JPS5829815A - Quick-curing polyurethane composition - Google Patents

Abstract

PURPOSE:A quick-curing polyurethane composition capable of providing foams with a uniform cell diameter and thickness, containing a polyether-polyol obtained by using tolylenediamine in a specified weight ratio and an alkyl titanate as a catalyst. CONSTITUTION:A polyether-polyol is prepared by mixing above 5wt% tolylenediamine with a polyhydroxy compound (e.g., sucrose, ethylene glycol) and a polyamino compound (e.g., ethylenediamine, phenylenediamine) and reacting the mixture with an oxirane ring-containing compound (e.g., ethylene oxide, propylene oxide). Then the resulting polyether-polyol is mixed with a polyisocyanate, a blowing agent, an alkyl titanate (e.g., tetrapropyl titanate, tetrabutyl titanate) as a catalyst and a foam stabilizer to form the purpose quick-curing polyurethane composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyurethane composition having rapid curing properties.

Conventionally, plastic foam consisting of closed cells has been prized as a heat insulating material and a cold insulating material, and in particular, hard urethane 7
Ohm is widely used as a heat insulating material for refrigerators. Such hard urethane foams are usually made of polyisocyanate as a main component (one-component liquid, polyol or polyether), and an amine-based or tin-based catalyst, water, and Freon R1.
It is produced by mixing a foaming agent such as R1 or R12 and a polyol side component liquid containing a foam stabilizer as a foaming stock solution, followed by foaming and curing. However, when manufacturing using a conventional composition, the time required from mixing the foaming stock solution to foaming and curing is usually around 1 to 5 minutes. Therefore, when producing 7-ohm foam using a high-speed mixer and distributing it onto a conveyor line, or when spraying it onto a wall, etc. using a spray gun, the unfoamed stock solution flows into the lower part of the foaming stock solution, creating 7-ohm bubbles. There are problems such as the diameter and thickness of the 7 ohm being non-uniform and the surface of the 7 ohm being extremely rough.

The present invention has been made in order to solve the above-mentioned problems, and the purpose is to create a polyurethane composition having quick hardening properties in order to obtain a 7-ohm urethane with uniform cell diameter and 7-ohm thickness. It's about providing things. The present inventors have found that the objective can be achieved by using tolylene diamine as a raw material for polyneedle polyol and adding an alkyl titanate as a catalyst, and have completed the present invention.

That is, the fast-curing polyurethane composition of the present invention contains a polyisocyanate, a polyether polyol, a blowing agent, a catalyst,
and a foam stabilizer, the polyether polyol contains 5% by weight or more of tolylene diamine as a raw material, and contains an alkyl titanate as a catalyst. be.

Below, the composition of the present invention will be explained in more detail.

The polyether polyol of the present invention has the following general formula [■] A-CM-CH-B \1 (n) [wherein A and B are the same] per mole of tolylene diamine represented by the following formula. 4 may be different, hydrogen atom,
Represents a methyl group. ] It contains a compound obtained by reacting 4 moles or more, preferably 4 to 8 moles, of the oxirane ring-containing compound shown below. The compound obtained by the above reaction has the following general formula [
1 [I) %Formula% [In the formula, R1-R4 may be the same, different, or different, and represent a hydrogen atom or a methyl group, and n is 1 to
It is an integer of 2. Also, in the case of n=2, A and B are units F
It may be different for each. ) means a group represented by ], and its hydroxyl value is 300 to 500
and preferably around 450.

Such compound (III) can be obtained, for example, by adding 8 moles of ethylene oxide to 1 mole of 2.4-)lylene diamine and reacting the mixture in a nitrogen atmosphere at 110 C for 3 hours in the presence of an alkali catalyst. The above reaction product is expressed by the following formula%) , may be used by mixing with the polyether polyol side component liquid, but in order to save labor in the process, tolylene diamine and oxirane ring-containing compound are mixed together with other raw materials for producing polyether polyol. It is preferable to use a

In such a case, synthesis is carried out by mixing and simultaneously reacting other raw materials with tolylene diamine and the oxirane ring-containing compound. The reaction conditions are, for example, 1
After reacting for 3 hours at 10C in the presence of an alkali catalyst, it is neutralized. Next, the polyether polyol is obtained by topping to remove unreacted oxirane leprosy compound. Such a polyether polyol contains tolylene diamine at 5 m1t% or more,
Its hydroxyl value is 400 to 500.

The tolylene diamine used in the present invention has a 2.4
-) lylene diamine and/or 2,6-tolylene diamine.

Examples of the oxirane ring-containing compound used in the present invention include ethylene oxide, propylene oxide, and butylene oxide, and one or more of these may be used.

Furthermore, other raw materials for l-ether polyol used in the present invention include those containing 2 hydroxyl groups and/or amino groups.
Examples include compounds containing more than one. These include polyhydric hydroxy compounds such as ethylene glycol, propylene glycol, sorbitol, neopentyl glycol, trimethylolpropane, pentaerythritol, sugar, and staniti, and polyvalent amine compounds such as ethylenediamine, Examples include trimethylene diamine, tetramethylene diamine, phenylene diamine, triaminoflopane, and amino/
Examples of the alcohol compound include monoethanolamine, jetanolamine, triethanolamine, and monomethylaminoethanol. These are selected and used depending on the purpose.

The polyurethane composition of the present invention further contains an alkyl titanate as a catalyst. The amount of alkyl titanate added is 1 g or more by weight, preferably 3 to 61 t parts, per 100 parts by weight of polyether polyol.

Examples of the alkyl titanate used in the present invention include tetrapropyl titanate, tetrabutyl titanate, tetrahexyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isobrobildodecylbenzenesulfonyl titanate, tetrapropyl bis(dioctyl titanate), and tetrapropyl bis(dioctyl titanate). phosphite)
Alkyl titanate monomers such as titanate, tetrabutyl bis(ditridecyl phosphite) titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(diotyl pyrophosphate) ethylene titanate, and partially hydrolyzed and condensed monomers thereof. Examples include the resulting polymers. The above alkyl titanate may be used alone, or 2111
The above may be used in combination.

Other compositions used in the present invention, which have been conventionally used in the production of hard urethane 7 ohms, will be briefly described below.

Examples of the polyisocyanane F that forms the main component of the isocyanate side component liquid include 2,4-)lylene diisocyanate (TDI), 2,6-)lylene diisocyanate) (
TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-s7tale diisocyanate,
Examples include hexamethylene diisocyanate (HMDI), prepolymers of these and sucrose-based polyols, diols, ) diols, etc., or crude TDI, crude MDI, etc.
Incyane) containing DI and the like alone or in an appropriate combination are used.

As a blowing agent, for example, trifluorochloromethane (
It is preferable to use halogenated alkanes such as R11) and dichlorodifluoromethane (R12).

It is optional to use a catalyst other than the alkyl titanate, but by using it, a 7-ohm urethane with slightly better performance can be obtained. Such catalysts include, for example, amine compounds, metal soaps containing tin, etc., and any one selected from these may be used, or two or more thereof may be used in combination.

Examples of the foam stabilizer include silicone-based or fluorine-based compounds. The foam stabilizer is usually used by being mixed into the polyol side component liquid, but if it does not have an active group that reacts with isocyanate, it may be mixed into the isocyanate side component liquid.

The desirable blending ratio of the above-mentioned components is polyether polyol 100f! /6, about 1 to 2 parts of catalyst, 0.5 to 2 parts of foam stabilizer, and 30 to 60 parts of foaming agent. The polyether polyol and the isocyanate are preferably blended so that the NCO index is in the range of i,to to 0.90.

When using the composition of the present invention, the time from mixing the foaming stock solution to completing curing is within 10 seconds.
The unfoamed stock solution does not flow into the lower part of the foamed stock solution, and the resulting 7 ohm bubbles have a uniform diameter and thickness.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Examples 1 to 11 To a compound consisting of 80 parts by weight (parts by weight, same hereinafter) and 20 parts of ethylenediamine, lO to Io parts of tolylenediamine were added, and then 100 parts of ethylene oxide was added.
Make sure to add some parts and mix. The mixture was heated for 11 hours in a nitrogen atmosphere.
After reacting for 3 hours at 0C in the presence of an alkali catalyst, the mixture was neutralized and shipped to remove unreacted ethylene oxide. The polyether diols synthesized in this manner contain tolylene diamine in the amounts shown in Table 1.

Kanana polyether contains 11 parts of dibutyl steel urate, 1150 parts of R, 2 parts of silicone foam stabilizer (XF43-004 manufactured by Toshiba Silicone), and tetrabutyl titanate as shown in Table 1, per 100 parts of diol. The amount was mixed to prepare a polyether polyol side component liquid. In addition, as the component liquid on the insea keyed side, isocyanate (MDI-TRs manufactured by Mitsui Nisso Polyurethane).

BX) 124 parts were used. The foaming stock solution thus prepared was instantaneously mixed using a two-component spray gun to form a 7-ohm urethane foam. The time required for the formed 7-ohm urethane to foam and harden, as well as the density and thermal conductivity (O
C), cell diameter, and low temperature dimensional stability were measured. The results are shown in Table-1.

The comparative example has the same composition as Examples 1 to 6 except that it does not contain tolylene diamine.

In the table, the numbers in parentheses for tolylene diamine content are parts by weight based on 200 parts of other polyether polyol components. Also, cream time is the time from mixing until just before it starts to expand, and tack-free time is the time from mixing until it becomes no longer sticky to the touch.

The low-temperature dimensional stability is the value obtained by cutting a 7 ohm piece into 101 cubic pieces 24 hours after foaming, and measuring the rate of change in size after leaving it at -30C for an additional 24 hours. Also, the gel time was not recorded because it was not a bright line.

As is clear from the table, when using the composition of the present invention,
Mixing* It quickly becomes a cloudy creamy liquid and begins to expand, indicating that surface hardening is complete.

The composition of the present invention has the characteristics of fast hardening and high expansion ratio, so the urethane foam produced from this composition can be used not only as a heat insulating material but also for life jackets, etc. This book can be used for Also, the hollow type 7 ohm is W! It is also possible to use 5U. Furthermore,
It can also be used as a packaging material, and compared to the currently used styrene foam, it can save labor in packaging processes.

Claims (1)

[Claims] t A polyurethane composition consisting of a polyisocyanate, a polyether polyol, a blowing agent, a catalyst, and a foam stabilizer, in which the polyether polyol is made by using at least 5 US of tolylene diamine as a raw material, and a catalyst A fast-curing polyurethane composition comprising an alkyl titanate as an alkyl titanate.