DE2910278A1 - RIGID POLYURETHANE FOAM - Google Patents

Description

DR.-ING. WALTER ABITZ

DR. DIETER F. MORF ι f * <> ***** <* «*« '* «« Add «™

- hm I ^{P.O. Box} 860109.8000 Munich 8Θ

DIPL.-PHYS. M. GRITSCHNEDER

Pienzenauerstrasse 28

Patent Attorneys ^{Τβ1βίοη ea3222}

Telegrams r Chemindus Munich Telex: (O) B23992

IR 2408

PENNWALT CORPORATION Philadelphia, Pennsylvania 19101, V.St.A.

Rigid polyurethane foam

90 98 44/0857

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The invention relates to rigid, smoke-suppressed polyurethane foams formed from a reaction mixture have been prepared, which as a smoke suppressing additive is a metal salt of a: dialkyldithioearbamate, a Mercaptobenzothiazole, a 2,5-dimercapto-1,3,4-thiädiazole, a mercaptotriazine, a hydroxythiophenol or an aliphatic dimercapto compound having 2 to 10 carbon atoms.

The invention relates to a rigid polyurethane foam composition with suppressed smoke formation. The invention relates to in particular the addition of organic, sulfur-containing metal compounds to rigid polyurethane foam compounds, to reduce smoke formation when burning.

Rigid foams are used as insulation material at the Manufacture of new buildings increasing in importance in order to reduce energy losses. Ask at the same time Building regulations stipulate that lower amounts of smoke are formed when the foams are burned, so that the exits are easier to make it easier for firefighters to enter and escape.

The smoke formation of polyurethane foams can be reduced by using sulfur-containing compounds, e.g. elemental sulfur, or certain organic sulfur compounds, e.g. di-t-butyl polysulphide and ethylene trithiocarbonate, used. The use of these materials is described, for example, in U.S. Patents 3,542,701, 3,876,568 and US Pat 3,933,694. These organo have sulfur compounds but the disadvantage that they are either too volatile or give an unpleasant odor during processing. Polyurethane foams containing these known sulfur compounds still generate significant amounts of smoke.

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The compounds used in the rigid foam according to the invention, the disadvantages of the prior art the technology, as the compounds significantly reduce the amount of smoke that is produced when polyurethanes burn is produced. This is shown in the examples below.

The invention relates to a rigid polyurethane foam with suppressed smoke, which is characterized in that it is made from a reaction mixture which is a smoke suppressant amount of a compound from the group.

-M,

N- -S-C,

-N

.C-S-

M.

and

M,

N.

R for lower alkyl with 1 to 5 carbon atoms stands,.

R _{1 represents} cycloalkyl with 3 to 10 carbon atoms or alkyl with 2- to 10 carbon atoms,

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η is an integer that corresponds to the * valence of M is equal, and;

X stands for S, 0 or NH and

M is selected from the group copper, zinc, aluminum, tin, antimony, bismuth, vanadium, chromium, molybdenum, manganese, iron, cobalt and nickel,
contains.

The invention relates to a rigid polyurethane foam with suppressed smoke formation. Polyurethanes are generally used by reacting toluene diisocyanate or polymethylene polyphenyl isocyanate or a mixture thereof with polyfunctional hydroxy compounds. Some typical examples of rigid polyurethane foams are provided by E.N. Doyle in "The Development and Use of Polyurethanes Products », McGraw-Hill Book Co., New York, 1971, and by W.C. Kuryla and A.J. Papa in "Flame Retardancy of Polymeric Materials ", Volume 3" Marcel Dekker, Inc., New York, 1975 ». The rigid polyurethane resins according to the invention you can also use flame retardants such as chloroethyl phosphate, Phosphorus-nitrogen compounds or brominated or chlorinated polyols contain.

The smoke suppressing additives used to make the rigid polyurethane foams according to the invention used can be made by reacting salts of metals from the group copper, zinc, aluminum, tin, antimony, bismuth ,. Vanadium, chromium, molybdenum, manganese, iron, cobalt and nickel with the sodium salts of sulfur-containing compounds from the group mercaptobenzothiazoles, 2,5-di-mercapto-1,3,4-thiadiazoles, Mercaptotriazines, dialkyldithiocarbamates, hydroxythiophenols and aliphatic dimercapto compounds with 2 to 10 carbon atoms. These Additives are either monomeric or polymeric salts and they can be cyclic or linear. You become physical

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with the starting materials for the production of the polyurethane foam in an amount of 0.1 to 20 parts by weight, based on the formulation of the starting materials (i.e. polyols, surface-active Agents, catalysts, water, blowing agents, flame retardants and isocyanate), mixed to the Manufacture of polyurethane foam.

Representative examples of suitable smoke suppressing additives are:

Iron (II) -2-mercaptobenzothiazole Copper (II) -2-mercaptobenzothiazole Zinc 2-mercaptobenzothiazole Iron (II) dimethyl dithiocarbamate Copper (II) dimethyldithiocarbamate zinc dimethyldithiocarbamate Iron (II) dibutyl dithioearbamate, copper (II) dibutyl dithiocarbamate Zinc dibutyl dithiocarbamate nickel (II) dibutyl dithiocarbamate Antimony (III) dibutyl dithiocarbamate Iron (II) dimercapto-1,3,4-dithiadiazole Copper (II) dimercapto-1,3,4-dithiadiazole Zinc dimercapto-i, 3,4-dithiadiazole iron (II) salt of p-hydroxythiophenol Zinc salt of p-hydroxythiophene iron (II) -2-mercaptobenzoxazole Iron (II) -2-mercaptobenzimidazole Zinc salt of trimercaptotriazine Iron (II) salt of 1,6-dimercaptohexane Copper (II) salt of 1,6-dimercaptohexane Cobalt (III) dimethyldithiocarbamate Nickel (II) dimethyl dithiocarbamate Tin (II) -2-mercaptobenzothiazole.

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Metals are preferred in practicing the invention for the smoke suppressants iron, copper and zinc.

The preferred organosulfur compounds used to prepare the metal salts are selected from the group Mercaptobenzothiazoles, dimercapto-1,3,4-thiadiazoles and dialkyldithiocarbamates selected.

The preferred smoke suppressants are: Iron (II) -2-mercaptobenzothiazole, Iron (II) dimethyl dithiocarbamate, iron (II) -2,5-dimercapto-1,3,4-thiadiazole, copper (II) -2-mercaptobenzothiazole ,. Copper (II) dimethyl dithiocarbamate, copper (II) -2,5-dimercapto-1,3,4-thiadiazole, zinc-2-mercaptobenzothiazole, Zinc dimethyl dithiocarbamate, zinc dibutyl dithiocarbamate and zinc-2,5-dimercapto-1,3,4-thiadiazole.

The invention is illustrated in the examples.

Rigid polyurethane foams used in the following examples are prepared by mixing the smoke suppressant additive with the polyol and then the catalysts, surfactant, water and / or blowing agent and isocyanate added as it is by K.C. Fresh and S.L. Reegan in "Advances in Urethane Science and Technology "Vol. 1 to 4, Technomic, Conn., 1971-1976. The rigid foams are prepared in such a way that the stirred reaction mixture in a box measuring 20.3 em x 20.3 cm x 12.7 cm (8 "x8" x5 ") pour. The foam will last 7 days Left to age for a long time and then to test specimens with the dimensions 3 "x3" x1 "(3" x3 "x1") cut to size, those in "the NÖS smoke chamber according to the flame method according to the ASTM Special Technical Publication 422 (1969) and NFPS 258-T, "Smoke Generated by Solid-Materials", May 1974, burned will. The mean of two or more values is given.

■ - 8 -

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Example 1 shows that a rigid polyurethane foam containing a phosphorus-based flame retardant agent and has no smoke suppressant, generates a large amount of smoke (D = 355).

mc

Examples 2 to 5 show that rigid polyurethane foams with the same composition as in Example 1, but with the metal dialkyldithiocarbamate or zinc mercaptobenzothidazole contain less smoke than a foam with the same load weight of contains elemental sulfur according to the prior art.

Examples 1 to 5 Approach parts

Polyol - Pluracol 383 (BASF Wyandotte) ^ 100.0 Surfactant - DC-193 (Dow

Corning) ^^ 1.0

Dirnethylaminoethanol (Pennwalt) 2.94

Dibutyltin Dilaurate (M&T) '0.06

Water 0.9

Propellant - Isotron 11 (Pennwalt) ^ 50.0

Flame retardant - Fyrol 6 (Stauffer) ' ^d ' 35.0 Isocyanate - PAPI (Upjohn) ^ 182.0

smoke suppressant as indicated below

(a) Polyol based on sucrose, OH number 483, contains < VA phosphorus;

(b) silicone wetting agents;

(c) fluorocarbon 11;

(d) Diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphonate:

(e) Polymethylene polyphenyl isocyanate, NCO equivalents lent = 133.

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- AA- pph 291 0278 IR 2408 Smoke suppressant - Ex.
No. none 20th ^D mc Percentage
Smoke min
change 1 sulfur 20th 355 0 2 Iron (II) -2-mereaptobenzo-
thiazole 20th 266. 25th 3 Zinc dimethyl dithiocarbamate 20th 216 39 4th Zinc-2,5-dimercapto-1,3 »4- 143 60 5 135 62

thiadiazole

Examples 6 to 10 show that rigid polyurethane foams which have been made flame retardant with an organobroin compound and which are provided according to the invention Organic metal sulfur compounds contain less smoke than foams that contain elemental sulfur contain the same percentage of sulfur.

Examples 6 to 10

approach

Polyol - Pluracol 383 (BASF Wyandotte) ^ Surfactant - DC-193 (Dow Corning)

Dimethylaminoethanol dibutyltin dilaurate water

Propellant - Isotron 11 (Pennwalt) ^

flame retardant - FR-1138 (Dow) ''

Isocyanate - PAPI (Upoohn) ^ ^e) smoke suppressant

Parts 100.0 1.0 2.94 0.06 0.9 50.0 30.0

173.0 as indicated below

(a) Polyol based on sucrose, OH number "= 483 »contains <1% phosphorus;

(b) silicone wetting agents;

(c) fluorocarbon 11;

(d) dibromo neopentyl glycol;

(e) Polymethylene polyphehyl isocyanate, NCO equivalent = 133. '

- 10 -.

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IR 2408

Ex. Smoke suppressant No.

pph D Percentage smoke reduction

6 none - 344 0

7 sulfur 8.1 264 23

8 Iron (II) dimethyldithiocarbamate 20.1 163 53

9 zinc dimethyl dithiocarbamate 20.8 179. 48

10 copper (II) dimethyl dithio- 20.4 194 44 carbamate

⁺ all additives are present in the same percentage by weight of sulfur.

Examples 11 to 12 show the effectiveness of zinc dimethyl dithiocarbamate as a smoke suppressant for rigid polyurethane which is a chlorinated, flame retardant Contains agent (Thermolin RF230). In Example 4 it has already been shown that this sulfur-containing metal salt also as A smoke suppressant for rigid polyurethane foam that is a phosphorus / nitrogen flame retardant is effective (Fyrol 6) contains.

Examples 11 to 12 Preparation of the sample

Polyol - Thermolin RF230 (Olin)

Polyol - Pluracol 383 (BASF Wyandotte) ^ Surfactant - DC-193 (Dow Corning)

Dimethylaminoethanol

Dibutyltin dilaurate

water

Propellant - Isotron 11 (Pennwalt)

Isocyanate - PAPI (Upjohn) ^ smoke suppressant

(c)

Parts 25.0 75.0 1.0 2.94 0.06 0.9 50.0 132.4

as stated below

• (a) Hydroxy number = 365; W chlorine;

(b) Polyol based on sucrose, OH number = 483, contains <1% phosphorus;

- 11 -

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(c) silicone wetting agents;

(d) fluorocarbon 11;

(e) Polymethylene polyphenyl isocyanate, NCO equivalent = 133

Ex.
No. He smokes oppressive agents phr mc Percentage
Roughing
reduction 11 none 220 0 12th Zinc dimethyl dithiocarbamate 11.6 136 38 at game 13

_{11.6 pph zinc dibutyl dithiocarbamate ZnC (C 1 Hg) 2} NCS ₂ J ₂ (Pennwalt's Butyl Ziram) are added to a batch for a rigid polyurethane foam, as described in Examples 11 Ms 12. The resulting rigid polyurethane foam produced smoke reductions in the region of about 30% on combustion - or about the same amount as that with zinc dimethyl dithiocarbamate according to Example 12.

Example 14 Production of zinc-2,5-dimercapto-i, 3,4-thiadiazole

2,5-Dimercapto-1,3,4-thiadiazole (50 g, 0.33 mol) is stirred _{in 100 ml H 2 O.} NaOH (26.7 g, 0.66 mol) is slowly added with stirring and cooling. A ZnCl ₂ solution (45.4 g, 0.33 mol, dissolved in 300 ml H ₂ O) is added to the sodium dimercapto-1,3,4-thiadiazo salt solution, "whereby a white precipitate is formed. The precipitate is filtered and dried to give a quantitative yield of zinc-2,5-dimercapto-1,3,4-thiadiazole.

The elemental and spectroscopic analyzes are consistent with the assigned structure.

- 12 *

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Example 15 Production of zinc dimethyl dithiocarbaisate

Sodium dimethyl dithiocarbamate (75.2 g, 0.66 mol) is dissolved in 100 ml H ₂ O. A ZnCl ₂ solution (45.4 g, 0.33 mol, dissolved in 300 ml HpO) is added to the sodium dimethyl dithiocarbamate solution. A white precipitate immediately forms which is filtered and dried to give a quantitative yield of zinc dimethyl dithiocarbamate.

The elemental and spectroscopic analyzes are available with the assigned structure

[(CH ₃ ) ₂ NCS-] ₂ Zn consistent.

Example 16

Production of copper (II) dimethyl dithiocarbamate

Sodium dimethyl dithiocarbamate (75.2 g, 0.66 mol) is dissolved in 100 ml H ₂ O. A CuCl ₂ solution (44.3 g, 0.33 mol, dissolved in 300 ml H ₂ O) is added to the sodium dimethyl dithiocarbamate solution. A precipitate forms immediately, which is filtered off and dried, whereby a quantitative yield of copper (II) dimethyl dithiocarbamate is obtained.

The elemental and spectroscopic analyzes are available with the assigned structure

in line.

End of description.

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909844 / 06S7

Claims (15)

DR.-ING. WALTER ABITZ DR. DIETER F. MORF DIPL.-PHYS. M. GRITSCHNEDER Patent attorneys Munich, March 15, 1979 Postal address / fetal address J Postfach 8601O9, 8OOO Munich Pianzenauerstrasse Telephone 983222 Telegrams: Chemlndus Munich. Telex: (O) 523993 IR 2408 Claims Rigid polyurethane foam, characterized in that that it has been prepared from a reaction mixture containing a smoke suppressing amount of a Connection from the group Il and O- S- N: Θ09844 / 0657 IR 2408 '-S- wherein R stands for lower alkyl with 1 Ms 5 carbon atoms, R _{1 represents} cycloalkyl with 3 to 10 carbon atoms or alkyl Mt 2 to 10 carbon atoms, η is an integer equal to the valency of M is equal to, X stands for S, 0 or NH, and M is selected from the group copper, zinc, aluminum, tin, antimony, bismuth, vanadium, chromium, molybdenum, manganese, iron, cobalt and nickel,
contains. 2. Rigid polyurethane foam according to claim 1, characterized in that the compound from the group of mercaptobenzothiazoles, dialkyldithiocarbamates and 2,5-dimercapto-1,3 »4-thiadiazoles is selected, and that M is iron, copper, zinc, cobalt, nickel, molybdenum, tin, antimony, Bismuth, vanadium, manganese or chromium. 3. Polyurethane foam according to claim 1, characterized in that the compound iron (II) -2-mercapto <benzothiazole is. .4. "Polyurethane foam according to claim 1, characterized in that characterized in that the compound zinc dimethyldithiocarbamate is. 5. Polyurethane foam according to claim 1, characterized in that the compound zinc-2,5-dimercapto-1,3,4-üiiadiazole is. 6 .. Polyurethane foam according to claim 1, characterized in that the compound iron (II) dimethyldithiocarbamate is. 909844 / Q657 IR 2408 -3- 7. Polyurethane foam according to claim 1, characterized characterized in that the compound copper (II) dimethyldithiocarbamate is. 8th.' Polyurethane foam according to Claim 1, characterized characterized in that the compound zinc dibutyl dithioecarbamate is. 9. Polyurethane foam according to claim 1, characterized in that the compound iron (Tl) - 2,5-dimercapto-1 »3,4-thiadiazole is. 10. Polyurethane foam according to claim 1, characterized in that the compound copper (II) -2-mercaptobenzothioazole is. 11. Polyurethane foam according to claim 1, characterized characterized that the compound KupferClI) -2,5-dimercapto Is 1,3,4-thiadiazole. 12. Polyurethane foam according to claim 1, characterized characterized in that the compound is zinc-2-mercaptobenzothioazole. 13 · Polyurethane foam according to claim 1, characterized in that the smoke-suppressing amount of the compound 0.1 to 20 wt. Parts, based on the foam. 909844/0667