JP4114198B2 - Method for reducing coloration of polymethylene polyphenylene polyisocyanate - Google Patents
Method for reducing coloration of polymethylene polyphenylene polyisocyanate Download PDFInfo
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- JP4114198B2 JP4114198B2 JP2002263666A JP2002263666A JP4114198B2 JP 4114198 B2 JP4114198 B2 JP 4114198B2 JP 2002263666 A JP2002263666 A JP 2002263666A JP 2002263666 A JP2002263666 A JP 2002263666A JP 4114198 B2 JP4114198 B2 JP 4114198B2
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- Prior art keywords
- mdi
- polymeric mdi
- silane coupling
- coupling agent
- polymethylene polyphenylene
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- 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.)
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Description
【0001】
【発明の属する技術分野】
本発明は、ポリメチレンポリフェニレンポリイソシアネートの着色低減方法に関する。
【0002】
【従来の技術】
ポリメチレンポリフェニレンポリイソシアネート(以下ポリメリックMDIと略記する)は極めて反応性に富む化合物であり、ポリウレタンフォーム、エラストマー、接着剤、塗料、シーリング剤等広範囲な分野で使用されている。ポリメリックMDIの工業的な製造方法は、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により得られるポリアミン混合物を、溶媒の存在下ホスゲンと反応させ(以下ホスゲン化と略記する)、更には、生成物からジフェニルメタンジイソシアネート(以下MDIと略記する)を減圧蒸留により分離し、更に必要に応じてMDI含有量や粘度を調整するという方法が一般的である。このホスゲン化を経て製造されるため、酸分及び加水分解性塩素(以下HCと略記する)等の不純物を有することになり、この不純物が多いとイソシアネート基の反応性が低下することが知られている。
【0003】
【発明が解決しようとする課題】
酸分及びHCを低減するために数多くの方法が提案されている。工業的に最も有利な方法は、減圧高温下での加熱処理による方法である。しかし、ポリメリックMDIは、この高温下での処理やMDI分離時の加熱によって着色し、またこのポリメリックMDIを用いたポリウレタン樹脂の着色原因にもなるため。このことから、着色が少なく、また酸分やHCの少ないポリメリックMDIが求められている。
【0004】
ポリメリックMDIの色相改善について、様々な方法が提案されている。例えば特許文献1では、アニリンとホルムアルデヒドとの縮合反応時において、生成したポリアミンを循環させることで、ポリアミン混合物の着色を低下させ、ひいてはポリメリックMDIの着色を低下させる方法が提案されている。特許文献2では、生成したポリメリックMDIを炭素数8以上脂肪族炭化水素を用いて、180℃以上で抽出してタール分を除去する方法が提案されている。しかし、前者の方法では、HCの原因となる2級アミンの生成量が増大しやすく、ひいてはポリメリックMDIの反応性が低下しやすい。後者では新たに抽出溶媒やタール分の処理という問題が発生する。
【0005】
【特許文献1】
特開昭63−227609号公報
【特許文献2】
特開昭60−58955号公報
【0006】
【発明を解決するための手段】
本発明者等は、工業的に経済的かつ簡単な方法でポリメリックMDIの着色を減少させるべく鋭意検討した結果、驚くべきことに着色したポリメリックMDIにシランカップリング剤を加えて加熱処理すると脱色し、非常に色相の優れたポリメリックMDIとなること、及び着色の少ないポリメリックMDIに対して同様な処理を施すと、着色の進行が極めて少ないことを見出し本発明に至った。
【0007】
すなわち本発明は、トリアルコキシシラン構造を分子中に有する化合物をポリメリックMDIに対して0.001〜10質量%添加し、30〜220℃で加熱処理することを特徴とする、ポリメリックMDIの着色を低減する方法である。
【0008】
【発明の実施の手段】
以下に本発明を詳細に説明する。
本発明に使用されるポリメリックMDI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により得られるポリアミン混合物を、溶媒の存在下でホスゲン化を行って得られる、重合度の異なるポリイソシアネート混合物である。更には、必要に応じて、ホスゲン化生成物からMDIを減圧蒸留により分離し、更に必要に応じてMDI含有量や粘度を調整したものである。このポリメリックMDIの組成は原料であるポリアミン混合物の組成あるいは蒸留によって抜き出されるMDI量等によって異なるが、本発明はいかなる組成のポリメリックMDIにも利用できる。代表的な組成を示すと、極微量の2,2′−MDI、0.1〜40質量%の2,4′−MDI、10〜80質量%の4,4′−MDI、20〜70質量%のベンゼン環が3個以上の高分子同族体(以下、3核体以上のP−MDIと略記)が挙げられる。
【0009】
本発明に用いられるトリアルコキシシラン基を分子中に有する化合物は、シランカップリング剤として市販されているものである。具体的には、日本ユニカー社から市販されている、エポキシ含有シランカップリング剤:A−187、イソシアネート基含有シランカップリング剤:A−1310、メルカプト基含有シランカップリング剤:A−189、フェニルアミン基含有シランカップリング剤:Y−9669、イソシアヌレート環含有シランカップリング剤:Y−11597等を挙げることができる。
【0010】
シランカップリング剤の添加量については、ポリメリックMDIに対して0.001質量%未満では、脱色の度合いが小さく、10質量%を超えると不溶解物を生成しやすくなる。本発明では、0.005〜5質量%が好ましい。
【0011】
処理温度は30〜220℃であり、高温になるほど処理時間は短くなる。過剰の加熱処理は着色の原因になるおそれがあるので、30〜100℃の温度が好ましい。更に好ましくは30〜80℃で2〜3日の処理条件である。
【0012】
本発明の方法は、着色したポリメリックMDIを脱色するだけでなく、着色の小さいポリメリックMDIに上記の処理を施すと着色の進行が極めて少ないポリメリックMDIが得られることが分かった。
【0013】
【実施例】
以下、実施例により本発明を更に詳細に説明するが、本発明は実施例に限定して解釈されるものではない。なお「%」は全て「質量%」を意味する。
【0014】
実施例1
200mlのガラス瓶に、ポリメリックMDI−1を100g入れ、そこへ、日本ユニカー製のA−187を1g添加し、良く振った後、80℃のオーブンに3日間入れて、室温に冷却してから液の状態を観察した。着色の程度はL*値(注2)で判定した。結果を表1に示す。
【0015】
実施例2〜10、比較例1〜6
実施例1で使用したポリメリックMDI−1を用いて、添加剤の種類・量を振って添加し、加熱後の液の状態を観察した。着色の程度はL*値で判定した。結果を表1〜3に示す。
【0016】
【表1】
【0017】
【表2】
【0018】
【表3】
【0019】
実施例1〜10、比較例1〜6、表1〜3において
A−187 :エポキシ含有シランカップリング剤:
A−1310 :イソシアネート基含有シランカップリング剤
A−189 :メルカプト基含有シランカップリング剤
Y−9669 :フェニルアミン基含有シランカップリング剤
Y−11597:イソシアヌレート環含有シランカップリング剤
全て日本ユニカー製
MeOH :メタノール
L−5340 :シリコン整泡剤(ジメチルシロキサン−ポリオキシアルキレンブロックポリマー、日本ユニカー製)
SZ−1642:シリコン整泡剤(ジメチルシロキサン−ポリオキシアルキレンブロックポリマー、日本ユニカー製)
ポリメリックMDI−1の品質
NCO含量=31.0%
25℃での粘度=175mPa・s
2,2′−MDI=痕跡
2,4′−MDI=1%
4,4′−MDI=39%
3核体以上のP−MDI=60%
酸度=0.014%
HC=0.072%
L*=36
L*の測定方法
JIS Z8729に準拠、スガ試験機製多光源分光測色計MSC−IS−2B型、d=5mmセル使用、サンプル量4〜5ml、液温25℃、環境温度25℃にて測定。
【0020】
実施例11
200mlのガラス瓶に、ポリメリックMDI−2を100g入れ、そこへ、日本ユニカー製のA−1310を1g添加し、良く振った後、80℃のオーブンに3日間入れた後、一旦室温に冷却した。その後50℃のオーブンにいれて、経時変化を観察した。結果を表4に示す。
【0021】
比較例7
A−187を用いない以外は実施例11と同様にして試験した。結果を表3に示す。
【0022】
【表4】
【0023】
実施例11、比較例7、表4において
ポリメリックMDI−2の品質
NCO含量=31.0%
25℃での粘度=165mPa・s
2,2′−MDI=痕跡
2,4′−MDI=1%
4,4′−MDI=40%
3核体以上のP−MDI=59%
酸度=0.010%
HC=0.057%
L*=74
【0024】
【発明の効果】
本発明は、工業的に経済的かつ簡単な方法で、酸分やHC等の不純物が少ないポリメリックMDIの着色を減少させることができ、工業的に大量に製造されるポリメリックMDIの製造方法の一工程として有利な方法である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a coloring reduction method for polymethylene polyphenylene polyisocyanate.
[0002]
[Prior art]
Polymethylene polyphenylene polyisocyanate (hereinafter abbreviated as polymeric MDI) is a highly reactive compound and is used in a wide range of fields such as polyurethane foam, elastomers, adhesives, paints, and sealing agents. An industrial production method of polymeric MDI is obtained by reacting a polyamine mixture obtained by condensation of aniline and formaldehyde in the presence of an acid catalyst with phosgene in the presence of a solvent (hereinafter abbreviated as phosgenation), In general, diphenylmethane diisocyanate (hereinafter abbreviated as MDI) is separated from the product by distillation under reduced pressure, and the MDI content and viscosity are adjusted as necessary. Since it is produced through this phosgenation, it has impurities such as acid content and hydrolyzable chlorine (hereinafter abbreviated as HC), and it is known that the reactivity of isocyanate groups decreases when there are many impurities. ing.
[0003]
[Problems to be solved by the invention]
A number of methods have been proposed to reduce acid content and HC. The most industrially advantageous method is a method by heat treatment under reduced pressure and high temperature. However, polymeric MDI is colored by the treatment at this high temperature and by heating at the time of MDI separation, and also causes the coloring of the polyurethane resin using this polymeric MDI. For this reason, polymeric MDI with less coloring and less acid content and HC is desired.
[0004]
Various methods have been proposed for improving the hue of polymeric MDI. For example, Patent Document 1 proposes a method of reducing the coloration of the polyamine mixture by circulating the produced polyamine during the condensation reaction of aniline and formaldehyde, and thus reducing the coloration of the polymeric MDI. Patent Document 2 proposes a method of removing the tar content by extracting the produced polymeric MDI using an aliphatic hydrocarbon having 8 or more carbon atoms at 180 ° C. or higher. However, in the former method, the amount of secondary amine that causes HC tends to increase, and the reactivity of polymeric MDI tends to decrease. In the latter case, a new problem of processing the extraction solvent and tar content occurs.
[0005]
[Patent Document 1]
JP 63-227609 A [Patent Document 2]
Japanese Patent Laid-Open No. 60-58955 [0006]
[Means for Solving the Invention]
As a result of intensive studies to reduce the coloration of the polymeric MDI by an industrially economical and simple method, the present inventors surprisingly decolored when a silane coupling agent was added to the colored polymeric MDI and heat-treated. As a result, the inventors have found that the polymer MDI having a very excellent hue and that the same process is applied to the polymer MDI with little coloration, the progress of the coloration is extremely small.
[0007]
That is, the present invention provides a coloring of polymeric MDI characterized by adding 0.001 to 10% by mass of a compound having a trialkoxysilane structure in the molecule to polymeric MDI and heat-treating at 30 to 220 ° C. This is a reduction method.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
The polymeric MDI used in the present invention is a polyisocyanate mixture having a different degree of polymerization obtained by phosgenating a polyamine mixture obtained by condensation of aniline and formaldehyde in the presence of an acid catalyst in the presence of a solvent. is there. Furthermore, MDI is separated from the phosgenation product by vacuum distillation as necessary, and the MDI content and viscosity are adjusted as necessary. The composition of the polymeric MDI varies depending on the composition of the raw material polyamine mixture or the amount of MDI extracted by distillation, but the present invention can be used for polymeric MDI having any composition. The representative composition is as follows: trace amount of 2,2′-MDI, 0.1 to 40% by weight of 2,4′-MDI, 10 to 80% by weight of 4,4′-MDI, 20 to 70% by weight. %, A polymer homologue having 3 or more benzene rings (hereinafter abbreviated as P-MDI having 3 or more nuclei).
[0009]
The compound having a trialkoxysilane group in the molecule for use in the present invention is commercially available as a silane coupling agent. Specifically, epoxy-containing silane coupling agent: A-187, isocyanate group-containing silane coupling agent: A-1310, mercapto group-containing silane coupling agent: A-189, phenyl, commercially available from Nippon Unicar Company. Amine group-containing silane coupling agent: Y-9669, isocyanurate ring-containing silane coupling agent: Y-11597, and the like.
[0010]
When the amount of the silane coupling agent is less than 0.001% by mass with respect to the polymeric MDI, the degree of decolorization is small, and when it exceeds 10% by mass, an insoluble matter is easily generated. In this invention, 0.005-5 mass% is preferable.
[0011]
Processing temperature is 30-220 degreeC, and processing time becomes short, so that it becomes high temperature. Since excessive heat treatment may cause coloring, a temperature of 30 to 100 ° C. is preferable. More preferably, the treatment conditions are 30 to 80 ° C. for 2 to 3 days.
[0012]
It has been found that the method of the present invention not only decolorizes the colored polymeric MDI, but also gives a polymeric MDI with very little color progression when the above-described treatment is performed on the polymeric MDI that is less colored.
[0013]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is limited to an Example and is not interpreted. “%” Means “% by mass”.
[0014]
Example 1
Add 100g of Polymeric MDI-1 to a 200ml glass bottle, add 1g of A-187 made by Nihon Unicar, shake it well, put it in an oven at 80 ° C for 3 days, cool to room temperature, and then liquid The state of was observed. The degree of coloring was determined by L * value (Note 2). The results are shown in Table 1.
[0015]
Examples 2-10, Comparative Examples 1-6
Using the polymeric MDI-1 used in Example 1, the type and amount of the additive were shaken and added, and the state of the liquid after heating was observed. The degree of coloring was determined by L * value. The results are shown in Tables 1-3.
[0016]
[Table 1]
[0017]
[Table 2]
[0018]
[Table 3]
[0019]
In Examples 1 to 10, Comparative Examples 1 to 6, and Tables 1 to 3, A-187: Epoxy-containing silane coupling agent:
A-1310: Isocyanate group-containing silane coupling agent A-189: Mercapto group-containing silane coupling agent Y-9669: Phenylamine group-containing silane coupling agent Y-11597: All isocyanurate ring-containing silane coupling agents MeOH: Methanol L-5340: Silicon foam stabilizer (dimethylsiloxane-polyoxyalkylene block polymer, manufactured by Nihon Unicar)
SZ-1642: Silicone foam stabilizer (dimethylsiloxane-polyoxyalkylene block polymer, manufactured by Nihon Unicar)
Quality of Polymeric MDI-1 NCO content = 31.0%
Viscosity at 25 ° C. = 175 mPa · s
2,2′-MDI = trace 2,4′-MDI = 1%
4,4'-MDI = 39%
P-MDI over 3 nuclei = 60%
Acidity = 0.014%
HC = 0.072%
L * = 36
L * measurement method Conforms to JIS Z8729, Suga Test Instruments multi-source spectrocolorimeter MSC-IS-2B type, d = 5 mm cell used, sample amount 4-5 ml, liquid temperature 25 ° C., environmental temperature 25 ° C. .
[0020]
Example 11
In a 200 ml glass bottle, 100 g of polymeric MDI-2 was added, and 1 g of A-1310 made by Nihon Unicar was added thereto, shaken well, placed in an oven at 80 ° C. for 3 days, and then cooled to room temperature. Thereafter, it was placed in an oven at 50 ° C. and the change with time was observed. The results are shown in Table 4.
[0021]
Comparative Example 7
The test was conducted in the same manner as in Example 11 except that A-187 was not used. The results are shown in Table 3.
[0022]
[Table 4]
[0023]
In Example 11, Comparative Example 7, Table 4, the quality NCO content of polymeric MDI-2 = 31.0%
Viscosity at 25 ° C. = 165 mPa · s
2,2′-MDI = trace 2,4′-MDI = 1%
4,4'-MDI = 40%
P-MDI over 3 nuclei = 59%
Acidity = 0.010%
HC = 0.057%
L * = 74
[0024]
【The invention's effect】
INDUSTRIAL APPLICABILITY The present invention is an industrially economical and simple method that can reduce the coloration of polymeric MDI that is low in impurities such as acid content and HC, and is a method for producing polymeric MDI that is industrially produced in large quantities. This is an advantageous method as a process.
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Cited By (3)
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US9545543B2 (en) | 2014-06-27 | 2017-01-17 | Bridgestone Sports Co., Ltd. | Golf ball manufacturing method |
US9776046B2 (en) | 2015-12-22 | 2017-10-03 | Bridgestone Sports Co., Ltd. | Golf ball |
US10046208B2 (en) | 2015-12-21 | 2018-08-14 | Bridgestone Sports Co., Ltd. | Golf ball |
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EP2204395B1 (en) | 2007-10-15 | 2013-10-09 | Mitsui Chemicals, Inc. | Polyurethane resin |
JP5386142B2 (en) * | 2007-11-16 | 2014-01-15 | 三井化学株式会社 | Polyurethane elastomers and molded products |
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JPH07173387A (en) * | 1991-06-05 | 1995-07-11 | Mitsubishi Kagaku Dow Kk | Polyisocyanate composition |
JP2512660B2 (en) * | 1992-02-28 | 1996-07-03 | 三菱化学ダウ株式会社 | Polyisocyanate composition |
JPH07233126A (en) * | 1994-02-21 | 1995-09-05 | Nissan Chem Ind Ltd | Iodoaniline derivative and its production |
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US9545543B2 (en) | 2014-06-27 | 2017-01-17 | Bridgestone Sports Co., Ltd. | Golf ball manufacturing method |
US10137334B2 (en) | 2014-06-27 | 2018-11-27 | Bridgestone Sports Co., Ltd. | Golf ball manufacturing method |
US10046208B2 (en) | 2015-12-21 | 2018-08-14 | Bridgestone Sports Co., Ltd. | Golf ball |
US10335641B2 (en) | 2015-12-21 | 2019-07-02 | Bridgestone Sports Co., Ltd. | Golf ball |
US9776046B2 (en) | 2015-12-22 | 2017-10-03 | Bridgestone Sports Co., Ltd. | Golf ball |
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