CA1312174C - Hot-foamable, thermosetting epoxy resin mixture - Google Patents
Hot-foamable, thermosetting epoxy resin mixtureInfo
- Publication number
- CA1312174C CA1312174C CA000566465A CA566465A CA1312174C CA 1312174 C CA1312174 C CA 1312174C CA 000566465 A CA000566465 A CA 000566465A CA 566465 A CA566465 A CA 566465A CA 1312174 C CA1312174 C CA 1312174C
- Authority
- CA
- Canada
- Prior art keywords
- epoxy resin
- resin mixture
- weight
- mixture according
- equivalents
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Abstract
Hot-foamable, thermosetting epoxy resin mixture Abstract Cured foams with a high degree of closed cellular structure, good stabil-ity under prolonged heat exposure and good compressive strength can be produced from a hot-foamable, thermosetting epoxy resin mixture contain-ing (a) an epoxy resin or a mixture of epoxy resins with an average epoxide content of 4.4 to 5.0 equivalents/kg and an average epoxide func-tionality of more than 2.0, (b) a novolak with a hydroxyl equivalent weight of 90 to 120, 0.8 to 0.95 hydroxyl equivalents of component (b) being present in the epoxy resin mixture per 1 epoxide equivalent of com-ponent (a), (c) 0.1 to 1% by weight, based on the amount of components (a) and (b), of a curing accelerator, (d) 0.5 to 10% by weight, based on the amount of components (a) and (b), of a blowing agent which splits off nitrogen above 100°C with decomposition, (e) 0.3 to 1% by weight, based on the total amount of the epoxy resin mixture, of an emulsifier, and if appropriate (f) foam modifiers.
Description
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Hot-foamable, thermosetting epoxy resin mixture The present invention relates to a hot-foamable, thermosett$ng epoxy resin mixture containing a novolak as the curing agent and, as the blow-ing agent, a compound which splits off nitrogen above 100C with decom-position, the use of the epoxy resin mixture for the production of foams and processes for the production of foams.
Foams based on epoxy resins are known and are generally distinguished by good mechanical strength and a good dimensional stability. For example, according to DE-OS 1,770,659, foams are produced by curing epoxy resins with cycloaliphatic polyamines at room temperature in the presence of polyhydric phenols as accelerators and of a blowing agent. The foams produced in this manner have a low compressive strength.
Foams with low compressive strength are likewise obtained by the process disclosed in DE-OS 2,~43,430, in which a certain epoxy resin foam mixture is cured at room temperature or somewhat elevated temperature using a Lewis acid or an addition or complex compound of a Lewis acid.
It has now been found that hardened Eoams which in particular have better compressive strength and compression values, especially at elevated tem-perature, are obtained by hot-foaming, that is to say at temperatures above 100C, an epoxy resin mixture containing a novolak as the curing agent in a certain equivalent ratio relative to the epoxide group and a blowing agent which splits off nitrogen above 100C.
The present invention thus relates to a hot-foamable, thermosetting epoxy resin mixture containing (a) an epoxy resin or a mixture of epoxy resins with an average epoxide content of 4.4 to 5.0 equivalents/kg and an aver-age epoxide functionality of more than 2.0, (b3 a novolak with a hydroxyl equivalent weight of 90 to 120, 0.8 to 0.95 hydroxyl equivalents of com-ponent (b) being present in the epoxy resin mlxture per 1 epoxide equiva-lent of component (a), (c) 0.1 to 1~ by weight, based on the amount of ~ ' .
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components (a) and (b), of a curing accelerator, (d) 0.5 to 10% by weight, based on the amount of components (a~ and (b), of a blowing agent which splits off nitrogen above 100C with decomposition, (e) 0.3 to 1%
by weight, based on the total amount of the epoxy resin mixture, of an emulsifier, and if appropriate (f) foam modifiers.
The hot-foamable epoxy resin mlxture according to the invention prefer-ably contains an epoxy resin or an epoxy resin mixture (a) with an aver-age epoxide content of 4.S to 5.0 equivalents/kg, a novolak (b) with a hydroxyl equivalent weight of 115 to 120 and a curing accelerator (c) in a~ounts of 0.3 to lYo by weight, based on the amount of components (a) and (b).
The epoxy resins or mixtures of epoxy resins contained as component (a)in the epoxy resin mixture according to the invention are known and are in some cases commercially available. Examples of such resins or resin mixtures which may be mentioned are: polyglycidyl esters of polycarboxy-lic acids, such as trime~litic acid, trimesic acid or pyromellitic acid, or of mixtures of polycarboxylic acids with dicarboxylic acids, such as phthalic acid or terephthalic acid; poly(N-glycidyl) compounds of dia-~ines, such as mrxylylenediamine, bis-(4-aminophenyl)-methane or bis-(3-methyl-4-aminophenyl)-methane or of mixtures of diamines with monoamines, such as aniline; glycidyl ethers of polynuclear phenols, such as novo-laks, which as i5 known are derived from aldehydes, such as formaldehyde, acetaldehyde, chloral or furfurylaldehyde, and phenols, such as phenol or phenol which is substituted on the ring by chlorine atoms or alkyl groups with up to 9 C atoms, such as 4-chlorophenol, 2-methylphenol or 4-tert-butylphenol, and glycidyl ethers of mixtures of polynuclear phenols and mono- or dinuclear phenols, such as resorcinol, hydroquinone, bis-(4-hydroxyphenyl)-methane, 4,4'-dihydroxydiphenyl, bis-(4-hydroxyphenyl) sulfone, 1,1,2,2-tetrakis-(4-hydroxyphenyl)-ethane, 2,2-bis-(4-hydroxy-phenyl)-propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.
The mixture according to the invention can furthermore contain, as compo-nent (a), triglycidyl isocyanurate or epoxy resins in which the glycidyl groups are bonded to different hetero atoms, for example the N,N,0-tri-131~ 7~
glycidyl derivative of 4-aminophenol.
The mixture according to the invention preferably contains, as component (a~, one or more aromatic glycidyl ethers, in particular a cresol novolak glycidyl ether or a mixture of a cresol novolak glycidyl ether and a bis-phenol A diglycidyl ether.
i The novolaks contained as component (b) in the mixture according to the invention are likewise known compounds, some of which are commercially available, and are condensation products prepared from a phenol, for example phenol itself or alkyl-, alkoxy- or halogen-substituted phenol, and an aldehyde, for example formaldehyde, acetaldehyde, chloral or fur-furyLaldehyde. Such novolaks correspond to the general formula I
~H Y ~H
.~i'\. .~ ~. . ,~
! I! CHR~- -~ I! CHR~ - -~+
~(R2~m (R2~m ln which R1 i9 a hydrogen atom, alkyl, aryl or a hetèrocyclic radical, R2 is a halogen atom, alkyl or alkoxy, m is zero or a number from 1 to 3 and n is a number such that the novolak has a hydroxyl equivalent weight of 90 to 120, preferably 115 to 120.
Preferred novolaks are those of the formula I in which R1 is a hydrogen atom, R2 is alkyl with 1 to 4 C atoms and m is zero or the number 1.
The mixtures according to the invention contain in particular, as compo-nent (b), a cresol novolak.
Curing accelerators (c) which can be used for the mixture according to the invention are the customary accelerators which can be used for curing an epoxy resin with a novolak, for example dicyandiamide, tertiary amines, such as tri-n-butylamine, tri-isobutylamine, benzyldlmethylamine, tri-n-propylamine, tri-(hexyl)-amine or 2,4,6-tris-(dimethylamino~ethyl)-phenol, quaternary ammonium compounds, such as tetramethylammonium chlor-ide, benzyltrimethylammonium hydroxide or benzyltrimethylammonium ... .
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~ 21489-7424 chloride, m-phenylenediamine, hexamethylenetetramine, imidazole or imi-dazole derivatives, for example 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or benzimidazole. The mixture according to the invention preferably contains an imidazole or an imi-dazole derivative, in particular 2-ethylimidazole, as the curing accele-rator.
Blowing agents (d) which can be used for the mixture according to the in-vention are substances which split off nitrogen with decomposition, when the mixture is heated above 100C, for example azo compounds, such as azoisobutyronitrile, or hydrazides, such as p-toluenesulfohydrazide (Genitron PTS~). The mixtures according to the invention preferably con-tain p-toluenesulfohydrazide as the blowing agent.
The emulsifiers (e~ contained in the mixture according to the invention are surface-active agents which act as pore regulators. They have the function of distributing the nitrogen formed from the blowing agent in regular bubbles throughout the entire foam, so that a foam with a sub-stantially closed cellular structure is obtained. Substances which are ; particulary suitable for regulating the pore structure are non-ionic substancesS for example hydroxyl-containing esters of fatty acids, such as lauric, palmitic, stearic or oleic acid, with polyhydric alcohols, such as sorbitol, and addition products thereof with polyoxyethylene onto the free hydroxyl groups (Tweens~), for example polyoxyethylene sorbitan monolaurate or monostearate, and furthermore polyoxyglycols (Pluronics~).
Silicone oils, such as are commercially available, for example, under the tradename Rhodorsil~ from Rhône-Poulencl are known to be good pore regu-lators. The mixture according to the invention contains in particular as the emulsifier a polyether-polymethylsiloxane copolymer (Tegopren~ 5851 from Goldschmidt).
If appropriate, the mixture according to the invention can also contain customary foam modifiers, that is to say substances which can reduce the viscosity of the mixture according to the invention during processing, can improve the flow behavior of the foam or can be used as solvents for additives. These foam modifiers can be reactive, that is to say they can ~ .
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react with a component of the foam, or non-reactive. To improve the flow behavior of the foam, nonylphenol, for example, can be added to the mix-ture according to the invention as a reactive modifier and ethylhexyl phthalate, for example, can be added as a non-reactive modifier. They are advantageously used in amounts of 0.5 to 10% by weight, based on the amount of components (a~ and (b).
Dyes, fillers, plasticizers or flameprooflng agents, for example Al203-3 H20, polyethylene, polypropylene or polyvinyl chloride, can furthermore be added to the mixture accordlng to the invention.
The mixture according to the invention can be processed to foams manually or by means of a suitable machine, by foaming and curing the mixture in the temperature range from 120 to 180C. The mixture according to the invention is advantageously suitable for mechanical production of a foam, for example by means of RDM machine (reactive injection moulding machine), since the viscosity of the mixture according to the invention does not change greatly during storage at elevated temperature and no severe evolution of heat occurs during curing of the foam in the closed mould, so that foam formation is not interfered with and a foam with a high degree of closed cellular structure is obtained. Cycle times of 10 to 20 minutes can be achieved in mechanical processing of the mixture ac-cording to the invention to give cured foams.
The present invention thu5 also relates to the use of the mixture accord-ing to the invention for mechanical production of a foam and a process for the production of crosslinked, insoluble and non-fusible epoxy resin foams by foaming and curing the mixture according to the invention in the temperature range from 120 to 180C, preferably from 130 to 160C.
The foams produced from the mixture according to the invention are dis-tinguished by a homogeneous pore structure and a high degree of closed cellular structure. The foams also have a good stability to prolonged heat exposure and a good compressive strength, also at elevated tempera-ture. The foams obtained from the mixture according to the invention are therefore particularly suitable as insulating materials against heat loss 1 7 ~
and against pressure and impact.
In the followlng examples, foams are ?roduced using a casting mould.
Ihis mould has internal dimensions of 250x250x30 m~ and consists of two outer metal plates (20 mm) which can be heated electrically and are sepa-rated 30 mm from one another by an unheated spacer frame. The spacer frame can be opened on one side so that the activated foam mixture can be poured in. The outer plates which can be heated and the metal spacer frame are held together by four screw clamps during curing of the foamed sheet. The sheets are cast upright, and for this the top screw clamp is removed and 1/4 of the spacer frame is removed. After the activated foam mixture has been poured in, the section of the spacer frame which has been removed is inserted and the screw clamp is closed. The still hot plates and the hot spacer frame are coated with OP wax or a silicone-containing release agent for better removal from the mould.
Example 1: A foam is produced using the following compounds:
bisphenol A diglycidyl ether (liquid, epoxide equivalent weight 185) 276.8 g (1.5 equivalents) cresol novolak glycidyl ether (solid, epoxide equivalent weight 230) 276.8 g (1.2 equivalents) cresol novolak (solid, hydroxyl equivalent weight 115) 287.2 g (2.5 equivalents) polyether-polymethylsiloxane copolymer (emulsifier) 6.2 g 2-ethylimidazole (accelerator) 4.5 g p-toluenesulfohydrazide (blowing agent) 7.0 g The bisphenol A diglycidyl ether (BPAD) is heated to about 145C in a glass beaker which stands in an oil bath heated at 170C and is equipped with a high-speed stirrer. The cresol novolak glycidyl ether (CNG) is sprinkled into the BPAD in portions at this temperature, and as soon as the CNG has dissolved the cresol novolak is introduced in small portions.
When everything has dissolved and the matrix has reached a temperature of about 145C, the polyether-polymethylsiloxane copolymer is added with stirring. The glass beaker with the hot resin-curing agent mixture is 13~7~
" , removed from the oil bath and 2-ethyl-imidazole and p-toluenesulfohydra-zide are stirred in homogeneously in the course of 20 - 30 seconds. The activated foam mixture is poured into the hot casting mould at 130 -140C in the course of a further 20 seconds. The casting mould is closed with screw clamps in the course of a further 20 seconds. The increase in pressure in the closed casting mould takes place after 1 - 5 minutes. After 10 - 20 minutes, the mould is opened and one plate of the still hot mould is removed. The cooled sheet of foam is split off into the desired test specimens with a circular saw. Exclusively test speci-mens without top coatings are tested. The properties of the foam obtain-ed are shown in Table I.
Example 2: Example 1 is repeated, but 11.8 g of p-toluenesulfohydrazide are now added to the resin-curing agent mixture. Curing conditions: 20 minutes/140c. The properties of the foam obtained are shown in Table I.
Example 3: ~ foam ls produced as in Example l using the following com-.
pounds:
bisphenol ~ diglycidyl ether (liquid, epoxide equivalent welght 185) 166.1 g (0.9 equivalent) cresol novolak glycidyl ether (solid, epoxlde equivalent weight 230) 166.1 g (0.7 equivalent) cresol novolak (solid, hydroxyl equivalent weight 115) 172.3 g (1.5 equivalents) polyether-polymethylsiloxane copolymer 3.6 g 2-ethylimidazole 3.3 g p-toluenesulfohydrazide 10.0 g Curing conditions: 20 minutes/145C. The properties of the foam obtained are shown in Table I.
Example 4: A foam is produced as in Example 1 using the following com-pounds:
'`': '' ' , ~312~74 bisphenol A diglycidyl ether (liquid, epoxide equivalent weight 185) 92.3 g (0.5 equivalent)cresol novolak glycidyl ether (solid, epoxide equivalent weight 230) 92.3 g (0.4 equivalent)cresol novolak (solid, hydroxyl equivalent weight 115) 95.7 g (0.8 equivalent)polyether-polymethylsiloxane copolymer 2.0 g 2-ethylimidazole 1.8 g p-toluenesulfohydrazide 13.0 g .
Curing conditions: 15 minutes/145C. The properties of the foam obtained are shown in Table I.
Example 5: Example 1 is repeated, but, instead of 287.2 g, 257.2 g (2.2 equivalents) of solid cresol novolak with a hydroxyl equivalent weight of 115 are now used. Curing conditions: 15 minutes/145C. The properties of the foam obtained are shown in Table I.
Example 6: A foam is produced as in Example 1 using the following com-pounds:
bisphenol A diglycidyl ether (liquid, epoxide equivalent weight 185)276.8 g (1.5 equivalents) cresol novolak glycidyl ether (solid, epoxide equivalent weight 230)276.8 g (1.2 equivalents) cresol novolak (solid, hydroxyl equivalent weight 115)257.2 g (2.2 equivalents) polyether-polymethylsiloxane copolymer 6.2 g 2-ethylimidazole 7.5 g p-toluenesulfohydrazide 7.0 g nonylphenol 30.0 g Curing conditions: 15 minutes/135C. The properties of the foam obtained are shown in Tables I and II.
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_ 9 _ Example 7: Example 6 is repeated, but, instead of 30.0 g, 60.0 g of nonylphenol are now used. Curing conditions: 15 mlnutes/135C. The pro-perties of the Eoam obtaLned are shown in Table I.-Example 8: Example 6 is repeated, but, instead of 30.0 g, 75 g of nonyl-phenol are now used. Curing conditions: 15 minutes/135C. The proper-ties of the foam obtained are shown in Table I.
Example 9: A foam is produced as in Example 1 using the following CO~r pounds:
bisphenol A diglycidyl ether (liquid, epoxide equivalent weight 185)221.5 g (1.2 equivalents) cresol novolak glycidyl ether (solid, epoxide equivalent weight 230)332.2 g (1.4 equivalents) cresol novolak (solid, hydroxyl equivalent weight 115)250.5 g (2.2 equivalents) polyether-polymethylsiloxane copolymer 6.0 g 2-ethylimidazole 7.5 g p-toluenesulfohydrazide 6.8 g nonylphenol 30.0 g Curing conditions: 15 minutes/135C. The properties of the resulting foam are shown in Tables I and II.
Example 10: ~ foam is produced as in Example 1 using ~he following com-pounds:
bisphenol A diglycidyl ether (liquid, epoxide equivalent weight 185) 166.1 g (0.9 equivalent) cresol novolak glycidyl ether (solid, epoxide equivalent weight 230) 387.5 g (1.7 equivalents) cresol novolak (solid, hydroxyl equivalent weight 115) 246.7 g (2.15 equivalents) polyether-polymethylsiloxane copoly=er 6.0 g ,,"
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2-ethyllmidazole 7.5 g p-toluenesulfohydrazide 6.8 g nonylphenol 30.0 g Curing conditions: 15 minutes/140C. The properties of the resulting foam are shown in Table I.
Example 11: A foam is produced as in Exa~ple 1 using the Eollowing com-pounds:
bisphenol A diglycidyl ether (liquid, epoxide equivalent weight 185)110.7 g (0.6 equivalent) cresol novolak glycidyl ether (solid, epoxide equivalent weight 230)442.9 g (1.9 equivalents) cresol novolak (solid, hydroxyl equivalent weight 115)240.1 g (2.1 equivalents) polyether-polymethylsiloxane copolymer 6.0 g 2-ethylimidazole 7.5 g p-toluenesulfohydrazide 6.8 g nonylphenol 30 0 g Curing conditions: 15 minutes/140C. The properties of the resulting foam are shown in Table I.
;
Example 12: Example 1 is repeated, but, instead of 4.5 g, 5.5 g of 2-ethylimidazole are now used. Curin~ conditions: 15 minutes/140C. The properties of the foam obtained are shown in Table I.
. :
Example 13: Example 1 is repeated, but, instead of 4.5 g, 6.5 g of 2-ethylimidazole are now used. Curing conditions: 15 minutes/140C. The properties of the foam obeained are shown in Table I.
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Hot-foamable, thermosetting epoxy resin mixture The present invention relates to a hot-foamable, thermosett$ng epoxy resin mixture containing a novolak as the curing agent and, as the blow-ing agent, a compound which splits off nitrogen above 100C with decom-position, the use of the epoxy resin mixture for the production of foams and processes for the production of foams.
Foams based on epoxy resins are known and are generally distinguished by good mechanical strength and a good dimensional stability. For example, according to DE-OS 1,770,659, foams are produced by curing epoxy resins with cycloaliphatic polyamines at room temperature in the presence of polyhydric phenols as accelerators and of a blowing agent. The foams produced in this manner have a low compressive strength.
Foams with low compressive strength are likewise obtained by the process disclosed in DE-OS 2,~43,430, in which a certain epoxy resin foam mixture is cured at room temperature or somewhat elevated temperature using a Lewis acid or an addition or complex compound of a Lewis acid.
It has now been found that hardened Eoams which in particular have better compressive strength and compression values, especially at elevated tem-perature, are obtained by hot-foaming, that is to say at temperatures above 100C, an epoxy resin mixture containing a novolak as the curing agent in a certain equivalent ratio relative to the epoxide group and a blowing agent which splits off nitrogen above 100C.
The present invention thus relates to a hot-foamable, thermosetting epoxy resin mixture containing (a) an epoxy resin or a mixture of epoxy resins with an average epoxide content of 4.4 to 5.0 equivalents/kg and an aver-age epoxide functionality of more than 2.0, (b3 a novolak with a hydroxyl equivalent weight of 90 to 120, 0.8 to 0.95 hydroxyl equivalents of com-ponent (b) being present in the epoxy resin mlxture per 1 epoxide equiva-lent of component (a), (c) 0.1 to 1~ by weight, based on the amount of ~ ' .
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components (a) and (b), of a curing accelerator, (d) 0.5 to 10% by weight, based on the amount of components (a~ and (b), of a blowing agent which splits off nitrogen above 100C with decomposition, (e) 0.3 to 1%
by weight, based on the total amount of the epoxy resin mixture, of an emulsifier, and if appropriate (f) foam modifiers.
The hot-foamable epoxy resin mlxture according to the invention prefer-ably contains an epoxy resin or an epoxy resin mixture (a) with an aver-age epoxide content of 4.S to 5.0 equivalents/kg, a novolak (b) with a hydroxyl equivalent weight of 115 to 120 and a curing accelerator (c) in a~ounts of 0.3 to lYo by weight, based on the amount of components (a) and (b).
The epoxy resins or mixtures of epoxy resins contained as component (a)in the epoxy resin mixture according to the invention are known and are in some cases commercially available. Examples of such resins or resin mixtures which may be mentioned are: polyglycidyl esters of polycarboxy-lic acids, such as trime~litic acid, trimesic acid or pyromellitic acid, or of mixtures of polycarboxylic acids with dicarboxylic acids, such as phthalic acid or terephthalic acid; poly(N-glycidyl) compounds of dia-~ines, such as mrxylylenediamine, bis-(4-aminophenyl)-methane or bis-(3-methyl-4-aminophenyl)-methane or of mixtures of diamines with monoamines, such as aniline; glycidyl ethers of polynuclear phenols, such as novo-laks, which as i5 known are derived from aldehydes, such as formaldehyde, acetaldehyde, chloral or furfurylaldehyde, and phenols, such as phenol or phenol which is substituted on the ring by chlorine atoms or alkyl groups with up to 9 C atoms, such as 4-chlorophenol, 2-methylphenol or 4-tert-butylphenol, and glycidyl ethers of mixtures of polynuclear phenols and mono- or dinuclear phenols, such as resorcinol, hydroquinone, bis-(4-hydroxyphenyl)-methane, 4,4'-dihydroxydiphenyl, bis-(4-hydroxyphenyl) sulfone, 1,1,2,2-tetrakis-(4-hydroxyphenyl)-ethane, 2,2-bis-(4-hydroxy-phenyl)-propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.
The mixture according to the invention can furthermore contain, as compo-nent (a), triglycidyl isocyanurate or epoxy resins in which the glycidyl groups are bonded to different hetero atoms, for example the N,N,0-tri-131~ 7~
glycidyl derivative of 4-aminophenol.
The mixture according to the invention preferably contains, as component (a~, one or more aromatic glycidyl ethers, in particular a cresol novolak glycidyl ether or a mixture of a cresol novolak glycidyl ether and a bis-phenol A diglycidyl ether.
i The novolaks contained as component (b) in the mixture according to the invention are likewise known compounds, some of which are commercially available, and are condensation products prepared from a phenol, for example phenol itself or alkyl-, alkoxy- or halogen-substituted phenol, and an aldehyde, for example formaldehyde, acetaldehyde, chloral or fur-furyLaldehyde. Such novolaks correspond to the general formula I
~H Y ~H
.~i'\. .~ ~. . ,~
! I! CHR~- -~ I! CHR~ - -~+
~(R2~m (R2~m ln which R1 i9 a hydrogen atom, alkyl, aryl or a hetèrocyclic radical, R2 is a halogen atom, alkyl or alkoxy, m is zero or a number from 1 to 3 and n is a number such that the novolak has a hydroxyl equivalent weight of 90 to 120, preferably 115 to 120.
Preferred novolaks are those of the formula I in which R1 is a hydrogen atom, R2 is alkyl with 1 to 4 C atoms and m is zero or the number 1.
The mixtures according to the invention contain in particular, as compo-nent (b), a cresol novolak.
Curing accelerators (c) which can be used for the mixture according to the invention are the customary accelerators which can be used for curing an epoxy resin with a novolak, for example dicyandiamide, tertiary amines, such as tri-n-butylamine, tri-isobutylamine, benzyldlmethylamine, tri-n-propylamine, tri-(hexyl)-amine or 2,4,6-tris-(dimethylamino~ethyl)-phenol, quaternary ammonium compounds, such as tetramethylammonium chlor-ide, benzyltrimethylammonium hydroxide or benzyltrimethylammonium ... .
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~ 21489-7424 chloride, m-phenylenediamine, hexamethylenetetramine, imidazole or imi-dazole derivatives, for example 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or benzimidazole. The mixture according to the invention preferably contains an imidazole or an imi-dazole derivative, in particular 2-ethylimidazole, as the curing accele-rator.
Blowing agents (d) which can be used for the mixture according to the in-vention are substances which split off nitrogen with decomposition, when the mixture is heated above 100C, for example azo compounds, such as azoisobutyronitrile, or hydrazides, such as p-toluenesulfohydrazide (Genitron PTS~). The mixtures according to the invention preferably con-tain p-toluenesulfohydrazide as the blowing agent.
The emulsifiers (e~ contained in the mixture according to the invention are surface-active agents which act as pore regulators. They have the function of distributing the nitrogen formed from the blowing agent in regular bubbles throughout the entire foam, so that a foam with a sub-stantially closed cellular structure is obtained. Substances which are ; particulary suitable for regulating the pore structure are non-ionic substancesS for example hydroxyl-containing esters of fatty acids, such as lauric, palmitic, stearic or oleic acid, with polyhydric alcohols, such as sorbitol, and addition products thereof with polyoxyethylene onto the free hydroxyl groups (Tweens~), for example polyoxyethylene sorbitan monolaurate or monostearate, and furthermore polyoxyglycols (Pluronics~).
Silicone oils, such as are commercially available, for example, under the tradename Rhodorsil~ from Rhône-Poulencl are known to be good pore regu-lators. The mixture according to the invention contains in particular as the emulsifier a polyether-polymethylsiloxane copolymer (Tegopren~ 5851 from Goldschmidt).
If appropriate, the mixture according to the invention can also contain customary foam modifiers, that is to say substances which can reduce the viscosity of the mixture according to the invention during processing, can improve the flow behavior of the foam or can be used as solvents for additives. These foam modifiers can be reactive, that is to say they can ~ .
: ;
~.
_ 5 ~3~2~7~
react with a component of the foam, or non-reactive. To improve the flow behavior of the foam, nonylphenol, for example, can be added to the mix-ture according to the invention as a reactive modifier and ethylhexyl phthalate, for example, can be added as a non-reactive modifier. They are advantageously used in amounts of 0.5 to 10% by weight, based on the amount of components (a~ and (b).
Dyes, fillers, plasticizers or flameprooflng agents, for example Al203-3 H20, polyethylene, polypropylene or polyvinyl chloride, can furthermore be added to the mixture accordlng to the invention.
The mixture according to the invention can be processed to foams manually or by means of a suitable machine, by foaming and curing the mixture in the temperature range from 120 to 180C. The mixture according to the invention is advantageously suitable for mechanical production of a foam, for example by means of RDM machine (reactive injection moulding machine), since the viscosity of the mixture according to the invention does not change greatly during storage at elevated temperature and no severe evolution of heat occurs during curing of the foam in the closed mould, so that foam formation is not interfered with and a foam with a high degree of closed cellular structure is obtained. Cycle times of 10 to 20 minutes can be achieved in mechanical processing of the mixture ac-cording to the invention to give cured foams.
The present invention thu5 also relates to the use of the mixture accord-ing to the invention for mechanical production of a foam and a process for the production of crosslinked, insoluble and non-fusible epoxy resin foams by foaming and curing the mixture according to the invention in the temperature range from 120 to 180C, preferably from 130 to 160C.
The foams produced from the mixture according to the invention are dis-tinguished by a homogeneous pore structure and a high degree of closed cellular structure. The foams also have a good stability to prolonged heat exposure and a good compressive strength, also at elevated tempera-ture. The foams obtained from the mixture according to the invention are therefore particularly suitable as insulating materials against heat loss 1 7 ~
and against pressure and impact.
In the followlng examples, foams are ?roduced using a casting mould.
Ihis mould has internal dimensions of 250x250x30 m~ and consists of two outer metal plates (20 mm) which can be heated electrically and are sepa-rated 30 mm from one another by an unheated spacer frame. The spacer frame can be opened on one side so that the activated foam mixture can be poured in. The outer plates which can be heated and the metal spacer frame are held together by four screw clamps during curing of the foamed sheet. The sheets are cast upright, and for this the top screw clamp is removed and 1/4 of the spacer frame is removed. After the activated foam mixture has been poured in, the section of the spacer frame which has been removed is inserted and the screw clamp is closed. The still hot plates and the hot spacer frame are coated with OP wax or a silicone-containing release agent for better removal from the mould.
Example 1: A foam is produced using the following compounds:
bisphenol A diglycidyl ether (liquid, epoxide equivalent weight 185) 276.8 g (1.5 equivalents) cresol novolak glycidyl ether (solid, epoxide equivalent weight 230) 276.8 g (1.2 equivalents) cresol novolak (solid, hydroxyl equivalent weight 115) 287.2 g (2.5 equivalents) polyether-polymethylsiloxane copolymer (emulsifier) 6.2 g 2-ethylimidazole (accelerator) 4.5 g p-toluenesulfohydrazide (blowing agent) 7.0 g The bisphenol A diglycidyl ether (BPAD) is heated to about 145C in a glass beaker which stands in an oil bath heated at 170C and is equipped with a high-speed stirrer. The cresol novolak glycidyl ether (CNG) is sprinkled into the BPAD in portions at this temperature, and as soon as the CNG has dissolved the cresol novolak is introduced in small portions.
When everything has dissolved and the matrix has reached a temperature of about 145C, the polyether-polymethylsiloxane copolymer is added with stirring. The glass beaker with the hot resin-curing agent mixture is 13~7~
" , removed from the oil bath and 2-ethyl-imidazole and p-toluenesulfohydra-zide are stirred in homogeneously in the course of 20 - 30 seconds. The activated foam mixture is poured into the hot casting mould at 130 -140C in the course of a further 20 seconds. The casting mould is closed with screw clamps in the course of a further 20 seconds. The increase in pressure in the closed casting mould takes place after 1 - 5 minutes. After 10 - 20 minutes, the mould is opened and one plate of the still hot mould is removed. The cooled sheet of foam is split off into the desired test specimens with a circular saw. Exclusively test speci-mens without top coatings are tested. The properties of the foam obtain-ed are shown in Table I.
Example 2: Example 1 is repeated, but 11.8 g of p-toluenesulfohydrazide are now added to the resin-curing agent mixture. Curing conditions: 20 minutes/140c. The properties of the foam obtained are shown in Table I.
Example 3: ~ foam ls produced as in Example l using the following com-.
pounds:
bisphenol ~ diglycidyl ether (liquid, epoxide equivalent welght 185) 166.1 g (0.9 equivalent) cresol novolak glycidyl ether (solid, epoxlde equivalent weight 230) 166.1 g (0.7 equivalent) cresol novolak (solid, hydroxyl equivalent weight 115) 172.3 g (1.5 equivalents) polyether-polymethylsiloxane copolymer 3.6 g 2-ethylimidazole 3.3 g p-toluenesulfohydrazide 10.0 g Curing conditions: 20 minutes/145C. The properties of the foam obtained are shown in Table I.
Example 4: A foam is produced as in Example 1 using the following com-pounds:
'`': '' ' , ~312~74 bisphenol A diglycidyl ether (liquid, epoxide equivalent weight 185) 92.3 g (0.5 equivalent)cresol novolak glycidyl ether (solid, epoxide equivalent weight 230) 92.3 g (0.4 equivalent)cresol novolak (solid, hydroxyl equivalent weight 115) 95.7 g (0.8 equivalent)polyether-polymethylsiloxane copolymer 2.0 g 2-ethylimidazole 1.8 g p-toluenesulfohydrazide 13.0 g .
Curing conditions: 15 minutes/145C. The properties of the foam obtained are shown in Table I.
Example 5: Example 1 is repeated, but, instead of 287.2 g, 257.2 g (2.2 equivalents) of solid cresol novolak with a hydroxyl equivalent weight of 115 are now used. Curing conditions: 15 minutes/145C. The properties of the foam obtained are shown in Table I.
Example 6: A foam is produced as in Example 1 using the following com-pounds:
bisphenol A diglycidyl ether (liquid, epoxide equivalent weight 185)276.8 g (1.5 equivalents) cresol novolak glycidyl ether (solid, epoxide equivalent weight 230)276.8 g (1.2 equivalents) cresol novolak (solid, hydroxyl equivalent weight 115)257.2 g (2.2 equivalents) polyether-polymethylsiloxane copolymer 6.2 g 2-ethylimidazole 7.5 g p-toluenesulfohydrazide 7.0 g nonylphenol 30.0 g Curing conditions: 15 minutes/135C. The properties of the foam obtained are shown in Tables I and II.
.~
1 3~ ~ 7 ~
,~ ~
_ 9 _ Example 7: Example 6 is repeated, but, instead of 30.0 g, 60.0 g of nonylphenol are now used. Curing conditions: 15 mlnutes/135C. The pro-perties of the Eoam obtaLned are shown in Table I.-Example 8: Example 6 is repeated, but, instead of 30.0 g, 75 g of nonyl-phenol are now used. Curing conditions: 15 minutes/135C. The proper-ties of the foam obtained are shown in Table I.
Example 9: A foam is produced as in Example 1 using the following CO~r pounds:
bisphenol A diglycidyl ether (liquid, epoxide equivalent weight 185)221.5 g (1.2 equivalents) cresol novolak glycidyl ether (solid, epoxide equivalent weight 230)332.2 g (1.4 equivalents) cresol novolak (solid, hydroxyl equivalent weight 115)250.5 g (2.2 equivalents) polyether-polymethylsiloxane copolymer 6.0 g 2-ethylimidazole 7.5 g p-toluenesulfohydrazide 6.8 g nonylphenol 30.0 g Curing conditions: 15 minutes/135C. The properties of the resulting foam are shown in Tables I and II.
Example 10: ~ foam is produced as in Example 1 using ~he following com-pounds:
bisphenol A diglycidyl ether (liquid, epoxide equivalent weight 185) 166.1 g (0.9 equivalent) cresol novolak glycidyl ether (solid, epoxide equivalent weight 230) 387.5 g (1.7 equivalents) cresol novolak (solid, hydroxyl equivalent weight 115) 246.7 g (2.15 equivalents) polyether-polymethylsiloxane copoly=er 6.0 g ,,"
" ,'''' ' , .
:. :
` ' ..
~312~7~
,. ~
2-ethyllmidazole 7.5 g p-toluenesulfohydrazide 6.8 g nonylphenol 30.0 g Curing conditions: 15 minutes/140C. The properties of the resulting foam are shown in Table I.
Example 11: A foam is produced as in Exa~ple 1 using the Eollowing com-pounds:
bisphenol A diglycidyl ether (liquid, epoxide equivalent weight 185)110.7 g (0.6 equivalent) cresol novolak glycidyl ether (solid, epoxide equivalent weight 230)442.9 g (1.9 equivalents) cresol novolak (solid, hydroxyl equivalent weight 115)240.1 g (2.1 equivalents) polyether-polymethylsiloxane copolymer 6.0 g 2-ethylimidazole 7.5 g p-toluenesulfohydrazide 6.8 g nonylphenol 30 0 g Curing conditions: 15 minutes/140C. The properties of the resulting foam are shown in Table I.
;
Example 12: Example 1 is repeated, but, instead of 4.5 g, 5.5 g of 2-ethylimidazole are now used. Curin~ conditions: 15 minutes/140C. The properties of the foam obtained are shown in Table I.
. :
Example 13: Example 1 is repeated, but, instead of 4.5 g, 6.5 g of 2-ethylimidazole are now used. Curing conditions: 15 minutes/140C. The properties of the foam obeained are shown in Table I.
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,; : O ~ O 6 . ~ ~
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;J~ O CL
~D O r C
__ r~ _ _ E 6 __ ~ L~ --O ~ _ c~
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O
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tq ~ ,~ Z .~, ~ o _ L
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~ ' i~i O ~ ~ c ~_ _ Q
:~ h ~ ~ ~ ~ O
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t.~ ., ~ ~ ~ L ~ ~.) ~ ti~ E c ~
. ` O _ C5~ ~ ~ ~ o ~ _ ~
L~ E ~ L J U~ O ~ ~ L~
:~ ~) n~ 10 ~ -O ~ L Z ~ ~ L~ ~ aJ r~l ~1) C
~1 X ~-- J,I U ~ \ L 1/~ ~ f~l E LLI C O L ~1/ E Z ~ 2 E I ' E Z I_ E~ 0 0 GJ. -- ~1 -- O ~ 0 L~ O 1 Ll_ ~J C~ L~ L~ (~ V C~ )C
_ - --~,' ~ , ' ' ` . ' '''''`' '' ' ~3~2~
Table II: Properties of the foams at elevated temperature .
. Foam according to Example 6 9 : _ Compressive strength (DIN 53 421-A) : at 23C [N/mm2] 12.7 12.6 ; Compression (DIN 53 421-A) . at 23C [%] 16.6 17.4 Compressive strength at 80C [N/mm2] 9.4 ô.9 Compression at 80C [%] 14.8 11.4 : Compressive strength at 100C [N/mm2]7.3 8.3 ~ Compression at 100C [%] 14.8 12.8 : Compressive strength at 120C [N/mm2]5.3 7.1 Compression at 120C [%] 14.7 15.2 Example 14: The procedure of Example 1 is followed, but, instead of p-toluenesulfohydrazide, 7.6 g of azo-isobutyronitrile are now used, and, instead of polyether-polymethylsiloxane copolymer, 6.0 g of silicone oil (RhodorsilR 3139~ are now employed. The foam matrix is poured at 105C
into the mould heated to 140C. Curing conditions: 15 minutes at 140C.
The cured foam has the following properties:
density = 0.36 g/cm3 closed cellular structure = 94.0%.
~3~ 2~
,- ~
Example 15_ The procedure is as in ~xample 1, the following compounds being used for production of the foam:
bisphenol A diglycidyl ether (highly viscous, epoxide equivalent weight 222) 574.0 g (2.58 equivalents) cresol novolak (solid, hydroxyl equivalent weight 115) 266.0 g (2.31 equivalents) polyether-polymethylsiloxane copolymer 6.0 g 2-ethylimidazole 7.5 g p-toluenesulfohydrazide 7.5 g Curing conditions: 15 minutes at 140C. The cured foam has a density of 0.39 g/cm3.
, . . .
~1 O ~ L
_ . ~ _ n~
. ~ E a~
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O _I O ~ r~ ~ C`.l ~ _ ~
O
~ ~ u~ ~
. , E ,~
tq ~ ,~ Z .~, ~ o _ L
E 0 U~ I ~
~ ' i~i O ~ ~ c ~_ _ Q
:~ h ~ ~ ~ ~ O
~ C E J ~ E ~ 1 L
t.~ ., ~ ~ ~ L ~ ~.) ~ ti~ E c ~
. ` O _ C5~ ~ ~ ~ o ~ _ ~
L~ E ~ L J U~ O ~ ~ L~
:~ ~) n~ 10 ~ -O ~ L Z ~ ~ L~ ~ aJ r~l ~1) C
~1 X ~-- J,I U ~ \ L 1/~ ~ f~l E LLI C O L ~1/ E Z ~ 2 E I ' E Z I_ E~ 0 0 GJ. -- ~1 -- O ~ 0 L~ O 1 Ll_ ~J C~ L~ L~ (~ V C~ )C
_ - --~,' ~ , ' ' ` . ' '''''`' '' ' ~3~2~
Table II: Properties of the foams at elevated temperature .
. Foam according to Example 6 9 : _ Compressive strength (DIN 53 421-A) : at 23C [N/mm2] 12.7 12.6 ; Compression (DIN 53 421-A) . at 23C [%] 16.6 17.4 Compressive strength at 80C [N/mm2] 9.4 ô.9 Compression at 80C [%] 14.8 11.4 : Compressive strength at 100C [N/mm2]7.3 8.3 ~ Compression at 100C [%] 14.8 12.8 : Compressive strength at 120C [N/mm2]5.3 7.1 Compression at 120C [%] 14.7 15.2 Example 14: The procedure of Example 1 is followed, but, instead of p-toluenesulfohydrazide, 7.6 g of azo-isobutyronitrile are now used, and, instead of polyether-polymethylsiloxane copolymer, 6.0 g of silicone oil (RhodorsilR 3139~ are now employed. The foam matrix is poured at 105C
into the mould heated to 140C. Curing conditions: 15 minutes at 140C.
The cured foam has the following properties:
density = 0.36 g/cm3 closed cellular structure = 94.0%.
~3~ 2~
,- ~
Example 15_ The procedure is as in ~xample 1, the following compounds being used for production of the foam:
bisphenol A diglycidyl ether (highly viscous, epoxide equivalent weight 222) 574.0 g (2.58 equivalents) cresol novolak (solid, hydroxyl equivalent weight 115) 266.0 g (2.31 equivalents) polyether-polymethylsiloxane copolymer 6.0 g 2-ethylimidazole 7.5 g p-toluenesulfohydrazide 7.5 g Curing conditions: 15 minutes at 140C. The cured foam has a density of 0.39 g/cm3.
, . . .
Claims (10)
1. A hot-foamable, thermosetting epoxy resin mixture containing (a) an epoxy resin or a mixture of epoxy resins with an average epoxide content of 4.4 to 5.0 equivalents/kg and an average epoxide functionality of more than 2.0, (b) a novolak with a hydroxyl equivalent weight of 90 to 120, 0.8 to 0.95 hydroxyl equivalents of component (b) being present in the epoxy resin mixture per l epoxide equivalent of component (a), (c) 0.1 to 1% by weight, based on the amount of components (a) and (b), of a curing accelerator, (d) 0.5 to 10% by weight, based on the amount of components (a) and (b) J of a blowing agent which splits off nitrogen above 100°C
with decomposition, (e) 0.3 to 1% by weight, based on the total amount of the epoxy resin mixture, of an emulsifier, and if appropriate (f) foam modifiers.
with decomposition, (e) 0.3 to 1% by weight, based on the total amount of the epoxy resin mixture, of an emulsifier, and if appropriate (f) foam modifiers.
2. An epoxy resin mixture according to claim 1, containing an epoxy resin or an epoxy resin mixture with an average epoxide content of 4.6 to 5.0 equivalents/kg, a novolak (b) with a hydroxyl equivalent weight of 115 to 120 and a curing accelerator (c) in amounts of 0.3 to 1% by weight, based on the amount of components (a) and (b).
3. An epoxy resin mixture according to claim 1, containing one or more aromatic glycidyl ethers as component (a).
4. An epoxy resin mixture according to claim 1, containing a cresol novo-lak glycidyl ether as component (a) or a mixture of a cresol novolak gly-cidyl ether and a bisphenol A diglycidyl ether.
5. An epoxy resin mixture according to claim 1, containing a cresol novo-lak as component (b).
6. An epoxy resin mixture according to claim 1, containing imidazole or an imidazole derivative as the curing accelerator (c).
7. An epoxy resin mixture according to claim 6, containing 2-ethylimida-zole as the curing accelerator.
8. An epoxy resin mixture according to claim 1, containing p-toluene-sulfohydrazide as the blowing agent (d).
9. An epoxy resin mixture according to claim 1, containing non-ionic sub-stances as the emulsifier (e).
10. A process for the production of crosslinked, insoluble and non-fusible epoxy resin foams, which comprises foaming and curing an epoxy resin mixture according to claim 1 in the temperature range from 120 to 180°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH183687 | 1987-05-13 | ||
| CH1836/87-2 | 1987-05-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1312174C true CA1312174C (en) | 1992-12-29 |
Family
ID=4219731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000566465A Expired - Lifetime CA1312174C (en) | 1987-05-13 | 1988-05-11 | Hot-foamable, thermosetting epoxy resin mixture |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0291455B1 (en) |
| JP (1) | JPH089677B2 (en) |
| CA (1) | CA1312174C (en) |
| DE (1) | DE3852206D1 (en) |
| NO (1) | NO177755C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11286335B2 (en) | 2018-05-17 | 2022-03-29 | Evonik Operations Gmbh | Fast-curing epoxy systems |
| US11359048B2 (en) | 2018-05-17 | 2022-06-14 | Evonik Operations Gmbh | Fast-curing epoxy systems |
| US11370876B2 (en) | 2018-05-17 | 2022-06-28 | Evonik Operations Gmbh | Fast-curing epoxy systems |
| US11370877B2 (en) | 2018-05-17 | 2022-06-28 | Evonik Operations Gmbh | Fast-curing epoxy systems |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210046036A (en) | 2018-08-21 | 2021-04-27 | 에보니크 오퍼레이션즈 게엠베하 | Rapid curing epoxy systems for making rigid foams and the use of foams in composites or as insulating materials |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1770659A1 (en) * | 1968-06-19 | 1971-11-04 | Hoechst Ag | Process for the production of hardened foams from polyepoxy compounds |
| CH593313A5 (en) * | 1974-07-29 | 1977-11-30 | Ciba Geigy Ag | |
| US4288565A (en) * | 1978-06-22 | 1981-09-08 | Ciba-Geigy Corporation | Storable, solid mixture for the preparation of plastics which are based on epoxide resin and are stable to hydrolysis, the use of this mixture for the preparation of such plastics and plastics obtained in this way |
| GB2055843A (en) * | 1979-07-20 | 1981-03-11 | Ciba Geigy Ag | Curable epoxide resin mixtures and their use in corrosion resistant coatings |
| JPH0699542B2 (en) * | 1985-06-03 | 1994-12-07 | チバ−ガイギ− アクチエンゲゼルシヤフト | Hardener mixture for epoxy resin and method of use thereof |
-
1988
- 1988-05-04 EP EP88810285A patent/EP0291455B1/en not_active Expired - Lifetime
- 1988-05-04 DE DE3852206T patent/DE3852206D1/en not_active Expired - Fee Related
- 1988-05-11 NO NO882069A patent/NO177755C/en not_active IP Right Cessation
- 1988-05-11 CA CA000566465A patent/CA1312174C/en not_active Expired - Lifetime
- 1988-05-12 JP JP63115971A patent/JPH089677B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11286335B2 (en) | 2018-05-17 | 2022-03-29 | Evonik Operations Gmbh | Fast-curing epoxy systems |
| US11359048B2 (en) | 2018-05-17 | 2022-06-14 | Evonik Operations Gmbh | Fast-curing epoxy systems |
| US11370876B2 (en) | 2018-05-17 | 2022-06-28 | Evonik Operations Gmbh | Fast-curing epoxy systems |
| US11370877B2 (en) | 2018-05-17 | 2022-06-28 | Evonik Operations Gmbh | Fast-curing epoxy systems |
Also Published As
| Publication number | Publication date |
|---|---|
| NO177755B (en) | 1995-08-07 |
| EP0291455A3 (en) | 1990-03-21 |
| DE3852206D1 (en) | 1995-01-12 |
| JPH089677B2 (en) | 1996-01-31 |
| JPS63305145A (en) | 1988-12-13 |
| NO882069D0 (en) | 1988-05-11 |
| EP0291455B1 (en) | 1994-11-30 |
| NO177755C (en) | 1995-11-15 |
| EP0291455A2 (en) | 1988-11-17 |
| NO882069L (en) | 1988-11-14 |
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