DE1745134B2 - Process for the production of polyurethane foams - Google Patents

Description

Cl

Cl

Cl

and or

Cl

Cl

Cl

Cl

COO-CH ₁ -CHv-OH

COO-CH ₁ -CH ₇ -OH

CO-N (CII ₁ -CH ₁ -OH),

CO-N (CH ₁ -CH ₁ -OHl ₁

Cl

used.

According to the method according to the invention mainly made of rigid polyurethane foams, although afterwards you also get soft or semi-hard

Foams with self-extinguishing properties can produce. According to a preferred embodiment is a mixture containing / u 60 to 90 percent by weight of polyhydroxy compounds chlorinated on the aromatic nucleus of the general formulas mentioned and 10 to 40 percent by weight of one amide or ester group-free organic pole oil with a functionality of 3 to 4 and one equivalent from 30 to 50, reacted with a PoK isocyanal in the presence of a propellant.

The production of the invention. ' used Polvole containing ester or amide groups is known per se.

According to a preferred embodiment of the invention, bis (2-hydroxyethyl) tetr; chlorophthalate is used \ used. The one using this polyhydroxyl compound Manufactured polyurethane foam fabrics are self-extinguishing, with little dimensional stability as well as good mechanical properties. It is also preferred to use organic polyisocyanates to be used with an average functionality greater than 2., preferably under 4..

Examples Door optionally together with the polyhydroxyl compounds chlorinated on the aromatic nucleus of the general formulas \ usable ester- and amide-group-free l'olyols with an equivalent weight less than 200 and a functionality of 2 to S are aliphatic polvoles. like alkanediols. Alkeniols or alkynediols, triols and tetrols. Pentoles. Hexols. Heplole and Octole. The following are named as individual representatives: Ethylene glycol. 1.2- and 1.3-propylene glycol. 1,4-butanediol. 1,5-pentanediol. 1.6-hexanediol. 1.7-heptanediol. also 1,3-butadiene-1,4-diol and 2-butadiene-2,4-diol. in addition, 1.3.6-Hcxanlriol. 1.4.8-octanetriol. 1.2,5,6-hexanetetrol. Glycerin. Trimethylol propane. Pentaerythritol. Sorbitol and cane sugar. Preferred such polyols are used. Which are produced by the reaction of alkylene oxides such as ethylene oxide. Propylene oxide and butylene oxide. with ammonia. Diethanolamine. Triethanolamine. Ethylenediamine. 2,4- or 2.6-T <> luylenediamine and 4,4'-diphynylmethanediamine. A particularly preferred compound is triethanolamine. Foams based on these compounds are particularly dimensionally stable, especially when the polyisocyanate is a condensation of aniline with formaldehyde and subsequent phosgenation prepared reaction product has been used.

As an additional polyhydroxyl compound free of ester or amide groups that may also be used Polyethers which have no tertiary nitrogen atoms are also suitable. Such polyethers can z. B. by reacting alkylon oxide. such as ethylene oxide or propylene oxide. with an initiator like Water, the amino compounds already mentioned, or alcohols such as ethylene glycol. Propylene glycol or I rimethylolpropane or sorbitol.

According to a preferred embodiment of the method, as ester or amide group-free Polvole with an equivalent weight below 200 and With a functionality of 2 to 8, chemically bound phosphorus can also be used contain.

Compounds of this type are well known and are also described, inter alia, in US Pat. Nos. 3,099,676,3,179,629. 32 25 010 and 32 35 517. Particularly preferred Compounds of this type are products of the conversion of phosphoric acid or mixtures of l'hosphorus pentoxide and water with alkylene oxides. So you can z. B. a mixture of 85% phosphorus pentoxide and 15 "» water by reacting with Ethylene oxide. Propylene oxide. Reacting butylene oxide or epichlorohydrin to a polyol that 3 to Has 6 hydroxyl groups per molecule. Another type of phosphorus that can be used with advantage Polvole is one that has nitrogen atoms in addition to the phosphorus atom, such as. B.

O CH ₄ -OH

I ₃ I ₂ PC ₂ H ₄ -N

C ₂ H ₄ -OH

The polyhydroxyl compounds and the polyisocyanate should be dimensioned in terms of their amount and type be that per crosslinking point a molecular weight of 600 to XOO. preferably \ on about 7 (X). available is.

Any aliphatic or aromatic polyisocyanate can be used as the polyisocyanate, however, aromatic di- or polyisocyanates with 2 to 4 NCO groups are preferably used will. Examples of suitable polyisocyanates are 1, 6-hexamethylene diisocyanate. 1,4-butylene diisocyanate. Furfurylide diisocyanate. 2,4- and 2,6-tolylene diisocyanate and mixtures of these isomers. 4.4'-Diphenyl methane diisocyanate. 1,5-naphthylene diisocyanate. 1-methyl-2,4- and 1-methyl-2,6-diisocyanatocyclohexane. m- and p-phenylene diisocyanate. 4.4'.4 "triphenyl methane triisocyanate, biuret polyisocyanates. the z. B. by reacting Hexamcthylcndiisocyanat can be prepared with water, as well as polyphenylpolymethylene polyisocyanates. by condensation of primary aromatic amines with aldehydes or ketones, such as formaldehyde or Methyl ethyl ketone, and subsequent phosgenation can be produced. Compounds in question of this type are disclosed, for example, in U.S. Patent Nos. 26 S3,730 and 2,760,953 and in British Patent Specification S74 43O and in Canadian Patent 6 65 495. A mixture of polyphenyl polymethylene polyisocyanates is particularly advantageous. made by phosgenating the reaction products of aniline with formaldehyde has been. This polyisocyanate is preferably prepared in such a way that aniline is first mixed with formaldehyde condensed under acidic conditions and in such proportions that 40 to 65% of the obtained mixture of Polyphcnylpolymethylenpolyamincn from diphenylmethanediamines. like 4,4-diphenylmethanediamine. and the rest from corresponding Triamines. Tetramines and higher polyamines. This polyamine mixture is then phosgenated. These polyaryl polyalkyl polyisocyanates are therefore preferably mixtures of di- and higher polyisocyanates. Polyaryl polyalkylene polyisocyanates are particularly suitable. 40 to 60% of which consist of 4,4'-diphenylmethane diisocyanates. a Amine equivalents from 120 to 140. 0.04 to 0.4% hydrolyzable Chlorine, a total chlorine reverberation of 0.1 to 0.6% and a flash point of over 204 C. exhibit.

So-called raw Tokyo diisoeyanate can also be used use the phosgeneic

1745

tion of relatively pure toluenediamine. /. H. one Mixture of S (J weight percent 2.4 and 20 weight percent 2,6-tolylenediamine. will echo and without subsequent distillation in liquid form is used.

Any 1 friction agent can be used for foaming to serve. One can /. B. both water and halogenated hydrocarbons such as trichlorofluoromethane. Dichlorofluoromethane and diehlordifluoromethane, or a relatively low boiling alkane. like butane. Hexane and keptane. use. Methylene chloride can also serve as a propellant.

The production of the foams can after the known statutes of limitations. /. B. according to the one-step or multi-step process, take place in the presence of water and / or other propellants.

In the production of the foams, aclivators can be used in the customary manner. for example dibutvl- / indilaural or tin III octoate. furthermore, amine synthesis. like Dimeihviben / ylamin. N-methylmorpholine. permethylated diethylamine or dietha'iolamine. use. In addition, emulsifiers, such as B. sulfonated castor oils or their sodium salts. Use linden. Herner can Foam stabilizers of the previously known type. B. hydrolysis-stable polysiloxane-oxyalkylene block copolymers or stabilizers such as those described in Canadian Patents 6 68 47S. 6 68 537 and 6 70 091 are described. Use linden. About that it is also worth seeing in many halls, add fillers to the polyurethane foam slabs. These fillers can be of any type be: Examples include: foam glass, foamed phenolic resin, expanded vermiculite. Ammonium phosphate. Ammonium polyphosphate, red phosphorus and antimony trioxide.

The polyurethane foams produced according to the invention are particularly valuable for use in the construction industry or for insulation purposes. In addition, they can also be used as upholstery material or soundproofing materials.

example 1

75 parts by weight of bis (2-hydroxyethylmetraclilorphthalate are with 25 parts by weight of triethanolamine mixed. This mixture is made with 30 parts by weight of tri: chlorofluoromethane and 1 part by weight of one Silicone oil of the Pormcl

C ₂ H ₅ - Si -) - O - Si

- (C _n H ^ _n O) ₃₀ C ₄ H ₉

in which (C _n H _2n O) ⁽ -in is a mixed polyoxyethylene and oxypropylene block copolymer with 17 oxyethylene and 13 oxypropylene units. This mixture is then mixed with 120 parts by weight of an organic polyisocyanate mixture of the general formula

OCN-

VNCO

CH,

7-NCO

machine \ crmi:> i.hi. as it is in the L.S-PS Re. 24 514 is described, and the Reaktinnsgemiseh is then entered in a cardboard canon form. After a short time, the reaction mixture begins to foam. The polyurethane cl, aum-.tolT has the following physical properties:

Volume weight, kg m ¹ 33.5

Compressive strength to break, kg cm ^: 2.11

Closed cells ΓΉ) 95

1 lamb idriüKcit as required
ASTM D-1692-59 T sclhsU expiring

Dimensional sensitivity = volume change in ⁰ O (70 C. KK) "'.,

relative humidity) 7.2

Volume change after 2 weeks
at 100 C.% ". 20

When the polyurethane foam is made so that 100 parts by weight of bis (2-hydroxyethyl) tetrachlorophthalate instead of the mixture of triethanolamine and bis (2-hydroxyethyl) tetrachlorophthalate and 60 parts by weight of the polyisocyanate mixture are used instead of 120 parts by weight, the result is a product which is inferior Has physical properties and which melts according to the flame test ^ according to ASTM D-1692-95 T.

Examples 2 to 16

The type and amount of reactants used and the properties of the polyurethane foams are shown in the following table.

In the table mean

1: bis (2-hydroxyethyl) tetrachlorophthalate
O

Cl

Π: Υ Cl

Cl

Il

CN- (CH ₂ -CH ₂ -OH),

CN- (CH ₂ -CH ₂ -OH),

in which / 1 has an average value of O.SH.

A: triethanolamine,

B: N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine,

C: Polyether obtained by the addition of propylene oxide to pentaerythritol, molecular weight 450

D: addition product of propylene oxide with << - methyl-D-glucoside. OH number 460,

E: Addition product of propylene oxide to cane sugar. OH number 450,

F: Mixture of 75 percent by weight of polyol E and 25 percent by weight of diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate.

In some cases the polyhydroxyl compound chlorinated on the aromatic nucleus is and ester group-free, an equivalent weight below 200 and a functionality of 2 to 8 Polyol premixed as indicated, so that a total of

7 8

always including 100 parts by weight of the mixture obtained in the table amount of a catalyst

will. The polyhydroxyl compound or the poly if a catalyst is used. The Kate

Oil mixture is then mixed with 30 parts by weight of trichloride is in each case Ν, Ν, Ν ', Ν'-tetramethylbut

fluoromethane added, also with the an-1,4-diamine in Example 1, and the polyisocyanate used c

given amount of silicone stabilizer and with the 5 speaks that of Example 1.

Example I parts by weight Il -._ IOIy ₁ ) I. Ver Gc- Ge Ge Physical Properties Days Dimensionslabililai 100 C with binding wichls- weight weight 100 one leile share share pressure 3.0 Equi- Polyiso Stabili Kataly strength Volume change 90 valentine cyanate sator sator until break in % 7.2 weight _ below 2 (X) (100% relative air 6.4 humidity) 80 Weight 1 4.6 I. share (kg cm ² | 7th 70 C 2 80 80 20th A. 105 2 2.12 1 5.8 7.0 7th 17.0 3 90 10 A. 83 Ί 1.83 1 13.0 6th 7th 21.0 4th 75 80 25th B. 93 ~) - 2.35 1 2.7 12th 7th 6.5 5 85 70 15th B. 80 -) 2.03 1 6.4 16 7th 11.0 6th - 70 . 115 1 1 2.07 1 16.2 4.1 7th 21.0 7th - 70 10 A. 135 1 1 2.34 1 12th 6.9 7th 18th 8th 70 30th C. 84 ■} 2 2.08 1 10 4.0 7th 10 9 - 20th C. 120 1 1.5 2.24 1 15th 7th 7th 25th 10 20th D. 115 1 1.5 1.55 1 17th 8th 7th 19th 11th 60 40 E. 81 2 1 2.81 1 3.3 6.5 7th 6.5 12th 20th E. 115 1 1.5 2.11 1 17th 7.0 7th 25th 13th ___ 30th C. 125 1 1.5 2.39 1 3 7th 7th 14th 30th D. 115 1 1.5 2.32 1 4th 7th 8th 15th 30th E. 115 I. 1.5 2.39 1 3 7th 7th 16 60 40 F. 80 2 1 2.81 3.5 6.8

The foams produced according to Examples 2 to 16 were self-viewing according to ASTM D-1692-95T. The density of the foams varied from 28 to 33 kg / m ³ .

Claims (1)

Claim: Process for the production of polyurethane foams by reacting polyisocyanates with chlorinated ones on the aromatic nucleus Polyhydroxyl compounds. optionally in a mixture with amide and estei group-free, an equivalent weight less than 200 and a functionality of 2 to 8 polyols. and propellants, characterized in that the compounds are called polyhydroxyl compounds chlorinated on the aromatic nucleus Cl Cl COO-CU, -CH, -OH Cl COO-CH, -CH ₁ -OH Cl and or Cl Cl CO-N (CH ₁ -CHv "OHl, Cl CO-N (CH ₁ -CH ₁ -OH), Cl used. 35 It is already known. Polyurethane foams through the conversion of organic polyisocyanates with organic compounds with at least two active hydrogen atoms in the presence of a propellant to manufacture. The organic compound has at least two active water loafalomes at least partially those compounds are used which have a molecular weight of at least 4s 500 exhibited. It was previously not considered appropriate to use polyurethane foams only on the basis of To manufacture such components that had a molecular weight below 500. While polyurethane foams based on relatively high molecular weight organic compounds with at least two active hydrogen atoms generally have a satisfactory to good mechanical world level, it has been found to be difficult in general. to equip them fiercely, and that they in addition, have relatively unsatisfactory dimensional stability in some fillings. Attempts have also been made to use flame guns Manufacture of polyurethane foams. The procedures in question for this, especially if they are based on the use of reactive chlorinated components, but are in many ! ■ 'all uneconomical and cause above all then unsatisfactory physical properties if sufficiently large amounts of chlorinated component used / t to achieve sufficient flame protection / u. You have already heard of the Manufacture of lamb-protected polyurethane foams tried to be nonreactive. Add flame retardant additives. This occurred many times the downside. that these additives migrate out of the polyurethane foam structure over time, so that the flamnuchuiz effect. dependent on by the time wears off. From US-PS 30 72 614 is already known. To produce polyurethane by reacting glycol triester of a benzene tricarboxylic acid with an organic diisocyanate. DT-AS 10 53 720 also describes the production of mixed polyurethanes by dissolving special aliphatic dialcohols. which are free of amide and ester groups, with diisocyanates and, inter alia, bis (2-hydroxyethyl) terephthalate known. However, these patents do not teach. the low molecular weight used according to the invention. Use polyhydroxyl compounds containing amide or ester groups and chlorinated on the aromatic core for the production of ion polyurethanes. > o that the surprising property profile of the process products from the disclosure of these patents could not be expected either. The production is finally from DT-AS 11 73 649 of flame-retardant foamed plastics through conversion of haloaryl groups having at least difunctional amino alcohols and optionally further polyhydric compounds mi: polyisocyanates in the presence \ un Propellants known. It has, however, been shown. that in the process according to the invention products obtained with an improved Dimcnsionsstabililät can be: in addition, it is also often undesirable to use such products as starting materials cin7.uscti.cn. which at the same time catalysis of the isocyanate groups effect, as the amino alcohols eemäl.fdcr DT-AS 11 73 649. The invention relates to a method for isolation of polyurethane foams by reacting polyisocyanates with chlorinated ones on the aromatic core Polyhydroxyl compounds. optionally in a mixture with amide and Eslergruppe-free. an equivalent weight less than 200 and a functionality of 2 to 8 polyols. and propellants. The process is characterized in that the polyhydroxyl compounds chlorinated on the aromatic nucleus are used the connections