JPS6099121A - Production of urethane-modified polyisocyanurate foam - Google Patents

Abstract

PURPOSE:To obtain a homogeneous system liquid, and obtain the titled product having improved heat-resistance and flame-retardance, by mixing a specific nonionic surface active agent to a polyol system liquid containing a halogenated hydrocarbon foaming agent and an isocyanate trimerization catalyst. CONSTITUTION:The objective product can be produced by compounding 100pts. (wt.) of a polyol preferably having an average OH value of about 150-400 and an average OH number of 2-8 with (A) 2-200pts. (<=5pts. in the case of using water) of a halogenated hydrocarbon foaming agent (e.g. CFCl3), (B) a polyol system liquid containing an isocyanate trimerization catalyst (e.g. fatty acid alkali metal salt, OH-containing organic quaternary ammonium salt, etc.) and (C) about 5-50pts. of a nonionic surface active agent of formula [R is 5-30C long-chain aliphatic hydrocarbon group; -(R'O)n- is polyoxyalkylene composed mainly of oxyethylene; k is 0 or 1; n is integer of >=3] and composed of an alkylene oxide adduct composed mainly of ethylene oxide or an aliphatic amine, and reacting the components with polyisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a urethane-modified polyin cyanurate film, and particularly relates to a method for producing a urethane-modified polyin cyanurate film. Modified polyisocyanurate foam (powerful)
There is a thing C that does 1v in the left.

When producing a urethane-modified polyisocyanate claw = 1, a polyol component obtained by adding a foaming agent, a catalyst, etc. to a polyol in advance is often used. This polyol component is called a polyol system liquid, and the method using this polyol system liquid is sometimes called the brimix method. One problem with this polyol system solution containing a blowing agent is the compatibility between the halogenated hydrocarbon blowing agent and the polyol. Since the halogenated hydrogen hydride foaming agent is hydrophobic, if the polyol is hydrophilic, the two are likely to separate, making it difficult to form a uniform system solution. Even if the tank charged with the polyol system liquid is used while being stirred, if there is a large difference in the properties of the two, it will be difficult to take out the system liquid of uniform composition from there.

On the other hand, as polyols for urethane-modified polyisocyanurate foams, highly hydrophilic polyols are effective in increasing heat resistance of 7 ohms and flame retardance. Hydrophilic sieve polyols include polyether polyols with high oxyethylene group content, polyester polyols, and low molecular weight polyhydric alcohols such as ethylene glycol. The amount of polyol used relative to the compound is small, and the amount of blowing agent used relative to the polyol is relatively large. Therefore, in the case of rigid polyurethane foams, comparison 17 between the compatibility of blowing agents with polyols! I! ! It's thicker than that. Furthermore, it is also possible to mix a blowing agent into the polyisocyanate compound to reduce the 1-;1 of the blowing agent added to the polyol system liquid in step 7, but in this case, If the amount of liquid in the polyol system liquid becomes extremely small, it is difficult to mix the two in a uniform ratio.

becomes. There is also a proposal to improve the compatibility of the blowing agent by blending a hydrophobic polyol with a water-based polyol (see, for example, Mon. Kosho 57-212', No. 052-); The use of polyols has poor physical properties in the form of mushrooms.

The present inventor investigated various ways to improve the compatibility between the polyol and the halogenated hydrocarbon blowing agent in the polyol system liquid, and found that the combination of a specific surfactant is extremely effective. This particular surfactant is a nonionic surfactant consisting of an alkylene oxide adduct of an aliphatic amine or aliphatic amide, mainly ethylene oxide, as described below. The present invention relates to a method for producing urethane-modified polyisocyanurate 7 ohm, which is characterized by using a polyol system liquid containing this nonionic surfactant, that is, a polyol, a halogenated hydrocarbon blowing agent.

In a method for producing a urethane-modified polyisocyanurate foam from a polyol system liquid and a polyisocyanate compound, which essentially include a polyol system liquid and an incyanate trimerization catalyst, the polyol system liquid contains IR (-0~N+←ROYH'12R: Long-chain aliphatic hydrocarbon group having 5 to 30 carbon atoms (R'o-
) - A nonionic surfactant represented by 0 or 1, n: an integer (however, the total n in one molecule is 3 or more) is blended into a polyoxyalkylene group mainly consisting of a -nioxyethylene group. A method for producing a urethane-modified polyisocyanurate foam.

It is.

In the nonionic surfactant represented by the above formula, R
is a long-chain, preferably straight-chain aliphatic hydrocarbon group which may have an unsaturated group, and preferably has 8 carbon atoms.
~24.

(-R'O-) is a polyoxyalkylene group mainly consisting of an oxyethylene group, and may have a small amount of oxypropylene group, but is preferably a polyoxyethylene group consisting only of oxyethylene groups. be. The number of n may be different between the two (R0-)-H in one molecule, but the total number of oxyalkylene groups in one molecule (i.e. 2n) is 3 to 5.
It is preferable that it is 5-20 in 0.4f. Further, it is more preferable that k is 0 (that is, it is a derivative of an aliphatic amine). The amount of the nonionic surfactant to be blended is not particularly limited, but it is suitably about 0.5 parts by weight or more, particularly about 5 to 50 parts by weight, per 100 parts by weight of the polyol.

Preferred polyols are polyols and polyol mixtures having an average hydroxyl value of about 100 or more. In particular, polyols having an average hydroxyl group restriction of 150 to 400° and an average number of hydroxyl groups of 2 to 8 are preferred.

Particularly preferred polyols include relatively highly hydrophilic polyols, such as polyether polyols, polyester polyols, and polyester polyols with a high content of oxyethylene groups.

Of course, polyether polyols having a low oxyethylene base f or f or containing no oxyethylene base or other polyols can also be used. Specifically, for example, polyalkylene such as polyethylene glycol,
Glycol: Polyhydric alcohol, poly(tTIiphenol, obtained by adding ethylene oxide or ethylene oxide to an alkanolamine initiator).
Or circular: L-sprue opening 1. I got it because of IJj's death. , polyester polyol; ;l: linonorbone I'J + poly1i1h alcohol, and a, J
Two or more kinds of polyester-1 nityl polyols obtained by reacting l/'-lene oxide may be used in combination, and polyols with low molecular weight, such as ethylene glycol, diethylene glycol, and globylene glycol, can be used in combination. NoLno.

Trimethylolpropane, glycerin, other polyhydric alcohols, jetanolamine, l-jetanolamine, and other alkano-nodoamines have all oxyalkylene groups, and the tyrene group is about 40 to
A polyether polyol having a diameter of 100 weight φ, especially 60 to 100 weight.

Hydrophilic polyols consisting of polyester ether polyols and polyester polyols.

It is also a polyol mixture containing it as a main component.

The polyol system liquid in the present invention contains a halogenated hydrocarbon blowing agent and a ynonate hexamerization catalyst as essential components in addition to the above-mentioned polyol and nonionic surfactant. As the blowing agent, water or the like may be used together with the halogenated hydrocarbon blowing agent. - As the halogenated hydrocarbon blowing agent, lower hydrocarbons containing fluorine and/or chlorine are suitable, such as l-1) chlorofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, dibromomonofluoromethane, dichlorofluoromethane, Tetrafluoroethane.

Examples include 1,1.2-trichloro-1,2.2-trifluoroethane and methylene chloride. A particularly preferred rhodanized hydrocarbon blowing agent is trichlorofluoromethane (R-1 1 ). The amount used is at least 1 part by weight per 100 parts by weight of the polyol,
Particularly preferred is 2 to 200 tons. If water is used, the amount is usually less than 5 parts.

All known IJ catalysts were used as the incyanate trimerization catalyst. For example, metal organic carboxylic acids such as alkali metal salts of specific carboxylic acids; organic quaternary ammonium salts; , phosphines, etc. 4! For J, an alkali metal salt with a fat concentration of 1 or an organic quaternary ammonia l-salt containing a watery ρ group may be used.

The polyol system liquid is blended with 10 optional additives according to the agreement. For example, in order to obtain a good foam, it is preferable to incorporate a polysiloxane foam stabilizer. In addition, various additives such as fillers, reinforcing fibers, flame retardants, colorants, stabilizers, etc. may be blended. Among these,
Substances inert to isocyanate groups: Vi Can also be used by being blended with the isonoanate compound.

As the polyisonoai-1 compound in the present invention, aromatic polyisocyanate compounds are preferred, but aliphatic or alicyclic polyisocyanate compounds may be used alone or in combination with aromatic polyisocyanates, etc. can. As the aromatic polyisocyanate compound, diphenylmethane diisocyanate, l-
Examples include, but are not limited to, lylene diisocyanate and polymethylene polyphenylinocyanate. It is also possible to use modified products of these aromatic polyisocyanate compounds, such as preformer-type modified products, carbodiimide modified products, urea modified products, etc., as well as crude products. The amount of polyincyanate compound used is expressed as a ratio to the total number of hydroxyl groups in the polyol system liquid, and the ratio of incyanate groups/number of hydroxyl groups is about 1.5 or more,
In particular, an amount of about 2 to 5 is preferred.

EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

■ Stability evaluation of polyol and trichlorofluoromethane tD mixture Trial polyol, trichlorofluoromethane.

and a nonionic surfactant f75:X:25 in a weight ratio of 25, left to stand for 10 days, and the uniformity of the solution was observed. If the entire surface is uniformly transparent, it is judged to be a gold phase bath (
○), and those with separation or turbidity 1) in the liquid were judged to have not been made into a bath (×). The types of polyols, surfactants, and nonionic surfactants are shown below, and the test results are shown in Table 1. In addition, in the comparative experiment, when a nonionic surfactant is not used, the mixing weight ratio of polyol and trichlorofluoromethane is 100:X.

Types of polyols> Polyol A: 60 parts by weight of polyether diol prepared by adding 3 mols of propylene oxide to 1 mol of bisphenol A, 20 parts by weight of 7-talic anhydride, and 20 parts by weight of ethylene oxide to 0.1 parts by weight of potassium hydroxide. A polyester ether polyol having a hydroxyl value of 200 obtained by reacting at 12'0° C. for 2 hours in the presence of i% weight and removing a small amount of unreacted materials.

Polyol B: 25 parts by weight of 1,4-butanediol, phthalic anhydride H4o, and 35 parts by weight of ethylene oxide
A polyester ether polyol with a hydroxyl value of 500 obtained by reacting M if fli with polyol A in the same manner.

Polyol C: A polyester polyol with a water Hits value of 320 obtained by reacting a mixture of 80% by weight of phthalate and adipic acid with ethylene glycol.

Polyol D - polyethylene glycol with a 400 (hydroxyl value 280) molecule.

Polyol E: Sorbitol-ethylene oxide adduct with a hydroxyl value of 300.

<Nonionic surfactant> In the above formula, +R'0+ are all oxyethylene groups, k, , R, and the total number of oxyethylene groups (
2n) is the following compound. However, R is linear.

Table 1 (Continued from Table 1) ■ Production test of urethane-modified poly-fonciamerate foam Polyol A-E15 weight) iIj (Tatashi, when non-ionic surfactant is not used t; L 20 fRL :.

1.0 parts), 511 parts of nonionic surfactant, 31 parts of isocyanate, and 31 parts of isocyanate (manufactured by Sankyo Air Products Co., Ltd., trade name 11 DABCO TMR11, quaternary ammonium salt thread 7i), 1.0 parts, Silicone foam stabilizer (Toray Silicone (product name: II S H-1931+)
, and trichloronorolomethane type 23 needle, and 80 parts by weight of polymethylene polyphenylisocyanate (Kasei Upjosen, good quality, trade name "PAPI-135") and total liquid temperature. 20
℃ and mix the mixture into 200 cylinders x 200g x 200
Free foaming was carried out in a wooden box of mn. After one day, the firing properties of the foam were determined according to J. ISA-9514. The types of polyols and nonionic surfactants, the dust density of the foam, and the combustion distance are shown in Table 2 below.

Table 2

Claims (1)

[Scope of Claims] 1. A method for producing a diurethane-modified polyisocyanurate foam from a polyol system liquid and a polyisocyanate compound that essentially include a polyol, a halogenated hydrocarbon blowing agent, and an isocyanate trimerization catalyst,
In the polyol system liquid 1 R÷C~N length R'O thick H] 2 R: long chain aliphatic hydrocarbon group fR'0+ with 5 to 30 carbon atoms
It is characterized by blending a nonionic surfactant represented by: 0 and 1 with n: an integer (however, the total n in one molecule is 3 or more) to a polyoxyalkylene group mainly consisting of a nioxyethylene group. A method for producing a urethane-modified polyisocyanurate foam. 2. The amount of nonionic surfactant is 100% polyol.
Approximately 5 to 50 parts by weight. 2. The method according to claim 1, wherein the method is ij rental department. 3. Nonionic surfactant % Ic agent has R carbon number of 8 to 24
2. The method according to claim 1, wherein the aliphatic amine is added with ethylene oxide.