CA1255865A - Process for the production of elastic moldings - Google Patents
Process for the production of elastic moldingsInfo
- Publication number
- CA1255865A CA1255865A CA000509132A CA509132A CA1255865A CA 1255865 A CA1255865 A CA 1255865A CA 000509132 A CA000509132 A CA 000509132A CA 509132 A CA509132 A CA 509132A CA 1255865 A CA1255865 A CA 1255865A
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- CA
- Canada
- Prior art keywords
- mold
- weight
- diamine
- methyl
- diethyl
- 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
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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
-
- 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
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6529—Compounds of group C08G18/3225 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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0033—Foam properties having integral skins
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
-
- 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
- C08G2120/00—Compositions for reaction injection moulding processes
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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)
- Injection Moulding Of Plastics Or The Like (AREA)
- Molding Of Porous Articles (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Mo-2799-Ca LeA 23,867-Ca A PROCESS FOR THE PRODUCTION OF ELASTIC MOLDINGS
ABSTRACT OF THE DISCLOSURE
The present invention is directed to a process for the production of optionally cellular, elastomeric moldings having a density of about 0.8 to 1.4 g/cm3 and a sealed surface layer based on polyurea elastomers optionally containing urethane groups which re prepared from a) di- or polyisocyanates based on diisocyanatodiphenylmethane which are liquid at room temperature, and b) solutions of alkyl-substituted diamines as chain lengthening agents in compounds having an average molecular weight of about 1800 to 12,000 which contain at least two isocyanate-reactive groups wherein components a) and b) are processed as a one shot system according to the reaction injection molding process and the moldings are released from the mold after a period in the mold of about 5 to 60 seconds and the mold is maintained at a temperature of at least 105°C.
Mo-2799-Ca
ABSTRACT OF THE DISCLOSURE
The present invention is directed to a process for the production of optionally cellular, elastomeric moldings having a density of about 0.8 to 1.4 g/cm3 and a sealed surface layer based on polyurea elastomers optionally containing urethane groups which re prepared from a) di- or polyisocyanates based on diisocyanatodiphenylmethane which are liquid at room temperature, and b) solutions of alkyl-substituted diamines as chain lengthening agents in compounds having an average molecular weight of about 1800 to 12,000 which contain at least two isocyanate-reactive groups wherein components a) and b) are processed as a one shot system according to the reaction injection molding process and the moldings are released from the mold after a period in the mold of about 5 to 60 seconds and the mold is maintained at a temperature of at least 105°C.
Mo-2799-Ca
Description
~ 6,~
Mo-2799-~ 1 - LeA 23,867-A PROCESS FOR THE PRODUCTION OF ELASTIC MOLDINGS
BACKGP~OUND OF THE INVENTION
FIELD OF THE INVENTION
The present invention relates to a one stage process for the production of elastomeric moldings with a sealed surface layer by means of the reaction injection molding process.
DESCRIPTION OF THE PRIOR ART
The production of~ell~stomeric moldings with a sealed surface layer by means of the reaction injection molding process is known (c.f. e.g. DE-AS 2,622,951 (US-PS 4,218,~43), EP-A-00,819701, US-PS 4,~96,212, US-PS 4,324,867 or US-PS 4,374,210).
By suitably selecting the starting components, it is possible according to these processes to produce both elastomeric and rigid products ~nd all variants in between.
The resulting moldings are used, for example, as shoe soles or particularly in ~he automotive industry as car body parts. The processing of the crude materials takes place according to the so-called reaction injection molding process (RIM process). This process entails a filling technique in whlch the highly reactive liquid starting components are injected into a mold in a short time via hi~h pressure metering assemblies with a large discharge capacity a~er mixing in so-called force-controlled mixing heads. It is described in DE-AS 2,622,951, for example, that even ex~remelv reactive systems, i.e., one-shot mixtures, can be processed from di- or polyisocyanates based on 4,4'-diisocyanato diphenyl methane which are liquid at room temperature, aromatic polyamines, high molecular weight polyhydroxyl compounds with primary hydroxyl Le A 23 867--~,~
.
:
.
~ 5
Mo-2799-~ 1 - LeA 23,867-A PROCESS FOR THE PRODUCTION OF ELASTIC MOLDINGS
BACKGP~OUND OF THE INVENTION
FIELD OF THE INVENTION
The present invention relates to a one stage process for the production of elastomeric moldings with a sealed surface layer by means of the reaction injection molding process.
DESCRIPTION OF THE PRIOR ART
The production of~ell~stomeric moldings with a sealed surface layer by means of the reaction injection molding process is known (c.f. e.g. DE-AS 2,622,951 (US-PS 4,218,~43), EP-A-00,819701, US-PS 4,~96,212, US-PS 4,324,867 or US-PS 4,374,210).
By suitably selecting the starting components, it is possible according to these processes to produce both elastomeric and rigid products ~nd all variants in between.
The resulting moldings are used, for example, as shoe soles or particularly in ~he automotive industry as car body parts. The processing of the crude materials takes place according to the so-called reaction injection molding process (RIM process). This process entails a filling technique in whlch the highly reactive liquid starting components are injected into a mold in a short time via hi~h pressure metering assemblies with a large discharge capacity a~er mixing in so-called force-controlled mixing heads. It is described in DE-AS 2,622,951, for example, that even ex~remelv reactive systems, i.e., one-shot mixtures, can be processed from di- or polyisocyanates based on 4,4'-diisocyanato diphenyl methane which are liquid at room temperature, aromatic polyamines, high molecular weight polyhydroxyl compounds with primary hydroxyl Le A 23 867--~,~
.
:
.
~ 5
- 2 -groups and strong catalysts, with start up times of less than one second.
The solidificatlon of the reation mixture after the shot thereby takes place 80 quickly with extremely reactive mixtures that the mold can be opened after 5 seconds and the part can be released from the mold.
One-shot mixtures of a polyisocyanate component, aromatic diamines and polyethers with primary and/or secondary amino groups :Lead to polyurea elastomers (c.f. e.~. EP-A-0,081,701).
For use as a material for car body part~, the hi~h rigidity of the polyurea elastomers is necessary By simultaneously using glycols as co-chain lengthening agents, the flexural strength can be incre~sed; however, at the same time, the thermal properties of the ~olded parts (such as the bending modulus at high and low temperatures as well as the heat sag) are disadvant~geously changed.
Limitations are likewise placed on an increase in the proportion of diamine chain lengthening agent in the one-shot svstem. Molded parts resulting under normal processing conditions ~tool temperature 50 to 70~C), cannot be released from the mold intact even 2~ after a long period in the mold due to their brittleness. For example, with materials based on the diethyl toluylene diamine (DETDA), an increase in the flexural modulus of about 350 to 400 MPa (corresponding to 23 to 25% by weight of DETDA based on all
The solidificatlon of the reation mixture after the shot thereby takes place 80 quickly with extremely reactive mixtures that the mold can be opened after 5 seconds and the part can be released from the mold.
One-shot mixtures of a polyisocyanate component, aromatic diamines and polyethers with primary and/or secondary amino groups :Lead to polyurea elastomers (c.f. e.~. EP-A-0,081,701).
For use as a material for car body part~, the hi~h rigidity of the polyurea elastomers is necessary By simultaneously using glycols as co-chain lengthening agents, the flexural strength can be incre~sed; however, at the same time, the thermal properties of the ~olded parts (such as the bending modulus at high and low temperatures as well as the heat sag) are disadvant~geously changed.
Limitations are likewise placed on an increase in the proportion of diamine chain lengthening agent in the one-shot svstem. Molded parts resulting under normal processing conditions ~tool temperature 50 to 70~C), cannot be released from the mold intact even 2~ after a long period in the mold due to their brittleness. For example, with materials based on the diethyl toluylene diamine (DETDA), an increase in the flexural modulus of about 350 to 400 MPa (corresponding to 23 to 25% by weight of DETDA based on all
3~ isocyanate-reactive components of the reaction mixture) is not possible without using fillers.
Therefore, it is an obJect of the present invention to provide an improved process for the produc~ion of elastomeric moldings with a sealed surface ~2 S r~iS
layer by the reactlon injection molding process which process maintains the advantages of the known processes (particularly short periods in the mold) and allows for the production of elastomeric moldings with particularly high flexural moduli.
This object is achieved with the proce&s according ~o the invention described in more detail below. It is possible by maintaining the mold temperature at least 105C in accordance with the invention to increase the proportion of diamine chain leng~hening agent such that the production of moldings w~th a flexural modulus of up to 1000 MPa can be achieved. It is especially 6urprising that in spite of the ~igh proportion of highly reactive diamine chaln lengthening agents in the reaction mixture and the high tool temperature, no sudden formation of polyurea takes place on the hot tool surface, which would impede all flow in the case of small tool cross sections. Namely it had to be assumed that an increase in the tool temperature ~o at least 105C would render impossible the use of diamine chain lengthening agents in a higher concentration when compared with the known processes.
The process according to the invention, described in more detail below, surprisingly renders possible the production of moldings which can be released perfectly fro~ the mold, have an increased flexural modulus and are chara~terized by very good mechanical-properties and a high heat stability.
SUMMA~Y_OF THE INVENTION
The presen~ invention is directed ~o a process for the production of optionally cellular, elastomeric moldings having a density of about O . 8 to 1. 4 g/cm3 and a sealed surface layer based on polyurea elastomers optionally containing urethane groups which are prepared from ~5~i~36 a) di- or polyisocyanateA based on diisocyanatodiphenylmethane which are liquid at room temperature, and b) solutions of alkyl-substltuted diamines as chain lengthening agents in compounds having an average molecular weight of about 1800 to 12,000 wh:ich contain at least two isocyanate-reactive groups wherein co~ponents a) and b) are processed as a one-shot system according to the reaction injection molding process and the moldings are rleleased from the mold after a period in the mold of ,about 5 to 60 seconds and the mold is maintained at a telmperature of at least 105C.
DETAILED DESCRIPTION OF THE INYENTION
The products according to the invention are polyureas optionally containing urethane groups. The products prepared according to the invention are preferably polyurethane polyureas; however, it is also possible to form pure polyureas according to the invention by using urethane group-free polyisocyanates and hydroxyl group-free, aminic reaction partners.
Starting components a) to be used according to the invention are any di- or polyisocyanates based on diisocyanatodiphenylmethane which are liquid at room temperature. ~xamples inrlude 1) mixtures of 2,4- and 4,4'-diisocyanato-diphenylmethane w~ich are liquid at room temperature, which can optionally contain small proportions of 2~2'-diisocyanatodiphenylmethane;
2) polyisocyanate mixtures of the diphenyl-methane series~ which are liquid at room temperature, as obtained in known manner by the phosgenation of aniline/formaldehyde condensation produ~ts, and which in .
' 55~6S
addition to diisocyan~tes of the type mentioned under 1) contain up to about 30, preferably up to about 10% b~
weight, based on the total mixture, of higher homologues of thesP. diisocyanates containing more than two isocyanate ~roups;
3) polyisocyanates which are liquid at room temperature, contain urethane ~roups and are obtained by reacting the di- and polyisocy,anates named under l) or 2), or 4,4'-diisocyanatodiphenylmethane which is solid at room temperature, with excess quantlties of low molecular weight diols or triols, preferably polypropylene glycols h~ving a molecular weight of up to about 700, particularly reaction produc~s of
Therefore, it is an obJect of the present invention to provide an improved process for the produc~ion of elastomeric moldings with a sealed surface ~2 S r~iS
layer by the reactlon injection molding process which process maintains the advantages of the known processes (particularly short periods in the mold) and allows for the production of elastomeric moldings with particularly high flexural moduli.
This object is achieved with the proce&s according ~o the invention described in more detail below. It is possible by maintaining the mold temperature at least 105C in accordance with the invention to increase the proportion of diamine chain leng~hening agent such that the production of moldings w~th a flexural modulus of up to 1000 MPa can be achieved. It is especially 6urprising that in spite of the ~igh proportion of highly reactive diamine chaln lengthening agents in the reaction mixture and the high tool temperature, no sudden formation of polyurea takes place on the hot tool surface, which would impede all flow in the case of small tool cross sections. Namely it had to be assumed that an increase in the tool temperature ~o at least 105C would render impossible the use of diamine chain lengthening agents in a higher concentration when compared with the known processes.
The process according to the invention, described in more detail below, surprisingly renders possible the production of moldings which can be released perfectly fro~ the mold, have an increased flexural modulus and are chara~terized by very good mechanical-properties and a high heat stability.
SUMMA~Y_OF THE INVENTION
The presen~ invention is directed ~o a process for the production of optionally cellular, elastomeric moldings having a density of about O . 8 to 1. 4 g/cm3 and a sealed surface layer based on polyurea elastomers optionally containing urethane groups which are prepared from ~5~i~36 a) di- or polyisocyanateA based on diisocyanatodiphenylmethane which are liquid at room temperature, and b) solutions of alkyl-substltuted diamines as chain lengthening agents in compounds having an average molecular weight of about 1800 to 12,000 wh:ich contain at least two isocyanate-reactive groups wherein co~ponents a) and b) are processed as a one-shot system according to the reaction injection molding process and the moldings are rleleased from the mold after a period in the mold of ,about 5 to 60 seconds and the mold is maintained at a telmperature of at least 105C.
DETAILED DESCRIPTION OF THE INYENTION
The products according to the invention are polyureas optionally containing urethane groups. The products prepared according to the invention are preferably polyurethane polyureas; however, it is also possible to form pure polyureas according to the invention by using urethane group-free polyisocyanates and hydroxyl group-free, aminic reaction partners.
Starting components a) to be used according to the invention are any di- or polyisocyanates based on diisocyanatodiphenylmethane which are liquid at room temperature. ~xamples inrlude 1) mixtures of 2,4- and 4,4'-diisocyanato-diphenylmethane w~ich are liquid at room temperature, which can optionally contain small proportions of 2~2'-diisocyanatodiphenylmethane;
2) polyisocyanate mixtures of the diphenyl-methane series~ which are liquid at room temperature, as obtained in known manner by the phosgenation of aniline/formaldehyde condensation produ~ts, and which in .
' 55~6S
addition to diisocyan~tes of the type mentioned under 1) contain up to about 30, preferably up to about 10% b~
weight, based on the total mixture, of higher homologues of thesP. diisocyanates containing more than two isocyanate ~roups;
3) polyisocyanates which are liquid at room temperature, contain urethane ~roups and are obtained by reacting the di- and polyisocy,anates named under l) or 2), or 4,4'-diisocyanatodiphenylmethane which is solid at room temperature, with excess quantlties of low molecular weight diols or triols, preferably polypropylene glycols h~ving a molecular weight of up to about 700, particularly reaction produc~s of
4,4'-diisocyanatodiphenylmethane with about 0,05 to 0.3 mol, per mol of diisocyanate, of di- and/o~ tripropylene glycol;
4) modification products of 4,4'-diisocyanatodiphenylmethane or the di- and polyisocyanates named under 1) and 2), containing carbodiimide and/or uretonimine groups which are liquid at room temperature or
4) modification products of 4,4'-diisocyanatodiphenylmethane or the di- and polyisocyanates named under 1) and 2), containing carbodiimide and/or uretonimine groups which are liquid at room temperature or
5) NCO semiprepolymers which are liquid at room temperature and obtained by reacting the di- and polyisocyanates named under 1~ and 2) or by reacting pure 4,4'-diisocyanatodiphenylmethane wi~h subequivalent quantities of organic polyhydroxyl compounds at an equivalent ratio of isocyanate groups to hydroxyl groups of about l:0.01 to 1:0.5, preferably about l:O.OlS to 1:0.25, wherein polyhydroxyl compounds of the type optionally present in component b) are, for example, used as the polyhydroxyl compounds. The production of such NC0 semiprepolymers is described, for example, in US-PS 4,37~,210.
, ., 2 ~ 5 Among the particularly prefer1red polyisocyanates to be used in the process according to the invention are the react~on products of 1 mol of 4,4'-diisocyanatodiphenylmethane with about 0.05 to 0.3 mol of pclypropylene glycols having a ma~imum molecular weight of 700, preferably di- and/or tripropylene glycol, obtainable according to DE PS 1,618,380. Also particularly preferred are the carbodiimide and/or uretonimine group-containing d:iisocyanates which are liquid at room temperature and based on 4,4'-diiso-cyanatodiphenylmethane and optionally 2,4-diisocyanatodiphenylmethanle. These dii.socyanates are obtainable, for example, according to DE-PS
1,092,007, DE-OS 2,537,685, US-PS 3,384,653, US-PS
3,449,256, US PS 4,154,752 or EP-A 00,57,862.
Naturally, mixtures of the polyisocyanates named by way of example can also be used in the process according to the invention as component a).
Component b) ~o be used according to the invention is based on solutions of aromatic diamines of the type named below in compounds having a molecular weight of about 1800 to 12,000 and containing at least two isocyanate-reactive groups in a molar ratio of the diamines to ~he compounds having a molecular weight of about 180Q to 12,000 of about 3:1 to 60:1, preferably about 10:1 to 30:1.
The known compo~mds having a molecular weigh~
of about 1800 to 12,000 and containing at least two isocyanate-reactive groups are preferably polyalkylene polyethers having a molecular weight of about 1800 to 12,000, preferably about 3000 to 7000~ having hydroxyl and/or amino groups. When using polyether mixtures, individual components of the mixture can also have a molecular weight below 1800, for example be~ween 500 and ~ 8~S
1800, provided that the average molecu:Lar welght of the mixture lies within the ranges given above. However, the use of such mixtures i.s less preferred. The polyethers used according to the invention having at least two, preferably from 2 to 3 hydroxyl ~roups, are known and produced, for example, by the polymerization of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin alone, for example in the pre6ence of BF3, or by adding these epoxides, optionally in admixture or successively to starting compounds with reactive hydrogen atoms such a~s water, ~lcohols, ammonia or amines. Suitable starting compounds include ethylene glycol, propylene glycol-(1,3) or -(1,2), trimethylol propane, 4,4'-dihydroxydiphenyl propane, aniline, ethanolamine or ethylenediamine. Sucrose polyethers, as described, for example, in German Auslegeschriften 1,176,358 and 1,064~938 can also be used according to the invention. In many cases, those polyethers which predominantly contain primary hydroxyl groups (up to about 90% by weight, based on all OH groups present in the polyPther) are preferred. Polyethers modified by vinyl polymers such as those formed by the polymeriza~ion of styrene and acryloni~rile in the presence of polyethers (US Patents 3,383,351, 3,50ll~273 3,523,093, 3,110,695, ~erman Patent 1,~52,536) are also suitable, likewise OH group-containing polybutadienes.
Amon~ the preferred polyhydroxypolyethers are the alkoxylation products of the di- and/or trifunctional starter molecule previously named using ethylene oxide and/or propylene oxide either in admixture or successively. Pure polyethylene oxide polyethers are less preferred. The prefPrred polyether polyols with predominantly primary hydro~yl groups are obtained in ~2~ 5 known manner by grafting ethylene oxide onto the end o the chain.
The polyethers used according to the invention can also partially or completely contain terminal amino groups. At least about 50, preferably about 80 to 100 equivalent ~ of primary and/or secondary aromatically-or aliphatically-bound preferably aliphatically-bound amino groups, the remaining groups, if any, being primary and/or secondary, aliphatically-bound hydroxyl groups. In these compounds, the terminal amino groups can also be bound ~o the polyether chain via urethane or es~er groups. The production of these "amino polyethers" takes place in known manner. Thus, for example, an aminat~on of polyhydroxypolyethers, such as polypropylene glycol ethers, can be carried out by a reaction with ammonia in the presence of Raney nickel and hydrogen (BE-PS 634,741). US-PS 3,654,370 describes the production of polyoxyalk~lene polyamines by reacting the corresponding polyol with ammonia and hydrogen in the presence of a nickel, copper or chromium catalyst.
In DE-PS 1,193,671, the produc~ion of polyethers with amino end groups by the hydrogenation of cyanoethylated polyoxypropylene ethers is described. Further methods for the production of polyoxyalkylene tpolyether) amines 25 are described in US-PS 3,155,728, US PS 3,236,895 and FR-PS 1,551,605. The production of secondary amino end group-cont~ining polyethers i9 describea inter alia in FR-PS 1,465,708.
~igh molecular weight polyhydro~yl polYethers can also be con~erted into the corresponding anthranilic acid esters by reacting with isatoic acid anhydride, as described, for example, in DE-OS 2,019,432, DE-OS
2,619,840, US-PS 3,808,250, UP-PS 3,975,428 or US-PS
4,016,143. In this manner, polyethers with terminal aroma~ic amino groups are formed.
- . , ~ S 5~ 6~
g _ High molecular weight, terminal amino group-containing compounds are obtained according to DE-OS 2,546,536 or US-PS 3,865,791 by the reaction of NCO prepolymers based on polyhydroxyl polyethers with hydroxyl group-containing enamines, aldimines or ketimines and subsequent hydrolysis.
The preferred amlno polyethers are obtained according to DE-OS 2,948,419 by the hydroly~is of terminal isocyanate Kroup-containing compounds. In this process, polyethers preferably containing two or three hydroxyl groups are reacted with polyisocyanates to produce NCO prepolymers and in a second stage, the isocyanate groups are converted by hydrolysis into an amino group.
The "amino polyethers" which may be used according to the invention as part of component b) often produce mixtures of the compounds named by way of example and contain (on a statistical average) from two to three terminal groups which are reactive in relation to isocyanate groups.
The "amino polyethers" named by way of example can optionally also be used in the process according to the invention in admixture with amino group-free polyhydroxypolyethers of the type named by way of example in US-PS 4,218,543, although this is less preferred.
Hydroxyl group-containing polyesters, polqthioethers, polyacetalsl polycarbonates and polyester amides may also be used according to the invention for the production of homogeneous and cellular polyurethanes.
Polyhydroxyl-(polyamino)- compounds in which high molecular weigh~ polyadducts or polycondensation products are contained in a finely-dispersed or ~2.~
dissolved form can also be used according to the invention.
Naturally, mixtures of compound~ named by way of example having isocyanate-reactive groups can also be used according to the invention as part of the startin~
component b).
The diamines to be dissolved in the compounds with a molecular weight of about 1800 to 12,000 are aroma~ic diamines which contain at least two groups which are reactive with isocyanate groups are aromatic diamines and are substituted in the ortho-position to the amino groups by alkyl grou1ps. In addition, the reactivity of the amino groups in relation to isocyanates should no~ be reduced by electron-attracting substituents such as halogen, ester, ether or disulphide groups9 as in ~ethylene-bis-chloroaniline.
Pre.ferred diamines to be used are aromatic diamines which have at least one alkyi substituent in an ortho-position to each amino group, particularly those which have at least one alkyi substituent in an ortho-position to the first amino group and two alkyl substituents in an ortho-position to the second amino group, the alkyl groups preferably having 1 to 4, particularly 1 to 3 carbon atoms. Particularly preferred aromatic diamines are those which have an ethyl, n-propyl and/or isopropyl substituent in at least one ortho-position to each amino group and optionally have methyl substituents in remaining ortho-positions to the amino groups.
Examples of preferred diamines are 2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diamino-benzene, 1,3,5-triisopropyl-2,4-diaminobenzene, l-me~hyl-3,5-diethyl-2,4-diaminobenzene, l-methyl-3,5-diethyl-2,6-diaminobenzene, 4,6-dimethyl-2-ethyl--' : .
~ 6~
1,3-diaminobenzene, 3,5,3',5'-tetraethyl-494'-diaminodiphenylmethane, 3,5,3',5'-tetraisopropyl-4,4'-diaminodiphenylmethane or 3,5-diethyl-3',5'-diisopropyl-4,4'-diaminodiphenylmethane, 1,3-diamino-2-t-butyl-4,6-dimethyl-benzene, 1,3 diamino-2,4-dimethyl-6-t-butyl-benzene and mixtures of these two isomers. Particularly preferred are l-methyl-3,5-diethyl-2,4-diaminobenzene and the industrial mixtures th~ereof with up to about 35%
by weight, based on the total mixture, of l-methyl-3,5-diethyl-2,6-diaminobenzene (DETDA). Also suitable are the alkyl-substituted aromatic diamines named by way of example in US-PS 4,324,867 or in EP-A-0,069,286. In the process according to the invention, any mixtures of the alkyl-substituted aromatic diamines named by way of example can naturally also be used as part of component b).
Accordlng to a preferred embodiment of the process according to the invention, component b) is based on a solution of (i) about 23 to 45% by wei.ght, preferably about 34 to 45% by weight, based on component b), of l-methyl-3,5-diethyl-2,4-diaminobenzene or a mixture thereof with up to about 35% by weight, based on the diamine mixture, of l methyl-3,5-di~thyl-2,6-diaminobenzene in (ii) one or more polyethers with terminal hydroxyl and/or amino groups of the type named above by way of example, wherein the molar ratio of the diamines to the compounds having a molecular weight of about 1800 to 12,000 is about 3:1 to 60:1.
Among the optional au~iliaries and additives c) are catalysts (which are necessary when using hydroxyl group-containing compounds as at least a portion of component b) 9 in order to obtain molded parts having technically interesting mechanical properties after a short period of time in the mold. However, the use of :.,, ~55865 such catalysts is often unnecessary when the high molecular weight portion of component b), i.e.
par~icularly the polyethers, exclusively or predominantly contains amino groups as the isocyanate reactive groups.
Among the preferred catalysts are organic tin compounds, for example the tin(II) salts of carboxylic acids such as tin(II) acetate, tin(II)-octoate, tin(II)-ethyl hexanoate and tin(II)-laurate and the dialkyl tin salts of carboxylic acids such as dibutyl tin diacetate, dimethyl tin dilaurate, dibutyl tin dilaurate, dibutyl tln maleate or dioctyl tin diacetate.
The known tertiary amines can also be used as catalysts. Ex~mples include triethylamine, tributyl-amine, N-methyl morpholine, N-ethyl morpholine, N-cocomorpholine, N,N,N',N'-tetramethyl ethylene diamine, 1,4-diazabicyclo-(2,2,2)-octane, N-methyl-N'-diethylaminoethyl piperazine, N,N-dimethyl-benzylamine, bis~(N,N-diethylaminoethyl)-adipate, N,N-diethylbenzylamine, pentamethyldiethylene trlamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethyl-1,3-butane diamines 1~2-dimethylimidazole and 2-methyl-imidazole.
1,4-diazabicyclo-(2,2,2)-octane is a preferred catalyst of this type.
~ hen using hydroxyl group-containing reactants, the tin catalysts are used, either alone or together with the amine ca~alysts. As already explained, the use of catalysts is often dispensable w~en the high molecular weight portion of component b) exclusively or predominantly contains amino groups as isocyanate-reactive groups. In this case, the amine catalysts alone are generally used as catalysts.
: , 13 ~
Further representatives of catalysts to be used according to the invention as well a~ details of the functioning o~ the catalysts are descrlbed in the Kunststoff-Handbuch, Volume VII, published by Vieweg and H~chtlen, Carl Hanser Verlag, Munich 1966, e.g. on pages 96 to 102.
The catalysts are used, i at all, in a quantity of about 0.001 to 10% by weight, preferably about 0.05 to lZ by weight9 based on the quantity of component b).
Further auxiliaries and additives c) are blowing agen~s which are used when molded parts with a sealed surface and a cellular core are to be obt~ined.
Suitable blowing agents include water (a "chemical blowing agent," the blowing action of w~ich is based on the release of carbon dioxide) and/or "physical blowing agents," i.e., readily volatile organic substances and/or di~solved inert gases. Among ~he readily volatile organic substances are compounds which are inert according to the isocyanate addition reaction and include acetone; ethyl acetate; halogen-subs~ituted alkanes such as methYlene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane and dichloridifluoromethane; butane; hexane; heptane and diethylether. Suitable inert gases include nitrogen, air and carbon dioxide.
A blowing action can also be achieved by the addition of compounds which decompose and split off gases such as nitrogen. Examples include azocor..pounds such as azoisobutyric acid nitrile. Further examples of blowing agents as well as details o th~ use of blowing agents are described in Kunststoff-Handbuch, Volume VII, published by Vieweg and H~chtlen, Carl-Hanser~V~rlag, Munich 1966, e.g. on pages 108 and 109, 453 to 455 and 507 to 510.
Additional auxiliaries and additives c~ are surface-ac~ive additives, emulsifiers and ~oam stabilizers. The sodium salts of castor oil sulphates and also fatty acids or salts of fatty acids with amines (such as oleic acid diethylamine and stearic aci~
diethanol amine) can be used as emulsifiers.
Alkali or a~monium salts of ~ulphonic acids (such as dodecyl benzene sulphonic acid or dinaphthyl methane disulphonic acid~, fatty acids (such as ricinoleic acid) and polymeric fatty acids can be used as surface-active additi~es.
Water-soluble polyether siloxanes may be used as foam stabilizers. Generally, in these co~pounds a copolymer of ethylene oxide and propylene oxide is bound to a polydimethyl siloxane radical. Such foam stabilizers are described9 for example, in US-P5 2,764,565.
Further auxiliaries and addi~ives c) are low molecular weight, polyhydric alcohols w~ich can optionally be used for modifying the properties of the moldings. The polyhydric alcohols are used in addition to the amine chain leng~hening agents of component b) in quantities of up to about 50 equivalent ~, based on the amino groups of the low molecular weight diamines of component b). Examples include ethylene glycol, butanediol-1,4, hexamethylene glycol trimethylol propane and mix~ures thereof. Additional examples include addition products having a molecular weight below 500, of alkylene oxides, particularly propylene oxide, s~ar~ed on such polyhydric alcohols or also on polyvalent amines such as ethylene diamine or die~hylene triamine.
~Z ~ ~ 6 - 15 ~
Auxiliaries and addi~ives c) also include c5) the known "internal mold release ~gents" described, for example, in DE-OS 1,953,637, DE-OS 2,122,670, DE-OS
2,431,968 or DE-OS 2,404,310. Among these are particularly the æalts (having at least 25 aliphatic carbon atoms) of fatty acids (having at least 12 aliphatic carbon atoms~ and pr:imary mono-, dl- or polyamines having two and more carbon atoms or amide or ester group-containing amines which have at l~ast one primary, secondary or tertiary amino group; ~aturated and/or unsaturated COOH- and/o.r OH group-containing esters of mono and/or polyfunctional carboxylic acids and polyfunctlonal alcohols with OH or acid numbers of at least 5; ester-type reaction products of ricinoleic acid and long-chain fatty acids~ ~alts of carboxylic acids and tertiary amines; and natural and/or synthetlc oils, fats or waxes.
Among the preferred internal release agents are (i) ester group-containing condensation products of ricinoleic acid and mono or polyhydric alcohols with an acid number below 5, as described, for example, in DE-OS
3,436,163, (ii) the metal salts, preferably zinc salts of aliphatic carboxylic acids having at least 12 carbon atoms, par~icularly zinc stearate and (iii) combinations 2~ of the release agents named under (i) and (ii).
Further internal mold release agents include reaction products of fa~ty acid esters and polyisocyanates (DE-OS 2,319,648), reaction products of reactive hydrogen atom-containing polysiloxanes and mono 3U and/or polyisocyanates tDE-OS 2,363,452), esters of hydroxymethyl group-containing polysiloxanes with mono and/or polycarboxylic acids (DE-OS 2,363,452) a~d salts of amino group-containing polysiloxanes and fatty acids ~DE-OS 2,427,273 and 2,445,648).
.
5 ~6 In prlnciple, mixtures of internal mold release agents name~ by w~y o example ean also be used. The lnternal mold release agents are used, if a~ all, in quantities of about 0.1 to 15% by weight, based on the to~al reaction mixture.
Further auxiliaries and additives c) include eell regulators such as paraffins, fatty alcohols and dimethyl polysiloxanes as well as pigments, dyes and flame protection agents, such as tris-chloroethyl phosphate, ammonium phosphate and ammonium polyphospha~e. Also included are stabilizers against aging and weathering influences, plasticiæer~ and fungistatically and bacteriostatically actlve substances as well as fillers such as barium sulphate, glass fibers, kieselguhr and chal k .
Further examples of surface-active auxiliaries and foam stabilizers, 1ame retarding substances, plasticizers, dyes and fillers and fungistatically and bacteriostatically active substances, as well as details of the use and functioning of these additives are described in Kunststoff-Handbuch, Volume VI, published by Vieweg and H~ctlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 103 to 113.
The auxiliaries a~d additives optionally used according to the process of the invention are preferably incorporated into component b) before carrying out the process according to the invention.
In the process according to the inv~ntion, the quantity of polyisocyanate is preferably calcula~ed such that an isocyanate index of about 70 to 130, particularly about 90 to 110 is present in the reaction mixture. Isocyanate index refers to the quotient of the number of isocyanate groups and the number of isocyanate-reactive ~roups, multiplied by lO0. In ':
.
~S5~fi~5 carrying out the process according to the invention, the known reaction in~ect~on molding process (RIM process) is employed. The quantity of the optionally foamable mixture introduced into the mold is calculated such that the molded product has a densitY of about 0.8 to l.4 g/cm3, preferably about 0.9 to l.3 g/cm3. Densities of grea~er than about 1.2 g/cm3 can particularly occur when heavy additives are used in the process according to the invention. The molds to be u~ed in the process according to the invention are the sealed metal molds known for reaction injection molding proceæs where the inner ~alls of which can optionally be coated with "external mold release agents" such as those based on wax, soap or silicone.
A temperature of about lO~ to 70C, preerably about 30 to 50C is selected as the starting temperature of the mlxture introduced into the mold.
The mold temperature essential to the invention refers to the temperature of the inner wall of ~he mold before filling the mold and is about 105 to 150C, preferably about llO to 130C.
The molded products obtained according to the process of the invention can be released from the mold after a period in the mold of about 5 to 60 seconds and are particularly suitable for the production of flexible motor car bumpers or car body parts.
The inven~ion iæ further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
,' .
~2'~ 3 EXAMPLES
The processing of the formulations descrlbed ln the following examples took place by means of the reaction injection molding (RIM) process.
The polyol (polyamine)- and polyisocyanate components were supplied to a high pressure metering assembly and after intensive mixing in a force-controlled mixing head, compressed into a temperable hot me~al mold in t!he shorte~t time possibLe.
The inner wall of the mold was coated with a ready for use commercial external mold release agent based on wax and silicon, (Fluoricon 36-134, by the firm Acmos, Bremen).
The plate mold of steel allowed for the production of tes~ plates with measurements of 535 x 300 x 3.5 mm. Filling the tool took place fro~ the side wall via a columnar feed.
EXA~LE 1 70.9 parts by weight of a polyether having an OH number of 28, obtained by adding 83% by weight of propylene oxide and subsequently adding 17~ by weight of ethylene oxide ~o trimethylol ~rop~ne, 2$.6 parts by weight of a mixture of 65 parts by weight of l-methyl-3,5-diethyl-2,4-di~minoben~ene and 3S parts by weight of l~methyl--3,5-diethyl-2,6-diaminobenzene, 0,3 parts by weight of triethylene diamine and 0.2 parts by weight of dimethyl tin dilaurate were combined to form a polyol component and processed according to the RIM
process with 65.5 parts by weight of a reac~ion product of tripropylene glycol and 4,4'-diphenyl methane diisocyanate (23% by weight of NCO). The ~emperature of the crude materials was 45C and a period in the mold of 30 seconds was selected.
The mold tempera~ure was îni~ially adjusted to 65C, ~hen to 100C. Under these conditions; a brittle molded part resulted at both temperatures which either broke on removal from the mold or was already cracked in the mold.
When the reaction was conducted at a mold temperature of 115C, the part released perfectly from the mold. During cooling of the molded part, no "brittle phase" was passed through.
The following mechanical values were determined thereafter on the test plate (after tempering for 45 10 minutes at 120C):
bulk density 112~ kg/m3 (DIN 53 420) tensile strength 19.1 MPa DIN 53 504) 15 breakin8 elongation 319 %
(~IN 53 504) Shore D 68 flexural modulus RT 451 MPa (ASTM-D 790-71) +120C 272 MPa E~MPLE 2 66.2 parts by weight of the polyether in Example 1, 33.3 parts by weight of a mi~ture of 65 parts by weight of l-methyl-395-diethyl-2,4 diaminobenzene and 35 part~ by weight of l-methyl-3,5-diethyl-296-diamino-benzene, 0.3 parts by weight of triethylene diamine and0.2 parts by weight of timethyl tin dilaurate were combined to ~orm a polyol component and processed according to the RIM process with 74.8 parts by weight of the semiprepolymer (23% of NCO) from Example 1, The ~emperature of the crude material~ was 45C
and a period in the mold of 30 seconds was selected.
Both at a tool temperature of 65C and also after raising the temperature to 100C, the molded parts were already broken at the time of opening of the mold. When ~ 52~o -the re~ction was carried Ollt at a tool temperature of 115C the parts released perfectly from the mold. The following mechanical values were determined on the test plate (after tempering for 45 minutes at 120C~:
5 bulk densitY 1131 kg/m3 (DIN 53 420) tensile strength 26.5 MPa (DIN 53 504) breaking elongation 287 %
(DIN 53 504) Shore D 73 flexural modulus RT 665 MPa (ASTM-D-790-71) ~120C 396 MPa 58.5 parts by weight of a polyethertriol having an OH number of 27, produced by the propo~ylation of trimethylol propane and subsequent ethoxylation of the propoxylation product (weight ratio PO:EO = 78:22), 41.0 parts by weight of a mixture of 65 parts by weight of 1-methyl-3,5-diethyl-2,4-diaminobenzene and 35 parts by weight of l-methyl-3,5-diethyl-2,6-diaminobenzene, 2.0 parts by weight of an adduct of 5 mol of propylene oxide started on 1 mol of ethylene diamine (OH number 630), 0.3 parts by weight of triethylene diamine and 0.2 parts by weight o~ dimethyl tin dilaurate were combined to form a polyol component and processed according to the RIM process with 99.3 parts by weight of a ~emiprepolymer having an NCO content of 24.5% and prepared by reacting a polyisocyanate mixture of the diphenyl methane series containing 82% by weight of 4,4'-diisocyanato diphenylmethane, 8% by weight of 2,4'-diisocyanato-diphenyl methane and 10% by weight of tri and higher functional polyisocyanates with dipropylene glycol. The temperature of the crude ~ 5~ ~5 materials was 45C and a period in the mold of 30 second~ was selected.
At a mold temperature of 120~C, a molded part with good green strength was released.
The polyurethane polyurea elastomers had the following mechanical properties without tempering:
bulk densitY 1142 kg/m3 (DIN 53 420~
tensile strength 42.7 MPa (DIN 53 504) lO breaking elongatlon 75 %
(DIN 53 504) Shore D 79 flexural modulus RT 994 MPa (ASTM-D-790-71 +120C 698 MP~
Although the invention has been described in detail in the foregolng for the purpose of illustra~ion, it is to be unders~ood 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 2C spirit and scope of the invention except as it may be limited by the claims.
,~ , .
, ., 2 ~ 5 Among the particularly prefer1red polyisocyanates to be used in the process according to the invention are the react~on products of 1 mol of 4,4'-diisocyanatodiphenylmethane with about 0.05 to 0.3 mol of pclypropylene glycols having a ma~imum molecular weight of 700, preferably di- and/or tripropylene glycol, obtainable according to DE PS 1,618,380. Also particularly preferred are the carbodiimide and/or uretonimine group-containing d:iisocyanates which are liquid at room temperature and based on 4,4'-diiso-cyanatodiphenylmethane and optionally 2,4-diisocyanatodiphenylmethanle. These dii.socyanates are obtainable, for example, according to DE-PS
1,092,007, DE-OS 2,537,685, US-PS 3,384,653, US-PS
3,449,256, US PS 4,154,752 or EP-A 00,57,862.
Naturally, mixtures of the polyisocyanates named by way of example can also be used in the process according to the invention as component a).
Component b) ~o be used according to the invention is based on solutions of aromatic diamines of the type named below in compounds having a molecular weight of about 1800 to 12,000 and containing at least two isocyanate-reactive groups in a molar ratio of the diamines to ~he compounds having a molecular weight of about 180Q to 12,000 of about 3:1 to 60:1, preferably about 10:1 to 30:1.
The known compo~mds having a molecular weigh~
of about 1800 to 12,000 and containing at least two isocyanate-reactive groups are preferably polyalkylene polyethers having a molecular weight of about 1800 to 12,000, preferably about 3000 to 7000~ having hydroxyl and/or amino groups. When using polyether mixtures, individual components of the mixture can also have a molecular weight below 1800, for example be~ween 500 and ~ 8~S
1800, provided that the average molecu:Lar welght of the mixture lies within the ranges given above. However, the use of such mixtures i.s less preferred. The polyethers used according to the invention having at least two, preferably from 2 to 3 hydroxyl ~roups, are known and produced, for example, by the polymerization of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin alone, for example in the pre6ence of BF3, or by adding these epoxides, optionally in admixture or successively to starting compounds with reactive hydrogen atoms such a~s water, ~lcohols, ammonia or amines. Suitable starting compounds include ethylene glycol, propylene glycol-(1,3) or -(1,2), trimethylol propane, 4,4'-dihydroxydiphenyl propane, aniline, ethanolamine or ethylenediamine. Sucrose polyethers, as described, for example, in German Auslegeschriften 1,176,358 and 1,064~938 can also be used according to the invention. In many cases, those polyethers which predominantly contain primary hydroxyl groups (up to about 90% by weight, based on all OH groups present in the polyPther) are preferred. Polyethers modified by vinyl polymers such as those formed by the polymeriza~ion of styrene and acryloni~rile in the presence of polyethers (US Patents 3,383,351, 3,50ll~273 3,523,093, 3,110,695, ~erman Patent 1,~52,536) are also suitable, likewise OH group-containing polybutadienes.
Amon~ the preferred polyhydroxypolyethers are the alkoxylation products of the di- and/or trifunctional starter molecule previously named using ethylene oxide and/or propylene oxide either in admixture or successively. Pure polyethylene oxide polyethers are less preferred. The prefPrred polyether polyols with predominantly primary hydro~yl groups are obtained in ~2~ 5 known manner by grafting ethylene oxide onto the end o the chain.
The polyethers used according to the invention can also partially or completely contain terminal amino groups. At least about 50, preferably about 80 to 100 equivalent ~ of primary and/or secondary aromatically-or aliphatically-bound preferably aliphatically-bound amino groups, the remaining groups, if any, being primary and/or secondary, aliphatically-bound hydroxyl groups. In these compounds, the terminal amino groups can also be bound ~o the polyether chain via urethane or es~er groups. The production of these "amino polyethers" takes place in known manner. Thus, for example, an aminat~on of polyhydroxypolyethers, such as polypropylene glycol ethers, can be carried out by a reaction with ammonia in the presence of Raney nickel and hydrogen (BE-PS 634,741). US-PS 3,654,370 describes the production of polyoxyalk~lene polyamines by reacting the corresponding polyol with ammonia and hydrogen in the presence of a nickel, copper or chromium catalyst.
In DE-PS 1,193,671, the produc~ion of polyethers with amino end groups by the hydrogenation of cyanoethylated polyoxypropylene ethers is described. Further methods for the production of polyoxyalkylene tpolyether) amines 25 are described in US-PS 3,155,728, US PS 3,236,895 and FR-PS 1,551,605. The production of secondary amino end group-cont~ining polyethers i9 describea inter alia in FR-PS 1,465,708.
~igh molecular weight polyhydro~yl polYethers can also be con~erted into the corresponding anthranilic acid esters by reacting with isatoic acid anhydride, as described, for example, in DE-OS 2,019,432, DE-OS
2,619,840, US-PS 3,808,250, UP-PS 3,975,428 or US-PS
4,016,143. In this manner, polyethers with terminal aroma~ic amino groups are formed.
- . , ~ S 5~ 6~
g _ High molecular weight, terminal amino group-containing compounds are obtained according to DE-OS 2,546,536 or US-PS 3,865,791 by the reaction of NCO prepolymers based on polyhydroxyl polyethers with hydroxyl group-containing enamines, aldimines or ketimines and subsequent hydrolysis.
The preferred amlno polyethers are obtained according to DE-OS 2,948,419 by the hydroly~is of terminal isocyanate Kroup-containing compounds. In this process, polyethers preferably containing two or three hydroxyl groups are reacted with polyisocyanates to produce NCO prepolymers and in a second stage, the isocyanate groups are converted by hydrolysis into an amino group.
The "amino polyethers" which may be used according to the invention as part of component b) often produce mixtures of the compounds named by way of example and contain (on a statistical average) from two to three terminal groups which are reactive in relation to isocyanate groups.
The "amino polyethers" named by way of example can optionally also be used in the process according to the invention in admixture with amino group-free polyhydroxypolyethers of the type named by way of example in US-PS 4,218,543, although this is less preferred.
Hydroxyl group-containing polyesters, polqthioethers, polyacetalsl polycarbonates and polyester amides may also be used according to the invention for the production of homogeneous and cellular polyurethanes.
Polyhydroxyl-(polyamino)- compounds in which high molecular weigh~ polyadducts or polycondensation products are contained in a finely-dispersed or ~2.~
dissolved form can also be used according to the invention.
Naturally, mixtures of compound~ named by way of example having isocyanate-reactive groups can also be used according to the invention as part of the startin~
component b).
The diamines to be dissolved in the compounds with a molecular weight of about 1800 to 12,000 are aroma~ic diamines which contain at least two groups which are reactive with isocyanate groups are aromatic diamines and are substituted in the ortho-position to the amino groups by alkyl grou1ps. In addition, the reactivity of the amino groups in relation to isocyanates should no~ be reduced by electron-attracting substituents such as halogen, ester, ether or disulphide groups9 as in ~ethylene-bis-chloroaniline.
Pre.ferred diamines to be used are aromatic diamines which have at least one alkyi substituent in an ortho-position to each amino group, particularly those which have at least one alkyi substituent in an ortho-position to the first amino group and two alkyl substituents in an ortho-position to the second amino group, the alkyl groups preferably having 1 to 4, particularly 1 to 3 carbon atoms. Particularly preferred aromatic diamines are those which have an ethyl, n-propyl and/or isopropyl substituent in at least one ortho-position to each amino group and optionally have methyl substituents in remaining ortho-positions to the amino groups.
Examples of preferred diamines are 2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diamino-benzene, 1,3,5-triisopropyl-2,4-diaminobenzene, l-me~hyl-3,5-diethyl-2,4-diaminobenzene, l-methyl-3,5-diethyl-2,6-diaminobenzene, 4,6-dimethyl-2-ethyl--' : .
~ 6~
1,3-diaminobenzene, 3,5,3',5'-tetraethyl-494'-diaminodiphenylmethane, 3,5,3',5'-tetraisopropyl-4,4'-diaminodiphenylmethane or 3,5-diethyl-3',5'-diisopropyl-4,4'-diaminodiphenylmethane, 1,3-diamino-2-t-butyl-4,6-dimethyl-benzene, 1,3 diamino-2,4-dimethyl-6-t-butyl-benzene and mixtures of these two isomers. Particularly preferred are l-methyl-3,5-diethyl-2,4-diaminobenzene and the industrial mixtures th~ereof with up to about 35%
by weight, based on the total mixture, of l-methyl-3,5-diethyl-2,6-diaminobenzene (DETDA). Also suitable are the alkyl-substituted aromatic diamines named by way of example in US-PS 4,324,867 or in EP-A-0,069,286. In the process according to the invention, any mixtures of the alkyl-substituted aromatic diamines named by way of example can naturally also be used as part of component b).
Accordlng to a preferred embodiment of the process according to the invention, component b) is based on a solution of (i) about 23 to 45% by wei.ght, preferably about 34 to 45% by weight, based on component b), of l-methyl-3,5-diethyl-2,4-diaminobenzene or a mixture thereof with up to about 35% by weight, based on the diamine mixture, of l methyl-3,5-di~thyl-2,6-diaminobenzene in (ii) one or more polyethers with terminal hydroxyl and/or amino groups of the type named above by way of example, wherein the molar ratio of the diamines to the compounds having a molecular weight of about 1800 to 12,000 is about 3:1 to 60:1.
Among the optional au~iliaries and additives c) are catalysts (which are necessary when using hydroxyl group-containing compounds as at least a portion of component b) 9 in order to obtain molded parts having technically interesting mechanical properties after a short period of time in the mold. However, the use of :.,, ~55865 such catalysts is often unnecessary when the high molecular weight portion of component b), i.e.
par~icularly the polyethers, exclusively or predominantly contains amino groups as the isocyanate reactive groups.
Among the preferred catalysts are organic tin compounds, for example the tin(II) salts of carboxylic acids such as tin(II) acetate, tin(II)-octoate, tin(II)-ethyl hexanoate and tin(II)-laurate and the dialkyl tin salts of carboxylic acids such as dibutyl tin diacetate, dimethyl tin dilaurate, dibutyl tin dilaurate, dibutyl tln maleate or dioctyl tin diacetate.
The known tertiary amines can also be used as catalysts. Ex~mples include triethylamine, tributyl-amine, N-methyl morpholine, N-ethyl morpholine, N-cocomorpholine, N,N,N',N'-tetramethyl ethylene diamine, 1,4-diazabicyclo-(2,2,2)-octane, N-methyl-N'-diethylaminoethyl piperazine, N,N-dimethyl-benzylamine, bis~(N,N-diethylaminoethyl)-adipate, N,N-diethylbenzylamine, pentamethyldiethylene trlamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethyl-1,3-butane diamines 1~2-dimethylimidazole and 2-methyl-imidazole.
1,4-diazabicyclo-(2,2,2)-octane is a preferred catalyst of this type.
~ hen using hydroxyl group-containing reactants, the tin catalysts are used, either alone or together with the amine ca~alysts. As already explained, the use of catalysts is often dispensable w~en the high molecular weight portion of component b) exclusively or predominantly contains amino groups as isocyanate-reactive groups. In this case, the amine catalysts alone are generally used as catalysts.
: , 13 ~
Further representatives of catalysts to be used according to the invention as well a~ details of the functioning o~ the catalysts are descrlbed in the Kunststoff-Handbuch, Volume VII, published by Vieweg and H~chtlen, Carl Hanser Verlag, Munich 1966, e.g. on pages 96 to 102.
The catalysts are used, i at all, in a quantity of about 0.001 to 10% by weight, preferably about 0.05 to lZ by weight9 based on the quantity of component b).
Further auxiliaries and additives c) are blowing agen~s which are used when molded parts with a sealed surface and a cellular core are to be obt~ined.
Suitable blowing agents include water (a "chemical blowing agent," the blowing action of w~ich is based on the release of carbon dioxide) and/or "physical blowing agents," i.e., readily volatile organic substances and/or di~solved inert gases. Among ~he readily volatile organic substances are compounds which are inert according to the isocyanate addition reaction and include acetone; ethyl acetate; halogen-subs~ituted alkanes such as methYlene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane and dichloridifluoromethane; butane; hexane; heptane and diethylether. Suitable inert gases include nitrogen, air and carbon dioxide.
A blowing action can also be achieved by the addition of compounds which decompose and split off gases such as nitrogen. Examples include azocor..pounds such as azoisobutyric acid nitrile. Further examples of blowing agents as well as details o th~ use of blowing agents are described in Kunststoff-Handbuch, Volume VII, published by Vieweg and H~chtlen, Carl-Hanser~V~rlag, Munich 1966, e.g. on pages 108 and 109, 453 to 455 and 507 to 510.
Additional auxiliaries and additives c~ are surface-ac~ive additives, emulsifiers and ~oam stabilizers. The sodium salts of castor oil sulphates and also fatty acids or salts of fatty acids with amines (such as oleic acid diethylamine and stearic aci~
diethanol amine) can be used as emulsifiers.
Alkali or a~monium salts of ~ulphonic acids (such as dodecyl benzene sulphonic acid or dinaphthyl methane disulphonic acid~, fatty acids (such as ricinoleic acid) and polymeric fatty acids can be used as surface-active additi~es.
Water-soluble polyether siloxanes may be used as foam stabilizers. Generally, in these co~pounds a copolymer of ethylene oxide and propylene oxide is bound to a polydimethyl siloxane radical. Such foam stabilizers are described9 for example, in US-P5 2,764,565.
Further auxiliaries and addi~ives c) are low molecular weight, polyhydric alcohols w~ich can optionally be used for modifying the properties of the moldings. The polyhydric alcohols are used in addition to the amine chain leng~hening agents of component b) in quantities of up to about 50 equivalent ~, based on the amino groups of the low molecular weight diamines of component b). Examples include ethylene glycol, butanediol-1,4, hexamethylene glycol trimethylol propane and mix~ures thereof. Additional examples include addition products having a molecular weight below 500, of alkylene oxides, particularly propylene oxide, s~ar~ed on such polyhydric alcohols or also on polyvalent amines such as ethylene diamine or die~hylene triamine.
~Z ~ ~ 6 - 15 ~
Auxiliaries and addi~ives c) also include c5) the known "internal mold release ~gents" described, for example, in DE-OS 1,953,637, DE-OS 2,122,670, DE-OS
2,431,968 or DE-OS 2,404,310. Among these are particularly the æalts (having at least 25 aliphatic carbon atoms) of fatty acids (having at least 12 aliphatic carbon atoms~ and pr:imary mono-, dl- or polyamines having two and more carbon atoms or amide or ester group-containing amines which have at l~ast one primary, secondary or tertiary amino group; ~aturated and/or unsaturated COOH- and/o.r OH group-containing esters of mono and/or polyfunctional carboxylic acids and polyfunctlonal alcohols with OH or acid numbers of at least 5; ester-type reaction products of ricinoleic acid and long-chain fatty acids~ ~alts of carboxylic acids and tertiary amines; and natural and/or synthetlc oils, fats or waxes.
Among the preferred internal release agents are (i) ester group-containing condensation products of ricinoleic acid and mono or polyhydric alcohols with an acid number below 5, as described, for example, in DE-OS
3,436,163, (ii) the metal salts, preferably zinc salts of aliphatic carboxylic acids having at least 12 carbon atoms, par~icularly zinc stearate and (iii) combinations 2~ of the release agents named under (i) and (ii).
Further internal mold release agents include reaction products of fa~ty acid esters and polyisocyanates (DE-OS 2,319,648), reaction products of reactive hydrogen atom-containing polysiloxanes and mono 3U and/or polyisocyanates tDE-OS 2,363,452), esters of hydroxymethyl group-containing polysiloxanes with mono and/or polycarboxylic acids (DE-OS 2,363,452) a~d salts of amino group-containing polysiloxanes and fatty acids ~DE-OS 2,427,273 and 2,445,648).
.
5 ~6 In prlnciple, mixtures of internal mold release agents name~ by w~y o example ean also be used. The lnternal mold release agents are used, if a~ all, in quantities of about 0.1 to 15% by weight, based on the to~al reaction mixture.
Further auxiliaries and additives c) include eell regulators such as paraffins, fatty alcohols and dimethyl polysiloxanes as well as pigments, dyes and flame protection agents, such as tris-chloroethyl phosphate, ammonium phosphate and ammonium polyphospha~e. Also included are stabilizers against aging and weathering influences, plasticiæer~ and fungistatically and bacteriostatically actlve substances as well as fillers such as barium sulphate, glass fibers, kieselguhr and chal k .
Further examples of surface-active auxiliaries and foam stabilizers, 1ame retarding substances, plasticizers, dyes and fillers and fungistatically and bacteriostatically active substances, as well as details of the use and functioning of these additives are described in Kunststoff-Handbuch, Volume VI, published by Vieweg and H~ctlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 103 to 113.
The auxiliaries a~d additives optionally used according to the process of the invention are preferably incorporated into component b) before carrying out the process according to the invention.
In the process according to the inv~ntion, the quantity of polyisocyanate is preferably calcula~ed such that an isocyanate index of about 70 to 130, particularly about 90 to 110 is present in the reaction mixture. Isocyanate index refers to the quotient of the number of isocyanate groups and the number of isocyanate-reactive ~roups, multiplied by lO0. In ':
.
~S5~fi~5 carrying out the process according to the invention, the known reaction in~ect~on molding process (RIM process) is employed. The quantity of the optionally foamable mixture introduced into the mold is calculated such that the molded product has a densitY of about 0.8 to l.4 g/cm3, preferably about 0.9 to l.3 g/cm3. Densities of grea~er than about 1.2 g/cm3 can particularly occur when heavy additives are used in the process according to the invention. The molds to be u~ed in the process according to the invention are the sealed metal molds known for reaction injection molding proceæs where the inner ~alls of which can optionally be coated with "external mold release agents" such as those based on wax, soap or silicone.
A temperature of about lO~ to 70C, preerably about 30 to 50C is selected as the starting temperature of the mlxture introduced into the mold.
The mold temperature essential to the invention refers to the temperature of the inner wall of ~he mold before filling the mold and is about 105 to 150C, preferably about llO to 130C.
The molded products obtained according to the process of the invention can be released from the mold after a period in the mold of about 5 to 60 seconds and are particularly suitable for the production of flexible motor car bumpers or car body parts.
The inven~ion iæ further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
,' .
~2'~ 3 EXAMPLES
The processing of the formulations descrlbed ln the following examples took place by means of the reaction injection molding (RIM) process.
The polyol (polyamine)- and polyisocyanate components were supplied to a high pressure metering assembly and after intensive mixing in a force-controlled mixing head, compressed into a temperable hot me~al mold in t!he shorte~t time possibLe.
The inner wall of the mold was coated with a ready for use commercial external mold release agent based on wax and silicon, (Fluoricon 36-134, by the firm Acmos, Bremen).
The plate mold of steel allowed for the production of tes~ plates with measurements of 535 x 300 x 3.5 mm. Filling the tool took place fro~ the side wall via a columnar feed.
EXA~LE 1 70.9 parts by weight of a polyether having an OH number of 28, obtained by adding 83% by weight of propylene oxide and subsequently adding 17~ by weight of ethylene oxide ~o trimethylol ~rop~ne, 2$.6 parts by weight of a mixture of 65 parts by weight of l-methyl-3,5-diethyl-2,4-di~minoben~ene and 3S parts by weight of l~methyl--3,5-diethyl-2,6-diaminobenzene, 0,3 parts by weight of triethylene diamine and 0.2 parts by weight of dimethyl tin dilaurate were combined to form a polyol component and processed according to the RIM
process with 65.5 parts by weight of a reac~ion product of tripropylene glycol and 4,4'-diphenyl methane diisocyanate (23% by weight of NCO). The ~emperature of the crude materials was 45C and a period in the mold of 30 seconds was selected.
The mold tempera~ure was îni~ially adjusted to 65C, ~hen to 100C. Under these conditions; a brittle molded part resulted at both temperatures which either broke on removal from the mold or was already cracked in the mold.
When the reaction was conducted at a mold temperature of 115C, the part released perfectly from the mold. During cooling of the molded part, no "brittle phase" was passed through.
The following mechanical values were determined thereafter on the test plate (after tempering for 45 10 minutes at 120C):
bulk density 112~ kg/m3 (DIN 53 420) tensile strength 19.1 MPa DIN 53 504) 15 breakin8 elongation 319 %
(~IN 53 504) Shore D 68 flexural modulus RT 451 MPa (ASTM-D 790-71) +120C 272 MPa E~MPLE 2 66.2 parts by weight of the polyether in Example 1, 33.3 parts by weight of a mi~ture of 65 parts by weight of l-methyl-395-diethyl-2,4 diaminobenzene and 35 part~ by weight of l-methyl-3,5-diethyl-296-diamino-benzene, 0.3 parts by weight of triethylene diamine and0.2 parts by weight of timethyl tin dilaurate were combined to ~orm a polyol component and processed according to the RIM process with 74.8 parts by weight of the semiprepolymer (23% of NCO) from Example 1, The ~emperature of the crude material~ was 45C
and a period in the mold of 30 seconds was selected.
Both at a tool temperature of 65C and also after raising the temperature to 100C, the molded parts were already broken at the time of opening of the mold. When ~ 52~o -the re~ction was carried Ollt at a tool temperature of 115C the parts released perfectly from the mold. The following mechanical values were determined on the test plate (after tempering for 45 minutes at 120C~:
5 bulk densitY 1131 kg/m3 (DIN 53 420) tensile strength 26.5 MPa (DIN 53 504) breaking elongation 287 %
(DIN 53 504) Shore D 73 flexural modulus RT 665 MPa (ASTM-D-790-71) ~120C 396 MPa 58.5 parts by weight of a polyethertriol having an OH number of 27, produced by the propo~ylation of trimethylol propane and subsequent ethoxylation of the propoxylation product (weight ratio PO:EO = 78:22), 41.0 parts by weight of a mixture of 65 parts by weight of 1-methyl-3,5-diethyl-2,4-diaminobenzene and 35 parts by weight of l-methyl-3,5-diethyl-2,6-diaminobenzene, 2.0 parts by weight of an adduct of 5 mol of propylene oxide started on 1 mol of ethylene diamine (OH number 630), 0.3 parts by weight of triethylene diamine and 0.2 parts by weight o~ dimethyl tin dilaurate were combined to form a polyol component and processed according to the RIM process with 99.3 parts by weight of a ~emiprepolymer having an NCO content of 24.5% and prepared by reacting a polyisocyanate mixture of the diphenyl methane series containing 82% by weight of 4,4'-diisocyanato diphenylmethane, 8% by weight of 2,4'-diisocyanato-diphenyl methane and 10% by weight of tri and higher functional polyisocyanates with dipropylene glycol. The temperature of the crude ~ 5~ ~5 materials was 45C and a period in the mold of 30 second~ was selected.
At a mold temperature of 120~C, a molded part with good green strength was released.
The polyurethane polyurea elastomers had the following mechanical properties without tempering:
bulk densitY 1142 kg/m3 (DIN 53 420~
tensile strength 42.7 MPa (DIN 53 504) lO breaking elongatlon 75 %
(DIN 53 504) Shore D 79 flexural modulus RT 994 MPa (ASTM-D-790-71 +120C 698 MP~
Although the invention has been described in detail in the foregolng for the purpose of illustra~ion, it is to be unders~ood 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 2C spirit and scope of the invention except as it may be limited by the claims.
,~ , .
Claims (6)
1. A process for the production of an optionally cellular, elastomeric molding having a density of about 0.8 to 1.4 g/cm3 and a sealed surface layer based on a polyurea elastomer optionally containing urethane groups comprising the reaction product of a) a di- or polyisocyanate which is liquid at room temperature and based on diisocyanato-diphenylmethane and b) a solution of an alkyl-substituted diamine as chain lengthening agent in a compound having an (average) molecular weight of about 1800 to 12,000 which contains at least two isocyanate-reactive groups wherein components a) and b) are processed as a one-shot system according to the reaction injection molding process, the molded product is released from the mold after a period in the mold of about 5 to 60 seconds and the mold is maintained at a temperature of at least 105°C.
2. The process according to Claim 1 wherein the molar ratio of said diamine to said compound is about 3:1 to 60:1.
3. The process according to Claim 1 wherein said diamine is 1-methyl-3,5-diethyl-2,4-diaminobenzene or a mixture thereof with l-methyl-3,5-diethyl-2,6-diamino benzene and said diamine is present in a quantity of about 23 to 45% by weight, based on component b).
4. The process according to Claim 2 wherein said diamine is 1-methyl-3,5-diethyl-2,4-diaminobenzene or a mixture thereof with 1-methyl-3,5-diethyl-2,6-diamino benzene and said diamine is present in a quantity of about 23 to 45% by weight, based on component b).
5. The process according to Claim 3 wherein said diamine is present in a quantity of about 34 to 45%
by weight, based on component b).
by weight, based on component b).
6. The process according to Claim 4 wherein said diamine is present in a quantity of about 34 to 45%
by weight, based on component b).
by weight, based on component b).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3520326.9 | 1985-06-07 | ||
| DE19853520326 DE3520326A1 (en) | 1985-06-07 | 1985-06-07 | METHOD FOR PRODUCING ELASTIC MOLDED BODIES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1255865A true CA1255865A (en) | 1989-06-20 |
Family
ID=6272601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000509132A Expired CA1255865A (en) | 1985-06-07 | 1986-05-14 | Process for the production of elastic moldings |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0204246B1 (en) |
| JP (1) | JPS61287920A (en) |
| KR (1) | KR870000162A (en) |
| AR (1) | AR240054A1 (en) |
| AT (1) | ATE49222T1 (en) |
| AU (1) | AU577195B2 (en) |
| BR (1) | BR8602621A (en) |
| CA (1) | CA1255865A (en) |
| DE (2) | DE3520326A1 (en) |
| ES (1) | ES8707981A1 (en) |
| ZA (1) | ZA864233B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3613973A1 (en) * | 1986-04-25 | 1987-10-29 | Bayer Ag | METHOD FOR PRODUCING POLYHARMONIC FOAM MOLDED PARTS |
| DE3703739A1 (en) * | 1987-02-07 | 1988-08-18 | Bayer Ag | METHOD FOR THE PRODUCTION OF MOLDED BODIES, MIXTURES SUITABLE FOR THEM FROM REACTIONABLE COMPOUNDS TO ISOCYANATE GROUPS AND THE MOLDED BODIES OBTAINED BY THE METHOD |
| BR8807445A (en) * | 1987-04-07 | 1990-05-15 | Dow Chemical Co | FLEXIBLE POLYURETH OR POLYURETH-POLYURETHANE FOAMS, PREPARED FROM COMPOUNDS FINISHED IN AMINE OF HIGH EQUIVALENT WEIGHT, AND PROCESS FOR THE PREPARATION OF THE SAME |
| DE4203215A1 (en) * | 1992-02-05 | 1993-08-12 | Bayer Ag | METHOD FOR PRODUCING MOLDED BODIES |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1479890A (en) * | 1965-05-14 | 1967-05-05 | Bayer Ag | Process for the preparation of crosslinked plastics using the polyaddition process of isocyanates |
| US4526905A (en) * | 1982-07-06 | 1985-07-02 | Ethyl Corporation | Polyurethanes from dialkyl diaminobenzenes and processes therefor |
| US4442235A (en) * | 1983-05-09 | 1984-04-10 | Mobay Chemical Corporation | Process and composition for the production of polyurethane elastomer moldings |
| JPS6018514A (en) * | 1983-07-12 | 1985-01-30 | Sanyo Chem Ind Ltd | Elastomer-forming composition |
| DE3436163A1 (en) * | 1984-10-03 | 1986-04-10 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING MOLDED BODIES |
| US4546114A (en) * | 1984-10-25 | 1985-10-08 | The Upjohn Company | Process for the preparation of polyurea elastomers |
-
1985
- 1985-06-07 DE DE19853520326 patent/DE3520326A1/en not_active Withdrawn
-
1986
- 1986-05-14 CA CA000509132A patent/CA1255865A/en not_active Expired
- 1986-05-27 EP EP86107148A patent/EP0204246B1/en not_active Expired - Lifetime
- 1986-05-27 DE DE8686107148T patent/DE3667987D1/en not_active Expired - Lifetime
- 1986-05-27 AT AT86107148T patent/ATE49222T1/en not_active IP Right Cessation
- 1986-05-28 AR AR304141A patent/AR240054A1/en active
- 1986-06-03 AU AU58311/86A patent/AU577195B2/en not_active Ceased
- 1986-06-05 BR BR8602621A patent/BR8602621A/en unknown
- 1986-06-06 ES ES555822A patent/ES8707981A1/en not_active Expired
- 1986-06-06 JP JP61130469A patent/JPS61287920A/en active Pending
- 1986-06-06 ZA ZA864233A patent/ZA864233B/en unknown
- 1986-06-07 KR KR1019860004520A patent/KR870000162A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61287920A (en) | 1986-12-18 |
| ZA864233B (en) | 1987-02-25 |
| ES8707981A1 (en) | 1987-09-01 |
| ES555822A0 (en) | 1987-09-01 |
| AU577195B2 (en) | 1988-09-15 |
| AR240054A1 (en) | 1990-01-31 |
| EP0204246A2 (en) | 1986-12-10 |
| AU5831186A (en) | 1986-12-11 |
| ATE49222T1 (en) | 1990-01-15 |
| BR8602621A (en) | 1987-02-03 |
| DE3667987D1 (en) | 1990-02-08 |
| EP0204246A3 (en) | 1987-05-13 |
| KR870000162A (en) | 1987-02-16 |
| EP0204246B1 (en) | 1990-01-03 |
| DE3520326A1 (en) | 1986-12-11 |
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