CA2030599A1 - Process for the preparation of plastic moldings - Google Patents
Process for the preparation of plastic moldingsInfo
- Publication number
- CA2030599A1 CA2030599A1 CA 2030599 CA2030599A CA2030599A1 CA 2030599 A1 CA2030599 A1 CA 2030599A1 CA 2030599 CA2030599 CA 2030599 CA 2030599 A CA2030599 A CA 2030599A CA 2030599 A1 CA2030599 A1 CA 2030599A1
- Authority
- CA
- Canada
- Prior art keywords
- casting composition
- process according
- liquid casting
- under pressure
- mold
- 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.)
- Abandoned
Links
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
- C08G18/08—Processes
- C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
- C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
-
- 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
- C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no 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
- C08G18/08—Processes
- C08G18/089—Reaction retarding agents
-
- 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
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
-
- 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
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1883—Catalysts containing secondary or tertiary amines or salts thereof having heteroatoms other than oxygen and nitrogen
-
- 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
- C08G18/58—Epoxy resins
Abstract
Mo3503 LeA 27,404 A PROCESS FOR THE PREPARATION OF PLASTIC MOLDINGS
ABSTRACT OF THE DISCLOSURE
The invention relates to the preparation of plastic moldings by curing reactive, liquid casting compositions at elevated temperatures using a process in which (1) a liquid casting composition is prepared by reacting (a) an organic polyisocyanate, and (b) an organic compound containing at least two epoxide groups in a quantity corresponding to an equivalent ratio of isocyanate groups to epoxide groups of about 1.2:1 to about 500:1, in the presence of (d) a stabilizing alkylating sulfonic acid alkyl ester, methyl iodide, or dimethyl sulfate, (e) a latent, heat-activatable catalyst (preferably a tertiary or quaternary ammonium salt of an alkylating or acidic ester of organic phosphonic acids or phosphoric acid and/or an addition complex of boron trihalides with tertiary amines), and (f) optional auxiliaries and/or additives;
(2) the liquid casting composition is transferred under pressure through a conduit into a heated mold having a temperature above 70°C; and (3) the casting composition is kept in the mold under pressure until curing is complete.
Mo3503
ABSTRACT OF THE DISCLOSURE
The invention relates to the preparation of plastic moldings by curing reactive, liquid casting compositions at elevated temperatures using a process in which (1) a liquid casting composition is prepared by reacting (a) an organic polyisocyanate, and (b) an organic compound containing at least two epoxide groups in a quantity corresponding to an equivalent ratio of isocyanate groups to epoxide groups of about 1.2:1 to about 500:1, in the presence of (d) a stabilizing alkylating sulfonic acid alkyl ester, methyl iodide, or dimethyl sulfate, (e) a latent, heat-activatable catalyst (preferably a tertiary or quaternary ammonium salt of an alkylating or acidic ester of organic phosphonic acids or phosphoric acid and/or an addition complex of boron trihalides with tertiary amines), and (f) optional auxiliaries and/or additives;
(2) the liquid casting composition is transferred under pressure through a conduit into a heated mold having a temperature above 70°C; and (3) the casting composition is kept in the mold under pressure until curing is complete.
Mo3503
Description
Mo3503 LeA 27,404 A PROCESS FOR THE PREPARATION OF PLASTTC MOLDINGS
BACKGROUND OF THE INVENTION
This invention relates to a process for the preparation of moldings by injection molding in which a combination of stabilized polyepoxides and polyisocyanates preactivated by latent catalysts is used as the casting composition and is cured under pressure in the mold.
German Offenlegungsschrift 2,017,506 describes a process for the preparation of plastic moldings by curing lo reactive liquid casting compositions in which the casting composition is transferred under pressure through a pipe into a mold having a higher temperature than the casting composition and remains in the mold under the pressure transferred by the liquid casting composition in the pipe until curing is complete. The liquid casting compositions are understood to be (1) mixtures of epoxy resins and catalysts, (2) mixtures of di-or polyisocyanates and compounds containing more than one hydroxyl group per molecule, and (3) mixtures of unsaturated polyester resins and polymerizable monomers.
The disclosed casting compositions, however, have disadvantages which seriously restrict the usefulness of the process. Thus, the most widely used epoxy resins based on 4,4'-dihydroxydiphenyldimethylmethanP and epichlorohydrin are solid or highly viscous at room temperature, so that the flow 25 Of the casting compositions produced therefrom is severely restricted. Another disadvantage is their low filler uptake.
If reduction of viscosity is desired, the temperature of the casting composition can be increased, but this complicates both the apparatus and the process and shortens the pot life of the 30- casting composition. If viscosity is reduced by addition of reactive diluents, such as butyl glycidyl ether, or non-reactive diluents, such as dibutyl phthalate, both the strength and the heat resistance of the plastic moldings are I
- -2~3~
reduced. Mixtures of di- or polyisocyanates and compounds containing more than one hydroxyl group per molecule generally have a pot life of less than one hour, so that their use requires expensive mixing-dosing units incorporating flow 5 mixers. A disadvantage of this method is that the silica flour or other high-quality fillers in the form of flat materials cannot be used for high-quality moldings.
Mixtures of unsaturated polyester resins and polymerizable monomers give moldings having inadequate strengths. Moldings of unsaturated polyesters acquire adequate mechanical strengths only through the incorporation of reinforcing materials, such as glass fibers. The use of reinforcing materials reduces the flow of the mixtures of ùnsaturated polyester resins and polymerizable monomers to such 15 an extent that the mixture either cannot be transported through the pipe or separates during transport through the pipe.
Only certain casting resins are suitable for injection molding on an industrial scale. German Offenlegungs-schrift 2,438,205 describes certain combinations of epoxy 20 resins and unsaturated polyester resins. Injection into the hot mold accelerates the curing reaction to such an extent that cracks are formed in the molding because of polymerization shrinkage and, although the molds are filled by the pressure applied, the moldings are rendered unusable.
U.S. Patent 4,788,224 discloses a two-stage process for preparing molded articles from storage-stable compositions similar to those of certain embodiments of the present invention. Similar compositions are also disclosed in German Offenlegungsschrift 3,807,660. These references, however, do 30 not recognize or suggest the advantages of curing such compositions in a pressurized mold, a critical feature of the present invention.
Accordingly, it must be regarded as extremely surprising that storable epoxy-isocyanate resins ("EPIC
35 resins") preactivated by latent catalysts should be ideally Mo3503 ~ 3 suitable for processing by injection molding because one skilled in the art would have expected the trimerization reaction and the oxazolidinone-forming reaction to take place so quickly during injection into hot molds that defective s moldings would be obtained even when using these resins.
Surprisingly, however, this is not the case with the present invention.
In the process of the invention, using casting resins according to the invention, defect-free moldings are obtained lo by curing under pressure and at elevated mold temperatures of about 60C.
The casting compositions of the invention have advantageously low viscosity and thus allow large amounts of mineral powders to be used as fillers. In addition, the casting compositions may even be mixed with the fillers and, optionally, other additives at room temperature. Another advantage is the long pot li~e which, in the absence of moisture, can amount to several months. As a result, mixing need only be carried out a few times in the course of tpplication. Therefore, mixing-dosing units incorporating flow mixers are not needed. Another advantage of the process of the invention is that the moldings undergo minimal shrinkage and exhibit properties typical of EPIC plastics, namely inherent flame retardancy (without halogen-containing compounds) and high long-term thermal stability.
SUMMARY OF THE INVENTION
The present invention relates to a process for the preparation of plastic moldings by curing reactive, liquid casting compositions at elevated temperatures comprising (1) preparing a liquid casting composition by reacting (a) at least one organic polyisocyanate, and (b) at least one organic compound containing at least two epoxide groups in a quantity corresponding to an equivalent ratio of isocyanate groups to epoxide groups of about 1.2:1 to about 500:1, Mo3503 4 ~ ~3 in the presence of (d) a stabilizing component comprising at least one alkylating sulfonic acid alkyl ester, methyl iodide, or dimethyl sulfate, (e) at least one latent, heat-activatable catalyst (preferably a tertiary or quaternary ammonium salt of an alkylating or acidic ester of organic phosphonic ac;ds or phosphoric acid and/or an addition complex of boron trihalides with tertiary amines), and (f~ optionally, standard auxiliaries and/or additives (preferably fillers and/or reinforcing materials);
(2) transferring the liquid casting composition under pressure through a conduit (preferably at room temperature) into a heated mold having a temperature preferably above 70C;
and (3) maintaining the casting composition in the mold (optionally containing reinforcing materials) under pressure (applied by the liquid casting composition or applied externally) until curing is complete.
In a preferred embodiment, the liquid casting composition is prepared by (A) reacting (a) at least one organic polyisocyanate, (b) at least one organic compound containing at least two epoxide groups in a 4uantity corresponding to an equivalent ratio of isocyanate groups to epoxide groups of about 1.2:1 to about 500:1, and (c) a tertiary amine as catalyst, to form a relatively high viscosity liquid intermediate 30` product containing oxazolidinone and isocyanurate groups;
(B) stopping the reaction after no more than S5% of the isocyanate groups present in the starting mixture have reacted by adding (d) a stabilizing component comprising at least one alkylating sulfonic acid alkyl ester, methyl iodide, Mo3503 ~, ~. - ., -, .. .
2~3~
BACKGROUND OF THE INVENTION
This invention relates to a process for the preparation of moldings by injection molding in which a combination of stabilized polyepoxides and polyisocyanates preactivated by latent catalysts is used as the casting composition and is cured under pressure in the mold.
German Offenlegungsschrift 2,017,506 describes a process for the preparation of plastic moldings by curing lo reactive liquid casting compositions in which the casting composition is transferred under pressure through a pipe into a mold having a higher temperature than the casting composition and remains in the mold under the pressure transferred by the liquid casting composition in the pipe until curing is complete. The liquid casting compositions are understood to be (1) mixtures of epoxy resins and catalysts, (2) mixtures of di-or polyisocyanates and compounds containing more than one hydroxyl group per molecule, and (3) mixtures of unsaturated polyester resins and polymerizable monomers.
The disclosed casting compositions, however, have disadvantages which seriously restrict the usefulness of the process. Thus, the most widely used epoxy resins based on 4,4'-dihydroxydiphenyldimethylmethanP and epichlorohydrin are solid or highly viscous at room temperature, so that the flow 25 Of the casting compositions produced therefrom is severely restricted. Another disadvantage is their low filler uptake.
If reduction of viscosity is desired, the temperature of the casting composition can be increased, but this complicates both the apparatus and the process and shortens the pot life of the 30- casting composition. If viscosity is reduced by addition of reactive diluents, such as butyl glycidyl ether, or non-reactive diluents, such as dibutyl phthalate, both the strength and the heat resistance of the plastic moldings are I
- -2~3~
reduced. Mixtures of di- or polyisocyanates and compounds containing more than one hydroxyl group per molecule generally have a pot life of less than one hour, so that their use requires expensive mixing-dosing units incorporating flow 5 mixers. A disadvantage of this method is that the silica flour or other high-quality fillers in the form of flat materials cannot be used for high-quality moldings.
Mixtures of unsaturated polyester resins and polymerizable monomers give moldings having inadequate strengths. Moldings of unsaturated polyesters acquire adequate mechanical strengths only through the incorporation of reinforcing materials, such as glass fibers. The use of reinforcing materials reduces the flow of the mixtures of ùnsaturated polyester resins and polymerizable monomers to such 15 an extent that the mixture either cannot be transported through the pipe or separates during transport through the pipe.
Only certain casting resins are suitable for injection molding on an industrial scale. German Offenlegungs-schrift 2,438,205 describes certain combinations of epoxy 20 resins and unsaturated polyester resins. Injection into the hot mold accelerates the curing reaction to such an extent that cracks are formed in the molding because of polymerization shrinkage and, although the molds are filled by the pressure applied, the moldings are rendered unusable.
U.S. Patent 4,788,224 discloses a two-stage process for preparing molded articles from storage-stable compositions similar to those of certain embodiments of the present invention. Similar compositions are also disclosed in German Offenlegungsschrift 3,807,660. These references, however, do 30 not recognize or suggest the advantages of curing such compositions in a pressurized mold, a critical feature of the present invention.
Accordingly, it must be regarded as extremely surprising that storable epoxy-isocyanate resins ("EPIC
35 resins") preactivated by latent catalysts should be ideally Mo3503 ~ 3 suitable for processing by injection molding because one skilled in the art would have expected the trimerization reaction and the oxazolidinone-forming reaction to take place so quickly during injection into hot molds that defective s moldings would be obtained even when using these resins.
Surprisingly, however, this is not the case with the present invention.
In the process of the invention, using casting resins according to the invention, defect-free moldings are obtained lo by curing under pressure and at elevated mold temperatures of about 60C.
The casting compositions of the invention have advantageously low viscosity and thus allow large amounts of mineral powders to be used as fillers. In addition, the casting compositions may even be mixed with the fillers and, optionally, other additives at room temperature. Another advantage is the long pot li~e which, in the absence of moisture, can amount to several months. As a result, mixing need only be carried out a few times in the course of tpplication. Therefore, mixing-dosing units incorporating flow mixers are not needed. Another advantage of the process of the invention is that the moldings undergo minimal shrinkage and exhibit properties typical of EPIC plastics, namely inherent flame retardancy (without halogen-containing compounds) and high long-term thermal stability.
SUMMARY OF THE INVENTION
The present invention relates to a process for the preparation of plastic moldings by curing reactive, liquid casting compositions at elevated temperatures comprising (1) preparing a liquid casting composition by reacting (a) at least one organic polyisocyanate, and (b) at least one organic compound containing at least two epoxide groups in a quantity corresponding to an equivalent ratio of isocyanate groups to epoxide groups of about 1.2:1 to about 500:1, Mo3503 4 ~ ~3 in the presence of (d) a stabilizing component comprising at least one alkylating sulfonic acid alkyl ester, methyl iodide, or dimethyl sulfate, (e) at least one latent, heat-activatable catalyst (preferably a tertiary or quaternary ammonium salt of an alkylating or acidic ester of organic phosphonic ac;ds or phosphoric acid and/or an addition complex of boron trihalides with tertiary amines), and (f~ optionally, standard auxiliaries and/or additives (preferably fillers and/or reinforcing materials);
(2) transferring the liquid casting composition under pressure through a conduit (preferably at room temperature) into a heated mold having a temperature preferably above 70C;
and (3) maintaining the casting composition in the mold (optionally containing reinforcing materials) under pressure (applied by the liquid casting composition or applied externally) until curing is complete.
In a preferred embodiment, the liquid casting composition is prepared by (A) reacting (a) at least one organic polyisocyanate, (b) at least one organic compound containing at least two epoxide groups in a 4uantity corresponding to an equivalent ratio of isocyanate groups to epoxide groups of about 1.2:1 to about 500:1, and (c) a tertiary amine as catalyst, to form a relatively high viscosity liquid intermediate 30` product containing oxazolidinone and isocyanurate groups;
(B) stopping the reaction after no more than S5% of the isocyanate groups present in the starting mixture have reacted by adding (d) a stabilizing component comprising at least one alkylating sulfonic acid alkyl ester, methyl iodide, Mo3503 ~, ~. - ., -, .. .
2~3~
or dimethyl sulfate in a quantity at least equivalent to the quantity of tertiary amine (c); and (C) adding (e) at least one latent, heat-activatable catalyst (preferably a tertiary or quaternary ammonium salt of an alkylating or acidic ester of organic phosphonic acids or phosphoric acid and/or an addition complex of boron trihalides with tertiary amines), and (f) optionally, standard auxiliaries and/or additives, (preferably fillers and/or reinforcing materials).
In another preferred embodiment of the process, the casting composition contains, in addition to the organic components, inorganic fillers or reinforcing materials of inorganic, organic, or metallic type (preferably of a crushed mineral, such as silica flour), as ~ell as other known auxiliaries and additives.
Another preferred embodiment of the invention relates to a process in which the casting composition is injected under pressure into a heated mold that contains glass wool, woven or knitted glass cloth, or glass mats as reinforcing materials and is closed under a pressure of about 1 to about 500 torr.
Yet another preferred embodiment of the invention relates to a process in which the casting composition is injected under pressure into a heated mold which contains woven or knitted cloths or mats of carbon fibers,~aramide fibers, polyamide and/or metal wire and is closed under a pressure of about 1 to about 500 torr.
In another preferred embodiment, the casting composition contains other known additives, such as release agents, plastici7ers, pigments, and/or flameproofing additives.
About 10 to nearly 100% (preferably 10 to 70%) by weight of the casting composition is comprised of the organic casting resin components (a) and (b).
Mo3503 - ;
.;
- - - ,, :
- . . .. .
In another preferred embodiment of the process, the casting composition contains, in addition to the organic components, inorganic fillers or reinforcing materials of inorganic, organic, or metallic type (preferably of a crushed mineral, such as silica flour), as ~ell as other known auxiliaries and additives.
Another preferred embodiment of the invention relates to a process in which the casting composition is injected under pressure into a heated mold that contains glass wool, woven or knitted glass cloth, or glass mats as reinforcing materials and is closed under a pressure of about 1 to about 500 torr.
Yet another preferred embodiment of the invention relates to a process in which the casting composition is injected under pressure into a heated mold which contains woven or knitted cloths or mats of carbon fibers,~aramide fibers, polyamide and/or metal wire and is closed under a pressure of about 1 to about 500 torr.
In another preferred embodiment, the casting composition contains other known additives, such as release agents, plastici7ers, pigments, and/or flameproofing additives.
About 10 to nearly 100% (preferably 10 to 70%) by weight of the casting composition is comprised of the organic casting resin components (a) and (b).
Mo3503 - ;
.;
- - - ,, :
- . . .. .
-6- 2~3~9~
DETAILED DESCRIPTION OF THE INVENTION
Starting components ~aJ may be selected from organic polyisocyanates of the type known from polyurethane chemistry.
Suitable organic polyisocyanates include aliphatic, cyclo-5 aliphatic, araliphatic, aromatic, and heterocyclic polyiso-cyanates of the type described for example by W. Siefken in Justus Liebiqs Annalen der Chemie, 'i62, pages 75 to 13~, such as those corresponding to the formu-la Q(N~O)n in which n is from 2 to 4 (preferably 2) and Q represents an aliphatic hydrocarbon group containing from 2 to 18 (preferably from 6 to 10) carbon atoms, a cycloaliphatic hydrocarbon group containing from 4 to 15 (preferably from 5 to 10) carbon atoms, an aromatic hydrocarbon group containing from 6 to 15 (preferably 6 to 13) carbon atoms, or an araliphatic hydrocarbon group containing from 8 to 15 (preferably from 8 to 13) carbon atoms. Examples of suitable polyisocyanates include 20 . ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diiso-cyanate and mixtures of these isomers, 1-isocyanato-3,3~5-trimethyl-5-isocyanatomethylcyclohexane (German Auslegeschrift 1,202,785, U.S. Patent 3,401,190), 2,4- and 2,6-hexahydro-toluene diisocyanate and mixtures of these isomers, hexahydro-1,3- and/or -1,4-phenylene diisocyanate, perhydro-2,4'- and/or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, ~,4- and 2,6-toluene diisocyanate and mixtures of these isomers, diphenylmethane-2,4'- and/or -4,4'-diisocyanate, and naphthylene-1,5-diisocyanate.
Suitable polyisocyanates also include, for example, triphenylmethane-4,4',4"-triisocyanate, polyphenyl poly-methylene polyisocyanates of the type obtained by condensing aniline with formaldehyde, followed by phosgenation (British Mo3503 , . ~ , ,. .
~3~
DETAILED DESCRIPTION OF THE INVENTION
Starting components ~aJ may be selected from organic polyisocyanates of the type known from polyurethane chemistry.
Suitable organic polyisocyanates include aliphatic, cyclo-5 aliphatic, araliphatic, aromatic, and heterocyclic polyiso-cyanates of the type described for example by W. Siefken in Justus Liebiqs Annalen der Chemie, 'i62, pages 75 to 13~, such as those corresponding to the formu-la Q(N~O)n in which n is from 2 to 4 (preferably 2) and Q represents an aliphatic hydrocarbon group containing from 2 to 18 (preferably from 6 to 10) carbon atoms, a cycloaliphatic hydrocarbon group containing from 4 to 15 (preferably from 5 to 10) carbon atoms, an aromatic hydrocarbon group containing from 6 to 15 (preferably 6 to 13) carbon atoms, or an araliphatic hydrocarbon group containing from 8 to 15 (preferably from 8 to 13) carbon atoms. Examples of suitable polyisocyanates include 20 . ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diiso-cyanate and mixtures of these isomers, 1-isocyanato-3,3~5-trimethyl-5-isocyanatomethylcyclohexane (German Auslegeschrift 1,202,785, U.S. Patent 3,401,190), 2,4- and 2,6-hexahydro-toluene diisocyanate and mixtures of these isomers, hexahydro-1,3- and/or -1,4-phenylene diisocyanate, perhydro-2,4'- and/or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, ~,4- and 2,6-toluene diisocyanate and mixtures of these isomers, diphenylmethane-2,4'- and/or -4,4'-diisocyanate, and naphthylene-1,5-diisocyanate.
Suitable polyisocyanates also include, for example, triphenylmethane-4,4',4"-triisocyanate, polyphenyl poly-methylene polyisocyanates of the type obtained by condensing aniline with formaldehyde, followed by phosgenation (British Mo3503 , . ~ , ,. .
~3~
Patent 874,430 and 848,671), m- and p-isocyanatophenylsulfonyl isocyanates (U.S. Patent 3,454,606), perchlorinated aryl polyisocyanates tU.S. Patent 3,277,138), polyisocyanates containing carbodiimide groups (U.S. Patent 3,152,162), norbornane diisocyanates (U.S. Patent 3,492,330), polyiso-cyanates containing allophanate groups (GB-PS 994,890), polyisocyanates containing isocyanurate groups (U.S. Patent 3,001,973), polyisocyanates containing urethane groups (U.S.
Patents 3,394,164 and 3,644,457), polyisocyanates containing acylated urea groups (German Patentschrift 1,230,77~), polyisocyanates containing biuret groups (U.S. Patents 3,124,605, 3,201,372, and 3,124,605), polyisocyanates produced by telomerization reactions (U.S. Patent 3,654,106), polyiso-cyanates containing ester groups (U.S. Patent 3,567,7~3), reaction products of the above-mentioned diisocyanates with acetals according (German Patentschrift 1,072,385), and polyisocyanates containing polymeric fatty acid esters (U.S.
Patent 3,455,883).
It is also possible to use the distillation residues 20 . containing isocyanate groups which are obtained in the production of isocyanates on an industrial scale, optionally in solution in one or more of the polyisocyanates described above.
Mixtures of the polyisocyanates described above may also be used.
In general, it is particularly preferred to use the commercially readily available polyisocyanates, such as 2,4-and 2,6-toluene diisocyanate or any mixtures of these isomers ~nTDI"), polyphenyl polymethylene polyisocyanates of the type obtained by phosgenation of aniline-formaldehyde condensates ~"crude MDI"), and polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups~ isocyanurate groups, urea groups, or biuret groups ("modified polyiso-cyanates"), particularly modified polyisocyanates of the type derived from 2,4- and/or 2,6-toluene diisocyanate or from 4,4'-and/or -2,4'-diphenylmethane diisocyanate.
Mo3503 2~3~
Patents 3,394,164 and 3,644,457), polyisocyanates containing acylated urea groups (German Patentschrift 1,230,77~), polyisocyanates containing biuret groups (U.S. Patents 3,124,605, 3,201,372, and 3,124,605), polyisocyanates produced by telomerization reactions (U.S. Patent 3,654,106), polyiso-cyanates containing ester groups (U.S. Patent 3,567,7~3), reaction products of the above-mentioned diisocyanates with acetals according (German Patentschrift 1,072,385), and polyisocyanates containing polymeric fatty acid esters (U.S.
Patent 3,455,883).
It is also possible to use the distillation residues 20 . containing isocyanate groups which are obtained in the production of isocyanates on an industrial scale, optionally in solution in one or more of the polyisocyanates described above.
Mixtures of the polyisocyanates described above may also be used.
In general, it is particularly preferred to use the commercially readily available polyisocyanates, such as 2,4-and 2,6-toluene diisocyanate or any mixtures of these isomers ~nTDI"), polyphenyl polymethylene polyisocyanates of the type obtained by phosgenation of aniline-formaldehyde condensates ~"crude MDI"), and polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups~ isocyanurate groups, urea groups, or biuret groups ("modified polyiso-cyanates"), particularly modified polyisocyanates of the type derived from 2,4- and/or 2,6-toluene diisocyanate or from 4,4'-and/or -2,4'-diphenylmethane diisocyanate.
Mo3503 2~3~
~ t is particularly preferred to use an isomer and/or homolog mixture of polyisocyanates of the diphenylmethane series containing more than 20% by weight 2,4'-diisocyanato-diphenylmethane. Such polyisocyanate mixtures of the diphenyl-s methane series contain more than about 20% by weight(preferably 30 to 70% by weight) 2,4'-diisocyanatodiphenyl-methane. In addition to the 2,4'-isomers, the particularly preferred polyisocyanate component generally contains other isomeric or homologous polyisocyanates of the diphenylmethane series. Thus, the particularly preferred polyisocyanate component is generally either a mixture of 2,~'-diisocyanato-diphenylmethane with 4,4'-diisocyanatodiphenylmethane and, optionally, up to about 20% by weight, based on the mixture as a whole, of 2,2'-diisocyanatodiphenylmethane or a mixture of 15 these isomers with more highly nuclear polyphenyl polymethylene polyisocyanates. Mixtures of the second type generally contain from about 10% by weight to about 60% by weight, based on the mixture as a whole, of the more highly nuclear polyisocyanates.
The first-mentioned diisocyanate mixture enriched with 2,4'-20 . isomers that is preferably used as the isocyanate component maybe obtained, for example, by removal of a diisocyanate mixture of the stated composition by distillation from a polyisocyanate mixture of the type formed by phosgenation of aniline-formaldehyde condensates. The other particularly preferred 25 mixture containing more highly nuclear polyisocyanates may be obtained, for example, by remixing of the distillation product of the first type with 4,4'-diisocyanatodiphenylmethane-depleted phosgenation product, for example, in accordance with 6erman Auslegeschrift 1,9~,21~. A mixt~re of this type, that 30 iS, a polyisocyanate mixture in which the 2,4'-diisocyanato-diphenylmethane content corresponds to the foregoing observations, ~ay also be obtained directly by appropriate control of the aniline-formaldehyde condensation. U.S. Patent 3,277,173, for example, describes a method for obtaining polyamine mixtures of the diphenylmethane series having a high Mo3503 % ~
The first-mentioned diisocyanate mixture enriched with 2,4'-20 . isomers that is preferably used as the isocyanate component maybe obtained, for example, by removal of a diisocyanate mixture of the stated composition by distillation from a polyisocyanate mixture of the type formed by phosgenation of aniline-formaldehyde condensates. The other particularly preferred 25 mixture containing more highly nuclear polyisocyanates may be obtained, for example, by remixing of the distillation product of the first type with 4,4'-diisocyanatodiphenylmethane-depleted phosgenation product, for example, in accordance with 6erman Auslegeschrift 1,9~,21~. A mixt~re of this type, that 30 iS, a polyisocyanate mixture in which the 2,4'-diisocyanato-diphenylmethane content corresponds to the foregoing observations, ~ay also be obtained directly by appropriate control of the aniline-formaldehyde condensation. U.S. Patent 3,277,173, for example, describes a method for obtaining polyamine mixtures of the diphenylmethane series having a high Mo3503 % ~
content of 2,4'-diaminodiphenylmethane. The particularly preferred polyisocyanates may then be directly obtained by phosgenation of these condensates enriched with 2,4'-diamino-diphenylmethane. Methods of obtaining polyisocyanate mixtures such as these are also described in German Offenlegungsschrift 1,937,685 and U.S. Patent 3,362,979. The particularly suitable polyisocyanate mixtures containing more highly nuclear polyisocyanates of the diphenylmethane series also contain more than about 20% by weight, based on the mixture as a whole, of lo 2,4'-diisocyanatodiphenylmethane.
Component (b) may be an aliphatic, cycloaliphatic, aromatic, or heterocyclic compound containing at least two epoxide groups, i.e., 1,2-epoxide groups. The preferred polyepoxides used as component (b) contain 2 to ~ (preferably 2) epoxide groups per molecule and have an epoxide equivalent weight of about 90 to about 500 (preferably 170 to 220).
Suitable polyepoxides include polyglycidyl ethers of polyhydric phenols, such as pyrocatechol, resorcinol, hydroquinone, and 4,4'-dihydroxydiphenylmethane; of 4,4'-dihydroxy-3,3'-dimethyl-diphenylmethane; of 4,4'-dihydroxydiphenylmethane, 4,4'-di-hydroxydiphenylcyclohexane; of 4,4'-dihydroxy-3,3'-dimethyl-diphenylpropane; of ~,4'-dihydroxydiphenyl, 4-hydroxyphenyl 4-hydroxybenzoate, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; of 4,~'-dihydroxydiphenyl sulfone; of .25 tris(4-hydroxyphenyl)methane; as well as the chlorination and bromination products of the diphenols mentioned above; of novolaks (i.e., reaction products of monohydric or polyhydric phenols with aldehydes, particularly formaldehyde, in the presence of acidic catalysts); of diphenols obtained by esterification of two moles of the sodium salt of an aromatic hydroxycarboxylic acid with one mole of a dihaloalkane or dihalodialkyl ether (see British Patent 1,017,612); or of polyphenols obtained by condensation of phenols and long-chain haloparaffins containing at least two halogen atoms ~see British Patent 1,024,28R). Other suitable polyepoxides include Mo3503 .
2 ~
polyepoxide compounds based on aromatic amines and epichloro-hydrin, such as N-di(2,3-epoxypropyl)aniline, N,N'-dimethyl-N,N'-diepoxypropyl-4,4'-diaminodiphenylmethane, N-diepoxy-propyl-4-aminophenyl glycidyl ether (see British Patents 772,830 and 816,923).
It is also possiole to use glycidyl esters of polybasic aromatic, aliphatic, and cycloaliphatic carboxylic acids, such as phthalic acid diglycidyl ester, adipic acid diglycidyl ester, and glycidyl esters of react;on products of one mole of an aromatic or cycloaliphatic dicarboxylic anhydride and 1/2 mole of a diol or l/n mole of a polyol containing n hydroxy groups, or hexahydrophthalic ac;d diglycidyl esters optionally substituted by methyl groups.
Glycidyl ethers of polyhydric alcohols, such as 1,4-butanediol, 1,4-butenediol, glycerol, trimethylolpropane, pentaerythritol, and polyethylene glycols, may also be used.
Also of interest are triglycidyl isocyanurate, N,N'-diepoxy-propyl oxamide, polyglycidyl thioethers of polyhydric thiols, such as bis(mercaptomethyl)benzene and diglycidyl trimethylene 20: trisulfone, and polyglycidyl ethers based on hydantoins.
In addition, it is also possible to use epoxidation products of polyunsatura~ed compounds, such as vegetable oils and their conversion products, epoxidation products of di- and polyolefins, such as butadiene, vinyl cyclohexene, 1,5-cyclo-25 octadiene, 1,5,~-cyclododecatriene, polymers and copolymers still containing epoxidizable double bonds, for example, those based on polybutad;ene, polyisoprene, butadienestyrene copolymers, divinylbenzene, dicyclopentadiene, and unsaturated polyesters; epoxidation products of olefins obtainable by 30 Diels-Alder addition and subsequent conversion into polyepox-ides by epoxidation with per compounds; or epoxidation products of compounds containing two cyclopentene or cyclohexene rings attached by bridge atoms or groups of bridge atoms. Polymers of unsaturated monoepoxides, for example of glycidyl methacrylate or allyl glycidyl ether, are also mentioned.
Mo3503 -11- 2~3~
Preferred polyepoxide compounds or mixtures thereof used as component (b) include polyglycidyl ethers of polyhydric phenols, particularly bisphenol A; polyepoxide compounds based on aromatic amines, more particularly bis(N-epoxypropyl)-aniline, N,N'-dimethyl-N,N'-diepoxypropyl-4,4'-diaminodiphenyl-methane, and N-diepoxypropyl-4-aminophenyl glycidyl ether;
polyglycidyl esters of cycloaliphatic dicarboxylic acids, more particularly hexahydrophthalic acid diglycidyl ester and polyepoxides of the reaction product of n moles hexahydro-phthalic anhydride and one mole of a polyol conta;ning n hydroxyl groups (n being an integer of 2 to about 6)~ more particularly three moles of hexahydrophthalic anhydride and one mole of 1,1,1-trimethylolpropane, 3,4-epoxycyclohexylme~hane-3,4-epoxycyclohexanecarboxylate.
In special cases, liquid polyepoxides or low viscosity diepoxides, such as bis(N-epoxypropyl)aniline or vinyl cyclohexane diepoxy, can further reduce the viscosity of already liquid polyepoxides or can convert solid polyepoxides into liquid mixtures.
20 . Component (b) is used in a quantity which corresponds to an equivalent ratio of isocyanate groups to epoxide groups of about 1.2:1 to about 500:1 (preferably 3:1 to 65:1 and, more preferably, 5:1 to 30:1).
Catalyst component (c) may be selected from mono-functional or polyfunctional organic amines containing tertiary amino groups. Preferred amines of this type generally have a molecular weight of up to about 353 and, more particularly, in the range from 101 to 18~. Preferred tertiary amines are those which are liquid at the reaction temperature of the first 30 . reaction stage. Examples of suitable and preferred amines include triethylamine, tributylamine, N,N,N',N'-tetramethyl-ethylenediamlne, N,N-dimethylbenzylamine, triethylenedia~ine, dimethyl octylamine, N-methylmorpholine, and bis(N,N-dimethyl-Mo3503 , . : ~ . ~ .. ....
aminoethyl) ether. Catalysts (c) are used in a quantity of about 0.01 to about 2% by weight (preferably 0.01 to 0.1% by weight) based on the total weight of components (a) and (b).
Stabilizer component (d) (also referred to as a 5 stopper) is a catalyst poison for catalysts (c). Suitable stabili~er components (d) include alkylating esters of organic sulfonic acids, preferably sulfonic acid alkyl esters having a molecular weight of about 110 to about 250. Suitable sulfonic acid alkyl esters include both aliphatic sulfonic acid alkyl esters, such as butanesulfonic acid methyl ester, perfluoro-butanesulfonic acid methyl ester, or hexanesulfonic acid ethyl ester, and aromatic sulfonic acid alkyl esters, such as benzenesulfonic acid methyl ester, ethyl ester, or butyl ester, p-toluenesulfonic acid methyl ester, ethyl ester, or butyl 15 ester, 1-naphthalenesulfonic acid methyl ester, 3-nitrobenzene-sulfonic acid methyl ester, or 2-naphthalenesulfonic acid methyl ester. The aromatic sulfonic acid esters mentioned are preferred, with p-toluenesulfonic acid methyl ester being particularly preferred. Methyl iodide and dimethyl sulfate are 20 also suitable, although less preferred, as component (d).
Component (d) is used in at least an equivalent quantity relative to the tertiary am;ne nitrogen atoms of component (c).
Component (d) acts both as a stopper (where catalyst (c) is used) and as a stabilizer (for the mixture of components (a) 25 and (b)).
Suitable latent catalysts (e) include ~el) tertiary or quaternary ammonium salts of (i~ organic amines and (ii) alkylating or acidic esters of organic phosphonic acids or phosphoric acid or (e2) addition complexes of boron trihalides with tertiary amines.
Constituent (i) of the latent catalysts (el) may be selected from monofunctional or polyfunctional organic amines containing secondary and/or tertiary amino groups. In the preparation of the catalysts, secondary amino groups may be converted into tertiary ammonium groups by alkylation and Mo3503 :
2~3~
tertiary amino groups may be converted into tertiary ammonium groups by neutralization or into quaternary ammonium groups by quaternization. Suitable amines oF this type generally have a molecular weight of about 45 to about 353 (preferably in the 5 range from 45 to 185). Examples of suitable amines include dimethylamine, trimethylamine, diethylamine, triethylamine, dibutylamine, tributylamine, N,N'-dimethylethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N-dimethylbenzylamine, triethylenediamine, dimethyloctylamine, diazabicyclooctane, methyl dioctylamine, N-methylmorpholine, and bis(N,N-dimethyl-aminoethyl) ether.
Constituent (ii) of the latent catalysts (el) may be selected from alkylating or acidic esters o~ organic phosphonic acids or phosphoric acid. Neutral alkylating esters o~ organic 15 phosphonic acids are preferably used as the phosphonic acid esters. These compounds generally have a molecular weight of about 124 to about 214. ~uitable compounds of this type include methanephosphonic acid dimethyl ester, methanephos-phonic acid diethyl ester, benzenephosphonic acid dimethyl 20 ester, benzenephosphonic acid diethyl ester, or ethanephos-phonic acid diethyl ester. Both monobasic acidic esters and neutral esters may be used as the phosphoric acid esters.
These compounds generally have a molecular weight o~ about 126 to about 266. Suitable compounds of this type include dimethyl 25 phosphate, diethyl phosphate, dibutyl phosphate, triethyl phosphate, or tributyl phosphate. Pre~erred constituents (ii) of the catalysts (el) crucial to thP invention are methane-phosphonic acid dimethyl ester and dibutyl phosphate.
Catalysts ~el) can be prepared in known manner (see, 30 for example, Houben-Weyl, Vol. XII/2, pages 262 et seq) by reaction of components (i) and (ii) (as described above), pre~erably in equivalent quantities, in the presence or absence o~ solvents at temperatures in the ranye ~rom about 20 to about 200~C. The reaction may advantageously be carried out in an 35 inert gas atmosphere and/or under pressure. It is also Mo3503 ~ . ~
~} ., : ~:
., ~
,, ; .
possible, for example, to use an excess of component (i) or (ii) and subsequently to remove any unreacted excess, for example, by distillation.
Particularly preferred examples of catalysts (el) are compounds having the formulas:
cH3-N ~ -CH3 C~3 + O
(Butyl)?-N-CH3 -0-P-OCH3 + O
(cH3cH2)3-N-H-o-P-O(Butyl)2 +
(CH3)2 ~ H o-p-o(Butyl)2 Suitable latent catalysts (e2) include the known addition complexes of boron trihalides (more particularly boron trichlorides or boron trifluorides) with tertiary amines.
Examples include the addition complexes of boron trichloride and tertiary amines described in German Patentschrift 2,655,367 corresponding to the following general formula in which Rl, R2, and R3 may be the same or different and represent aliphatic, aromatic, heterocyclic, or aryl aliphatic groups or may be taken together (e.g., in pairs) to form part Mo3503 .,., ::
-: , -2 ~
of heterocyclic rings. Also suitable are the analogous complexes o~ boron trifluoride corresponding to the following formula RIR2R3N ~ BF3 in which Rl, R2 and R3 are as defined above.
Particularly suitable latent catalysts include boron trichlDride or boron trifluoride complexes of tertiary amines of the type mentioned by way of example in the description of components (c) and (el) or even of heterocyclic tertiary amines, such as 1,2-dimethylimidazole or l-benzyl-2-phenyl-imidazole. The amine component of the complexes generally has a molecular weight within the ranges mentioned above in 15 connection with component (c).
The latent catalysts (e) are generally used in a quantity of about 0.01 to about 20 parts by weight (preferably 0.1 to lO parts by weight and more preferably 0.5 to 2 parts by weight) per 100 parts by weight of the intermediate formed in ~o the "B stage" (that is, the resin present after poisoning of the catalyst (c)).
As with catalysts (c), mixtures of the compounds mentioned by way of example may also be used as the catalysts (e). The reaction time and the reaction temperature, both 25 - during preparation of the intermediate stage ("B stage"~ and during curing of the resin present in the intermediate stage, may be adapted to meet particular requirements through the type and concentration of the catalysts (c) and (e).
The optional auxiliaries and additives (f) include 30 (fl) polymerizable, olefinically unsaturated monomers and may be used in quantities of up to 100% by weight (preferably in quantities of up to 50% by weight) based on the total weight of components (a) and (b). Examples of additives (fl) include olefinically unsaturated monomers that do not contain any -35 NC0-reactive hydrogen atoms, such as diisobutylene, styrene, Mo3503 ~ ` :
, -16~
(C1 4 alkyl) styrenes (for example, ~-methyl styrene or n-butyl styrene), vinyl chloride, vinyl acetate, maleic imide derivatives (for example, bis(4-maleimidophenyl)methane), (C
alkyl) acrylates (for example, methyl acrylate, butyl acrylate, 5 or octyl acrylate) or the corresponding methacrylates, acrylonitrile, or diallyl phthalate. Mixtures of these olefinically unsaturated monomers may also be used. When used at all, the preferred additives (fl) are styrene and/or (C1 4 alkyl) acrylates or methacrylates are preferred. ~hen o additives (fl) are used, conventional polymerizatinn inhibitors, such as benzoyl peroxide, may be used but are generally not necessary.
The optional auxiliaries and additives (f) also include (f23 organic compounds containing at least 2 15 (preferably, 2 to 8 and more preferably 2 to 3) alcoholic hydroxyl groups and having a molecular weight in the range from about 62 to about 2,000, of the type known as synthesis components for polyurethanes. Examples of such compounds include simple polyhydric alcohols, such as ethylene glycol, 20. 1,6-hexanediol, glycerol, or trimethylolpropane; polyols containing dimethylsiloxane units, such as bis(dimethylhydroxy-methylsilyl) ether; polyhydroxy compounds containing ester groups, such as castor oil or polyhydroxypolyesters of the type obtainable by polycondensation of excess quantities of simple 25 monohydric alcohols of the type mentioned above with carboxylic acids (preferably dibasic carboxylic acids) or their anhydrides, such as adipic acid, phthalic acid, or phthalic anhydride; or polyhydroxypolyethers of the type obtainable by addition of alkylene oxides, such as propylene oxide and/or 30 ethylene oxide, with suitable starter molecules, such as water, the simple monoalcohols mentioned above, or even amides containing at least two amine NH bonds.
If used at all, the additives (f2) are used in a maximum quantity corresponding to an NCO:OH equivalent ratio, 35 based on the isocyanate groups of component (a) and -the Mo3503 :~ .
.
-17- ~ s~
hydroxyl groups of component (f2), of at least 2:1 (preferably at least 2.5:1). In any event, the quantity of component (a) must be selected in such a way that the equivalent ratio of isocyanate groups of component (a) to the sum of the epoxide 5 groups of component (b), the hydroxy1 groups of component (f2), and the hydroxyl groups present in optional component (b) is at least 1.2:1 (more preferably from 4:1 to 30:1).
In general, the auxiliaries and addit;ves (fl) and (f2) are not necessary. However, the additives mentioned by way of example for (fl) are preferred to the compounds mentioned by way of example for (f2). Both types of auxiliaries and additives may be used at the same time.
Other optional auxiliaries and additives (f) include fillers, such as mineral powders (for example, quartz powder, 15 chalk, or aluminum oxide); pigments, such as inorganic pigments (for example, titanium dioxide or iron oxide) or organ;c p;gments (for example, phthalocyanine pigments); plasticizers, such as dioctyl phthalate or tributyl or triphenyl phosphate;
dyes, including soluble dyes; or reinforcing materials, such as 20 . glass fibers or glass cloths. Carbon fibers or carbon fiber cloths and other organic polymeric fibers, such as aramide fibers or liquid crystal ("LC") polymer fibers, are also suitable. Woven or knitted cloths of polyamide and/or metal wire are also suitable.
The auxiliaries and additives may be incorporated in the starting materials (a) and (b) before the process of the invention is carried out or may even be subsequently added to the resin present in the intermediate stage, optionally after melting.
30 . In one preferred embodiment, the process of the invention is carried out by mixing the starting materials (a), (b), and (c) and, optionally, auxiliaries and additives (f), or a part thereof, with one another and reacting the resultant mixture at a temperature in the range from about 20 to about 150C (preferably from 60 to 130C). The reaction is Mo3503 -18- 2~ 3~
term;nated by addition of the stopper (d) after conversion of no more than 65% (preferably 30 to 60%) of the isocyanate groups orig;nally introduced into the start;ng mixture as component (a).
The relatively high Viscclsity intermediate product that accumulates in the "B stage" is generally a liquid at room temperature or a solid that is fusible at temperatures no higher than 120C and may be introduced into the second stage of the process of the invention, optionally after an inde~inite o storage period. To this end, the latent catalyst (e), as well as any other optional auxiliaries and additives, are added to the intermediate product, optionally after melting. If particularly low-viscosity mixtures are preferred, the starting components (a) and (b) are mixed with poisons (d) and briefly heated (0.5 to 1 hour) under nitrogen to about 120DC. Storable EPIC resins of very low viscosity (that is, viscosity <100 mPa.s at 25C) are thus obtained. After these low viscosity EPIC resins are cooled, the latent catalyst (e) and any ~ther optional auxiliaries and additives are added.
20 . Other suitable auxiliaries and additives include "reactive diluents," such as polyisocyanates that are liquid at room temperature of the type mentioned above under (a) and polyepoxides that are liquid at room temperature of the type mentioned above under (b), although such mixtures must always contain an excess of NCO groups over epoxide and hydroxyl groups corresponding to an equivalent ratio of at least 1.2:1 (preferably of at least 3:1).
Curing takes place under pressure in molds heated to temperatures of at least about 70C (preferably in the range from 70 to 180DC). To achieve optimal properties, it is often advisable to post-cure the resulting plastics at temperatures of about 150 to about 250C (preferably at temperatures of 200 to 230C).
Mo3503 .. .
-. .. : :
"' . ~. :
. . :. ~, ,, :
- , - ., .
- . :: .
2~3~5~
,9 When the resins of the invention are processed in combination with suitable blowing agents, it is even possible to prepare foams.
In addition, laminates having outstanding properties may be prepared by the process of the invention using glass cloth, glass mats, paper, plastic films, veneers, cloth made of KEYLAR~ fibers, woven or knitted carbon fiber cloth, glass nonwovens, or mineral wool.
The outstanding properties of the moldings include their inherent ~lame retardancy and their high long-term thermal stability.
The following examples further illustrate details for the process of this invention. The inYention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions of the following procedures can be used. Unless otherwise noted, all temperatures are degrees Celsius and all parts and percentages are parts by weight and percentages by weight.
20 . FXAMPLES
Example 1 A mixture of 60% 2,4'-diisocyanatodiphenylmethane and 40YO 4,4'-diisocyanatodiphenylmethane ~NC0 content 33.6%) ~950 9 wa~ mixed at 50~C with 5Q g of 25 ` the diglycidyl ether of bisphenol A (epoxide value 0.585) and 0.43 9 (3.2 mmole) of dimethylbenzylamine. The resulting mixture was heated to 120C. The slightly exothermic reaction indicates the immediate commencement of isocyanurate and oxazolidinone formation. After a reaction time of 15 minutes without external heating, the reaction mixturè was cooled with ice water to establish an internal temperature of approximately 90~C. A sample taken from the mixture was a solid, tacky resin at room temperature and had an NC0 content of 18.4% NC0. The reaction was terminated by adding 6.5 ml o~ stopper solution I
(a solution of 15.4% by weight of p-toluenesu1fonic acid methyl Mo3503 ester in a mixture of 60% 2,4'-diisocyanatodiphenylmethane and 40% 4,4'-diisocyanatodiphenylmethane). Another 5969 of the diisocyanate composition described above and 31 9 of the diglycidyl ether described above were then added to the mixture and the whole was st;rred at 120C
until a clear homogeneous solution was formed. A clear yellow, storable res1n that was liquid at room temperature and had a viscosity of 9,300 mPa-s at 25C and an NC0 content of 23.6%
was obtained.
Example 2 Dimethylbenzylamine (0.26 9) was added at 80C to 120 g of the diglycidyl ether described in Example 1 and 480 g of the polyisocyanate mixture described in Example 1. Under the effect of the exothermic isocyanurate-forming reaction, the 15 temperature of the reaction mixture increased to 120C over a period of 2 hours without further heating. Stopper solution I
(see Example 1) (3.82 ml) was then added to the reaction mixture, followed by stirring for 30 minutes at 129C. The resultant resin had an NC0 content of 20.0%. Mixing this resin 20 . with 327 9 of the diisocyanate component described above and 81.8 9 of the diglycidyl ether described above, followed by stirring for 30 minutes at 1~0C, yielded a clear yellow, storable resin that was liquid at room temperature and had a ~iscosity of 2,016 mPa~s (25C) and an NC0 content of 21.1%
25 Example 3 A mixture of 60% 2,4'-diisocyanatodiphenylmethane and 40% 4,4'-diisocyanatodiphenylmethane (NC0 content 33.6%) (120 g3 was mix~d with 30 9 of the diglycidyl ether of bisphenol A (epoxide value 0.5) and 1.5 ml 30 of a separately prepared 1 M sulution of p-toluenesulfonic acid methyl ester in the diisocyanate mixture described above. The resultant mixture was heated with stirring under nitrogen for 30 minutes to a temperature of 120C. After cooling, a reactive resin (I) having an NC0 content of 26.2% (based on the Mo3503 ~3~59~
mixture as a whole) and a viscosity of 55 mPa.s (25C) was obtained.
The reactive resin (I) (lO0 9~ was stirred for 10 hours at room temperature with 1 9 5 of the complex of B~13 and dimethylbenzylamine. The catalyst dissolved completely and the viscosity of the reactive resin remained unaffected. A prereacted casting resin of very low viscosity, which maintained a stable NC0 content and viscosity over a period of 6 months, was obtained in this way and could o be used in the process of to the invention.
Example 4 Reactive resin (I) of Example 3 (100 9) was mixed at room temperature with 19 dimethyl-benzylammonium dibutyl phosphate. The mixture was homogeneous, the liquid catalyst having dissolved completely, and the viscosity of the reactive resin remained unaffected. A pre-activated casting resin of very low viscosity, which maintained a stabie NC0 content and viscosity over a period of at least 7 days, was obtained in this way and could be used in the process of the invention.
ExamDle 5 The EPIC resin prepared according to Example 2 ~100 9) was stirred under nitrogen ~or 10 hours at room temperature with 1 9 of the complex of BC13 and dimethyl-benzylamine. The catalyst dissolved completely. Silicaflour (150 9) was then added to the mixture. A ready-to-use casting composition ~as obtained after stirring for 10 minutes in vacuo under a pressure of 12 torr.
The resultant casting composition was introduced into 30 a pressure vessel that was connected by a hose to an injection nozzle equipped with a valve. The pressure vessel was pressurized with compressed air at 4 atm gauge pressure through a valve in the cover of the vessel. The injection nozzle opened into the lower part of a self-heated, hydraulically 35 opened and closed mold having a temperature of 160C and a Mo3503 ;. ~
~ ~3 3 ~ P~
cavity representing a plate measuring 200 x 200 x 4 mm. After the injection nozzle valve was opened, the casting composition in the pressure vessel entered the hot steel mold while the air escaped through the gap between the two mold halves. After 6 5 minutes, the valve in the injection nozzle was closed and the hydraulics opened the mold. A homogeneous, bubble-free plastic plate free from sink marks was obtained. After the plate was heated for 4 hours at 160C, then for 4 hours at 200C, and finally for 4 hours at 250C, it had the fol70wing properties:
o Tensile strength (DIN 53,455) 80 N/mm2 Elongation at break (DIN 53,455) 1 %
E modulus in tension (DIN 53,457) 10,000 N/mm2 Flexural strength (DIN 53,452) 130 N/mm2 Outer fiber strain (DIN 53,452) 1.5 %
Impact strength (DIN 53,453)12 kJ/m2 Martens temperature (DIN 53,458) >250 C
Glass transition temperature300 C
Example 6 The reactive resin (I) prepared according to Example 3 (100 9) was stirred under nitrogen for 8 hours at room temperature with 1 9 of the complex of BCl3 and dimethylbenzylamine. The catalyst dissolved completely. The preact;vated resin was stable in storage for at least 6 months at room temperature in closed containers.
A glass mat was introduced into an opened plate mold arranged in a heatable hydraulic press in a quantity such that the mold was filled with 80% by weight glass. The mold was closed by the hydraulic press under a prPssure of 30 torr.
After precompression, the mold was opened again, impregnated 30 . with 20% by weight of the preactivated EPIC resin, and, after closure of the resin inlet valve, was closed under a pressure of 30 torr. With the mold heated to 160C, the cast resin cured in 4 to 10 minutes to form a homogeneous plate. After the mold was opened, the plate was removed and heated for 4 Mo3503 "
, . . .
hours at 160DC, then for 4 hours at 200C, and finally for 4 hours at 250C.
The plate was then suitable for use as a catalyst cover plate in car construction or for the insulation of very 5 hot parts or spacers, for example, in combustion engines. The plate prepared according to the invention could withstand brief heating to 600C without carbonizing or any loss of dimensions.
Mo3503
Component (b) may be an aliphatic, cycloaliphatic, aromatic, or heterocyclic compound containing at least two epoxide groups, i.e., 1,2-epoxide groups. The preferred polyepoxides used as component (b) contain 2 to ~ (preferably 2) epoxide groups per molecule and have an epoxide equivalent weight of about 90 to about 500 (preferably 170 to 220).
Suitable polyepoxides include polyglycidyl ethers of polyhydric phenols, such as pyrocatechol, resorcinol, hydroquinone, and 4,4'-dihydroxydiphenylmethane; of 4,4'-dihydroxy-3,3'-dimethyl-diphenylmethane; of 4,4'-dihydroxydiphenylmethane, 4,4'-di-hydroxydiphenylcyclohexane; of 4,4'-dihydroxy-3,3'-dimethyl-diphenylpropane; of ~,4'-dihydroxydiphenyl, 4-hydroxyphenyl 4-hydroxybenzoate, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; of 4,~'-dihydroxydiphenyl sulfone; of .25 tris(4-hydroxyphenyl)methane; as well as the chlorination and bromination products of the diphenols mentioned above; of novolaks (i.e., reaction products of monohydric or polyhydric phenols with aldehydes, particularly formaldehyde, in the presence of acidic catalysts); of diphenols obtained by esterification of two moles of the sodium salt of an aromatic hydroxycarboxylic acid with one mole of a dihaloalkane or dihalodialkyl ether (see British Patent 1,017,612); or of polyphenols obtained by condensation of phenols and long-chain haloparaffins containing at least two halogen atoms ~see British Patent 1,024,28R). Other suitable polyepoxides include Mo3503 .
2 ~
polyepoxide compounds based on aromatic amines and epichloro-hydrin, such as N-di(2,3-epoxypropyl)aniline, N,N'-dimethyl-N,N'-diepoxypropyl-4,4'-diaminodiphenylmethane, N-diepoxy-propyl-4-aminophenyl glycidyl ether (see British Patents 772,830 and 816,923).
It is also possiole to use glycidyl esters of polybasic aromatic, aliphatic, and cycloaliphatic carboxylic acids, such as phthalic acid diglycidyl ester, adipic acid diglycidyl ester, and glycidyl esters of react;on products of one mole of an aromatic or cycloaliphatic dicarboxylic anhydride and 1/2 mole of a diol or l/n mole of a polyol containing n hydroxy groups, or hexahydrophthalic ac;d diglycidyl esters optionally substituted by methyl groups.
Glycidyl ethers of polyhydric alcohols, such as 1,4-butanediol, 1,4-butenediol, glycerol, trimethylolpropane, pentaerythritol, and polyethylene glycols, may also be used.
Also of interest are triglycidyl isocyanurate, N,N'-diepoxy-propyl oxamide, polyglycidyl thioethers of polyhydric thiols, such as bis(mercaptomethyl)benzene and diglycidyl trimethylene 20: trisulfone, and polyglycidyl ethers based on hydantoins.
In addition, it is also possible to use epoxidation products of polyunsatura~ed compounds, such as vegetable oils and their conversion products, epoxidation products of di- and polyolefins, such as butadiene, vinyl cyclohexene, 1,5-cyclo-25 octadiene, 1,5,~-cyclododecatriene, polymers and copolymers still containing epoxidizable double bonds, for example, those based on polybutad;ene, polyisoprene, butadienestyrene copolymers, divinylbenzene, dicyclopentadiene, and unsaturated polyesters; epoxidation products of olefins obtainable by 30 Diels-Alder addition and subsequent conversion into polyepox-ides by epoxidation with per compounds; or epoxidation products of compounds containing two cyclopentene or cyclohexene rings attached by bridge atoms or groups of bridge atoms. Polymers of unsaturated monoepoxides, for example of glycidyl methacrylate or allyl glycidyl ether, are also mentioned.
Mo3503 -11- 2~3~
Preferred polyepoxide compounds or mixtures thereof used as component (b) include polyglycidyl ethers of polyhydric phenols, particularly bisphenol A; polyepoxide compounds based on aromatic amines, more particularly bis(N-epoxypropyl)-aniline, N,N'-dimethyl-N,N'-diepoxypropyl-4,4'-diaminodiphenyl-methane, and N-diepoxypropyl-4-aminophenyl glycidyl ether;
polyglycidyl esters of cycloaliphatic dicarboxylic acids, more particularly hexahydrophthalic acid diglycidyl ester and polyepoxides of the reaction product of n moles hexahydro-phthalic anhydride and one mole of a polyol conta;ning n hydroxyl groups (n being an integer of 2 to about 6)~ more particularly three moles of hexahydrophthalic anhydride and one mole of 1,1,1-trimethylolpropane, 3,4-epoxycyclohexylme~hane-3,4-epoxycyclohexanecarboxylate.
In special cases, liquid polyepoxides or low viscosity diepoxides, such as bis(N-epoxypropyl)aniline or vinyl cyclohexane diepoxy, can further reduce the viscosity of already liquid polyepoxides or can convert solid polyepoxides into liquid mixtures.
20 . Component (b) is used in a quantity which corresponds to an equivalent ratio of isocyanate groups to epoxide groups of about 1.2:1 to about 500:1 (preferably 3:1 to 65:1 and, more preferably, 5:1 to 30:1).
Catalyst component (c) may be selected from mono-functional or polyfunctional organic amines containing tertiary amino groups. Preferred amines of this type generally have a molecular weight of up to about 353 and, more particularly, in the range from 101 to 18~. Preferred tertiary amines are those which are liquid at the reaction temperature of the first 30 . reaction stage. Examples of suitable and preferred amines include triethylamine, tributylamine, N,N,N',N'-tetramethyl-ethylenediamlne, N,N-dimethylbenzylamine, triethylenedia~ine, dimethyl octylamine, N-methylmorpholine, and bis(N,N-dimethyl-Mo3503 , . : ~ . ~ .. ....
aminoethyl) ether. Catalysts (c) are used in a quantity of about 0.01 to about 2% by weight (preferably 0.01 to 0.1% by weight) based on the total weight of components (a) and (b).
Stabilizer component (d) (also referred to as a 5 stopper) is a catalyst poison for catalysts (c). Suitable stabili~er components (d) include alkylating esters of organic sulfonic acids, preferably sulfonic acid alkyl esters having a molecular weight of about 110 to about 250. Suitable sulfonic acid alkyl esters include both aliphatic sulfonic acid alkyl esters, such as butanesulfonic acid methyl ester, perfluoro-butanesulfonic acid methyl ester, or hexanesulfonic acid ethyl ester, and aromatic sulfonic acid alkyl esters, such as benzenesulfonic acid methyl ester, ethyl ester, or butyl ester, p-toluenesulfonic acid methyl ester, ethyl ester, or butyl 15 ester, 1-naphthalenesulfonic acid methyl ester, 3-nitrobenzene-sulfonic acid methyl ester, or 2-naphthalenesulfonic acid methyl ester. The aromatic sulfonic acid esters mentioned are preferred, with p-toluenesulfonic acid methyl ester being particularly preferred. Methyl iodide and dimethyl sulfate are 20 also suitable, although less preferred, as component (d).
Component (d) is used in at least an equivalent quantity relative to the tertiary am;ne nitrogen atoms of component (c).
Component (d) acts both as a stopper (where catalyst (c) is used) and as a stabilizer (for the mixture of components (a) 25 and (b)).
Suitable latent catalysts (e) include ~el) tertiary or quaternary ammonium salts of (i~ organic amines and (ii) alkylating or acidic esters of organic phosphonic acids or phosphoric acid or (e2) addition complexes of boron trihalides with tertiary amines.
Constituent (i) of the latent catalysts (el) may be selected from monofunctional or polyfunctional organic amines containing secondary and/or tertiary amino groups. In the preparation of the catalysts, secondary amino groups may be converted into tertiary ammonium groups by alkylation and Mo3503 :
2~3~
tertiary amino groups may be converted into tertiary ammonium groups by neutralization or into quaternary ammonium groups by quaternization. Suitable amines oF this type generally have a molecular weight of about 45 to about 353 (preferably in the 5 range from 45 to 185). Examples of suitable amines include dimethylamine, trimethylamine, diethylamine, triethylamine, dibutylamine, tributylamine, N,N'-dimethylethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N-dimethylbenzylamine, triethylenediamine, dimethyloctylamine, diazabicyclooctane, methyl dioctylamine, N-methylmorpholine, and bis(N,N-dimethyl-aminoethyl) ether.
Constituent (ii) of the latent catalysts (el) may be selected from alkylating or acidic esters o~ organic phosphonic acids or phosphoric acid. Neutral alkylating esters o~ organic 15 phosphonic acids are preferably used as the phosphonic acid esters. These compounds generally have a molecular weight of about 124 to about 214. ~uitable compounds of this type include methanephosphonic acid dimethyl ester, methanephos-phonic acid diethyl ester, benzenephosphonic acid dimethyl 20 ester, benzenephosphonic acid diethyl ester, or ethanephos-phonic acid diethyl ester. Both monobasic acidic esters and neutral esters may be used as the phosphoric acid esters.
These compounds generally have a molecular weight o~ about 126 to about 266. Suitable compounds of this type include dimethyl 25 phosphate, diethyl phosphate, dibutyl phosphate, triethyl phosphate, or tributyl phosphate. Pre~erred constituents (ii) of the catalysts (el) crucial to thP invention are methane-phosphonic acid dimethyl ester and dibutyl phosphate.
Catalysts ~el) can be prepared in known manner (see, 30 for example, Houben-Weyl, Vol. XII/2, pages 262 et seq) by reaction of components (i) and (ii) (as described above), pre~erably in equivalent quantities, in the presence or absence o~ solvents at temperatures in the ranye ~rom about 20 to about 200~C. The reaction may advantageously be carried out in an 35 inert gas atmosphere and/or under pressure. It is also Mo3503 ~ . ~
~} ., : ~:
., ~
,, ; .
possible, for example, to use an excess of component (i) or (ii) and subsequently to remove any unreacted excess, for example, by distillation.
Particularly preferred examples of catalysts (el) are compounds having the formulas:
cH3-N ~ -CH3 C~3 + O
(Butyl)?-N-CH3 -0-P-OCH3 + O
(cH3cH2)3-N-H-o-P-O(Butyl)2 +
(CH3)2 ~ H o-p-o(Butyl)2 Suitable latent catalysts (e2) include the known addition complexes of boron trihalides (more particularly boron trichlorides or boron trifluorides) with tertiary amines.
Examples include the addition complexes of boron trichloride and tertiary amines described in German Patentschrift 2,655,367 corresponding to the following general formula in which Rl, R2, and R3 may be the same or different and represent aliphatic, aromatic, heterocyclic, or aryl aliphatic groups or may be taken together (e.g., in pairs) to form part Mo3503 .,., ::
-: , -2 ~
of heterocyclic rings. Also suitable are the analogous complexes o~ boron trifluoride corresponding to the following formula RIR2R3N ~ BF3 in which Rl, R2 and R3 are as defined above.
Particularly suitable latent catalysts include boron trichlDride or boron trifluoride complexes of tertiary amines of the type mentioned by way of example in the description of components (c) and (el) or even of heterocyclic tertiary amines, such as 1,2-dimethylimidazole or l-benzyl-2-phenyl-imidazole. The amine component of the complexes generally has a molecular weight within the ranges mentioned above in 15 connection with component (c).
The latent catalysts (e) are generally used in a quantity of about 0.01 to about 20 parts by weight (preferably 0.1 to lO parts by weight and more preferably 0.5 to 2 parts by weight) per 100 parts by weight of the intermediate formed in ~o the "B stage" (that is, the resin present after poisoning of the catalyst (c)).
As with catalysts (c), mixtures of the compounds mentioned by way of example may also be used as the catalysts (e). The reaction time and the reaction temperature, both 25 - during preparation of the intermediate stage ("B stage"~ and during curing of the resin present in the intermediate stage, may be adapted to meet particular requirements through the type and concentration of the catalysts (c) and (e).
The optional auxiliaries and additives (f) include 30 (fl) polymerizable, olefinically unsaturated monomers and may be used in quantities of up to 100% by weight (preferably in quantities of up to 50% by weight) based on the total weight of components (a) and (b). Examples of additives (fl) include olefinically unsaturated monomers that do not contain any -35 NC0-reactive hydrogen atoms, such as diisobutylene, styrene, Mo3503 ~ ` :
, -16~
(C1 4 alkyl) styrenes (for example, ~-methyl styrene or n-butyl styrene), vinyl chloride, vinyl acetate, maleic imide derivatives (for example, bis(4-maleimidophenyl)methane), (C
alkyl) acrylates (for example, methyl acrylate, butyl acrylate, 5 or octyl acrylate) or the corresponding methacrylates, acrylonitrile, or diallyl phthalate. Mixtures of these olefinically unsaturated monomers may also be used. When used at all, the preferred additives (fl) are styrene and/or (C1 4 alkyl) acrylates or methacrylates are preferred. ~hen o additives (fl) are used, conventional polymerizatinn inhibitors, such as benzoyl peroxide, may be used but are generally not necessary.
The optional auxiliaries and additives (f) also include (f23 organic compounds containing at least 2 15 (preferably, 2 to 8 and more preferably 2 to 3) alcoholic hydroxyl groups and having a molecular weight in the range from about 62 to about 2,000, of the type known as synthesis components for polyurethanes. Examples of such compounds include simple polyhydric alcohols, such as ethylene glycol, 20. 1,6-hexanediol, glycerol, or trimethylolpropane; polyols containing dimethylsiloxane units, such as bis(dimethylhydroxy-methylsilyl) ether; polyhydroxy compounds containing ester groups, such as castor oil or polyhydroxypolyesters of the type obtainable by polycondensation of excess quantities of simple 25 monohydric alcohols of the type mentioned above with carboxylic acids (preferably dibasic carboxylic acids) or their anhydrides, such as adipic acid, phthalic acid, or phthalic anhydride; or polyhydroxypolyethers of the type obtainable by addition of alkylene oxides, such as propylene oxide and/or 30 ethylene oxide, with suitable starter molecules, such as water, the simple monoalcohols mentioned above, or even amides containing at least two amine NH bonds.
If used at all, the additives (f2) are used in a maximum quantity corresponding to an NCO:OH equivalent ratio, 35 based on the isocyanate groups of component (a) and -the Mo3503 :~ .
.
-17- ~ s~
hydroxyl groups of component (f2), of at least 2:1 (preferably at least 2.5:1). In any event, the quantity of component (a) must be selected in such a way that the equivalent ratio of isocyanate groups of component (a) to the sum of the epoxide 5 groups of component (b), the hydroxy1 groups of component (f2), and the hydroxyl groups present in optional component (b) is at least 1.2:1 (more preferably from 4:1 to 30:1).
In general, the auxiliaries and addit;ves (fl) and (f2) are not necessary. However, the additives mentioned by way of example for (fl) are preferred to the compounds mentioned by way of example for (f2). Both types of auxiliaries and additives may be used at the same time.
Other optional auxiliaries and additives (f) include fillers, such as mineral powders (for example, quartz powder, 15 chalk, or aluminum oxide); pigments, such as inorganic pigments (for example, titanium dioxide or iron oxide) or organ;c p;gments (for example, phthalocyanine pigments); plasticizers, such as dioctyl phthalate or tributyl or triphenyl phosphate;
dyes, including soluble dyes; or reinforcing materials, such as 20 . glass fibers or glass cloths. Carbon fibers or carbon fiber cloths and other organic polymeric fibers, such as aramide fibers or liquid crystal ("LC") polymer fibers, are also suitable. Woven or knitted cloths of polyamide and/or metal wire are also suitable.
The auxiliaries and additives may be incorporated in the starting materials (a) and (b) before the process of the invention is carried out or may even be subsequently added to the resin present in the intermediate stage, optionally after melting.
30 . In one preferred embodiment, the process of the invention is carried out by mixing the starting materials (a), (b), and (c) and, optionally, auxiliaries and additives (f), or a part thereof, with one another and reacting the resultant mixture at a temperature in the range from about 20 to about 150C (preferably from 60 to 130C). The reaction is Mo3503 -18- 2~ 3~
term;nated by addition of the stopper (d) after conversion of no more than 65% (preferably 30 to 60%) of the isocyanate groups orig;nally introduced into the start;ng mixture as component (a).
The relatively high Viscclsity intermediate product that accumulates in the "B stage" is generally a liquid at room temperature or a solid that is fusible at temperatures no higher than 120C and may be introduced into the second stage of the process of the invention, optionally after an inde~inite o storage period. To this end, the latent catalyst (e), as well as any other optional auxiliaries and additives, are added to the intermediate product, optionally after melting. If particularly low-viscosity mixtures are preferred, the starting components (a) and (b) are mixed with poisons (d) and briefly heated (0.5 to 1 hour) under nitrogen to about 120DC. Storable EPIC resins of very low viscosity (that is, viscosity <100 mPa.s at 25C) are thus obtained. After these low viscosity EPIC resins are cooled, the latent catalyst (e) and any ~ther optional auxiliaries and additives are added.
20 . Other suitable auxiliaries and additives include "reactive diluents," such as polyisocyanates that are liquid at room temperature of the type mentioned above under (a) and polyepoxides that are liquid at room temperature of the type mentioned above under (b), although such mixtures must always contain an excess of NCO groups over epoxide and hydroxyl groups corresponding to an equivalent ratio of at least 1.2:1 (preferably of at least 3:1).
Curing takes place under pressure in molds heated to temperatures of at least about 70C (preferably in the range from 70 to 180DC). To achieve optimal properties, it is often advisable to post-cure the resulting plastics at temperatures of about 150 to about 250C (preferably at temperatures of 200 to 230C).
Mo3503 .. .
-. .. : :
"' . ~. :
. . :. ~, ,, :
- , - ., .
- . :: .
2~3~5~
,9 When the resins of the invention are processed in combination with suitable blowing agents, it is even possible to prepare foams.
In addition, laminates having outstanding properties may be prepared by the process of the invention using glass cloth, glass mats, paper, plastic films, veneers, cloth made of KEYLAR~ fibers, woven or knitted carbon fiber cloth, glass nonwovens, or mineral wool.
The outstanding properties of the moldings include their inherent ~lame retardancy and their high long-term thermal stability.
The following examples further illustrate details for the process of this invention. The inYention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions of the following procedures can be used. Unless otherwise noted, all temperatures are degrees Celsius and all parts and percentages are parts by weight and percentages by weight.
20 . FXAMPLES
Example 1 A mixture of 60% 2,4'-diisocyanatodiphenylmethane and 40YO 4,4'-diisocyanatodiphenylmethane ~NC0 content 33.6%) ~950 9 wa~ mixed at 50~C with 5Q g of 25 ` the diglycidyl ether of bisphenol A (epoxide value 0.585) and 0.43 9 (3.2 mmole) of dimethylbenzylamine. The resulting mixture was heated to 120C. The slightly exothermic reaction indicates the immediate commencement of isocyanurate and oxazolidinone formation. After a reaction time of 15 minutes without external heating, the reaction mixturè was cooled with ice water to establish an internal temperature of approximately 90~C. A sample taken from the mixture was a solid, tacky resin at room temperature and had an NC0 content of 18.4% NC0. The reaction was terminated by adding 6.5 ml o~ stopper solution I
(a solution of 15.4% by weight of p-toluenesu1fonic acid methyl Mo3503 ester in a mixture of 60% 2,4'-diisocyanatodiphenylmethane and 40% 4,4'-diisocyanatodiphenylmethane). Another 5969 of the diisocyanate composition described above and 31 9 of the diglycidyl ether described above were then added to the mixture and the whole was st;rred at 120C
until a clear homogeneous solution was formed. A clear yellow, storable res1n that was liquid at room temperature and had a viscosity of 9,300 mPa-s at 25C and an NC0 content of 23.6%
was obtained.
Example 2 Dimethylbenzylamine (0.26 9) was added at 80C to 120 g of the diglycidyl ether described in Example 1 and 480 g of the polyisocyanate mixture described in Example 1. Under the effect of the exothermic isocyanurate-forming reaction, the 15 temperature of the reaction mixture increased to 120C over a period of 2 hours without further heating. Stopper solution I
(see Example 1) (3.82 ml) was then added to the reaction mixture, followed by stirring for 30 minutes at 129C. The resultant resin had an NC0 content of 20.0%. Mixing this resin 20 . with 327 9 of the diisocyanate component described above and 81.8 9 of the diglycidyl ether described above, followed by stirring for 30 minutes at 1~0C, yielded a clear yellow, storable resin that was liquid at room temperature and had a ~iscosity of 2,016 mPa~s (25C) and an NC0 content of 21.1%
25 Example 3 A mixture of 60% 2,4'-diisocyanatodiphenylmethane and 40% 4,4'-diisocyanatodiphenylmethane (NC0 content 33.6%) (120 g3 was mix~d with 30 9 of the diglycidyl ether of bisphenol A (epoxide value 0.5) and 1.5 ml 30 of a separately prepared 1 M sulution of p-toluenesulfonic acid methyl ester in the diisocyanate mixture described above. The resultant mixture was heated with stirring under nitrogen for 30 minutes to a temperature of 120C. After cooling, a reactive resin (I) having an NC0 content of 26.2% (based on the Mo3503 ~3~59~
mixture as a whole) and a viscosity of 55 mPa.s (25C) was obtained.
The reactive resin (I) (lO0 9~ was stirred for 10 hours at room temperature with 1 9 5 of the complex of B~13 and dimethylbenzylamine. The catalyst dissolved completely and the viscosity of the reactive resin remained unaffected. A prereacted casting resin of very low viscosity, which maintained a stable NC0 content and viscosity over a period of 6 months, was obtained in this way and could o be used in the process of to the invention.
Example 4 Reactive resin (I) of Example 3 (100 9) was mixed at room temperature with 19 dimethyl-benzylammonium dibutyl phosphate. The mixture was homogeneous, the liquid catalyst having dissolved completely, and the viscosity of the reactive resin remained unaffected. A pre-activated casting resin of very low viscosity, which maintained a stabie NC0 content and viscosity over a period of at least 7 days, was obtained in this way and could be used in the process of the invention.
ExamDle 5 The EPIC resin prepared according to Example 2 ~100 9) was stirred under nitrogen ~or 10 hours at room temperature with 1 9 of the complex of BC13 and dimethyl-benzylamine. The catalyst dissolved completely. Silicaflour (150 9) was then added to the mixture. A ready-to-use casting composition ~as obtained after stirring for 10 minutes in vacuo under a pressure of 12 torr.
The resultant casting composition was introduced into 30 a pressure vessel that was connected by a hose to an injection nozzle equipped with a valve. The pressure vessel was pressurized with compressed air at 4 atm gauge pressure through a valve in the cover of the vessel. The injection nozzle opened into the lower part of a self-heated, hydraulically 35 opened and closed mold having a temperature of 160C and a Mo3503 ;. ~
~ ~3 3 ~ P~
cavity representing a plate measuring 200 x 200 x 4 mm. After the injection nozzle valve was opened, the casting composition in the pressure vessel entered the hot steel mold while the air escaped through the gap between the two mold halves. After 6 5 minutes, the valve in the injection nozzle was closed and the hydraulics opened the mold. A homogeneous, bubble-free plastic plate free from sink marks was obtained. After the plate was heated for 4 hours at 160C, then for 4 hours at 200C, and finally for 4 hours at 250C, it had the fol70wing properties:
o Tensile strength (DIN 53,455) 80 N/mm2 Elongation at break (DIN 53,455) 1 %
E modulus in tension (DIN 53,457) 10,000 N/mm2 Flexural strength (DIN 53,452) 130 N/mm2 Outer fiber strain (DIN 53,452) 1.5 %
Impact strength (DIN 53,453)12 kJ/m2 Martens temperature (DIN 53,458) >250 C
Glass transition temperature300 C
Example 6 The reactive resin (I) prepared according to Example 3 (100 9) was stirred under nitrogen for 8 hours at room temperature with 1 9 of the complex of BCl3 and dimethylbenzylamine. The catalyst dissolved completely. The preact;vated resin was stable in storage for at least 6 months at room temperature in closed containers.
A glass mat was introduced into an opened plate mold arranged in a heatable hydraulic press in a quantity such that the mold was filled with 80% by weight glass. The mold was closed by the hydraulic press under a prPssure of 30 torr.
After precompression, the mold was opened again, impregnated 30 . with 20% by weight of the preactivated EPIC resin, and, after closure of the resin inlet valve, was closed under a pressure of 30 torr. With the mold heated to 160C, the cast resin cured in 4 to 10 minutes to form a homogeneous plate. After the mold was opened, the plate was removed and heated for 4 Mo3503 "
, . . .
hours at 160DC, then for 4 hours at 200C, and finally for 4 hours at 250C.
The plate was then suitable for use as a catalyst cover plate in car construction or for the insulation of very 5 hot parts or spacers, for example, in combustion engines. The plate prepared according to the invention could withstand brief heating to 600C without carbonizing or any loss of dimensions.
Mo3503
Claims (20)
1. A process for the preparation of plastic moldings by curing a reactive, liquid casting composition at elevated temperatures comprising (1) preparing a liquid casting composition by reacting (a) at least one organic polyisocyanate, and (b) at least one organic compound containing at least two epoxide groups in a quantity corresponding to an equivalent ratio of isocyanate groups to epoxide groups of 1.2:1 to 500:1, in the presence of (d) a stabilizing component comprising at least one alkylating sulfonic acid alkyl ester, methyl iodide, or dimethyl sulfate, (e) at least one latent, heat-activatable catalyst, and (f) optionally, auxiliaries and/or additives;
(2) transferring the liquid casting composition under pressure through a conduit into a heated mold having a temperature above 70°C; and (3) maintaining the casting composition in the mold under pressure until curing is complete.
(2) transferring the liquid casting composition under pressure through a conduit into a heated mold having a temperature above 70°C; and (3) maintaining the casting composition in the mold under pressure until curing is complete.
2. A process according to Claim 1 for the preparation of plastic moldings by curing a reactive, liquid casting composition at elevated temperatures comprising (1) preparing a liquid casting composition by (A) reacting (a) at least one organic polyisocyanate, (b) at least one organic compound containing at least two epoxide groups in a quantity corresponding to an equivalent ratio of isocyanate groups to epoxide groups of 1.2:1 to 500:1, and (c) a tertiary amine as catalyst, Mo3503 to form a relatively high viscosity liquid intermediate product containing oxazolidinone and isocyanurate groups;
(B) stopping the reaction of step (B) after no more than 65% of the isocyanate groups present in the starting mixture have reacted by adding (d) a stabilizing component comprising at least one alkylating sulfonic acid alkyl ester, methyl iodide, or dimethyl sulfate in a quantity at least equivalent to the quantity of tertiary amine (c); and (C) adding (e) at least one latent, heat-activatable catalyst, and (f) optionally, standard auxiliaries and/or additives;
(2) transferring the liquid casting composition under pressure through a conduit into a heated mold having a temperature above 70°C; and (3) maintaining the casting composition in the mold under pressure until curing is complete.
(B) stopping the reaction of step (B) after no more than 65% of the isocyanate groups present in the starting mixture have reacted by adding (d) a stabilizing component comprising at least one alkylating sulfonic acid alkyl ester, methyl iodide, or dimethyl sulfate in a quantity at least equivalent to the quantity of tertiary amine (c); and (C) adding (e) at least one latent, heat-activatable catalyst, and (f) optionally, standard auxiliaries and/or additives;
(2) transferring the liquid casting composition under pressure through a conduit into a heated mold having a temperature above 70°C; and (3) maintaining the casting composition in the mold under pressure until curing is complete.
3. A process according to Claim 1 wherein the latent, heat-activatable catalyst (e) is (1) a tertiary or quaternary ammonium salt of an alkylating or acidic ester of an organic phosphonic acid or phosphoric acid, and/or (2) an addition complex of a boron trihalide with a tertiary amine.
4. A process according to Claim 2 wherein the latent, heat-activatable catalyst (e) is (1) a tertiary or quaternary ammonium salt of an alkylating or acidic ester of an organic phosphonic acid or phosphoric acid, and/or (2) an addition complex of a boron trihalide with a tertiary amine.
Mo3503
Mo3503
5. A process according to Claim 1 wherein components (a) and (b) comprise 10 to 70% by weight of the liquid casting composition.
6. A process according to Claim 2 wherein components (a) and (b) comprise 10 to 70% by weight of the liquid casting composition.
7. A process according to Claim 1 wherein component (f) comprises an inorganic filler and/or a reinforcing material.
8. A process according to Claim 2 wherein component (f) comprises an inorganic filler and/or a reinforcing material.
9. A process according to Claim 7 wherein the inorganic filler is a mineral powder.
10. A process according to Claim 8 wherein the inorganic filler is a mineral powder.
11. A process according to Claim 1 wherein component (f) comprises release agents, plasticizers, pigments, and/or flameproofing additives.
12. A process according to Claim 2 wherein component (f) comprises release agents, plasticizers, pigments, and/or flameproofing additives.
13. A process according to Claim 1 wherein the conduit used in step (2) is at room temperature.
14. A process according to Claim 2 wherein the conduit used in step (2) is at room temperature.
15. A process according to Claim 1 wherein the liquid casting composition is injected under pressure into a heated mold containing glass wool, woven or knitted glass cloth, or glass mats as reinforcing materials and wherein said mold is closed under a pressure of 1 to 500 torr.
16. A process according to Claim 2 wherein the liquid casting composition is injected under pressure into a heated mold containing glass wool, woven or knitted glass Mo3503 cloth, or glass mats as reinforcing materials and wherein said mold is closed under a pressure of 1 to 500 torr.
17. A process according to Claim 1 wherein the liquid casting composition is injected under pressure into a heated mold containing woven or knitted cloths or mats of carbon fibers, aramide fibers, polyamide and/or metal wire and wherein said mold is closed under a pressure of 1 to 500 torr.
18. A process according to Claim 2 wherein the liquid casting composition is injected under pressure into a heated mold containing woven or knitted cloths or mats of carbon fibers, aramide fibers, polyamide and/or metal wire and wherein said mold is closed under a pressure of 1 to 500 torr.
19. In a method for preparing a high-temperature resistant insulating material or construction material, the improvement comprising curing a reactive, liquid casting composition according to Claim 1 in a heated mold under pressure.
20. In a method for preparing a high-temperature resistant insulating material or construction material, the improvement comprising curing a reactive, liquid casting composition according to Claim 2 in a heated mold under pressure.
Mo3503
Mo3503
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3942890.7 | 1989-12-23 | ||
| DE19893942890 DE3942890A1 (en) | 1989-12-23 | 1989-12-23 | METHOD FOR PRODUCING PLASTIC MOLDED PARTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2030599A1 true CA2030599A1 (en) | 1991-06-24 |
Family
ID=6396391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2030599 Abandoned CA2030599A1 (en) | 1989-12-23 | 1990-11-22 | Process for the preparation of plastic moldings |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0435060A3 (en) |
| JP (1) | JPH04120118A (en) |
| CA (1) | CA2030599A1 (en) |
| DE (1) | DE3942890A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150322197A1 (en) * | 2012-06-15 | 2015-11-12 | Dow Global Technologies Llc | Latent catalytic curing agent |
| CN105377928A (en) * | 2013-05-13 | 2016-03-02 | 巴斯夫欧洲公司 | Isocyanate-epoxide hybrid resins |
| RU2667523C2 (en) * | 2013-07-26 | 2018-09-21 | Басф Се | Isocyanate-epoxy-foam system |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2687551A1 (en) | 2012-07-17 | 2014-01-22 | Huntsman International Llc | Intermediate polyisocyanurate comprising materials |
| WO2021081154A1 (en) * | 2019-10-22 | 2021-04-29 | Sodano Henry A | Manufacture of fiber reinforced composite materials with isocyanate resin |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3323122A1 (en) * | 1983-06-27 | 1985-05-23 | Siemens AG, 1000 Berlin und 8000 München | METHOD FOR PRODUCING REACTION RESIN MOLDINGS |
| 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 |
| DE3644382A1 (en) * | 1986-12-24 | 1988-07-07 | Bayer Ag | METHOD FOR THE TWO-STAGE PRODUCTION OF MOLDED BODIES |
| DE3807660A1 (en) * | 1988-03-09 | 1989-09-21 | Bayer Ag | STABLE REACTIVE RESIN MIXTURE, MANUFACTURE AND USE |
| DE3828689A1 (en) * | 1988-08-24 | 1990-03-01 | Bayer Ag | MULTILAYER MOLDED BODY BASED ON POLYAMIDES |
-
1989
- 1989-12-23 DE DE19893942890 patent/DE3942890A1/en not_active Withdrawn
-
1990
- 1990-11-22 CA CA 2030599 patent/CA2030599A1/en not_active Abandoned
- 1990-12-11 EP EP19900123785 patent/EP0435060A3/en not_active Withdrawn
- 1990-12-21 JP JP2412624A patent/JPH04120118A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150322197A1 (en) * | 2012-06-15 | 2015-11-12 | Dow Global Technologies Llc | Latent catalytic curing agent |
| CN105377928A (en) * | 2013-05-13 | 2016-03-02 | 巴斯夫欧洲公司 | Isocyanate-epoxide hybrid resins |
| RU2673674C2 (en) * | 2013-05-13 | 2018-11-29 | Басф Се | Isocyanate-epoxide hybrid resins |
| US10329370B2 (en) | 2013-05-13 | 2019-06-25 | Basf Se | Isocyanate-epoxide hybrid resins |
| CN105377928B (en) * | 2013-05-13 | 2021-03-09 | 巴斯夫欧洲公司 | Isocyanate-epoxide hybrid resins |
| RU2667523C2 (en) * | 2013-07-26 | 2018-09-21 | Басф Се | Isocyanate-epoxy-foam system |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0435060A2 (en) | 1991-07-03 |
| EP0435060A3 (en) | 1991-08-07 |
| JPH04120118A (en) | 1992-04-21 |
| DE3942890A1 (en) | 1991-06-27 |
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