JP4920187B2 - Method for producing methylene-crosslinked polyphenylene polyisocyanate - Google Patents
Method for producing methylene-crosslinked polyphenylene polyisocyanate Download PDFInfo
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- -1 polyphenylene Polymers 0.000 title claims description 32
- 229920000265 Polyparaphenylene Polymers 0.000 title claims description 30
- 229920001228 polyisocyanate Polymers 0.000 title claims description 29
- 239000005056 polyisocyanate Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000000034 method Methods 0.000 claims description 38
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 33
- 239000011541 reaction mixture Substances 0.000 claims description 27
- 150000001491 aromatic compounds Chemical class 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012442 inert solvent Substances 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229920000768 polyamine Polymers 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 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 60
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 18
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 16
- 238000002835 absorbance Methods 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229960004889 salicylic acid Drugs 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001577 simple distillation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
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- UYDGECQHZQNTQS-UHFFFAOYSA-N 2-amino-4,6-dimethylpyridine-3-carboxamide Chemical compound CC1=CC(C)=C(C(N)=O)C(N)=N1 UYDGECQHZQNTQS-UHFFFAOYSA-N 0.000 description 1
- ZHLQYPNVDAMSFD-UHFFFAOYSA-N 2-hydroxy-3-methyl-6-propan-2-ylbenzoic acid Chemical compound CC(C)C1=CC=C(C)C(O)=C1C(O)=O ZHLQYPNVDAMSFD-UHFFFAOYSA-N 0.000 description 1
- ZJWUEJOPKFYFQD-UHFFFAOYSA-N 2-hydroxy-3-phenylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1O ZJWUEJOPKFYFQD-UHFFFAOYSA-N 0.000 description 1
- XGAYQDWZIPRBPF-UHFFFAOYSA-N 2-hydroxy-3-propan-2-ylbenzoic acid Chemical compound CC(C)C1=CC=CC(C(O)=O)=C1O XGAYQDWZIPRBPF-UHFFFAOYSA-N 0.000 description 1
- DLGBEGBHXSAQOC-UHFFFAOYSA-N 2-hydroxy-5-methylbenzoic acid Chemical compound CC1=CC=C(O)C(C(O)=O)=C1 DLGBEGBHXSAQOC-UHFFFAOYSA-N 0.000 description 1
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- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- NJESAXZANHETJV-UHFFFAOYSA-N 4-methylsalicylic acid Chemical compound CC1=CC=C(C(O)=O)C(O)=C1 NJESAXZANHETJV-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
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- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、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方法に関する。 The present invention relates to a method for producing a methylene-bridged polyphenylene polyisocyanate.
メチレン架橋ポリフェニレンポリイソシアネート（以下、「ポリＭＤＩ」と略記）は、工業的には、酸触媒の存在下、アニリンとホルムアルデヒドとの縮合により生成するポリアミン混合物を溶媒下でホスゲンと反応させ、次いで溶媒を除去した後、減圧蒸留によってジフェニルメタンジイソシアネート（以下ＭＤＩと略記）を分離することにより製造され、所望のＭＤＩ含有量および粘度を有するポリＭＤＩに調整されるのが一般的である。しかし、この方法により得られたポリＭＤＩは、蒸留による精製ができないために製造過程での着色がそのまま製品の着色となり、暗色を示す。この結果、このポリＭＤＩから形成される発泡体も着色し、無色にはならない。この着色は、機械特性に悪影響を及ぼすものではないが、使用者は本質的に無色のものを好み、また、無色のものは着色したものよりも用途範囲が広がる。 Methylene-bridged polyphenylene polyisocyanate (hereinafter abbreviated as “poly MDI”) is industrially produced by reacting a polyamine mixture formed by condensation of aniline and formaldehyde with phosgene in a solvent in the presence of an acid catalyst, In general, it is produced by separating diphenylmethane diisocyanate (hereinafter abbreviated as MDI) by distillation under reduced pressure, and adjusted to poly MDI having a desired MDI content and viscosity. However, since the poly MDI obtained by this method cannot be purified by distillation, the color in the production process becomes the color of the product as it is and shows a dark color. As a result, the foam formed from this poly-MDI is also colored and does not become colorless. Although this coloring does not adversely affect the mechanical properties, the user prefers the essentially colorless one, and the colorless one has a wider range of applications than the colored one.
ポリＭＤＩの色相改善については、多くの方法が知られている。たとえば、特許文献１には、ポリＭＤＩから着色成分を除去する方法が開示されている。この方法は、抽出溶媒として炭素数８以上の脂肪族炭化水素を用いて、ポリＭＤＩを８０〜１８０℃で抽出し、タール分を除去する方法である。しかし、抽出溶媒の除去や抽出されなかったタール分の処理が必要になるため、工業的製法として好ましい方法ではない。また、特許文献２には、ホスゲン化された粗生成物に添加剤を添加する方法が開示されている。この方法は、ホスゲン化の完了後で反応混合物からのホスゲンの除去の完了前に水を添加する方法である。しかし、この方法は、得られるポリＭＤＩのイソシアネート含有率の低下および粘度の増加を引き起こすという点で好ましくない。ポリＭＤＩの着色を抑える方法として、さらに、ホスゲン化終了後、ホスゲン含有混合物に種々の添加物を添加する方法がある。特許文献３には、低分子量アルカノールおよび／または多価アルコールを添加する方法、特許文献４には、ポリオキシアルキレンアルコールを添加する方法、特許文献５には、カルボン酸を添加する方法が記載されている。しかしながら、これらの方法は、いずれも得られる粗ＭＤＩの酸度を上昇させる二次的反応を伴い、得られたポリＭＤＩの品質が低下するという点で好ましくない。
本発明は、蒸留による精製が困難なために製造過程での着色がそのまま製品の着色の原因となる従来の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方法を改良したものであって、簡便かつ効果的にメチレン架橋ポリフェニレンポリイソシアネートの着色を抑制する製造方法を提供することを課題としている。 The present invention is an improvement of a conventional method for producing a methylene-bridged polyphenylene polyisocyanate in which coloring in the production process causes coloring of the product as it is because purification by distillation is difficult. An object of the present invention is to provide a production method that suppresses coloring of the crosslinked polyphenylene polyisocyanate.
本発明者は、上記問題点を解決すべく鋭意研究し、驚くべきことに、従来の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方法におけるホスゲン化反応終了後、ホスゲン含有反応混合物からホスゲンを除去し、得られた粗製のポリＭＤＩに水酸基とカルボキ
シル基を含有する特定の芳香族化合物を添加して加熱処理するという簡便かつ経済的な方法によって、着色が少ないメチレン架橋ポリフェニレンポリイソシアネートを、二次的反応が原因である最終製品の酸度の上昇を伴うことなく製造できることを見出し、本発明を完成するに至った。
The present inventor has eagerly studied to solve the above problems, and surprisingly, after the phosgenation reaction in the conventional method for producing a methylene-bridged polyphenylene polyisocyanate is completed, phosgene is removed from the phosgene-containing reaction mixture. Due to the secondary reaction, methylene-crosslinked polyphenylene polyisocyanate with little coloration is produced by a simple and economical method in which a specific aromatic compound containing a hydroxyl group and a carboxyl group is added to the crude poly MDI and heated. It was found that the final product can be produced without increasing the acidity, and the present invention was completed.
すなわち、本発明に係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方法は、酸触媒の存在下でアニリンとホルムアルデヒドとの縮合反応により生成したポリアミン混合物を、不活性溶媒の存在下、ホスゲンと反応させて、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において、
（１）上記ホスゲン化反応後、得られた粗製のメチレン架橋ポリフェニレンポリイソシアネートを含む反応混合物から残存ホスゲンを除去した後、
（２）該粗製のメチレン架橋ポリフェニレンポリイソシアネートに、下記式（Ｉ）
That is, the method for producing a methylene-bridged polyphenylene polyisocyanate according to the present invention comprises reacting a polyamine mixture formed by the condensation reaction of aniline and formaldehyde in the presence of an acid catalyst with phosgene in the presence of an inert solvent, In a method for producing a crosslinked polyphenylene polyisocyanate,
(1) After removing the residual phosgene from the reaction mixture containing the crude methylene-crosslinked polyphenylene polyisocyanate obtained after the phosgenation reaction,
(2) To the crude methylene-crosslinked polyphenylene polyisocyanate, the following formula (I)
（式中、Ｒ1、Ｒ2、Ｒ3およびＲ4は、それぞれ独立に、水素または炭素数１〜６の炭化水素基である。）
で表されるオルト位にカルボキシル基を有する水酸基含有芳香族化合物を加えて加熱処理することを特徴としている。
(Wherein R 1 , R 2 , R 3 and R 4 are each independently hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.)
It is characterized by adding a hydroxyl group-containing aromatic compound having a carboxyl group to the ortho position represented by
前記粗製のメチレン架橋ポリフェニレンポリイソシアネート１００重量部に対して、上記（Ｉ）で表される水酸基を有する芳香族化合物を、好ましくは１重量部以下、より好ましくは０．４重量部以下の量添加することが望ましい。 The aromatic compound having a hydroxyl group represented by the above (I) is preferably added in an amount of not more than 1 part by weight, more preferably not more than 0.4 parts by weight with respect to 100 parts by weight of the crude methylene-bridged polyphenylene polyisocyanate. It is desirable to do.
上記工程（１）において、好ましくは１８０℃以下、より好ましくは１４０℃以下の温度で加熱して残存ホスゲンを除去することが望ましい。
上記工程（２）において、好ましくは３０〜１８０℃、より好ましくは５０〜１４０℃の範囲の温度で加熱処理することが望ましい。
In the step (1), it is preferable to remove residual phosgene by heating at a temperature of preferably 180 ° C. or lower, more preferably 140 ° C. or lower.
In the step (2), the heat treatment is preferably performed at a temperature in the range of preferably 30 to 180 ° C, more preferably 50 to 140 ° C.
本発明によると、色相に優れたメチレン架橋ポリフェニレンポリイソシアネートを簡便に製造することができる。また、本発明は、従来の方法と比較して、二次的副生成物による品質の低下を防ぐことができるという点で有用である。 According to the present invention, a methylene-bridged polyphenylene polyisocyanate excellent in hue can be easily produced. In addition, the present invention is useful in that the deterioration of quality due to secondary byproducts can be prevented as compared with the conventional method.
以下、本発明に係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方法を詳細に説明する。
〔粗製ポリＭＤＩの製造〕
ホスゲン化反応に使用するポリアミン混合物は、塩酸などの酸触媒の存在下、アニリンとホルムアルデヒドとの縮合反応により生成するメチレン架橋ポリフェニレンポリアミン（以下、「ポリＭＤＡ」と略記。）を含有する混合物である。ポリＭＤＡの組成は、縮合
時のアニリン／酸／ホルムアルデヒドの混合比および縮合温度によって異なるが、本発明では、いずれの組成のポリＭＤＡも使用できる。
Hereinafter, the manufacturing method of the methylene bridge | crosslinking polyphenylene polyisocyanate which concerns on this invention is demonstrated in detail.
[Production of crude poly-MDI]
The polyamine mixture used for the phosgenation reaction is a mixture containing a methylene-bridged polyphenylene polyamine (hereinafter abbreviated as “poly MDA”) formed by the condensation reaction of aniline and formaldehyde in the presence of an acid catalyst such as hydrochloric acid. . The composition of poly MDA varies depending on the mixing ratio of aniline / acid / formaldehyde at the time of condensation and the condensation temperature, but in the present invention, any composition of poly MDA can be used.
このようなポリアミン混合物を不活性溶媒の存在下でホスゲンと反応させることにより、粗製のメチレン架橋ポリフェニレンポリイソシアネート（以下、「粗製ポリＭＤＩ」と略記）が得られる。この粗製ポリＭＤＩは、４，４−ＭＤＩ、２，４−ＭＤＩ、２，２−ＭＤＩ、３個以上のイソシアネート基を有するポリＭＤＩ同族体および同定されていない副生成物を含有する。 By reacting such a polyamine mixture with phosgene in the presence of an inert solvent, crude methylene-bridged polyphenylene polyisocyanate (hereinafter abbreviated as “crude poly MDI”) is obtained. This crude poly MDI contains 4,4-MDI, 2,4-MDI, 2,2-MDI, poly MDI homologs with 3 or more isocyanate groups and unidentified by-products.
ホスゲン化に使用される不活性溶媒は、有機イソシアネート類の製造に通常用いられる溶媒であれば、特に制限されない。たとえば、トルエン、キシレン等の芳香族炭化水素類；クロロトルエン、クロロベンゼン、ジクロロベンゼン等のハロゲン化芳香族炭化水素類；酢酸ブチル、酢酸アミル等のエステル類；およびメチルイソブチル等のケトン類等が挙げられる。 The inert solvent used for phosgenation is not particularly limited as long as it is a solvent usually used for the production of organic isocyanates. Examples include aromatic hydrocarbons such as toluene and xylene; halogenated aromatic hydrocarbons such as chlorotoluene, chlorobenzene, and dichlorobenzene; esters such as butyl acetate and amyl acetate; and ketones such as methyl isobutyl. It is done.
ホスゲン化の方法は、一般的に用いられている方法であれば特に限定されず、塩酸塩法、冷熱２段法、ホスゲン加圧法などいかなる方法も適用できる。
〔残存ホスゲンの除去〕
上記ホスゲン化反応後の反応混合物には、粗製ポリＭＤＩと不活性溶媒と残存ホスゲンとが含まれている。本発明では、加熱、減圧または不活性ガスの装入、あるいはこれらを適宜組み合わせた方法により、上記反応混合物から残存ホスゲンを除去することができる。具体的には、ホスゲンが残存する反応混合物を、好ましくは１００℃以上１８０℃以下の範囲に加熱し、窒素、ヘリウム、アルゴン等の不活性ガスを装入したり、あるいは減圧下で不活性溶媒の沸点まで加熱したりすることにより残存ホスゲンを除去できる。これらのうち、減圧法が効率的に残存ホスゲンを除去できる点で好ましい。このような操作により、反応混合物中の残存ホスゲンの量を１重量％以下にすることができる。
The phosgenation method is not particularly limited as long as it is a generally used method, and any method such as a hydrochloride method, a two-stage cooling method, and a phosgene pressurization method can be applied.
[Removal of residual phosgene]
The reaction mixture after the phosgenation reaction contains crude poly-MDI, an inert solvent, and residual phosgene. In the present invention, residual phosgene can be removed from the reaction mixture by heating, decompression, introduction of an inert gas, or a combination thereof. Specifically, the reaction mixture in which phosgene remains is preferably heated to a range of 100 ° C. or higher and 180 ° C. or lower and charged with an inert gas such as nitrogen, helium or argon, or an inert solvent under reduced pressure. Residual phosgene can be removed by heating to the boiling point of. Among these, the reduced pressure method is preferable in that the residual phosgene can be efficiently removed. By such an operation, the amount of residual phosgene in the reaction mixture can be reduced to 1% by weight or less.
加熱して残存ホスゲンを除去する場合、加熱温度は、通常１８０℃以下、好ましくは１４０℃以下が望ましい。ホスゲンが残存する反応混合物を１８０℃より高い温度で加熱すると、反応混合物が着色することがあり、後述する特定の水酸基含有芳香族化合物の添加による効果が十分に得られないことがある。これは、既に着色が進行した反応混合物に特定の水酸基含有芳香族化合物を添加しても退色が起こらないためである。 When removing residual phosgene by heating, the heating temperature is usually 180 ° C. or lower, preferably 140 ° C. or lower. When the reaction mixture in which phosgene remains is heated at a temperature higher than 180 ° C., the reaction mixture may be colored, and the effect of adding a specific hydroxyl group-containing aromatic compound described later may not be sufficiently obtained. This is because fading does not occur even when a specific hydroxyl group-containing aromatic compound is added to the reaction mixture that has already been colored.
加熱時間は、残存するホスゲンの量によって適宜設定され、通常１分〜１時間である。
残存ホスゲンの除去方法は、この種の除去処理に一般的に用いられる方法を適宜用いることができ、回分式、連続式のいずれでも行うことができる。
The heating time is appropriately set depending on the amount of remaining phosgene, and is usually 1 minute to 1 hour.
As a method for removing residual phosgene, a method generally used for this kind of removal treatment can be used as appropriate, and it can be carried out either batchwise or continuously.
〔芳香族化合物の添加と加熱処理〕
上記のようにして残存ホスゲンが除去され、少なくとも粗製ポリＭＤＩを含有する反応混合物に、下記式（Ｉ）
[Addition of aromatic compounds and heat treatment]
Residual phosgene is removed as described above and a reaction mixture containing at least crude poly-MDI is added to the following formula (I):
（式中、Ｒ1、Ｒ2、Ｒ3およびＲ4は、それぞれ独立に、水素または炭素数１〜６の炭化水素基である。）
で表されるオルト位にカルボキシル基を有する水酸基含有芳香族化合物を加えて加熱処理する。
(Wherein R 1 , R 2 , R 3 and R 4 are each independently hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.)
And a hydroxyl group-containing aromatic compound having a carboxyl group at the ortho position represented by
上記式（Ｉ）で表される水酸基含有芳香族化合物としては、たとえば、サリチル酸、３−メチルサリチル酸、４−メチルサリチル酸、５−メチルサリチル酸、３−イソプロピルサリチル酸、３，５−ジ−ｔ−ブチルサリチル酸、３−メチル−６−イソプロピルサリチル酸、３−イソプロピル−６−メチルサリチル酸、３，５−ｔ−ジイソプロピルサリチル酸、２−ヒドロキシ−３−フェニル安息香酸等が挙げられる。 Examples of the hydroxyl group-containing aromatic compound represented by the above formula (I) include salicylic acid, 3-methylsalicylic acid, 4-methylsalicylic acid, 5-methylsalicylic acid, 3-isopropylsalicylic acid, 3,5-di-t-butyl. Examples include salicylic acid, 3-methyl-6-isopropylsalicylic acid, 3-isopropyl-6-methylsalicylic acid, 3,5-t-diisopropylsalicylic acid, 2-hydroxy-3-phenylbenzoic acid, and the like.
上記式（Ｉ）で表される芳香族化合物は、反応混合物から不活性溶媒を除去せずに、粗製ポリＭＤＩと不活性溶媒とを含む反応混合物に添加してもよいし、反応混合物から不活性溶媒を除去した後、粗製ポリＭＤＩに添加してもよい。 The aromatic compound represented by the above formula (I) may be added to the reaction mixture containing the crude poly-MDI and the inert solvent without removing the inert solvent from the reaction mixture, or may be removed from the reaction mixture. After removing the active solvent, it may be added to the crude poly-MDI.
上記式（Ｉ）で表される芳香族化合物の添加量は、粗製のポリＭＤＩ１００重量部に対して、通常５重量部以下、好ましくは１重量部以下、より好ましくは０．４重量部以下である。 The amount of the aromatic compound represented by the above formula (I) is usually 5 parts by weight or less, preferably 1 part by weight or less, more preferably 0.4 parts by weight or less with respect to 100 parts by weight of the crude poly-MDI. is there.
上記式（Ｉ）で表される芳香族化合物は、そのまま、粗製ポリＭＤＩ、または粗製ポリＭＤＩを含む反応混合物に添加してもよいが、不活性溶媒に溶解して添加してもよい。ここで使用される不活性溶媒としては、イソシアネートと反応せず、加熱処理温度域において安定で加熱処理反応を阻害しないものであれば特に制限されず、たとえば、ヘキサン、シクロヘキサン、トルエン、キシレン、クロロベンゼン、ジクロロベンゼン等を挙げることができる。好ましくは、ホスゲン化反応で使用した不活性溶媒である。 The aromatic compound represented by the above formula (I) may be added as it is to the crude poly MDI or the reaction mixture containing the crude poly MDI, or may be added after being dissolved in an inert solvent. The inert solvent used here is not particularly limited as long as it does not react with isocyanate, is stable in the heat treatment temperature range and does not inhibit the heat treatment reaction. For example, hexane, cyclohexane, toluene, xylene, chlorobenzene And dichlorobenzene. The inert solvent used in the phosgenation reaction is preferable.
このようにして、少なくとも粗製ポリＭＤＩを含有する反応混合物に、上記式（Ｉ）で表される芳香族化合物を添加した後、通常３０〜１８０℃、好ましくは５０〜１４０℃の範囲の温度で反応混合物を加熱処理する。加熱処理温度が１８０℃を超えると着色が進行することがあり、上記芳香族化合物を添加した効果が小さくなることがあり、１８０℃を超える温度で加熱処理することは好ましくない。また、３０℃より低い温度で加熱処理しても特に問題はないが、上記芳香族化合物が完全に溶解しないことあり、好ましくない。 In this way, after adding the aromatic compound represented by the above formula (I) to the reaction mixture containing at least crude poly-MDI, it is usually at a temperature in the range of 30 to 180 ° C., preferably 50 to 140 ° C. The reaction mixture is heat treated. When the heat treatment temperature exceeds 180 ° C., coloring may proceed, and the effect of adding the aromatic compound may be reduced. Further, there is no particular problem even if the heat treatment is performed at a temperature lower than 30 ° C., but the aromatic compound is not completely dissolved, which is not preferable.
加熱処理時間は、反応混合物中のホスゲン化副生成物の量、上記芳香族化合物の添加量、および加熱処理の温度によって適宜設定され、通常１分〜１時間の範囲である。
この加熱処理の方法は、この種の加熱処理に一般的に用いられる方法を適宜用いることができ、回分式、連続式のいずれでも行うことができる。
The heat treatment time is appropriately set depending on the amount of the phosgenation by-product in the reaction mixture, the amount of the aromatic compound added, and the temperature of the heat treatment, and is usually in the range of 1 minute to 1 hour.
As a method for this heat treatment, a method generally used for this kind of heat treatment can be appropriately used, and either a batch method or a continuous method can be used.
上記のようにして、上記式（Ｉ）で表される芳香族化合物を添加して加熱処理された反
応混合物に不活性溶媒が含まれている場合には、これを除去する。除去方法は、この種の除去処理に一般的に用いられる方法を適宜用いることができる。
As described above, when an inert solvent is contained in the reaction mixture heated by adding the aromatic compound represented by the above formula (I), this is removed. As a removal method, a method generally used for this kind of removal treatment can be appropriately used.
このようにして得られたポリＭＤＩまたはこのポリＭＤＩからＭＤＩを分離したものを、さらに１８０℃〜２４０℃で加熱することにより、ポリＭＤＩの酸分およびＨＣを減少させることができる。本発明に係る製造方法により製造されたポリＭＤＩは、このような高温での加熱処理を施しても色相の悪化を最小限に抑えることができる。 The poly MDI thus obtained or a product obtained by separating MDI from the poly MDI is further heated at 180 ° C. to 240 ° C., whereby the acid content and HC of the poly MDI can be reduced. The poly MDI manufactured by the manufacturing method according to the present invention can suppress the deterioration of the hue to the minimum even when the heat treatment is performed at such a high temperature.
なお、酸分とは、イソシアネート中に含まれる酸性起因物質の総称であり、その量は、ＪＩＳ Ｋ１６０３（ポリメチレンポリフェニレンポリイソシアネート試験方法）に定義された酸度の測定方法により求められ、塩化水素量に換算した値である。 The acid content is a general term for acid-derived substances contained in isocyanate, and the amount is determined by the acidity measuring method defined in JIS K1603 (polymethylene polyphenylene polyisocyanate test method), and the amount of hydrogen chloride. It is the value converted into.
また、ＨＣとは、加水分解性塩素と呼ばれるものであり、イソシアネート中に含まれ、加水分解により塩酸を生成する物質の総称であり、その量は、ＪＩＳ Ｋ１５５６（トリレンジイソシアネート試験方法）に定義された加水分解性塩素測定方法により求められ、塩素量に換算した値である。 HC is called hydrolyzable chlorine and is a general term for substances that are contained in isocyanate and generate hydrochloric acid by hydrolysis. The amount is defined in JIS K1556 (tolylene diisocyanate test method). It is the value calculated | required by the hydrolyzable chlorine measuring method performed, and converted into the amount of chlorine.
［実施例］
以下、本発明を実施例により説明するが、本実施例は本発明を具体的に説明したものであり、本発明はこの実施例により何ら限定されるものではない。なお、特に断りのない限り、実施例中の「部」および「％」は、それぞれ「重量部」および「重量％」を示すものとする。以下に、実施例および比較例で使用した粗製ポリＭＤＩの製造方法、およびポリＭＤＩの色相の評価方法を示す。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, a present Example demonstrates this invention concretely, This invention is not limited at all by this Example. Unless otherwise specified, “parts” and “%” in the examples represent “parts by weight” and “% by weight”, respectively. Below, the manufacturing method of the crude poly MDI used by the Example and the comparative example, and the evaluation method of the hue of poly MDI are shown.
（粗製ポリＭＤＩの製造方法）
塩酸存在下でアニリンとホルマリンとを縮合させ、中和、脱水等の精製を行い、ポリアミン混合物を得た。このポリアミン混合物を、ｏ−ジクロロベンゼン中でホスゲンと反応させ、フラッシュ蒸留を行い、ｏ−ジクロロベンゼン溶媒４７０部と、残存ホスゲン１８部と、粗製ポリＭＤＩ１００部（該粗製ポリＭＤＩは、４，４−ＭＤＩ、２，４−ＭＤＩ、２，２−ＭＤＩ、３個以上のイソシアネート基を有する同族体からなるポリＭＤＩおよび同定されていない副生成物を含む。）とからなる反応混合物を得た。粗製ポリＭＤＩに含まれるポリＭＤＩのうち、ＭＤＩ（４，４−ＭＤＩ、２，４−ＭＤＩおよび２，２−ＭＤＩ）は５６．３％、３個以上のイソシアネート基を有するポリＭＤＩ同族体は４３．７％であった。
(Method for producing crude poly-MDI)
In the presence of hydrochloric acid, aniline and formalin were condensed, and purification such as neutralization and dehydration was performed to obtain a polyamine mixture. This polyamine mixture is reacted with phosgene in o-dichlorobenzene, flash distilled, 470 parts of o-dichlorobenzene solvent, 18 parts of residual phosgene, 100 parts of crude poly MDI (the crude poly MDI is 4,4 -MDI, 2,4-MDI, 2,2-MDI, poly MDI consisting of homologues with 3 or more isocyanate groups and unidentified by-products.). Of the poly MDIs contained in the crude poly MDI, MDI (4,4-MDI, 2,4-MDI and 2,2-MDI) is 56.3%, and poly MDI homologs having 3 or more isocyanate groups are It was 43.7%.
（ポリＭＤＩの色相評価方法）
得られたポリＭＤＩ１重量部をトルエン５０重量部に溶解し、２０℃で波長４３０ｎｍおよび５２０ｎｍにおける吸光度を測定し、その値で評価した。
(Poly MDI hue evaluation method)
1 part by weight of the obtained poly-MDI was dissolved in 50 parts by weight of toluene, the absorbance at wavelengths of 430 nm and 520 nm was measured at 20 ° C., and the value was evaluated.
（酸分の測定方法）
得られたポリＭＤＩの酸分は、ＪＩＳ Ｋ１６０３に準拠して酸度を測定し、塩化水素量に換算した値で評価した。
(Method for measuring acid content)
The acid content of the obtained poly-MDI was evaluated based on the value obtained by measuring the acidity according to JIS K1603 and converting it into the amount of hydrogen chloride.
（ＨＣの測定方法）
得られたポリＭＤＩのＨＣは、ＪＩＳ Ｋ１５５６に記載の加水分解性塩素の測定方法に準拠して測定し、塩素量に換算した値で評価した。
(Measurement method of HC)
HC of the obtained poly MDI was measured in accordance with the method for measuring hydrolyzable chlorine described in JIS K1556, and evaluated by a value converted into the amount of chlorine.
コンデンサーを取付けた５００ｍＬ四つ口フラスコに上記反応混合物５００部（このうち、粗製ポリＭＤＩは８５部）を装入し、撹拌しながら１７．３ｋＰａまで減圧した後、
１２０℃まで昇温した。この温度で１０分間撹拌して残存ホスゲンを完全に除去した。
A 500 mL four-necked flask equipped with a condenser was charged with 500 parts of the above reaction mixture (of which 85 parts of crude poly MDI), and the pressure was reduced to 17.3 kPa while stirring.
The temperature was raised to 120 ° C. Stirring was continued at this temperature for 10 minutes to completely remove residual phosgene.
次いで、これに、滴下ロートを用いて、大気圧下、サリチル酸０．８５部をｏ−ジクロロベンゼン１０部に溶解した溶液を１２０℃にて装入し、大気圧下、１２０℃にて３０分間撹拌して加熱処理した。その後、これを８０℃まで冷却し、単蒸留装置を用いて１．３〜４．０ｋＰａの条件にて、大部分のｏ−ジクロロベンゼンを除去した。 Subsequently, using a dropping funnel, a solution prepared by dissolving 0.85 part of salicylic acid in 10 parts of o-dichlorobenzene at atmospheric pressure was charged at 120 ° C., and at atmospheric pressure at 120 ° C. for 30 minutes. Heated with stirring. Thereafter, this was cooled to 80 ° C., and most of o-dichlorobenzene was removed using a simple distillation apparatus under conditions of 1.3 to 4.0 kPa.
上記のようにしてホスゲンおよび大部分の溶媒を除去した反応混合物を、２１５℃、１３．３ｋＰａの条件にて２０分間加熱して、ｏ−ジクロロベンゼンを完全に除去し、ポリＭＤＩを得た。得られたポリＭＤＩの４３０ｎｍの吸光度は０．０６２、５２０ｎｍの吸光度は０．００９、酸分は０．０１６％、ＨＣは０．１０％であった。 The reaction mixture from which phosgene and most of the solvent had been removed as described above was heated at 215 ° C. and 13.3 kPa for 20 minutes to completely remove o-dichlorobenzene to obtain poly MDI. The obtained poly-MDI had an absorbance at 430 nm of 0.062, an absorbance at 520 nm of 0.009, an acid content of 0.016%, and HC of 0.10%.
サリチル酸を０．８５部から０．１７部に変更した以外は実施例１と同様にしてポリＭＤＩを得た。得られたポリＭＤＩの４３０ｎｍの吸光度は０．０８１、５２０ｎｍの吸光度は０．０２３、酸分は０．０１５％、ＨＣは０．１０％であった。 A poly MDI was obtained in the same manner as in Example 1 except that salicylic acid was changed from 0.85 part to 0.17 part. The obtained poly MDI had an absorbance at 430 nm of 0.081, an absorbance at 520 nm of 0.023, an acid content of 0.015%, and HC of 0.10%.
実施例１と同様にして上記反応混合物５００部（このうち、粗製ポリＭＤＩは８５部）から残存ホスゲンを完全に除去した後、得られた反応混合物を５０℃まで冷却した。これに、滴下ロートを用いて、大気圧下、サリチル酸０．１７部をｏ−ジクロロベンゼン１０部に溶解した溶液を５０℃にて装入し、大気圧下、その温度にて３０分間撹拌して加熱処理した。その後、単蒸留装置を用いて８０℃、１．３〜４．０ｋＰａの条件にて大部分のｏ−ジクロロベンゼンを除去した。 Residual phosgene was completely removed from 500 parts of the reaction mixture (of which 85 parts were crude poly-MDI) in the same manner as in Example 1, and then the resulting reaction mixture was cooled to 50 ° C. A solution obtained by dissolving 0.17 part of salicylic acid in 10 parts of o-dichlorobenzene was charged at 50 ° C. using a dropping funnel at atmospheric pressure and stirred at that temperature for 30 minutes under atmospheric pressure. And heated. Then, most o-dichlorobenzene was removed on condition of 80 degreeC and 1.3-4.0 kPa using the simple distillation apparatus.
上記のようにしてホスゲンおよび大部分の溶媒を除去した反応混合物から、実施例１と同様にしてｏ−ジクロロベンゼンを完全に除去し、ポリＭＤＩを得た。得られたポリＭＤＩの４３０ｎｍの吸光度は０．０６３、５２０ｎｍの吸光度は０．０１５、酸分は０．０１５％、ＨＣは０．１１％であった。 From the reaction mixture from which phosgene and most of the solvent were removed as described above, o-dichlorobenzene was completely removed in the same manner as in Example 1 to obtain poly MDI. The obtained poly MDI had an absorbance at 430 nm of 0.063, an absorbance at 520 nm of 0.015, an acid content of 0.015%, and an HC of 0.11%.
［比較例１］
実施例１と同様にして上記反応混合物５００部（このうち、粗製ポリＭＤＩは８５部）から残存ホスゲンを完全に除去した。これを、大気圧下、１２０℃にて３０分間撹拌して加熱処理した後、８０℃まで冷却し、単蒸留装置を用いて１．３〜４．０ｋＰａの条件にて、大部分のｏ−ジクロロベンゼンを除去した。
[Comparative Example 1]
Residual phosgene was completely removed from 500 parts of the reaction mixture (of which 85 parts were crude poly MDI) in the same manner as in Example 1. This was stirred and heated at 120 ° C. for 30 minutes under atmospheric pressure, then cooled to 80 ° C., and most of o--under conditions of 1.3 to 4.0 kPa using a simple distillation apparatus. Dichlorobenzene was removed.
上記のようにしてホスゲンおよび大部分の溶媒を除去した反応混合物から、実施例１と同様にしてｏ−ジクロロベンゼンを完全に除去し、ポリＭＤＩを得た。得られたポリＭＤＩの４３０ｎｍの吸光度は０．１０３、５２０ｎｍの吸光度は０．０４０、酸分は０．０１５％、ＨＣは０．１１％であった。 From the reaction mixture from which phosgene and most of the solvent were removed as described above, o-dichlorobenzene was completely removed in the same manner as in Example 1 to obtain poly MDI. The obtained poly MDI had an absorbance at 430 nm of 0.103, an absorbance at 520 nm of 0.040, an acid content of 0.015%, and HC of 0.11%.
［比較例２］
サリチル酸の替わりに安息香酸０．８５部を用いた以外は、実施例１と同様にしてポリＭＤＩを得た。得られたポリＭＤＩの４３０ｎｍの吸光度は０．０６３、５２０ｎｍの吸光度は０．０１２、酸分は０．０９６％、ＨＣは０．１７％であった。
[Comparative Example 2]
Poly MDI was obtained in the same manner as in Example 1 except that 0.85 part of benzoic acid was used instead of salicylic acid. The obtained poly MDI had an absorbance at 430 nm of 0.063, an absorbance at 520 nm of 0.012, an acid content of 0.096%, and an HC of 0.17%.
［比較例３］
サリチル酸の替わりに水酸基価１２００ｍｇＫＯＨ／ｇのポリエチレングリコール０．８５部を用いた以外は、実施例１と同様にしてポリＭＤＩを得た。得られたポリＭＤＩの４３０ｎｍの吸光度は０．１０７、５２０ｎｍの吸光度は０．０４１、酸分は０．０４０
％、ＨＣは０．１３％であった。
[Comparative Example 3]
A poly MDI was obtained in the same manner as in Example 1 except that 0.85 part of polyethylene glycol having a hydroxyl value of 1200 mgKOH / g was used instead of salicylic acid. The resulting poly-MDI had an absorbance at 430 nm of 0.107, an absorbance at 520 nm of 0.041, and an acid content of 0.040.
%, HC was 0.13%.
［比較例４］
サリチル酸の替わりにｐ−ヒドロキシ安息香酸０．１７部を用いた以外は、実施例１と同様にしてポリＭＤＩを得た。得られたポリＭＤＩの４３０ｎｍの吸光度は０．０６７、５２０ｎｍの吸光度は０．０１８、酸分は０．０４１％、ＨＣは０．１４％であった。
[Comparative Example 4]
A poly MDI was obtained in the same manner as in Example 1 except that 0.17 part of p-hydroxybenzoic acid was used instead of salicylic acid. The obtained poly MDI had an absorbance at 430 nm of 0.067, an absorbance at 520 nm of 0.018, an acid content of 0.041%, and an HC of 0.14%.
本発明によると、従来の方法と比較して、色相に優れたメチレン架橋ポリフェニレンポリイソシアネートを簡単に製造することができ、また、二次的副生成物による品質の低下も防止できる。さらに、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を用いることによって色相に優れた発泡体を得ることができる。
According to the present invention, compared with the conventional method, a methylene-bridged polyphenylene polyisocyanate excellent in hue can be easily produced, and the deterioration of quality due to secondary by-products can be prevented. Furthermore, a foam excellent in hue can be obtained by using the obtained methylene-crosslinked polyphenylene polyisocyanate.
Claims (6)
（１）上記ホスゲン化反応後、得られた粗製のメチレン架橋ポリフェニレンポリイソシアネートを含む反応混合物から１８０℃以下の温度で加熱して残存ホスゲンを除去した後、
（２）該粗製のメチレン架橋ポリフェニレンポリイソシアネートに、下記式（Ｉ）
で表されるオルト位にカルボキシル基を有する水酸基含有芳香族化合物を加えて加熱処理する
ことを特徴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方法。 In a method for producing a methylene-bridged polyphenylene polyisocyanate by reacting a polyamine mixture formed by a condensation reaction of aniline and formaldehyde in the presence of an acid catalyst with phosgene in the presence of an inert solvent,
(1) After the phosgenation reaction, after removing residual phosgene by heating at a temperature of 180 ° C. or less from the obtained reaction mixture containing the crude methylene-crosslinked polyphenylene polyisocyanate,
(2) To the crude methylene-crosslinked polyphenylene polyisocyanate, the following formula (I)
A process for producing a methylene-crosslinked polyphenylene polyisocyanate, which comprises adding a hydroxyl group-containing aromatic compound having a carboxyl group at the ortho position represented by
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