a main component.
【０００２】本発明の目的物であるジフェニルメタント
リイソシアネート類を主要成分とするメチレン架橋ポリ
フェニレンポリイソシアネートは、従来のジフェニルメ
タンジイソシアネートおよびトリフェニレントリイソシ
アネートを主要成分とするメチレン架橋ポリフェニレン
ポリイソシアネートに比べて、架橋点間距離が小さく、
またＮＣＯ基の反応性差が大きいため、発泡したとき、
高耐久性、高反発弾性、低ヒステリシスロス等の物性の
向上が期待できる。また、その蒸気圧の高さから作業環
境改善が求められている、トリレンジイソシアネートの
代替としても有用である。The object of the present invention, the methylene-bridged polyphenylene polyisocyanate containing diphenylmethane triisocyanate as a main component, has a higher crosslinking point than the conventional methylene cross-linked polyphenylene polyisocyanate containing diphenylmethane diisocyanate and triphenylene triisocyanate as a main component. The distance between them is small,
Also, because of the large difference in reactivity between NCO groups,
Improvements in physical properties such as high durability, high resilience, and low hysteresis loss can be expected. It is also useful as a substitute for tolylene diisocyanate, which is required to improve the working environment because of its high vapor pressure.
【０００３】[0003]
【従来の技術】ジフェニルメタントリイソシアネート類
を含有するメチレン架橋ポリフェニレンポリイソシアネ
ート混合物はアニリンとホルムアルデヒドを縮合し、そ
こへ引き続き芳香族ジアミンを添加し得られたポリアミ
ン混合物のホスゲン化によって得られる。従って、ジフ
ェニルメタントリイソシアネート類を含有するメチレン
架橋ポリフェニレンポリイソシアネート混合物の組成は
原料のポリアミン混合物の組成によって決まり、ウレタ
ン形成時の反応性や分子構造を左右する重要な因子であ
るため、その組成を自由に変える技術が望まれている。2. Description of the Prior Art A methylene-bridged polyphenylene polyisocyanate mixture containing diphenylmethane triisocyanates is obtained by condensing aniline and formaldehyde and subsequently adding an aromatic diamine thereto to phosgenate the resulting polyamine mixture. Therefore, the composition of the methylene-crosslinked polyphenylene polyisocyanate mixture containing diphenylmethane triisocyanate is determined by the composition of the raw material polyamine mixture, and is an important factor influencing the reactivity and molecular structure during urethane formation. There is a demand for a technology to change the
【０００４】メチレン架橋ポリフェニレンポリイソシア
ネート混合物の抽出による精製については特開昭６０−
５８９５５に記載されているが、ここで使用している原
料のメチレン架橋ポリフェニレンポリイソシアネート混
合物はジフェニルメタンジイソシアネートおよび／ある
いはトリフェニレントリイソシアネートを主要成分とし
て含んだものであり、ジフェニルメタントリイソシアネ
ート類を含んだものではない。さらに、８０℃以上で抽
出を行っており、この方法をジフェニルメタントリイソ
シアネート類を含有するメチレン架橋ポリフェニレンポ
リイソシアネート混合物に応用した場合、多量の多核体
（３核体以上）ポリイソシアネート類が抽出相に含有
し、脱溶媒後、引き続き薄膜型蒸発装置を用いた蒸発を
行った際、粘度が高く薄膜型蒸発装置への供給が困難で
あり作業性が悪く、かつ低沸分への多核体（３核体以
上）ポリイソシアネート類の含有量が増加し好ましくな
い。The purification of a methylene-crosslinked polyphenylene polyisocyanate mixture by extraction is described in JP-A-60-1985.
No. 58955, the raw material methylene-crosslinked polyphenylene polyisocyanate mixture used herein contains diphenylmethane diisocyanate and / or triphenylene triisocyanate as a main component, and those containing diphenylmethane triisocyanate are not used. Absent. Furthermore, extraction is performed at 80 ° C. or higher, and when this method is applied to a methylene-crosslinked polyphenylene polyisocyanate mixture containing diphenylmethane triisocyanates, a large amount of polynuclear (three or more nuclei) polyisocyanates is contained in the extraction phase. After removing the solvent and removing the solvent, evaporation using a thin-film evaporator is continued, the viscosity is so high that supply to the thin-film evaporator is difficult, workability is poor, and the polynuclear substance (3 Nucleus) The content of polyisocyanates is undesirably increased.
【０００５】また、特開平５−３１０６７６では温度４
０℃未満で抽出することが挙げられているが、ここで原
料に使用しているメチレン架橋ポリフェニレンポリイソ
シアネート混合物もジフェニルメタンジイソシアネート
および／あるいはトリフェニレントリイソシアネートを
主要成分として含んだものであり、ジフェニルメタント
リイソシアネート類を含んだものではない。さらに、４
０℃未満で抽出を行っており、この方法をジフェニルメ
タントリイソシアネート類を含有するメチレン架橋ポリ
フェニレンポリイソシアネート混合物に応用した場合、
ジフェニルメタントリイソシアネート類の抽出率の低下
により収量が減少し問題がある。In Japanese Patent Application Laid-Open No. Hei 5-310676, a temperature of 4
Although extraction at a temperature lower than 0 ° C. is mentioned, the methylene-crosslinked polyphenylene polyisocyanate mixture used here as a raw material also contains diphenylmethane diisocyanate and / or triphenylene triisocyanate as a main component. It does not include any kind. In addition, 4
When the extraction is performed at a temperature lower than 0 ° C., and this method is applied to a methylene-crosslinked polyphenylene polyisocyanate mixture containing diphenylmethane triisocyanates,
There is a problem that the yield is reduced due to a decrease in the extraction rate of diphenylmethane triisocyanate.
【０００６】さらに抽出後、蒸留法による多核体（３核
体以上）ポリイソシアネート類の除去が考えられるが、
通常の蒸留法では熱履歴によりジフェニルメタントリイ
ソシアネート類のタール化が起こり、収量が減少してし
まう。After the extraction, removal of polynuclear (three or more) polyisocyanates by a distillation method is considered.
In the ordinary distillation method, tarification of diphenylmethane triisocyanates occurs due to heat history, and the yield decreases.
【０００７】[0007]
【発明が解決しようとする課題】本発明は上記製造法の
欠点を解決し、工業的に有用なジフェニルメタントリイ
ソシアネート類を主要成分とするメチレン架橋ポリフェ
ニレンポリイソシアネートの製造法を提供することであ
る。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned disadvantages of the production method and to provide a method for producing an industrially useful methylene-crosslinked polyphenylene polyisocyanate containing diphenylmethane triisocyanate as a main component.
【０００８】[0008]
【課題を解決するための手段】本発明者らは上記のジフ
ェニルメタントリイソシアネート類を含有するメチレン
架橋ポリフェニレンポリイソシアネート混合物から効率
よく、ジフェニルメタントリイソシアネート類を主要成
分とするメチレン架橋ポリフェニレンポリイソシアネー
トを製造する方法を鋭意検討した結果、ジフェニルメタ
ントリイソシアネート類を含有するメチレン架橋ポリフ
ェニレンポリイソシアネート混合物から特定の条件下で
抽出を行い、引き続き薄膜型蒸発装置を用いた蒸発を行
うことによって、多核体（３核体以上）のポリイソシア
ネート類を除去でき、ジフェニルメタントリイソシアネ
ート類を主要成分とするメチレン架橋ポリフェニレンポ
リイソシアネートが得られることを見い出し、本発明を
完成した。Means for Solving the Problems The present inventors efficiently produce a methylene-crosslinked polyphenylene polyisocyanate containing diphenylmethane triisocyanate as a main component from the above methylene-crosslinked polyphenylene polyisocyanate mixture containing diphenylmethane triisocyanate. As a result of diligent studies of the method, extraction from a methylene-bridged polyphenylene polyisocyanate mixture containing diphenylmethane triisocyanate under specific conditions and subsequent evaporation using a thin film type evaporator gave a polynuclear (trinuclear) It has been found that the above-mentioned polyisocyanates can be removed and a methylene-crosslinked polyphenylene polyisocyanate containing diphenylmethane triisocyanate as a main component can be obtained, and the present invention has been completed.
【０００９】即ち、本発明はジフェニルメタントリイソ
シアネート類を含有するメチレン架橋ポリフェニレンポ
リイソシアネート混合物から、 １）炭素数が５以上の脂肪族および／または脂環式炭化
水素を用い、 ２）温度４０℃以上８０℃未満で抽出し、 ３）引き続き、薄膜型蒸発装置を用いた蒸発を行うこと
を特徴とするジフェニルメタントリイソシアネート類を
主要成分とするメチレン架橋ポリフェニレンポリイソシ
アネートの製造法である。That is, the present invention provides a method for producing a methylene-bridged polyphenylene polyisocyanate mixture containing diphenylmethane triisocyanate, which comprises the following steps: 1) using an aliphatic and / or alicyclic hydrocarbon having 5 or more carbon atoms; 3) A method for producing a methylene-crosslinked polyphenylene polyisocyanate containing diphenylmethane triisocyanate as a main component, wherein the extraction is carried out at a temperature lower than 80 ° C., and 3) subsequent evaporation using a thin film evaporator.
【００１０】[0010]
【発明の実施の形態】以下に本発明を詳細に説明する。
本発明に使用できるジフェニルメタントリイソシアネー
ト類を含有するメチレン架橋ポリフェニレンポリイソシ
アネートは、酸触媒の存在下、アニリンとホルムアルデ
ヒドを縮合し、そこへ引き続き芳香族ジアミンを添加し
得られたポリアミン混合物のホスゲン化によって得られ
る混合物である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The methylene-bridged polyphenylene polyisocyanate containing diphenylmethane triisocyanate which can be used in the present invention is obtained by condensing aniline and formaldehyde in the presence of an acid catalyst, and subsequently adding an aromatic diamine thereto to phosgenate the resulting polyamine mixture. The resulting mixture.
【００１１】ここで得られたジフェニルメタントリイソ
シアネート類を含有するメチレン架橋ポリフェニレンポ
リイソシアネート混合物中のジフェニルメタンジイソシ
アネートの含有率は０〜５０％であるが、含有量が多い
と得られたメチレン架橋ポリフェニレンポリイソシアネ
ート中のジフェニルメタントリイソシアネート類の含有
率が低下するので、好ましくは２０％以下が有利であ
る。The content of diphenylmethane diisocyanate in the resulting methylene-crosslinked polyphenylene polyisocyanate mixture containing diphenylmethane triisocyanate is 0 to 50%, but when the content is large, the obtained methylene-crosslinked polyphenylene polyisocyanate is obtained. Since the content of diphenylmethane triisocyanate therein decreases, the content is preferably 20% or less.
【００１２】本発明に使用できる溶媒は、ペンタン、ヘ
キサン、ヘプタン、オクタン等の炭素数５以上の脂肪族
炭化水素、シクロヘキサン、メチルシクロヘキサン、シ
クロオクタン等の炭素数５以上の脂環式炭化水素あるい
は、これらの溶媒を任意の割合で混合した溶媒である。
好ましくは、ジフェニルメタントリイソシアネート類の
収量が多い脂環式炭化水素である。Solvents usable in the present invention include aliphatic hydrocarbons having 5 or more carbon atoms such as pentane, hexane, heptane and octane; alicyclic hydrocarbons having 5 or more carbon atoms such as cyclohexane, methylcyclohexane and cyclooctane; , A solvent obtained by mixing these solvents in an arbitrary ratio.
Preferably, it is an alicyclic hydrocarbon having a high yield of diphenylmethane triisocyanates.
【００１３】抽出に必要な溶媒量はジフェニルメタント
リイソシアネート類を含有するメチレン架橋ポリフェニ
レンポリイソシアネート混合物に対し１〜５０重量倍で
あり、容積効率を考慮すると好ましくは１〜５重量倍で
ある。The amount of the solvent required for the extraction is 1 to 50 times by weight based on the methylene-crosslinked polyphenylene polyisocyanate mixture containing diphenylmethane triisocyanate, and preferably 1 to 5 times by weight in view of the volumetric efficiency.
【００１４】抽出温度が４０℃未満ではジフェニルメタ
ントリイソシアネート類の収量が減少し、８０℃以上で
は抽出相の多核体（３核体以上）ポリイソシアネート類
の含有量が増加し、脱溶媒後、薄膜型蒸発装置を用いた
蒸発を行った際、粘度が高く薄膜型蒸発装置への供給が
困難であり作業性が悪く、かつ低沸分への多核体（３核
体以上）ポリイソシアネート類の含有量が増加し好まし
くない。したがって、好ましい抽出温度は４０℃以上８
０℃未満、さらに好ましくは５０℃以上７０℃以下であ
る。When the extraction temperature is lower than 40 ° C., the yield of diphenylmethane triisocyanates decreases. When the extraction temperature is higher than 80 ° C., the content of polynuclear (trinuclear or higher) polyisocyanates in the extraction phase increases. When evaporation using a vacuum evaporator is carried out, the viscosity is so high that supply to the thin film vaporizer is difficult, workability is poor, and polynuclear (three or more) polyisocyanates are contained in a low boiling point. The amount increases, which is not preferable. Therefore, a preferable extraction temperature is 40 ° C. or more and 8
The temperature is less than 0 ° C, more preferably 50 ° C or more and 70 ° C or less.
【００１５】抽出法としては槽型、向流型等、一般に知
られている抽出法を採用することができる。As the extraction method, generally known extraction methods such as a tank type and a countercurrent type can be employed.
【００１６】また、本発明方法において、抽出は常圧下
ではもちろんのこと、加圧下、減圧下でも行うことがで
きる。In the method of the present invention, the extraction can be performed not only under normal pressure but also under increased or reduced pressure.
【００１７】さらに本発明方法は抽出後、薄膜型蒸発装
置を用いた蒸発により多核体（３核体以上）ポリイソシ
アネート類を除去する場合、通常の方法が採用できる。
例えば、加熱温度１９０℃、真空度０．３ｍｍＨｇ、供
給速度７．０ｇ／ｍｉｎの条件下で蒸発を行い、多核体
（３核体以上）ポリイソシアネート類を除去することが
できる。また、薄膜型蒸発装置を用いた蒸発の代わりに
通常の蒸留法により多核体（３核体以上）ポリイソシア
ネート類を除去しようとした場合、熱履歴によりジフェ
ニルメタントリイソシアネート類のタール化が起こり、
収量が減少してしまう。Further, in the method of the present invention, when polynuclear (three or more nuclei) polyisocyanates are removed by evaporation using a thin film type evaporator after extraction, a usual method can be adopted.
For example, polynuclear (three or more) polyisocyanates can be removed by performing evaporation under the conditions of a heating temperature of 190 ° C., a degree of vacuum of 0.3 mmHg, and a supply rate of 7.0 g / min. When polynuclear (three or more) polyisocyanates are to be removed by a normal distillation method instead of evaporation using a thin film evaporator, tarification of diphenylmethane triisocyanates occurs due to heat history,
The yield is reduced.
【００１８】[0018]
【実施例】以下、実施例により本発明をさらに詳細に説
明する。 実施例１ ３００重量部のメチレン架橋ポリフェニレンポリイソシ
アネート混合物（ジフェニルメタンジイソシアネート
０．５％、２，４，４’−ジフェニルメタントリイソシ
アネート ４２．０％、多核体（３核体以上）ポリイソ
シアネート類５７．５％）に９００重量部のシクロヘキ
サンを加え、７０℃で６０分間撹拌し、３０分間静置し
た後、下相を分液除去した。上相から溶媒を留去すると
１８３重量部のメチレン架橋ポリフェニレンポリイソシ
アネート混合物（ジフェニルメタンジイソシアネート
０．７％、２，４，４’−ジフェニルメタントリイソシ
アネート６２．３％、、多核体（３核体以上）ポリイソ
シアネート類 ３７．０％）が得られた。得られたメチ
レン架橋ポリフェニレンポリイソシアネート混合物を加
熱温度１９０℃、真空度０．３ｍｍＨｇの薄膜型蒸発装
置（神鋼フアウドラー株式会社製ガラス薄膜蒸発装置、
蒸発面積０．０３４ｍ２）内に供給速度７．０ｇ／ｍｉ
ｎで供給し、低沸分として２，４，４’−ジフェニルメ
タントリイソシアネートを主要成分とするメチレン架橋
ポリフェニレンポリイソシアネートが得られた。最終的
な分析値と収量を表１に示す。The present invention will be described in more detail with reference to the following examples. Example 1 300 parts by weight of a methylene-crosslinked polyphenylene polyisocyanate mixture (diphenylmethane diisocyanate)
To 0.5%, 42.0% of 2,4,4'-diphenylmethane triisocyanate, 57.5% of polynuclear (three or more nuclei) polyisocyanates, 900 parts by weight of cyclohexane is added, and the mixture is added at 70 ° C. for 60 minutes. After stirring and standing for 30 minutes, the lower phase was separated and removed. The solvent was distilled off from the upper phase to obtain 183 parts by weight of a methylene-crosslinked polyphenylene polyisocyanate mixture (diphenylmethane diisocyanate).
0.7%, 62.3% of 2,4,4'-diphenylmethane triisocyanate, and 37.0% of polynuclear (three or more) polyisocyanates were obtained. The obtained methylene-crosslinked polyphenylene polyisocyanate mixture was heated at a heating temperature of 190 ° C. and a degree of vacuum of 0.3 mmHg in a thin film evaporator (a glass thin film evaporator manufactured by Shinko Faudler Co., Ltd.
Feed rate 7.0 g / mi within evaporation area 0.034 m2)
n, and methylene-crosslinked polyphenylene polyisocyanate containing 2,4,4'-diphenylmethane triisocyanate as a main component as a low boiling point was obtained. Table 1 shows the final analytical values and yields.
【００１９】実施例２ ４５０重量部のシクロヘキサンを用いた以外は実施例１
と同様に行った。最終的な分析値と収量を表１に示す。Example 2 Example 1 except that 450 parts by weight of cyclohexane were used.
The same was done. Table 1 shows the final analytical values and yields.
【００２０】実施例３ ４０℃で抽出する以外は実施例１と同様に行った。。最
終的な分析値と収量を表１に示す。Example 3 The procedure of Example 1 was repeated, except that extraction was performed at 40 ° C. . Table 1 shows the final analytical values and yields.
【００２１】実施例４ ヘキサンを用いて４０℃で抽出する以外は実施例１と同
様に行った。最終的な分析値と収量を表１に示す。Example 4 The procedure of Example 1 was repeated, except that extraction was performed at 40 ° C. with hexane. Table 1 shows the final analytical values and yields.
【００２２】実施例５ ４５０重量部のヘキサンを用いて４０℃で抽出する以外
は実施例１と同様に行った。最終的な分析値と収量を表
１に示す。Example 5 The procedure of Example 1 was repeated except that the mixture was extracted at 450 ° C. with 450 parts by weight of hexane. Table 1 shows the final analytical values and yields.
【００２３】比較例１ ８０℃で抽出する以外は実施例１と同様に行った。最終
的な分析値と収量を表１に示す。Comparative Example 1 The procedure of Example 1 was repeated, except that extraction was performed at 80 ° C. Table 1 shows the final analytical values and yields.
【００２４】比較例２ ３０℃で抽出する以外は実施例１と同様に行った。最終
的な分析値と収量を表１に示す。Comparative Example 2 The procedure of Example 1 was repeated, except that extraction was performed at 30 ° C. Table 1 shows the final analytical values and yields.
【００２５】比較例３ ３００重量部のメチレン架橋ポリフェニレンポリイソシ
アネート混合物（ジフェニルメタンジイソシアネート
０．５％、２，４，４’−ジフェニルメタントリイソシ
アネート ４２．０％、多核体（３核体以上）ポリイソ
シアネート類５７．５％）に９００重量部のシクロヘキ
サンを加え、７０℃で６０分間撹拌し、３０分間静置し
た後、下相を分液除去した。上相から溶媒を留去すると
１８３重量部のメチレン架橋ポリフェニレンポリイソシ
アネート（ジフェニルメタンジイソシアネート ０．７
％、２，４，４’−ジフェニルメタントリイソシアネー
ト６２．３％、多核体（３核体以上）ポリイソシアネー
ト類 ３７．０％）混合物が得られた。得られたメチレ
ン架橋ポリフェニレンポリイソシアネート混合物を加熱
温度１９０℃、真空度０．３ｍｍＨｇの条件下、蒸留に
より留出液として２，４，４’−ジフェニルメタントリ
イソシアネートを主要成分とするメチレン架橋ポリフェ
ニレンポリイソシアネートが得られた。最終的な分析値
と収量を表１に示す。Comparative Example 3 300 parts by weight of a methylene-crosslinked polyphenylene polyisocyanate mixture (diphenylmethane diisocyanate)
To 0.5%, 42.0% of 2,4,4'-diphenylmethane triisocyanate, 57.5% of polynuclear (three or more nuclei) polyisocyanates, 900 parts by weight of cyclohexane is added, and the mixture is added at 70 ° C. for 60 minutes. After stirring and standing for 30 minutes, the lower phase was separated and removed. When the solvent was distilled off from the upper phase, 183 parts by weight of methylene-crosslinked polyphenylene polyisocyanate (diphenylmethane diisocyanate 0.7
%, 2,4,4'-diphenylmethane triisocyanate, 62.3%, and a mixture of polynuclear (three or more) polyisocyanates (37.0%). The obtained methylene-crosslinked polyphenylene polyisocyanate mixture is distilled by distillation under the conditions of a heating temperature of 190 ° C. and a degree of vacuum of 0.3 mmHg, and as a distillate, a methylene-crosslinked polyphenylene polyisocyanate containing 2,4,4′-diphenylmethane triisocyanate as a main component was gotten. Table 1 shows the final analytical values and yields.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】本発明によれば、特定の条件下での抽出
操作と薄膜型蒸発装置を用いた蒸発操作を組み合わせる
ことにより、工業的に有用なジフェニルメタントリイソ
シアネート類を主要成分とするメチレン架橋ポリフェニ
レンポリイソシアネートを効率的に製造することができ
る。According to the present invention, a methylene bridge containing industrially useful diphenylmethane triisocyanates as a main component is obtained by combining an extraction operation under specific conditions and an evaporation operation using a thin film evaporator. Polyphenylene polyisocyanate can be produced efficiently.
Claims (1)
含有するメチレン架橋ポリフェニレンポリイソシアネー
ト混合物から、 １）炭素数が５以上の脂肪族および／または脂環式炭化
水素を用い、 ２）温度４０℃以上８０℃未満で抽出し、 ３）引き続き、薄膜型蒸発装置を用いた蒸発を行うこと
を特徴とするジフェニルメタントリイソシアネート類を
主要成分とするメチレン架橋ポリフェニレンポリイソシ
アネートの製造法。1. A methylene-crosslinked polyphenylene polyisocyanate mixture containing diphenylmethane triisocyanate, comprising: 1) an aliphatic and / or alicyclic hydrocarbon having 5 or more carbon atoms, and 2) a temperature of 40 ° C. to less than 80 ° C. 3) A method for producing a methylene-crosslinked polyphenylene polyisocyanate containing diphenylmethane triisocyanate as a main component, which is followed by evaporation using a thin film evaporator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31919196A JPH10158231A (en) | 1996-11-29 | 1996-11-29 | Production of methylene cross-linked polyphenylene polyisocyanate containing diphenylmetane triisocyanate as main component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31919196A JPH10158231A (en) | 1996-11-29 | 1996-11-29 | Production of methylene cross-linked polyphenylene polyisocyanate containing diphenylmetane triisocyanate as main component |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10158231A true JPH10158231A (en) | 1998-06-16 |
Family
ID=18107433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31919196A Pending JPH10158231A (en) | 1996-11-29 | 1996-11-29 | Production of methylene cross-linked polyphenylene polyisocyanate containing diphenylmetane triisocyanate as main component |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10158231A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007115971A1 (en) * | 2006-04-12 | 2007-10-18 | Basf Se | Process for preparing polyurethanes |
| KR101215428B1 (en) | 2004-07-21 | 2012-12-26 | 미쯔이카가쿠 가부시기가이샤 | Process for the preparation of methylene？bridged polyphenylene polyisocynate |
-
1996
- 1996-11-29 JP JP31919196A patent/JPH10158231A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101215428B1 (en) | 2004-07-21 | 2012-12-26 | 미쯔이카가쿠 가부시기가이샤 | Process for the preparation of methylene？bridged polyphenylene polyisocynate |
| WO2007115971A1 (en) * | 2006-04-12 | 2007-10-18 | Basf Se | Process for preparing polyurethanes |
| RU2444536C9 (en) * | 2006-04-12 | 2013-07-10 | Басф Се | Method of producing polyurethanes |
| US8592497B2 (en) | 2006-04-12 | 2013-11-26 | Basf Aktiengesellschaft | Process for preparing polyurethanes |
| KR101502441B1 (en) * | 2006-04-12 | 2015-03-17 | 바스프 에스이 | Process for producing polyurethane |
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