DE1595189B2 - STABILIZED BASE MIXTURE FOR A LATER IMPLEMENTATION WITH A POLYISOCYANATE - Google Patents

Description

The invention relates to a stabilized base mixture for a later reaction with a polyisocyanate containing one of the reaction product a polyhydroxyl compound containing from about 3 to about 8 hydroxyl groups per molecule with one Polyol consisting of alkylene oxide, a polyol made from the reaction product of an alkylene oxide having 2 to 6 carbon atoms per molecule with an ester of an alcohol having 1 to 4 hydroxyl groups per molecule and an acid having a phosphoryl or thiophosphoryl group containing phosphorus Polyol, a urethane formation catalyst, a blowing agent and optionally a surfactant Middle.

Polyurethane foams that are z. B. by reacting a liquid mixture of a compound with several hydroxyl groups per molecule and a compound with two or more isocyanate groups can be produced per molecule under foaming conditions, in the past, along with many desirable properties, particularly a high level of resistance to transmission of heat, the disadvantage of being highly flammable. This flammability was then counteracted by adding the basic mixture to be reacted with the polyisocyanate the mentioned phosphorus-containing polyol was added. This started the manufacture of fire retardants Polyurethane foams made possible in a one-step process without the synergistic effect of a phosphoropolyamide was required in the master batch. Polyisocyanates can be those which contain 2.3 to 6 isocyanate groups per molecule and essentially no urethane bonds, be used. . ;

Basic mixtures which, in addition to the above-mentioned phosphorus-containing polyol, contain certain other ingredients the polyurethane foams, namely the also mentioned polyol, a catalyst for urethane formation, contain a propellant and optionally an emulsifier and other agents and those the polyisocyanate is added later as a separate portion in order to obtain the complete foamable mixture obtain, however, have a limited shelf life. The basic mixture can be used fresh be of good responsiveness; however, should it be kept for weeks or months, so it loses its ability to harden rapidly when mixed with the polyisocyanate.

The stability is based on the reactivity of the catalyst as a function of storage time and temperature. It has been observed that amine catalysts as well as organic tin catalysts come into contact lose their effectiveness with the phosphor polyol in the reaction mixture, which is probably due to a Complex effect with the phosphorus-containing polyol

30; is due. It often happens that basic mixtures, which contain the phosphorus-containing polyol when mixed with a polyisocyanate Foam formed and hardened quickly and effectively and lost its effectiveness after a short storage period and the mixtures to which they were added formed foam only slowly and incompletely, and hardened.

The invention is based on the object of a basic mixture for a later implementation with a A polyisocyanate containing one of the reaction product of about 3 to about 8 hydroxyl groups per molecule containing polyhydroxyl compound with an alkylene oxide consisting of a polyol of the reaction product of an alkylene oxide having 2 to 6 carbon atoms per molecule with an ester from an alcohol with 1 to 4 hydroxyl groups per molecule and an acid with a phosphoryl or Thiophosphoryl group consisting of phosphorus-containing polyol, a urethane formation catalyst, a blowing agent and optionally a surfactant to stabilize it so that it can be stored for an extended period of time can be without losing its reactivity before it is reacted with the polyisocyanate will.

According to the invention, this object is achieved in that the basic mixture also includes a Reaction product of an alkylene oxide having 2 to 6 carbon atoms per molecule with an alkylene polyamine Contains with 1 to 4 alkylene radicals or with triethanolamine existing hydroxyalkylamine.

The phosphorus-containing polyol contained in the basic mixture according to the invention is preferably produced by reacting an alcohol with phosphoric acid per se or preferably with its acid anhydride. The preferred acid is orthophosphoric acid (H ₃ PO ₄ ) or even better its acid anhydride (P ₂ O ₅ ) or thiophosphoric acid or other acids,

which the -> P = O group or its anhydrides included, e.g. B.

phosphorous acid (H ₃ PO ₃ ),
Meta-phosphoric acid,
Pyrophosphoric acid,
Polyphosphoric acid

or their oxides or anhydrides (where they occur), which can be represented by P ₂ O ₅ , P ₂ O ₄ or P ₂ O ₃ . The acid (or its anhydride) is reacted with the alcohol component in a conventional manner to give an acid ester which is at least the monoester. The alcohol is represented by the formula ROH, in which R denotes alkyl radicals such as ethyl, methyl, propyl, isopropyl, isobutyl, tertiary butyl or amyl radicals, hydroxyalkyl radicals, alkoxyalkyl radicals, hydroxyalkoxyalkyl radicals, aromatic (benzene) radicals or hydroxybenzene radicals . Mixtures of the monoester and the diester can of course also be included. These esters also contain one or more acidic OH groups of phosphoric acid.

However, at least some of the acidic esters formed should be acidic from the oxyalkylation stage two OH groups retained so that a polyol is formed in the oxyalkylation stage, i.e. H. a connection with at least two hydroxyl groups supplied by corresponding oxyalkylation side chains.

The phosphorus-containing polyols can also by mutual action of monoalcohols and Glycols can be made on phosphoric acid in place of phosphorus pentoxide. This reaction takes place not as smooth as with phosphorus pentoxide, and more complex acidic phosphate esters are achieved.

The acidic esters from the alcohol and the phosphorus acid are with alkylene oxide molecules implemented with 2 to 6 carbon atoms. Corresponding oxides are ethylene oxide, propylene oxide and butylene oxide (1,2 or 2,3) or styrene oxide. These oxides can be acidic under pressure with the one described above Implement ester. The resulting oxyalkylation products are represented by the following formula:

R-O

Il
- ρ

R,

OCH ₇ CH

in which η is a number from 0 to 6, m is a number from 1 to 2 and ο is a number from 1 to 2, the sum of the numbers ο and m being 3. R has the same meaning as above and R is hydrogen, _{-CH 3} or -CH ₂ CH ₃ . It can be observed that this material terminates with a hydroxyl group on each oxyalkylation side chain so that the material contains active hydrogen atoms and reacts with the polyisocyanate component to produce parts of the polyurethane molecules. The oxyalkylation side chains provide essentially the only free hydroxyl groups in the molecule. The material is usually essentially neutral and has a hydroxyl number in the range from about 150 to about 400. The alkylene oxide may have been used in the oxyalkylation in an amount of from about 1 to about 12 moles per mole of acidic ester of phosphoric acid.

The polyols contained in the basic mixture of the invention, which essentially consist of carbon, Consist of hydrogen and oxygen, are preferably oxyalkylation products of a saccharide or Glucosides such as B. cane sugar, fructose or grape sugar, or sorbitol, and contain at least 3 and preferably 6 to 8 hydroxyl groups per molecule. At present, cane sugar represents because of it Availability and low cost represent the preferred starting polyol for the oxyalkylation. The Oxyalkylation products usually have a hydroxyl number in the range from about 150 to about 700. Preferably, the oxyalkylation of glucoside or saccharide with an epoxy compound is with carried out relatively low molecular weight, which contains only a single oxirane ring, z. B. ethylene oxide, propylene oxide or butylene oxide. With butylene oxide you can either use the 1,2 or who used 2,3-oxide isomer. Obviously, mixtures can also be used to effect the reaction from the 1,2- and 2,3-butylene oxide isomers. be. Styrene oxide can also be used to meet all or part of the requirements for oxirane compounds.

The hydroxyalkylamines contained according to the invention to stabilize the basic mixture, which are composed of the reaction product of an alkylene oxide having 2 to 6 carbon atoms per molecule with an alkylene polyamine with 1 to 4 alkylene radicals or with triethanolamine, can easily by reaction these alkylene oxides with the corresponding primary, secondary or tertiary alkylene polyamines or be made with triethanolamine. If ethylenediamine is reacted with propylene oxide, a Material with the following structural formula:

OH OH

CH ₃ -CH-CH ₂ CH ₂ -CH-CH ₃

N-CH ₂ -CH ₂ -N

CH ₃ -CH-CH ₂ CH ₂ -CH-CH ₃

OH OH

The reaction of diethylenetriamine with propylene oxide results in a material that is resistant to the the following formula can be represented:

OH η -O- CH ₃ CH ₂ tr / ~ \
H ₃ U -CH-CH ₂ - -0- -CH- CH ₂ H ₃ C- -CH-CH ₂ -
I. -CH- OH η CH ₃

CH ₃
CH ₇ -CH-O-

OH
CH ₇ -CH-CH,

N-CH ₂ -CH ₂ -N-CH ₂ -CH ₂ -N

-CH ₂ -CH-CH ₃
OH

CH ₂ CH ₂ -CH-O-

CH-CH ₃ CH ₃

CH ₂ -CH-CH ₃
OH

where η can mean a number from 0 to about 5.

The reaction of triethanolamine with propylene oxide leads to the formation of a Hydroxyaikylamins with the following formula:

CH ₇ - CH ₇ - O

CH ₃
CH ₇ -CH-O

CH ₇ CH ₇ O

CH ₃
CH ₇ -CH-O

CH ₇ - CH ₇ - O

CH ₃
CH ₇ -CH-O

OH
CH ₂ - CH - CH ₃

OH
CH ₂ - CH - CH ₃

OH
CH ₂ - CH - CH ₃

where η is a number from 0 to about 5. These hydroxyalkylamines which contain tertiary amino groups have hydroxyl numbers in the range between 200 and 800. They can be contained in the basic mixture in amounts of from about 3 to about 60, preferably at least about 5 percent by weight, based on the total foamable mixture.

The stabilized base mixture according to the invention also contains a catalyst for urethane production. Usable catalysts for this are, for. B. tetramethylguanidine, tetramethyl-1,3-butanediamine, Triethylenediamine or dimethylethanolamine. Esters of tin can also be used, such as z. B. tin oleate, tin octoate or dibutyltin dilaurate.

The catalyst is preferably used in an amount of from about 0.1 to about 5 percent by weight, based on the reactive components in the foamable mixture are used.

The basic mixture according to the invention also contains a propellant, for example a chlorofluorocarbon such as CCl ₃ F or CCl ₂ F ₂ or another recognized system which causes a gas release in the foamable mixture. So z. B. a small amount of water, e.g. B. about 1 to about 3 percent by weight, based on the reactive constituents of the foamable mixture, may be included in order to later effect the production of carbon dioxide with some of the isocyanate groups on site.

The amount of blowing agent used depends on the density desired in the foam. This is usually from about 0.016 to about 0.160 g / cm ³ , but higher or even lower densities may also be useful for special purposes. In the event that a chlorofluorocarbon is used as the blowing agent, about 5 to about 40 percent by weight, based on the foamable mixture, can be included.

In addition to the main constituents mentioned, the basic mixture according to the invention can also contain further constituents Contain additives that promote the stability and cell formation of the foam masses obtained. To the For example, an amount sufficient to emulsify, e.g. B. about 0.1 to 3%, of a surfactant Be included by means of such. B. usually in the manufacture of polyurethane foams can be added.

Similarly, additives to increase the stability of the foam compositions can optionally be included be e.g. B. cellulose ethers, such as. B. methyl cellulose or esters, such as. B. cellulose acetate butyrate, which the toughness of the foam masses during the

Increase capture levels before the resin-forming ingredients have had an opportunity to achieve more rigid ones Structures to respond.

This is followed by a list of suggested ranges for the properties and proportions of the various constituents of the basic mixture according to the invention, the amounts given are based on the total foamable mixture.

Oxyalkylation product of
Polyhydroxyl compound
(Polyether polyol),
Hydroxyl number

Phosphorous polyol
(Flame retardant)

Chlorofluorocarbon
(Propellant)

Surface active agent ..

catalyst

Hydroxyalkylamine

Hydroxyl number

minimum

300

3%

5% 20% 0.005% 3% 0.1% 5% 5% 60% 150 700

maximum

750

20%

This basic mixture is later used with the polyisocyanate mixed in a ratio of polyisocyanate to polyol such as 0.9: 1 to 1.3: 1. The following preparations explain the preparation of the phosphorus-containing used in the following examples Polyols. .

Preparation A

950 g of an acidic phosphoric acid ester which had been obtained from 3.09 mol of H ₃ PO ₄ , 1.0 mol of P ₂ O ₅ and 2.68 mol of ethylene glycol and had an acid number of 808 and a phosphorus content of 27.68% were reacted with 1840 g of propylene oxide.

The organophosphate was heated to 66 ⁰ C. The propylene oxide was added at a rate sufficient to maintain acceptable pressure in the system and the system was cooled to maintain a temperature below about 113 ° C. The reaction was continued for 6 hours and 48 minutes. The unreacted propylene oxide was separated from the reaction product. A yield of 2143 g was achieved with the following properties of the product:

Acid number 3.25

Hydroxyl number 343.8

Phosphorus content 10.05%

Preparation B

1050 g of an acidic phosphoric acid ester, which had been obtained from 1 mol of P ₂ O ₅ , 1 mol of propylene glycol and 1.82 mol of n-butanol and had an acid number of 535, were reacted with 1212 g of propylene oxide.

The ester was heated to 66 ° C. and then the propylene oxide was added. The reaction temperature was kept below about ⁰ HO C. The reaction was continued for 3 hours and 36 minutes. The maximum pressure during the reaction was about 14.5 kg.

The crude product had an acid number of 2.9. It was purified under vacuum at a temperature up to 100 ⁰ C. An oxyalkylation product was obtained with the following properties:

Acid number 0.3

Hydroxyl number 297.4

Phosphorus content 10.44%

Preparation C

32.16 kg of an acidic phosphoric acid ester made from 1.26 mol of phosphorus pentoxide and 1.26 mol of ethylene glycol and 2.55 mol of n-butanol was obtained and had an acid number of 516 and a phosphorus content of 19.4% was reacted with 31.9 kg of propylene oxide.

The resulting product had the following properties:

Acid number 3.89

Hydroxyl number 295.6

Phosphorus content 10.85%

Preparation D

20.6 kg of an acidic phosphoric acid ester, which had been obtained from 8.06 kg of P ₂ O ₅ and 16.85 kg of n-butanol and had an acid number of 464, were reacted with 18.8 kg of propylene oxide.

The ester was heated to a temperature of 66 ^° C. and the propylene oxide was added at a rate which allowed the reaction to be regulated. The total reaction time was 6 hours, and after it was completed, the mixture was purified in vacuo to remove the unreacted propylene oxide. The yield was 29.9 kg of a product with an acid number of 0.17 and a hydroxyl number of 278.5.

The hydroxyalkylamine with a hydroxyl number contained in the basic mixture according to the invention as a stabilizer from Z. B. 150 to 700 can by reacting an alkylene polyamine with 1 to 4 alkylene radicals, z. B. ethylenediamine, diethylenetriamine or triethylenetetramine or triethanolamine with an alkylene oxide and 2 to 6 carbon atoms, ζ. Β. Propylene oxide, ethylene oxide or butylene oxide be. This hydroxyalkylamine is generally added to the base mixture in an amount of about 5 up to about 60 percent by weight, based on the foam-forming mixture.

example 1

In this example, 4 different basic mixtures 1 to 4 were used, which are preparations D, C, A or B as the phosphorus-containing polyol, a cane sugar polyol made from 1 mol of cane sugar, 11 mols of propylene oxide and 4 mols of ethylene oxide as the polyether polyol, and a mixture of 4 as a catalyst Parts by weight of this cane sugar polyol and 1 part by weight of triethylenediamine, a commercially available silicone soluble in the mixture as a surface-active agent, CCl ₃ F as a propellant and a hydroxyalkylamine as a stabilizer, which had been obtained by reacting diethylenetriamine with propylene oxide and had a hydroxyl number of 475.

These basic mixtures contain all components of the foamable mixture with the exception of the polyisocyanate contained, could be stored and shipped as trade items. Needed for their use

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you only add a polyisocyanate that was free of urethane bonds, and z. B. about 15 seconds to stir on a turbo mixer.

A commercially available polyphenylene polymethylene polyisocyanate was used as the polyisocyanate in this example used with an isocyanate function over 2.5 per molecule.

The foam-forming mixtures were caused to foam and without external heat cured and were then cut into samples that underwent 1 and 4 weeks of moisture aging, respectively

IO

exposed at about 7O ⁰ C and 100% relative humidity. At the end of this time, the color and tendency of the foam sample to expand under humid conditions were observed. Additional groups of samples were subjected to flame testing according to ASTM method 1692-59T after aging under humid conditions.

The composition of the stabilized base mixes and the finished foam batches as well as the Test data for the foams produced therefrom are listed in the table below.

composition Foam 1 Foam 2 Foam 3 Foam 4 Polyisocyanate 100.0 about 24 ^° C 100.0 about 24 ° C 100.0 about 24 ° C 100.0 about 24 ° C Cane sugar polyol 54.7 54.5 52.2 54.5 Hydroxyalkylamine 20.0 ■ 20.0 20.0 20.0 P-polyol (preparation D) ... 20.5 - - - P-polyol (preparation C) ... - 20.5 - - P-polyol (preparation A) ... - 16 ° C - 16 ° C 20.5 16 ° C - 16 ° C P-polyol (preparation B) ... - - - 20.5 Surface active middle 1.0 1.0 1.0 1.0 catalyst 3.5 3.5 3.5 3.5 Propellant 32.4 32.4 32.0 32.4 Cream time 26 sec. 25 sec. 23 sec. 22 sec. Solidification time 52 sec. 50 sec. 48 sec. 49 sec. Foam appearance Well Well Well Well colour light brown light brown light brown light brown Cell structure fine fine fine fine strength strong, not crumbling strong, not crumbling strong, not crumbling strong, not crumbling density 0.03186 0.031059 0.03042 0.031059 Try flames directly after manufacture 2.54 cm - 34 sec. 2.38 cm - 33 sec. 2.54 cm - 36 sec. 2.54 cm - 34 sec. Flame out Flame out Flame out Flame out Aged 1 week 2.54 cm - 26 sec. 2.54 cm - 27 sec. 2.54 cm - 22 sec. 2.38 cm - 28 sec. 4.2862 cm - 30 sec SA *) Flame out 3.775 cm - 27 sec. SA *) Flame out Aged 2 weeks 2.54 cm - 24 sec. 2.54 cm - 27 sec. 2.54 cm - 20 sec. 2.54 cm - 23 sec. 3.775 cm - 30 sec. SA *) 4.286 cm - 32 sec. SA *) 3.81 cm - 31 sec SA *) 3.775 cm - 32 sec. SA *) Aged 4 weeks 2.54 cm - 25 sec. 2.54 cm - 24 sec. 2.54 cm - 21 sec. 2.54 cm - 19 sec. 3.775 cm - 30 sec. SA *) 3.775 cm - 30 sec. SA *) 3.65 cm - 28 sec. SA *) 3.333 cm — 30 sec. SA *) Elongation and discoloration Aged 1 week 0.3175 cm 0.3175 cm 0.3175 cm 0.3175 cm very little discoloration very little discoloration very little discoloration very little discoloration Aged 2 weeks 0.3175 cm 0.635 cm 0.635 cm 0.635 cm very little discoloration very little discoloration very little discoloration very slight discoloration Aged 4 weeks 0.476 cm 0.3175 cm 0.476 cm 0.635 cm slight discoloration slight discoloration slight discoloration slight discoloration *) Self-extinguishing.

It can be seen from the data in the table that the foams obtained are of good structure and appearance was. Although they were low in density, they were strong and did not crumble. aside from that

fabrics withstood aging with only slight elongation. In addition, they exhibited the property that they underwent aging even after maximum times (4 weeks) wet conditions after just a few seconds

the foams weren't sticky. The foam burning time itself extinguishes.

B e i s ρ

In order to show the stabilizing effect of the hydroxyalkylamine on the base mixture, the carried out the following tests:

Trial a (control)

This experiment serves as a control, with the basic mixture without the use of a stabilizing Hydroxyalkylamine was prepared.

The phosphorus-free polyol component (polyether polyol) consisted essentially (89 parts) of the

iel 2

Oxyalkylation product of 1 mole of cane sugar, 11 moles of propylene oxide and 4 moles of ethylene oxide, which 5 parts of trimethylolpropane and 6 parts of the oxyalkylation product of trimethylolpropane and propylene oxide had been added, said oxyalkylation product having a hydroxyl number of 740 had. The emulsifier added to the basic mixture consisted of that in the example used liquid silicone. The phosphorus-containing polyol (flame retardant) corresponded to im essential to the preparation D.

The catalyst consisted of a solution of 1 part of tertiary amine (triethylenediamine) in 4 parts a solvent which is the oxyalkylation product of 1 mole of cane sugar, 11 moles of propylene oxide and was 4 moles of ethylene oxide. The basic mix consisted of

Parts by weight

Polyether polyol 75.5

Emulsifier 1

Phosphorous polyol 15

Catalyst solution 4

CCl ₃ F (propellant) 30

A portion of this base mixture was then mixed with the polyphenylene polymethylene polyisocyanate used in Example 1 put together to form the following foam-forming mixture:

_,. Parts by weight

Polyisocyanate

(at room temperature) 100

Basic mixture (15.6 ° C) 125.5

The ingredients were stirred and poured into a mold, and then allowed to foam and freeze. The cream time of the mixture was 28 seconds and the setting time 65 to 68 seconds. The mixture of the unaged base mixture and the polyisocyanate provided a good one Foam with a fine-cell structure.

A second part of the base mix was aged at 43 ° C for 24 hours. Then became the base mix combined with the same polyisocyanate in the same amounts and the mixture was combined poured into a mold. The cream time of this mixture was 130 to 140 seconds and the mixture did not freeze. Obviously, this mixture could neither be foamed nor cured satisfactorily, and the product was removed without first solidifying. The basic mix was obvious inconsistent.

Attempt b

In this experiment, the same constituents as used in the foamable mixture were used previous experiment, but in this case the basic mixture was a hydroxyalkylamine stabilized, which had been obtained by oxyalkylation of diethylenetriamine with propylene oxide and had a hydroxyl number of 700. The basic mix consisted of

Parts by weight

Polyether polyol (as in experiment a) ... 41.5 Phosphorus-containing polyol

(as in preparation D) 15

Hydroxyalkylamine 20

Emulsifier 1

CCl ₃ F (propellant) 32

A portion of this base mixture was combined with a polyisocyanate composed mainly of diphenylmethane-4,4'-diisocyanate and contained an average of about 2.5 isocyanate groups per molecule, resulting in a foamable mixture received which consisted of

Polyisocyanate.
Basic mixture

Parts by weight of temperature

100 109.5

24 ° C 15.6 ⁰ C

The ingredients were stirred together and immediately exposed to foaming and curing. Other parts were exposed to aging at 43 ° C for various periods of time in order to obtain the To determine the stability of the mixtures. The results obtained are shown in the table below.

Aging of the base mix Cream time Solidification time Remarks (Seconds) (Seconds) Unaged 45 to 50 84 to 87 Good foam, fine cells 17 hours 47 to 51 82 to 86 Good foam, fine cells 3 days 47 to 52 84 to 89 Good foam, fine cells 8 days 52 85 to 95 Good foam, fine cells 15 days 60 88 to 98 Good foam, fine cells 22 days 58 to 65 104 to 107 Good foam, fine cells 30 days 60 to 70 100 to 110 Good foam, fine cells 62 days 60 to 70 105 to 115 Good foam, fine cells

The aging tests for the base mix were ended after 62 days, and the foams still showed good structure. The hydroxyalkylamine was found to be a most effective stabilizing agent for the components of the basic mixture.

60

When experiment b was repeated, a basic mixture was obtained from the following ingredients manufactured:

65 parts by weight

Polyether polyol (as in experiment a) ... 41.5

Hydroxyalkylamine 20

Catalyst mixture

(as in experiment a) 0.4

Phosphorous polyol

(according to preparation D) 15

Surfactant 1

CCl ₃ F (propellant) 32

A portion of this base mix was used to make a foamable mix which consisted the end

Polyisocyanate (like experiment b) ...
Unaged basic mixture

Parts by weight

100
109.9

temperature

24 ⁰ C
15.6 ° C

The two ingredients (base mixture and polyisocyanate) were stirred together in a mold poured and made to foam. Other parts of the same basic mix became different during different Periods of aging exposed at 43 ° C. The aged samples were then added to the above described manner mixed with the polyisocyanate, and the mixtures were used for foaming and Brought to freeze. This is followed by the data on the properties of the various foams.

Aging time of the
Basic mixture Cream time 40 Freezing
Time to 62 Remarks (Seconds) 40 (Seconds) to 71 Unaged .. 35 to 43 60 to 77 goods
Foam 1 day 35 to 67 to 93 goods
Foam 3 days 37 to 72 d goods
Foam 25 days .... 52 89 goods
Foam attempt

In this experiment, a polyol component was by the oxyalkylation of a mixture of pipe

sugar and triethanolamine produced, the proportions of the two 1 mol of cane sugar: 0.8 mol of triethanolamine being. The ingredients were dissolved in a small amount of water containing sodium hydroxide as a catalyst, and then they were subjected to reaction with propylene oxide and ethylene oxide in an amount ratio of 13.5 moles of propylene oxide: 5.1 moles of ethylene oxide. The oxyalkylation was initiated at a temperature in the range of about 93 to about 104 ⁰ C. The oxyalkylation was continued until the hydroxyl number 456 was reached. A base mixture was prepared from the oxyalkylation product obtained, which consisted of

Polyether polyol (containing parts by weight

hydroxyalkylamine) 82

Emulsifier (as in experiment a) ... 1.5

CCl ₃ F (propellant) 38.5

Catalyst (dibutyltin dilaurate) ... 0.05
Catalyst (dimethylethanolamine) 1.3

This mixture was combined with polyphenylene polymethylene polyisocyanate to form a mixture which consisted of

Polyisocyanate 100.0 g

Basic mixture 138.55 g

This mixture was allowed to foam and solidify immediately, so that you get a good foam received.

Other parts of the base mixture was allowed to age for various periods of time at 43 ⁰ C and then mixed them to a foamable mixture with the same composition. This is followed by a list of the results achieved:

Aging of the base mix Cream time Solidification time Remarks (Seconds) (Seconds) Unaged 34 to 35 68 to 69 Good foam, small cell 4 days 48 to 52 90 to 92 Good foam, small cell 8 days 67 to 70 111 to 113 Good foam, small cell 4 weeks 65 to 75 110 to 120 Good foam, small cell

Obviously, the masterbatches in this experiment had much better stability than those in the experiment a, where no hydroxyalkylamine was included.

Try

The basic mix of this experiment consisted of

Polyether polyol containing

Hydroxyalkylamine (as in

Experiment d) 77 g

Emulsifier (as in experiment a) ... 1.5 g
Phosphorous polyol

(according to preparation D) 15 g

Hydroxyalkylamine (as in

Example 1) 5 g

Catalyst (dibutyl tin dilaurate) ... 0.2 g
CCl ₃ F (propellant) 39 g

The hydroxyalkylamine provided greater stability to the master batch than is otherwise achieved let. It also acted as an amine catalyst.

To produce a foamable mixture, the following were mixed:

Polyphenylene polymethylene polyiso parts by weight

cyanate 105

Basic Mix 137

Before aging the base mix, a sample was used to make a foamable mix, while other samples of the base mix were exposed to aging at 43 ° C for various periods of time became. Then the master mix samples were combined with the polyisocyanate and the Mixtures made to foam. The following results were achieved:

Aging time of the
Basic mixture Cream time Freezing
Time Remarks (Seconds) (Seconds) Unaged .. 53 78 Goods
Foam 4 days 55 81 to 82 Goods
Foam 8 days 60 99 to 110 Goods
Foam 4 weeks .. 60 100 to 110 Goods
Foam

Apparently the polyether polyol containing hydroxyalkylamine and the hydroxyalkylamine worked from diethylenetriamine and propylene oxide (OH number 475) as a stabilizer in the Basic mixture and resulted in an increase in the shelf life of the basic mixture.

For base mixtures that contain a hydroxyalkylamine as a stabilizing agent a significant advantage on the fact that the base mix and the isocyanate component act as coatings can be applied to a surface by spraying.

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Claims (4)

Patent claims: 1. Containing stabilized base mixture for subsequent reaction with a polyisocyanate one from the reaction product of one containing from about 3 to about 8 hydroxyl groups per molecule Polyhydroxyl compound with an alkylene oxide, a polyol consisting of the reaction product of an alkylene oxide having 2 to 6 carbon atoms per molecule with an ester of an alcohol with 1 to 4 hydroxyl groups per molecule and an acid with a phosphoryl or thiophosphoryl group consisting of phosphorus-containing polyol, a urethane formation catalyst, a propellant and optionally a surface-active agent, characterized in that that there is also one from the reaction product of an alkylene oxide having 2 to 6 carbon atoms per molecule with a Alkylenepolyamine with 1 to 4 alkylene radicals or with triethanolamine existing hydroxyalkylamine contains. 2. Stabilized base mixture according to claim 1, characterized in that it is used as a hydroxyalkylamine contains one having a hydroxyl number of about 200 to 800. 3. Stabilized base mixture according to claim 2, characterized in that it is used as a hydroxyalkylamine the oxyalkylation product of diethylenetriamine and propylene oxide having a hydroxyl number of about 475 contains. 4. Stabilized base mixture according to one of the preceding claims, characterized in that that it is the hydroxyalkylamine in an amount of at least about 5 percent by weight, based on contains the entire foamable mixture.