CA1184333A - Solutions of oligo-urethane ethers in polyether polyols and their use in a process for the production of polyurethane foams - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE The invention relates to solutions of A) from 3 to 60% by weight, based on the combined ether-polyol content, of separately prepared oligo-urethane ethers containing terminal OH-groups in the form of reaction products of a) diisocyanates with b) dialcohols having an average molecular weight of from 200 to 800, the stoichiometric ratio of a) to b) amounting to various values based on the average molecular weight of the dialcohols, in B) polyether polyols containing at least 2 hydroxyl groups and having an average molecular weight of from 1000 to 12,000 and to their use in a process for the production of polyurethane foams capable of being effectively flame-laminated and (high-frequency) welded without any adverse effect upon their other properties. The process for producing flame-laminatable and high-frequency-weldable flexible polyurethane foams is characterized by the reaction of i) polyisocyanates with ii) relatively high molecular weight compounds containing at least 2 hydroxyl groups, iii) optionally other relatively high molecular weight and/or low molecular weight compounds containing isocyanate-reactive hydrogen atoms and water, iv) optionally in the presence of other blowing agents, catalysts, foam stabilizers and other additives, such solutions described above being exclusively or partly used as the relatively high molecular weight compounds which contain hydroxyl groups.

Description

~ 4333 Mo-2346 I,e~ 20,842 SOLUTIONS OF OLIGO-URETHANE ETHERS IN
POLYETHER POLYOLS AND THEIR USE IN A PRO-CESS FOR THE PRODUCTION OF POLYURETHANE FO~MS
B~CKGROUND OF THE INVENTION
This invention relates to solutions of separa-- tely-prepared oligo-urethane ethers containing terminal OH-groups in relatively high molecular weight poly-ethers containing terminal hydroxyl groups and to the use of these solutions as modified polyols in the pro-duction of polyurethane foàms characterized by excellent high-frequency weldability and flame-laminatability.
Applications where high-frequency weldability is a particularly desirable property inc1ude, for example, the production of door linings for motor vehicles, in which sheets of foam have to be welded to one another or to other materials; the manufacture of articles with guilted surface appearances; or the production of moldings. In addition, flame lamination is used for the production of composite systems of foams with textiles, such as in upholstery backings which are subsequently profiled and/or formed by high-frequency (e.g~ where the welding energy is provided by an electromagnetic fieldl. (HF welding).
It is known that flame-laminatable and, to a certain extent, high-frequency-weldable foams can be produced from polyisocyanates and polyester polyols using suitable auxiliaries and additives. However, these foams can only be produced in special processing machines and are inferior in many properties to poly-ether-polyurethane foams. ~or example, their open-cell structure is poorer, their elasticity lower and their resistance to moisture and heat inferior.

LeA 20,842 ~.~

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Flame-laminatable ahd high-fre~uency-wèldable polyurethane foams can be produced fro~ polyether polyols, polyisocyanates, water and/or blowing agents in the presence of emulsifiers, stabili.zers, catalysts and other auxiliaries, by the addition of special auxiliaries.
Thus, US Patent No. 3,205,120 describes the production of flame-laminatable polyether-polyurethane foams by the addition of,a,relatively small quantity of a polyol (particularly phosphorous-containing poly-ols, such as tris-(dipropylene glycol)-phosphite~having a molecular weight in the range from 20~ to 1500.
~isadvantages of this process include a deterioration in processing reliability, a certain tendency towards c~re ~ discoloration and a flame-lamination behavior which is distinctly inferior to that of a polyester-polyurethane foam because of the polyol quantities normally used.
US Patent No. 4,060,439 describes the co-foaming of small quantities of alkylene glycolscontaining from 2 to 8 carbon atoms, or triols con-taining from 3 to 10 carbon atoms, dialkanolamines containing from 2 to 10 carbon atoms with short-chain glycol ethers and polyhydric phenols into flexible polyether foam formulations. However, experience has shown that the co-foaming of compounds such as these makes foaming more difficult and, in particular, very considerably narrows the processing gap between an open-cell and a closed-cell structure.
In addition, US Patent No. 3,497,416 describes the foaming of a polyether polyol with a modified Le~ 20,842 polyisocyanate ~the reaction product of dipropylene glycol and/or dibutylene glycol with an excess of poly-isocyanate) for the production of a weldable poly~
urethane foam. The disadvantage of this process ]ies in the fact that, to obtain sufficient open cells, dimethyl formamide ~ a toxicologically-unacceptable substance, has to be used as cell-opening agent. In addition, foams of this type have a high compression set, and polyether-NCO-p~epo~lymers o~ this type used show only moderate stability in storage.
In view of the disadvantages of polyether-polyurethane foams which account for the fact that, ~on the-whole,-polyester-polyurethane foams are used for flame lamination and for high-frequency welding, there is a considerable need for a flame-laminatable and high-frequency (HF)-weldable polyether foam which can be manufactured safely.
Solutions of polyisocyanate-polyaddition com--pounds in polyols are also known. Thus, German Offen-20 legungsschrift No. 2,638,759 describes solutions of this type having solids contents of from 5 to 70~, by weight, which are obtained by either reacting diiso-cyanates with H-active compounds (including, among many others, diprimary diols) in polyhydric alcohols 25 having a molecular weight of from 62 to 450 (but gener-ally, from 62 to around 200) as reaction medium or by subsequently dissolving the powdered, separately-produced polyaddition compounds in the polyhydric alcohols.
Although solutions of this type may frequently be used as starting materials .in the production of polyurethane plastics, they are not suitable for the LeA 20,842 33~

production of flexible coatings and, in particular, flexible foams. The introduction of significant amount,s of the polyaddition compound into the polyurethane foam formulation is only possible if relatively large quantities of the low molecular weight polyhydric alcohols (the solvents) are used at the same time.
This seriously affects processing reliability in the manufacture of flexible foams (effecting the critical links between open-cell s.tructure and shrin~age pro-perties) or it makes the production of an open-cell flexible foam completely impossible.
It has now surprisingly been found that oligo-ùrethane eth-ers containing terminal OH-groups of-di-isocyanates and dihydric, relatively short-chain poly-ether diols form clear t stable solutions in relativelyhigh molecular weight, polyhydric polyether polyols-optionally at elevated temperature- and that solutions `
of this type may readily be processed into flexible foams characterized by good mechanical properties and by good high-frequency weldability.
DESCRIPTION OF THE INVF.NTION
Accordingly, the present invention relates to solutions of A) from 3 to 60%, by weight, and preferably from 5 to 30%, by weight, based on the combined ether-polyol content, of separately prepared oligo-urethane ethers containing terminal OH-groups which are the reaction products of a) organic diisocyanates with b) short-chain polyether diols having an average molecular weight of from 200 to 800, and preferabl~ fxom 200 to 600, the stoichiometric ratio of a3 to b) being between ~eA 20,842 0.5 and 0,7 in the case of diols havin~ an average molecular weight of from 200 to 280; to bet~een 0.5 and 0.9 in the case of diols having an average molecular weight of from 280 to 600; and to between 0.5 and 0.75 in the case of diols having an average molecular weight of from 600 to 800, in B) polyether polyols containing at least two hydroxyl groups and having an average molecular weight of from 1000 to 12,000, and preferably from 2000 to 8000.
~he present invention also relates -to a process for the production of flame-laminatable~and high-freq-ue~cy-weldable flexible polyurethane foams by reacting polyisocyanates with relatively high molecular weight compounds containing at least two hydroxyl groups, optionally other relatively high and/or low molecular weight compounds containing isocyanate-reactive hydrogen atoms, and water, optionally in the presence of other blowing agents, catalysts, ~oam stabilizers and other additives. The solutions according to the invention are exclusively or partially used as the relatively high molecular weight compound.
Organic diisocyanates suitable for use in the preparation of the solutions according to the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic diisocyanates. Appropriate diiso-cyanates are of the type described, for example, by W. Sie~ken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example, those corresponding to the formula: Q (NCO)2 in which "Q" is an aliphatic hydrocarbon radical containing from 2 to 18, and pre-ferably from 6 to 10 C-atoms; a cycloaliphatic hydrocarbon radical containing from 4 to 15, Le~ 20,842 and preferably from 5 to 10 C-ato~s; an aroma~ic hydr~-carbon radical containing from 6 to 15, and preferably from 6 to 13 C-atoms; or an araliphatic hydrocarbon radical containing from 8 to 15, and preferably from 8 to 13 C-atoms. Examples of such diisocyanates include 1,4-tetramethylene diisocyanate; 1,6-hexamethylene di-isocyanate; 1,12-dodecane diisocyanate; cyclobutane-l, 3-diisocyanate; cyclohe~ane-1,3- and -1,4-diisocyanate and mixtures of these ~somers; l-isocyanato-3,3,5-tri-methyl-5-isocyanatomethyl cyclohexane; 2,4- and 2,6-hexahydrotolylene diisocyanate; hexahydro-1,3- and/or -1~,4''-phe'nylene diisocyanate; perhydro-2,4l- and70r -4,4'-diphenylmethane diisocyanate and mixtures of these position-and/or stereoisomers; and 1,3- and 1,4- phenyl-ene diisocyanate; 2,4- and/or 2,6-tolylene di.isocyanate diphenyl methane-2,4l- and/or -4,4l-diisocyanate and mixtures of these isomers~
Preferred diisocyanates for use in the production of the oligo-urethane ethers are the isomeric tolylene diisocyanates and diphenyl methane diisocyanates;
hexamethylene diisocyanate; dicyclohe~yl methane di-isocyanates; and l-isocyanato-3,3,5-trimethyl-5-iso-cyanatomethyl cyclohexane or mixtures of these iso-cyanates. Particularly preferred are 2,4~ and/or 2,6-tolylene dilsocyanate and the diphenyl methane di-isocyanates and their nucleus-alkylated derivatives.
The oliyo-urethane ethers (A) containing terminal hydroxyl groups which are dissolved (optionally, at elevated temperature) in accordance with the invention in relatively high molecular weight polyhydric polyether polyols (B) are formed by separately reacting the diiso-cyanates (a) described in the ~oregoing with short-chai~

LeA 20,842 - -~ ~L8i~;333 polyether diols (b) having an average molecular weight of from 200 to 800. Polyether diols of this type are produced in the known manner, for example, by the alkali catalyzed polymerization of propylene oxide, optionally together with ethylene oxide (preferably up to 50 mole percent of ethylene oxide) onto starter compounds preferably containing two reactive hydrogen atoms. Suitable starter compounds include, for example, water or dihydric diols, such as ethylene glycol; 1,2-or 1,3-propylene glycol; 1,2-, 1,3~ or 1,4-butylene glycol; 1,6-hexane diol; 1,8-octane diol; neopentyl glycol; 1,4 bis-hydroxymethyl cyclohexan-ei methyl-l, ~3-propane.diol; resorcinol; hydroquinone; or 2,~is(4-hydroxyphenyl)-propane. Monoamines such as methyl amines, stearyl amine, cyclohexyl amine, aniline and mixtures of these compounds are also suitable.
It is particularly preferred to use polyether diols having an average molecular weight of from 200 to 600, especially polypropylene glycols which may contain up to 30 mole percent of ethylene oxide units.
Relatively high molecular weight polyether polyols having molecular weights in the range from 1000 to 12,000 (preferably in the range of from 2000 to 8000) are obtained in known manner, for example, by the alkali-catalyzed polymerization of propylene oxide, optionally together with up to 60 mole percent, and pxeferably with up to 30 mole percent, of ethylene oxide, onto dihydric or polyfunctional starter compounds containing reactive hydrogen atoms. Examples of suitable starter compounds include water; ethylene glycol; 1,2- or 1,3-propylene glycol; 1,2~, 1,3- or 1,4- butylene glycol; 1,6-hexane diol; 1,8-octane LeA 20,842 diol; neopentyl glycol; 1,4~~is-hydroxymethyl cyclo- i hexane; 2-methyl-1,3-propane diol; glycerol; trimethylol ethane and propane; pentaerythritol; mannitol; sorbitol;
formitol; and cane sugar. Additional examples include resorcinol; hydroquinone; 2,2-bis-(4~hydroxy-phenyl)-propane; ammonia; methylamine; ethylene diamine; tetra-methylene or hexamethylene diamine; ethanolamine; di-ethanolamine; triethanola-mine; aniline; 2,4- and 2,6-diaminotoluene; and polyphenyl polymethylene polyamines of the type obtained by condensing aniline with formal-dehyde, and also mixtures of these compounds. Other suitable starters are resin-like materials of the novolak and resol type.
Additional suitable polyether polyols are de-scribed in terms of their composition and modification in German Offenlegungsschrift No, 2,920,501. ~
Other polyhydroxyl components suitable for use in the production of foams by standard methods are described, for example, in German Offenlegungsschrift 20 No: 2,854,384, page 14 and pages 16 to 19; other low molecular weight compounds are described on pages 20 to 25 of that reference; and other polyisocyanates suitable for foam formation are described on pages 8 to 11 of that reference.
The reaction of the diisocyanates with the dialcohols by which the oligo-urethane ethers are separately produced is carried out in known manner at temperatures in the range of from about 0 to 200C, and preferably at temperatures in the range of from 30 30 to 150Co For example, -the hydroxyl component may be initially introduced and the diisocyanate added either all at once or gradually, the temperature being LeA 20,842 -~
.

kept constant by external or internal cooling ox to rise under the effect of the exothermic reaction without cooling.
The oligo-urethane ethers according to the invention may of course also be continuously produced.
The hydroxyl component may be combined with the iso-cyanate in a statistical o~ dynamic straight flow mixer, the reaction mixture being delivered from this mixer to a following stirrèr-equipped vessel in which the reaction is completed, for example. Cascades of stirrer-equipped vessels or Zellar reactors are also s~itable for continuously carxying out the polyaddition reaction.
If desired, the reaction may be accelerated by known catalysts commonly used in polyurethane chemistry, such as, for example, tertiary amines, amidines, metal hydroxides, alcoholates, phenolates or carboxylates or carboxylates and chelates of the transition metals.
Finally, solutions according to the invention are obtained by dissolving the oligo-urethanes in the relatively high molecular weight polyether polyols mentioned above using known mixi~gunits.
Considerable importance is attached to the stoichiometric NCO/OH-ratio between the diisocyanate and the short-chain polyether diol in order to both obtain a clear solution of the oligo-urethane ethers in the relatively high molecular weights, poly-functional polyether polyols and to maintain the viscosity preferably beIow 3500 mPas required for the proauction of flexible foams. As mentioned above, this ratio should amount to between 0.5 and 0.7 in the case of dialcohols having an average molecular LeA 20,842 ~433;3 weight of from 200 to.~280, to between a~out 0,5 and 0.9 in the case of dialcohols having an average moleculax weight of from 280 to 600 and to between about 0.5 and 0.75 in the case of dialcohols having an average molecu-lar weight of from 600 to 800.
Although the high content of oligo-urethane ethers in the solution may amount to between 3 and 60%, by weight, concentrations of from S to 30~ by weight are preferred. On the one h~nd, solutions of the type in question - in concentrations below 5%, by weight-only bring about minimal changes in the properties of the polyurethane plastics produced from ~~he solutions, while on the other hand, concentrations above 30~, by weight, can frequently give rise to high viscosities which have an adverse effect upon processing.
The solutions according to the invention are used in the usual way as modified polyether polyols for the production of flexible polyurethane foams. The flex-ible foams obtainable in this way may be welded very effectively by means of known welding machines and, in addition, are characterized by excellent overall properties.
Comparison in the production of flexible poly-urethane foams of the oligo-urethane soluti.ons according to the invention wîth other foam ~ormulations (cf., Foaming Examples 6 through 9 with E~amples 10 and 11), in which the polyether diols are used as additives or (together with polyether polyols of relatively high molecular weight) as urethane-modi-fied polyols, proves the superiority of the formersolutions. This advantage is reflected in p:a~ticular in the safety of the foaming-processj in the properties -~of the resulting foams and in the low LeA 20,842 .

vi~cosity of the polyol component, The addition of corresponding quantities of linear dialcohol leads either to shrinkage or gives a foam characterized by poor mechanical properties (Foam Examples 10 and 11). If the addition of linear dialcohol and diisocyanate is carried out in polyether as the reaction medium (cf., Solutions Bl to B4), solutions of relatively high ~iscosity are obtained because of the subse~uent reaction o the polyether.
Further, if the reaction of~dialcohoi and diisocyanate were to be carried out in polyethers predominantly containing primary OH-terminated groups, the end products would have extremely high viscosities e~en despite very low solids contents.
In addition to the starting components already mentioned, water and/or other blowing agents, acti-vators, and optionally, other known additives and auxiliaries of the type mentioned in the publications cited earlier (for example, on pages 25 to 31 of 20 German Offen:Legungsschrift No. 2,854,384) may be used in the production of flexible foams in accordance with the invention.
According to the invention, the reaction com-ponents are reacted by the known one-shot process, by the prepolymer process or by the semi-prepolymer process, often using machines, for example of the type described in US Patent No. 2,764,565. Information on processing machines which may also be used in accordance with the invention can be found in Kunststoff-Handbuch, Vol. VII, b~ Vieweg and Hochtlen, Carl-H~nser-Verlag, Munich 1966, fox example, on page 121 to 247.

LeA 20,842 3~

In the production of foams,in accordance with the invention, foaming is often carried out with the reaction mixture introduced into a mold where it foams and forms the molding. Suitable mold materials include metals, such as aluminumt or plastics, such as epoxide resin. In~mold foaming may be carried out in such a way that the molding has a cellular structure at its surface, although it may also be carried out in such a way that the molding has a compact skin and a cellular core. In this conné~tion, -t is possible, in accordance with the invention, to introduce foamable reaction mixture into the mold in such a ~uantity that the foam formed just ~ills the mold. However, it is also possible to introduce into the mold more foamable reaction mixture than is required for filling the interior of the mold with foam (called "overcharging" and described for example, in VS Patent Nos. 3,178,490 and 3,182,104).
Where foaming is carried out in molds,known "external release agents" such as silicone oils, are fre~uently used. However, it is also possible to use so-called "internal release agents", optionally in admixture with external release agents, of the type known, fox example, from German Offenlegungsschriften

2,121,670 and 2,307,589.
~ccording to the invention, it is also possible to produce cold-hardening foams (cf., British Patent No. 1,162,517 and German Offenlegungsschrift No.
~,153,086).
However, it is, of course, also possible to produce foams by block foaming or by the known laminator process.
The invention is illustrated by the following Examples in which the quantities quoted xepresent - ¦

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~13-parts by wei~ht or percentages by weight, unless otherwise indicated The designations used have the following meanings:
Dialcohol I: polypropylene oxide having an OH-number of 515 Dialcohol II: polypropylene oxide having an . OH-number of 265 Dialcohol III: polypropylene glycol ethoxylate lC (15% of ethylene oxide units at the chain ends) ha~ing an OH-number of 150 ---Glycol (b) I: polypropylene ether diol, OH-number 515 Glycol (b) II: polypropylene ether diol, OH-number 265 Polyether I: started with 90% glycerol and 10% 1,2-propylene glycol; 10%
ethylene oxide and 90~ propylene oxide in the chain; more than 95 mole percent of secondary OH-groups; OH-number 46 Polyether K: started with 90% glycerol and 19%
1,2-propylene glycol; 10% of ethylene oxide and 90~ of propylene oxide units in the chain; OH-number 46 Polyether L: started with trimethylol. propane, 18% of ethylene oxide and 82%
of propylene oxide units in the chains; approximately 90 mole percent of primary OH-terminal groups, ~H-number 35 LeA 20,842 TDI 65: . tolylene diisocyanate (65% 2,4-and 35% 2,6 isomer) TDI 80. tolylene diisocyanate (80~ of 2,4~
and 20% of 2,6-isomer) MDI: diphenyl methane-4,4'-dii.socyanate HDI: 1,6-hexamethylene diisocyanate EXAMPLES
1. Production of the- solut~ions EXAMPL~ A 1:
- -69.6 (=0.4 mole) of tolylene diisocyanate (TDI
80) are added over a period of 10 to 15 minutes at 90_to. 100C~to 211.5 g (-0.5 mole) of a polypropylene oxide having an OH-number of 265. The reaction mixture is then stirred at 100C until no more NCO-groups can be detected ~2 to 5 hours). The oligo-urethane ether formed is then stirred into 2530 g of Polyether K heated to 100C. The clear solution (solids content 10%) has a viscosity of 1100 mPas at 2SC.
The following solutions of oligo-urethanes in polyethers of relatively high molecular weight are prepared in exactly the same way.

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87 g of TDI 80 (= 0.5 mole) are added at 100C
to 217.9 g (= 1 mole) of dialcohol I and 1219.6 g of Polyether K, followed by stirring for 5 hours. The clear solution (solids content 20%) has a viscosity of 2450 mPas at 25C.
Solution B 4 is prepared in exactly the same way.
Alcohol component:, `,,Dialcohol II
Isocyanate component: TDI 80 Molar ratic of dialcohol to diisocyanate: 7:6 High molecular weight polyether: Polyether K
'Soli'ds cont'ent: 20% ~~~' Viscosity at 25C: 5750 mPas.
3. APPLICATION EXAMPLES
Production of flexible polyurethane foams Flexible foams were produced from solutions A 1 to A 5, B 1 to B 4 and C l to C 9. In each case, flexible foams were produced by the hand foaming process (through mixing of the polyols with stabilizer, water and activator; then addition of the isocyana-te;
and foaming after further mixing in a paper packet).
The fo~ms obtained were welded with a flat electrode 1 cm wide and 10 cm long (surface area 10 cm ) under a pressure of 9 kp/cm using 10 mm thick foam sheets (foam/foam) and a composite system of a polyamide velours, 8 mm foam sheet and a poly-amide Charmeuse. The welding voltage was 650 V and the current 480 m~. The HF-weldiny unit used was an HG 600 S high-frequency generator (manufactured by the Herfurth Company of Hamhurg-Altona), The frequency was 27,12 MHz and the generator output 600 W.
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Claims (4)

The embodiments of the invention in which exclu-sive property or privilege is claimed are defined as follows:

1. Solutions of:
A) from 3 to 60%, by weight, based on the combined ether-polyol content, of separately prepared oligo-urethane ethers containing terminal OH-groups in the form of reac-tion products of a) diisocyanates with b) short-chain polyether diols having an average molecular weight of from 200 to 800, the stoichio-metric ratio of a) to b) amounting to between 0.5 and 0.7 in the case of diols having an average molecular weight of from 200 to 280; to between 0.5 and 0.9 in the case of diols having an average molecular weight in the range from 280 to 600;
and to between 0.5 and 0.75 in the case of diols having an average molecular weight of from 600 to 800, in B) polyether polyols containing at least two hydroxyl groups and having an average molecular weight from 1000.
to 12,000.

2. Solutions as claimed in Claim 1, characterized in that polypropylene glycols having an average molecu-lar weight of from 200 to 600 are used as the dialcohol.

3. Solutions as claimed in Claims 1 or 2, charac-terized in that 2,4- and/or 2,6-tolylene diisocyanate and/or diphenyl methane-2,4'- and/or -4,4'-diisocyanate are used as the diisocyanate.

4. A process for the production of flame-laminatable and high-frequency-weldable flexible poly-urethane foams by involving reacting i) polyisocyanates;
ii) relatively high molecular weight compounds containing at least two hydroxyl groups;
iii) optionally other relatively high molecular weight and/or low molecular weight compounds containing isocyanate-reactive hydrogen atoms and water;
iv) optionally, in the presence of other blowing agents, catalysts, foam stabilizer and other additives, characterized in that the solutions claimed in Claim 1 are exclusively or partly used as the relatively high molecular weight compounds containing hydroxy groups.