JPH02178261A - Polyisocyanate composition and polyurethane resin using the same - Google Patents

Abstract

PURPOSE:To obtain the subject readily handleable composition, containing a specific polyisocyanate and triisocyanate in a specified proportion, excellent in low-temperature stability, capable of keeping a liquid state for a long period and useful for producing various polyurethane resins. CONSTITUTION:A mixture, consisting of (A) one or more polyisocyantes selected from diphenylmethane diisocyanate, uretonimine-modified diphenylmethane diisocyanate, tolylene diisocyanate and polymethylene polyphenyl polyisocyanate and (B) a triisocyanate, expressed by formula I (R1 and R2 are 1-4C alkyl; m and n are 0-2), which is a solid at ambient temperature and containing 3-30wt.% ratio expressed by expressed formula II is thermally melted to produce the objective composition, which is then placed in a container avoiding contact with moisture and stored in a dry nitrogen atmosphere at ambient temperature if possible. The composition is reacted with an active hydrogen-containing compound to produce a polyurethane resin, such as polyurethane foam.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyisocyanate composition with good low temperature stability and a polyurethane resin using the same.

More particularly, the present invention relates to low temperature storage stable liquid polyisocyanate compositions and polyurethane resins using the polyisocyanate compositions.

[Conventional technology]

Diphenylmethane diisocyanate (hereinafter referred to as MDI) and tolylene diisocyanate (hereinafter referred to as TDI) are the most commonly used polyisocyanates.
Although MDI has a significantly lower vapor pressure than TDI and is advantageous in terms of safety and health, it is inconvenient to handle because it is solid at room temperature. For this reason, liquefaction of MDI has been observed for a long time.

A method of making so-called polymeric MDI (liquid) containing dinuclear and polynuclear bodies (Special Publication No. 1983-
26337 1C1), non-catalytic heating method with branched aliphatic dihydroxy compounds (Japanese Patent Publication No. 45-20700 B
In addition, there is a carbodiimidation method using a phosphorus catalyst method (Japanese Patent Application No. 37057/1983).

Furthermore, a method CD in which carbodiimidized MDI is further reacted with excess MDI to modify it with uretonimine and liquefy it;
P, 1,092,007 (1959) Bayer Company]
It has been known. Furthermore, there is also a method of liquefying hydrogenated diaminodiphenylmethane as a raw material [e.g.
du Pont company "1lylene W' (du Po
nt company trademark)].

[Problem to be solved by the invention]

In order to rationalize the liquefaction of MDI, the use of heat sources is minimized, and the use of catalysts avoids leaving catalyst residue in the product. 'lDI, and
It is necessary that the quality of the polyurethane product obtained by this liquid MDI is excellent.

[Means for Solving the Problems] In order to solve the above problems, the present inventors have conducted extensive research and have
Uretonimine-modified MDI, TDI that is already liquid at room temperature
, a composition in a limited weight ratio consisting of polymethylene polyphenyl polyisocyanate, MDI which is solid at room temperature, and triisocyanate represented by the following formula (1) is storage stable at low temperatures for a long time, and this polyisocyanate composition The present invention was achieved by discovering that a polyurethane resin using a polyurethane resin has excellent physical properties.

That is, the present invention is as follows.

(1) (8) One or two selected from the group consisting of diphenylmethane diisocyanate, uretonimine-modified diphenylmethane diisocyanate, tolylene diisocyanate, and polymethylene polyphenyl polyisocyanate.
(B) triisocyanate represented by the general formula (1) (where R, R2 are the same or different alkyl groups having 1 to 4 carbon atoms, and mSn is an O to 2 positive alkyl group); (Indicates an integer.) A certain polyisocyanate composition.

(2) A polyurethane resin obtained by reacting an active hydrogen-containing compound with the polyisocyanate composition according to claim (1).

The MDI used in the present invention is 2.4'-MDI, 4.4"
-MDI or mixtures of both isomers in various weight ratios. Both are solids (melting point: about 38°C) at room temperature.

In the triisocyanate represented by the general formula (1) used in the present invention, R, , R, are the same or different lower alkyl groups, specifically methyl group, ethyl group, propyl group (
(including isomers) or butyl group (including isomers).

All of the triisocyanes 1. represented by the general formula (1) are solid at room temperature.

The TDI used in the present invention may be a 2.4 or 2,6 monoisomer or various weight ratios of these isomers (e.g. 80/2
0.65/35) mixture.

To prepare the polyisocyanate composition of the present invention, a mixture of a predetermined weight ratio is heated and melted, placed in a container that can avoid contact with moisture, and stored at room temperature, preferably under a dry nitrogen atmosphere.

Moderately cloudy or solidifies at room temperature.

The polyurethane resin of the present invention includes soft, semi-hard, and hard foams, elastomers, and paints. Coating agent,
Includes adhesives, binders, caulks, sealants, elastic fibers, synthetic leathers, etc.

The active hydrogen-containing compound (polyol) used in the present invention includes known polyalkylene ether polyols, modified polyalkylene ether polyols such as polymer polyols, polyester polyols, and the like.

Examples of the polyalkylene ether polyol used in the present invention include water, di- to tetrahydric polyhydric alcohols, such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, propylene oxide, etc. / or obtained by addition polymerization of ethylene oxide, and its molecular weight is 200 to 20,00.
It is 0.

In addition, for example, ethanolamine, jetanolamine, triethanolamine, tripropaturamine,
Tetra(hydroxyethyl)ethylenediamine, tetra(hydroxypropyl)ethylenediamine, are obtained by addition polymerizing propylene oxide and/or ethylene oxide to ethylenediamine, and their molecular weights are the same (200 to 20,000. The amount of alkylene ether polyol used is 90% by weight or more of the polyol mixture.In addition, the amount of alkylene ether polyol used is 0.7 to 3% by weight of the polyol mixture as it is without adding alkylene oxide to the various amines on the upper side. It is also possible to adjust the reactivity and quality of the polyurethane resin in the product.

Examples of the organic polysiloxane copolymer used as a foam stabilizer in the present invention include L-5 manufactured by Nippon Unicar Co., Ltd.
01, L-520, L-532, L-540, L-54
4, L-3550, L-3600, L-3601, L-
5302, L-5305, Shi-5320, L-5340
, L-5350, L-5410, L-5420, Shi-5
710, L-5720, etc., and 511-190.5H-192, 5H-193, manufactured by Tomu Silicone Co., Ltd.
5H-194, 5H-195, 511-200, 5RX
-274C, 5RX-253, etc., F-114, F-121, F-122, F-2 manufactured by Shin-Etsu Silicone Co., Ltd.
20, F-230, F-258, F-260, F-30
5, F-306, F-317, F-341, F-601
etc., and the one manufactured by Toshiba Silicone Company is TFA-4.
200, TP^-4202, etc.

The appropriate amount to use is 0.7 to 3% by weight of the polyol mixture.

Useful catalysts include, for example, N, N, N'', N''-tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, dimethylpalmitylamine, trimethylaminoethylpiperazine, triethylamine, triethylenediamine, N, N, N', N' -tetramethylpropanediamine, N, N, N', N'-tetramethylhexane 1,6-diamine, N, N, N', N'-1,
3-butanediamine, N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl)ether,
N, N''.

N"-1-lis(dimethylaminoethyl)hexahydrotriazine, N,N',N"-(diethylaminopropyl)hexahydrotriazine, 2,4-bis(dimethylaminomethyl)phenol, 2,4.6 -Amines such as tris(diethylaminomethyl)phenol and tetramethylguanidine. The amount used is suitably 0.1-1% by weight of the polyol mixture.

As a blowing agent, water, trichloromonofluoromethane,
1 such as dichlorodifluoromethane, methylene chloride, trichlorotrifluoroethane, dibromotetrafluoroethane, trichloroethane, pentane, hexane, etc.
Use one or more species.

Other flame retardants, plasticizers, colorants, etc. may also be added as necessary.

In this specification, an example of polyurethane flexible foam is given as a typical use of the polyurethane resin using the polyisocyanate composition of the present invention, but the present invention is not limited to this example.

(Example) The present invention will be specifically described below with reference to Examples and Comparative Examples.

Examples 1 to 3, Comparative Examples 1 to 2 A mixture of various polyisocyanates shown in Table 1 was
Place in a 0cc sealable glass container, heat to approximately 60°C in a dry nitrogen atmosphere to melt the contents, mix uniformly, and leave in a 10°C low temperature chamber to visually check the low temperature stability of the contents. The gender was evaluated.

As shown in the Examples and Comparative Examples in Table 1, the compositions have approximately the same NGO weight %, but the low-temperature stability of the polyisocyanate compositions that do not contain triisocyanate is poor;
The amount of triisocyanate was changed to 5%, 10%, 20% (heavy N
), the low temperature stability improved. That is, in Example 1, it solidified after 4 days of standing, and in Examples 2 and 3, it remained liquid even after 6 days of standing.

Examples 4 to 9, Comparative Examples 3 to 5 The types and amounts of polyols and other compositions (g) listed in Table 2 were placed in a container and thoroughly stirred and mixed. A well-mixed polyisocyanate composition (g) of the type and amount was added to the container containing the above-mentioned "r polyol and other" composition, and after mixing with vigorous stirring for 6 seconds,
350 x 350 x 100 preheated to approximately 50°C
Pour into an aluminum mold with a diameter of about 10 mm at room temperature.
It was left to stand for a minute to expand and foam in the mold and cure. Next, the formed foam was released from the mold, and the physical properties of the foam were measured. The results are also shown in Table 2.

As shown in Table 2, the triisocyanate of the present invention [Table 2]
1 (see Note *1)], and the foams of Examples 4 to 9 using a specific weight ratio of polyisocyanate compositions had a lower permanent compression set than Comparative Examples 3 to 5, which did not use triisocyanate. was small, and all cells were in good condition.

In Comparative Example 3, the foam collapsed during foam expansion, making it impossible to form a foam, and in Comparative Examples 4 and 5, the cell condition was also poor. In Comparative Examples 4 and 5, it can be seen that the permanent compression strain is large and the foams undergo severe aging.

〔Effect of the invention〕

The polyisocyanate composition of the present invention has extremely good low-temperature stability and can remain in a liquid state for a long time, making it convenient to handle.Also, the polyurethane foam using this polyisocyanate composition has good cell conditions and is permanent. It has small compressive strain (and good aging resistance), and the above liquid polyisocyanate composition is useful for producing various polyurethane resins.

Procedural amendment 1 system April 5, 1989

Claims (2)

[Claims] (1) (A) One or two selected from the group consisting of diphenylmethane diisocyanate, uretonimine-modified diphenylmethane diisocyanate, tolylene diisocyanate, and polymethylene polyphenyl polyisocyanate.
(B) Triisocyanate represented by the general formula (I) ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (I) (where R_1 and R_2 are the same or different carbon numbers 1 to 4
alkyl groups, m and n represent positive integers of 0 to 2. ) and (B)/[(A)+(B)] is 3 to 3
0% by weight polyisocyanate composition. (2) A polyurethane resin obtained by reacting an active hydrogen-containing compound with the polyisocyanate composition according to claim (1).