JPH0578304A - Method for stabilizing isocyanate compound and stabilized isocyanate composition - Google Patents

Abstract

PURPOSE:To obtain a stabilized isocyanate composition by simultaneously suppressing yellowing property and white turbidity over a long period to stabilize an isocyanate compound. CONSTITUTION:Phenol of 10-5000ppm, especially 100-200ppm is added to an isocyanate compound (especially aliphatic polyisocyanate, preferably xylylene diisocyanate) to stabilize the isocyanate compound. By this method, the occurrence of white turbidity by self polymerization and coloring with the passage of time are suppressed, and the isocyanate compound exhibits excellent storage stability. Phenol especially exhibits an outstanding stabilizing action on unstable xylylene diisocyanates. The lowering in purity of the isocyanate compound is also suppressed by addition of the phenol and the effect is remarkably exhibited in the case of the aliphatic polyisocyanates.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizing method for suppressing yellowing and white turbidity of an isocyanate compound due to aging, and an isocyanate composition stabilized by the method. The thing is especially useful as a raw material for optical urethane resin such as a plastic lens which is required to be colorless and transparent.

[0002]

2. Description of the Related Art Isocyanate compounds have the drawback that they are unstable due to the high reactivity of the isocyanate group and easily colored or self-polymerized during storage. Therefore, it is essential to add a stabilizer that suppresses coloring and self-polymerization. Conventionally, various compounds are known as stabilizers for isocyanate compounds, and typical stabilizers are phenols such as 2,6-ditertiarybutyl-p-cresol (US 3,715,381) and tris Phenyl phosphite
5-33438) and other phosphite esters are known. In addition, ureas, carbamates, acid amides (JP-B-45-7044, JP-A-50-36546),
Acidic substances such as perchloric acid and trifluoromethanesulfonic acid (Ger. 2837770), carbon dioxide and sulfur dioxide (US Pat. No. 3,247,236), organic amines (JP-A-50-101344), acid chlorides (JP-A-50-134344). 63-
179917), siloxane (Belg. 85892).
1), an organic tin compound (EP 203874), an acyl isocyanate compound (Japanese Patent Publication No. 48-3825), and many other stabilizers are known.

Examples of compounds known as phenolic stabilizers related to the present application include pyrogallol, catechol,
Guaiacol, eugenol, pentachlorophenol (Japanese Patent Publication No. 48-3825, Japanese Patent Publication No. 45-7044),
2,6-Ditertiarybutyl-p-cresol, metacresol (JP-A-51-48619), other alkyl-substituted phenols, bisphenols (JP-B-46-27)
594, Pol 100154, Brit. 1315
520, US Pat. No. 3,682,902, JP-A-59-9805.
0) can be mentioned.

However, even with these stabilizers, it is difficult to suppress the coloration of the isocyanate compound and the white turbidity due to self-polymerization at the same time, and a satisfactory result has not been obtained yet. In particular, aliphatic polyisocyanates, especially xylylene diisocyanate, are 1-based on self-polymerization.
It is known that white turbidity is likely to occur due to the formation of a nylon-type polymer [Journal of the Chemical Society, Vol. 82, page 866 (1960)], and the stabilizer according to the existing patent can be stably stored for 3 months or more at room temperature. I knew I couldn't. Therefore, it has been desired to develop a stabilizer that simultaneously suppresses yellowing and cloudiness of the isocyanate compound for a long period of time.

[0005]

The first object of the present invention is to provide a stabilizing method for simultaneously suppressing yellowing and white turbidity of an isocyanate compound for a long period of time, and the second object is to provide a stabilized isocyanate. Providing a nat composition.

[0006]

Means for Solving the Problems As a result of earnest search for a stabilizer of an isocyanate compound, the present inventors have found that phenols are relatively effective, and among them, phenol exhibits excellent coloring and cloudiness suppressing effects. Found. Particularly unstable xylylene diisocyanate can be stably stored at 20 ° C. for 6 months or more by adding phenol. Although it has hitherto been known that phenols are effective as stabilizers, surprisingly, such an outstanding stabilizing effect of phenol, which is the simplest compound, has never been known so far. That is, the first of the present invention is a method for stabilizing an isocyanate compound, which comprises adding 10 to 5000 ppm of phenol to the isocyanate compound,
The second invention is the addition of 10 phenols to the isocyanate compound.
This is an isocyanate composition added with ˜5000 ppm.

An appropriate amount of phenol added to the isocyanate compound is 10 to 5,000 ppm, preferably 100 to 5,000 ppm.
2000 ppm is preferred. If it is less than 10 ppm, a sufficient stabilizing effect is not exhibited, and if it exceeds 5000 ppm, the coloring of the isocyanate compound may be rather promoted, which is not preferable. Examples of the isocyanate compound to which phenol can be applied as a stabilizer include monoisocyanate compounds such as methyl isocyanate, butyl isocyanate, phenyl isocyanate and benzyl isocyanate.

Examples of the polyisocyanate compound include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2 '. -Dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-
1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato- 4-isocyanatomethyloctane, 2,5,7-trimethyl-
1,8-diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-α, α'-diisocyanate, lysine di Isocyanato methyl ester, lysine triisocyanate, 2-isocyanatoethyl 2,6
-Diisocyanatohexanoate, 2-isocyanatopropyl 2,6-diisocyanatohexanoate, xylylene diisocyanate, bis (isocyanatoethyl)
Benzene, bis (isocyanatopropyl) benzene,
α, α, α ', α'-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, messy Tyrylene triisocyanate, 2,6-di (isocyanatomethyl) furan, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethyl Methane diisocyanate, 2,2'-dimethyldicyclohexyl methane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol, diisocyanate diisocyanate, 2-iso Anatomechiru-3- (3
-Isocyanatopropyl) -5-isocyanatomethyl-
Bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane,
2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,2
1] -heptane, 2-isocyanatomethyl-2- (3-
Isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5- (2-
Isocyanatoethyl) -bicyclo- [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo- [2,2,2 1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-
(2-Isocyanatoethyl) -bicyclo- [2,2,
1] -heptane, 2-isocyanatomethyl-2- (3-
Isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo- [2,2,1] -heptane, 2,5
(Or 6) -bis (isocyanatomethyl) -bicyclo [2,2,1] -heptane, thiodiethylene diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl Aliphatic polyisocyanates such as diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, phenylene diisocyanate, tolylene diisocyanate, ethyl phenylene diisocyanate, isopropyl phenylene diisocyanate, dimethyl phenylene diisocyanate Nato, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate , Methylnaphthalene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-
Diisocyanate, bibenzyl-4,4'-diisocyanate, bis (isocyanatophenyl) ethylene, 3,
3'-dimethoxybiphenyl-4,4'-diisocyanate, triphenylmethane triisocyanate, polymeric MDI, naphthalene triisocyanate, diphenylmethane 2,4,4'-triisocyanate, 3-
Methyldiphenylmethane-4,6,4'-triisocyanate, 4-methyl-diphenylmethane-3,5
2 ', 4', 6'-Pentaisocyanate, Phenylisocyanatomethylisocyanate, Phenylisocyanatoethylisocyanate, Tetrahydronaphthalene diisocyanate, Hexahydrobenzene diisocyanate, Hexahydrodiphenylmethane-4,4'-di Isocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate,
Diethylene glycol diphenyl ether diisocyanate, dibenzofurandiocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, diphenylsulfide-2,4'-diisocyanate, diphenylsulfide-4,4'-diisocyanate Nart, 3,3 '
-Dimethoxy-4,4'-diisocyanatodibenzylthioether, bis (4-isocyanatomethylphenyl)
Aromatic isocyanate having a sulfide bond such as sulfide, 4,4′-methoxyphenylthioethylene glycol-3,3′-diisocyanate, diphenyldisulfide-4,4′-diisocyanate, 2,2′-
Dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-6,6'-diisocyanate,
4,4'-Dimethyldiphenyldisulfide-5,5 '
-Diisocyanate, 3,3'-dimethoxydiphenyldisulfide-4,4'-diisocyanate, 4,4 '
-Aromatic isocyanate having disulfide bond such as dimethoxydiphenyl disulfide-3,3'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidine Sulfone-4,4'-diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate, 4-methyldiphenylsulfone-2,
4'-diisocyanate, 4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3 '
-Dimethoxy-4,4'-diisocyanatobenzyldisulfone, 4,4'-dimethyldiphenylsulfone-3,
3'-diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate, 4,4'-methoxyphenylethylenesulfone-
Aromatic isocyanate having sulfone bond such as 3,3′-diisocyanate and 4,4′-dicyclodiphenylsulfone-3,3′-diisocyanate, 4-methyl-3-isocyanatophenylsulfonyl-4 Aromatic isocyanate having sulfonic acid ester bond such as'-isocyanatophenol ester, 4-methoxy-3-isocyanatophenylsulfonyl-4'-isocyanatophenol ester, 4-methyl-3-isocyanatophenylsulfonylanilide- 3'-methyl-4'-isocyanate, diphenylsulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-methoxyphenylsulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3 -Isocyanatophenylsulfonylanilide-4-methyl An aromatic polyisocyanate such as an aromatic isocyanate having a sulfonic acid amide bond such as -3'-isocyanate can be used. In addition, sulfur-containing heterocyclic compounds such as thiophene-2,5-diisocyanate, and 1,4-dithiane-2,5-diisocyanate are also included.

Further, it can be applied to an isocyanate compound having an isothiocyanate group, for example, 1-isocyanato-3-isothiocyanatopropane, 1-isocyanato-5-isothiocyanatopentane, 1-isocyanato-.
Aliphatic or alicyclic compounds such as 6-isothiocyanatohexane, isothiocyanatocarbonyl isocyanate, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3 -Aromatic compounds such as isocyanato-1-isothiocyanatobenzene, heterocyclic compounds such as 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, and further 4-isocyanato-
In addition to isothiocyanato groups such as 4'-isothiocyanatodiphenyl sulfide and 2-isocyanato-2'-isothiocyanatodiethyl disulfide, compounds containing a sulfur atom and the like can be mentioned.

In the method for stabilizing an isocyanate compound according to the present invention, the isocyanate compound is added in an amount of 10 to 5,000 p.
For the addition method when adding pm phenol,
There is no need to take any special measures. However, it is preferable to adjust the addition amount depending on the type and storage period of the target isocyanate compound, storage method, storage atmosphere, and the like.

Further, the stabilized isocyanate composition of the present invention may be used in combination with a known stabilizer usually used for an isocyanate compound, as long as it does not impair the effects of the present invention. The stabilized isocyanate composition of the present invention exhibits favorable storage stability even under a high temperature condition such as 80 ° C., for example, as shown in Examples below.

As described above, the isocyanate composition containing the phenol of the present invention in an amount of 10 to 5000 ppm exhibits excellent storage stability by suppressing coloration due to aging and clouding due to self-polymerization. Especially for unstable xylylene diisocyanate, phenol has an excellent stabilizing effect as compared with known stabilizers. Further, as shown in Table 2, the decrease in the purity of the isocyanate compound is also suppressed by the addition of phenol, and the effect is remarkable with respect to the aliphatic polyisocyanate.

[0013]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Examples 1 to 3 and Comparative Examples 1 to 31 m-xylylene diisocyanate (purity 99.8%, hydrolyzable chlorine 0.010%, JIS K1556 5.1)
Stabilizers shown in Table 1 were added to the hue APHA10) according to the above, and the glass container was replaced with nitrogen and sealed up and stored at 20 ° C. When the presence or absence of white turbidity and APHA were visually observed every week, the results are shown in Table 1. The storage test was stopped when the visual turbidity or APHA exceeded 20, and the test period was 24 weeks at the longest.

[0014]

[Table 1]

[0015]

[Table 2]

Examples 4 to 12 and Comparative Examples 32 to 40 Samples of a product containing 500 ppm or more of phenol and 500 ppm of phenol with respect to various isocyanate compounds of APHA10 having a purity of 99.8% or more, glass containers, nitrogen substitution, sealing plugs, 80 It was stored under the condition of ° C. 1 g of each day was sampled, dissolved in 20 ml of toluene, and the number of days until cloudiness was observed was measured. In addition, APHA and purity shall be measured on the 6th day for those in which no cloudiness was observed for 6 days or more,
The test period was up to 10 days. The results are shown in Table 2.

[0017]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C07C 323/45 7419-4H 331/20 8619-4H (72) Inventor Teruyuki Nagata Asamu, Omuta, Fukuoka 30 Mutacho Mitsui Toatsu Chemical Co., Ltd.

Claims (6)

[Claims] 1. An isocyanate compound containing 10 to 5000
A method for stabilizing an isocyanate compound, which comprises adding ppm of phenol. 2. The stabilizing method according to claim 1, wherein the isocyanate compound is an aliphatic polyisocyanate. 3. The stabilizing method according to claim 2, wherein the aliphatic polyisocyanate is xylylene diisocyanate. 4. A phenol is added to the isocyanate compound.
An isocyanate composition added with 0 to 5000 ppm. 5. The isocyanate composition according to claim 4, wherein the isocyanate compound is an aliphatic polyisocyanate. 6. The isocyanate composition according to claim 5, wherein the aliphatic polyisocyanate is xylylene diisocyanate.