Multicomponent epoxide resin composition and curing agent component therefor

Abstract

A curing agent component is useful for a multicomponent epoxide resin composition. An epoxide resin composition produced using the curing agent component, wherein the curing agent component includes, as a curing agent, at least one Mannich base and an amine that is reactive with respect to epoxide groups, as well as at least one polyphenol from the group of novolac resins as an accelerant. The Mannich base can he obtained by reacting a phenolic compound selected from phenol, styrenated phenol, catechol, resorcinol, hydroquinone, hydroxyhydroquinone, phloroglucinol, pyrogallol, o-cresol, m-cresol, p-cresol and bisphenols, with an aldehyde or an aldehyde precursor and an amine having at least two active hydrogen atoms in the molecule which are bonded to a nitrogen atom. The novolac resin is contained in the curing agent component in a proportion of 5-30 wt. %, based on the organic proportions of the curing agent component.

Claims

1. A curing agent component for a multicomponent epoxide resin composition, comprising: as a curing agent, at least one Mannich base and at least one amine that is reactive with respect to epoxide groups, and at least one polyphenol selected from the group consisting of novolac resins as an accelerant, wherein the at least one Mannich base can be obtained by: reacting at least one phenolic compound selected from the group consisting of phenol, styrenated phenol, catechol, resorcinol, hydroquinone, hydroxyhydroquinone, phloroglucinol, pyrogallol, o-cresol, m-cresol, p-cresol, bisphenols, and mixtures thereof, with at least one aldehyde or at least one aldehyde precursor and at least one amine having at least two active hydrogen atoms in the molecule which are bonded to a nitrogen atom, said Mannich base is contained in the curing agent component in a proportion of from 10 to 70 wt. %, based on the organic proportion of the curing agent component, said at least one polyphenol is contained in the curing agent component in a proportion of from 5 to 30 wt. %, based on organic proportions of the curing agent component, said at least one polyphenol corresponds to the following formula: ##STR00003## in which R.sub.1 and R.sub.2 represent, independently of one another, H or —CH.sub.3; R.sub.3, R.sub.4, R.sub.5, and R.sub.6 represent, independently of one another, H, —CH.sub.3, an aliphatic radical, or an alkaryl radical: and where n is 0 to 20: and said at least one amine is contained in the curing agent component in a proportion of from 60 to 80 wt. % based on the organic proportion of the curing agent component.

2. The curing agent component according to claim 1, wherein the at least one amine that is reactive with respect to epoxide groups is at least one selected from the group consisting of aliphatic, alicyclic, araliphatic, and aromatic amines, the amine having on average at least two reactive hydrogen atoms per molecule which are bonded to a nitrogen atom.

3. The curing agent component according to claim 2, wherein the at least one amine that is reactive with respect to epoxide groups is a polyamine having at least two amino groups in the molecule which are bonded to a nitrogen atom.

4. The curing agent component according to claim 1, wherein the at least one phenolic compound is selected from the group consisting of phenol and styrenated phenol, and mixtures thereof.

5. The curing agent component according to claim 1, wherein the at least one aldehyde is an aliphatic aldehyde, and wherein the at least one aldehyde precursor comprises trioxane or paraformaldehyde.

6. The curing agent component according to claim 5, wherein the at least one aldehyde is formaldehyde.

7. The curing agent component according to claim 1, wherein the at least one Mannich base is formed using the at least one amine that is reactive with respect to epoxide groups.

8. The curing agent component according to claim 7, wherein the at east one amine is a polyamine.

9. The curing agent component according to claim 1, wherein the at least one polyphenol corresponds to the following formula: ##STR00004## in which R.sub.1 represents H; R.sub.2 represents a C.sub.1-C.sub.15 alkyl; m is 0, 1, or 2; and n is 0 to 15.

10. The curing agent component according to claim 9, wherein R.sub.2 represents —CH.sub.3 and m is 1 or 2, or R.sub.2 represents tert-butyl or a C.sub.1-C.sub.15 alkyl and m is 1.

11. The curing agent component according to claim 1, wherein the at least one polyphenol is contained in the curing agent component in a proportion of from 8 to 25 wt. %.

12. The curing agent component according to claim 1, wherein the curing agent component further comprises at least one additive selected from the group consisting of diluents, solvents, accelerants, silanes, thickeners, and inorganic fillers.

13. A multicomponent epoxide resin composition, comprising: at least one epoxide resin component (A) containing at least one curable epoxide resin and optionally a reactive diluent, and at least one curing agent component (B) according to claim 1, wherein the at least one epoxide resin component (A) and the curing agent component (B) are separate from one another.

14. The multicomponent epoxide resin composition according to claim 13, wherein the multicomponent epoxide resin composition further comprises at least one additive selected from the group consisting of co-accelerants, adhesion promoters, reactive diluents, thickeners, and fillers.

15. The curing agent according to claim 1, wherein n=1-20.

Description

DETAILED DESCRIPTION OF EMBODIMENTS

(1) Further advantages of the invention can be found in the following description of preferred embodiments, which, however, are not understood to be in any way limiting.

(2) Preparation of the Mannich Base

(3) General Preparation instructions

(4) The Mannich bases can be prepared according to methods known per se, as specified in the following:

(5) 2 mol of one or more amines are provided in a 250 ml three-necked flask having a thermometer, a dropping funnel and a stirrer. The amine provided is mixed with approximately 1 mol of phenol or styrenated phenol by stirring. The mixture is heated to approximately 80° C. Then, with vigorous stirring, approximately 0.7 mol of formaldehyde is added in drops as a 37% formaldehyde solution in water for approximately 45 minutes. After completion of the addition of formaldehyde, the reaction mixture is reheated to approximately 105° C., and the reaction mixture is held at this temperature for approximately 120 minutes. Then, water is distilled off under increasing vacuum at a suitable temperature (e.g. approximately 110° C.). Once the pressure is reduced enough (e.g. to approximately 50 mbar), the temperature may be further increased to approximately 130° C. and then held at this temperature for some time, for example approximately 60 minutes, in order to remove the remaining water from the reaction mixture.

(6) Synthesis of the Mannich Base MBS2

(7) 220 g (0.91 mol) of Novares LS 500 (styrenated phenol from Rutgers Novares GmbH, Germany, average molar mass 243 g/mol) is mixed with 190.4 g (221 ml, corresponding to 1.64 mol, 1.8 eq) of 1,5-diamino-2-methylpentane in a 1 L three-necked flask having a KPG stirrer and an internal thermometer, and the reaction mixture is heated to 80° C. (internal temperature). Subsequently, 115 ml (1.46 mol, 1.6 eq) of formaldehyde (37%; 10-15% MeOH as a stabilizer, d=1.09 g/cm.sup.3) is carefully added in drops. During the addition of formaldehyde, the temperature of the reaction mixture should not exceed 90° C. (exothermic reaction). After complete addition of the formaldehyde solution, the reaction mixture is stirred for a further 45 minutes at 85 to 90° C. The mixture is then heated to 100° C. and kept at this temperature for 1 h. Subsequently, at approximately 140° C. the resulting water and excess formaldehyde are blown off in a strong stream of nitrogen for 3 h. The product solidifies on cooling to room temperature.

(8) The yield of Mannich base amounts to 456 g of raw product.

(9) Synthesis of the Mannich Base MBS1

(10) 504 g (2.07 mol) of Novares LS 500 is mixed with 601 ml (4.6 mol; 2.2 eq; d=1.032 g/cm.sup.3) of m-xylylenediamine in a 2 L three-necked flask having a KPG stirrer and an internal thermometer, and the reaction mixture is heated to 80° C. (internal temperature). Subsequently, 327 ml (4.15 mol) of formaldehyde (37%; 10-15% MeOH as a stabilizer, d=1.09 g/cm.sup.3) is slowly added for approximately 1.5 h. During the addition of formaldehyde, the temperature of the reaction mixture should not exceed 90° C. (exothermic reaction). After complete addition of the formaldehyde solution, the reaction mixture is stirred for a further 2 h at 85 to 95° C. The mixture is then heated to 100° C. and kept at this temperature for approximately 1 h. Subsequently, at approximately 140° C., the resulting water and excess formaldehyde are blown off in a strong stream of nitrogen for 3 h. The product solidifies on cooling to room temperature.

(11) The yield of Mannich base amounts to 1.13 kg of raw product.

Examples 1 to 4 and Comparative Examples 1 and 2

(12) Determination of the Reaction Kinetics by Temperature Measurement

(13) Curing agent components having a different proportion of novolac resin and different novolac resins were prepared in order to achieve curing of the mixtures of curing agent component and epoxide resin component over the temperature curve of the curing reaction. It was found in this case that the temperature curve of the curing reaction can be adjusted in a wide range by varying the novolac resin and the proportion thereof in the curing agent component.

(14) The amount specifications in the following examples are in weight percent (wt. %).

(15) In order to prepare the epoxide resin component A, the constituents specified in the following table were mixed in a speed mixer. The epoxide equivalent EEW of the mixture was 158 g/EQ.

(16) In addition, different curing agent components B composed as specified in the following table 2 were prepared. The Mannich base MBS2 obtained according to the above-described synthesis instructions and m-xyylenediamine (mXDA; manufacturer; Aldrich. Germany) were used as amine curing agents. The phenol novolac resin available under the trade name Phenolite TD-2093Y from DIC Europe, Germany, was used as an accelerant.

(17) TABLE-US-00001 TABLE 1 Composition of the epoxide resin component A Substance Function Wt. % Trade name Manufacturer Country Bisphenol A- Epoxide 52 DER 330 Dow Europe CH based resin epoxide resin Bisphenol F- Epoxide 28 DER 354 Dow Europe CH based resin epoxide resin 1,4-butanediol- Reactive 10 Polypox R3 Dow Europe CH diglycidyl ether diluent Trimethyol- Reactive 10 Araldite DY-T Huntsman BE propane- diluent triglycidyl ether

(18) TABLE-US-00002 TABLE 2 Composition of the curing agent component B Weight ratio Phenol component MBS2 mXDA novolac AHEW A:B Comparative 20 80 0 40.77 3.88 example 1 Comparative 50 50 0 58.12 2.72 example 2 Example 1 50 48 2 60.18 2.63 Example 2 50 45 5 63.55 2.49 Example 3 20 65 15 49.71 3.18 Example 4 10 68 22 48.78 3.24

(19) The epoxide component A was in each case mixed with one of the curing agent components B in the weight ratio specified in table 2 in the speed mixer. The mixture was poured into a 20 ml rolled-edge glass. A temperature sensor was placed in the middle of the rolled-edge glass and the change in temperature of the mixture was recorded (device: Yokogawa, DAQ station, model: DX006-3-42). The change in temperature overtime serves as a measure for the curing of the mixture. If there is acceleration of the curing, the maximum temperature is shifted to shorter times. Furthermore, there is also a higher maximum temperature in most cases. The time t.sub.−10K after which a temperature increase of 10 K has taken place, the maximum temperature T.sub.max reached and the time t.sub.Tmax after which the maximum temperature was reached are measured.

(20) The results of the changes in temperature achieved for the different curing agent components B during the curing reaction are given in the following table 3.

(21) TABLE-US-00003 TABLE 3 Temperature curve during curing t.sub.+10K T.sub.max t.sub.Tmax [h:min:sec] [° C.] [h:min:sec] Comparative example 1 — 29.1 04:26:57 Comparative example 2  1:26:45 129.6 02:39:55 Example 1  1:13:51 138.3 01:39:28 Example 2 00:53:25 151.9 01:15:01 Example 3 00:35:40 150.1 01:09:33 Example 4 00:19:24 189.3 00:39:27

(22) The results of the curing reaction temperature curve for the different curing agent components B show that there is no temperature increase of 10 K with the composition of comparative example 1. The maximum temperature, measured after approximately 4.5 hours, is merely 29° C. The curing agent component B of comparative example 2 produces a temperature increase of 10 K after approximately 1.5 hours, and the maximum temperature of 130° C. is measured after approximately 2.65 hours.

(23) The curing agent components B according to examples 1 to 4 achieve a temperature increase of 10 K after 19 to 74 minutes, and the maximum temperatures are from 138 to 190° C. The maximum temperatures are therefore significantly above those of the comparative examples. In particular, the maximum temperatures are already reached after a time of between 39 minutes and 1.65 hours, and therefore at least one hour earlier than in comparative example 2. Adding the novolac resin thus leads to a significant acceleration of the reaction and thus of the curing. The acceleration depends on the concentration of the phenol novolac—it being possible to achieve a significant acceleration with higher concentrations—and on the type of phenol novolac used.

Examples 5 and 6 and Comparative Example 3

(24) Determination of the Reaction Kinetics by Temperature Measurement

(25) In order to prepare the epoxide resin component A, the constituents specified in the above table 1 were mixed in a speed mixer. The epoxide equivalent EEW of the mixture was 158 g/EQ.

(26) In addition, different curing agent components composed as specified in the following table 4 were prepared. A Mannich base based on bisphenol A and the amine mXDA and available under the trade name Epikure 132 from Momentive Specialty Chemicals, the Netherlands, as well as mXDA (manufacturer Aldrich, Germany) and 1,3-cyclohexanediemethanamine (1,3-BAC) from Itochu Deutschland were used as amine curing agents. A phenol novolac resin available under the trade name Phenolite TD-2131 from DIC Europe, Germany, was used as an accelerant.

(27) TABLE-US-00004 TABLE 4 Composition of the curing agent component B Weight ratio Epikure 1,3- Phenol component 132 mXDA BAC novolac AHEW A:B Example 5 50 38 0 12 48.50 3.26 Example 6 50 0 38 12 63.55 2.49 Comparative 100 0 0 0 53.0 2.98 example 3

(28) The epoxide component A was in each case mixed with one of the curing agent components B in the weight ratio specified in table 2. The mixture was poured into a 20 ml rolled-edge glass. A temperature sensor was placed in the middle of the rolled-edge glass and the change in temperature of the mixture was recorded (device: Yokogawa, DAQ station, model: DX1006-3-4-2). The change in temperature over time serves as a measure for the curing of the mixture. If there is acceleration of the curing, the maximum temperature is shifted to shorter times. Furthermore, there is also a higher maximum temperature in most cases. The time t.sub.+10K after which a temperature increase of 10 K has taken place, the maximum temperature T.sub.max reached and the time t.sub.Tmax after which the maximum temperature was reached are measured.

(29) The results of the changes in temperature achieved for the different curing agent components B during the curing reaction are given in the following table 5.

(30) TABLE-US-00005 TABLE 5 Change in temperature during curing t.sub.+10K T.sub.max t.sub.Tmax [h:min:sec] [° C.] [h:min:sec] Example 5 00:22:49 183.8 00:48:03 Example 6 00:13:36 200.0 00:36:18 Comparative example 3 00:33:30 80.0 01:27:06

(31) Again, the compositions comprising the curing agent components B according to the invention exhibit more rapid curing behavior according to examples 5 and 6 than comparative example 3. Both the temperature increase by 10 K and the time after which the maximum temperature is reached are shorter than in the comparative example. The maximum temperature reached for the curing agent components B in examples 5 and 6 is, at 184 and 200° C., respectively, also significantly higher than the maximum temperature of 80° C. reached for the curing agent component of comparative example 3.

Examples 7 to 10 and Comparative Examples 4 to 7

(32) Determination of the Failure Load after Different Curing Times

(33) In order to prepare the epoxide resin component A, the constituents specified in the following table 6 were mixed in a speed mixer. The epoxide equivalent EEW of the mixture was 257 g/EQ.

(34) TABLE-US-00006 TABLE 6 Composition of the epoxide resin component A Component Function Wt. % Trade name Manufacturer 3-glycidyloxy-propyl- Adhesion 2.6 Dynasylan Evonik trimethoxysilane promoter GLYMO Industries, DE Bisphenol A-based Epoxide 31.1 DER 330 Dow Europe, epoxide resin resin CH Bisphenol F-based Epoxide 16.6 DER 354 Dow Europe, epoxide resin resin CH 1,4-butanediol- Reactive 6 Polypox R3 Dow Europe, diglycidyl ether diluent Trimethyolpropane- Reactive 6 Araldite DY-T Huntsman, triglycidyl ether diluent BE Quartz Filler 35 Millisil W12 Quarzwerke Frechen, DE Silica Thickener 2.7 Cab-O-Sil TS- Cabot 720 Rheinfelden, DE

(35) In order to prepare the different curing agent components B, the constituents specified in the following table 7 were used and mixed together in the composition specified in the following table 8. The mXDA-resorcinol-based Mannich base was synthesized analogously to the synthesis instructions in EP 0645 408. The mXDA-resorcinol-based Mannich base, dissolved in mXDA, was used as a curing agent. The content of free mXDA was 60%.

(36) TABLE-US-00007 TABLE 7 Constituents of the curing agent components B Manu- Coun- Constituent Function Trade name facturer try Mannich base MBS2 Curing agent Mannich base MBS1B Curing agent mXDA-bisphenol Curing agent Epikure 132 Momentive NL A-based Mannich Specialty base in mXDA Chemicals mXDA- Curing agent resorcinol-based Mannich base, dissolved in mXDA Novolac Accelerant Phenolite DIC Europe DE TD-2131 4,4′-dihydrodi- Accelerant Bisphenol F TCl Europe BE phenylmethane 2,4′-dihydroxydi- Accelerant 2,4-Bisphenol TCl BE phenylmethane F Europe 1,3-cyclohexane- Curing agent 1,3-BAC Itochu DE dimethanamine Deutschland m-xylylenediamine Curing agent mXDA Itochu DE Deutschland 3-aminopropyl- Adhesion Dynasylan Evonik DE triethoxysilane promoter AMEO Degussa 2,4,6-tris(dimethyl- Accelerant Ancamine Air Products NL amino-methyl)phenol, K54 bis[(dimethylamino)- methyl]phenol Quartz Filler Millisil W12 Quarzwerke DE Frechen Silica Thickener Cab-O-Sil Cabot DE TS-720 Rheinfelden

(37) TABLE-US-00008 TABLE 8 Composition of the curing agent components B Com- Com- Example parative Example parative Constituent 7 example 4 8 example 5 MBS2 26.3 26.3 MBS1B (MBS1, 75% 35.2 35.2 dissolved in mXDA) Novolac 6.3 6.3 1,3-BAC 26.1 32.4 mXDA 17.1 23.4 3-aminopropyl- 1.9 1.9 1.9 1.9 triethoxysilane Ancamine K54 1.9 1.9 1.9 1.9 Quartz 35 35 35.1 35.1 Silica 2.5 2.5 2.5 2.5 AHEW 113 g/EQ 94 g/EQ 92 g/EQ 78 g/EQ Com- Com- Example parative Example parative Substance 9 example 6 10 example 7 Epikure 132 47.4 54 mXDA-resorcinol-based 49.3 49.3 Mannich base in mXDA Novolac 6.4 6.7 mXDA 3.9 3.4 6.7 3-aminopropyl- 1.9 2 2 2 triethoxysilane AncamineK54 1.9 2 2 2 Quartz 35.9 36 37.3 37.3 Silica 2.6 2.6 2.7 2.7 AHEW 97 g/EQ 88 g/EQ 96 g/EQ 81 g/EQ Example Example Example Example Substance 11 12 13 14 Epikure 132 — 49.0 49.0 50.8 mXDA-resorcinol-based 49.3 — — — Mannich base in mXDA 4,4- 6.7 5.0 2.5 1.5 dihydroxydiphenylmethane 2.0 2,4'- — — 2.5 1.6 dihydroxydiphenylmethane mXDA — 3.4 3.4 3.5 3-aminopropyl- 2.0 2.0 2.0 2.0 triethoxysilane Ancamine K54 2.0 2.0 2.0 2.0 Quartz 37.3 36.0 36.0 36.0 Silica 2.7 2.6 2.6 2.6 AHEW 96 g/EQ 96 g/EQ 96 g/EQ 93 g/EQ

(38) In order to prepare curable epoxide resin compositions, components A and B are mixed in the speed mixer in a ratio resulting in a balanced stoichiometry according to the EEW and AHEW values. The mixture is poured into a 1 L cartridge, as far as possible without bubbles, and is immediately introduced into the borehole.

(39) The following process is carried out for extraction tests using threaded rods M12, according to ETAG 001 PART 5:

(40) Firstly, boreholes (diameter 14 mm; depth 72 mm) are made in a horizontal concrete test piece (concrete type C20/C25) using a hammer drill. The boreholes are cleaned by means of compressed air (2×6 bar), a wire brush (2 x) and again by compressed air (2×6 bar). For fastening purposes, the boreholes are then filled up, by two thirds from the bottom of the bore, with the relevant curable epoxide resin composition to be tested. A threaded rod is manually pressed into each borehole. The mortar excess is removed using a spatula. After the time specified for the particular test, the threaded rod is pulled until failure and the failure load is measured.

(41) TABLE-US-00009 TABLE 9 Failure load in N/mm.sup.2 after a predetermined curing time: Composition of the organic proportion 3 h 6 h 24 h of the curing agent component Example 7 0.5 28.2 37.3 45% MBS2 +12% novolac + 43% 1,3-BAC Comparative <0.4 2.4 37.8 45% MBS2+55% 1,3-BAC example 4 Example 8 1.2* 21.3 38.2 45% MBS1B + 12% novolac + 43% mXDA Comparative <0.4 0.9 38.8 45% MBS1B + 55% mXDA example 5 Example 9 4 33.8 39.1 3% Epikure 132 + 12% novolac + 5% mXDA Comparative <0.4 26.1 39.0 94% Epikure 132 + 6% mXDA example 6 Example 10 1.8 29.2 37.1 88% mXDA-resorcinol-based Mannich base in mXDA + 12% novolac Comparative <0.4 23.5 38.9 88% mXDA-resorcinol-based Mannich example 7 base in mXDA + 12% mXDA Example 11 4.5 34.0 35.6 88% mXDA-resorcinol-based Mannich base in mXDA + 12% bisphenol F Example 12 1.5 30.9 32.6 92% Epikure 132 + 8% bisphenol F Example 13 1.2 31.4 37.8 92% Epikure 132 + 8% bisphenol F- isomer mixture Example 14 <0.4 29.8 38.3 95% Epikure 132 + 5% bisphenol F- isomer mixture *after 4.5 h

(42) The epoxide resin compositions according to the invention comprising curing agent components according to examples 7 to 14 exhibit substantially more rapid curing than the epoxide resin composition comprising the curing agent components according to comparative examples 4 to 7. The mortar compositions produced using the curing agent components according to the invention can be subjected to loading after only 6 h. This makes it possible to considerably reduce waiting times before the next processing step and to allow subsequent processing works to be carried out much earlier.