SU385455A1 - FUND W ^ EXPERT - Google Patents

Description

one

This invention relates to the preparation of polyurethane foams.

A known method for the preparation of oenopolyurethanes by the interaction of a hydroxyl-containing compound and a polyisyanate is carried out in the presence of a blowing agent. An organic polyisocyanate is used as a polyisocyanate, and a polyether with terminal hydroxyl rpynna (M ') is used as a hydroxyl-containing compound.

CHrKHCO-C C- (H) 2.n (-A) i, -i where the A groups are -CONH-CH.-NHCO-CH. II OR, -COOH, -SOYg, -CONHCHsOR; Ri.iRa, Rs, R4 - alkyl radicals with 1-18 carbon atoms, haloalkyl with 1-4 carbon atoms, cycloalkyl or aryl radicals;

(2

However, foam polyphenols, (obtained pb by this method, combustible, THAT limits the scope of their application.

The aim of the invention is to obtain polyurethane foam having high fire resistance. This gap is achieved in that the process is carried out in the presence of a phosphorus-containing compound of formula I

f-f-HVp№ v, (- HV,

, (- A),., -) p., (- UH2A), J (-H) „.,

--Jo t. OHZ 20 R and R and J are hydrogen atoms or methyl groups; R is an alkyl radical with 1-4 carbon atoms or a hydrogen atom; - Integers I or 2. Compounds of formula I are obtained from p- and a-ethylenically unsaturated amides of mono- and dicarboxylic acids with 3-5 carbon atoms. If l and p in formula I are equal to 1, then get derivatives of itaconic acid if. 8 a p 2, then - acrylic, meta.crylic and crotopic acids. If n 2, then get Produced with maleic or fumaric acid. Preferably, p 2, R is a hydrogen atom or a methyl group and R is an atom of 5 R.-oo: P I Bb-O, 0-KH in which Rs and Re are alkyl or halogen-S alkyl residues with at most four carbon atoms , X and Y-methyl groups, mainly hydrogen atoms. In formulas I and II, the residues Ri, Ra, Ra, R4 and Rs, Re may be the same or different. Preferably, Ri-R4 and Rs-Re are the same. They may be on HjC-O. 0 HcC-O CH7-CH7-CpKN Compounds of formula I are prepared as follows; In a manner: I .a) the action on the amide of a- or p-non-unsaturated-25 scandic mono- and di-1 -carboxylic acids 3- (dialkyl, haloalkyl, cycloalkyl - or arylphosphono) -Y-methylolpropioamide with water splitting off; b) under the action of 3- (dialkyl-, halogenalkyl-, cycloalkyl-arylphosphono) -propioamide with -.-iso-p-unsaturated mono- or dicarboxylic acids on methyl methamolamide; 6CH2-SNSOKNg + TOH-H UHNC-8CH-CHCONH-CHrHNC Methylene-acrylamide-N-3- (Methylene-M-acrylamide-M-3 - (dimethylphosphono) -propioamide.45 The phosphorus-containing compounds of the invention are introduced into the original This composition consists of a polyether with a free p-hydroxyl group, polyiso-50-hh cyanate and a blowing agent. 4,4-diphenylmethane diisocyanate or toluene diisocyanate is used as polyisocyanates, IB as fluorizing agent or fluoroglumethanemetrafluoromethiene diisocyanate is used as polyisocyanates. ib composition can be entered as e of the activating agents tertiary amines, for example, triethylamine. The phosphorus-containing compounds according to the invention are used in an amount of 1-15%, preferably Juves.% .60 The phosphorus-containing compounds of the invention, incorporated into the compositions for the preparation of Polyurethane Foams, make it possible to obtain polyurethane foams with high flame retardant. In addition, they provide hydrogen-good .. ..; 4 hydrogen. If R is an alkyl residue, it is preferably a methyl residue, X is usually a hydrogen atom, preferably the compound formulas II Y CH7-KH-CO-C CH2 - - - .. drimer, chloroalkyl groups (2-chloroethyl or 2,3-dibromopropyl), alkyl residues (n-butyl, egor-and tert-butyl, n- and " anti-propyl and preferably ethyl and especially methyl group). According to the invention, predominantly compounds of the formula III are used: CH7-III-CO-CH 2 SN 3) under the action of the amide of the p- or a-unsaturated IMOHO- or dccarboxylic acids, substituted at the amide nitrogen atom by the N-methylene-p-chloropropioamide group, dialkyl- , haloalkyl-, cycloalkyl- or arylphosphite. The first method is preferred. It consists in the condensation of a carbonic amide with methylphosphonopropionic acid. If acryl amide and 3- (dimethylphosphorous) -methylolamide nropionic acid are used, the reaction is carried out according to the equation OCHoCHo-PC -CH, -CH9-PC ° and OCHj dtethyl ( The rissrono-propioamtny effect on the orodes of the formation of polyurethane does not affect the mechanical properties of the resulting foams. The phosphorus-containing compounds according to the invention are liquid substances. making it easy to dose, the invention is illustrated by the following examples. Example 1. In a vessel with a blender, equipped with a reflux condenser, a thermometer and a device for separating water, boil with strong stirring at 200 wt. including benzene, 211 wt. hours (1 mol) methylolamide - 3 - (dimethylphosphono) -propionic acid (anhydrous product), 72.5 weight. including 98% acrylamide (1 ol), 0.15 weight. including hydroquinone monomethyl ether and 1 wt. t-toluenesulfonic acid until water ceases to form. Get 16 weight. including water, which corresponds to the 89% conversion of the theoretical. Then the reaction mixture was cooled to room temperature, slowly poured into 2000 ml of acetone, and part of the precipitated polymer, due to vigorous stirring, was finely suspended. After filtering out this portion in half a meter (30 parts by weight) from the filtrate under vacuum at 50 ° C, benzene-acetone is evaporated. The result is 227 weight. including a viscous colorless liquid which corresponds to the compound of formula III. The product is polymerized in a water solution in the presence of traces of ammonium persulfate at 70 ° C.

Example 2. In the apparatus described in Example 1, boil with vigorous stirring with reverse cooling. 21il wt. h (1 mol)

0 0

O GH-CHa-QO-NH-CH-HN-OC-C-GH -CO-NH-CH, methylolamide - 3 - (dimethylphoofono) -propiO new acid, 64 wt. including (0.5 mol) diamidium, canine acid, 0.15 weight. including hydroxylnonmonomethyl ether and 1 wt. including p-toluensulfonate in 200 weight. including toluene. At the same time receive 19 weight. h of water. The mixture is then cooled to 60 ° C, if possible, the toluene is completely separated by siphoning, the residue is dissolved in 150 ml of methanol, filtered from the undissolved impurities, and the methanol is removed along with the residual amount of toluene under vacuum at 50 ° C. Get 264 weight. h | viscous yellow product, a good solution of yush, egos in water, answer its formula

sn

0

-HN-OC-CH -CH -p-OCHi

OSI,

Example 3. A mixture of 20 g of any slowly reacting ioliol, 8 g of fluorotrichloromethane, 21.4 g of 4,4-diphenylmethane diisocyanate, 4 g of phosphorus containing, its compounds of formula III are mixed for 1 min with a simple paddle stirrer at 1000 rpm. Z. then foaming the ayush, yus mass is placed in a tube with a diameter of 5.5 cm, where the reaction ends. At the same time, polyurethane foam is obtained without the addition of phosphorus content;

table 2

Example 4. A mixture of 20 g of polyether containing hydroxyl groups, 8 g of fluorotrichloromethane, 0.2 mg of reaction promoter, 21.4 g of polyether containing isocyanate groups, and 5 g of phosphorus-containing compound of formula III are foamed in the manner described

Further, both samples are tested for fire resistance. To do this, each specimen with dimensions of 120XOX10 mm is fixed with a face of 120 mm at an angle of 45 ° to the horizontal and a face of 30 mm horizontally. Marks are placed at a distance of 25 iH 100 mm. From the lower ends, the samples are ignited with the aid of a dovetail-type torch. Get the results shown in the table. one

t a b .4 and c a 1

in Example 3. At the same time, polyurethane foam is obtained without the addition of a phosphorus-containing compound. Each specimen with dimensions of 120X XOXY mm is fixed horizontally with a 120 mm face and ignited with a dovetail-type burner. Get the results shown in table 2

Subject invention

A method for producing polyurethane foams by reacting hydroxyl-containing compounds and polysociaates in the presence of a blowing agent, characterized in that, in order to increase the fire resistance of polyurethane foams, the process is carried out in the presence of a phosphorus-containing compound of the formula

-CH2-CH-CONH-GHrNHCO-C C- (K) 2-nC-A) n-i

and

X where A is the -CONH-CH -NHCO-CH, -CH, -P -COOH, -CONH2, -CONHCHaOR groups; Ri, R2, Rs, R4 - alkyl radicals with 1-18 is

5ShV

p (-n), p№) p .; (-n) „.,

C- (K) 2-lC-A) p-, U-R) p., L-CH, A) J (-HV,

I - J M 10 carbon atoms, halogenoalkyl radicals with 1-4 carbon atoms, cycloalkyl or aryl radicals; iR, R, and X are hydrogen atoms or methyl groups; R is an alkyl radical "1-4 carbon atoms or a hydrogen atom; “Ir 1 or 2.