CA2002946C - Process for the preparation of molded articles and the molded articles obtainable by said process - Google Patents
Process for the preparation of molded articles and the molded articles obtainable by said processInfo
- Publication number
- CA2002946C CA2002946C CA002002946A CA2002946A CA2002946C CA 2002946 C CA2002946 C CA 2002946C CA 002002946 A CA002002946 A CA 002002946A CA 2002946 A CA2002946 A CA 2002946A CA 2002946 C CA2002946 C CA 2002946C
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- Prior art keywords
- polyisocyanate
- molecular weight
- weight
- products
- polyaddition
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/5048—Products of hydrolysis of polyether-urethane prepolymers containing isocyanate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
This invention relates to a process for the preparation of single-layered or multilayered molded articles from particles of polyisocyanate-polyaddition products comprising thermoplastically shaping under pressure (i) polyisocyanate-polyaddition products prepared by reacting (a) aliphatic, cycloaliphatic, or aromatic polyisocyanates;
(b) compounds having a molecular weight of from about 1800 to about 12,000 and containing, on statistical average, at least 2.5 isocyanate-reactive groups;
(c) optionally, diamines having a molecular weight of from about 108 to about 400 with two primary and/or secondary aromatically bound amino groups; and (d) optionally, alkane polyols, cycloalkane polyols, alkane polyamines, and/or cycloalkane polyamines having a molecular weight of from about 60 to about 1799 and containing ether groups;
with the proviso that at least one of components (c) or (d) has a molecular weight of from about 60 to about 400 and comprises at least 5% by weight based on the weight of component (b);
in the presence of (ii) one or more processing auxiliaries selected from solvents that swell the surface of the products, compounds that can react with the products, radical formers, and other thermoplastic materials.
This invention also relates to the molded articles prepared by the process of the invention.
(b) compounds having a molecular weight of from about 1800 to about 12,000 and containing, on statistical average, at least 2.5 isocyanate-reactive groups;
(c) optionally, diamines having a molecular weight of from about 108 to about 400 with two primary and/or secondary aromatically bound amino groups; and (d) optionally, alkane polyols, cycloalkane polyols, alkane polyamines, and/or cycloalkane polyamines having a molecular weight of from about 60 to about 1799 and containing ether groups;
with the proviso that at least one of components (c) or (d) has a molecular weight of from about 60 to about 400 and comprises at least 5% by weight based on the weight of component (b);
in the presence of (ii) one or more processing auxiliaries selected from solvents that swell the surface of the products, compounds that can react with the products, radical formers, and other thermoplastic materials.
This invention also relates to the molded articles prepared by the process of the invention.
Description
Mo3244 LeA 26,438 PROCESS FOR THE PREPARATION OF MOLDED
ARTICLES AND THE MOLDED ARTICLES
OBTAINABLE BY SAID PROCESS
BACKGROUND OF THE INVENTION
This invention relates to an improved process for the preparation of single-layered or multilayered molded articles from certain polyisocyanate polyaddition products by thermoplastic shaping and to the molded articles thereby obtained.
o According to German Patent Application P 3,733,756.4, molded articles can be prepared by thermoplastic shaping of granulates, shavings, or other small and very small particles of the kind obtained from the preparation and processing of polyisocyanate polyaddition products. According to German Patent Application P 3,809,524.6, complex structures and laminates can be prepared from such small particles and used either as such or in the form of semi-finished goods produced by a separate step.
It has been found, however, that disintegration may occur if materials differing substantially in their properties, for example, in their surface tension, are to be molded together in a single complex material. This problem can arise, for example, when using materials differing greatly in their hardness or materials not formulated to be readily releasable from the mold and containing internal mold release agents.
Such disintegration may also occur, for example, when lacquered and unlacquered materials are to be bonded together.
It is, therefore, an object of the present invention to provide an improved process by which all types of size-reduced polyisocyanate polyaddition products of the type mentioned below can be joined to form composite materials, regardless of their chemical composition and their physical properties.
Mo3244 It has surprisingly been found that problem described above can be solved with the aid of certain processing auxiliaries described below.
SUMMARY OF THE INVENTION
The present invention relates to a process for the preparation of single-layered or multilayered molded articles from small and very small particles of polyisocyanate-polyaddition products comprising thermoplastically shaping under pressure (i) polyisocyanate-polyaddition products prepared by reacting, in a single stage or multistage process at an isocyanate index of from about 60 to about 140, (a) aliphatic, cycloaliphatic, or aromatic polyisocyanates;
(b) compounds having a molecular weight of from about 1800 to about 12,000 and containing, on statistical average, at least 2.5 isocyanate-reactive groups;
(c) optionally, diamines having a molecular weight of from about 108 to about 400 with two primary and/or secondary aromatically bound amino groups;
(d) optionally, alkane polyols, cycloalkane polyols, alkane polyamines, and/or cycloalkane polyamines having a molecular weight of from about 60 to about 1799 and containing ether groups; and (e) optionally, auxiliary agents and additives conventionally used in polyurethane chemistry;
with the proviso that at least one of components (c) or (d) has a molecular weight of from about 60 to about 400 and comprises at least 5% by weight based on the weight of component (b);
in the presence of (ii) one or more processing auxiliaries selected from the group consisting of solvents that swell the surface of the polyisocyanate-polyaddition products, compounds that can undergo an addition or condensation reaction with the Mo3244 20()2946 polyisocyanate-polyaddition products, radical formers, and materials that are different from said polyisocyanate-polyaddition products and that can be thermoplastically processed under the conditions of the process.
This invention also relates to the molded articles prepared by the process of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The process according to the invention not only enables widely differing polyurethane materials or poly(urethane)urea materials to be combined without preselection but often also enables the thermoplastic shaping to be carried out under much milder operating conditions. The small and very small particles to be used in the process according to the invention may be, for example, granulates, shavings, sawdust, or other small and very small particles of polyisocyanate-polyaddition products based on the starting materials mentioned above.
Suitable aromatic polyisocyanates for the preparation of the polyisocyanate-polyaddition products include, in particular, the compounds described in European Patent Application 81,701 at column 3, line 30, to column 4, line 25, of which the polyisocyanates mentioned as preferred are also preferred for the purpose of the present invention.
Suitable aliphatic and cycloaliphatic polyisocyanates (a) include any organic diisocyanates having a molecular weight abo~e about 137 (preferably from 168 to 290) and containing only aliphatically or cycloaliphatically bound isocyanate groups. Examples of suitable aliphatic and cycloaliphatic diisocyanates include 1,6-diisocyanatohexane, 1,12-diiso-cyanatododecane, 1,3-diisocyanatocyclobutane, 1,3- and 1,4-diisocyanatocyclohexane and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (~IPDI~), 2,4'- and/or 4,4'-diisocyanatodicyclohexylmethane, and any mixtures of such polyisocyanates. Also suitable are polyisocyanates based on the aliphatic or cycloaliphatic Mo3244 diisocyanates exemplified above (or mixtures thereof) that are modified with urethane, allophanate, isocyanurate, urea, biuret, or uretdione groups. Mixtures of unmodified diisocyanates with the above-mentioned modified polyisocyanates may also be used as component (a).
Component (b) consists of compounds in the molecular weight range of from about 1800 to about 12,000 (preferably from 3000 to 7000) containing isocyanate-reactive groups, or of mixtures of such compounds. The compounds used as component (b) have an (average) functionality in isocyanate addition reactions greater than 2.5 (preferably from 2.6 to 3.0 and most preferably from 2.8 to 3.0). In accordance with this definition, polyether polyols and mixtures of polyether polyols disclosed in German Auslegeschrift 2,622,951 at column 6, line 65, to column 7, line 47, are particularly suitable compounds for use as component (b). Also preferred are polyether polyols in which at least 50% of the hydroxyl groups (preferably at least 80%) are primary hydroxyl groups. The hydroxyl-containing polyesters, polythioethers, polyacetals, polycarbonates, and polyester amides disclosed as examples in German Auslegeschrift 2,622,951 are in principle also suitable for use as component (b), provided they conform to the conditions mentioned above, but are less preferred than polyether polyols.
Suitable starting components (b) also include aminopolyethers and mixtures of aminopolyethers conforming to the above conditions, that is, polyethers containing isocyanate-reactive groups and comprising at least 50 equivalents percent (preferably at least 80 equivalents percent) of primary and/or secondary aromatic or aliphatic (preferably aro~atic) amino groups, with the remainder being primary and/or secondary aliphatic hydroxyl groups. Examples of suitable aminopolyethers of this type include compounds described in European Patent Application 81,701 at column 4, line 26, to column 5, line 40.
Mo3244 Polyesters in the above-mentioned molecular weight range containing amino groups are also suitable as starting component (b) but are less preferred.
Mixtures of the polyhydroxyl compounds described above with the aminopolyethers may, of course, also be used as component (b).
Optional component (c) consists of aromatic diamines of the type described in European Patent Application 81,701 at column S, line 58, to column 6, line 34, of which the diamines mentioned as preferred are also preferred for the purpose of the present invention. Preferred aromatic diamines include diethyltolylenediamines or isomeric mixtures thereof, especially a mixture of 65 percent by weight 1-methyl-3,5-diethylphenylene-2,4-diamine and 35 percent by weight 1-methyl-3,5-diethylphenylene-2,6-diamine (~DETDAn).
The polyols and polyamines optionally used as additional starting components (d) include non-aromatic compounds in the molecular weight range of from about 60 to about 1799 (preferably from 62 to 500 and especially from 62 to 400) containing at least two isocyanate-reactive groups.
Examples of such compounds include polyhydric alcohols such as those described in European Patent Application 81,701 at column 9, lines 32 to 50. Other suitable compounds for use as component (d) include aliphatic polyamines containing ether groups, such as polypropylene oxides in the above-mentioned molecular weight range containing primary amino end groups.
Also suitable are cycloaliphatic-containing polyols, such as 1,4-dihydroxycyclohexane and 1,4-bis(hydroxymethyl)cyclohexane, and polyamines, such as 1,4-cyclohexanediamine, isophorone-diamine, bis(4-aminocyclohexyl)methane and bis(3-methyl-4-aminocyclohexyl)methane.
It is preferred to use at least one of the components (c) or (d) for the preparation of the elastomers, preferably in such quantities that the proportion by weight of components (c) and/or (d) based on the weight of component (b) is at least 5%
~ Mo3244 by weight (preferably at least 10% by weight). The nature and quantitative proportions of components (b), (c) and/or (d) are preferably chosen so that the molar ratio of urea groups to urethane groups in the elastomers is at least 2:1 (most 5 preferably at least 5:1).
The auxiliary agents and additives (e) optionally used in the preparation of polyisocyanate-polyaddition products may be, for example, internal mold release agents, catalysts for the polyisocyanate-polyaddition reaction, blowing agents, surface-active additives, cell regulators, pigments, dyes, UV
stabilizers, plasticizers, and fungistatic or bacteriostatic substances, such as those described in European Patent Application 81,701 at column 6, line 40, to column 9, line 31.
When used, the preferred auxiliary agents and additives include 15 known fillers and/or reinforcing substances, such as barium sulfate, kieselguhr, whiting, mica, and especially glass fibers, liquid crystal fibers, glass flakes, glass balls, aramide fibers, and carbon fibers. These fillers and/or reinforcing materials may be added in quantities of up to 80%
20 by weight (preferably up to 30X by weight) based on the total quantity of filled or reinforced polyisocyanate-polyaddition products.
The polyisocyanate-polyaddition products are preferably prepared by the one-shot process in which 25 polyisocyanate component (a) is mixed with components (b), (c), (d), and (e) in a suitable mixing apparatus, where the mixed components react. It is also possible in principle to react the polyisocyanate-polyaddition products by a ~modified one-shot process" in which polyisocyanate component (a) is reacted with part of component (b) and, optionally, part of component (d) to form isocyanate semiprepolymers which are then reacted with the mixture of the remaining components in a single stage. The elastomers can also be prepared by the well-known prepolymer process. The isocyanate index (number of 3s isocyanate groups divided by the number of isocyanate-reactive Mo3244 2002946 .
groups and multiplied by 100) is always from about 60 to about 140 (preferably from 80 to 120 and more preferably from 95 to 115).
The starting materials used for the process according 5 to the invention are most preferably small or very small particles of the kind obtained from the production and use of molded articles based on polyisocyanate-polyaddition products obtained from the aforesaid starting material. In the past, such materials have been disposed of by burning.
The processing auxiliaries (ii) of the invention may be a "solvent typen, a "reactive type", or a ~thermoplast type"
or may be radical formers.
Suitable processing auxiliaries of the solvent type cause the surface of the polyisocyanate-polyaddition products 15 to swell, thereby rendering them softer and more plastic.
Examples of such agents include alcohols, such as methanol, ethanol, propanol, isopropyl alcohol, and higher alcohols;
diols, such as ethylene glycol and glycol monoethers and monoesters; ether solvents, such as dioxane, tetrahydrofuran, 20 and dimethoxyethane; halogenated hydrocarbons; ketones and lower aliphatic aldehydes, optionally in an acetal or ketal form; esters, such as ethyl acetate; and aprotic polar solvents, such as acetonitrile, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, dimethyl sulfone, and 25 tetramethylurea.
Suitable processing auxiliaries of the reactive type include, for example, the type which react with the polyisocyanate-polyaddition products by the formation of chemical bonds, in particular by an addition reaction with the active hydrogen atoms present in the polyisocyanate-polyaddition products. Examples include organic poly-isocyanates of the type described abo~e for starting component (a) above, prepolymers containing isocyanate groups obtained from polyisocyanates, and compounds containing isocyanate-Mo3244 reactive groups of the type described for component (b), as well as compounds containing epoxide groups of the type known from the chemistry of epoxide resins, such as the known reaction products of bisphenol-A and epichlorohydrin. Also s suitable as processing auxiliaries of the reactive type are phenol resins, melamine resins, and other formaldehyde resins, provided they are capable of undergoing a condensation reaction with the polyisocyanate-polyaddition products.
Suitable processing auxiliaries also include radical o formers, particularly peroxidic processing auxiliaries of the kind used as radical starters for the processing of rubber.
Particularly suitable are peroxidic processing auxiliaries which have a short half life compared with the molding time at the most preferred molding temperatures. Examples include 15 lauroyl peroxide, dilauroyl peroxide, cumene hydroperoxide, t-butyl peroxide, di-t-butyl peroxide, t-butyl perbenzoate, t-butyl hydroperoxide, benzoyl peroxide, dibenzoyl peroxide, ethyl methyl ketone peroxide, and dicumyl peroxide (e.g., Perkadox SB of Akzo), as well as other radical formers, such as 20 2,2'-azobis(2-methylpropionitrile).
The processing auxiliaries of the reactive type and the radical formers may be used in either the liquid or the solid form, but when used as solids they must become fluid at the stage of thermoplastic shaping. Solid processing 25 auxiliaries may also be introduced as a suitable solution using a solvent that preferably is capable of wetting the granulate and of escaping before processing or, at the latest, during processing.
Suitable processing auxiliaries of the thermoplast 30 type are mainly thermoplastic resins that are themselves thermoplastically processible under the conditions of the process of the invention and in which the polyisocyanate-polyaddition products become embedded when the process of the invention is carried out. Examples of suitable auxiliary 35 agents of this type include polyolefines, aromatic polyether Mo3244 Z()02~346 g esters, polycarbonates, and other thermoplastically processible materials.
Thermoplastic molding is generally carried out under a pressure of at least 5 bar (preferably in the pressure range of from 5a to 430bar) at a temperature of at least 50-C
(preferably at 10~to 200-C). The molding times under these conditions may be from about 1 second to about 10 minutes.
Thermoplastic processing is carried out in apparatus conventionally used for this purpose, such as deep drawing presses, rolling mills, calendering rollers, presses, modified extruders, and modified injection molding apparatus. When using modified apparatus, the modifications must be such that the particles of granulate can be forced into a given mold at the filling pressure in a substantially unmolten state.
Examples of such modifications include the use of a large outlet die and large conveyor channels in the extruder or injection molding machine and in the channels leading into the mold. Shearing forces occurring shortly before or during the process of filling the mold help to keep the molded products together.
The processing auxiliaries (ii) required for the invention are preferably added before the molding process to the polyisocyanate-polyaddition products that are to be thermoplastically molded. Under these conditions, the small or 25 very small particles of polyisocyanate-polyaddition product become intimately mixed with the processing auxiliaries.
Combinations of various processing auxiliaries may be used for carrying out the process of the invention, in which case the auxiliary agents may be added to the small particles of polyisocyanate-polyaddition product either as a mixture or individually in sequence. The auxiliary agents are generally used in a quantity of from about 0.01 to about 50X by weight (preferably from 1 to 10% by weight) based on the weight of the polyisocyanate-polyaddition products.
Mo3244 - io -The mixture used in the process of the invention for thermoplastic molding composed of (i) small and very small particles of polyisocyanate-polyaddition products of the type described above and (ii) processing auxiliaries that are essential for the invention may be mixed with (iii) additional auxiliary agents which serve to improve the properties of the resulting composite products. These additional auxiliary agents may include, for example, antistatic agents, flame-retardants, agents for increasing the electric o conductivity, reinforcing materials such as glass or carbon fibers, or fillers such as barium sulfate or mica.
The products obtained by the process of the invention may be finished parts or articles or they may be semi-finished goods that may be converted into finished articles in a further 15 process step, either alone or in combination with any other materials.
The process according to the invention allows the preparation of particularly high quality composite products, especially composite sheet products suitible for a wide variety 20 of applications. Thus, the composite products prepared according to the invention may be used, for example, in the form of hollow bodies for use as linings, beakers, and containers of various dimensions and capacities, as facings for dashboards and switchboards, as flat parts of car body elements 25 such as door panels, side parts, mudguards, hoods, or trunk lids, and as wheel caps. In a flat form, the composite bodies are also suitable for use as writing surfaces, indicator boards with magnetic holders, adhesive labels, protective films, and coatings for various purposes. Products obtained by the process of the invention may also be used in the form of small parts not previously economically obtainable by the RIM
process, such as keyboards parts, rigid elastic sealing parts and sleeves, handles and recessed grips, small damping elements, and washers and spacer discs. The products of the process of the invention may also be used for the manufacture Mo3244 of reinforced or unreinforced cable duct sections and sealing lips or for the production of any other solid small articles.
The following examples further illustrate details for the process of this invention. The invention, which is set 5 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 temperatures are degrees Celsius, all parts are o parts by weight, and all percentages are percentages by weight.
EXAMPLES
Preparation of a polyisocyanate-polyaddition product (polyurea-based molded part) The formulation described below was processed as 15 follows to prepare molded parts:
Apparatus: Laboratory piston dosing apparatus Mold: Steel plate mold, internal dimensions 300 x 200 x 4 mm Mixing head: MQ 8 mixing head of Hennecke, Sankt Augustin Operating pressure: 180 bar Filling time: 1 second Temperature of raw materials A component: 65-C
B component: 50'C
Mold temperature: 70-C
Residence time in mold: 30 seconds External mold release agent: RCTW 2006 of Chemtrend Mo3244 .
2002g~
A Component:
58.6 parts an aromatic amino polyether (NH number of 44) prepared by the hydrolysis at 90-C of an isocyanate prepolymer using a mixture of 3.5 parts by weight of dimethylformamide, O.l part by weight of sodium hydroxide, and 100 parts by weight of water per 1000 parts by weight of the prepolymer, followed by removal of the volatile components by distillation o 28.8 parts DETDA
O.9 parts commercial stabilizer based on a polyether polysiloxane (L 5430 of Union Carbide);
5.6 parts a mixture of equal parts by weight of (i) zinc stearate and (ii) the product of addition of 5 mol of propylene oxide to 1 mol of ethylene diamine (internal mold release agent);
6.1 parts a high molecular weight polyricinoleic acid having an acid number below 5 as internal mold release agent The isocyanate prepolymer (isocyanate content 3.4%) was obtained by the reaction of 2,4-diisocyanatotoluene with a subequivalent quantity of a polyether mixture. The polyether mixture consisted of equal parts by weight of (i) the propoxylation product (OH number 56 and OH functionality 2.4) 25 of a mixture of water and trimethylolpropane and (ii) a polyether polyol (OH number 35) prepared by the propoxylation of glycerol followed by the ethoxylation of the propoxylation product (ratio by weight PO:EO - 87:13).
Mo3244 ;
1" 2 0 0 ~ ~ 4 ~
B Component:
Desmodur* M 53 (polyester-modified 4,4'-diisocyanatodiphenyl-methane having an isocyanate content of 19% by weight; product of Bayer AG).
Components A and B were worked up under the operating conditions indicated above at an isocyanate index of 100 to produce elastomer plates having a density of 1.15 g/cm3.
Preparation of a ~ranulate:
A granulate with an average particle size of 2 to 3 mm was prepared in a cutting mill from the plates described above.
FY~rnples 1-4 Process according to the invention In the foll~wing Examples 1 to 4, the granulate particles were compressed to 4-mm thick plates in a closed plate mold using a laboratory press (Model 200 T press of Schwabenthan) for 2 minutes at 180~C at a pressure of 350 bar. The plates were cut into rods which were used to determine the elongation at break and resistance to breakage in the tension test (see Table below).
Fxample 1 Untreated granulate described.
Example 2 The granulate described above mixed with 10% by weight, based on the polyisocyanate-polyaddition product, of a granulate of a commercial thermoplastic polyurethane (Desmopan* 359 of Bayer AG) having a particle size of 2 to 3 mm. The thermoplastic polyurethane has a Shore D hardness according to DIN 53,505 of 59, a modulus of elasticity according to DIN 53,455 of 160 mPa, a stress at break according to DIN 53,504 of 50 mPa, an elongation at break according to DIN 53,504 of 350%, and a density of 1.23 g/cm3.
Fl~ample 3 The granulate described above mixed with 10% by weight, based on the mixture, of an ABS granulate having a particle size of 2 to 3 mm. The ABS granulate was based on an *) Trade-mark Mo3244 s~
acrylonitrile/butadiene/styrene copolymer having a Vicat softening temperature according to DIN 53,460 of 92-C and a notched impact strength according to DIN 53,453 of 12 kJ/m2.
Example 4 Particles of granulate completely wetted with a saturated solution of a polyisocyanate in toluene, dried in air, and then treated overnight with a saturated solution of dicumyl peroxide in heptane. The polyisocyanate was a polyisocyanate mixture of the diphenylmethane series having a viscosity of 200 mPa.s (23-C). The remainder of the solvent was removed by drying in a drying cupboard (80-C, 1 h).
ExamDle 5 A reference sample of undisturbed test body (unblended, original plate of polyisocyanate-polyaddition product of the type described above).
TABLE
Example Tensile strength Elongation at break (mPa) at break (%) Mo3244
ARTICLES AND THE MOLDED ARTICLES
OBTAINABLE BY SAID PROCESS
BACKGROUND OF THE INVENTION
This invention relates to an improved process for the preparation of single-layered or multilayered molded articles from certain polyisocyanate polyaddition products by thermoplastic shaping and to the molded articles thereby obtained.
o According to German Patent Application P 3,733,756.4, molded articles can be prepared by thermoplastic shaping of granulates, shavings, or other small and very small particles of the kind obtained from the preparation and processing of polyisocyanate polyaddition products. According to German Patent Application P 3,809,524.6, complex structures and laminates can be prepared from such small particles and used either as such or in the form of semi-finished goods produced by a separate step.
It has been found, however, that disintegration may occur if materials differing substantially in their properties, for example, in their surface tension, are to be molded together in a single complex material. This problem can arise, for example, when using materials differing greatly in their hardness or materials not formulated to be readily releasable from the mold and containing internal mold release agents.
Such disintegration may also occur, for example, when lacquered and unlacquered materials are to be bonded together.
It is, therefore, an object of the present invention to provide an improved process by which all types of size-reduced polyisocyanate polyaddition products of the type mentioned below can be joined to form composite materials, regardless of their chemical composition and their physical properties.
Mo3244 It has surprisingly been found that problem described above can be solved with the aid of certain processing auxiliaries described below.
SUMMARY OF THE INVENTION
The present invention relates to a process for the preparation of single-layered or multilayered molded articles from small and very small particles of polyisocyanate-polyaddition products comprising thermoplastically shaping under pressure (i) polyisocyanate-polyaddition products prepared by reacting, in a single stage or multistage process at an isocyanate index of from about 60 to about 140, (a) aliphatic, cycloaliphatic, or aromatic polyisocyanates;
(b) compounds having a molecular weight of from about 1800 to about 12,000 and containing, on statistical average, at least 2.5 isocyanate-reactive groups;
(c) optionally, diamines having a molecular weight of from about 108 to about 400 with two primary and/or secondary aromatically bound amino groups;
(d) optionally, alkane polyols, cycloalkane polyols, alkane polyamines, and/or cycloalkane polyamines having a molecular weight of from about 60 to about 1799 and containing ether groups; and (e) optionally, auxiliary agents and additives conventionally used in polyurethane chemistry;
with the proviso that at least one of components (c) or (d) has a molecular weight of from about 60 to about 400 and comprises at least 5% by weight based on the weight of component (b);
in the presence of (ii) one or more processing auxiliaries selected from the group consisting of solvents that swell the surface of the polyisocyanate-polyaddition products, compounds that can undergo an addition or condensation reaction with the Mo3244 20()2946 polyisocyanate-polyaddition products, radical formers, and materials that are different from said polyisocyanate-polyaddition products and that can be thermoplastically processed under the conditions of the process.
This invention also relates to the molded articles prepared by the process of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The process according to the invention not only enables widely differing polyurethane materials or poly(urethane)urea materials to be combined without preselection but often also enables the thermoplastic shaping to be carried out under much milder operating conditions. The small and very small particles to be used in the process according to the invention may be, for example, granulates, shavings, sawdust, or other small and very small particles of polyisocyanate-polyaddition products based on the starting materials mentioned above.
Suitable aromatic polyisocyanates for the preparation of the polyisocyanate-polyaddition products include, in particular, the compounds described in European Patent Application 81,701 at column 3, line 30, to column 4, line 25, of which the polyisocyanates mentioned as preferred are also preferred for the purpose of the present invention.
Suitable aliphatic and cycloaliphatic polyisocyanates (a) include any organic diisocyanates having a molecular weight abo~e about 137 (preferably from 168 to 290) and containing only aliphatically or cycloaliphatically bound isocyanate groups. Examples of suitable aliphatic and cycloaliphatic diisocyanates include 1,6-diisocyanatohexane, 1,12-diiso-cyanatododecane, 1,3-diisocyanatocyclobutane, 1,3- and 1,4-diisocyanatocyclohexane and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (~IPDI~), 2,4'- and/or 4,4'-diisocyanatodicyclohexylmethane, and any mixtures of such polyisocyanates. Also suitable are polyisocyanates based on the aliphatic or cycloaliphatic Mo3244 diisocyanates exemplified above (or mixtures thereof) that are modified with urethane, allophanate, isocyanurate, urea, biuret, or uretdione groups. Mixtures of unmodified diisocyanates with the above-mentioned modified polyisocyanates may also be used as component (a).
Component (b) consists of compounds in the molecular weight range of from about 1800 to about 12,000 (preferably from 3000 to 7000) containing isocyanate-reactive groups, or of mixtures of such compounds. The compounds used as component (b) have an (average) functionality in isocyanate addition reactions greater than 2.5 (preferably from 2.6 to 3.0 and most preferably from 2.8 to 3.0). In accordance with this definition, polyether polyols and mixtures of polyether polyols disclosed in German Auslegeschrift 2,622,951 at column 6, line 65, to column 7, line 47, are particularly suitable compounds for use as component (b). Also preferred are polyether polyols in which at least 50% of the hydroxyl groups (preferably at least 80%) are primary hydroxyl groups. The hydroxyl-containing polyesters, polythioethers, polyacetals, polycarbonates, and polyester amides disclosed as examples in German Auslegeschrift 2,622,951 are in principle also suitable for use as component (b), provided they conform to the conditions mentioned above, but are less preferred than polyether polyols.
Suitable starting components (b) also include aminopolyethers and mixtures of aminopolyethers conforming to the above conditions, that is, polyethers containing isocyanate-reactive groups and comprising at least 50 equivalents percent (preferably at least 80 equivalents percent) of primary and/or secondary aromatic or aliphatic (preferably aro~atic) amino groups, with the remainder being primary and/or secondary aliphatic hydroxyl groups. Examples of suitable aminopolyethers of this type include compounds described in European Patent Application 81,701 at column 4, line 26, to column 5, line 40.
Mo3244 Polyesters in the above-mentioned molecular weight range containing amino groups are also suitable as starting component (b) but are less preferred.
Mixtures of the polyhydroxyl compounds described above with the aminopolyethers may, of course, also be used as component (b).
Optional component (c) consists of aromatic diamines of the type described in European Patent Application 81,701 at column S, line 58, to column 6, line 34, of which the diamines mentioned as preferred are also preferred for the purpose of the present invention. Preferred aromatic diamines include diethyltolylenediamines or isomeric mixtures thereof, especially a mixture of 65 percent by weight 1-methyl-3,5-diethylphenylene-2,4-diamine and 35 percent by weight 1-methyl-3,5-diethylphenylene-2,6-diamine (~DETDAn).
The polyols and polyamines optionally used as additional starting components (d) include non-aromatic compounds in the molecular weight range of from about 60 to about 1799 (preferably from 62 to 500 and especially from 62 to 400) containing at least two isocyanate-reactive groups.
Examples of such compounds include polyhydric alcohols such as those described in European Patent Application 81,701 at column 9, lines 32 to 50. Other suitable compounds for use as component (d) include aliphatic polyamines containing ether groups, such as polypropylene oxides in the above-mentioned molecular weight range containing primary amino end groups.
Also suitable are cycloaliphatic-containing polyols, such as 1,4-dihydroxycyclohexane and 1,4-bis(hydroxymethyl)cyclohexane, and polyamines, such as 1,4-cyclohexanediamine, isophorone-diamine, bis(4-aminocyclohexyl)methane and bis(3-methyl-4-aminocyclohexyl)methane.
It is preferred to use at least one of the components (c) or (d) for the preparation of the elastomers, preferably in such quantities that the proportion by weight of components (c) and/or (d) based on the weight of component (b) is at least 5%
~ Mo3244 by weight (preferably at least 10% by weight). The nature and quantitative proportions of components (b), (c) and/or (d) are preferably chosen so that the molar ratio of urea groups to urethane groups in the elastomers is at least 2:1 (most 5 preferably at least 5:1).
The auxiliary agents and additives (e) optionally used in the preparation of polyisocyanate-polyaddition products may be, for example, internal mold release agents, catalysts for the polyisocyanate-polyaddition reaction, blowing agents, surface-active additives, cell regulators, pigments, dyes, UV
stabilizers, plasticizers, and fungistatic or bacteriostatic substances, such as those described in European Patent Application 81,701 at column 6, line 40, to column 9, line 31.
When used, the preferred auxiliary agents and additives include 15 known fillers and/or reinforcing substances, such as barium sulfate, kieselguhr, whiting, mica, and especially glass fibers, liquid crystal fibers, glass flakes, glass balls, aramide fibers, and carbon fibers. These fillers and/or reinforcing materials may be added in quantities of up to 80%
20 by weight (preferably up to 30X by weight) based on the total quantity of filled or reinforced polyisocyanate-polyaddition products.
The polyisocyanate-polyaddition products are preferably prepared by the one-shot process in which 25 polyisocyanate component (a) is mixed with components (b), (c), (d), and (e) in a suitable mixing apparatus, where the mixed components react. It is also possible in principle to react the polyisocyanate-polyaddition products by a ~modified one-shot process" in which polyisocyanate component (a) is reacted with part of component (b) and, optionally, part of component (d) to form isocyanate semiprepolymers which are then reacted with the mixture of the remaining components in a single stage. The elastomers can also be prepared by the well-known prepolymer process. The isocyanate index (number of 3s isocyanate groups divided by the number of isocyanate-reactive Mo3244 2002946 .
groups and multiplied by 100) is always from about 60 to about 140 (preferably from 80 to 120 and more preferably from 95 to 115).
The starting materials used for the process according 5 to the invention are most preferably small or very small particles of the kind obtained from the production and use of molded articles based on polyisocyanate-polyaddition products obtained from the aforesaid starting material. In the past, such materials have been disposed of by burning.
The processing auxiliaries (ii) of the invention may be a "solvent typen, a "reactive type", or a ~thermoplast type"
or may be radical formers.
Suitable processing auxiliaries of the solvent type cause the surface of the polyisocyanate-polyaddition products 15 to swell, thereby rendering them softer and more plastic.
Examples of such agents include alcohols, such as methanol, ethanol, propanol, isopropyl alcohol, and higher alcohols;
diols, such as ethylene glycol and glycol monoethers and monoesters; ether solvents, such as dioxane, tetrahydrofuran, 20 and dimethoxyethane; halogenated hydrocarbons; ketones and lower aliphatic aldehydes, optionally in an acetal or ketal form; esters, such as ethyl acetate; and aprotic polar solvents, such as acetonitrile, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, dimethyl sulfone, and 25 tetramethylurea.
Suitable processing auxiliaries of the reactive type include, for example, the type which react with the polyisocyanate-polyaddition products by the formation of chemical bonds, in particular by an addition reaction with the active hydrogen atoms present in the polyisocyanate-polyaddition products. Examples include organic poly-isocyanates of the type described abo~e for starting component (a) above, prepolymers containing isocyanate groups obtained from polyisocyanates, and compounds containing isocyanate-Mo3244 reactive groups of the type described for component (b), as well as compounds containing epoxide groups of the type known from the chemistry of epoxide resins, such as the known reaction products of bisphenol-A and epichlorohydrin. Also s suitable as processing auxiliaries of the reactive type are phenol resins, melamine resins, and other formaldehyde resins, provided they are capable of undergoing a condensation reaction with the polyisocyanate-polyaddition products.
Suitable processing auxiliaries also include radical o formers, particularly peroxidic processing auxiliaries of the kind used as radical starters for the processing of rubber.
Particularly suitable are peroxidic processing auxiliaries which have a short half life compared with the molding time at the most preferred molding temperatures. Examples include 15 lauroyl peroxide, dilauroyl peroxide, cumene hydroperoxide, t-butyl peroxide, di-t-butyl peroxide, t-butyl perbenzoate, t-butyl hydroperoxide, benzoyl peroxide, dibenzoyl peroxide, ethyl methyl ketone peroxide, and dicumyl peroxide (e.g., Perkadox SB of Akzo), as well as other radical formers, such as 20 2,2'-azobis(2-methylpropionitrile).
The processing auxiliaries of the reactive type and the radical formers may be used in either the liquid or the solid form, but when used as solids they must become fluid at the stage of thermoplastic shaping. Solid processing 25 auxiliaries may also be introduced as a suitable solution using a solvent that preferably is capable of wetting the granulate and of escaping before processing or, at the latest, during processing.
Suitable processing auxiliaries of the thermoplast 30 type are mainly thermoplastic resins that are themselves thermoplastically processible under the conditions of the process of the invention and in which the polyisocyanate-polyaddition products become embedded when the process of the invention is carried out. Examples of suitable auxiliary 35 agents of this type include polyolefines, aromatic polyether Mo3244 Z()02~346 g esters, polycarbonates, and other thermoplastically processible materials.
Thermoplastic molding is generally carried out under a pressure of at least 5 bar (preferably in the pressure range of from 5a to 430bar) at a temperature of at least 50-C
(preferably at 10~to 200-C). The molding times under these conditions may be from about 1 second to about 10 minutes.
Thermoplastic processing is carried out in apparatus conventionally used for this purpose, such as deep drawing presses, rolling mills, calendering rollers, presses, modified extruders, and modified injection molding apparatus. When using modified apparatus, the modifications must be such that the particles of granulate can be forced into a given mold at the filling pressure in a substantially unmolten state.
Examples of such modifications include the use of a large outlet die and large conveyor channels in the extruder or injection molding machine and in the channels leading into the mold. Shearing forces occurring shortly before or during the process of filling the mold help to keep the molded products together.
The processing auxiliaries (ii) required for the invention are preferably added before the molding process to the polyisocyanate-polyaddition products that are to be thermoplastically molded. Under these conditions, the small or 25 very small particles of polyisocyanate-polyaddition product become intimately mixed with the processing auxiliaries.
Combinations of various processing auxiliaries may be used for carrying out the process of the invention, in which case the auxiliary agents may be added to the small particles of polyisocyanate-polyaddition product either as a mixture or individually in sequence. The auxiliary agents are generally used in a quantity of from about 0.01 to about 50X by weight (preferably from 1 to 10% by weight) based on the weight of the polyisocyanate-polyaddition products.
Mo3244 - io -The mixture used in the process of the invention for thermoplastic molding composed of (i) small and very small particles of polyisocyanate-polyaddition products of the type described above and (ii) processing auxiliaries that are essential for the invention may be mixed with (iii) additional auxiliary agents which serve to improve the properties of the resulting composite products. These additional auxiliary agents may include, for example, antistatic agents, flame-retardants, agents for increasing the electric o conductivity, reinforcing materials such as glass or carbon fibers, or fillers such as barium sulfate or mica.
The products obtained by the process of the invention may be finished parts or articles or they may be semi-finished goods that may be converted into finished articles in a further 15 process step, either alone or in combination with any other materials.
The process according to the invention allows the preparation of particularly high quality composite products, especially composite sheet products suitible for a wide variety 20 of applications. Thus, the composite products prepared according to the invention may be used, for example, in the form of hollow bodies for use as linings, beakers, and containers of various dimensions and capacities, as facings for dashboards and switchboards, as flat parts of car body elements 25 such as door panels, side parts, mudguards, hoods, or trunk lids, and as wheel caps. In a flat form, the composite bodies are also suitable for use as writing surfaces, indicator boards with magnetic holders, adhesive labels, protective films, and coatings for various purposes. Products obtained by the process of the invention may also be used in the form of small parts not previously economically obtainable by the RIM
process, such as keyboards parts, rigid elastic sealing parts and sleeves, handles and recessed grips, small damping elements, and washers and spacer discs. The products of the process of the invention may also be used for the manufacture Mo3244 of reinforced or unreinforced cable duct sections and sealing lips or for the production of any other solid small articles.
The following examples further illustrate details for the process of this invention. The invention, which is set 5 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 temperatures are degrees Celsius, all parts are o parts by weight, and all percentages are percentages by weight.
EXAMPLES
Preparation of a polyisocyanate-polyaddition product (polyurea-based molded part) The formulation described below was processed as 15 follows to prepare molded parts:
Apparatus: Laboratory piston dosing apparatus Mold: Steel plate mold, internal dimensions 300 x 200 x 4 mm Mixing head: MQ 8 mixing head of Hennecke, Sankt Augustin Operating pressure: 180 bar Filling time: 1 second Temperature of raw materials A component: 65-C
B component: 50'C
Mold temperature: 70-C
Residence time in mold: 30 seconds External mold release agent: RCTW 2006 of Chemtrend Mo3244 .
2002g~
A Component:
58.6 parts an aromatic amino polyether (NH number of 44) prepared by the hydrolysis at 90-C of an isocyanate prepolymer using a mixture of 3.5 parts by weight of dimethylformamide, O.l part by weight of sodium hydroxide, and 100 parts by weight of water per 1000 parts by weight of the prepolymer, followed by removal of the volatile components by distillation o 28.8 parts DETDA
O.9 parts commercial stabilizer based on a polyether polysiloxane (L 5430 of Union Carbide);
5.6 parts a mixture of equal parts by weight of (i) zinc stearate and (ii) the product of addition of 5 mol of propylene oxide to 1 mol of ethylene diamine (internal mold release agent);
6.1 parts a high molecular weight polyricinoleic acid having an acid number below 5 as internal mold release agent The isocyanate prepolymer (isocyanate content 3.4%) was obtained by the reaction of 2,4-diisocyanatotoluene with a subequivalent quantity of a polyether mixture. The polyether mixture consisted of equal parts by weight of (i) the propoxylation product (OH number 56 and OH functionality 2.4) 25 of a mixture of water and trimethylolpropane and (ii) a polyether polyol (OH number 35) prepared by the propoxylation of glycerol followed by the ethoxylation of the propoxylation product (ratio by weight PO:EO - 87:13).
Mo3244 ;
1" 2 0 0 ~ ~ 4 ~
B Component:
Desmodur* M 53 (polyester-modified 4,4'-diisocyanatodiphenyl-methane having an isocyanate content of 19% by weight; product of Bayer AG).
Components A and B were worked up under the operating conditions indicated above at an isocyanate index of 100 to produce elastomer plates having a density of 1.15 g/cm3.
Preparation of a ~ranulate:
A granulate with an average particle size of 2 to 3 mm was prepared in a cutting mill from the plates described above.
FY~rnples 1-4 Process according to the invention In the foll~wing Examples 1 to 4, the granulate particles were compressed to 4-mm thick plates in a closed plate mold using a laboratory press (Model 200 T press of Schwabenthan) for 2 minutes at 180~C at a pressure of 350 bar. The plates were cut into rods which were used to determine the elongation at break and resistance to breakage in the tension test (see Table below).
Fxample 1 Untreated granulate described.
Example 2 The granulate described above mixed with 10% by weight, based on the polyisocyanate-polyaddition product, of a granulate of a commercial thermoplastic polyurethane (Desmopan* 359 of Bayer AG) having a particle size of 2 to 3 mm. The thermoplastic polyurethane has a Shore D hardness according to DIN 53,505 of 59, a modulus of elasticity according to DIN 53,455 of 160 mPa, a stress at break according to DIN 53,504 of 50 mPa, an elongation at break according to DIN 53,504 of 350%, and a density of 1.23 g/cm3.
Fl~ample 3 The granulate described above mixed with 10% by weight, based on the mixture, of an ABS granulate having a particle size of 2 to 3 mm. The ABS granulate was based on an *) Trade-mark Mo3244 s~
acrylonitrile/butadiene/styrene copolymer having a Vicat softening temperature according to DIN 53,460 of 92-C and a notched impact strength according to DIN 53,453 of 12 kJ/m2.
Example 4 Particles of granulate completely wetted with a saturated solution of a polyisocyanate in toluene, dried in air, and then treated overnight with a saturated solution of dicumyl peroxide in heptane. The polyisocyanate was a polyisocyanate mixture of the diphenylmethane series having a viscosity of 200 mPa.s (23-C). The remainder of the solvent was removed by drying in a drying cupboard (80-C, 1 h).
ExamDle 5 A reference sample of undisturbed test body (unblended, original plate of polyisocyanate-polyaddition product of the type described above).
TABLE
Example Tensile strength Elongation at break (mPa) at break (%) Mo3244
Claims (8)
1. A process for the preparation of a single-layered or multilayered molded article from small and very small particles of polyisocyanate-polyaddition products comprising thermoplastically shaping under pressure (i) a polyisocyanate-polyaddition product prepared by reacting, in a single stage or multistage process at an isocyanate index of from about 60 to about 140, (a) an aliphatic, cycloaliphatic, or aromatic polyisocyanate;
(b) a compound having a molecular weight of from about 1800 to about 12,000 and containing, on statistical average, at least 2.5 isocyanate-reactive groups;
(c) optionally, a diamine having a molecular weight of from about 108 to about 400 with two primary and/or secondary aromatically bound amino groups;
(d) optionally, an alkane polyol, cycloalkane polyol, alkane polyamine, and/or cycloalkane polyamine having a molecular weight of from about 60 to about 1799 and containing ether groups; and (e) optionally, auxiliary agents and additives conventionally used in polyurethane chemistry;
with the proviso that at least one of components (c) or (d) has a molecular weight of from about 60 to about 400 and comprises at least 5% by weight based on the weight of component (b);
in the presence of (ii) one or more processing auxiliaries selected from the group consisting of a solvent that swells the surface of the polyisocyanate-polyaddition product, a compound that can undergo an addition or condensation reaction with the polyisocyanate-polyaddition product, a radical former, and a material that is different from said polyisocyanate-polyaddition products and that can be thermoplastically processed under the conditions of the process.
(b) a compound having a molecular weight of from about 1800 to about 12,000 and containing, on statistical average, at least 2.5 isocyanate-reactive groups;
(c) optionally, a diamine having a molecular weight of from about 108 to about 400 with two primary and/or secondary aromatically bound amino groups;
(d) optionally, an alkane polyol, cycloalkane polyol, alkane polyamine, and/or cycloalkane polyamine having a molecular weight of from about 60 to about 1799 and containing ether groups; and (e) optionally, auxiliary agents and additives conventionally used in polyurethane chemistry;
with the proviso that at least one of components (c) or (d) has a molecular weight of from about 60 to about 400 and comprises at least 5% by weight based on the weight of component (b);
in the presence of (ii) one or more processing auxiliaries selected from the group consisting of a solvent that swells the surface of the polyisocyanate-polyaddition product, a compound that can undergo an addition or condensation reaction with the polyisocyanate-polyaddition product, a radical former, and a material that is different from said polyisocyanate-polyaddition products and that can be thermoplastically processed under the conditions of the process.
2. A process according to Claim 1 wherein the thermoplastic shaping is carried out at a pressure of at least 5 bar.
3. A process according to Claim 1 wherein the thermoplastic shaping is carried out at a pressure of from 50 to 400 bar.
4. A process according to Claim 1 wherein the thermoplastic shaping is carried out at a temperature of at least 50-C.
5. A process according to Claim 1 wherein the thermoplastic shaping is carried out at a temperature of from 50 to 200°C.
6. A process according to Claim 1 wherein the thermoplastic shaping is carried out at a pressure of from 50 to 400 bar and at a temperature of from 50 to 200°C.
7. A molded article prepared according to Claim 1.
8. A molded article prepared according to Claim 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3840167.3 | 1988-11-29 | ||
| DE3840167A DE3840167A1 (en) | 1988-11-29 | 1988-11-29 | METHOD FOR THE PRODUCTION OF MOLDED BODIES AND THE MOLDED BODIES AVAILABLE BY THIS METHOD |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2002946A1 CA2002946A1 (en) | 1990-05-29 |
| CA2002946C true CA2002946C (en) | 1997-10-07 |
Family
ID=6368065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002002946A Expired - Fee Related CA2002946C (en) | 1988-11-29 | 1989-11-14 | Process for the preparation of molded articles and the molded articles obtainable by said process |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0371330B1 (en) |
| JP (1) | JP2896907B2 (en) |
| CA (1) | CA2002946C (en) |
| DE (2) | DE3840167A1 (en) |
| ES (1) | ES2049794T3 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4309139A1 (en) * | 1993-03-22 | 1994-09-29 | Bayer Ag | Process for the production of powders and other small and ultra small particles |
| PL2125311T3 (en) * | 2007-01-22 | 2016-12-30 | Composite panel with solid polyurethane binder, and process for manufacture |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1435445A1 (en) * | 1960-07-15 | 1968-11-21 | Bayer Ag | Process for regulating the modulus of elasticity of highly elastic fibers and films |
| DE2025900C3 (en) * | 1970-05-27 | 1979-10-31 | Bayer Ag, 5090 Leverkusen | Process for the production of polyurethane elastomers |
| DE2854386A1 (en) * | 1978-12-16 | 1980-07-03 | Bayer Ag | METHOD FOR PRODUCING THERMOPLASTIC CHEMICAL MATERIALS |
| DE3132760A1 (en) * | 1981-08-19 | 1983-03-03 | Basf Ag, 6700 Ludwigshafen | Process for improving the flow properties of polyurethane elastomers |
| DE3600764A1 (en) * | 1986-01-14 | 1987-07-16 | Bayer Ag | THERMAL-CURABLE REACTION RESIN MIXTURES AND A METHOD FOR PRODUCING MOLDED BODIES USING THESE MIXTURES |
| DE3820704A1 (en) * | 1988-06-18 | 1989-12-21 | Basf Ag | POLYURETHANE MOLDED BODIES PROVIDED WITH A CONTOURED, MULTILAYER FILM, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| DE3822331A1 (en) * | 1988-07-01 | 1990-01-04 | Bayer Ag | METHOD FOR THE PRODUCTION OF FORM BODIES AND THE FORM BODY RECEIVED BY THIS PROCESS |
-
1988
- 1988-11-29 DE DE3840167A patent/DE3840167A1/en not_active Withdrawn
-
1989
- 1989-11-14 CA CA002002946A patent/CA2002946C/en not_active Expired - Fee Related
- 1989-11-16 ES ES89121177T patent/ES2049794T3/en not_active Expired - Lifetime
- 1989-11-16 EP EP89121177A patent/EP0371330B1/en not_active Expired - Lifetime
- 1989-11-16 DE DE89121177T patent/DE58907096D1/en not_active Expired - Fee Related
- 1989-11-27 JP JP1304968A patent/JP2896907B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ES2049794T3 (en) | 1994-05-01 |
| EP0371330A2 (en) | 1990-06-06 |
| EP0371330A3 (en) | 1991-01-16 |
| EP0371330B1 (en) | 1994-03-02 |
| CA2002946A1 (en) | 1990-05-29 |
| JP2896907B2 (en) | 1999-05-31 |
| DE58907096D1 (en) | 1994-04-07 |
| DE3840167A1 (en) | 1990-05-31 |
| JPH0333132A (en) | 1991-02-13 |
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