JPS5823405B2 - Nannen Safe Home - Google Patents

Description

[Detailed description of the invention] This invention relates to a method of manufacturing a flame retardant foam, one layer group.

In other words, it relates to a method for producing a flame-retardant foam obtained by applying the reactivity of isocyanates.

Conventionally, foams obtained by applying the reactivity of isocyanate include polyurethane foam obtained in the process of polyurethane bond formation by reaction between polyisocyanate and polyol, and polyurethane foam obtained by the formation of polyurethane bonds and trimerization reaction of isocyanate. In addition to the resulting polyurethane-modified isocyanurate foam, the polyisocyanurate foam obtained only by trimerization reaction of isocyanate, polyimide, polyamide, polycarbodiimide, polyurea, and polyoxazolidone bonds are added to these foams by reaction during foam formation or Various forms are known that are introduced before form generation.

Typically, these foams are prepared by the presence of an inocyanate and a blowing agent, optionally one or more compounds capable of reacting with the isocyanate, such as polyols, epoxy compounds, polycarboxylic acids, acid anhydrides, etc. Catalysts, surfactants, flame retardants, and other additives are used as necessary.

All of these various foams can be made flame retardant to a certain extent depending on the type of material used.

In particular, isocyanurate foams obtained by the trimerization reaction of incyanate have good flame retardancy.

The present inventors continued their research with the aim of further improving the flame retardance of various foams obtained by utilizing the reactivity of isocyanates, and as a result, when producing these foams, they found that ethylenediamine metal, which is soluble in the foaming stock solution, It has been found that the addition of a chelate compound significantly improves the flame retardancy of the resulting foam, particularly the surface flame retardance and flame resistance.

It is therefore an object of the present invention to provide a method for producing isocyanate-based foams with improved flame retardancy, in particular with improved surface flame retardancy and flame resistance. agent, and optionally at least one type of polyol, epoxy compound, polycarboxylic acid, acid anhydride, and other compounds capable of reacting with incyanate, and optionally a catalyst,
When foams are produced by adding foam stabilizers and other auxiliary agents and applying the reactivity of isocyanates, this is achieved by adding a soluble ethylenediamine metal chelate compound to the foam production stock solution.

Next, the present invention will be explained in detail.

The ethylenediamine metal chelate compound used in the method of the present invention has the general formula M(H2NCH2CH2Nu2)mRn (wherein M is aluminum, ii transition metal such as lead, zirconium, cobalt, titanium, nickel, and manganese, and R is an inorganic or an organic anion, m and n are integers of 1-3.

) is a compound represented by In the above formula, n is related to the coordination number specific to the metal M, and a specific example of R is CH3C
OO-1CH3(CH2)kCoo-(k-1~8),
Examples include inorganic anions such as 5O4-.

The metal chelate compound must be soluble in the foaming stock solution.

Representative examples of such compounds include the following.

Bis(ethylenediamine) copper acetate, bis(ethylenediamine) octanoate, bis(ethylenediamine) copper benzoate, bis(ethylenediamine) cobalt acetate, bis(ethylenediamine) zinc acetate, bis(ethylenediamine) manganese acetate, bis(ethylenediamine) ) Nickel chloride, bis(ethylenediamine) nickel acetate.

Therefore, in the method of the present invention, one type or two or more types of ethylenediamine metal chelate compounds can be used.

When adding an ethylenediamine metal chelate compound during foaming, if the chelate compound is a powder, it is best to dissolve it in a foaming solution other than polyisocyanate, such as a polyol, a catalyst, a surfactant, and in some cases a flame retardant. good.

In addition, if it is not soluble in these single components, it may be soluble in a mixture of these components, so in such cases it is preferable to dissolve it in the mixture.

When the above chelate compound V$ is in liquid form, it may be added directly.

In short, it is sufficient that most of the added ethylenediamine metal chelate compound is uniformly dispersed in the foam at the molecular level after foaming, or that it reacts uniformly with incyanate.

For foams that use polyols, in some cases, it is industrially advantageous to synthesize an ethylenediamine metal chelate compound in the polyol that is the raw material for the foam, and if this compound is dissolved in the polyol, it can be used as it is as the raw material for the foam. It is.

The amount of the ethylenediamine chelate compound added is 0.1 to 20% (wt%, the same applies hereinafter), preferably 0.5%, based on the total amount of the chelate compound and the polyisocyanate and polyols reactive therewith. -10%, more preferably 0.5-5%.

The chelate compound must be soluble in the foam stock solution as described above, and must be an ethylenediamine metal compound that is insoluble in the foam stock solution, such as evapoethylenediamine copper dichloride, ethylenecyamine copper sulfate, ethylenediamine iron chloride, or ethylenediamine iron. Addition of 1 to 5% acetate hardly improved flame retardancy.

Isocyanates that can be used in the present invention include diphenylmethane diisocyanate (MDI), polyphenylene polymethylene polyisocyanate (crude MDI), 2.4
-Tolylene diisocyanate (2.4-TDI), 2.
Aromatic polyisocyanates such as 6-tolylene diisocyanate (2,6-TDI) and xylylene diisocyanate (MDI), aliphatic polyisocyanates such as hexamethylene diisocyanate, and fats such as isophorone diisocyanate. These include cyclic polyisocyanates, and organic polyisocyanates used in ordinary urethanization reactions can be used alone or in combination of two or more.

Polyols that can be used in polyurethane foams, urethane-modified isocyanurate foams, urethane-modified carbodiimide foams, etc. to which an ethylenediamine metal chelate compound is added may be those with hydroxyl values in any range as long as they are normally used in the production of polyurethane. Preferred are polyether polyols, polyester polyols, and polyester polyols having a hydroxyl value within the range of 300 to 800, which are used in the production of general rigid polyurethane foams.
or a mixture thereof.

Typical examples of polyether polyols include polypropylene ether glycol, polyethylene polypropylene ether glycol, polytetramethylene ether glycol, polyhentamethylene ether glycol, polyhexamethylene ether glycol, polyoctamethylene ether glycol, bisphenol A and propylene oxide. or polyether glycol such as glycol having an aromatic ring obtained by adding ethylene oxide;
and glycol, alkylene oxide, substituted derivatives thereof, or mixtures thereof, sucrose, nrubitol, styrene-vinyl alcohol copolymer, hexanetriol, pentaerythritol, glycerin, trimethylolphenol, trimethylolpropane, 1.4
- Branched polyether polyols obtained by reacting materials such as butanediol, ethylenediamine or similar compounds thereof in the presence of suitable catalysts.

Further, a typical example of polyester polyol is one made from dibasic carboxylic acid and polyhydric alcohol.

Dibasic carboxylic acids useful for making this polyester are those that do not have any active hydrogen-containing functional groups other than their carboxyl groups; specific examples include phthalic acid, terephthalic acid, isophthalic acid, succinic acid, and glutaric acid. Acids such as , adipic acid, pimelic acid are suitable.

These acid anhydrides can also be used.

Among the forms to which an ethylenediamine metal chelate compound is added, the carboxyl group-containing compound used in the production of the amide-modified or amide-urethane-modified isocyanurate foam is the combination of the tribasic acid and the tribasic acid with the polyhydric alcohol. These are polyesters having carboxyl groups at the ends, which are obtained by reaction.

To produce the foam, these dibasic carboxylic acids are reacted in advance with isocyanate, which is the main raw material used, to synthesize an amide prepolymer having inocyanate groups at the ends, and this is used as the isocyanate component. A method of making ceteform in the presence of an ethylenediamine metal chelate compound, a trimerization catalyst, a blowing agent and a surfactant, and optionally a polyol, i.e. a prepolymer method, in which a dibasic carboxylic acid is added directly to the foam production stock solution. There is a method called the one-step method.

When using the one-stage method, if the dibasic carboxylic acid used is a solid, it is preferable to dissolve the remainder in ol or the like before use.

The process included in the process of the invention, i.e. the production of polyimide-modified or polyimide-urethane-modified incyanurate foams with the addition of an ethylenediamine metal chelate compound, involves the reaction of an isocyanate with an acid anhydride; Typical anhydrides include trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarbo/acid anhydride, and the like.

In order to produce foam using these, these acid anhydrides are reacted with isocyanate in advance to synthesize a prepolymer containing an imide bond and having an incyanate group at the end, and this is used as the isocyanate component to form a prepolymer as described above. It can be produced in the same manner as amide-modified or amide-urethane-modified incyanurate.

Regarding the catalyst used when making the foam according to the method of the present invention, in the case of urethane foam, the foam can be obtained by the ethylenediamine metal chelate compound acting as a urethanization catalyst without using a normal urethanization catalyst. However, if a urethanization catalyst is added, the reaction will proceed more smoothly.

Examples of the urethanization catalyst include organic tin compounds, phosphine, and tertiary amines.

Specific examples of the above tertiary amine include triethylamine,
Triethylenediamine, N-N-N'-N'-tetramethylethylenediamine, N-N-N'・y-tetraethylethylenediamine, N-methylmorpholine, ■・1・
3,3-tetramethylguanidine, N-N-N'/N'
Examples include -tetramethyl-1,3-butanediamine, N-N-dimethylethanolamine, and N-N-diethylethanolamine.

In addition, as a catalyst for producing various modified isocyanurate foams including the trimerization reaction of incyanate or pure incyanurate foam, alkaline alcohols such as polypropylene glycol sodium salt derived from polypropylene glycol are used. lard, potassium benzoate, sodium acetate, potassium oleate, alkali metal salts such as polymerized linseed oil fatty acid potassium salts, and N-N'.N'-tris(dialkylaminoalkyl)-sym-hexahydrotriazine, 2. All known trimerization catalysts are effective, such as tertiary amines such as 4,6-tris(dimethylaminoalkyl)phenol and triethylenediamine, and these may be used alone or in mixtures.

Furthermore, it is even more effective to use an epoxy compound in combination with these trimerization catalysts.

Epoxy compounds used in this case include substituted monooxides such as shrimp chlorohydrin, allyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, styrene oxide, propylene oxide, butadiene monoxide, dicrycidyl ether, and bisphenol A. Examples include glycidyl ethers such as digly-4 cidyl ether.

In the process of the present invention, surfactants may be added during foam production to assist in homogenizing the components of the reaction mixture and to adjust the cell structure of the resulting foam.

Suitable surfactants include silicon-containing compounds such as polysiloxane-polyoxyalkylene polymers and other organopolysiloxanes.

Also effective as surfactants are oxyethylated alkylphenols, oxyethylated aliphatic alcohols, and block copolymers of ethylene and propylene oxide.

The blowing agent used in carrying out the process of the present invention is C, which is produced by adding water to the mixture of reactants.
02 or externally added CO2, N2,.

Gaseous substances such as mixtures thereof are also included.

Other preferred blowing agents include low boiling liquids that evaporate due to the heat of reaction generated during foam formation.

Fluorinated and/or chlorinated hydrocarbons with boiling points of -50°C to +110°C are good blowing agents with good compatibility; typical examples of such are trichloromonofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, and dichloromonofluoromethane. Methane, monochlorodifluoromethane, dichlorotetrafluoroethane, 1,1,2-trichloro-1,2,2-
Examples include trifluoroethane, cyfuromofluoromethane, monopromotrifluoroethane, and the like.

In addition, nitrogen, toluene, methylene chloride, hexane, etc. are also used.

These blowing agents can be used alone or in combination.

In the method of the present invention, a flame retardant may be added depending on the case.

As such flame retardants, those used in ordinary polyurethane foams, V-tanned incyanurate foams, etc. are effective.

Typical examples include halogenated organic phosphorus compounds such as tris(chloroethyl)phosphate, tris(dichloropropyl)phosphate, and tris(dichloropropyl)phosphate, and inorganic flame retardants such as antimony oxide.

Next, examples of the method of the present invention and production examples (experimental examples) of raw materials thereof will be explained, but the present invention does not depart from the gist thereof.
It is not intended to be bound by these examples.

Experimental Example 1 Synthesis of bis(ethylenediamine) copper acetate: 71 moles of anhydrous ethylenediamine (6
of) and add 0 copper acetate while stirring with a stirrer.
．． Add 5 mo/L/(90.7 f?) and stir for a while to obtain a deep blue uniform solution.

This product is filtered once and the P solution is concentrated to obtain bis(ethylenediamine) copper acetate.

Example 1 PAP1135 (polymethylene-polyphenylene-polyisocyanate, NGO equivalent weight 135, manufactured by Upjohn Company, USA) as the polyisocyanate, S as the polyol
c -1O00 (Sucrose polyether polyol, OH value 44 g, manufactured by Sanyo Chemical Co., Ltd.), N - as a catalyst
N'・v'-tris(dimethylaminopropyl) -s
ym-hexahydrotriazine (hereinafter abbreviated as HHT), 5H-193 (silicon-based surfactant, manufactured by Toshi Co., Ltd.) as a foam stabilizer, and trichloromonofluoromethane (hereinafter abbreviated as R-11) as a foaming agent. Ethylenediamine copper acetate synthesized in Experimental Example 1 [hereinafter referred to as C
It is abbreviated as u(EDA)2(AeO)2.

] and equivalence ratio (-NGO/-OH+8XCu (E
A foam with DA) 2 (Ac O) 2 , l (equivalent ratios are expressed by similar calculations in subsequent examples) is made at the blending ratio shown in Table 1 below, and Cu(EDA) 2 (AcO) 2 The relationship between the amount added and surface combustibility, resistance to flame, and flame resistance was investigated.

The results are shown in Table 1. In Table 1, Cu (EDA)
2 (Act) The amount (%) of 2 is based on the formula.

In the following examples, the amount of ethylenediamine metal chelate compound was calculated in the same manner.

The surface flammability test was carried out by the Journal of Cellular Plastics (Journal of Cellular Plastics).
The flame penetration time, which indicates flame resistance, was determined by the Butlar Chimney test described on page 497 of the November 1967 issue. Penetration test (Bureau of m1nes flameP)
enetration test).

To manufacture the foam, PAPI-135 and R-11 are used as liquid A, and other components are used as liquid B. Both liquids A and B are thoroughly mixed in advance, and when foaming, these two liquids are combined and heated. The mixture was rapidly stirred with a drill and foamed.

Judging from the results in Table 1, Cu (E DA) 2 (A
It is clear that the addition of CO)2 improves the surface combustibility and flame resistance, and that increasing the amount added further improves each of the properties.

Example 2 The same raw materials as in Example 1 were used, and the equivalent ratios were I, 2.3.
Cu (EDA) 2 (Ac O) 2 so that it becomes 5
When adding (Table 2) and not adding (Table 2)
A surface flammability test was conducted on the foams shown in Table 3).

The results are shown in Tables 2 and 3. From Tables 2 and 3 above, both polyurethane and polyurethane-modified isocyanurate contain Cu (EDA) 2 (AcO
) It can be seen that the addition of 2 improves the surface flammability.

Example 3 Polyol 5c-1000 used in the blending of Experiment No. 1 (comparative example) and Experiment No. 3 (inventive example) of Example 1
5p-600 (sorbitol-based polyether polyol, OH value 560, manufactured by Sanyo Kasei Co., Ltd.) was used to produce foam, and the surface flammability (residual weight and afterflame time) and flame resistance (flame penetration time) were tested. went.

Table 4 shows the formulation and flame retardant test results.

From Table 4 above, it can be seen that the addition of Cu(EDA)2(AcO)2 significantly improves the surface combustibility and flame resistance.

Example 4 Polyol 5c-1000 of Experiment No. 4 of Example 2 (Table 2, Inventive Example) and Experiment No. 8 (Table 3, Comparative Example) was
A urethane-modified isocyanurate foam was prepared in place of p-600 and tested for surface flammability (residual weight and afterflame time) and flame resistance (through flame time).

The formulation and test results during foam production are shown in Table 5 below.

From Table 5 above, it can be seen that even in the urethane-modified incyanurate foam, the addition of Cu(EDA)2(AcO)2 reduces the surface combustibility and significantly improves the flame resistance.

Example 5 In the formulation of experiment number 6 of Example 2 (Table 3), Cu(ED
A) A foam was prepared by adding 61 grams of 2(AcO)2, and a surface flammability test was conducted.

This foam had a residual weight of 53% and an afterflame time of 5 seconds, indicating that the flame retardance was improved compared to the foam without Cu(EDA)2(AcO)2 (Experiment No. 6 of Example 2). it is obvious.

Example 6 Adding Cu(ED) to the formulation of Experiment No. 6 (Table 3) of Example 2
A) A foam was prepared by adding 6 g of n(AcO)2 (n of 10 q, 1.5 g), and a surface flammability test was conducted.

This foam had a residual weight of 54% and an afterflame time of 6 seconds, and its flame retardance was significantly improved compared to the foam to which the metal chelate compound was not added (Experiment No. 60 foam of Example 2).

Example 7 PAP in the formulation of Experiment No. 6 of Example 2 (Table 3)
I-135 was replaced with PAPI-901 (crude MDI modified with carbodiimide, NCO equivalent: 133, manufactured by Upjohn, USA), and Cu(EDA) was added to this product.
2(AcO)2 was added to form a foam, which was cured overnight at about 70°C, and then subjected to a surface flammability test.

At the same time, a foam without the addition of Cu (EDA) 2 (Ac O) 2 was prepared, and the results are also shown in Table 6.

From Table 6 above, it can be seen that when the method of the present invention is used, the surface combustibility and flame resistance are significantly improved.

Example 8 A prepolymer was prepared by adding 30° 1 of adipic acid to 97 (1) PAPI-135 and heating at about 80° C. for 3 hours (NCO equivalent weight 145).

This is the PAP in Experiment No. 2 (Table 2) of Example 2.
A form with an equivalence ratio of 2 was created by using it in place of I-135.

The residual weight of this product in the surface flammability test was 55%.

Note that the foam made at an equivalent ratio of 2 without adding Cu(EDA)2(AcO)2 had a residual weight of 36%.

Example 9 Epicote 819 to 180.61 PAPI-135
(Epoxy resin, manufactured by Mitsubishi Yuka Co., Ltd.) 91 was added and R-11 of 251 was dissolved in this to make solution A, while G
P-250 (glycerin-based polyether polyol, O
H value 674, manufactured by Mitsubishi Chemical Corporation) 9? Cu (EDA)
2 Dissolve 41 of (A c O)2 and add 41 of HH to this.
A solution B was prepared by adding T and 18.3 f of 5H-193, and solution A was added to solution B and mixed with an electric drill to form a foam.

The flame penetration time of this foam was 150 minutes, and the residual weight in the surface flammability test was 82%.

For comparison, Cu(EDA)2(Ac
The flame penetration time of the foam made without O)2 was 75 minutes,
The residual weight was 75%.

Example 10 Ethylenediamine chelate (Cu(EDA)2(C5H5COO)2''J) of benzoic acid steel was added to the formulation of Experiment No. 6 of Example 2 (Table 3).
A foam was prepared by adding 6 f, and a surface flammability test was conducted.

This foam had an afterflame weight of 58% and a residual time of 6 seconds, indicating that the flame retardance was significantly improved compared to the foam to which the chelate compound was not added (Experiment No. 6 of Example 2).

Example 11 Ethylenediamine chelate of copper octoate CCu(EDA)2 (C7Ht5COO)2. A foam was prepared by adding +6Y, and a surface flammability test was conducted.

This foam had a residual weight of 50% and an afterflame time of 8 seconds, and its flame retardance was significantly improved compared to the foam to which the chelate compound was not added (the foam of Experiment No. 6 of Example 2).

Example 12 6 grams of ethylenediamine chelate of cobalt acetate (Co(EDA)z(AeO)2) was added to the formulation of Experiment No. 6 of Example 2 (Table 3) to create a foam, and a surface flammability test was conducted. .

This foam had a residual weight of 53% and an afterflame time of 7 seconds, and the flame retardance was significantly improved compared to the foam without the chelate compound (Table 3).

Example 13 Ethylenediamine chelate of nickel acetate (Ni(EDA)2(AcO)2)6'f? was added to the formulation of Experiment No. 6 of Example 2 (Table 3). A foam was made by adding the following:

This foam had a residual weight of 53% and an afterflame time of 8 seconds, and its flame retardance was significantly improved compared to the foam without the chelate compound (Table 3).

Claims (1)

[Claims] 1. Polyisocyanate, blowing agent, and case. In some cases, at least one or more compounds such as polyols, epoxy compounds, polycarboxylic acids, acid anhydrides, and other compounds capable of reacting with isocyanates are present, and if necessary, catalysts, foam stabilizers, and other auxiliaries are added. A method for producing a flame-retardant foam, which comprises adding a soluble ethylenediamine metal chelate compound to a foam production stock solution in producing the foam by applying the reactivity of incyanate.