SU1634673A1 - Tri- or pentabromophenoxyisocyanate organourethanes as binder for impregnating cellulose-containing materials, and composition for impregnating cellulose-containing materials - Google Patents

Description

(21) (22) (46)

one

4471191/05

06/15/88

03/15/91. Bul N ° 10

(71) Dnepropetrovsk Chemical and Technological Institute named after Dzerzhinsky and the Ukrainian Scientific and Production Wood Processing Association

(72) N.Ya.Kuzmenko, Yu.G.Smol Ninov, V.V. Bugrym, B.Ya.Zaozhay,

N.S.Malovichko and N.Yu.Melnik

(53) 678.664 (088.8)

(56) US Patent No. 2428843, cl. 8-116.2, pub. 1947.

(54) THREE- OR PENTABROMPHENOXYESIZIO-NATURA ORGANOURETHANES AS A BINDER FOR IMPLEMENTATION OF CELLULOSE-CONTAINING MATERIALS AND A COMPOSITION FOR IMPUITATION OF CELLULOSE SAMPLEMER

(57) The invention relates to the preparation of flame retardant binders for the impregnation of cellulosic materials and can be used in the construction and furniture industry. The invention improves fire resistance, flexural strength up to 13 wt.% And hydrophobicity of materials up to 41 wt.% In 7 days due to the content in the composition as a binder of tri- or pentabromophenoxy isocyanatoorganourethane of the general formula OCN-R-NHCOOR, where R - tri- or pentabromophenyl; R, is hexamethylene, toluene, 4,4-diphenylmethane. As a solvent, the composition contains methyl ethyl ketone. 2 sec ff, 3 tab.

SS

(L

The invention relates to the preparation of binders for the flame retardant impregnation of cellulosic materials and compositions based on them and can be used in the furniture industry and in construction.

The aim of the invention is to obtain a binder that provides increased fire resistance, hydrophobicity and flexural strength of cellulosic materials after impregnation.

€ Intez tribromphenoxyisocyanothoorganic-urethane.

67.8 g (0.41 mol) of hexamethylene diisocyanate, 129 g of dry methyl ethyl ketone are loaded into a four-neck reactor equipped with a stirrer, a thermometer, a dropping funnel and 129 g of dry methyl ethyl ketone, 0.38 g (0.01 mol) of a tin octoate catalyst are added, heated to and a solution of 132 g (0.4 mol) of tribromophenol in 70 g of dry methyl ethyl ketone is added dropwise. The reaction temperature is maintained at a constant level by controlling the rate of addition of the tribromophenol solution and in methyl ethyl ketone.

After completion of the addition, the mixture is heated at the same temperature for another 4 hours until the calculated content of free isocyanates of the groups is reached. Then the solvent is distilled off, the residue is evacuated at the same temperature and pressure of 1 mm Hg to

em

Bo

4 O5 L

go

Constant mags. In cubes, 194.5 g (, 8 wt.% of the theoretical) product with a TPD of 198 C) C and a content of free isocyanate groups of 8.27 Mac.% j and Br content of 48.1 wt.% are obtained (Table. 1, compound No. 2).

Table 1 shows the physicochemical constants of the compounds. The synthesis is performed as in the previous case, but with the replacement of tribromophenol by an equimolar amount of bromophenol. Synthesis of pentabromophenoxyisocyano-ororgan-urethane.

178.0 g (1.02 mol) of a mixture of isomers of toluene diisocyanate are poured into a four-neck reactor, equipped with a stirrer, an addition funnel, a thermometer and a reflux condenser, 200 ml of dry methyl ethyl ketone are poured in, the result is 1, 2 g (0.01 mol) The catalyst is dimethylanaline and heated to 55 + 1 ° C. A solution of 489 g is then added dropwise (I mol 9 pentabromophenol in 443 g of dry methyl ethyl ketone. The temperature is maintained at 55tl ° C, adjusting the speed of dropping the solution of pentabromophenol. After the end of the dropping, the mixture is heated at this same temperature still h until the calculated free-flowing isocyanate groups are reached, the solvent is then distilled off. The isolated product is evacuated at a pressure of 1 mm Hg and a temperature not higher than 60 ° C to constant weight. 646 g (98.9% by weight of theoretical product) C. T. 262 ° C and a content of free PSO groups of 6.46 wt.%, Br 61.72 wt.%, corresponding to compound No. 5. Compound No. is obtained in a similar way with the replacement of pentabromophenol by an equimolar amount of bromophenol or tribromophenol, and toludendiisocyanate is equivalent to an equimolar amount of diphenylmeth ndi isocyanate.

The samples of the studied materials are impregnated with a series of halogen-containing oligourethanisocyanates in a bath containing a solution of oligourethanisocyanates heated to 60 ° C in methyl ethyl ketone. To complete the urethane formation reaction between the free isocyanate groups, halo-containing oligourethanisocyanate and hydroxyl cellulose, a catalyst is added to the bath (from the series: dimethyl inine, tin octoate, or tetra-Outoxytitanium).

d

0

15

0

five

Then, samples of cellulose-containing materials to be impregnated, preheated to 60-65 ° C, are immersed in the bath, kept for 60 s, removed, the solution residues are allowed to drain, and cured at 125 ° C for 4 h in an oven. Then they are taken out, cooled, incubated for 24 hours and tested according to the indicators listed in Table 3.

The time and temperature of heat treatment are taken as the best of the conditions for the termination of the urethane formation reaction by the absence in the IR spectra of (impregnated samples and warmed up times) the absorption band in the 2270 region characteristic of free NCO groups.

In tab. 2 shows the formulations of the compositions.

Table 3 shows the physicomechanical properties of the test samples.

The numbers of experiments in table 3 correspond to the numbers of impregnating compositions in table 2.

To assess the quality of impregnation of cellulose containing materials (chipboard and fibreboard, plywood) and impart fire resistance to them, the following samples were used: 1 to impart fire resistance to wood chip boards on a carbamide formaldehyde binder — plates (P-1 grade, density of 700 kg / m, 16 mm thick, three-layer, made on resin KF-MT); static bend test specimens 250x50x16 mm; plates for testing plates for water absorption and water swelling in mm size; 10k16N50 mm samples for testing fire resistance plates according to the fire tube method, for imparting fire resistance to fiberboard boards - samples of T-400 brand, with a density of 1000 kg / m, 3.3 mm thickness, 100x100 3.2 mm for water absorption and water absorption swelling; for determining the strength of static bending - size, 2 mm; for fire resistance determination using the plywood specimen method, size 70x140 3.2 mm; for imparting fire resistance to plywood - three-layer plywood samples for a urea binder, birch veneer, 3 mm thick; for the determination of water absorption and swelling, samples 100x100x3 mm; for the determination of fire resistance according to the method of plywood samples, samples of size 70 140x3 mm.

An alcohol burner is used as a combustion source.

In all cases, the evaluation of the increase in fire resistance of materials is assessed by weight loss and flame retardant consumption. Water absorption is estimated by the difference in the mass of the sample treated with halogen-containing oligourethanesocyanates, aged in distilled water, referred to the mass of the dry sample before swelling, expressed as a percentage. The change in linear dimensions is determined from the difference in the thickness of the samples treated with halogen-containing oligourethanosocyanate and aged in water to the original samples, referred to the initial thickness and expressed as a percentage. The consumption of the impregnating agent is determined by the difference in the mass of the sample before and after the impregnation, referred to the mass of the initial one, and expressed as a percentage.

For samples of chipboard and fibreboard, the strength of the impregnated samples for static bending is additionally determined and kept in water for 24 hours at 20 ° C.

1634673

0

Formupa invention

1.Tri- or pentabromophenoxyisocystatic anato-orgluourethanes of the general formula

5OCN-R, -NHCOO-R,

where R is tri- or pentabromophenyl;

RI - hexamethylene, toluene or

4,4-diphenylmethane,

as a binder for impregnation of 0 cellulose-containing materials.

2, the composition for impregnation of L and L-containing materials, including a binder and a solvent, characterized in that

5 increase the fire resistance, hydrophobicity and strength of materials in bending, as a binder it contains three- or pentabromophenoxyisocyanato - organurethane of the general formula

OCN-R "-NHCOO-R

where R is tri- or pentabromophenyl R (is hexamethylene, toluene or

4,4-diphenylmethane,

the solvent is methylethylketone and, additionally, a catalyst selected from the group including dimethylaniline, tin octoate or tetrabutoxy titanium, in the following ratio of composition components, wt.h .: Tri- or pentabromofenoxyisocyanatoorgano-urethanes39, 8-59 , 7

Methyl ethyl ketone 40-60

Catalyst0,2-0,3

 OCN- (CH7) 6-NC-0-SVM 3 32

And Br

Vg

OCN- (CH V-NC-0- 5ter 97 | ft Ј99 27 l98 33-8S 308 wMs 33 "7 3- ° in" 2

Y v

H Br

(, $. 6 347..S.95

H

9 wg

®vg

n in

 

(

97.9 505.11 178

SNZ O vg W (HJ) Br N

98.9 663.15 26226.90 1.02 4.42 61.72 6.36 p. 27.18 1.074.23 60.28 6.35

 n

“OSM (O)) 8.8 581.33 210

II

n n

49.3 4.83 8.28 23.312.1 C „NPs, 49.2 4.988.21 23.412.3

51.65 3.52 7.922.912.2 С, .ПХО | НМВ 51.8 3.68.05 23.012.1

ST and

oh-j and

97.9 505.11 17835.7 1.65.447.36., 35.6 1,, 55 47.56.7

43.5 2.7 4.64 41.17,15 Cz, ntO, H ,, B 43.4 2,244.82 41.31 7.22

Consumption impregnated akd "go" go, mas.X

Fire-rubbed by the method of the fire tube. wt.X

Strength at a static bend. MPa,

soaked

drunk for two hours

6.4

4.5 5.3

4.6 5.5

6.1

5.5 5.4 5.5

5.5 5.5 5.4

5.5 5.5

5.5

5.5 5.4

97 "2.8 73-4 16,174,5 13.3 6.0 15.3 16.5 13.5 13.7 13.5 13.6 13.5 13.5 13, 13.5 13.5

attenuated tatu.

Drayesni-fiber raw plates

38.040.3 44.4 45, J 44.5 44.9 45.7 45.9 44.2 45.3 44.3 44.6 37.2 41.4 44.9 44.8 45.2 42.9

34.235.1 42.5 41.1 42.6 41, I 42.1 42.3 41.1 42.6 41.5 41.7 30.J 40.9 41. 41.7 42.5 41.5

6.4

4.5 5.3

4.6 5.5

6.1

5.5 5.4 5.5

5.5 5.5 5.4

5.5 5.5

5.5

5.5 5.4

Indicators

Original sample

Dopogloarvm distilled water at wt.X, through:

1 day 7 days

Distilled water distilled water p -, mas.X,

1 day

48840.2 30.3 32.4 11.3 32.6 35.7 32.3 32.4 3.2.in 31.6 32.7 45.6 33.9 32.6 32.5 35.6 33.2

60.851.1 41.1 43.2 4J.3 42.9 44.6 42.8 42. W.I 42.7 42.8 5v, 1 48.4 42.9 42.9 44.5 46.3

14.36,32.9 3.3

j.O 3.4 4.5 3.6 3.3 3.43.4 3.4 13.1 8.4 3.4 3.4 4.5 5.9

7 days 26.8

Consumption of impregnated agent, wt.X. Fire resistance - cashier losses according to the method of plywood samples, wt.Х99,9

Water absorption at 20 ° C in distilled water. ias.h, through:

24 hours 7 days

Consumption of the impregnating agent, wt.X

Fire resistance - mass loss by the method of plywood samples, mas.Х93,4

5.2.90,80,90,750,91,00,90,80,90,90,94,61,200,90,91,0I.I

06.15 -5.64,54.74,44.64.84,74,54,74,54.75,45,64.64.64.75.1

4.32.53,52,93,13.43.33,13,13.13.13,13,13,13,13,13,13

19,677,316,876,415,67,217,115,315,915.515,616,316,115.615,37,115.9

ProtoExperience I

I I 2I 3 4 Ti | 6 J 8 J 9 Gyu Til) - 12 | 3 | 14 1 15, 16

j.O 3.4 4.5 3.6 3.3 3.43.4 3.4 13.1 8.4 3.4 3.4 4.5 5.9

16.8 8.2 8.98.7 8.8 10.1 8.9 8.7 8.98.7 8.9 23.4 14.6 8.8 8.7 10.0 11.7

3.9 4.0 4.2 4.24.2 3.2 4.24.2 4.2 4.2 3.9 4.2

3.7 4.13.8 4.2

70.1 16.4- 71.6 14.6 7.8 16.5 14.5 14.9 14.3 14.8 16.8 14.7 14.6 14.6 7.8 14.6 Three-layer plywood on a urea-formaldehyde binder, mas.X, "tone birch

.p ON

-vj

to

Claims (4)

Claim 1 /> so g * h gV) w <L "L iTt" L "Ί V4 1L and 1 gh g * h IA about gh • 4 MS ΙΛΙ “o • e“ g • e g ”y gh b. Continuation of the table I I ( Other tn • · SP f <* "* 3 40 And 1L eaten -0 PE about »eat cm‘ m 40 04 cm count e * 4 "4 O '• N * P -her ze »P v Mt and in • 0 in OP * - - “4“ η 1 1 ¢ 4 gh <· (h gch <2 G-4 SP (*> * h "Oh sch gch o gh gh <*> оо (Ч • е W4 GB w <N w ib U6 with tn • l r *> gh GB her GB s with 1A with r / h G- " G *. • ft sl »l l G ** G * 12 1. Tri- or pentabromophenoxyisocyanatoorgananurethanes of the general formula OCN-R (-NHCOO-R, where R is tri- or pentabromophenyl; R | - hexamethylene, toluene or 4, 4 * -diphenylmethane, as a binder for the impregnation of cellulose-containing materials. 2, Composition for the impregnation of L 'LLULOS-containing materials, comprising a binder and a solvent, characterized in that, in order to increase the fire resistance, hydrophobicity and bending strength of materials, it contains as a binder Λ J, tri- or pentabromophenoxyisocyanatoorgananourethanes of the general formula OCN-R "-NHCOO-R where R is tri- or pentabromophenyl; R (- hexamethylene, toluene or 4,4 ^1- diphenylmethane, as a solvent - methylethyl-ketone and optionally a catalyst selected from the group comprising dimethylaniline, tin octoate or tetrabutoxytitanium, in the following ratio of components of the composition, parts by weight: Tri- or pentabromophenoxyisocyanatoorganourethanes 39.8-59.7 Methyl ethyl ketone 40-60 Catalyst 0.2-0.3 Ί) 0.-4 f « W. X h yo “oo” oo О © * «η FROM? About about ΙΛ о о <п о © * <н 9 "g * s s" • 1 " 9 "in -G g *. 9 "g * 9 * σ " 3 I "b and o and r * GC. * N Oh oh tn Ο o * l cn o o "l o o * l g". o o kL g * "p o Η X " X o o X X о f · ф X § * l s; s> x <h l b kC with O © b “c: * h about with Approx. 4 s Ι * n I and R ah? with IK c s o © ag k a> < • »f? iSf ABOUT § n sh o h h 'x i I9 04 "- About MG ate · * in • * ate * JV Mt mg - * even count eL Mt And, in view of this, «« 0 p * \ 0 GL -6 h £> & Hech GC eat <y g * C *, - * m e * < ch0 e • e <g e Eaten Calculated • Ο «· - * * * <r m <η 0h Г * - о -e <η ο * «η - Ο "0 ate Ο> Γ * - Ο «· m« 0 Ο "0 SL cg g * hl 0-0 ate ABOUT • 0 0 ate O '40 - o <r ate m g- <g σ " About 0 o'clock g * * p O 0 eat with sh * p »* ABOUT' O '40 Midrange in 0 With 0 hh O 'O' • 40 W about I> 4 G 0 midrange I> 4 and g * Flame retardant 16.1 15.6 15.3 7.1 15.9