DE1520125A1 - Process for the production of polymeric substances - Google Patents

Description

PATENT LAWYERS i C O Π Ι Ο C

DR.-ING. !!. FIhCKE ' ° * - U 1 ^ 5

dip · ..- .: ■ · ■: -: 2 8.ftU6.1963

Folder No. _o 19367 St / T Case Do 16298

Dr. Expl.

description

to the patent book

from Imperial Chemical Industries Limited, London SW ₀ 1 (England),

concerning

"Ancestors also. · Manufacture of polymeric fabrics"

• κ * -π

Eusats sru: Pf ^ önt .... {Aktss-, s J 19 630 IVb / 39o)

Priority? Aug. 28, 1962 - Great Britain

The invention focuses on improvements in manufacture of polymeric substances, in particular polymeric substances from polymers containing hydroxyl groups and organic polyisocyanates π

909828/1591

BATH ORIGINAL

The German patent * .. o (Aktz ₀ : I 19630 IVb / 39o) has already described the production of polymeric substances by the reactions of organic polyisocyanates with hydroxyl-containing polymers which have at least two isocyanate-reactive groups per molecule is characterized in that the reaction is carried out in the presence of a lead II salt of a carboxylic acid. These lead salts are excellent catalysts for the urethane formation reaction and are particularly valuable in the production of polyurethane foams by a one-step process, in which a hydroxyl group-containing polymer, an organic polyisocyanate, water and / or a low-boiling liquid are reacted simultaneously with one another. »

Particularly useful lead II salts are the lead octaates (lead salts of monocarboxylic acids with 8 carbon atoms), in particular 2-ethylcaproai; but the addition of these salts in sufficient quantities to the polyurethane batch has presented various difficulties up to now > Since lead octaates are highly viscous liquids or elastic solids at normal temperatures, can not without modification with the usual pumps and measuring devices to the mixed feed of the other polyurethane raw materials While it is, however, for small-scale approaches, for example in the laboratory possible suspensions of the lead octoate in one of the or

909828/1591

BATH ORIGINAL

To use another starting material, these suspensions are but not sufficiently stable, so that they have no practical value in the production of polyurethane on an economic scale »

It has now been established that lead octoate with the reaction products of an alkylene oxide containing active hydrogen Compounds can be mixed;,; so that he mixes will hold »which are suitable for incorporation in polyurethane raw materials Suitable> These mixtures have a much lower viscosity than the lead octoates themselves and can be used without difficulty in the equipment and accessories that normally used in the production of polyurethanes o They are also miscible with a large number of hydroxyl-containing polymers that are present in the generally used as polyurethane raw materials,, and therefore these polymers can never be mixed before they are concocted with the other components of the system be o

Thus, the present invention provides a method for making molded, optionally foamed polyurethane articles AUB - ^r orgeschlagen, duroh mii reacting organic isocyanates; compounds containing hydroxyl groups in the presence of a catalyst, the catalyst being a lead salt

909828/1591
BATH ORIGINAL

a carboxylic acid is used, n * oh patent o .. ₀ (AktZo I 19650 IVb / 39c), which is characterized in that the lead salt is a lead salt of a monocarboxylic acid with 3 carbon atoms »which is in the form of a mixture with a reaction product of an alkylene oxide with an active hydrogen-containing compound is used,

Eintoesonders suitable lead octoate for use in the present invention is lead "2-ethylhexanoate, as ZJO by stirring in 147 _f 3 wt, parts by litharge (PbO) in a · solution of 190 _P 2 Gewo-parts of 2-Äthylcapronsäure in 507 _e ~ wt parts of chloroform is obtained at a temperature of 4O ⁰ C. the mixture is stirred for 48 hours continuously and then filtered * the filtered solution is heated and the pressure above it at about 15 Torr reduced until the OHI. τ .form and there: · ileakijionewasser are separated o A colorless, highly viscous liquid is obtained which contains 42.3 # lead and mainly consists of lead acid (2 ~ ethyl caproate),

Some reaction products can be Although the lead octoate advantageously in admixture with a wide range of Alkylenoxydreaktionaprodukten used, r, j ,, but preferably lighter and PWAR the miscibility weighed with lead

because
octoat t or / the lower viscosity or the increased

909828/1591

_BATH ORIGINAL

Stability of the mixtures obtained »

Among these reaction products, the products with a molecular weight not greater than 1500 should be emphasized, which are produced by the reaction of at least one alkylene oxide _{P selected} from the group consisting of ethylene and propylene oxide, with an active hydrogen-containing compound and block polymerization of ethylene oxide and propylene oxide with a molecular weight of 1000 to 2400 can be obtained, as never iioB _{o are produced} by the reaction of ethylene oxide with a product which in turn is obtained by reacting propylene oxide with an active hydrogen-containing compound a

The active Viuserstoff-containing compound having the dae alkylene oxide ι! ₉ is set is a compound ,, containing at least one active hydrogen atom in the molecule _o Suitable active *-containing compounds are hydrogen water ,, mono ™ hyßroxyverbindungβ zobo ethanol ₉ Dodeoanol, Octy! Phenol and Nonylphenol Dl-hydroxy compounds, ZoB * ethylene glycol, diethylene glycol and 1 _t 2 ~ propylene glycol ihydroxy compounds, ζ, Βο trläthai / iiUamin »urlisopropanolamine and hexane triol as well as other polyhydroxy compounds containing actives, which are also used as _{other polyhydroxy compounds, Z 0 Bo pentaerythritol} ! tons, are amines »z ^ Bo ethylenediamine and

909828/1591
BATH ORIGINAL

! Eolylendlaraiiij acids a »Bo stearic acid and adipic acid; and Compounds that are more than one type of active fiber * - stofi "contained® !! groups possess ^ SoBo Iv Ethanolamine ,,

Particularly suitable alkylene oxide reaction products of compounds containing active hydrogen are the reaction products of triethanolamine or triisopropanolarain with propylene oxide, which have molecular weights in the range from 200 to 10,000? Block copolymers of ethylene oxide and propylene oxide, and have molecular weights in the range 1900-2300 Äthylenoxydgehalta of 10 to 40 wt _o - have $ »and in particular reaction products of nonylphenol with Ootyl- or a two to eight times the amount of molecular Äthylenojcydo

When prepared as usual ₉ the alkylene oxide reaction products contain one or more hydroxyl groups per molecule. The products can be used in the process of the present invention without further modification or in their lower alkyl ethers ^ A suitable product is the diethyl ether of diethylene glycol ^

The alkylene oxide reaction products can be made by processes will." dia fully in the description of the Main patent application for the production of such substances explained

■ - "7 -

909828/1591

BATH ORIGINAL

Bind Thus, the alkylene oxide, with the active hydrogen-containing compound at a temperature of 50 am 15O ⁰ C and at a pressure as high as 5.6 Atü preference "- in the presence of a catalyst, κ-B. Potassium hydroxide * are implemented »

Mixtures of the lead octoate and alkyleneoxyaceaction product can be prepared by mixing the components at normal or slightly elevated temperatures. »It is normally preferred? Mixtures to use, ranging from 0 _f 5 to 5 percent "- contain lead octoate> parts per weight Alkylenpxydreaktionsprodukte" part, although some AXlfiylenoxydreaktionsprodukten it may be cheaper * amounts outside this preferred range to use..

The mixtures of lead octoate and Alkylenoxydreaktionsprodukten wevcien tr normally employed amounts in the present methods, so that the Eleioctoat in an amount of 0.01 to 5 wt ..- 76, preferably 0.05 to 1 wt., 6, with respect to Polymer containing hydroxyl groups! ο τ * "?: which is to be reacted with the organic isocyanates is introduced» If necessary, larger or smaller amounts can also be used * abes *

909828/1591
BATH ORIGINAL

larger amounts do not result in additional benefits, and smaller amounts do not result in the most technical Effects corresponding to requirements However, the optimal amounts are bound to vary considerably of the respective Heaktiona components used and »conditions from *

The process according to the invention is particularly valuable in the production of rigid or flexible, cellular or homogeneous polyurethane products by the reaction of organic polyisocyanates with polymers containing hyssyl groups which have at least two groups per molecule which are reactive with Ieooyanat. Such polyurethane products can be produced, for example, by methods and from materials that are fully described in the description of the main patent application. ', .- ä «ri are ^*:: n fm-m ■ η ObeyfläehenbeiSgen, panels, i-AIAT & cases ny; adhesive layers "

Thus, the polymer containing hydroxyl groups can be a ZoBo Polyester, a polyester amide or a polyether or a mixture thereof.

The polyester or polyester amides can, for example, contain dicarboxylic acids and nutritious alcohols and if necessary

909828/1591

BATH ORIGINAL

be prepared with the use of smaller amounts of diamines or amino alcohols. Suitable dicarboxylic acids and bssptainic, (aitaric, adipic, cork, asselaic, and sebacic acids), as well as aromatic acids such as "phthalic, Ieoifthal" and terejalic acids Ea, can also be used as mixtures of acids. Examples of polyhydric alcohols are glycols, such as · Xthylenglycol, 1 _f 2 ~ _p propylene glycol 1,3-butylene glycol, 2,3-butylene glycol, diethylene glycol, tetraethylene "methylene glycol and 2,2-Dimethyltrimethylenglyool, Other polyhydric alcohols which more than two Hydroxy! Groups per molecule can also be used, e.g. "B, Triraethylölpropane, Trimethyloläthan, Pentaerythritol and Glycerin", Such compounds can be added in different amounts according to the desired strength of the product "

In addition to the polyhydric alcohols and dicarboxylic acids compounds containing more than two groups, consisting of hydroxyl, carboxyl, and eekun— can be reacted with (Tares and primary amino groups are selected, ”Of which Examples are diethanolamine, (primesic acid, dihydroxy stearic acid and Tricarballyls & ure

Examples of diamines and amino alcohols that can be used in making polyateramides are

10

BATH ORIGINAL 909828/1591

liyleiKliamiß, Hex & insthyleiiaiaiBin, Monoethariolamine, Phenylenediamine ua & üe & zidin »

Di ν üolyuuivv ^ hC polyester amides »which according to the? Processes of the present invention can be used have molecular weights νου 5? OO bxs 5000 with ife.ywiegeM primary hydroxyl group

As examples of polyethers for use in the process according to the invention, eolleii can be mentioned? hydroxylabgeschlössen "polymers and copolymers of cyclic oxides such 'B' 1, S-Alkylenosqjrde _t * such as ethylene oxide, Epichlorhydria, 1» 2-PropylenoxyU, 1.2 ~ Butylenoxya and 2,3-butylene oxide, and substituted Oxacyolobutan Oxacyclobutane, aowie! Tetrahydrofuran · Such fiiyethers can be linear polyether glycols, as they can be prepared, for example, by the polymerization of an alkylene oxide in the presence of a basic catalyst. by the polymerisation of an alkylene oxide in the presence of a basic catalyst and a substance which contains more than two active hydrogen atoms per molecule, see below. Ammonia and Polyhydroxyverbinaungen _s as KoB _0th Glycerin, kexanetriol, 3? Rimethylol ~ ethane, ethanolarala, pentaerythritol, sorbitol, sucrose and

11 -

8 / 15h bad ORIGINAL

Pnenol-yormaldehyde reaction products, amino alcohols, such as «.Be monoethanolamine and diethanolamine, as well as polyamines, such as ethylenediarain, tolylenediamine, diaminodiphenylmethane. It is also possible to produce branched polyethers by copolymerizing a cyclic oxide of the "already mentioned type with cyclic oxides which are more than bifunctional, e.g. diepoxides, glycidol and 3» Bydroxymethyloxeugyclobutano.

The poly used in the process according to the invention ethers usually have molecular weights from 200 to 8000 If necessary, mixtures of Ii Cf r © n and branched polyethers can also be used * H is sometimes used in the manufacture of polyurethanes aiv a polyether which is an alkylene oxide polymer ist5 günotlg, the lead octoate mixed with one small amount of the same alkylene oxide polymer use.

Examples of suitable organic polyisocyanates are aliphatic: .s Diisocyanates, such as Z ₀ E ₀ . Hsxamethylendiiötj-

grcmatisohe diisocyanates such "B '" tolylene 2-4 ~ rai ;, tolylene ^ jo-diisocyanate Diihenylmethan "4 _r 4' NaU, 5-methyldiphenylmethane - = - 4.4 x '-diisocyanate m- and p ~ Pkenylene diisocyanate, chlorophenylene-2,4-diisocyanate, 5,3 ^f -dircsthyl-diphenyl'-4,4'-diisocyanate and dipheii

909828/1591 ^BAD ORIGINAL

dlüsocyenat, and cycloaliphatic diisocyanates, such as e »B. Dioyelohexyl methane diisocyanate. Triisocyanates that can be used are aromatic trilsooyanates such as ζ, Β * 2,4,6-trilsocyanatοtoluene and _2f 4 »4'-triieooyanatodiphenylethero

Examples of other suitable organic polyisocyanate include the reaction products of an excess of diisocyanate with polyhydric alcohols, such as 8..B ₀ , trimethylolpropane, and urdtdione dimers, as well as reoxyanurate polymers of diisocyanates, for example. of tolylene-2,4-dlieooyanat * Ee mixtures of polyisocyanates can also be used «Examples of suitable mixtures are the polyisocyanate compositions, which are produced by the phosgenation of the mixed polyamine reaction products of formaldehyde and aromatic amines, such as β, Β» aniline and ortho to luidine, will be received »

It has now been found that the method of the present invention is particularly advantageous when it is used in the production of cellular Polyurethanechaumetoffen "duroh the reaction of hydroxyl-containing polymers, such as z * B ₀ polyesters, polyester and polyether, the w least« « i contain isocyanate-reactive groups per molecule, with organic Polylsooyana-

- 13 -

90 9 8 2.8 / 1 59 1

BATH ORIGINAL

th in the presence of water and / or low sMen Liquids.

Suitable low-boiling liquids are liquids that are chemically inert to isocyanates and water, and have boiling points that do not exceed at atmospheric pressure over 75 ⁰ C and preferably between 40 and 5O ⁰ C, eg · fluorinated alkanes, such as AB "monofluorotrichloromethane, dibromodifluoromethane , Dichloromonofluoromethane, Diohlortetrafluoräthan, Monoehlordi— uormethane and Trifluoräthylbromid or mixtures thereof

Mixtures of these low-boiling liquids with one another and / or with substituted ones that do not contain fluorine or unsubstituted hydrocarbons can also be used «.

Such fluids are usually found in Kengen from 1 to 100 GeWo #, preferably from 5 to 25 GeWe. »^, based on the hydroxyl-containing polymer, used «

Water is usually used in amounts of 1 to 10 wt .- ^, based on the hydroxyl-containing polymer used, it is used as a source of carbon dioxide propellant gas

909828/1591

«14 - ^ßAD

The preparation of the sselligen polyurethane foams can be done by the general methods fully described in the description of the main patent application aindo Thus the materials may be mixed continuously or discontinuously, and the polymer containing hydroxyl groups may first of the organic polyisocyanates are reacted with a part or the total amount, Before the final reaction to produce a foam is carried out in a second process step, it is generally preferred, however, that the foam production is carried out in just one process step, namely by simultaneous reaction of the foam-forming constituents, namely the hydroxyl-containing polymer »of the organic polyisocyanate , as well as the water and /

cheap or the low-boiling liquid * This / one-stage process cannot always be carried out satisfactorily with all polymers containing hydroxyl groups. In particular, those polymers that contain predominantly secondary hydroxyl end groups do not normally give satisfactory foams when using a step process ₉ unless more specific catalysts are used it

- ίξ> -.

909828/1591

_B AD

in the form of a mixture with a ^ reaction product of a Alkylene oxide with an active hydrogen containing Connection exists.

Examples of predominantly terminated with secondary hydroxyl groups. Polymers are polyesters and polyester _{amides 9} which are produced by an excess of a polyhydric alcohol and an amino compound via a dioarboxylic acid, in which the polyhydric alcohol contains secondary hydroxyl groups, aB · propylene glycol, 1,3-butylene glycol, or glycerine »polyethers terminated with secondary hydroxyl groups are polymers and copolymers of substituted 1,2-alkylene oxides, such as BB »propylene and butylene oxides. It is preferred to use polymers of propylene oxide that are predominantly terminated with secondary hydroxyl groups, especially those with molecular weights from 400 to 6000 *

The advantageous results when using lead arylate in the form of a mixture, as described above, are increased by the additional eu these lead iodine coatings Use of catalysts containing basic tertiary amines, never them b.B »in the description of the main patent as catalysts for the reaction of

«16 -

909828/1591

^ßAD ORIGINAL

Isocyanates with hydroxy compounds which bind described in particular for the production of polyurethanes * Such tertiary amine catalysts! Can ζ .B se5.n ₀ basisohe compounds containing bound at least one nitrogen atom directly to two or three organic beds »z, B ₆ hydrocarbon radicals which have a or contain several heteroatoms «. The radicals can be aromatic radicals such as phenyl, or heterocyclic radicals such as pyridine, but it is preferred that at least two, and preferably all, be aliphatic, cycloaliphatic, or arylaliphatic radicals can form a ring with the nitrogen atom of the tertiary amine, for example a piperidine ring with a pentamethylene radical. The nitrogen atom can also be part of several rings, e.g. as in triethylenediamine.

Its particularly preferred class of tertiary amines is the group of compounds in which at least one of the radicals is an aliphatic radical, in particular a Methyl or ethyl *

Examples of suitable tertiary amine catalysts are: triethylamine, triethylamine, tri (n-butyl) amine, dimethylethylamine, dimethyloyclohexylamine, dimethyl- and diethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, F «butylmorpholine, N-methyl, F-ethyl, and If-propylpiperidine,

- 17 -

909828/1591

BATH

Triethylenediamine, KN ^ H ^ -PentamethjLdiäthylentriamin, Η-methylpyrrolidine, Pyrcolizidin, 8-Methylpyrrollzldin, quinuclidine ₉ J ^ N'-Otetramethyläthylendiamin, N, N ~ ^fl Tetraraethylhexemethylendiamin, pentamethylguanidine, tetramethyl-1,3 butancliamin _"t 2 Diäthylaminoäthylphenyläther, 2 ~ Diethylaminoethylbenzyl ether, 1 _f 4-bis- (pyrrolidine) hi-butane, ΙΓ, Ιί ⁸ -dimethylpiperazine »ß-diethyl aminopropionamide _t 2-diethylamioethyl acetate, 2-dimethylaminoethylearbanilaty di (2- ° diethylaminoethy1) adipate»

Particularly advantageous results are obtained if completely ff-substituted 4-aminopyridines, in particular 4-diraethylaminopyridine and 4-pyrrolidinopyridine, are used in conjunction with lead arylate. It is also possible to use more than one tertiary amine at the same time. that the above list of tertiary amines is only a list of compounds which variously represent classes of tertiary amines suitable for use in the process according to the invention

The tertiary amine catalyst is usually used in amounts from O ₉ O25 to 2 "5 # and preferably from 0.1 to Ι ^ Ο ^^ based on the weight of the hydroxyl-containing polymer ρ»

- 18th

909828/1591

BATH ORIGINAL

The improvements achieved through the use of bleloetoate in conjunction with tertiary amines are surprisingly much greater than would be expected from the effects achieved by the use of each type of catalyst alone. The effects achieved are particularly valuable in the single-stage process Production of foams through the simultaneous implementation of an over-

secondary hydroxyl-terminated polyether and an organic polyisocyanate in the water »

complete As explained in the description of the main application /, the general methods of making polyurethanes include the incorporation of various additives into the poly t> ret hai .V-Oanäe Vn.achv.ng

such as Bo-Bt, of surface-active agents, such as oxyethylated phenols ₉ oxyethylated fatty alcohols, such as ZoB ₀ . Oxyethylated oleyl alcohol or sulfated methyl oleate of polyalkylsiloxanes and biochemical polymers thereof with polyalkylene oxide, of fire-retardant additives, such as A ₀ -B ₀ . ^A 'ri (ß ~ chloroethyl} ~ phosphate and Alifciuonoxyd, of plasticizers, such as z <.B, trioresyl phosphate and dioctyl phosphate, of dyes and fillers, such as ζ ,, ^ ό * \ ιΒ and silicon dioxide and parbo stabilizers and bleaching agents agents Other Katalysatoriypen, z "B _o-soluble organic compounds of metals such as Z ^ ₀ B ₀ of the i) transition metals, for example, _{9 s} iron and Manganace-

909828/1591

tylaoetonat and tin compounds, such as. Dibutylzinnt ^l i-> laurate and £ inn-II ~ caprylate can ebeneo incorporated been "Another class of additives * which can be added include antioxidants _t z, B _o tertiary B'jtylcatechol and eterisoh hindered phenols"

The invention is illustrated by the following examples, but is in no way restricted »All parts and percentages are expressed in weight.

example 1

100 parts of a polyether from Mol-ßew · 510, which had been produced by the oxypropylation of trimethylolpropane, were mixed with 15 parts of tri- (ß-chloroethyl) phosphate, 1 part of dimethylsiloxane / xthylene oxide / propylene oxide block polymer _r 40 parts of monofluorotriochloromethane and 2 parts of a Composition mixed, the latter having been prepared by mixing equal parts of lead-2-ethylcaproate and the reaction product of octylphenol with 7.5 times the molecular amount of ethylene dioxide. 142 parts of a biphenylmethane diisocyanate composition were added to the homogeneous mixture thus obtained obtained by the phosgenation of impure diaminodiphenylmethane containing about 15 $> polyamines (mainly thiamines), and in turn by the

- 20 -

09 828/1591
¹ AD Ofüü

Condensation of aniline with formaldehyde in the presence of Hydrochloric acid had been produced. Haoh a 35 seconds constant mixing a solid foam was obtained, which has a fine cellular texture and a density of 0.038 g / cm * owned »

Example. 2

0.05 part of lead 2-ethyl caproate was mixed with 0.05 part of a condensate of oxylphenol with a 7-fold molecular weight of ethylene oxide. The solution was a · Gly <MVln / Fropylenozydkondeneat8 from the Hol. "Crew" 3000 dissolved "in five parts. This Iusung was continuously mixed with 95 parts of a 60/20 Misohung of tolylene 2,4-and 6-diieooyanaten "2 _r same glycerol / Propylenoxydkondensats, 44 parts and 5.3 parts by a mixture comprising 0.3 Parts of triethylenediamine contained 3.5 parts of water and 1.5 parts of a dimethylsiloxane / ethylene oxide / propylene oxide block

The mixed ingredients were transferred to a mold » After 30 minutes it became an elastic product obtained, 4ε π had a density of 0.05 g / onr.

Example 3

0.1 part of lead-2-ethyloapronate was mixed with 0.1 part of a

Condensates from octylphenol with a 7-fold molecular

- 21 -909828/1591

Amount of ethylene oxide mixed The mixture was dissolved in 5 parts of a grlycerine / propylene oxide condensate with a molecular weight of 4,000. The solution was continuously mixed with 95 parts of the same glycerine / propylene oxide condensate, 42 parts of an 80/20 mixture of tolylene-2,4 and 2 ₉ 6 "diisocyanates and 5 _{tons of} 3 parts of a mixture containing 0.3 parts of triethylenediamine, 3 * 5 parts of water and 1.5 parts of dimethylsiloxane / ethylene oxide / propylene oxide block monopolymer

The mixed ingredients were transferred to a Jona. Ο After 50 minutes, an elastic, zelligee product was obtained which had a density of Oj.029 g / crar »

Example _ £

The procedure of Example 2 was repeated using the mixture of 2-ethylcaproate and the octylphenol condensate with a 7-fold molecular amount of ethylene oxide was released by the mixtures contained in the the following.! Table and in which the " Density (: 2 foams are also specified »

- 22

909828/1591

Tabel

Π) n l ~ 2 »ä! Hhyloaproat

Condensate aua yp not and 2 moles of ethylene ox / d -

Condensate of nonylphenol and 5.5 moles Ethylene oxide

Uxypropyliertee Tri- '-ethanolamine, Molc-Gewo 400

ypropylated hexane xriol »mol. wt. 700

Polypropylene glycol, lo 425

Ethylenoxide / PropylenoK.ydblookmieohpolymer * MoX. Q ^ w ,. 2000, ethylene oxide content $ 10>

Ethylene oxide / propylene oxyc

block milk polymer p

Mol.-Öow ^ 2000,

₀ Ät hy lenoxydgehalt 40 ° / o

Foam B g / cnr

O7Ö5

0.1

0.029

0.2

0.031

0.1

0.030

υ, υρ ι υ, ι - S

0.05

0.032

0.1

0.030

0.05

0.031

0.1

0.030

909823/1591

COPY BAD ORIGINAL

Claims (8)

Claims t Process for the production of shaped, optionally foamed objects made of polyurethane by reacting organic isocyanates with hydroxyl groups » containing compounds in the presence of a catalyst »where the catalyst is a lead salt of a carboxylic acid is used, according to patent ... »(Aktz · I 19 630 IVb / 39c), characterized in that the lead salt is a lead II salt of a monocarboxylic acid with 8 carbon atoms, welohes in the form of a mixture with a reaction product of an alkylene oxide with an active hydrogen-containing one Connection is used. 2. The method according to claim 1, characterized in that that the reaction product used has a molecular weight of not more than 1500 and duroh the Reaction τοη Äthylenoocyd or propylene oxide with a active hydrogen-containing compound is produced 3. The method according to claim 1, characterized in that the reaction product used is a Blookmieoh- - 909828/1591 BAD ORIGINAL COPY is polymer of ethylene oxide and propylene oxide and has a molecular weight of 1000 to 2400 » 4. The method naoh Anapruoh 2, characterized in that a reaction product of triethanolamine or triisopropanolamine with propylene oxide is used, which is a mol. "Wiper 203 and 1000 owns" 5. Verfahr.ι according to claim 2, characterized in that a reaction product of ootyl- or nonylphenol with a 2- to 8-fold molecular amounts of ethylene oxide are used will ο 6. The method according to Anrpruoh 3 »characterized in that ain Blockali schpolymer of ethylene oxide and propylene oxide is used, which is a Mol.-Ge w «. from 1900 to 2300 and a "n Äthxlenoxyd Content of 10 to 40 Gew" - # has " 7. The method according to any one of the preceding claims, characterized in that a mixture is used, which of 0.5 to 5 "C parts by weight of reaction product contains per part by weight of lead salt" 8. The method naoh one of the preceding claims, characterized characterized ρ that the mixture is used in such amounts - 25 - 909828/1591 BATH ORIGINAL is, so that the lead salt in an amount of 0.01 to 5 wt .- $, preferably from 0.05 # to 1 öew · - ^, based on the polymer containing hydroxyl groups that is to be reacted with the organic polyisocyanate, is brought in » 9 · Method according to one of the preceding claims, characterized in that a hydroxyl group-containing Polymer, like »3ο a polyester, a polyester amide or a polyether containing at least two isoyanate reactive groups per molecule, with one organic polyisooyanate in the presence of water and / or one.? low-boiling liquid is reacted, so that cellular, polyurethane foam products are obtained 10 * Verfairen according to claim 9, characterized in that that one terminated with secondary hydroxyl groups Polymer, ain organic polyisocyanate and water and / or a low-boiling liquid is reacted at the same time. 11c method according to claim 10, characterized in that that it has closed secondary hydroxyl groups Polymer a Polyäthsr - 26th 909828/1591
BATH ORIGINAL 12c Visri'aVrnn according to any one of the preceding claims, characterized £ · _s indicates that the reaction in the presence of a tertiary amine is carried out " I3ο method according to claim 12, characterized in that dag tertiary amine in an amount of 0.025 to 2 _P 5 6reWo- #, preferably from 0.1 5 ^ to 1.0 GeWo-fli based on the hydroxyl group-containing. Polymer, is added » VVÄUg ., _NtHr .. _; . _<t; , _; ,. ..... _{H. EAR} 909828/1591 BATH ORIGINAL