CA1245416A - Process for the production of molded articles - Google Patents

Process for the production of molded articles

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Publication number
CA1245416A
CA1245416A CA000474572A CA474572A CA1245416A CA 1245416 A CA1245416 A CA 1245416A CA 000474572 A CA000474572 A CA 000474572A CA 474572 A CA474572 A CA 474572A CA 1245416 A CA1245416 A CA 1245416A
Authority
CA
Canada
Prior art keywords
reaction
reaction mixture
isocyanate
polyisocyanate
lea
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000474572A
Other languages
French (fr)
Inventor
Otto Ganster
Ulrich Knipp
Bruno Luckas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
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Publication of CA1245416A publication Critical patent/CA1245416A/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/302Water
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2120/00Compositions for reaction injection moulding processes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987With nonvoid component of specified composition
    • Y10T428/249988Of about the same composition as, and adjacent to, the void-containing component
    • Y10T428/249989Integrally formed skin

Abstract

Mo-2650 LeA 22,922 PROCESS FOR THE PRODUCTION OF MOLDED ARTICLES
ABSTRACT OF THE DISCLOSURE
The present invention is directed to a process for the production of a molded article having a compact surface layer and a gross density above 900 kg/m3 via the reaction injection molding technique, comprising introducing a reaction mixture into a closed mold, said reaction mixture comprising:
a) a polyisocyanate component consisting of at least one polyisocyanate in which all the isocyanate groups are aromatically bound, b) compounds having molecular weights of from 400 to 12,000 and having at least two isocyanate reactive hydrogen atoms, c) water, in a quantity of at least 0.15 mol per mol of isocyanate groups of component a), and d) optionally compounds having molecular weights of from 60 to 399 and having at least two isocyanate reactive hydrogen atoms, wherein the isocyanate index, based on all the reactants taking part in the reaction is from 70 to 125, and wherein a pressure of above 40 bar is maintained in the reaction mixture during the reaction so that the carbon dioxide formed in the course of the reaction remains completely or predominantly in solution in the reaction mixture and in the molded article produced.

Mo-2650 LeA 22,922-US

Description

4~i PROCESS FOR THE PRODUCTION OF MOLDED ARTICLES
BACKGROUND OF T~ INVENTION
The present invention relates to a new process for the production of molded articles having gross densities above 900 kg/m3. In this process, the urea groups required for obtaining the superior mechanical properties are produced mainly by the reaction of aromatic polyisocyanates with aromatic amines which are obtained in situ ~rom aromatic polyisocyanates and 10 water~
It is known to produce molded articles from polyurethanes containing urea groups by reactin~ a reaction mixture of aromatic polyisocyanates, relatively high molecular weight polyhydroxvl compounds and aromatic diamines containing primary or secondary amino ~roups in closed molds using the reaction injection molding technia.ue (see ~.S. ~atent 4,21~,543 or German Offenlegungs~chrift 3,147,736). The molded articles obtained by this method have excellent ~echanical properties due to their high urea group content. In the known art processes, the urea groups (which are necess2ry for obtaining these mechanical properties), are incorporate~ in the polyurethane structure by using aromatic diamines. In the known art processes, however, the above-mentioned ~dvantage of the excellent mechanical properties is obtained at the expense of having to use eY.pensive, special aromatic diamines, such as l-methyl-3,5-diethyl-2,4-diamino-benzene or mixtures thereof with 1-methyl-3,5-diethyl-
2,6-diaminobenzene. These diamines react very vigorollsly with aromatically bound isocyanate groups, with the result that the highly reactive reaction mixtures of the kno~l art must be introduced into the Mo-2650 Le A 22,922 r. _ ~

~4~

molds within a very short time. For fillin~ large molds, this can only be achieved by using special, high power dosing apparatus.
It was therefore an object of the present invent on to provide a new process for the production of molded articles based on polyisocyanates having a gross density above 900 kg/m3 (DIN 53 42n) 9 in which the use of such generally expensive aromatic diamines is either no longer necessary or in comparatively very minor quantities, so that the advantages of the known art processes can be obtained without the above-mentione~ disadvantages.
D RIPTION OF THE INVE~TION
The above problems were solved by the process according to the present invention. The basic principle underlying the process according to the invention is that the amino groups required for producing urea groups are obtained in situ by the reaction of part of the isocyanate groups of the polyisocyanate component with water. At the same time, the formation of foam structures is prevented ~y the mai~enance of an e~ternal pressure.
The production of polyurethanes containing urea groups by the reaction of organic polyisocyanates with organic polyhydroxyl compounds in the presence of water is already known. In the known processes, the water has been used mainly or exclusively for the reaction of isocyanate groups with water to produce carbon dioxide as blowing agents for the purpose of producing foam structures (see ~unststoff Handbuch, Volume VII "Polyurethane", Carl Hanser Verlag Munich (1966), pages 440 et seq). The production of solid, non-cellular polyurethane elastomers bv the two-stage Mo-2650 LeA 22,922 process, using water as chain lengthening agent, is also already known (see Kunststoff Handbuch, pages 270-271), but this method of producing non-cellular elastomers also went through the intermediate stage of producing foam structures which were subsequently compacted on rollers and finally compressed to form solid elastomers.
The process according to the invention, on the other hand, for the first time enables an aqueous reaction mixture to be converted into a virtually unfoamed urea-modified product w thout the intermediate formation of oams which must subsequently be compressed to ~orm unfoamed polyurethanes. This is achieved according to the invention by exerting such a pressure on the liquid reaction mixture during the reaction that the carbon dioxide formed remains predominately or completely in solution in the reaction mixture and in the resulting product.
This invention more particularly relates to a process for the production of a non-cellular or micro-cellular molded article having a compact surface layer and a gross density above 900 kg/m3 via the reaction in~ection molding technique comprising introduc~ng a reaction mixture into a closed mold, said reaction mixture comprising:
a) a polyisocyanate component consisting of at least one polyisocyanate having only aromaticallv bound isocyanate groups b) compounds having molecular weights of 400-12,000 and having at least two isocyanate reactive hydro~en atoms, c) water in a quantity of at least 0.15 mol per mol of isocyana~e groups of component a) Mo-2650 LeA 22,922 4~

d) optionally compounds having molecular weights of 60 to 399 having at least two isocyanate reactive hydrogen atoms, and e) optionally the usual auxiliary agents and additives, wherein the isocvanate index, based on all the reactarts taking part in the reaction, is from 70 to 125, and wherein a pressure of above 40 bar is maintained in the reaction mixture during the reaction so that the carbon dioxide formed during the reaction remains completely or predo-minantly in solution in the reaction mixture and in the molded articles obtained therefrom, and wherein the re-sulting molded articles are removed from the mold after-termination of the chemical reaction.
The reaction iniection molding technique (abbreviated: RIM) is a standard process for the production of molded polyisocyanate-based articles and has been described, for example, in "Reaction Injection Molding" by W.E. Becker, ~.7an Nostrand P~einhold Company, New York, Cincinnati, London, Atlanta, Toronto, Dallas, San Francisco, Melbourne (1979).
The starting materials a) include any organic polyisocyanates in which all the isocyanate groups are aromatically bound and in particular the technically important aromatic polyisocyanates known from poly-urethane chemistry, such as 2,4-diisocyanatotoluene, its commercial mixtures with 2,6-diisocyanatotoluene and polyisocyanates or polyisocyanate mixtures of the diphenyl methane series. The polyisocyanates may be used in their unmodified form or they may be modified with urethane, carbodiimide and/or isocyanurate groups. The "polyisocyanates and polyisocyanate mixtures of the diphenylmethane series" of 4,4'-diiso-cyanatodiphenyl methane and mixtures thereof with 2,4'-Mo-2650 LeA 22,922 and optionally 2,2'-diisocyanatodiphenyl methane and/or with their higher functional homologues. Mixtures of this kind whicll also contain the hi~her functional homologues may be obtained in kno7~n manner by the phosgenation of the corresponding anil ne/formaldehyde condensates. Polyisocyanate mixtures of the diphenylmethane series used in the process according to the invention preferably have a difunctional isocyanate content of at least 60,~ by weight. If used for the production O r rigid molded products with exceptionally high impact strength or of elastic molded articles, their difunctional isocyanate content is preferably at least 90% by weight. The polyisocyanates to be used in the process according to the invention are preferably liquid at room temperature. To be included among the particularly preferred polyisocyanates are the reaction products of 1 mol of ~,4'-diisocyanatodiphenyl methane with 0.05 to Q.3 mols of low molecular weight diols or triols, preferably polypropylene glycols having a molecular weight below 700 or carbodiimide-modi~ied (or uretone imine-modified) 4,4'-diisocyanatodiphenyl methane such as those obtainab~e, for example, according to U.S. Patent 3,152,162. Mixtures of these urethane-modified or carbodiimide-modified diiso-cyanates with each other or with similarly modified orunmodified 2,4'-diisocyanatodiphenyl methane or with the above-mentioned, similarly modified or unmodified, higher functional homologous polyisocyanates are also particularly preferred. These mixtures may be prepared by suitable modification of mixtures of corresponding starting polyisocyanates or by mixing polyisocyanates which have already been at least partly modified.
Isocyanate prepolymers and isocyanate semi-prepolymers Mo-2650 LeA 22,922 basec on the polyisocyanates exemplified above and on the polyhydroxyl compounds b) and d) mentioned below may also be used as polyisocyanate component a).
Suitable starting components b) include particular polyester polyols and polyether polyols having molecular weights of from 400 to 12,000, preferably from 900 to 6,000, and mixtures of such compounds. These polyhydroxyl compounds have at least 2, preferably 2 to 6 alcoholic hydroxyl groups and are prepared from known starting materials by known methods.
Suitable polyester polyols may be obtained, for example, by the reaction o~ excess quantities of polyhydric alcohols wi.h polybasic, preferably dibasic carboxylic acids or carboxylic acid anhydrides.
Suitable carboxylic acids, carboxylic acid anhydrides and low molecular weight, polyhydric alcohols are, for example, described in U.S. Patent 4,218,543, column 8, lines 27-52.
Polyether polyols suitable for the process according to the invention may be obtained, for example, by the known method of alkoxylating suitable starter molecules, in particular using ethylene oxide and/or propylene oxide, optionally as mixtures or in any sequence. Examples of suitable starter molecules include water, ethylene glycol, 1,2-dihydroxy propane, trimethylol propane and/or glycerol.
In addition to or instead of the above-mentioned polyester polyols and/or polye~her polyols~
other relatively high molecular weight compounds within the stated molecular weight range and containing isocyanate reactive groups may also be used as component b) in the process according to the Mo-2650 LeA 22,922 invention. These include, for example, polyesters based on lactone, such as poly-~-caprolactones, or polyesters base~ on ~ -hydroxyaL~ne carboxylic acids, such as ~-hydroxy caproic ac~d, polycarbonate polyols, polyester amides or hydroxyl group-containing polyacetals within the stated molecular weight range. The well-known aminopoly-ethers within the stated molecular weight range may also be used as compound b). These "aminopolyethers" are co~unds whose isocyanate-reactive groups consist at least p~ly of primary or secon~ amino groups. ~le manufacture of such "amino~olyethers" is descr~d in numerousFulications such as, for ~le, m Gen~n Offenlegungs-schrifts 3,231,399, 2,019,432, 2,619,840, 2,546,536, 2,948,419,
3,039,600 or ~n U.S. Patents 3,654,370, 3,236,895, 3,808,250, 3,975,428,4,016,143 or 4,218,543. Ihe polyester polyols and polyether polyols mentioned ~x~e as examples are preferred.

The low molecular weight compounds d~ having molecular weights of 60 to 399 are optionally also used in the process. These include preferably polyhydric, aliphatic alcohols with molecular weights of 62 to 39S, (optionally containing ether groups) such as ethylene 20 glycol, 1,2-dihydroxy propane, 1,3-dihydroxy propane, 1,4-dihydroxy butane, 1,6-dihydroxy hexane, diethylene glycol, triethylene glycol, dipropylene glycol, tri-propylene glycol, trimethylol propane, glycerol, low molecular weight alkoxylation products of the above-25 mentioned polyhydric alcohols, or mixtures of such lowmolecular weight chain lengthening agents or cross linking agents. Organic diamines with molecular weights of 60 to 399 having at least 2 primary and/or secondary amino groups may also be used ~s component d). Examples include 1,2-diamino ethane, 1,6-diamino hexane, 2,4-diaminotoluene, 4,4'-diaminodiphenyl methane and in particular aromatic diamines with sterically hindered amino groups, which are liquid at room temperature and examples of which are given in German Offenlegungsschrift 2,916,485, page 17, line 26 to page 18, line 9. Mixtures of the diam;nes mentioned there may also be used, if they are liquid at room temperature. Since, however, it was an object underlying this invention to be able to dispense with Mo-2650 Le~ 22,922 ~L2~

such amines to a large extent, these would only be used, if at all, in minor quantities of at the most 30 mol %, based on the quantity of water, to act as "viscosity regulators". Since the reaction between isocyanate groups and amino groups begins immediately, these may be used, where required, to increase the viscosity of the liquid reaction mixture before the main reaction begins. This is in many cases advantageous for reasons connected with the apparatus (sealing off the plane of separation9 the ejectors and the core drafts).
The auxiliary agents and additives e) optionally used include, for example, emulsifiers, catalysts, lubricants, internal mold release agents, stabilizers, pulverulent or fibrous reinforcing fillers, flame retarding agents or plasticizers of the type mentioned, for example, in German Offenlegungs-schrift 3,147,736 or in the Kunststoff Handbuch already referred to above, on pages 96 et seq.
An essential feature of this invention is the use of water as an additional reaction component. In the process according to the invention, water is used in a quantity of at least 0.15 mol, and preferably from 0.25 to 0.49 mol per mol of isocyanate groups present in component a).
The reactants are otherwise used in quantities corresponding to an isocyanate index of rom 70 to 125, preferably from 85 to ~15. By "isocyanate index" is meant the number of isocyanate groups present in the reaction mixture per 100 isocyanate reactive groups (water being counted in the calculation as a di-functional compound).

Mo-2650 LeA 22,922 ~2~ 6 g The process according to the invention is carried out by reacting the components by the reaction injection molding technique, preferably combining components b) to e) to form a "polyol component" which is combined with polyisocyanate component a), using the mixing apparatus conventionally used for the reaction injection molding technique, to form the liquid mixture which reacts to yield the urea-modified product. The quantity of component a) used in this process is generally from 15 to 300% by weight, preferably 35 to 2007 by weight, based on the total quantity of components b), d) and e), not counting any inert auxiliary agents and additives used. Isocyanate excesses which are large in terms of weight may be present if isocyanate prepolymers based on simple poly-isocyanates are used as polyisocyanate component a) and the polyhydroxyl compounds mentioned under b) and optionally under d) are used. In all cases, however, the quantity of component b) is at least 25~ by weight, based on the entire reaction mixture, not counting any inert auxiliary agents and additives used. The particulars given above concerning the isocyanate index apply to the individual components such as, that is to say, any polvhydroxyl compounds already built into component a) are not taken into account when calculating the isocyanate index.
A second essential feature of the invention is that the reaction mixture, which is preferably produced by high pressure injection mixing, is introduced into a liquid-tight tool preferably tempered to a temperature in the region of 30-70C, this tool being preferably made of metal, in particular steel. During the reaction, the pressure in this tool is maintained at Mo-2650 LeA 22,922 ~245~

level above 40 bar so that the carbon dioxide formed in the course of the reaction remains completely or predominately in solution. Maintaining this pressure is achieved either a) by application of an external pressure, for example by means of a press (mold closure unit) or b? by the use of rigid, pressure resistan~
tools.
The molding tools used are preferably completely filled with the liquid reaction mixture before chemical reaction takes place to any significant extent.
When liquid-tight, pressure resistant molds are used, it is sufficient, for the purpose of generating and maintaining the necessary pressure, to seal the mold tightly after it has been filled.
If the molding tools are of such a nature that the internal pressure produced by the evolution of carbon dioxide causes an increase in their internal volume, the generation and maintenance of the required internal pressure must be ensured by the application of an external pressure. For the production of micro-cellular molded articles having a gross densi~y only ~5 slightly below the density of the corresponding non-cellular molded articles but still above 900 kg/m3, the external pressure may be controlled to bring about a controlled change in the internal volume of the molding tool to correspond to the desired denslty of the molded article. Care must always be taken to ensure that the internal pressure in the tool is sufficient to enable most of the carbon dioxide formed to remain in solution.

~o-2650 LeA 22,922 ~ Z~ 6 Since the viscosity of the fresh reaction mixture may sometimes be very low and the molding tool can in many cases only be sealed off by very elaborate measures, it is frequently advisable not to apply the external pressure until the viscosity has already risen as a result of the reaction having already begun. This time delay in the application of pressure may be realized technically by, for example, using so called immersion edge tools with corresponding presses or by employing the after pressurization method. Suitable immersion edge tools are known and have been described, for example, in "Kunststoff Handbuch", Carl-Hanser-Verlag, Munich (1973~, Volume 8, "Polyester" on page
4~. Apparatus suitable for the so called after pres-surization method have been described, for example, inEuropean Patent 0 024 610. The condition required by the invention, that the carbon dioxide formed must remain completely or predominately in solution means that in the case of a non-cellular or only slightly micro-cellular structure (gross density at least 1050 kg/m3), the final products must contain, in solution, at least 70% by weight, preferably at least 85% by weight of the carbon dio~ide calculated to be theoretically obtainable from the quantity of water put into the process. The theoretically obtainable quantity of carbon dioxide calculated corresponds to the quantity of water put into the process if the isocyanate index is at least 100, i.e., 1 mol of carbon dioxide is formed per mol of water put into the process. For isocyanate indexes below 100, it is assumed, when calculating the theoretically obtainable quantity of carbon dioxide, that the molar quantity of carbon dioxide formed ~o-2650 LeA 22,922 ~2~Lr9~:~L6 corresponds, as a first approximation, to the number of mols of water put into the process multiplied by the isocyanate index and divided by 100. When producing molded articles having gross densities of from 900 to 1050, it may also be assumed that more than 50% by weight of the theoretical quantity of carbon dioxide is dissolved in the molded article since even when the gross density is only 900 kg/m3 (assuming that the density of the corresponding unfoamed ar~icle is 1100 kg/m3), the gas volume of the pores is only 22%, based on the total volume of the molded article. On the assumption that the gas present in the pores is not under excess pressure, this would mean that in a molded article having a density of 900 kg/m3, 22Q cm3 of carbon dioxide, corresponding to 0.01 mol of water, are present per 1000 cm3 of volume. In fact, however, the quantity of water used in the process according to the invention is generally more than 0.30 mol of water per 900 g of reaction mixture. Even if the pressure of carbon dio~ide in the pores were 10 bar (which would be sufficier.t to cause deformation or even bursting of the molded article), the pores would only contain 0.1 mol of carbon dioYide per 900 g, i.e., less than one third of the quantity calculated from the quantity of water put into the process.
The internal pressure required in the molding tool for the process according to the invention is generally within the range of from 40 to 180 bar, preferably from 80 to 150 bar. When the quantity of water used is less than 2.5% by weight, based on the total reaction mixture, a pressure of 40 to 120 bar is generally sufficient. When larger quantities of water are used, a pressure above 120 bar may be necessary.

Mo-2650 LeA 22,922 ~L2g~ 6 If the cavity of the mo~ding tool is completely filled and the molding tools used have a constant internal volume, the molded articles obtained by the process according to the invention are non-cellular. If controlled increase in the interna~
volume of the molding tool is effected during the chemical reaction (for e}:ample, by a slight outwar~
movement of the mold core or of a part thereof from the cavity of the mold, which can be controlled by the closing force applied by the closure cover) or if a slight increase in the interna] volume of the mold occurs due to the elastic deformabil;ty of the molding tool, the products obtained are micro-cellular articles, but they always have a non-cellular surface layer.
The same results may in principle be obtained by only part]y filling a pressure stable mold h~ving a constant internal volume. As already mentioned above, however, for the process according to the invention, the molds are preferably completely filled with the liquid reaction mixture before the chemical reaction sets in. In all variations of the process, whether using molding tools having a variable internal volume or whether only partly filling the mold, it is always necessary to ensure that the molded product obtained have a gross density (DIN 53 420) above 900 kg/m3, preferably above 1050 kg/m3.
It is extremely surprising that the molded articles, containing such large quantities of carbon dioxide, can be removed from their mold very rapidly without tearir.g, blistering or undergoing any deformation due to the sudden release of pressure. The molded articles may generally be removed after they Mo-2650 LeA 22,92^

have been left in the mold for 2 to 5 minutes at 30 to 70C, preferably 50 to 60C.
When the molded products released from their molds are stored at room temperature, the carbon dioxide dissolved in them is gradually released by diffusion. After about 12 hours storage at room temperature, about 60% of the carbon dioxide originally dissolved in the products has disappezred. After this time, the molded articles may be heated, e.g. to 120~C, without tearing or blistering. When large quantities of water and high isocyanate indexes are used and correspondingly large quantities of carbon dioxide are dissolved in the molded articles, heating of the molded articles to 120-150C may result in tearing even after 12 hours storage at room temperature. This formation of cracks may be avoided by heating step-wise. The fact that this findin~ is observed to an equal extent in non-cellular as in micro-cellular molded articles according to the invention pro~es that the sharp increase in internal pressure in the "fresh" molded articles when heated, resulting in "bursting" of the molded articles, is almost due entirely to the rapid conversion of dissolved carbon dioxide into gaseous carbon dioxide with corresponding increase in pressure is not due to the comparatively low gas pressure of the ~aseous carbon dioxide present in comparatively small quantities in the pores of the micro-cellular articles.
The molded articles obtained in the process according to the invention have a density above 900 kg/m3, preferably a density of from 1050 to 1200 kg/m3. The density may exceed 1200 kg/m3 if the reaction mixtures contain a high proportion of hi~h density fillers. The molded articles always have a Mo-2650 LeA 22,922 ;4~

compact, i.e. non-cellular surface la~er.
Exceptionally homogeneous molded articles which are free from any pits, bubbles or surface porosities are obtained if the principle of the process according ~o the invention is combined with the after pressuri~-ation technique described in European Patent 00 24 610, i.e., if the process according to the invention is carried out in molding tools of the type described in the said prior publication.
The process according to the invention enables high quality molded products to be obtained within a very wide range of hardnesses, from about 65 Shore A
(elas~rs) to at least 80 Shore D. Preferably, the s~ting ma-14 terlals i.e. their m~lecular weight and their functionality as well as the am~t~t of water are selecbed so that the re~ting mDldmgs exhibit a ~trdness of at least 70 Shore A, more preferably of at least 40 Shore D and mDst preferably fr~40 to 80 Shore D.
The special advantage of the process according to the invention is to be seen in that it enables substantially non-cellular, solid urea-modified polyurethanes to be produced with the aid of a toxicologica]ly completely harmless chain lengthening agent (water), and tha1 these polyurethanes are entirely equal in their excellent mechanical properties to the corresponding amine-lengthened polyurethanes known in the art and can be produced entirely or almost entirely without the use of diamine chain lengthening agents. Another advantage of the reactive systems used accor~ing to the invention compared with the systems known in ~he art, (which contain highly reactive aromatic diamines as chain lengthening agents), is the prolonged flow time of the reaction mixtures used according to the invention, which enables the mixtures to be e?sily introduced even into large molds with complicated forms before the chemical reaction leading to formation of the polyurethane begins.

Mo-265C
LeA 22,922 ~ ~ ~r'~

The products of thP process according to the invention may be used in many different fields of application, e.g., as wear-resistant linings, screen plates, filter plates, technical driving and transmission parts, seals, bellows, tires, cylinders, rollers, bearing elements, shoe soles, heels, boots, shock-absorbers, buffers, body parts for motor vehicles, containers, trunks, housings and molded parts for computers, copying machines, television apparatus, teleprinters, electrical apparatus, air conditioning apparatus, household appliances and refrigerators, cable junction boxes, skis and similar articles of daily use.
The invention if further illustrated, but is not intended to be limited by the following eY~amples in which all parts and percentages are by weight unless otherwise specified.
XAMPLES
The following raw materials were used in the following examples:
Component a):
Polyisocyanate I:
Polyisocyanate mixture o the diphenyl methane series prepared by the phosgenation of an aniline/
formaldehyde condensate, having an isocvanate content of 31.5% and a viscosity at 25C of 100 mPa.s.
Polyisocyanate II:
Reaction product of a polyisocyanate mixture of the diphenyl methane series containing 90% o diisocyanatodiphenyl methane isomers with triprvpylene glycol. Isocyanate content: 24.6%.

Mo-2650 LeA 22,922 s`~

Polyisocyanate III:
Isocyanate semiprepolymer having an isocyanate content of 19.5%, prepared by the reaction of 4,4'-diisocyanatodiphenyl methane with a polyester diol having a molecular weight o~ 2000 obtained from adipic acid and a mixture of e~hylene glycol and butanediol in proportions by weight of 70:3C.
Polyisocyanate IV:
2,4-diisocyanatotoluene.
Component b):
Polyol I:
Polyether polyol with OH number 28 prepared by the propoxylation of sorbitol and ethoxvlation of the propoxylation product (proportions by weight of PO:EC =
83:17).
Polyol II:
Pol~Tether polyol with OH nu~!ber 28 prepred bv the propoxylation of trimethylol propane followed by ethoxylation of the propoxylation products (proportlons by weight of PO:EC = 78:22).
Polyol III:
Polyester diol with OH number 56 prepared by the reaction of adipic acid with a mixture of 1,4-dihydroxy bu~ane and ethylene glycol in propcrtions by weight of 50:50.
_m~onent c?
Chain lengthening agent I:
Mixture of 70% of 2,4-diamino-3,5-diethyl-toluene and 30% of 2,6-diamino-3,5-diethyl-toluene.
Chain lengthening agent II:
Propoxylation product of ethylene diamine, O~
number 800.

~o-2650 LeA 22,922 ~2~

Component d):
Additi~e I:
Commercial polyether polysiloxane stabilizer ("Stabilizer OS 50" of Bayer AG, Leverkusen).
Additive II:
Salt containing amide groups, obtained from 2 mols of oleic acid and 1 mol of l~-dimethylamino-propyl-amine, This additive fulfills the double function of an emu]slfier and an internal mold release agent.
General description of experimental method The materials were processed Gn commercial high pressure dosing and mixing apparatus. Components b) to e) were mixed together to form a polyol mixture, as is customary in the preparation of polyurethane fo&m. The temperature of the raw materials durin~
processing was about 35C with the exception of EY.ample 11, where the polyol mixture and isocyanate were preheated to 50-55C.
Moldin~ Tools:
Plate mold having the internal dimensions, 5Q
x 8Q x o.lj5 cm, the internal surfaces of which had been coated with a commercial eY~ternal mold release agent based on wax (Acmosil 180 of Acmos, Bremen). The tool was an oil tempered immersion edge tool of steel.
The tool was maintained at a temperature of 50-60C (surface temperature) during the e~periments.
Mixin~ Head MQ 18/4K of Fa. Hennecke, Birlinghoven.
Measurement o~ internal pressure of tool:
Pressure receiver (P3M/200; manufacturer: Fa.
Hottinger, Darmstadt) at the center of the plate.
Determination of CO2 loss:
The carbon dioxide loss was determined by weighing the molded article a) directly after its Mo-2650 LeA 22,922 ~2~

removal from the mold and b) after 12 hours storage at room temperature followed by tempering at 120C for 60 minutes.
Closure mechanism:
A commercial press (Model: 300K400PO) of Firma. Paul Ott, Waibling-Neustadt, having a closing force of 400 t was used.
General remarks:
Examples 1 to ~ and Example 7 are examples illustrating the cross linking action of water at different quantities of water and using different types of polyisocyanates of the diphenyl methane series.
Examples 6A to 6D and 7A to 7C show the possible variations in the isocyanate index. Example 6C is a comparison example (index = 1~5) showing that at this isocyanate inde~;, unacceptable mold release times are required because hardening proceeds too slowlv. As may be seen from the examples, the molded articles produced with an isocyanate index below 100 have significantly lower hardnesses.
Example 8 is similar to E-~ample 7 apart from polyisocyanate component a).
Examples 9 and 10 illustrate the cross linking with water with concomitant use of about 30 mol %, based on the quantity of water, of an aromatic diamine as chain lengthening agent.
Examples 11 and 12 illustrate the prodllction of comparatively flexible elastomers.
The nature and quantitative proportions of the starting materials used in the examples and the analytical data and test results found are summari~ed in the following Tables 1 and 2. The figures given in Table 1 relating to the formulations denote parts by weight unless otherwise indicated.
Mo-2650 LeA 22,922 ZZ6' ZZ ~aq OSgz-o~

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- ~6 -Although the invention has been described in detall 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 art without departing from the spirit and scope of the invention except as it may be limited by the claims.

~o-265C
LeA 22,922

Claims (3)

The embodiments of the invention in which exclusive property or privilege is claimed are defined as follows:
1. A process for the production of a molded article having a compact surface layer and a gross density above 900 kg/m3 via the reaction injection molding technique, comprising introducing a reaction mixture into a closed mold, said reaction mixture comprising:
a) a polyisocyanate component consisting of at least one polyisocyanate in which all the isocyanate groups are aromatically bound, b) compounds having molecular weights of from 400 to 12,000 and having at least two isocyanate reactive hydrogen atoms, c) water, in a quantity of at least 0.15 mol per mol of isocyanate groups of component a), and d) optionally compounds having molecular weights of from 60 to 399 and having at least two isocyanate reactive hydrogen atoms, wherein the isocyanate index, based on all the reactants taking part in the reaction is from 70 to 125, and wherein a pressure of above 40 bar is maintained in the reaction mixture during the reaction so that the carbon dioxide formed in the course of the reaction remains completely or predominantly in solution in the reaction mixture and in the molded article produced, and wherein the resulting molded articles are removed from the mold after termination of the chemical reaction.

Mo-2650 LeA 22,922
2. The process of Claim 1, characterized in that polyisocyanate or polyisocyanate mixtures of the diphenyl methane series which may be modified with urethane, carbodiimide and/or isocyanurate groups are used as polyisocyanate component a).
3. The process of Claim 1, characterized in that polyester polyols and/or polyether polyols having molecular weights of from 400 to 12,000 are used as compound b).

Mo-2650 LeA 22,922
CA000474572A 1984-03-03 1985-02-18 Process for the production of molded articles Expired CA1245416A (en)

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DEP3407931.9 1984-03-03

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US4696849A (en) * 1985-09-16 1987-09-29 The Dow Chemical Company Process for preparing polyurethane-backed textiles
DE3725198A1 (en) * 1987-07-30 1989-02-09 Bayer Ag METHOD FOR PRODUCING ELASTOMERIC MOLDED BODIES BASED ON POLYISOCYANATE POLYADDITION PRODUCTS HAVING UREA GROUPS
JPH0332811A (en) * 1989-06-30 1991-02-13 Tokyo Seat Kk Manufacture of urethane foam molded product
DE3921861A1 (en) * 1989-07-04 1991-01-31 Bayer Ag METHOD FOR PRODUCING HIGH-ELASTIC PLASTICS
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JP2518481B2 (en) * 1991-09-26 1996-07-24 豊田合成株式会社 Method and apparatus for producing polyurethane foam with self-skin layer
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JPH07113052B2 (en) 1995-12-06
AU570302B2 (en) 1988-03-10
ATE44965T1 (en) 1989-08-15
DE3407931A1 (en) 1985-09-05
DK97185A (en) 1985-09-04
AU3927285A (en) 1985-09-05
BR8500932A (en) 1985-10-22
US4576970A (en) 1986-03-18
ES540873A0 (en) 1985-12-01
JPS60206816A (en) 1985-10-18
ZA851575B (en) 1985-11-27
DE3571821D1 (en) 1989-08-31
EP0154275A3 (en) 1987-05-06
DK97185D0 (en) 1985-03-01

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