ALDIMINES AND KETIMINES AS INITIATORS IN HARDENER SYSTEMS AND CORRESPONDING RESIN COMPOSITIONS INTER ALIA FOR FIXING TECHNOLOGY

Abstract

A hardener system for a synthetic resin composition having free-radical-polymerisable compounds, which includes the following constituents: a) at least one activator in the form of a metal salt, and as free-radical starter b1) (i) at least one aldehyde and/or ketone and at least one primary amine, and/or b2) (ii) at least one aldimine or (iii) at least one ketimine, or a mixture of two or more of constituents (i) to (iii). In addition, synthetic resin compositions having such a hardener system for application especially in fixing technology, and subject matters related thereto.

Claims

1.-18. (canceled)

19. A hardener system for a synthetic resin composition which includes free-radical-polymerisable compounds, comprising: at least one activator in the form of a metal salt; and a free-radical starter comprising one or both of: (b1) at least one aldehyde and/or ketone and at least one primary amine; and (b2) an imine which includes one or more imine structural increments of the formula (I): ##STR00003## wherein independently of one another: the wavy line represents an organic radical of an amine, or hydrogen; and R.sub.2 and R.sub.3 each independently of the other denotes hydrogen or an unsubstituted or substituted organic radical which includes at least one aliphatic, heteroaliphatic, alicyclic or heterocyclic molecular structure, or a salt thereof.

20. The hardener system according to claim 19, wherein: the at least one activator in the form of a metal salt comprises one or more salts of organic and/or inorganic acid with one or more metals, the one or more metals comprising one or more of copper, iron, vanadium, manganese, cerium, cobalt, zirconium, and bismuth; the inorganic acid comprising one or more of a sulfate radical and a carbonate radical; and the organic acid comprising a carboxylate radical; and the free-radical starter comprises (b2) the imine which includes one or more imine structural increments of the formula (I), the imine comprising at least one aldimine or ketimine, obtainable by condensation, with removal of water, of a mono-, di- or poly-amine with one or more aldehydes or ketones, wherein: the mono-, di- or poly-amine comprises one or more of aminol; alkyl/alkylene(mono- or di-)amine; cycloalkyl/cycloalkylene(mono- or di-)amine; heterocycloalkyl/heterocycloalkylene(mono- or di-)amine; a compound of the formula H.sub.2N(CH.sub.2).sub.iNH[(CH.sub.2).sub.jNH].sub.k(CH.sub.2).sub.lNH.sub.2, wherein i, j and l each independently of the others denotes from 2 to 4 and k denotes 0, 1, 2, 3 or 4; aminoamide; polyaminoamide; Mannich base; amine adduct; and aminoalkylsilane that includes at least one hydrolysable group; and the one or more aldehydes or ketones are of the formula (II), ##STR00004## wherein: R.sub.2, R.sub.3 each independently of the other denotes hydrogen or an unsubstituted or substituted organic radical which includes at least one aliphatic, heteroaliphatic, alicyclic, or heterocyclic molecular structure; and the one or more aldehydes and/or ketones are compounds which have at least one or more primary and/or secondary hydrogen atoms at the carbon atom in the -position to the carbonyl group.

21. The hardener system according to claim 19, wherein (b2) the imine which includes one or more imine structural increments of the formula (I) includes one or more aldimines and no ketimine.

22. The hardener system according to claim 19, wherein: the activator in the form of a metal salt comprises one or more salts of organic and/or inorganic acids with metals, the one or more metals comprising one or more of copper, iron, vanadium, manganese, cerium, cobalt, zirconium, and bismuth; the inorganic acid comprising one or more of a sulfate radical and a carbonate radical; and the organic acid comprising a carboxylate radical; and the free-radical starter comprises (b2) the imine which includes one or more imine structural increments of the formula (I), the imine comprising at least one aldimine or ketimine, obtainable by condensation, with removal of water, of a mono-, di- or poly-amine with one or more aldehydes or ketones, wherein: the mono-, di- or poly-amine comprises one or more of aminol; alkyl/alkylene(mono- or di-)amine; cycloalkyl/cycloalkylene(mono- or di-)amine; heterocycloalkyl/heterocycloalkylene(mono- or di-)amine; a compound of the formula H.sub.2N(CH.sub.2).sub.iNH[(CH.sub.2).sub.jNH].sub.k(CH.sub.2).sub.lNH.sub.2, wherein i, j and l each independently of the others denotes from 2 to 4 and k denotes 0, 1, 2, 3 or 4; aminoamide, polyaminoamide, Mannich base, amine adduct; and aminoalkylsilane that includes at least one hydrolysable group; and the one or more aldehydes or ketones are of the formula (II), ##STR00005## wherein: R.sub.2, R.sub.3 each independently of the other denotes hydrogen or an unsubstituted or substituted organic radical which includes at least one aliphatic, heteroaliphatic, alicyclic, or heterocyclic molecular structure; and the one or more aldehydes and/or ketones are compounds which have at least one or more primary and/or secondary hydrogen atoms at the carbon atom in the -position to the carbonyl group; and the free-radical starter further comprises at least one aldehyde and/or ketone and as primary amine and one or more aminosilanised fillers that carry primary amino groups.

23. The hardener system according to claim 19, wherein (b2) the imine which includes one or more imine structural increments of the formula (I) includes one or more aldimines as a reaction product of isobutyraldehyde and 3-aminopropyl-trimethoxysilane; of isobutyraldehyde and m-xylylenediamine; of isobutyraldehyde and 1,3-bis(aminomethyl)-cyclohexane; of isobutyraldehyde and Jeffamine D230; of isobutyraldehyde and isophoronediamine; of isobutyraldehyde and Jeffamine DER-148; of isobutyraldehyde and diethyltoluenediamine; and of isobutyraldehyde and cyclohexane-1,2-diamine; or mixtures of two or more of those reaction products.

24. The hardener system according to claim 19, wherein: the activator in the form of a metal salt comprises one or more salts of organic and/or inorganic acid with one or more metals, the one or more metals comprising one or more of copper, iron, vanadium, manganese, cerium, cobalt, zirconium, and bismuth; the inorganic acid comprising one or more of a sulfate radical and a carbonate radical; and the organic acid comprising a carboxylate radical; and the free-radical starter comprises (b1) the at least one aldehyde and/or ketone and the at least one primary amine, the at least one aldehyde or ketone being of the formula (II), ##STR00006## wherein: R.sub.2, R.sub.3 each independently of the other denotes hydrogen or an unsubstituted or substituted organic radical which includes at least one aliphatic, heteroaliphatic, alicyclic or heterocyclic molecular structure; and the one or more aldehydes and/or ketones are compounds which have at least one or more primary and/or secondary hydrogen atoms at the carbon atom in the -position to the carbonyl group; the at least one primary amine comprising one or more of mono-, di- and poly-amines, heteroalkyl- or heteroalkylene-(mono- or di-)amines, amine-functionalised polyoxyalkylenes [Jeffamines], cycloalkyl- or cycloalkylene-(mono- or di)amines, heterocycloalkyl- or heterocycloalkylene-(mono- or di-)amines, arylalkyl- or arylalkylene-(mono- or di-)amines, aminosilanised fillers, aminoamides, polyaminoamides, Mannich bases or amine adducts and aminoalkylsilanes; wherein the constituents aldehyde and/or ketone on the one hand and the constituent primary amine on the other hand are divided separately between two components for mixing when the hardener system is used.

25. The hardener system according to claim 19, wherein the activator in the form of a metal salt comprises one or more salts of organic and/or inorganic acids with metals, and the free-radical starter comprises: (b1) the at least one aldehyde and/or ketone and the at least one primary amine, wherein: the at least one aldehyde and/or ketone is a compound which has at least one or more primary and secondary hydrogen atoms at the carbon atom in the -position to the carbonyl group, and the at least one primary amine comprises one or more mono-, di- and poly-amines, heteroalkyl- or heteroalkylene-(mono- or di-)amines, amine-functionalised polyoxyalkylenes [Jeffamines], cycloalkyl- or cycloalkylene-(mono- or di)amines, heterocycloalkyl- or heterocycloalkylene-(mono- or di-)amines, arylalkyl- or arylalkylene-(mono- or di-)amines, aminosilanised fillers, aminoamides, polyaminoamides, Mannich bases or amine adducts and aminoalkylsilanes; wherein the constituents aldehyde and/or ketone on the one hand and the constituent primary amine on the other hand are divided separately between two components and are only provided for mixing when the hardener system is used; or (b2) the imine which includes one or more imine structural increments of the formula (I), the imine obtainable by reaction of at least one aldehyde and/or ketone with at least one primary amine, the aldehyde and/or ketone comprising a compound which has at least one or more primary and/or secondary hydrogen atoms at the carbon atom in the -position to the carbonyl group, and the at least one primary amine comprising one or more of mono-, di- and poly-amines, heteroalkyl- or heteroalkylene-(mono- or di-)amines, amine-functionalised polyoxyalkylenes [Jeffamines], cycloalkyl- or cycloalkylene-(mono- or di)amines, heterocycloalkyl- or heterocycloalkylene-(mono- or di-)amines, arylalkyl- or arylalkylene-(mono- or di-)amines, aminosilanised fillers, aminoamides, polyaminoamides, Mannich bases or amine adducts and aminoalkylsilanes; or both the at least one aldehyde and/or ketone and the at least one primary amine as mentioned under (b1) and the imine mentioned under (b2).

26. An initiator system comprising the hardener system according to claim 19 and at least one synthetic resin composition comprising a free-radical-polymerisable compound.

27. The initiator system according to claim 26, wherein the at least one free-radical-polymerisable compound comprises a free-radical-hardening unsaturated reactive resin with at least 2 or more reactive non-aromatic unsaturated bonds, or a mixture of two or more reactive resins.

28. A synthetic resin composition, comprising: the hardener system according to claim 19, wherein (b2) the imine which includes one or more imine structural increments of the formula (I) comprises at least one ketimine or especially aldimine; and at least one free-radical-polymerisable compound comprising a free-radical-hardening unsaturated reactive resin with at least 2 or more reactive non-aromatic unsaturated bonds, or a mixture of two or more reactive resins.

29. The synthetic resin composition according to claim 28, wherein the hardener system comprises (b2) the imine which includes one or more imine structural increments of the formula (I).

30. The synthetic resin composition according to claim 28, wherein the hardener system comprises (b1) the least one aldehyde and/or ketone and the at least one primary amine.

31. The synthetic resin composition according to claim 28, wherein the activator in the form of a metal salt comprises one or more salts of organic and/or inorganic acid with metals, the one or more metals comprising one or more of copper, iron, vanadium, manganese, cerium, cobalt, zirconium, and bismuth, the inorganic acid comprising one or more of a sulfate radical and a carbonate radical; and the organic acid comprising a carboxylate radical; and the free-radical starter comprises (b2) the imine which includes one or more imine structural increments of the formula (I), the imine comprising at least one aldimine or ketimine, obtainable by condensation, with removal of water, of a mono-, di- or poly-amine with one or more aldehydes or ketones, wherein: the mono-, di- or poly-amine comprises one or more of aminol; alkyl/alkylene(mono- or di-)amine; cycloalkyl/cycloalkylene(mono- or di-)amine; heterocycloalkyl/heterocycloalkylene(mono- or di-)amine; a compound of the formula H.sub.2N(CH.sub.2).sub.iNH[(CH.sub.2).sub.jNH].sub.k(CH.sub.2).sub.lNH.sub.2, wherein i, j and l each independently of the others denotes from 2 to 4 and k denotes 0, 1, 2, 3 or 4; aminoamide; polyaminoamide, Mannich base; amine adduct; and aminoalkylsilane that includes at least one hydrolysable group; and the one or more aldehydes or ketones are of the formula (II), ##STR00007## wherein: R.sub.2, R.sub.3 each independently of the other denotes hydrogen or an unsubstituted or substituted organic radical which includes at least one aliphatic, heteroaliphatic, alicyclic, or heterocyclic molecular structure; and the one or more aldehydes and/or ketones are compounds which have at least one or more primary and/or secondary hydrogen atoms at the carbon atom in the -position to the carbonyl group.

32. The synthetic resin composition according to claim 28, wherein the activator in the form of a metal salt comprises one or more salts of organic and/or inorganic acid with metals, the one or more metals comprising one or more of copper, iron, vanadium, manganese, cerium, cobalt, zirconium, and bismuth, the inorganic acid comprising one or more of a sulfate radical and a carbonate radical; and the organic acid comprising a carboxylate radical; and the free-radical starter comprises (b1) the at least one aldehyde and/or ketone and the at least one primary amine, the at least one aldehyde or ketone being of the formula (II), ##STR00008## wherein: R.sub.2, R.sub.3 each independently of the other denotes hydrogen or an unsubstituted or substituted organic radical which includes at least one aliphatic, heteroaliphatic, alicyclic or heterocyclic molecular structure; and the one or more aldehydes and/or ketones are compounds which have at least one or more primary and/or secondary hydrogen atoms at the carbon atom in the -position to the carbonyl group; and the at least one primary amine comprising one or more of mono-, di- and poly-amines, heteroalkyl- or heteroalkylene-(mono- or di-)amines, amine-functionalised polyoxyalkylenes [Jeffamines], cycloalkyl- or cycloalkylene-(mono- or di)amines, heterocycloalkyl- or heterocycloalkylene-(mono- or di-)amines, arylalkyl- or arylalkylene-(mono- or di-)amines, aminosilanised fillers, aminoamides, polyaminoamides, Mannich bases or amine adducts and aminoalkylsilanes.

33. The synthetic resin composition according to claim 28 in the form of a multi-component system or kit.

34. An adhesive comprising the synthetic resin composition according to claim 28.

35. A coating material, or moulding composition comprising the synthetic resin composition according to claim 28.

36. A moulding composition comprising the synthetic resin composition according to claim 28.

37. A method of fixing of an anchoring means in a hole or crevice in a substrate, comprising: providing the synthetic resin composition according to claim 28 together with the anchoring means in the hole or crevice.

38. A method of reinforcing a structure, comprising: providing the synthetic resin composition according to claim 28 together with one or more of fibres, non-crimp fabrics, woven fabrics or composites; and fixing the one or more of fibres, non-crimp fabrics, woven fabrics or composites to the structure using the synthetic resin composition.

Description

EXAMPLE 1: GENERAL WORKING PROCEDURE I: ALTERNATIVE SYNTHESIS OF ALDIMINES

[0095] The appropriate amine is placed in a round-bottomed flask. With vigorous stirring, the aldehyde is slowing added from a dropping funnel, during which the temperature of the mixture rises. Once the addition is complete, the volatile constituents are not removed. Depending upon the amine used (hydrophobic amines), the water of reaction that forms separates from the aldimine. The residual water present in the aldimine does not interfere with its use as initiator. Using hydrophilic amines, no phase separation takes place. If desired, it is also possible for the aldehyde to be used as initial charge and the amine to be added dropwise. The reaction (freedom from imine groups demonstrable by IR spectroscopy) is checked by means of FT-IR.

EXAMPLE 2: EXEMPLARY FORMULATION FOR AN ALDIMINE FROM ISOBUTYRALDEHYDE AND JEFFAMINE D230

[0096] The formulation for an aldimine produced or producible according to Example 1 (general working procedure I) is as follows:

TABLE-US-00002 TABLE 2 Formulation for aldimine from isobutyraldehyde and Jeffamine D230 Raw material m [g] M [g/mol] n [mol] % by weight Isobutyraldehyde 15.00 72.11 0.208 38.54 D230 23.92 230.00 0.104 61.46 Total 38.92 100.00

[0097] The water of reaction that forms slowly separates from the aldimine and collects at the bottom of the flask.

[0098] The aldimines used below are produced analogously to general working procedure I, or are commercially available.

EXAMPLE 3: SIMPLIFIED RESIN FORMULATIONS

[0099] For the simplified resin formulations the following raw materials are mixed together:

TABLE-US-00003 TABLE 3 Simplified resin formulation I (RFI) Raw material % by weight Ethoxylated bisphenol-A-dimethacrylate* 88.76 BDDMA 7.14 HPMA 4.10 *technical product - various degrees of ethoxylation possible.

TABLE-US-00004 TABLE 4 Simplified resin formulation II (RFII) Raw material % by weight UM resin 54.86 BDDMA 40.00 HPMA 5.00 Additives 0.14

[0100] The UM resin is produced in a manner known to the person skilled in the art. Reference is made here by way of example to the patent DE 4111828 A1. As isocyanate there is used a polymeric diphenylmethanediisocyanate with isomers and higher homologues.

TABLE-US-00005 TABLE 5 Simplified resin formulation III (RFIII) Raw material % by weight Ethoxylated bisphenol-A-dimethacrylate* 80.00 SR210 20.00 *technical product - various degrees of ethoxylation possible.

[0101] The simplified resin formulation III is particularly interesting for the production of non-hazard-classified reactive resins and fixing systems and constitute particularly preferred implementations of the invention.

EXAMPLE 4: DETERMINATION OF THE GEL TIMES WITH VPLS2142 AS FREE-RADICAL STARTER B2)

[0102] In order to assess the applicability of the hardener system imine-metal salt to cold-hardening vinyl ester resins, exemplary formulations with the above-described resin formulation I and various metal salts are prepared. As free-radical starter there is used an imine from isobutyraldehyde and isophoronediamine (CSTICO phen VP LS 2142). Table 6 below lists the gel times and the maximum temperatures achieved during the polymerisations:

TABLE-US-00006 TABLE 6 Gel times of the initiator systems from VPLS2142 and varying metal salts t Temp. RFI VPLS2142 Metal salt >35 C. T.sub.max Item name [g] [g] [g] Total [g] Metal [hh:mm:ss] [ C.] VPLS2142- 9.75 0.25.sup.X 0.10 10.10 SolCop8 00:00:57 89.1 004 VPLS2142- 9.75 0.25.sup.X 0.10 10.10 Mn(III) 00:02:06 74.9 006 VPLS2142- 9.75 0.25.sup.X 0.10 10.10 OxyC 00:02:17 71.0 007 VPLS2142- 9.75 0.25.sup.X 0.10 10.10 VP0132 00:00:20 100.0 008 VPLS2142- 9.75 0.25.sup.X 0.10 10.10 CF31 00:01:23 88.7 010 Comp-Ex-01 9.75 0.25 10.00 >04:00:00 Comp-Ex-02 9.75 0.10 9.85 SolCop8 >18:00:00 .sup.Xadded as hardener

[0103] It will be apparent from Table 6 that using the exemplary formulations exothermic and in some cases rapid polymerisations of vinyl ester resins at room temperature are achieved. In addition, Table 6 shows that the hardener system imine-metal salt functions with all metals. The Comparison Examples Comp-Ex-01 and Comp-Ex-02, which are not according to the invention, show that without the presence of constituent a) or b2), no effective polymerisations are initiated.

EXAMPLE 5: DETERMINATION OF THE PROCESSING TIMES WITH VPLS2142 AS INITIATOR B2)

[0104] Table 7 shows the processing times of the initiator system consisting of CSTICO phen VP LS 2142 in combination with Octa Soligen Manganese 6 with different contents of initiator and metal salt:

TABLE-US-00007 TABLE 7 Processing times of the initiator systems from VPLS2142 and Mn6. RFI VPLS2142 Mn6 Total t.sub.processing time n (CC):n n (NC):n Item name [g] [g] [g] [g] (hh:mm:ss] (NC) (Mn) VPLS2142- 9.75 0.10 0.10.sup.X 9.95 00:01:14 74 6 013 VPLS2142- 9.75 0.50 0.10.sup.X 10.35 00:00:34 15 29 015 VPLS2142- 9.75 0.10 0.02.sup.X 9.87 00:01:54 74 29 017 VPLS2142- 9.75 0.05 0.01.sup.X 9.81 00:03:22 147 29 018 VPLS2142- 9.75 0.10 0.20.sup.X 10.05 00:01:04 74 3 020 VPLS2142- 9.75 0.25 0.10.sup.X 10.20*.sup.1 00:08:15 021 VPLS2142- 9.75 7.37 0.10.sup.X 17.22 00:00:20 1 430 023 VPLS2142- 9.75 0.0025*.sup.2 0.10.sup.X 10.10 00:56:30 2950 0.15 026 .sup.Xadded as hardener *.sup.1additionally 0.1 g of t-BBC 10% in BDDMA weighed in. *.sup.20.25 g of a 1% solution of VPLS2142 in BDDMA weighed in.

[0105] The model mixtures from Table 7 show that both the initiator b2) and the metal salt can be varied within wide ranges (see in this connection also the molar ratios n (CC):n (NC) (imine increment) and n (NC):n (metal). The use of an aerobic inhibitor and the retarding effect thereof is shown with reference to the model mixture VPLS2142-021.

EXAMPLE 6: DETERMINATION OF THE GEL TIMES WITH SOLCOP8 OR SOLMN6 AND VARYING ALDIMINES AS FREE-RADICAL STARTER B2)VARIATION OF THE AMINES AND THE ALDEHYDES

[0106] Tables 8a and 8b below illustrate the gel times and the maximum temperatures achieved during the polymerisations of the hardener systems consisting of Soligen Copper 8 or Soligen Manganese 6 and different imines:

TABLE-US-00008 TABLE 8a Gel times of the initiator systems from SolCop8 and various aldimines (produced in each case from isobutyraldehyde and varying amines) t Temp. RFI Aldimine SolCop8 Total >35 C. T.sub.max Item name [g] [g] [g] [g] Amine [hh:mm:ss] [ C.] Isob-MXDA 9.75 0.25.sup.X 0.10 10.10 MXDA 00:00:52 87.6 Isob-BAC 9.75 0.25.sup.X 0.10 10.10 1,3-BAC 00:00:46 95.9 Isob-EDR148 9.75 0.25.sup.X 0.10 10.10 EDR148 00:01:17 97.0 Isob-DCH 9.75 0.25.sup.X 0.10 10.10 DCH 00:01:13 93.2 Isob-DETDA 9.75 0.25.sup.X 0.10 10.10 DETDA 00:20:07 39.6 .sup.Xadded as hardener

TABLE-US-00009 TABLE 8B Gel times of the initiator systems from SolMn6 and various aldimines (produced in each case from Jeffamine D230 and varying aldehydes). t Temp. Aldimine SolMn6 Total Aldehyde/ >35 C. T.sub.max Item name RFI [g] [g] [g] [g] ketone [hh:mm:ss] [ C.] Isob-D230- 9.75 0.25.sup.X 0.10 10.10 Isob 00:01:47 96.6 005 2MVal-D230 9.75 0.25.sup.X 0.10 10.10 2MVal 00:01:43 94.8 Val-D230 9.75 0.25.sup.X 0.10 10.10 Val 00:12:25 42.8 LS2965 9.75 0.25.sup.X 0.10 10.10 MIBK * * .sup.Xadded as hardener *fully hardened the next day

[0107] Tables 8a and 8b clearly show that the vinyl ester resin formulation can be polymerised very satisfactorily using an extremely wide variety of free-radical starters b2). In addition, Table 8a is intended to underline that all kinds of primary amines can be used for the production of the imines without suffering any loss or impairment of the polymerisation-initiating action. It will be apparent from Table 8b that the aldehydes that are especially preferredfor imine synthesispolymerise significantly more quickly and with greater exothermy. Table 8a further shows that any (residual) water of reaction present (for example Isob-DCH) or even homogeneously distributed water of reaction (for example Isob-EDR148) has no effect on the polymerisation.

EXAMPLE 7: DETERMINATION OF THE GEL TIMES WITH THE ALDIMINE ISOB-AM AS INITIATOR B2)

[0108] The aldimine Isob-AM is produced from the two starting materials isobutyraldehyde and 3-aminopropyltrimethoxysilane. Silanes are reactive towards water and therefore react with hydrolysis and condensation. By virtue of that fact, during the aldimine synthesis oligomerisation of the silane units takes place in situ as a result of the water of reaction. It is therefore possible to generate REACH-polymeric initiators. Table 9 shows the gel times and the associated maximum achieved temperatures of the hardener systems Isob-AM with varying metal salts.

TABLE-US-00010 TABLE 9 Gel times of the initiator systems from Isob-AM and varying metal salts Isob- t Temp. RFI AM Metal salt >35 C. T.sub.max Item name [g] [g] [g] Total [g] Metal [hh:mm:ss] [ C.] Isob-AM-001 9.75 0.25 0.10.sup.X 10.10 SolCop8 00:01:00 95.1 Isob-AM-003 9.75 0.25 0.10.sup.X 10.10 OxyC 00:01:36 80.1 Isob-AM-004 9.75 0.25 0.10.sup.X 10.10 VP0132 00:00:18 86.7 Isob-AM-010 9.75 0.25 0.10.sup.X 10.10 CF31 00:00:58 90.5 Isob-AM-014 9.75 0.25 0.10.sup.X 10.10 END15 00:01:53 85.3 Isob-AM-021 9.75 0.25 0.10.sup.X 10.10 DCer 00:07:16 74.4 Isob-AM-029 9.75 0.25 0.10.sup.X 10.10 NDryC 00:02:13 84.8 .sup.Xadded as hardener

[0109] It is also apparent from the model formulations of Table 9 that an exothermic and in some cases rapid polymerisation of methacrylates at room temperature can be achieved with different metal salts. Furthermore, Table 9 is intended to emphasise that not only monomeric initiators but also oligomeric up to polymeric (REACH polymer) initiators can be used. The model mixture Isob-AM-029 is especially interesting for coating applications, because the activator used therein does not have an inherent colour in the resin, that is to say it has a colourless appearance.

EXAMPLE 8: PULL-OUT TESTS FROM CONCRETE WITH FREE-RADICAL STARTERS B2)

[0110] Setting tests are carried out in accordance with the afore-mentioned parameters for pull-out tests from concrete.

TABLE-US-00011 TABLE 10 Formulations for carrying out setting tests and bond stresses determined with free-radical starters b2) ST-Isob- ST-Isob- ST-Isob- ST-VPLS2142- Item name MXDA-001 D230-001 AM-001 016 RFI [g] 29.13 28.85 29.13 29.07 Aldimine [g] 0.75 1.48 0.75 0.75 Metal salt [g] 0.30.sup.X 0.30.sup.X 0.30.sup.X 0.47.sup.X SolCop8 Iro7/8 OxyC CuSO.sub.4 Sand [g] 44.82 44.38 44.82 44.72 Total [g] 75.00 75.00 75.00 75.00 Bond stress 20.1 17.1 19.5 17.9 [N/mm.sup.2] .sup.Xadded as hardener

[0111] The appropriate starting materials for the aldimines can be assigned by reference to the abbreviations used in the item names and to Table 1 above which gives the abbreviations. Table 10 shows that the hardener system according to the invention is very effective and, in addition, indicates the enormous potential of such initiator systems.

EXAMPLE 9: DETERMINATION OF THE GEL TIMES WITH FREE-RADICAL STARTERS B1) AND VARYING METAL SALTS

[0112] In order to demonstrate the applicability of free-radical starters b1) in combination with metal salts, exemplary formulations with the above-described resin formulation I (RFI) and different metal salts are produced. Table 11 below shows the gel times and the maximum temperatures achieved during the curing reactions.

TABLE-US-00012 TABLE 11 Gel times of the hardener systems consisting of Isob and D230 in combination with different metal salts. t Temp. RFI D230 Metal Isob >35 C. T.sub.max Item name [g] [g] [g] [g] Total [g] Metal [hh:mm:ss] [ C.] Process- 9.75 0.24 0.10 0.15.sup.X 10.24 SolCop8 00:02:35 99.6 Metals-001 Process- 9.75 0.24 0.10 0.15.sup.X 10.24 Iro7/8 00:07:16 69.6 Metals-002 Process- 9.75 0.24 0.10 0.15.sup.X 10.24 OxyC 00:02:56 71.1 Metals-003 Process- 9.75 0.24 0.10 0.15.sup.X 10.24 VP0132 00:00:52 82.4 Metals-004 Process- 9.75 0.24 0.10 0.15.sup.X 10.24 SolMn6 00:03:30 92.3 Metals-005 Process- 9.75 0.24 0.10 0.15.sup.X 10.24 END15 00:13:16 83.2 Metals-011 Process- 9.75 0.24 0.10 0.15.sup.X 10.24 CuSO.sub.4 00:05:14 84.6 Metals-015 H.sub.2O Process- 9.75 0.24 0.10 0.15.sup.X 10.24 CuSO.sub.4 00:05:06 92.8 Metals-016 MEG .sup.Xadded as hardener

[0113] Table 11 shows that the free-radical starters b1) according to the invention in combination with metal salts also initiate polymerisations of unsaturated reactive resins at room temperature. Moreover, it will be apparent from the model formulations that all metal salts can be used for that purpose. The possible use and the functionality of metal salts of inorganic and inorganic acids is shown in the formulations Process-Metals-001 (metal salt of organic acids) and Process-Metals-015 and Process-Metals-016 (metal salt of inorganic acids).

EXAMPLE 10: DETERMINATION OF THE GEL TIMES WITH FREE-RADICAL STARTERS B1) AND SOLMN6/SOLCOP8 AS METAL SALTS

[0114] Table 12 below illustrates the gel times and the maximum achieved temperatures of the free-radical starters b1) according to the invention using different amines and aldehydes.

TABLE-US-00013 TABLE 12 Gel times of free-radical starters b1) with varying amines and aldehydes t Temp. Item RFI Aldehyde Metal Amine Total Amine/ >35 C. T.sub.max name [g] [g] [g] [g] [g] aldehyde [hh:mm:ss] [ C.] Process- 9.75 0.15 0.10 0.37.sup.X 10.37 AMMO/ 00:01:50 89.4 Amines- SolMn6 Isob 001 Process- 9.75 0.15 0.10 0.14.sup.X 10.14 MXDA/ 00:03:27 68.2 Amines- SolMn6 Isob 002 Process- 9.75 0.15 0.10 0.15.sup.X 10.15 BAC/ 00:03:37 91.3 Amines- SolMn6 Isob 004 Process- 9.75 0.15.sup.X 0.10 0.24 10.24 D230/ 00:02:12 104.8 Ald-001 SolCop8 Isob Process- 9.75 0.21.sup.X 0.10 0.24 10.30 D230/ 00:03:35 94.4 Ald-002 SolCop8 2MVal Comp-Ex- 9.75 0.15 0.10 10.00 /Isob >18:00:00 03 SolCop8 Comp-Ex- 9.75 0.15 0.24 10.14 D230/ >04:00:00 04 Isob Comp-Ex- 9.75 0.10 0.24 10.09 D230/ >18:00:00 05 SolCop8 .sup.Xadded as hardener

[0115] Table 12 shows that not only a variety of primary amines but also a variety of aldehydes can be used as free-radical starters b1) according to the invention. This is demonstrated by the rapid and exothermic polymerisations. The Comparison Examples Comp-Ex-03 to Comp-Ex-05, which are not according to the invention, show that effective polymerisations do not take place in the absence of a constituent of the hardener systems according to the invention.

EXAMPLE 11: DETERMINATION OF THE GEL TIMES WITH FREE-RADICAL STARTERS B1) USING AMINE-FUNCTIONALISED FILLERS

[0116] Table 13 below is intended to show the possibility of using amine-functionalised or amine-silanised fillers as polyamines in free-radical starters b1).

TABLE-US-00014 TABLE 13 Gel times of the free-radical starters b1) with amine-functionalised fillers as polyamines t Temp. Item RFI H30RA Metal Isob >35 C. T.sub.max name [g] [g] [g] [g] Total [g] Metal [hh:mm:ss] [ C.] H30RA- 9.75 1.16 0.10 0.03.sup.X 11.04 SolCop8 00:06:26 78.9 06 H30RA- 9.75 1.16 0.10 0.03.sup.X 11.04 CuSO.sub.4 00:08:44 72.1 07 MEG H30RA- 9.75 1.16 0.10 0.03.sup.X 11.04 OxyC 00:05:41 61.1 08 .sup.Xadded as hardener

[0117] The amine-functionalised silica used has an approximate nitrogen content of 0.5%. Table 13 shows that amine-functionalised fillers can also be used as polyamines for free-radical starters b1) and accordingly the reactive resin can be polymerised very satisfactorily.

EXAMPLE 12: PULL-OUT TESTS FROM CONCRETE WITH FREE-RADICAL STARTERS B1)

[0118] In order also to show the performance potential of the free-radical starters b1) in an as application-oriented way as possible, setting tests are carried out in accordance with the afore-mentioned parameters for pull-out tests from concrete.

TABLE-US-00015 TABLE 14 Formulations for carrying out setting tests and bond stresses determined with free- radical starters b1). ST- ST- ST- ST- ST- ST- ST- ST- Item Process- Process- Process- Process- Process- Process- Process- Process- name 01 02 03 04 05 06 08 16 RFI or II 28.97 28.97 28.97 28.97 28.97 28.91 28.82 28.97 Isob [g] 0.45 0.45 0.45.sup.X 0.45.sup.X 0.45 0.59 0.44 1.34 SolCop8 0.30 0.30 0.30 0.30 0.30.sup.X 0.30.sup.X 0.30.sup.X 0.30.sup.X [g] Sand [g] 44.57 44.57 44.57 44.57 44.57 44.48 44.34 42.25 D230 [g] 0.71.sup.X 0.71.sup.X 0.71 0.71 0.71.sup.X 0.71.sup.X 1.09.sup.X 2.14.sup.X Total [g] 75.00 75.00 75.00 75.00 75.00 75.00 75.00 75.00 Bond 18.6 16.1 17.5 14.1 17.2 13.9 17.1 22.0 stress [N/mm.sup.2] the raw materials marked .sup.X are added as hardener or hardener formulation.

[0119] In formulations ST-Process-02 and ST-Process-04, instead of the simplified resin formulation I (RFI) there is used the urethane-methacrylate-based resin formulation II (RFII) according to Example 3. In formulation ST-Process-06, 2-methylvaleraldehyde is used instead of isobutyraldehyde. In formulation ST-Process-08, the metal salt SolCop8 and the amine D230 are replaced by OxyC and AM. Table 14 shows that the free-radical starters b1) in combination with metal salts also form effective hardener systems for unsaturated reactive resins and achieve suitable bond stresses. Formulations ST-Process-01 and ST-Process-02 show that it is also possible for different basic resins to be hardened with the initiator system according to the invention. Moreover, in formulations ST-Process-01, ST-Process-03 and ST-Process-05 it becomes apparent that the constituents of the free-radical starters b1) and the hardener systems according to the invention can in each case be employed as hardener or hardener formulations and so a variety of distributions between different components are possible.

EXAMPLE 13: GEL TIMES OF FREE-RADICAL STARTERS B1) AND B2) USING NON-HAZARD-CLASSIFIED REACTIVE RESINS

[0120] Non-hazard-classified reactive resins and fixing systems are playing an increasing role in the field of chemical fixing technology. In this field the initiator systems according to the invention exhibit great advantages over the previous prior art and for the first time allow the formulation of non-hazard-classified multi-component reactive resin systems. Table 15 shows the gel times and the maximum temperatures achieved during the polymerisations of non-hazard-classified reactive resin formulations initiated by the free-radical starters b1) and b2) according to the invention.

TABLE-US-00016 TABLE 15 Gel times of the free-radical starters b1) and b2) in non-hazard-classified reactive resins NHCR- NHCR- NHCR- NHCR- NHCR- Item name 01 06 03 04 05 RFIII [g] 9.85 9.95 9.75 9.75 9.85 VPLS2142 0.10.sup.X 0.10.sup.X 0.10.sup.X [g] Isob [g] 0.15 0.15.sup.X SolCop8 [g] 0.10 0.05 0.10 CuSO.sub.4 0.10 0.10 MEG [g] D230 [g] 0.24.sup.X 0.24 Total [g] 10.05 10.10 10.24 10.24 10.05 t Temp > 00:01:50 00:02:37 00:09:35 00:09:29 00:03:41 35 C. [hh:mm:ss] T.sub.max [ C.] 110.0 82.3 80.4 92.4 95.7 the raw materials marked .sup.X are added as hardener.

[0121] In the exemplary formulation NHCR-01, instead of the simplified resin formulation RFIII there is used a reactive resin based on epoxymethacrylate (CN159) and a reactive diluent (SR210)ratio 50:50. In addition, in formulation NHCR-06 the reactive diluent (SR210) of the simplified resin formulation III is replaced by a biobased reactive diluent (Sarbio6105). Table 15 shows that the hardener systems according to the invention also lead to an exothermic and effective polymerisation of non-hazard-classified and partially biobased reactive resins.

EXAMPLE 14: REFERENCING TESTS IN COMPARISON WITH EP 2 824 117 A1

[0122] In order to demonstrate that the imines suitable for use according to the invention (free-radical starters b1) and/or b2)) in combination with metal salts lead to significantly more effective initiator systems and to higher bond stresses in comparison with the tertiary aliphatic amines claimed in EP 2 824 117 A1, the following referencing tests (RefT) are carried out:

RefT-1: Assessment of Curing with PMDETA as Initiator and Varying Metal Salts

[0123] In order to assess the applicability of the initiator system PMDETA-metal salt to cold-hardening vinyl ester resins, exemplary formulations with the above-described resin formulation I and various metal saltsanalogous to Example 4are prepared.

TABLE-US-00017 TABLE 16a PMDETA as initiator with varying metal salts Metal PMDETA salt Total Item name RFI [g] [g] [g] [g] Metal Note PMDETA-001 9.75 0.25 0.10.sup.X 10.10 SolCop8 liquid* PMDETA-009 9.75 0.50 0.10.sup.X 10.35 SolCop8 gelled* PMDETA-002 9.75 0.25 0.10.sup.X 10.10 Iro7/8 liquid* PMDETA-003 9.75 0.25 0.10.sup.X 10.10 VP0132 liquid* PMDETA-004 9.75 0.25 0.10.sup.X 10.10 OxyC liquid* PMDETA-005 9.75 0.25 0.10.sup.X 10.10 Mn6 liquid* .sup.Xadded as hardener *after 24 h

[0124] It will be clear from Table 16a that the concentrations analogous to Example 4 in the hardener systems PMDETAmetal salts do not lead to polymerisation of the vinyl ester resin. Only by increasing the concentration of initiator (PMDETA-009) was gelling ascertained.

RefT-2: Pull-Out Tests from Concrete with PMDETA as Initiator

[0125] Example 1 and Example 4a of EP 2 824 117 A1 are subjected to a setting test. Table 16b shows the formulations for carrying out setting tests and the bond stresses determined.

TABLE-US-00018 TABLE 16b Formulations for carrying out setting tests for differentiation and bond stresses determined ST- ST- ST- ST- PMDETA- PMDETA- PMDETA- PMDETA- Item name 010 011 012 013 BDDMA [g] 26.46 27.97 RFI [g] 26.84 28.37 PMDETA [g] 2.28 2.31 1.12 1.13 SolCop8 [g] 1.40 1.42 0.56 0.57 Sand [g] 43.81 44.43 44.29 44.92 H18 1.05 1.05 Total [g] 75.00 75.00 75.00 75.00 Bond stress 0.37 1.56 1.02 0.10 [N/mm.sup.2]

[0126] Since in Examples 1 and 4a of EP 2 824 117 A1 solely BDDMA is used as vinyl ester resin, further setting tests are carried out using the resin formulation RFI. For reinforcement, sand is added in amounts analogous to Example 8: Pull-out tests from concrete. The bond stresses determined for the hardener system PMDETAcopper(II) salt are significantly below those of the hardener systems according to the invention (see Table 10).

[0127] Consequently it has been established that the initiator system iminemetal salt according to the invention leads to hardener systems that are significantly more effective and capable of greater variation than the systems claimed in EP 2 824 117 A1. This is manifested both in the higher bond stresses and in the wider choice of possible metal salts as accelerator, which is not limited to copper only. As a fundamental difference with respect to EP 2 824 117 A1 it has again been established that the free-radical starters in the form of imines (aldimines and/or ketimines) suitable for use according to the invention contain an sp.sup.2-hybridised nitrogen. The nitrogen-containing ligands in the form of a tertiary aliphatic amines claimed in the EP have spa-hybridised nitrogen atoms.