CA2144465A1 - Method of producing polyurethanes which are optionally cellular - Google Patents

Abstract

A process of producing polyurethanes which are optionally cellular, by reacting a) polyisocyanates with b) mixtures comprising i) salts of fatty acids with basic polyols and ii) non-functional fatty acid esters and/or hydrocarbons, and, optionally, c) compounds of molecular weight 62 to 399 having at least two hydrogen atoms which are active in relation to isocyanates, and, optionally, d) compounds of molecular weight 400 to 10,000 having at least two hydrogen atoms which are active in relation to isocyanates, optionally, in the presence of e) foaming agents, catalysts and other process materials and additives known in the art.
This invention also relates to the polyurethanes produced by this process.

Description

21~465 Mo4178 LeA 30,148 METHOD OF PRODUCING POLYURETHANES
WHICH ARE OPTIONALLY CELLULAR

BACKGROUND OF THE rNVENTION

As is known, there is an increasing interest in the use of natural, e.g.
reproductively grown, raw materials for industrial purposes, and therefore for the purposes of polyurethane chemistry also.
As described in European Patent application 0,563,682 (page 2, line 20) in 10 connection with soft foams, the use of fats and oils as softeners in foamed materials is known in principle.
Thus, the German Patent 1,113,810 has already described a combination of castor oil and basic polyols in the manufacture of polyurethane foamed materials.
In this connection, the castor oil functions as a polyhydroxy compound and is 15 chemically incorporated in the PU framework (as are the polyols which are used conjointly). In other words, part of the polyol component of the foamed m~t~ri7~1 formulation is replaced by a natural oil.
In a comparable manner, U.S. Patent 2,955,091 describes polyurethane foamed m~t~ri~ls based on a combination of fatty acid glycerides with OH
20 numbers not less than 100, wherein castor oil is cited, and propylene glycol polyethers with molecular weights around 1000.
According to European Patent application 0,563,682, edible margarine is used in combination with polyether polyols, the OH numbers of which are between 14 and 50, to impart thixotropic properties to soft foam reaction mixtures 25 and for their additional activation. The reaction mixtures, which are characterized by long chain polyethers, may contain up to 30% by weight of margarine without impairment of the properties of the foamed material being observed. There is probably quite a good compatibility between the margarine fat and the long, relatively hydrophobic polypropylene ether chains of the soft foam polyols, so that 30 as a result the properties of the product are not impaired.
LeA30 148-US - 1 --Secondly, it is also known from German Offenlegungschrift 4,303,556 that PU foamed materials can be prepared from mixtures of hydroxylated esters of natural fatty acids and hydroxylated or functit)n~ ed oligomeric hydrocarbons, and analogous foamed materials are known from German Offenlegungschrift 4,315,841 for which non-functionalized polyolefins can also be used instead of functionalized hydrocarbons. In this latter case, the hydroxylated fatty acid esters function as "emulsifying agents" for the polyolefins, which make the latter compatible.
In both cases, however, the simultaneous use of considerable proportions of functi- n~li7ed fatty acid esters is necessary; these can only be prepared chemically and expensively.
The preparation of function~ ed fatty acid esters such as these is described in European Patent application 0,544,590 and in Fat. Sci. Technol.
Volume 95, No. 3, page 91 et seq., for example.
A method has been sought which also enables non-functional or non-functi-)n~li7ed fatty acid esters and hydrocarbons or polyolefin oligomers, particularly non-functional natural, reproductively grown oils also such as those which can be extracted directly from oil seeds, to be processed to form PU
foamed materials without recourse to special functionalized fatty acid esters, e.g.
those according to the descriptions cited above, or to OH-functional natural oils which are generally more expensive.
It has now surprisingly been found that large amounts, i.e. about 30-60%
by weight of a PU foamed material can be synthesized from what are almost non-functional fatty acid esters, e.g. natural fatty acid esters, such as, for example, rapeseed oil or edible oil. If these natural fatty acid esters which are almost non-functional are combined with relatively small amounts of fatty acid salts of basic polyols, particularly of basic polyether polyols, and are then reacted with polyisocyanates in the presence of stabilizers which are customary in the chemistry of foamed materials, and optionally with water and other process materials, in a manner which is known in principle, a PU foamed material can be produced.

Le A 30 148-US - 2 --The new reaction mixtures cont~ining non-functional components according to the invention are mostly fluid and are created as regards their hydrophilicity or hydrophobicity so that directly compatible mixtures of salts and non-functional components can first be produced, and secondly so that PU materials can be 5 produced which are highly hydrophobic but which have not been significantly softened. This particular combination of properties is surprising.
Moreover, it has surprisingly been found that the non-functional fatty acid esters, which have at least a certain polarity, can be completely or partially substituted by hydrocarbons or oligomeric polyolefins.
Finally, it has surprisingly been found that even polyols or polyether polyols with relatively short chains are suitable for this method. The presence of long, hydrophobic poly~ ylene glycol ether chains with molecular weights around 1000 or higher are not necessary to achieve incorporation of the non-functional oil into the polyurethane foamed m~t~
It has also surprisingly been found that despite their high content of fluid oil, these new types of foamed materials have a character which is more similar to that of non-sticky foams than of soft foams. On the other hand, foamed materialshaving the characteristics of a soft foam may also optionally be produced.
A further technical advantage of these new foamed materials is that when 20 the oils used contain air-hardening groupings such as those which are known to be used in the paint industry, optionally with the simultaneous use of driers, products can be obtained in which the incorporated oils can still be chemically crosslinked by reaction with air.
DESCRIPTION OF THE INVENTION

The present invention relates to a process of producing polyurethanes which are optionally cellular. This process comprises reacting a) polyisocyanates with b) mixtures comprising i) salts of fatty acids with basic polyols and ii) non-functional fatty acid esters and/or hydrocarbons.
This process may also comprise mixing b) with Le A 30 14~-US - 3 -c) compounds having molecular weights of 62 to 399 and cont~ining at least two hydrogen atoms which are active in relation to isocyanates, or d) compounds having molecular weights of 400 to 10,000 and cont~ining at least two hydrogen atoms which are active in relation to isocyanates, or in the presence of e) foaming agents, catalysts and other process materials and additives known in polyurethane chemistry, to form a mixture, prior to reacting this mixture with the polyisocyanates.
It is also within the scope of this invention to use any of the possible combinations of components c), d), and e) in conjunction with b). When optional components c), d) and/or e) are present, there must be a minimllm amount of component b) of 10% by weight, based on the total weight of b), c), d) and/or e), present.
According to the invention, it is preferred that the non-functional fatty acid esters are the natural fatt,v acid glycerides; the basic polyols are those polyols having an OH number greater than 50, particularly an OH number greater than 400; the basic polyols are polyalkylene glycol polyethers; the fatt,v acids are those monocarboxylic acids having more than 9 carbon atoms; the non-functional hydrocarbons are those hydrocarbons having boiling points above 200C and melting points less than 1 00C; and the non-functional hydrocarbons are polyolefins.
The present invention also relates to polyurethane foamed materials which are produced by the process according to the invention.
The components used for the process according to the invention are described in more detail below.
In principle, any aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates are suitable as polyisocyanate a). However, the polyisocyanates are preferably liquid at room temperature. Such materials include those described in, for example, Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, by W. Siefken, and include, for example, those of formula Le A 30 148-US - 4 -Q(NCO)n wherein n is 2 to 4, preferably 2 and 3, and Q denotes an aliphatic hydrocarbon radical having 2 to 18, preferably 6 to 10, carbon atoms, a cycloaliphatic hydrocarbon radical having 4 to 15, preferably 5 to 10, carbon atoms, an aromatic hydrocarbon radical having 6 to 15, preferably 6 to 13, carbon atoms or an araliphatic hydrocarbon radical having 8 to 15, preferably 8 to 13 carbon atoms, such as, for example, those polyisocyanates which are described in German Offenlegungschrift 2,832,253, pages 10 to 11.
Aromatic polyisocyanates are preferably used.
In general, polyisocyanates which are easily accessible commercially are particularly preferred, such as, for example, toluene 2,4- and 2,6-diisocyanate and any desired mixtures of these isomers ("TDI"), polyphenylpolymethylene polyisocyanates such as those which may be prepared by an aniline-formaldehyde condensation and subsequent treatment with phosgene ("crude MDI"), and polyisocyanates having carbodiimide groups, urethane groups, allophanate groups,isocyanurate groups, urea groups or biuret groups ("modified polyisocyanate"), particularly those modified polyisocyanates which are derived from toluene 2,4-and/or 2,6-diisocyanate or from 4,4'- and/or 2,4'-diphenylmethane diisocyanate.
The polyisocyanates are used in a stoichiometric amount of 60- 150%, preferably 80-120%, with respect to the OH and/or NH groups contained in the reaction mixture.
With respect to component b), it is preferred to use those carboxylic acids having more than 9 carbon atoms the fatty acids to form the salts thereof.
The fatty acids used for salt formation with the basic polyethers include predomin~ntly saturated and/or unsaturated monocarboxylic acids having more than 9 carbon atoms. It is also possible to use those di- and polycarboxylic acids as fatty acids such as, for example, the so-called dimeric and trimeric acids of fat chemistry which are obtainable by oligomerization.
The carboxylic acids may be of synthetic origin, such as those which are accessible, for example, by the reaction of amines or alcohols with di- or Le A 30 148-US - 5 -2144~65 polycarboxylic acids; or by the saponification of amides, nitriles or (poly)esters; or by the oxidation or ozonolysis of polyolefins which optionally contain unsaturated structural groups such as, for example, butyl rubbers; or from fatty alcohols.
However, they are preferably of natural origin and are often mixtures of fatty acids, including, for example, oleic acid, elaidic acid, stearic acid, isostearic acid, tall oil fatty acid, coconut oil fatty acid, abietic and other resin acids, linoleic acid, linolenic acid, erucic acid, rapeseed oil fatty acid, fish oil fatty acids, tall oil fatty acids, castor oil fatty acids, montan wax fatty acids, and shale oil fatty acids, etc.
Fatty acids or fatty acid mixtures used may be either completely hardened, partially hardened or preferably unhardened. Those which are liquid at room temperature are preferably used.
Those fatty acids having melting points less than 50C are used in stochiometric amounts of 30 to 150% by weight, preferably 80-120% by stochiometric weight, based on the weight of the basic polyols.
Those fatty acids having melting points above 50C, such as, for example, stearic acid, surprisingly behave similarly to the non-functional hydrocarbon waxes. These fatty acids may be used in amounts similar to the non-functional hydrocarbon waxes.
Polyols, including polyethers, cont~ining one or more amino groups and having OH numbers greater than 50, preferably greater than 400, are suitable foruse as the basic polyols. The polyalkylene glycol polyethers are preferably used as the polyols. Polyethers such as these are preferably those which contain polyether groups based on polyethylene oxide and/or polypropylene oxide.
The basic polyols, polyalkylene glycol polyethers or polyalkylene glycol polyether mixtures used for salt formation contain at least one, preferably 1-7,most preferably 1-4 amino groups within and/or at the end of the molecular chain.
Suitable basic polyols comprise alkanolamines which, like mono-, di- or triethanolamine or -propanolamine, or tell~propoxyethylenediamine~ contain at least one alkanol grouping on the nitrogen. However, basic polyalkylene glycol polyethers are preferred as the framework substance, particularly those which contain at least one polyether chain, which is at least a two-membered chain, on Le A 30 148-US - 6 -the amine nitrogen. Their OH number is at least 50, preferably at least 150, andmost preferably greater than 400.
Polyethers such as these are usually produced commercially by the alkoxylation of primary or secondary aliphatic, araliphatic, cyclic, heterocyclic or 5 aromatic amines, preferably from ammonia and/or propylenediamine, and preferably from ethylene~i~mine and/or polyalkylene polyamines or their mixtures.
Alkylene oxides, preferably ethylene oxide and/or propylene oxide in particular, are generally used for alkoxylation. Salt formation of the fatty acids with the basic polyols is effected by simple mixing of the components, preferably at 5-50C.
As a rule, the content of fatty acid salts of basic polyols in the reaction mixture which is to be reacted with polyisocyanates is 10-80% by weight, and preferably 20-65% by weight, based on the total weight of component b). In this respect, the percentages of these fatty acid salts b)i) and that of component b)ii) total 100% by weight of component b).
In addition, the fatty acid esters may be of synthetic origin, but preferably the non-functional natural fatty acid glycerides, and particularly those nonfunctional triglycerides which are liquid at room temperature, are employed as non-functional fatty acid esters.
The non-functional hydrocarbons include those such as, for example, the fractions and oligomers obtained from coal chemistry and petroleum chemistry.
Those which are liquid at room temperature or which melt below 100C are preferred, and those with boiling points above 200C are most preferred.
By use of the phrase "non-functional" with respect to suitable components of the reaction mixture in the sense of the present invention is meant preferably those compounds having boiling points above 200C and melting points below 100C. These may comprise fractions, for example, from the upgrading of coal or from the refining of crude oil or from recycling processes and include, for example, paraffin oils, paraffin waxes, spindle oils, or light and heavy oils, of a saturated or unsaturated, aliphatic, araliphatic, cyclic or aromatic nature.
They may also comprise oils obtainable by the polymerization, oligomerization or telomerization of unsaturated basic components such as, for Le A 30 148-US - 7 -.. 2144465 example, ethylene, propylene, butene, isobutene, isobutylene, pentene or octene or mixtures thereof. Liquid oligomers of isobutylene are preferred. These liquid oligomers can have a particularly favorable effect on the hydrophobicity or gas permeability of the products produced by this process.
Substances which are of particular interest as non-functional components in the sense of the present invention comprise synthetic oils and waxes, and particularly natural, animal and preferably vegetable oils and waxes, which mostly contain mixed saturated and unsaturated fatty acid esters in the form of glycerides, and which may be used as such or in admixture with each other or with the aforementioned non-functional components, such as edible oils of varying different ongins, tall oils, rapeseed oils, nut oils, linseed oils, root oils and other extracted olls.
The non-functional components are contained in the reaction mixture, which is to be reacted with polyisocyanates, in amounts of 20-85% by weight, preferably 50-70% by weight, based on the total weight of component b). In this respect, the percentages of these components b)ii) and those of the fatty acid salts b)i) total 100% by weight of component b).
Additional starting mat~rial components optionally comprise component c).
Suitable compounds for use as component c) include, for example, those compounds having at least two hydrogen atoms which are reactive towards isocyanate groups and having molecular weights of 32 to 399. Such components are also to be understood in this case as comprising compounds containing hydroxyl groups and/or thiol groups and/or carboxyl groups, and preferably compounds cont~ining hydroxyl groups and/or amino groups, which serve as chain extenders or cro.silinking agents. As a rule, these compounds contain 2 to 8, preferably 2 to 4, hydrogen atoms which are reactive with isocyanate groups.
Some examples of these are described in, for example, Gerrnan Offenlegungschrift2,832,253, at pages 19-20.
Suitable compounds for component d) comprise, for example, those compounds having at least two hydrogen atoms which are reactive to isocyanate groups and which generally have molecular weights of 400-10,000. In addition to compounds containing amino groups, suitable compounds are to be understood as Le A 30 148-US - 8 -214~465 those compounds cont~ining thio groups or carboxyl groups, preferably hydroxyl groups, particularly compounds containing 2 to 8 hydroxyl groups, especially those of molecular weight 1000 to 6000, preferably 2000 to 6000, such as, for example, polyethers and polyesters cont~ining at least 2, generally 2 to 8, and preferably 2 to 6, hydroxyl groups, and also polycarbonates and polyester amidessuch as those known in the art for the production of homogeneous and cellular polyurethanes and which are described in, for example, German Offenlegungschrift2,832,253, at pages 11 -18.
Suitable components e) include, for example, foaming agents known in the art of polyurethane chemistry, optionally used in conjunction with other compounds such as, for example, water or readily volatile hydrocarbons such as butane, pentane, cyclopentane, hexane, dimethyl ether or hexafluorobutane. In addition, other process materials and additives may also be used, including additives such as, for example, catalysts of the type known in the art, in amounts of up to 10 weight % based on the weight of component b), surface-active additives, such as emulsifying agents and foam stabilizers, reaction retarders such as substances with an acid reaction, such as hydrochloric acid or organic acid halides, or also cell re~ tors of the type known in the art such as paraff1ns orfatty alcohols or dimethyl polysiloxanes, as well as pigments or colorants and/or also flame retardants of the type known in the art such as, for example, tricresyl phosphate or exfoliated graphite, as well as stabilizers against the effects of ageing and weathering, softeners, substances with a fungistatic or bacteriostatic effect, and fillers such as barium sulphate, silaceous earth, carbon black or whiting.
These types of process materials and additives which are optionally used are described in, for example, German Offenlegung~fhrift 2,732,292, pages 21-24.Additional examples of surface-active substances and foam stabilizers suitable for use according to the invention, as well as cell regulators, reaction retarders, stabilizers, flame retardant substances, softeners, colorants and fillers, and also substances with a fungistatic or bacteriostatic effect, and details on the mode of use and mode of action of these additives, are described in the Kunststoff-Handbuch [Plastics Handbook], Volume VII, edited by Vieweg and Hochtlen, Carl Hanser Verlag, Munich 1966, e.g. on pages 103-113.
Le A 30 148-US - 9 -214446~

A suitable description of completing this process for the production of polyurethane plastics follows.
The reaction components are reacted by the single-stage process known in the art, by the prepolymer process or by the semi-prepolymer process. Mechanicaldevices are often employed in these processes, including, for example, those which are described in U.S. patent 2,764,565. Details of the processing devices (for batch and continuous processes) which may also be used according to the invention are described in the Kunststoff-Handbuch, Volume VII, edited by Vieweg and Hochtlen, Carl Hanser Verlag, Munich 1966, e.g. on pages 121-205, for example. The foamed m~tP.rial.~ may also of course be produced by bulk foaming or by the double conveyor belt method known in the art.
The new foamed m~tPrial~ which are produced according to the invention are naturally substantially based on materials which are advantageously inexpensive and which are readily accessible commercially, such as, for example,polyolefins, paraffins or paraffin waxes, or framework matPrial~ which are predominantly naturally reproductively grown materials, including the fatty acids to be used in this process. The foams produced generally have a character which is predominantly that of a hard foam. Depending on the type of non-functional components to be used in this process and on the amounts of these components used, the foamed materials may have closed or open pores, are hydrophobic, in part have a low gas permeability and a low water absorption, or may be permeableto water as a result of porous cell walls. They are often characterized by particularly good demolding properties. They are suitable to be used, for example, for the production of moldings, for sound insulation, for filling cavities, as athermal or electrical insulation m~tPrial as a p~aging material with a good capacity for absorbing impact energy, for the manufacture of sandwich structures, as a constructional material, or for the manufacture of so-called integral foamed moldings. They may also be used in comminllted, open-pored or leached form for absorption purposes or as a filter material.
These new foamed materials may also be provided with organic and/or inorganic fillers, and with reinforcing fibers.

Le A 30 148-US - 10 -Surprisingly, however, the simultaneous use of catalysts is often unnecessary. This is possibly because the fatty acid salts exert an activating effect which is sufficiently good despite the relatively large proportions of non-reactive, diluent components.
In addition, the combined use of driers which accelerate the drying of air-drying oils, such as those which are known from paint chemistry, can also be considered, as can the combined use of decomposition stabilizers and preservatives which restrict atmospheric or biological attack on the foamed materials. The combined use of flame retardants, fragrances, colorant additives, int~rn~l parting agents, fillers and reinforcing fibers is also possible.
The following examples further illustrate details for the process of this invention. The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions of the following procedures can be used. Unless otherwise noted, all tempelalules are degrees Celsius and all parts and percentages quoted are parts by weight and weight percentages.

Le A 3 0 1 48-US - 1 1 214qq65 -Examples The following starting materials were used in the following examples.
Fatty acids: .
FA: a commercially available oleic acid manufactured by Henkel of Dusseldorf 5 FB: a commercially available abietic acid FC: a commercially available soya oil fatty acid FD: a commercially available tall oil fatty acid FE: an isobutylene oligomer carboxylic acid with an acid number of 17, obtained by the ozonolysis of commercially available butyl rubber in 10methylene chloride FF: a commercially available coconut oil fatty acid mixture FG: a commercially available so-called dimeric fatty acid (manufactured by Unichem) Basic polyols:
15 BA: diethanolamine BB: triethanolamine BC: a propoxylation product of triethanolamine with an OH number of 500 BD: a propoxylation product of ethylene~ mine with an OH number of 155 BE: a propoxylation product of ethylene(1i~rnine with an OH number of 480 20 BF: a propoxylation product of ethylenediamine with an OH number of 60 BG: a reaction product of triethanolamine with equal parts of ethylene oxide and propylene oxide, said reaction product having an OH number of 505 Non-functional oils:
NA: a commercially available edible oil (manufactured by Brolio Handelsges., 25of Hamm) NB: a commercially available polyisobutylene oligomer (known as Oppanol B3, available from BASF, Ludwigshafen) NC: a commercially available spindle oil ND: a commercially available rapeseed oil 30 NW: a commercially available paraffin wax, having a melting point about 60C.

LeA30 148-US - 12-The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
5 Example 1 20 parts of FA were mixed with 40 parts of NA and 16.4 parts of BE to form a clear solution. 1.3 parts of a commercially available stabilizer (PU 1836, Bayer AG) and 1 part of water were then added.
This mixture was intensively stirred for 10 seconds with 25 parts of a 10 commercially available MDI polyisocyanate (Desmodur(~ 44 V 20, Bayer AG), cast into a flask mould and allowed to foam therein.
A homogeneous, fine-pored hard foam was produced, which had an appal~nl density (AD) of about 60 g/l and which was non-sticky.
Example 2 The same procedure as described in Example 1 was used, including the same materials in the same quantities with the exception that the amount of NA
was doubled and the amount of isocyanate was increased to 31.5 parts. A f1ne-pored, semi-hard, non-sticky foam was produced, with an AD of about 50 g/l.
Examples 1 and 2 illustrate the absorption capacity of the polyurethane 20 material according to the invention for non-functional oils. Foamed materials such as these are suitable for impact-absorbing purposes, and as an insulation m~t~ri~l.
Example 3 48 parts of FA and 100 parts of NA, together with 45.8 parts of BC, 5 parts of BB, 4.6 parts of water and 2.6 parts of the stabilizer used in Example 1 25 were mixed well at room temperature.
A fluid, slightly turbid, homogeneous mixture was obtained, which contained more than 70% of reproductively grown raw materials. This was subsequently intensively mixed in a nozzle mixing head unit with 133.6 parts of the same polyisocyanate used in Example 1 :and introduced into a flask mold. The30 material foamed in the mold to form a block with an apparent density of about 45 g/l.

Le A 30 148-US - 13 -214~465 The foam had a homogeneously fine-pored structure, was tough and hard, felt dry to the touch and was non-sticky. It had fine-pored cell walls. Foamed materials of this type are suitable as insulation and filter materials and for the production of sandwich core layers. If the foaming process was conducted in a closed mold, moldings were obtained which were easily demolded and which had a compacted edge zone.
Example 4 45 parts of abietic acid were dissolved in 100 parts of NA and 50 parts of BC. The mixture was then cooled to room temperature and mixed with 5 parts of BB and 5 parts of water and with 3 parts of a commercially available, polyether polysiloxane-based stabilizer (Stabilizer OS 20). A fluid, homogeneous solution was obtained, which was intensively mixed with a commercial MDI (Desmodur~
44 V 10; Bayer AG) and introduced into a cup mold. After fo~ming, the reaction mixture produced a homogeneous, fine-pored, hard, tenacious foamed m~t~ri~l with an apparenl density of about 50 g/l.
Example 5 The same procedure was used herein as that described in Example 3, including the same materials in the same quantities, except that a mixture comprising equal parts of ND and NC, or comprising equal parts of NC and NA, was used instead of oil NA. In both cases a tough, hard foam was produced, with an appearance comparable to that of Example 3.
Example 6 The same procedure was used here as that described in example 3. Similar quantities of the same materials were also used, except that component NA in Example 3 was replaced by the same amount of component ND. A rapeseed oil hard foam was produced, which had comparable properties to that of example 3.
Example 7 20 parts of BE, 30 parts of FA and l part of BA and l part of BB were stirred with 45 parts of NB and 3 parts of the stabilizer used in Example l, andwith 0.5 parts of tin octoate, 0.5 parts of water and 5 parts of cyclopentane toform a fluid, homogeneous mixture. Then, this was intensively stirred for 10 seconds with 32 parts of the MDI polyisocyanate from Example 1 and introduced Le A 30 148-US - 14 -21~65 into a flask mold. The reaction mixture foamed in the mold to yield a fine-pored, hard foamed material which had an AD of about 70 g/l.
Example 8 The procedure used here was the same as that in Example 1, with all ' 5 materials and quantities thereof being the same except that equal amounts of FC, or FD, or FF, or FG were used in each case instead of FA. In all three cases foamed materials were produced with properties comparable with those of Example 1.
Example 9 The procedure was similar to that used in Example 2. However instead of 20 parts of FA, either a) 100 parts of FE or b) 150 parts of FE were used in admixture with 112 parts of FD. In each case a defect-free foamed m~t~ri~l was produced, which had an app~nl density of about 60 g/l. Foamed materials of this type can be used as impact-absorbing foamed p~c~ging m~t~ri~l~
Example 10 20 parts of FA were intensively stirred with 13.1 parts of BF, 50 parts of NA, and with 11 parts of glycerine, 5 parts of water, 1.5 parts of the stabilizer from Example 1 and (as an additional activator) 2 parts of dimethylb~n7~mine, and finally with 152 parts of the polyisocyanate from Example 1. The reaction mixture was introduced into a flask mold and foamed there to yield a tough, fine-pored hard foam with an apparenl density of about 55 g/l. The foam was non-sticky and was particularly suitable for par~ging purposes.
Example 11 24 parts of FD, 20 parts of NB, 20 parts of NC, 20 parts of ND, 50 parts of BD, 6.4 parts of BB, 1.4 parts of the stabilizer from Example 1 and 2 parts of water were stirred to form a fluid, homogeneous mixture, and were then intensively stirred with 62 parts of the polyisocyanate from Example 1. The reaction mixture was introduced into a cup mold and formed a homogeneous, fine-pored, tough, hard foam there, with an apparent density of about 60 g/l.
The foam was dry and non-sticky, and was suitable for use as a sandwich structure inner layer.

Le A 30 148-US - 15 -214~465 Example 12 50 parts of FE, 100 parts of NA, 50 parts of NB and 56 parts of BC were stirred with 5 parts of water and 3 parts of a commercially available, silicone-based foam stabilizer, and with 10 parts of cyclopentane, to form a slightly turbid, homogeneous phase, and were then reacted with intensive mixing with 136 parts of commercial MDI (Desmodur6~) 44 V 20, Bayer AG). The reaction mixture foamed in a flask mold to form a hard foamed m~t~ri?~l with homogeneous pores, which had an AD of about 40 g/l and was of interest as an impact-absorbing paç~ging foam.
Example 13 34 parts of FA, 20 parts of NA and 30 parts of BC were mixed and reacted with 38 parts of MDI (see Example 2) with intensive stirring. The reaction was allowed to proceed to completion in a board mold, whereupon a non-sticky, flexible, hard, solid board was produced, with an AD of about 0.9 g/cm3.
Example 14 As in the preceding example, the same process and m~t~ri~ were used except that a mixture of 50 parts of BF and 5.7 parts of butanediol was used instead of BC. A flexible board with some cellularity was produced, with an AD
of about 0.8 g/cm3.
Solid products of this type obtained by the method are used for the production of moldings, sealing boards and coatings.
Example 15 A mixture was prepared comprising 65 parts of a propylene glycol polyether produced using trimethylolpropane as a starting m~t.~.ri~l and which had an OH number of 35; 15 parts of BB; 30 parts of FC; 60 parts of light heating oil and 60 parts of N C. 3 parts of water, 1 part of the commercially available stabilizer used in Example 1 and 5 parts of cotton wool fiber were added to thismixture.
The castable mixture obtained in this manner was intensively stirred with 50 parts of the MDI used in Example 1 and allowed to react completely in a flaskmold. A defect-free, non-sticky foamed material was obtained, with an apparent Le A 30 148-US - 16 --density of about 60 g/l. Foamed materials of this type, e.g. produced on a textile backing, are suitable for cleaning soiled machine parts.
Example 16 A fat-like, homogenized mixture was prepared from 15 parts of FA, 5 parts of FF, 10 parts of FG, 18 parts of BB, 20 parts of the polyol used in Example 15, 80 parts of NB, 4.5 parts of water and 1 part of the stabilizer used in Example 1.
153 parts of this mixture per unit time (1 second) were intensively mixed in a stirrer-mixer head with 85 parts of the MDI used in Example 1 and the mixture was discharged into a flask mold. The reaction mixture foamed in the mold to form a homogeneous, fine-pored foamed material with an appar~n~ density of about 30 g/l. The foam was non-sticky after 30 seconds and was of a semi-hard nature. Foams of this type are suitable for pa~ ging purposes.
Example 17 48 parts of FA, 250 parts of NB, 46 parts of BC and 5 parts of BB were intensively mixed with 25 parts of cyclopentane, 11.6 parts of water and 5 parts of a commercially available polyether polysiloxane-based stabilizer, and were intensively stirred for 6 seconds thereafter with 183 parts of a commercial type of MDI (Desmodur~ 44 V 10; Bayer AG). The mixture was then cast into a flask mold in which the foaming process took place. The foaming process was complete after about 65 seconds and the foam formed was solid and non-sticky. Ithad a substantially closed-pore structure, and was fine-pored with a homogeneouscell appearance. It had an AD of about 28 g/l, no core coloration and had the character of a hard foam.
Foamed materials of this type are suitable for the production of double-bonded insulating boards with paper outer layers, for the production of sandwichstructures, and for the production of moldings and impact-absorbing materials.
Example 18 The procedure was as in Example 17, except that a mixture comprising 83 parts of NB and 167 parts of NA was used instead of 250 parts of NB. The essential features of the foam obtained corresponded to the those of the foam type obtained in Example 17.
Example 19 LeA30 148-US - 17--The procedure was as in Example 17, except that. a mixture comprising 83 parts of NB, 85 parts of pork fat and 85 parts of coconut fat in molten form (40C) was used instead of 250 parts of NB. The foamed material obtained corresponded to the type obtained in Example 18.
In comminllted form, the foamed materials from Examples 2, 3, and 19 integrated into a compost within 6 months.
Example 20 20 parts of FA, 200 parts of NB and 25 parts of BB, together with 20 parts of cyclopentane, 4.6 parts of water and 3 parts of the stabilizer from Example 1were well mixed and then intensively stirred for 10 seconds with the polyisocyanate (134 parts) used in Example 1. The reaction mixture was then castinto a flask mold. It foamed in the mold to form an almost non-sticky hard foam with an appalelll density of about 70 g/l. Foamed m~t~ri~l~ ofthis type can be used for pa~ging and impact-absorbing purposes.
In this formulation component NB may be replaced by equal amounts by weight of components NA or NC, for example.
Apart from the isocyanate component, the resulting foamed m~t~ri~l then consists almost exclusively of reproductively grown raw m~t~ri~l~
Example 21 10 parts of FA, 10 parts of FD, 40 parts of ricinoleic acid, 25 parts of BB, 50 parts of castor oil, 40 parts of cyclopentane, 11 parts of water and 3 parts of the stabilizer from Example 4 were mixed well using a rapidly rotating stirrer and were then intensively mixed with 220 parts of the polyisocyanate from Example 1.After about 10 seconds the reaction mixture was emptied into a flask mold in which it foamed to produce a dry, non-sticky hard foam with an appalen~ density of about 50 g/l. Foamed materials of this type, can be obtained, as in the preceding examples, without the combined use of amine or metallic activators, and can be used like those from Example 20.
Example 22 50 parts of FD, 20 parts of FE, 250 parts of NB, 6 parts of BB and 50 parts of BC, together with 25 parts of cyclopentane, 5.2 parts of the stabilizer used in Example 1 and 11.6 parts of water, were stirred to form a homogeneous LeA30 148-US - 18-214~465 -mixture and were then intensively mixed with 1.83 parts of the MDI
polyisocyanate used in Example 1. After about 10 seconds the mixture was introduced into an open flask mold, in which it foamed. A hard foam was obtained, which was non-sticky after 50 mimltes, and which had a homogeneous, 5 fine-pored cell structure and an appalenl density of about 20 g/l.
In a continuous procedure in a normal industrial foaming in.~t~ tion, an apparent density was obtained which was lower by about 3 g/l.
Foamed m~t~rial.~ of this type are suitable for pack~ging and insulation purposes.
10 Example 23 50 parts of FA, 150 parts of NVV, 50 parts of BC, 5 parts of BB, 3 parts of a commercially available polyether polysiloxane-based stabilizer, 20 parts of cyclopentane and 5 parts of water were maintained as a melt in an autoclave at about 60C whilst being well stirred. This mixture was added via an industrial PU
nozzle mixing head to 145 parts of a commercially available MDI (Desmodur~) 44 V 10; Bayer AG) and introduced into a board mold. The well mixed reaction mixture expanded in the mold to form a homogeneous, fine-pored hard foam with an apparent density of about 25 g/l.
The foam was strongly hydrophobic and could be used for insulation 20 purposes where minimal water absorption by the insulating material is required.
Example 24 As in Example 23, except that the same amount by weight of stearic acid was used instead of FA.
A foam was obtained which was comparable to that obtained from 25 Example 23. It could be used for the production of sandwich structures.
Example 25 The following components were mixed in the melt whilst being well stirred, as in Example 23: 50 parts of FA, 100 parts of stearic acid, 50 parts of BC, 5 parts of BB, 3 parts of the same stabilizer, 5 parts of water and 20 parts of 30 cyclopentane.
This mixture was intensively mixed in a nozzle mixer head with 145 parts of the polyisocyanate from Example 23 and discharged into a flask mold, in which Le A 30 148-US - 19 -214446~

the reaction mixture foamed to form a very fine-pored, tough, hard foam with an apparent density of about 24 g/l. This foam exhibited the property of transforming its character from a that of hard foam into that of a soft foam under mechanicalstress. It was strongly hydrophobic and was suitable for packaging purposes, since 5 it had good impact-absorbing properties.
Example 26 The procedure was similar to that of Example 23, except that 100 parts of wax, 50 parts of stearic acid, 10 parts of cyclopentane and 2 parts of the stabilizer were added.
10In a comparable manner, a hard foam was obtained which had an appale~
density of about 25 g/l and a fine-pored structure. About 60% of this foamed m~t~ri~l conciRted of wax and fatty acid. It had a strongly hydrophobic character and would be suitable for filling inR~ ting walls in appliances of very different types, e.g. refrigel~tol~.
15Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the artwithout departing from the spirit and scope of the invention except as it may belimited by the claims.

Le A 30 148-US - 20 -

Claims (10)

1. A process of producing polyurethanes which are optionally cellular, by reacting a) polyisocyanates with b) mixtures comprising i) salts of fatty acids with basic polyols and ii) non-functional fatty acid esters and/or hydrocarbons, and optionally, c) compounds of molecular weight 62 to 399 having at least two hydrogen atoms which are active in relation to isocyanates, and optionally, d) compounds of molecular weight 400 to 10,000 having at least two hydrogen atoms which are active in relation to isocyanates, optionally in the presence of e) foaming agents, catalysts and other process materials and additives known in the art.

2. The process of Claim 1, wherein said non-functional fatty acid esters are natural fatty acid glycerides.

3. The process of Claim 1, wherein said basic polyols are polyols having an OH number greater than 50.

4. The process of Claim 1, said basic polyols are polyols having an OH number greater than 400.

5. The process of Claim 1, wherein said basic polyols are basic polyalkylene glycol polyethers.

6. The process of Claim 1, wherein said fatty acids are monocarboxylic acids having more than 9 carbon atoms.

7. The process of Claim 1, wherein said non-functional hydrocarbons are those hydrocarbons with boiling points above 200°C and melting points less than 100°C.

8. The process of Claim 1, wherein said non-functional hydrocarbons are polyolefins.

9. The polyurethanes produced by the process of Claim 1.

10. Polyurethane foamed materials produced by the process of Claim 1.