DE1259097B - Process for the production of optionally foamed plastics containing phosphorus atoms and urethane groups - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C08f

German class: 39 b -22/10

Number: 1259 097

File number: F 34854IV c / 39 b

Filing date: September 5, 1961

Opening day: January 18, 1968

The production of high molecular weight crosslinked plastics from linear or branched polyhydroxyl compounds and polyisocyanates and optionally crosslinking agents are known. Here are generally used starting components due to their high carbon content lead to flammable plastics. For this reason, various methods have already been described in which by the use of phosphorus and / or halogen-containing components the Plastics become more flame-resistant. For example, halogenation can optionally be carried out by using Phosphates such as tris (chloroethyl) phosphate or triphenyl phosphate, as plasticizers, provide a flame retardant reach, but these additives are not built into the plastic. You wander in the course time out so that the flame protection is lost. Furthermore, such flame retardants tend as a result Their plasticizer effect leads to a deterioration in the mechanical values with regard to their flame resistance made plastics.

According to other procedures, polyisocyanates or polyhydroxyl compounds containing phosphorus atoms are used to make polyurethane plastics flame resistant, with phosphites of alkylene glycols or polyalkylene glycols containing hydroxyl groups as well as adducts obtained by addition of triesters of phosphorous acid to α, / 3-unsaturated esters in the group of phosphorus-containing polyhydroxyl compounds with phosphonic ester groups are known. In these processes for the production of phosphorus atoms
and containing urethane groups,
optionally foamed plastics

Applicant:

Paint factories Bayer Aktiengesellschaft,

5090 Leverkusen

Named as inventor:
Dr. Rudolf Merten, 5090 Leverkusen;
Dr. Günter Oertel, 5000 Cologne-Flittard;
Dr. Hans Holtschmidt, 5090 Leverkusen;
Dr. Günther Braun, 4260 Sterkrade-Nord;
Dr. Günther Nischk, 5090 Leverkusen

Process, the possibilities of internal plasticization and migration are avoided.

So is z. B. from German Patent 1 106 489 known, reaction products of phosphoric acids or phosphorous acid with alkylene oxides or alkylene glycols of one of the following formulas, if appropriate in mixtures with other polyhydroxyl compounds for the production of polyurethane foams to use:

P ^ - OR ₆ H
OR ₀ H

P ^ OR ₆ H OR _C H

or HO

Ii
■ ρ -

Op

- O - P - OH

In these formulas, a, b, c, d, e and / represent numbers from 1 to 35, η is 0 to 20, and R represents an alkoxy group.

In contrast, there has now been an advantageous process for the production of foams based on polyurethane found that on the use of such triesters of phosphorous acid, which at least 2 phosphorus atoms in the molecule are based as polyhydroxyl compounds.

Build such Polyhydroxylphosphorigsäuretriester with at least 2 phosphorus atoms in the molecule on the one hand in the plastic and on the other hand, in contrast to the already known possibilities, especially for the use of phosphoric acid or Phosphorous acid triesters according to the German Patent specification 1106 489, a significantly better flame retardant effect with otherwise the same or even improved physical values due to their Addition of flame-resistant plastics. The increased flame retardancy to be used according to the invention Polyhydroxyl compounds also apply to the polyphosphoric acid esters of the German ones Patent specification 1106 489, which has a relatively low phosphorus content with a high ester content.

709 719/449

3 4

show or with a small ester content only in very small or hexachlorocyclopentadiene. For modification

Amounts together with the other phosphorus-free can also higher-boiling monofunctional components

Polyhydroxyl compounds can be used, components such as 2,3-dibromopropanol (l) or penta

so that the phosphorus content of the end products in these chlorophenol, are added. Instead of the down-falls is also very low. The molecular polyhydroxy compounds according to the invention can also

to be used Polyhydroxylphosphorigsäuretri- already higher molecular weight polyhydroxyl compounds,

esters with at least 2 phosphorus atoms in the molecule such as the polyethers already mentioned, also polyester

are not subject to this restriction. In addition, polyfunctional alcohols and acids such as

in numerous cases processing-related advantages castor oil and its halogenation products, poly-derived, by the mostly low-viscosity polyesters from the above alcohols and polycarboxylic acids,

hydroxyl compounds a viscosity-lowering such as adipic, sebacic, maleic, phthalic acid or

Mixing components represent what is particularly polymerized fatty acids, adducts of unsaturated

in the production of foams from essential di- or monocarboxylic acids to abietic acid or

is important. Due to their good flame retardant-related natural products, if necessary with assistance can often with small amounts of the use of monofunctional alcohols or

According to the invention to be used compounds a carboxylic acids, such as oleic acid, tall oil fatty acid, abietic

good flame retardant effect can be achieved. acid, also polyacetals from polyhydroxyl compounds

The invention relates to a method for gene and aldehydes, especially formaldehyde, polythio

Production of phosphorus atoms and urethane groups ether from thiodiglycol and polyalcohols, with the containing, optionally foamed synthetic 20 trialkyl phosphites are reacted. Essential

substances from triesters of phosphorous acid and is that a hydrolysis of the phosphites, ζ. Β.

possibly further linear ones or branched ones from anything that has arisen during an esterification

Polyhydroxyl compounds, polyisocyanates and water of reaction, is avoided,

optionally crosslinking agents, with shaping, The production of the starting materials can in characterized in that as a triester of the phos- 25 known manner at elevated temperatures and

phosphoric acid those with at least 2 phosphorus, optionally reduced pressure, where

atoms in the molecule are used, which are determined by the proportions of the phos-

Implementation of less than 3 mol of a polyalcohol phoretic acid triester and polyhydroxyl compound

with 1 mole of a phosphorous acid derivative you get 1: <3 moles.

have been. 30 Only if this molar ratio is adhered to, the triester which is not used according to the teaching of the German Auslegeschrift 1106 489 at least 2 phosphorus atoms, one arrives at the phosphoric acid according to the invention, the starting materials for the phosphorous triesters to be used Processes according to the invention can be carried out after acid with at least 2 phosphorus atoms in the molecule, various generally known methods. 35 which according to the invention can also be used as the sole OH component can be used by transesterification of phosphorous acid trinents, that is to say must be present in sufficient esters with low-boiling alcohols in full and predominant amounts. constant or partial exchange of the origin- In general, the hydroxyl content of the esterification components to be awarded, such as the trim-reversing phosphorous acid triester with several thylphosphite, triethylphosphite, triphenylphosphite, 40 phosphorus atoms and free hydroxyl groups in the trischloroethylphosphite or tris- ^ - chloropropyl- molecule between 0.5 and 25, preferably between 1 phosphite with a polyhydric alcohol in one and 20 ° / ₀ >.

most technically a phosphoric acid triester as the starting point In addition, the phosphoric acid used

material can be obtained. triester be substituted in any way, in particular

As polyhydric alcohols, they can contain halogen atoms, over the esterification alcohol of the original Depending on the phosphorus and hydroxyl content, the Phosphite higher-boiling polyvalent hydroxyl-containing triesters of phosphorous acid alone bonds in question, such as ethylene glycol, diethylene or in a mixture with other known polyglycol, Triethylene glycol, polyethylene glycols, propyhydroxyl compounds in the manufacture of the polyethylene glycols, Dipropylene glycol, polymers of alkylene 50 urethane plastics used, being due to the good Oxides, such as ethylene oxide, propylene oxide, butylene oxide, have a flame retardant effect in numerous cases Epichlorohydrin, styrene oxide, trimethylene oxide, 3,3-bis small amounts of those used according to the invention (Chloromethyl) trimethylene oxide or tetrahydrofuran, polyphosphites are completely sufficient, or their adducts to polyfunctional starter molecules Phosphoric acid, cane sugar, aniline, trichloro 55 hydroxyl compounds include polyester, polyether, aniline, toluenediamines, phenol-aldehyde condensates, polythioethers or polyacetals, with the Amine-aldehyde condensates, also butanediol (1,3), mixtures expediently have a hydroxyl content such as Butanediol- (1,4), hexamethylene glycol, octadecanediols, have indicated above. To implement with these Glycerin, trimethylolalkanes, pentaerythritol, tetra- polyhydroxyl compounds are any polyisomethylolcyclohexanol, Sorbitol, mannitol, glucose, fructose 60 cyanate are suitable. Aromatose are preferred or cane sugar or its, if appropriate, internal diisocyanates. For example: Inversion n-butylene diisocyanate, hexamethylene diisocyanate, m-xy products, produced in the presence of acids, Cane sugar solutions according to Belgian pallylene diisocyanate, p-xylylene diisocyanate, 4,6-dimethyltentcript 596 556, alkoxylated polyphenols, thiodi- 1,3-xylylene diisocyanate, cyclohexane-l ^ -diisocyanate, glycol or its oxyalkylation products, oxyalkylated 65 dicyclohexylmethane ^^ - 'diisocyana ^ m-phenylenediiso-amines with at least two hydroxyl groups, dicyanate, p-phenylene diisocyanate, l-alkylbenzene-2,4-dihalogenated Butyne-2-diol- (1,4), adducts of butene isocyanate, 3 - (α - isocyanatoethyl) - phenyl isocyanate, 2-diol-1,4 or butyn-2-diol-1,4 in cyclopentadiene, 1-alkylbenzene-i.ö-diisocyanate, 2,6-diethylbenzene-

5 6

1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, A 3

3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate or analogue A 1 are 952 parts by weight of pentaerythritol,

Naphthylene-1,5-diisocyanate. At higher functional 3150 parts by weight of triethylene glycol and 3780 parts

Polyisocyanates are z. B. l-methylbenzene- ^ Aö-tri parts by weight of tris (chloroethyl) phosphite up to 15O ⁰ C to

isocyanate or reaction products of 1 mol of a 54,918 parts by weight of a colorless polyphosphite

trihydric alcohol with 3 mol of a diisocyanate with 11.7% OH, acid number 0.6, viscosity 210 cP / ·

called. 25 ° C »3.4% chlorine and 8.75% P interesterified.

From the polyhydroxy compounds and the polyisocyanates according to the isocyanate polyaddition process

drive, if necessary with additional crosslinking io Analog A 1, 140 parts by weight of pentaerythritol,

Medium, manufactured plastics are suitable as 850 parts by weight of a linear polypropylene glycol

Adhesives or coating materials. They have an average molecular weight of 270 and 538

possibly in solution to form lacquer coatings and parts by weight tris (chloroethyl) phosphite up to 150 ° C /

Moldings including foams in known 12 Torr to 1125 parts by weight of a colorless poly

ter way process. A foam manufacture 15 phosphites transesterified. 5.1% OH, acid number 1.0,

takes place, for example, by simply mixing the 2.73% Cl, 5.3% P.

Components in the presence of propellants, such as λ 5
Water, low-boiling halogenated hydrocarbons

or azo compounds, as well as catalysts, 343 parts by weight cane sugar, 410 parts by weight

Emulsifiers and stabilizers, optionally also 20 40% formalin, 424 parts by weight diethylene glycol

in a multi-stage process, with one flameproof and 1 ml of HBF ₄ being heated to 90 ° C for 4 hours

solid foam is created. Rubber-elastic Ma- and then in a vacuum at 90 ° C the formed and

materials can be removed from the water added after the pouring process. Then you still bet

as well as via a storable intermediate stage. 212 parts by weight of diethylene glycol and 270 parts by weight

Normally, when using at least 25 parts of tris (chloroethyl) phosphite at 90 ° C and

at least 2 phosphorus atoms containing phosphorus distilled at the same temperature and 15 Torr the

Acid triester as a polyhydroxyl compound is not necessary, volatile components off. Obtained as a reaction product

to change the usual rules of procedure. one 1120 parts by weight of a yellow condensate.

The polyhydroxyl compounds mentioned can contain 14.1% OH, acid number 11.4, 2.2% Cl, viscosity

also due to its low viscosity as a thinner - 30 10,000 cP / 25 ° C, 1.8% P.
agent to reduce the viscosity of the
Mix lead, which is a further simplification

the processing technology means. 686 parts by weight cane sugar, 1200 parts by weight

The triethylene glycol, 2 parts by weight of a 30% HBF ₄

Phcsphoratome and urethane groups placed on 35 and 300 parts by weight of water are 4 hours on

Pointing plastics are characterized by their 90 ° C heated and then at the same temperature in the

flame-retardant or flame-retardant character when the vacuum is on, the added water is removed. After discovery

otherwise unchanged or improved mechanics of the water are measured at 80 ° C and 20 Torr in

niche properties. You will find use 5 hours 1080 parts by weight of tris (chloroethyl) -phos-

in particular for building purposes, insulation or Auspphit with simultaneous distilling off by the

clothes. Transesterification of liberated ethylene chlorohydrin

Preparation of the starting materials added dropwise. As soon as no more ethylene chlorohydrin

escapes, the temperature is increased to 90 C and

Al the product was stirred for 4 hours at 90 ° C / 15 Torr.

To a mixture of 1400 parts by weight of penta " ^AIs reaction product, 2183 parts by weight are obtained

erythritol and 2200 parts by weight of diethylene glycol ^^^^^^^^ ", 60

1500 parts by weight of tris (chloroethyl) phosphite OH acid number 15, viscosity 7320 cP / 25 ° C, 2.15%

added and the mixture heated ^{to 8O 0 C.} Under ^u > ⁵ ' ⁸ ' ° ^F A 7

reduced pressure of 15 to 20 Torr will result in the "," _. . _M _,. , "._ _. ,

distil off chloroethanol formed by transesterification- ⁵ ° 140 weight point pentaerythritol and 240 weight-

lates. In proportion to the proportions that are distilled off, ^tede ₁ ^H 5 ^candl0l - _o ¹ ^ ^w ^ ^{rden in} ? Y ^ ^UI ? ^b ? ⁸⁰ _Λ1 °

then in the course of about 15 hours another 3888 Ge within 8 hours according to the instructions of the

parts by weight of tris (chloroethyl) phosphite were added dropwise. So- ^ f ¹¹ ™ ^d f ethylene chlorohydrins with 540 g Tns-

soon at 80 ° C / 15 Torr no more ethylene chlorohydrin (chloroethyl) phosphite added. Then you increase

escapes, the temperature will rise to ⁵⁵ t ^le jTi ^Vem } ^U u J ^^ ^gSam ? fu in 6 hours,

Increased 14O ⁰ C and then 6 hours at 140 ⁰ C. ^ 4 hours at 150 C / 12. Now you get in

post-condensed. 4110 parts by weight of a 90 g yield of a colorless oil are obtained. Viscosity 0450 cP /

colorless polyphosphites containing 12.7% OH, 14.2% 25 ° C. 11.5% OH, acid number 5.6, 5.7% Cl, 11.9% P.

Phosphorus, 4.4% chlorine and a viscosity of Example 1

11800cP / 25 ° C. ^6o . ,, "_. , ". _. . . "_. ,.,

148 parts by weight of A 7 are used in 150 parts by weight

Ethyl acetate — acetone (1: 1) and then with a

Analogously to A 1, instead of the diethylene glycol, a solution of 249 parts by weight of the addition product

3100 parts by weight of triethylene glycol used and tes of toluene diisocyanate to trimethylolpropane—

as a reaction product in a transesterification up to 65 butane-1,3-diol (NCO content 13%) ^m 250 weight

150 ° C / 15 Torr 5610 parts by weight of a colorless part of ethyl acetate — glycol monomethyl ether acetate (1: 1)

Get condensate. 10.5% OH, 10.05% P, 4.4% offset. The lacquer solution is applied to glass, wood, paper

Cl, acid number 2.0, viscosity 245 cP / 25 ⁰ C. or painted on metal. After the

Dry a colorless, solvent-resistant coating with good flame-retardant properties.

Examples 2 to 10

The components specified in the table below are used in the amounts specified there in a mechanical mixer quickly and thoroughly mixed with one another. The liquid reaction mixture is filled in forms in which it soon becomes elastic or hard, heavy finds combustible foam with the properties given in the second table.

2 3 4th 5 6th 7th 8th 9 10 Al 30th 40 30th 40 - - - 100 A2 - - 40 70 - A3 70 60 70 - - 30th 70 - 50 A4 160 60 - - A 5 - - - - - 30th - A6. .. .. 137
2
0.3
6th 135
2
0.3
6th 92
1
0.5
30th 92
2 115
2
0.3
6th 153
2
0.3
6th 161
1
0.3
6th 140
0.5
0.3
6th A7 - - 2
0.2 - - - - B. - - - 1
5.4 - - - - C .. - - - - 0.1 - - D. E ... F. 50 G 148
1
0.3
6th H I. K. . . L. M. - N O . . .. P. Q

B = polyester from adipic acid, phthalic anhydride, oleic acid and trimethylolpropane (11.3% OH);

C = branched polypropylene glycol ether (OH-ZaW 56); D = branched polypropylene glycol ether (11.3% OH);

E = adduct of propylene oxide with ethylenediamine (OH number 450);

F = adduct of propylene oxide with tolylenediamine (15.2% OH);

G = 4,4'-diphenylmethane diisocyanate (90% pure product);

H = permethylated dimethylaminopiperazine; I = organopolysiloxane polyalkylene glycol ester; K = sodium castor oil sulfate (50% water); L = trichlorofluoromethane;
M = dimethylbenzylamine;
N = triethylenediamine;
O = tin (U) octoate;
P = water;
Q = dibutyltin dilaurate.

A. B. C. D. E. F. G H I. K 2 50
43
35
32 3.1
3.3
2.0 0.2
0.3
0.3 140
145
88 3.8
3.0
3.4 0.8 185 38 34 3 43
36
37
46
44 3.1
1.3
2.1
3.4
2.8 0.7
0.3
0.3
0.6
0.4 113
150
141
128
132 4.0
3.5
2.9
3.4
2.4 4th 5 12th 6th 7th 8th 9 10 -

A = volume weight, kg / m ³ ,
B = compressive strength, kg / cm ² ,
C = impact strength, kg / cm,
D = thermal flexural strength, ⁰ C,
. E = water absorption,%,

Example 11 a) Preparation of the starting material

Parts by weight (1 mol) of triethylene glycol are added dropwise to 540 parts by weight (2 mol) of tri (chloroethyl) phosphite (technical) at 120 ° C. in vacuo. With a vigorous reaction, ethylene chlorohydrin is split off and distilled off in vacuo. After about the theoretical amount, ie 160 parts by weight F = tensile strength, kg / cm ² ,
G = elongation,%,

H = compressive strength at 40% compression, g / cm ² , I = elasticity,%,
K = permanent deformation,%.

Chlorohydrin is distilled off, a further 375 parts by weight (2.5 mol) of triethylene glycol are gradually added at 120 to 130 ° C added dropwise, the elimination of ethylene chlorohydrin continues continuously. After this all of the triethylene glycol has been added dropwise, the reaction temperature is increased to 145.degree and held until no more ethylene chlorohydrin distilled off in vacuo. Distill all together in the transesterification 296 parts by weight of ethylene chlorine

hydrin. The residue obtained is 768 parts by weight of the desired polytrialkyl phosphite, which is a colorless oil (OH number 233).

b) 30 parts by weight of the starting material thus obtained are mixed with 30 parts by weight of a polyester from adipic acid, phthalic anhydride, oleic acid and trimethylolpropane (OH content 11.3%), 30 parts by weight a propoxylated phosphoric acid with 11.4% OH, 10 parts by weight of a propoxylated Ethylenediamine with 22.3% OH, 0.5 parts by weight of permethylated aminoethylpiperazine, 0.3 parts by weight. share organopolysiloxane polyalkylene glycol ester and 6 parts by weight sodium castor oil sulfate (50% water) thoroughly mixed. After adding 137 parts by weight of 4,4'-diphenylmethane diisocyanate (90%) the Mixture filled in molds in which a flame-retardant rigid foam with the following mechanical Properties arises:

Volume weight 46 kg / m ³

Compressive strength 3.8 kg / cm ²

Impact strength 0.3 kg / cm

Thermal flexural strength 132 ° C

Water absorption 3.6%

Example 12

a) Production of the starting material

540 parts by weight (2 mol) of technical grade tri- (chloroethyl) phosphite are with a total of 600 parts by weight (4 mol) of triethylene glycol in the example 11 implemented in the specified manner. A total of 300 parts by weight of ethylene chlorohydrin are split off. The residue obtained is 830 parts by weight of a colorless polyester (viscosity 340 cP / 20 ° C; OH number 266).

b) 70 parts by weight of the starting material thus obtained are mixed with 30 parts by weight of a propoxylated Ethylenediamines with 13.6% OH, 0.3 parts by weight of organopolysiloxane polyalkylene glycol ester and 6 parts by weight of sodium castor oil sulfate (50% water) were stirred thoroughly. After addition of 116 parts by weight of 4,4'-diphenylmethane diisocyanate (90%) a flame-retardant rigid foam with the following physical properties:

Volume weight 53 kg / m ³

Compressive strength 3.4 kg / cm ²

Impact strength 0.7 kg / cm

Thermal flexural strength 118 ⁰ C

Water absorption 2.7%

Example 13
a) Production of the starting material

To 540 weight parts (2 moles) of tri (chloroethyl) phosphite is from 100 to 12O ⁰ C, a mixture of 340 weight parts (1 mole) of glycerol-1-pentachlorphenyläther and 450 parts by weight (3 moles) of triethylene glycol was added dropwise for several hours in the course. Here, 410 parts by weight of ethylene chlorohydrin are distilled off in vacuo. Thereafter, the reaction mixture is heated for about 2 hours at 150 ⁰ C in vacuum to the last remnants of the present in the mixture to remove Äthylenchlorhydrins. The residue is a colorless oil (910 parts by weight) (viscosity 1125 cP / 20 ° C; OH number 191).

709 719/449 1.68

b) 40 parts by weight of the starting material thus obtained with 160 parts by weight of one with Trimethylolpropane slightly branched polyether (OH number 56), 2 parts by weight of dimethylbenzylamine, 0.2 part by weight of triethylenediamine, 1 part by weight of tin dioctoate, 2 parts by weight of organopolysiloxane polyalkylene glycol ester and 5.4 parts by weight of water mixed thoroughly. After adding 76 parts by weight of tolylene diisocyanate, a heavy one is obtained

ίο flammable elastic foam, the following has physical values: '

Volume weight 35 kg / m ³

Tensile strength 1.1 kg / cm ²

Elongation 225%

Compression hardness 39 g / cm ² at 40%

Compression

Elasticity 34%

Permanent deformation 12%

Example 14

Parts by weight of a phosphorous acid ester analogous to Example 12, a) with an OH number of 352 are mixed with parts by weight of a polyester (viscosity 2450 cP / 25 ⁰ C; isocyanate consumption 75 g C ₆ H ₅ NCO / 100 g polyester) from 1500 parts by weight polyethylene glycol (17, 8% OH), 500 parts by weight of diethylene glycol, 300 parts by weight of maleic anhydride and 1200 parts by weight of rosin B, 1 part by weight of permethylated aminoethylpiperazine, 0.3 part by weight of polysiloxane polyalkylene glycol ester and 6 parts by weight of sodium castor oil sulfate (50% water) are thoroughly mixed. After adding 120 parts by weight of 4,4'-diphenylmethane diisocyanate (90%), the mixture begins to foam, and a tough and fine-pored rigid foam with good flame retardancy and the following properties is obtained:

Volume weight: .... 37 kg / m ³

Compressive strength 1.6 kg / cm ²

Impact strength 0.3 kg / cm

Thermal flexural strength 123 ⁰ C

Water absorption 2.3%

Claims (2)

Patent claims: 1. Process for the preparation of phosphorus atoms and urethane groups containing, optionally foamed plastics from Trieste of phosphorous acid and optionally further linear or branched polyhydroxyl compounds, polyisocyanates and optionally Crosslinking agents, with shaping, characterized in that as a triester of phosphorous acid, those with at least 2 phosphorus atoms in the molecule are used, by reacting less than 3 moles of a polyalcohol with 1 mole of a phosphorous acid derivative have been received. 2. The method of claim 1, characterized labeled in ₄ characterized in that triesters of phosphorous acid are used, which additionally contain halogen atoms in the molecule. Documents considered: German Auslegeschrift No. 1106 489. Bundesdruckerei Berlin