JPS5823381B2 - Isocyanate materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to stabilized organic incyanate compositions.

Organic incyanates are unstable due to the high reactivity of the incyanate group and can become colored and polymerize during storage, reducing their commercial value.

Conventionally, in order to prevent coloration during storage of incyanates, triallylphosphites such as triphenyl phosphite and trinonylphenyl phosphite have been used.
It is known to add trialkyl phosphites such as -ethylhexyl) phosphites.

However, none of these has a sufficient stabilizing effect on incyanates and is not necessarily satisfactory.

As a result of intensive research into this problem, the present inventors found that a specific tetraphenylalkylene glycol diphosphite
The present invention was completed based on the discovery that the compound not only inhibits dimerization and trimerization of incyanate compounds and prevents coloration during storage, but also discolors previously colored incyanate.

That is, the present invention is based on the general formula (where alkylene is an alkylene group having 1 to 5 carbon atoms,
n is an integer of 1 to 5).

For example, +R1-0-R2-0+□, (-R1-0-R2-
0-R, -0+, (-R1-0-)-mR2-0- [
In the formula, R1 and R2 are each different and have 1 to 5 carbon atoms.
m represents 1 or 2;

It may also be polyoxyethylene represented by

Examples of the alkylene group represented by R1 and R2 include methylene, ethylene, isopropylene, trimethylene, 2,3-butylene, tetramethylene, bentelene, and substituted alkylenes such as chloropropylene.

The isocyanate compound in the present invention may have at least one incyanate group in the molecule, and specific examples include diphenylmethane diisocyanate (MDI), phenyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, bis( incyanate methyl) cyclohexane, dicyclohexylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylethane diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenylmethane triisocyanate, bitolylene diisocyanate,
Also included are triphenylmecune triisocyanate and polymers thereof, as well as adducts containing terminal incyanate groups between excess of these incyanates and various active hydrogen compounds.

Specific examples of the compound represented by the general formula CI) include tetraphenylethylene glycol diphosphite, tetraphenyldiethylene glycol diphosphite, tetraphenyltriethylene glycol diphosphite, tetraphenyltetraethylene glycol diphosphite, tetra 71, Nylpentaethylene glycol diphosphite, tetraphenylpropylene, glycol diphosphite, tetraphenyldiethylene glycol diphosphite, tetraphenyltriethylene glycol diphosphite, tetraphenyltetrapropylene glycol diphosphite, tetraphenylpentapropylene glycol diphosphite , tetraphenylchloropropylene glycol diphosphite, tetraphenyltrimethylene glycol diphosphite, tetraphenylbutylene glycol diphosphite, tetraphenyltetramethylene glycol diphosphite, tetraphenylbenzene gelicold diphosphite, and the like.

In order to incorporate the compound [■] into the incyanate, it is preferable to add it to the isocyanate compound in a liquid or molten state and mix it in a nitrogen atmosphere to homogenize it.

Of course, it may be added to either incyanate compound products or intermediate products.

The amount added is about 0.01 to 2.0% by weight, preferably 0.
．． It is best to add about 0.02 to 0.2% by weight, and even if more than this is added, the effect will hardly change.

According to the present invention, polyisocyanates can be stored stably, and by adding and mixing the present stabilizer to polyisocyanate that has been colored to some extent, a polyisocyanate composition with a low color number can be obtained, and this composition can be further polymerized. A similar effect can be exerted on a polymer obtained by the reaction.

Other known stabilizers in the compositions of the invention, such as B
There is no problem in using an antioxidant such as HT, m-cresol, etc. in combination.

Furthermore, the present stabilizer does not pose any hindrance to the application of polyinsyanate.

Next, an explanation will be given taking an example of MDI which is particularly susceptible to deterioration, but the present invention is not limited to these examples.

Example 1 (initial fading effect) Purity 99.8%, cyclohexane insoluble content 0.1% or less,
100 parts of MDI with a freezing point of 38.8°C was placed in a colorless transparent bottle, a stabilizer was added and mixed, and the mixture was heated at 45°C for 15 hours in a nitrogen stream.
After being left to stand, the degree of coloring was compared.

In addition, the degree of coloring of the raw material MDI before adding additives is APHA.
It was 50.

Example 2 (fading effect) M 99.9%, cyclohexane insoluble content 0.1% or less,
MDI1 with a freezing point of 388°C and a coloring degree of APHA 300
0.00 parts of tetraphenyltetramethylene glycol diphosphite was added and mixed (stored in a transparent bottle at 60° C. in a nitrogen atmosphere).

The degree of coloration after 10 hours was APHA30, and after another 30 hours it was APRA15.

Example 3 (Gradual fading effect during low temperature storage) Purity 99
．． 8%, cyclohexane insoluble content 0.1% or less, freezing point 3
100 parts of a mixture of MDI with an initial coloration degree of APHA 50 and various stabilizers was placed in a transparent bottle at 8.8°C and stored at 0°C ± 5°C, which is considered to be the most stable temperature in a nitrogen atmosphere, to examine changes over time. .

The results are shown in Table-2.

Note that the measurement was performed after melting at 60°C.

Example 4 (Prevention of discoloration during high temperature heating) After adding and mixing a stabilizer to 100 parts of the same MDI as in Example 3, the mixture was placed in a colorless transparent bottle and kept at 100°C in a nitrogen atmosphere.
When the change over time was measured, the following results were obtained.

Example 5 Purity 99.9%, hydrolyzable chlorine ω of 0.01% or less,
ω′-diisocyanate dimethylcyclohexane (H6
XDI) and influorone diisocyanate (IPD
A stabilizer was added to 100 parts of each of I), the mixture was placed in a transparent bottle, and the mixture was stored at 25±5° C. in a nitrogen atmosphere to examine changes in the degree of coloration over time.

The results are shown in Table 4.

Note, PPGP: Tetraphenyldiglopyrene glycol diphosphite

Claims (1)

[Claims] 1 General formula (wherein, alkylene represents an alkylene group having 1 to 5 carbon atoms,
n is an integer of 1 to 5).