DE1595189A1 - Process for the production of stabilized base mixtures for polyurethane foam - Google Patents

Description

PITl'JiluRGH PLiIiE GLAJS GOIdPANY Pittsburgh Pa., V.St.A.

Process for the production of stabilized G-Rundgemisohe for

Po lyur e thans chäuiae

-us Hurae already realized that polyurethane resin foam ma sen, which z.i3. üureh conversion of a liquid mixtureu3. the end. a connection with several hydroxyl groups per!,. molecule and a compound with two or more isocyanate groups Produce per l / lolek'il under foaming conditions louse, in addition to many properties that are worth growing, ins'j-eson'dere a high degree of resistance to the 'Transfer of;' / poor, are highly flammable. When they catch fire, they often support them Aor .-, rerinang bii-i they themselves are completely consumed. In ■ raanchori cases glow when the foam massoti is burned the resulting charred masses go a // hurry further after the material has stopped burning, This applies in particular in those cases in which the PoIyο 1 component by converting a carbohydrate, such as cane sugar, with a jüK / lenoxide to make polyether poly oil is.

By that described in patent application P 52 345 IVc / 39b Invention is the manufacture of fire-retardant polyurethane attach foam materials enabled in a one-step process ^

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without the synergistic effect of a phosphor polyamide is required.- This patent application describes the use of a phosphor polyol in conjunction with a specific group of polyisocyanates, namely those which per I / Iolecule 2, 3 to 6 isocyanato groups in the contains essentially no CJr ethane compounds.

When using the phosphorus polyols in the so'.eriaanten "basic mixtures ¹¹ , in many certain constituents cL, -r polyurethane foam compounds such as ..." 3. Polyol, catalyst for the tire than formation, emulsifier, blowing agent and sometimes other agents are combined and the one aua I ': oc ;, ^r ari :. 5 constituent can be added as a separate part in order to maintain a complete foamable mixture. Only a limited shelf life of the basic mixture should be expected. When fresh, the mixture can be of good quality. Ui ;. it; - _quali -; 'ke.it be; are to the base mix but loou ^ ii or months, stored, so it loses its ^{| 1f} ihi ^ - ness for rapid curing when mixed with the pole · / Ujocyuru bbestandteil.

.iis has now been found that the basic mixes are successful let stabilize, if you bea fciiautte tertiary imines which contain hydroxyalkyl groups.

The stability is based on the reaction capability of the ICa talysatora as a function of the layer time and temperature. Us has been observed dajj aminka balysers as well as organic Tin catalysts in contact with the phosphor polyol in iieactiona ^ eminch lose their effectiveness, which is .probably to create a complex effect with the phosphorus polyol is. It often happens that basic Many of the invention contain phosphor polyols that

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quickly and effectively when mixed with a polyisocyanate Foam formed and hardened after a short storage period Effectiveness' lost and the mixtures to which they were added, only slowly and incompletely formed foam and hardened. It has now been observed that G-round mixtures can be achieved with good resistance if you add the basic mixes, .which contain one or more tertiary amino groups in their molecule, adds polyols. This appearance is surprising and a full explanation for it has not yet been found.

u-euiäß. of the above patent application should be the Polyisocycmatkoinponente, which with the stabilized basic - Mixture is implemented au the foams, preferably about Contain 2, 3 to about 6 isocyanate (N = G = O) groups per molecule. These values only represent averages within of the molecule. Undoubtedly, some molecules may contain only 2 isocyanate groups, while others may contain 4 or 6 contain. In most cases, the average is Range from 2, 4 to about 3, 5 · The polyisocyanate compounds used preferably do not contain any significant

TJ Q

number of preformed urethane / _R , _ "■""\ bonds on average molecule.

Examples of useful polyisocyanate compounds are xr Diphe.'iyl-niethandiisocyanat linear Äralkylpolyisocyanatver.indungen wherein the hydrocarbon portion of the molecule is linear OAER linear and alternating aryl and Alkylongruppen contains T, 2,4-3enzoltriisocyanat, 1,2,2-Triißocyanatcuten, .1,3 »3-pentane triisocyanate, 1, 2,4-3uttin triisocyanate and triphenylmethane triisocyanate. These Larsaen polyisocyanates can be used individually or mixed with one another, or with the addition of a polyisocyanate such as, for example, ioluene diisocyanate, diphenyl diisocyanate, triphenyl diisocyanate, chlorophenyl-2, ^ l-diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate , p-phenylene diinocyanate, hexamethylene

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isoeyanet, 3,3'-dimethyl- 4,4'-biphenylenecliisoeyana t, 5, 3'-dimethoxy-4,4'-birphenylenea isocyanate, polymethylene-so "lypheylisQoyanat and diphenylmethanH - ^" - aiisocyanate.

The polyisocyanate constituents can advantageously be in use a so-called "one-shot" system in which they stored separately from the polyol components including the phosphor polyol until the Sctiaummasse is made shall be. The polyisocyanate component is then added to the other components made up of one preformed Grundgemlseh exist, daö the so-called "Pack (B)" represents which of the polyisocyanate component (A-) is added as quickly as possible. Spell lets foam and harden the G-emlsch. All of the polyisocyanate will usually approach about the equivalence in terms of the active hydrogen atoms in the mixture, the is represented by the hydrogen atoms of the hydroxyl groups, _

The phosphorus-containing polyol used in the present 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-PO ₄ ) or even better its acid anhydride (P2O5) · In addition, the invention includes the use of thiophosphoric acid · or other acids in which the P = O group or its anhydrides contain, eBt

Phosphoric acid (HjPO,) . Metaphoric acid '

Pyrophosphoric acid

Polyphosphoric acid

and their oxides or anhydrides (where they occur), which sioh duroh P ₂ OcJ ^i> 2 ⁰ 4 ^{un <} * ^? Show 2 ^ 3. The acid (or its anhydride) is reacted in the usual way with the alcohol component, so that an acid ester is obtained.

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who is at least the Moiioeater iat. The alcohol is represented duroii the formula HOH, groups in weloher H Alky!, Hydroxyalky! Groups Alkoxyalkylgrupp @ n _s Hydroxyalkaxyalkylgruppen, aromatic (benzene) or means Hydroxybenzolgruppen, characterized by ethyl, methyl, propyl »Iaopropyl, isobutyl, tertiary butyl or amyl. 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 β

However, should at least some of the Säureester formed before Oxyalkylierungastufe two acid-OH-Gruppen.übrigbehalten so that a Ba Iy is formed in the oil Oxyalkylierungsatufe, that is, a compound having at least Awei by corresponding oxyalkylation a eitenketten supplied hydroxyl groups.

The phosphor polyols can also be mutual Effect of monoalcohols and ßlycolane with phosphoric acid instead of using Phiäbpnorpentoxyd. This reaction does not run as smoothly as with Phosphorpentoayd,; and naturally complex phosphate acid esters are achieved *:

The acid test®! ⁹ bus Stm alcohol and the phosphorus-containing -.Säur © laisem E3lola with Alkylenoxyämoiekillen with 2-8 carbon atoms, vorsugsw (5IS © 2-6 G-Atomön umsetzea "from which jeäss a- (Y © 3? S! I'g9weiae a single group)

which can be denoted as * woxyr.Lng, bezeiqhß # n-.. 'Corresponding Oxyd® aind Abh / l ^ noxyit Prspyleaoxyd, Btttylenoxyd "iif2 Qdtr 2 _f 3) or Styrcioxyd. These oxides let aioh

fen-. '

i BATH

React under pressure with the acid ester described above . The resulting oxyalkylation products are represented by the following® formula »

H-O

• ^R 2 OGH ₂ OH "

"OCH ₂ GH-

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 0 and m being 3. R has the same meaning as above and H ₀ iat hydrogen, -CH, or OH ₉ CH ,. It can be observed that this material ends with a hydroxyl group at 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 can be used in the oxyalkylation in an amount of from about 1 to about 12 moles per mole of acid ester of phosphoric acid. When carrying out the oxyalkylation for the preparation of the preferred Phsbphorpolyöle the acid ester of phosphoric acid can be contained in a reaction vessel which is either equipped with a stirrer, temperature regulators and a charge for alkylene oxide, or preferably an autoclave, in which the temperature is the reaction components and the rate of addition of the alkylene oxide can be regulated. ■ S

The phosphorus-free polyol bed part of the resin. I.

The polyols that can be used in the practice of the present invention, which essentially consist of carbon, oxygen and oxygen, it is advisable to use oxyalky-

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.U595189

lierungsprodukte of saccharides or G-lucoslds such as cane sugar, fructose, Traubenzuo-ker and SsbitoJL, and contain mindestene 2 and preferably 3 to 8 hydroxyl groups per molecule ".Z ₀ Zt ₀ represents Hohrzuoker- because of its availability and low cost DAA starting polyol preferred for the oxyalkylation. The oxyalkylation products usually had a hydroxyl number Xm. Range of about 150 to about 700. Preferably, the oxyalkylation of G-lucosia or saecharide is effected with an oxirane compound of relatively low molecular weight which only has a single oxirane ring includes, for example, "propylene oxide and butylene oxide Äthylenoxyds, in butylene oxide can be either aas 1 ₉ 2- or 2,3-Oxydisomer use" Obviously could be to effect Reaktion- mixtures of the 1,2- and 2,3-Butylenoxydisomeren Likewise, styrene oxide can be used to meet all or some of the requirements for oxirane compounds to fill.

The alkylene oxide or epoxy compound may be used in an amount exceeding the equivalent amount with respect to the hydroxyl groups of the saccharide compound to be oxyalkylated. For example, in the case of cane sugar, the ratio of alkylene oxide to cane sugar is in a range from about 10 to about 30 mol: 1 mol, so that at least some of the ether chains formed contain several oxyalkyl units. The production of these compounds is the subject of a further patent application 3? 25 436 JYJ? / 39c "by the same applicant. The process essentially consists in dissolving the cane sugar in a small amount of water, for example about 5 % to about 17% water, in a pressure vessel such as an autoclave, and the The resulting solution is brought into contact with the alkyloxide under pressure until the desired degree of oxyalkylation is reached. The reaction can be carried out with a base such as a sodium

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catalyze hydroxide, sodium carbonate or ^{x <} atrium acetate, which can be used in an amount between about 1 and about 10 $. Once the oxyalkylation is complete, the water and other volatile components can be removed by evaporation.

The polyether polyol products mentioned are characterized by viscosity in a range from about 2000 to about 400 Oeritipoise, hydroxyl values in the range of about 250 to about 750 and molecular weights from about 700 to about 1800.

A second process for the oxyalkylation of cane sugar is described in the pending patent application P 27 065 IVb / 12 ο described, laughs at the procedure described therein the drill sugar is first dissolved in a small amount of water and then partially oxyalkylated, e.g. to such an extent, that about 6 moles of alkylene oxide are reacted with the cane sugar hydroxyls, the water is then removed and it becomes another oxyalkylation is carried out to use side chains Establish several Ither bonds, each chain with ends with a hydroxyl group.

In the case of the preferred polyols, namely the oxyalkylation products The polyether polyols of cane sugar can be represented by the following formula:

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ORIGINAL INSPECTED

- 10 - ■ ■. '

In the formula, RH or - CH, and η-, n _o , n ^, n ", n, -, ng, Ur, and n _Q 'are integers from 0 to 8 and their sums are in the range of about 2 up to about 18, depending on the number of ethylene oxide, propylene oxide or 1,2-butylene oxide molecules introduced. The high sugar polyether polyols typically have a hydroxyl number in the range of about 200 to about. 600.

Similar processes can be used for the oxyalkylation of other saccharides such as fructose, grape sugar or Sorbitol or mixtures of them such as sj.B. Invert sugar using Also oxyalkylated starch or oxyalkylated Cellulose can be used, mixtures of real sugar and glucosides such as methyl glucoside can be used as the polyol component find use in the foam compositions according to the invention.

Polyoley which contain tertiary amino groups.

The polyols, which contain tertiary amino groups and are used to stabilize the base mixtures in the production of fire- retardant polyurethane foam compositions, can easily be produced by reacting alkylene oxides with primary, secondary and tertiary amines. If ethylenediamine is reacted with propylene oxide, an itoterial with the following structural formula is formed

OH OH ;

ΟΕ, -ΟΗ-ΟΗη * ,. ^ CH ₉ -OH-OH

³ ^ NCH f ^ ^ά

OH ^; OH

wtlohes is commercially available under the name Quadrol.

0088 5 0 / J % ORIGINAL INSPECTED

- Il -

The reaction of diethylenetriamine with propylene oxide leads • to produce a material that is calibrated by the following 'Formula can be represented;

OH

H ₃ C-CH-CH,

H-C-GH-OH,

OH

11

"CH, 0-CH-CH,

0-GH-CHr

s.

CH,

-CH-CH, OH

OH

CH ₂ -CH-OJ-Ch ₂ -CH-GH ₅

η "GH ₀ - GH- oil CHo- GH- CH

CH,

OH

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

The reaction of triethanolamine with propylene oxide leads to form an AmiÄs with the following formula:

OftiT prr r \ ρττ ριτ rtrr

■■ J ¹ "OIir) ~ Vil" ~ w "^ - · - VjXIq - OXL - wXl ·;

OH ι

, -04-CH ₂ -CH-OI-CHo-CH-CH,

OH

-O - CHo-CH-O- -CHo-CH-CH

GIi

where η is a number from 0 to about 5. The pblyole, .which contain tertiary amine groups have hydroxyl numbers

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in the range between 200 and 800. Me polyols can be used in quantities from about 3 to about 60, preferably at least about 5 percent by weight, based on the total foamable Mixture, can be used.

To create polyurethane bonds between the polyol component or the polyol ingredients and the polyisocyanate in the resin production reaction are often drawn before adding a catalyst material for urethane production to the stabilized base batch mixture. Useful Catalysts for this are the following:

Tetramethylguanidine

Tetramethyl-1,3-butanediamine

Triethylenediamine (sold as DABCO) Dimethylethanolamine

Esters of tin can also be used, e.g.

Tin oleate,

Tin octoate,

Dibutyl tin dilaurate and others.

In Pallen, in which large amounts of polyols with tertiary Amine groups, or where a rapid reaction is not required, the catalyst component can be omitted will. If catalysts are used, they are preferably used in an amount of from about 0.1 to about 5 Percentage by weight, based on the reactive components in the foamable mixture.

The propellant, for example a chlorofluorocarbon, can either be the basic batch or the polyisocyanate compo-. nent of the foamable mixture are added. Recognized systems for effecting the release of gas in the foaming mixture in which the polyurethane-producing mixture can be used · For example a small amount

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Water, ζ.B-. about 1 to about 3 wt. $ based on the reactive components of the foaming mixture, can sur üeaktion with some of the isocyanate groups are added and thus cause the production of carbon dioxide on the spot. If necessary, you can Also produce carbon dioxide separately and beat into the foaming mixture or by means of pressure or by combined Impact and printing process imports. As soon as carbon dioxide is used under sufficient pressure, it goes into solution and when the pressure is released it separates in the form of puffs and provides a foam.

A preferred system for foam formation consists in adding a propellant or blowing agent such as a chlorofluorocarbon with the formula GCl ₃ F, CCl ₂ F ₂ or another formula of this type to the polyurethane preparation mixture, which is then added to the solution in incorporated into the polyurethane production mixture and volatilized in order to prevent blowing or foaming during the exothermic hardening of the material! mix "to effect.

Combinations of carbon dioxide and chlorofluorocarbon compounds can be used may be used, e.g. approximately equal parts by volume of each. Often one prefers the foaming; Mixture or the component of it, which the blowing agent is added to cool to prevent premature volatilization to prevent the latter. To facilitate foam formation temperatures can range from about 10 "to about 15» 6 C in the liquid can be used. When initiating the

Ürethanher position, the temperature rises, d * h. the beak j tion is exothermic, so that the propellant is released »! before the mixture gels or solidifies.

The amount of propellant used depends on the im Söhaum desired density from, Dleee is gawöMlioh

., «16.01 bivouiW! J.6Q, it fcg / cm ⁵ , but Wnnm tüv aptaieUe twist twists auoh higher or even lower densities

0 0 ffS 0 / JOIl. _BATH

-H-

be appropriate. For the Pail that a chlorofluorocarbon as blowing agent Is used, about 5 to about 40 percent by weight, based on the foaming mixture can be used will. - -

In addition to the main components mentioned above, the base mixture used for the production of polyurethane resin foams can also contain additives which promote the stability and cell formation of the foam compositions obtained. Z.3. For example, an amount sufficient for emulsification can be added, for example about 0.1 3 io of a surface-active agent such as are usually added in the production of polyurethane foam compositions. Suitable surface-active substances (surfactants) are the liquid silicon resins such as Silicon 521. Silicon 521 has the following formula:

(See U.S. Patent 3,034,996). In addition, you can still other surface agents to promote foam formation have been used including Ionic and non-oleosonic Emulsifiers such as Tween 20 (polyoxyethylene; Sorbitanmon ^ laurat), Tween 40 (Polyaxyätnylen-Polyoxyäthanol * and other.;

/ "" SOrbitan monopalmitut), Taiton X 100 (laooczylphenyl-

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Similarly, additives can be used to increase the Stability of the foam masses can optionally be added, e.g. cellulose ethers such as methyl cellulose and esters such as cellulose acetate butyrate and others that use the Toughness of the foam masses during the initial stages increase before the resin-forming ingredients have had an opportunity to achieve rigid structures react. .

This is followed by a list of suggested areas for the properties and proportions '. the various components of the foam-forming hiss. ^:

• Minimum max imum

P ο Iy äth er · ρ ο Iy oil

(Hydroxyl number) 300,750

Hydro / phosphoryl ester

(Fire retardants) 3 ° / ° 20 i?

Propellant ■

(Chlorxluorocarbons) 5 fo 20 i

Surface average 0.005 i ° 3 '#

Catalyst 0 3 ^c / °

Polyisocyanate / polyol number polyisocyanate. 0.9 1.3

While it is often possible to use acid esters of phosphoric \ to refer containing acids as commercial products and put them to produce a substantially neutral ester with Alkyloxyd, it may happen that some of them are not available r.egenwärtig und'aus this ■ - Basically, it can sometimes be useful for the consumer!

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manufacture the acid esters in his own factory. the The following examples illustrate the preparation of typical acid esters of oxyacids of phosphorus, which are further developed let react with an alkylene oxide, so that hydroxyphosphoryl ester arise, which are then in the polyurethane resin foam compositions according to the invention as fire retardation ■ let use remedies.

Example Ai . ■

This example illustrates the oxyalkylation of a Säureester of phosphoric acid, wherein a Säureester was used, which is produced by reaction of the following mixture ■

H ₃ PO ₄ 3.09 Hol -

P ₂ O ₅ "1.0 Hol.

Ethylene glycol 2.68 moles

The acid value of the product was 808 and the phosphorus content was 27.68 ° ß>.

For the production of an oxyalkylation product from this Material, a feed was made from the following components:

Acid ester (as described above) 950 g propylene oxide 1840 g.

In the reaction of Säureester was inserted into a Reäktionsgefäß and heated to 66 ⁰ C. The propylene oxide was added at such a rate that an acceptable pressure was maintained in the system and the system was cooled to maintain a temperature below about 113 ° C. and the reaction continued for 6 hours and 48 minutes. The reaction product was subjected to a separation process to remove the unreacted propylene oxide

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subjected «- Ea vrarde a yield of 2143 g with the achieves the following properties

Acid value - 3, 25th Hydroxyl number 343, 8th Phosphorus content 10, 05 <? ° Example B:.

This example illustrates the oxyalkylation of the acid phosphate obtained by reacting a mixture of the following Components was manufactured »

1 Mole Propylene glycol V. ■ 1 Mole n-butanol 1 , 82 mol

The acid value of this product was 535. For preparation a mixture of an oxyalkylation product was used

Acid ester 1050 g

Propylene oxide 1212 g.

The Säureester ßeaktionsgefäß was introduced into a heated to 66 ⁰ G and then began dem.Zusatz of propylene oxide. The reaction temperature was kept below about 110 ^° C. and was continued for 3 hours and 36 minutes; The maximum pressure during the reaction was about 14.5 kg.

DSs crude product was purified an acid value of 2.9, it was VeLkuum at a temperature up to 100 ⁰ O. One obtains an oxyalkylation product with the following characteristics

.Acid value 0.3 \

Hydroxyl Steel 297.4

Piioapiior salary 10 »44 ^, *

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Example 0:

According to this example, an acid ester of ethylene glycol and n-butanol produced by reaction with phosphorus pentoxide, the mixture consisting of:

Ethylene glycol. 1.26 moles (35.5 kg) n-butanol 2.55 moles (84.7 kg)

Phosphorus pentoxide 1.26 moles (81.5 kg)

This mixture was reacted to give 181.2 kg of a product with the following properties:

Acid value 516

Phosphorus content x 19.4 io

A portion of the resulting mixed acid ester then became further oxyalkylated in the reaction vessel, with the entire charge from

Acid ester (as above) 32.16 kg propylene oxide 31.9 kg

confessed. The resulting product had the following common equivalents *

Acid value 3.89

OH value. · 295.6

Pnoaphor content 10.85 #

Example D:

Bar acid ester of this example was the mono-di-n-butyl acid phosphate, which by reaction of j

n-lu-feylai alcohol 16.85kg

Jhoiphorpentoxyd 8.06 kg

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was produced. The phosphorus pentoxide was added in 6 doses. The total reaction time was 4 hours and 52 minutes. The acid number of the ester obtained was 464. This acid ester was then oxyalkylated, with the reaction mixture the end" "

laono-di-n-butyl acid phosphate 20, -6. kg "

Propylene oxide 18, -8 kg

duration. The Säureester was heated to a temperature of 66 ⁰ C una the propylene oxide was eye set at a rate which allowed a .Regulierung the .Reaktion. The total reaction time was 6 hours and after it had ended, the mixture was cleaned in vacuo in order to remove the unreacted propylene oxide. Finally, a yield of 29.9 kg was achieved, the product having an acid value of 0.17 and an OH value of 278.5.

When used in a "one-shot" foam with a 'Hicht-Jräuiaari-PolyiBoeyanat with an isocyanate function above about 2.1, the fire retardation of this material was very high Well. -. ""

The following examples serve to illustrate the preparation of .uyäroxyalkylphOsphorylestern with a low acid value by a one-step reaction of the alkylene oxide with PhRopho - "acidic. These have retardant properties, if you use them for the production of polyurethane foam masses used, in which the isocyanate compound does not come from U rs than exists and has a function of 2.3 or more. However, the quality of the foam masses is below average in that the volume is small and they are even remain sticky and uncured for a long time.

Example E: >

This example illustrates the preparation of an ester of pnaphoric acid by the reaction of orthophosphoric acid with

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BATH ORIGINAL

Propylene oxide without intermediate reaction of the acid (or its anhydride) with an alcohol. According to this example, a total charge was made
Phosphoric acid (85 #) 228 g propylene oxide 1044 g

manufactured. . -

The phosphoric acid was placed in a 3 liter Yier neck flask fitted with a dropper, thermometer,
equipped with a dry ice condenser and an agitator
was. The temperature was maintained by a water bath within a range of about 25 to about .32 ⁰ C. The propylene oxide was added dropwise and the reaction
continued for about 10 hours and 55 minutes. The reaction product was purified to remove unreacted propylene oxide. The resulting product was obtained in a yield of 97.6 <$> . The product had the following properties:

Hyaroxyl number 212

Acid value '2.41 -'

Phosphorus content $ 5.03 ■

The molar ratio of alkylene oxide to phosphoric acid in the final product was 9 to 1.

Example ff:

This example illustrates the preparation of a propylene oxide phosphor polyol by reaction of propylene oxide with phosphoric acid. The entire reaction charge consisted of

Propylene oxide 814 g

Phosphoric acid 228 g

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The reaction was carried out by adding the phosphoric acid into a 2 liter Yierhala flask, which with ^ a thermometer, a stirrer, a condenser cooled with dry ice and a dropper. was equipped. The reaction was carried out over a water bath. The reaction time was about 10 hours. The product was cleaned in vacuo and had an acid value of 60.18 and a hydroxy value of 324.3

Example Gr .

In this example propylene oxide was reacted directly with phosphoric acid, so that a phosphor polyol is obtained without intermediate formation of the acid ester. After this reaction, the total charge consisted of -

Phosphoric acid 228 g "(85 io)

Propylene Oxide 1044 S

The system used was a flask equipped with a stirrer, drop counter and dry ice condenser. The phosphoric acid was introduced into the flask and the propylene oxide was added dropwise. The reaction was continued for a period of 3 hours and 30 minutes. After the completion of the reaction, the product in the flask was purged with inert gas for 2 hours and then subjected to vacuum purification to remove unreacted propylsnoxide. Mön achieved a yield of $ 97> of a product with the following bigenso contents

Hydroxyl number 420.3 _ \

gäurawett 5.98

According to the basic approach, according to the invention. added Stabilizer- is a hydroxyalkylamine with a corresponding Hydroxyl number, e.g. 150 to 70 for the basic mixture, wherein the hydroxyalkylamine by reaction of an amine such as ethylenediamine, diethylenetriamine, trietuylenetetramine or another polyalkyl polyamine with an alkylene oxide such as propylene oxide, ethylene oxide or butylene oxide can be produced. This hydroxyalkyl polyamine is used Base mixture generally in an amount of about 5 to about 60% by weight, based on the foam-forming mixture. Using the hydroxyalkyl polyamine in a master batch is effective in maintaining the efficiency of the catalyst.

Example:.

Following the procedure of this example passed the polyisooyanate component from a commercially available product which is sold under the name "PaPI" and from a polyethylene polyisocyanate with an isocyanate function above 2.5 per molecule. It could be due to other polyisocyanates be replaced that are free of urethane bonds and have sufficient functionality. The foam mass passed from a so-called "one-shot" system, wherein the polyisocyanate as a component or a package of the System was used. This component was with d.en other ingredients to produce a foam-forming Mixture mixed in the following table means Polylsooyanat PAPI «The high sugar polyol consisted of 1 mol Hoiirzuoker, 11 moles of propylene oxide and 4 moles of ethylene oxide. the Phosphor polyols came from Examples D, G, A and B. A commercially available one was used as the surface agent Silicon substance, which was soluble in the mixture and as 0 was distributed.

The catalyst consisted of a mixture of the above-mentioned Rolirzucker-Polyätherpolyol (4 parts by weight) and UAiC (J (1 'part by weight). This catalyst could be replaced by another of the above-mentioned catalysts, e.g. by tin catalysts such as dibutyltin dilaurate, in an amount-of 0.1 ° f bis 5 wt.> S based on the final foam-forming mixture.

The basic mixture, which contains all components of the foam-forming Mixture with the exception of the. Polyisocyanate contains, left store and ship as a trade item. For your use all you had to do was add polyisocyanate, it was free of urethane connections and e.g. about 15 seconds on one Stir the turbo mixer. "

The foam-forming mixtures were used without any heat from the outside Foam 'brought and cured and were then cut into samples, which were 1 week, 2 weeks and 4 weeks respectively Exposed to aging in humid conditions after cessation this time one observed the color and the inclination of the foam samples for expansion under humid conditions. Additional groups of specimens were taken after aging humid conditions flame tests according to the ASTM method 1692-59T.

.A number of examples of such stabilized basics mix and the finished Sclieumverbindunjen as well as the Test data for the foam masses produced from them are given in listed in Table I below.

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composition

/ Polyisocyanate (PAPI)
\ Jlohrzuckerpolyol

Hydroxyalkylamine *

P. polyol. (Example D)
Jp.Polyol (Example C)
^M 'P.Polyol (Example A)

P.Polyol (Example 3.)

Surface agent

catalyst
\ 31asmittel.

Cream time

Solidification time

See foam from

? work e

Cell structure

strength

Density kg / cbm
Initial control request

'TABLE I "PAPI" "One shot" system (stabilized)

Foam 1 Foam 2 Foam 3

1 week approx. 70 ° FA

100.0 ca, 54.5 \ 20.0

24 '

fine

strong, not crooked, ind 31.86 ■

2.54 cm - 34 3 sec. ? read out

20.5

1.0

3.5

32.4.

25 sec. 50 sec. Good

light brown fine

24 ^V

light brown

fine

Foam 4

strong, not crooked Ind. strong not crooked Ind strong, not crooked, 31.059 ■ 30.42 ■ 31.059

2.38 cm - 33 3ek iPlamme from ■ 2.54 - 36 sec.
flame out

2.54 - 34 seconds flame out

2.54- 'cm - 26 sec. 2.54 cm - 27 sec. 4.2562cm - 30 sec SA * ', plamme from 2.54 cm - 22 sec. 2.3S - 23 sec. 3.775cm - 27 sec. SA Flame clus

Weeks approx to ⁰ PA

punch approx. 70 ° P.A

Table I (continued) Foam 1 Foam 2

Foam 3

Foam 4

2.54 cm-24 sec. 2.54 cm 3.775 cm-3C sec. SA4,286cin

2.54 cm - 25 sec. 2.54 cm 3.775 cm - 30 sec SA 3.775 cm

27 sec. 32 sec. SA 2.54 cm - 20 sec.
3.31cm - 31 sec SA

2.54cm-23 sec. 3.775cm-32 sec SA

Sec. 2.54 cm - 21 sec. 2.54 cm - 19 sec. Sec. 3.65 cm - 28, sec. 3.333 cm-3O sec. Sa

ITTMT abbreviated

loci »approx. 70 ° P.A.

Weeks approx. 70 ⁰ PA
Weeks approx. 70 ° PA

lamin =

· # ■ P.A.

0.3175 cm stretch. 0.3175 cm stretch very low availability very low availability

0.3175 cm elongation "0.635 cm elongation very little war. Very little war.

0.476 cm elongation

slight discoloration

0.3175 cm elongation, slight discoloration. 0.3175 cm elongation
very low availability

0.635 cm elongation
very low availability

0.476 cm elongation
slight discoloration

0.3175 cm elongation very low distortion

0.635 ^cl & elongation

very little discoloration

0.635 cm elongation low def. ^

Diethylenetriamine and propylene oxide, OH value 475 (this ingredient can optionally be used for Flame delay, but must be used for the stability of the basic mixture)

Humidity aging at 100 fs relative humidity

self-extinguishing
(Jrundb es ch ic kung

■ CD Ol

OO CO

From the data in Table I, it can be seen that the foams obtained were of good structure and appearance. Although they were low in density, they were strong and did not crumble. In addition, the foam masses were not sticky. The foam masses withstand aging with only slight elongation. Aul3erdem they showed the property that aie selost according peak times (4 V / ochen) aging under humid conditions ¹ after only a few seconds burning time extinguished itself.

In addition, the following operations were carried out to the stabilizing effect of the hydroxyalkylain component to show a basic mixture which consists of the phosphorus content igen poly oil, the phosphorus-free polyol and the catalyst for the polyurethane reaction.

Operation a (control)

This operation serves as a control, whereby one the basic mixture from the polyols and the catalyst for the polyurethane reaction without the use of a stabilizing hydroxyalkylamine manufactured.

The non-phosphorus polyol component consisted essentially (89 parts) from the oxyalkylation product of 1 mole of cane sugar, 11 moles of propylene oxide and 4 moles of ethylene oxide, which 5 'file trimethylolpropane and 6 parts of the oxyalkylation product a of trimethylolpropane and propylene oxide had been added, said oxyalkylation product being a had ilydroxyVvert of 740. That added to the basic mixture Emulsifier consisted of the liquid mentioned above Silicone Resin Surfactant (L-5310). The fire retardant essentially corresponded to example 3.

The catalyst consisted of a solution of 1 part tertiary Amine (DAßOQ) in 4 parts of a solvent, which the Oxyalkylation product of 1 mole of cane sugar, 11 moles of propylene

■ ORIGINAL BATHROOM

009850/2066

~ 27 -

oxy & _. and; Jl jdoX Ä-thji-leiipxyct was. The basic mix existed

' ^: Weight position

Phosphorus-free polyol _. ■■ 75.5 emulsifiers · _(I-5310), ■. 1 ■ ... phosphorus ppi ;; oil («" your-

15 Ca ^ alytsator solution 4

CGl-i ¹ . C'3L) s: nittel) "30

A portion of this premix then became the following foaming mixture compiled:

Parts by weight

Polyisocyanate (ΡΔΡΙ) ■ ^v ■ "■

(at la unit e; up era door) - ■. . ■ 100 anticipation (15.6. ⁰ Q) 125.5 ■.

The ingredients were stirred and poured into an iorrn and then you let them foam and stare. The cream time des Jemis-ches was - 2ö üekundeu and the time of solidification was 65 up to 68 seconds. The composition of matter from the unaged (Jrundgemiseii uni dei.t Polyisocy; .mat provided one good Schauai with a fine-cell structure.

A second part of the Grundiaischun - was allowed to age for 24 hours at 43 °. Then. ". The Grundiaiachun ^ was cleaned with the same Polyifiocyanut in the same j.,. En,; en ν ^ and the mixture was in a ii'orm. _C ; igOosen. The üremeseit of this mixture oetruj 130 bit 140 3- ekunien and the mixture did not solidify. Obviously, this mixture could still be cured satisfactorily, while foaming, and the product was removed without it: it lost solidification. The basic mixture or premix was "originally unstable" - '

009860/2066

BATH ORIGINAL

Work aisle b

In this operation, the components of the foaming mixture was the same as in the previous step, but in this case the basic mixture was used stabilized with a hydroxyalkyl polyamine, which the Was the oxyalkylation product of diethylenetriamine and propylene oxide, has a hydroxyl value of 700 and below that Trade name LA-700 was marketed. The basic or Premix consisted of: = "■

Parts by weight

Phosphorus-free polyol

(as in step a) 41.5

Fire retardant phosphor polyol

(as in example S) 15

Hydroxyalkyl min (LA-700) 20

Emulsifier (E-5310) 1

CCl ₃ F (blowing agent) 32

Part of this base or premix was made with polyisocyanate (Mondur MR) combined so that a foamable mixture was obtained, which consisted of:

Parts by weight of temperature

Polyisocyanate 100 24 °.

Premix 109.5 15.6 °

The ingredients were stirred together and immediately the foam formed and exposed to hardening. Other parts were exposed to aging at 43 ° C for various periods of time to determine the stability of the mixtures. The results obtained are listed in the table below.

0098507206 «| -%

■ t t -

Aging cream time setting time

Reason (seconds (seconds notes

OTGMLTüJHT
■. hours 45 - 50 84 -87 'Good one
fine Foam,
Cells 17th Days 47 - 51 82 - 86 Goods
fine Foam,
Cells 3 Days 47 - 52 84 - 89 Goods
fine Foam,
■ cells 8th Days
■ 52 85 - 95 Goods
fine Foam,
Cells 15th Days 60 88 - 98 Goods
fine Foam,
Cells 22nd Days 58 - 65 104 - 107 Goods
fine Foam,
Cells 30th Days 60 - 70 100 - 110 Goods
fine Foam,
Cells 62 60 - 70 105 - 115 Goods
fine Foam,
Cells

The aging tests for the basic mixture were carried out after 62 Ta ^ en finished and the foam masses still showed a good structure. The hydroxyalkyl polyamine was found to be highly effective stabilizing agent for the basic mix ingredients'.

Operation c

With a repetition of work course b, a basic mix was created made from the following components:

Weight parts

Phosphorus-free polyol

(as in step a) 41.5

Hydroxyaik.y la min (LA-700). 20th

Catalyst mixture

(as in step a j 0.4

Fire retardant phosphor polyol "

(as in example S) ..

Surface agent (1-5310) 001 ,? (Biamittel)

008860/2080

15th BATH ORIGINAL " 1 1 32

A part of this basic mixture was used to form a foamable mixture, _# which consisted of:

Parts by weight of temperature

Mondur MR

Unaged basic mixture

100 109.9

24 ^U
15.6 °

The two ingredients (Grundiaiachung and Mondur LIR) were stirred together, poured into a mold and made to foam. Other parts of the same master batch were exposed to aging at 43 ° for various periods of time. The aged samples were then mixed in the manner described above with polyisocyanate (Mondur ILi) and the mixtures were caused to foam and solidify. This is followed by the data on the properties of the various foam compounds:

Aging time of the cream time solidification time basic mixture (seconds) (seconds) Poor announce

Unaged
1 day
3 days
25 days

Operation d

35 35 37 52

40 40 43

62 71 77 93

-lufcer foam filter foam good foam good foam

In this operation, a polyol component was through the Oxyalkylation of a mixture of cane sugar and triethanolamine produced, the quantities of the two Moles of cane sugar: 0.8 moles of triethanolamine were. The constituents 4 * »wH; hurry were dissolved in a small amount of v / as-aer, which contained sodium hydroxide as a catalyst, and then they were the reaction with propylene oxide and Äfchyienoxyd in a proportion of 13.5 ml propylene oxide: 5.1 mol Ethylene oxide subjected. The oxyalkylation was carried out at a

0098 50/2066

BATH ORIGINAL

Temperature in the range of about 93 to about 104 C.-The initiated Oxyalkylation was continued until Hydroxylzalil 456 was reached. From the oxyalkylation product obtained a basic mixture was prepared, which consisted of:

Parts by weight

Polj'ol (which contains oxyalkylated amine)

Emulsifier (I / -531O)

OGl-F (blowing agent)

Catalyst (dibutyltin dilaurate) ■

KytaIysator (dimethylethanolamine)

82
1.5

38.5
0.05 1.3

This mixture became a mixture with polyisocyanate (PAPI) united, which consisted of:

Polyisocyanate base

100.0 g
13S, 55, g

This j-eruiscii was allowed to foam and solidify immediately, like this daj-3 a good foam mass was obtained.

Other parts of the basic mixture are used during different Periods of age at 43 G and then consumed them A foamable mixture with the same composition. This is followed by a list of the results achieved:

Aging of the Creirie time solidification time

Basic measurement (seconds) (seconds) Notes

68-69

Unaged
4 days
8 days
4 weeks

34-35 48-52 67-70 65-75

90 - 92 1.11 - 113 110 - 120

good foam, small cell

good foam, small cell

good foam, small cell

good foam, small cell

009850/2066

BATHROOM ORIGINAL ¹

1, 5 G 1ί3 G b IT
O O, 2 G yj G

\ 595189

Obviously, the basic misunderstandings in this aroeitsgang much better stability than that in step a, wherein no polyol containing oxyalkylated Auiin as 3 stabilizing agent was used.

Operation e

The composition of this working line consisted of ■

Phosphorus-free poly oil 77 g

(like In Arbeisyang d)

Emulsifier (L-5310) '

Fire retardant phosphor polyol

Hydroxyalkylamine (LA-475)

Catalyst (dibutyltin dilaurate)

CCl ^ F (glass medium)

The hydroxyalkylamine provided greater stability to the Basic mixture than it could otherwise be achieved. aside from that it acted as an amine catalyst.

To produce a foamable aeuisches, mixtures were used

Gewi clit st ei 1 e

Polyisocyanate (PAPI) TG5

Basic mix 157

Prior to the aging of the Grundniischung a sample was used at a schäumbai'en Geiuisch, while other samples of the master batch were subjected to aging at 43 ⁰ C for various times, and d; after the basic mixture samples were combined with the polyisocyanate and the mixtures caused to foam. The following results were obtained.

009 8 50/2066

BATH ORIGINAL

Alteru.nj3 time of the Or «me tent replacement time

Grundmachung (seconds) " (express) comments

unaged 53 78 82 goods foam 4 days - 55 81 - 110 Il Il 8 days 60 99 - 110 Il Il 4 i / o hurry 60 100 - II ' Il

Obviously the use of the phosphorus-free one worked Polyol and hydroxyalkylamine (IA-475) as stabilizers in the Grundmisehung and caused an increase in Shelf life of the above-mentioned basic mixture.

In -Gr and mixture en., In which a hydroxyalkyl polyamine as Stabilizing agent. Is used, is based on an important one Advantage of the fact that the basic mixture and the iso- -oyanate component as coatings by spraying on a surface can be applied.

SchaummaHsen of basic mixtures containing one amine polyol, often do not require the addition of a catalyst for the ^above retharibildang since the polyol itself contains tertiary amine groups, which catalyze the reaction effectively.

Amine polyols can be obtained by reacting triethanolamine or ammonia with an alkylene oxide such as ethylene oxide or Make propylene oxide, so that one obtains tertiary amines, which are hydroxyalkyl groups with hydroxyl values in the range of 150 to 700 included. These tertiary amines can be mLt or without the addition of polyols, which essentially consist of carbon, ', VasBeratoff and Oxygen are made for the production of stable basic mixtures as used in Example 3 will.

009 θ % 072 0 8 0

BATH ORIGINAL

Polyhydric alcohols such as 2 ..- 3. the üz.yalkylierun /; products of cane sugar for the / erwead-urr; as phosphorus L-free polyols in the manufacture of the fire-retardant foam masses preferred, but polyhydric alcohols can also be used, the same oxyalkylation products of polyphenols or Λ ± 3 girants from polypheriols. · ■ and polyhydric alcohols are. The polyhydric phenols which can be used in this way usually contain 3 or more hydroxy-substituted benzene rings per molecule which are linked to 1 or more alkyl groups. These polyphenols can be obtained by reacting an aldehyde or a ketone with a phenol. They can be represented by the so-called Itfovolacke. with the following formula:

(OH)

1 'n

(OH)

1 'n

(OH)

where H _{1 is} hydrogen or an alkyl group, R _{2 is} hydrogen or an alkyl group having fewer than 5 carbon atoms, ρ is a number from 1 to 3, η is a number from 0 to 3 and m is a number from 0 to 6. Other molecules may be present, but the structure given above is typical. The preferred novolak resins have a puncture capacity of about 2, b to about 6 or 7 and a hydroxyl number of about 200 to 6 g per molecule. In addition, other poly phenols can also be used.

The ae polyphenols can contain about 1 to 4 moles per hydroxyl group an alkylene oxide having from about 2 to about 4 carbon atoms be oxyalkylated per molecule, e.g. with ethylene oxide, Propylene oxide, and n-butylene oxide. The oxyalkylation can be done with a single alkylene oxide or one can go forward

009850/2086

BATH ORIGINAL

15951

Mixing two or more alkyloxides with the oxyalkali, while a third possibility is to oxyalkylate the polyphenol with a portion of one alkylene oxide and then with a portion of a second or even third Alcohols then contain hydroxyalkyl groups which are bonded to the iazole rings through iither bonds. Alkylene radicals of the alkylene oxides are linked to one another by ether bonds in chains. The üxyalkylierang. the poly phenols can in the presence of a catalyst, e.g. 3. Ti'iinetiiatjolarain, l'riäthanolamin, Katriumhydroxyd, or · Kaliamhydroxyd can be carried out. The Mrmge • .an: i about 1 to 1 oO; i, based on the -Cu group.

. Optionally, Ica-nn .nan Oxyalk · lieruni'sprodu-kte a PoIyphenols with about 1 to 99 weight percent of a ^{Bohrzuckerpolyl:} tiierpolyols mix as it was rubbed beach above. ■ The percentages relate to the combined weights of the two polyols. In a similar way, one can mix poly phenols or partly οχ_ν a Iky liebte polyether phenols with a partly alkylated .ilohriiucicer, e.g. cane sugar, which is oxyalkylinrt with about 3 to 6 moles of ethylene oxide or propylene oxide, but has been freed from water as much as possible, and then the (Jemisch "further oxyalkylierün with the same Alkyloxyd so that G-emic ersielt a, vielches 1 to 6 or, - ^ - ■ Alk _residues; lenoxyd ih in the Nebeuketten per Hydroxylgrupp'j may contain the PoIyölen.

The oxyalkylated phenols, with or without the addition of phosphorus-free polyol, can be mixed with fire-retardant phosphor polyol, blowing agents, catalysts, etc., as described above for the cane sugar polyols, to produce a foamable mixture.

- BAD ORIGINAL

009850/2066

Claims (8)

Claims ·. 1. Process for the production of a stabilized base formation, which in the presence of a ürethan.jil-j.un _c : skatalyst with. to be mixed with a polyisocyanate and a polyol, v.which is the reaction product of a polyol containing about 3 uia etv.a b hydroxyl groups per lole'cul, hydroxy compound with a filiC ^ lenoxide, furthermore a phoa ;. : iiorhalti _v -'es polyol-Uxyalkylierun ^ sprodukt and optionally contains a blowing agent and / or a surface-active agent and / or a urethane formation catalyst, characterized in that a hydroxyalkylamine is added to the basic mixture, which is the reaction product of an alkylene oxide and a basic nitrogen compound . 2. The method according to claim 1, characterized in that one a hydroxyalkylamine is used, which is the reaction product one alkylene oxide containing 2 to 6 carbon atoms and one containing T up to 4 alkyl groups. Is alkyl polyamine, if several alkyl groups are present, these are linked to one another by the amine groups. 3. Method according to claim 1 or 2, characterized in that da; 3 one is a hydroxylamine with a hydroxyl number of about 200 until about. 8GO used. 4. The method according to claim 3, characterized in that one a hydroxyalkylamine is used, which initiates the oxyalkylation of Mäthyltriamine and Propylenox / d, and which has a hydroxyl number of about 475. 5. The method according to any one of the preceding claims, characterized characterized that a polyisocyanate is used, which is essentially free of urethane bonds and a Has isocyanate functionality from about 2.3 to "about 6" BATH ORIGINAL - J57 - 6. The method naoh one of the preceding claims, characterized characterized that one is used as a urethane formation catalyst organic tin ester is used. 7. The method according to any one of the preceding claims, characterized in that a phosphorus-containing polyol oxyalkylation product is used used, which is the .Reaktionsprodukt one containing 2 to 6 carbon atoms per molecule Alkylene oxide with an ester of 1 to 4 hydroxyl groups per molecule containing alcohol and an acid containing a phosphoryl or thiophosphoryl group or the anhydride this acid is. 8. '/ experience according to one of the preceding claims, characterized in that that the hydroxylamine in an amount of at least about 5 Gew.yi, based on the total foamable Mixture, used. For Pittsburgh Plate Glass Company 00981ITfJOiS