Curable epoxy systems containing phenolic polymers

Abstract

An epoxy system including an epoxy resin and a phenolic polymer having a number average molar mass (Mn) of 200 to 1,500 g / mol. The use of this phenolic polymer in an epoxy resin can accelerate the curing of the epoxy resin.

Description

[Technical Field]

[0001] The present invention relates to an epoxy system comprising an epoxy resin and a phenolic polymer. The present invention also relates to the use of the phenolic polymer as an accelerator or curing agent for the epoxy resin, for example in coating and adhesive systems. [Background technology]

[0002] Epoxy resins constitute a wide variety of polymers that have good adhesive and electrical properties, high glass transition temperatures, excellent corrosion and solvent resistance, and are well known for their use in adhesives, coatings, and composites.

[0003] These resins feature epoxide groups that cure by crosslinking with nucleophilic multifunctional curing agents, such as amines, or by reaction with themselves. This curing process is usually accelerated or even induced by Lewis acidic or basic catalysts. Commonly known accelerators for epoxy / amine systems include alkylated phenols, especially bisphenol A, nonylphenol, or styrenated phenols, as well as combinations of these alkylated phenols with tertiary amines, salicylic acid, or benzyl alcohol. Frequently applied commercial accelerators include Novares® LS500, Sanko® MSP, or Kumanox® 3111.

[0004] Although both of these systems are highly efficient and inexpensive, they face various application and processing challenges. For example, bisphenol A has allergenic and teratogenic properties and exhibits a high tendency to crystallize in formulated systems, resulting in reduced performance. Nonylphenol acts as an endocrine disruptor, limiting its applicability; styrenated phenols and salicylic acid are currently under similar consideration. Benzyl alcohol, a volatile substance, produces a migration effect and lowers the glass transition temperature of cured epoxy resins, a property of great importance in many applications.

[0005] EP 0 126 625 A1 describes a phenol product obtained by reacting a phenol compound substituted with OH, an alkyl or alkenyl group having 1 to 8 carbon atoms, or a phenyl group, -C(CH3)2C6H5 or -C(CH3)2C6H4OH group with a benzene compound having two independently occurring -C(CH3)CH2 or -C(CH3)2OH substitutions in the presence of an acid catalyst.

[0006] U.S. Pat. No. 9,074,041 describes a curable epoxy resin composite formulation for preparing a composite molded article containing a reinforcement material and an epoxy resin composition, the epoxy resin composition comprising at least one epoxy resin having, on average, two or more glycidyl ether groups per molecule, at least one alkanolamine curing agent, and at least one styrenated phenol.

[0007] US Patent No. 9,464,037 describes adducts of styrenated phenols and hydroxylamines and methods for their synthesis. The resins are prepared by an acid-catalyzed alkylation reaction. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] European Patent Application Publication No. 0 126 625 [Patent Document 2] U.S. Patent No. 9,074,041 [Patent Document 3] U.S. Patent No. 9,464,037 Summary of the Invention [Problem to be solved by the invention]

[0009] It is an object of the present invention to provide an accelerator for epoxy resins that does not have the above-mentioned drawbacks. In particular, it would be desirable to have a non-volatile, non-toxic polymeric accelerator system for curing epoxy resins that has the same or improved acceleration properties as prior art accelerators. [Means for solving the problem]

[0010] The purpose of this is to Epoxy resin, The problem is solved by an epoxy system containing a phenolic polymer which comprises a phenolic compound, a linker group L and a terminal group E, and which has a number average molar mass (Mn) of 200 to 1,500 g / mol, and which has a structure represented by the following formula (1):

[0011] [ka]

[0012] wherein the linker group L has the meaning of the following formula (2), (3), (4), (5) or (6):

[0013] [ka]

[0014] The end group E has the meaning of H or is a group of the formula (2), (3), (4), (5) or (6) which has only one bond to the phenolic compound of the formula (1), or has the meaning of the following formula (2c1), (2c2), (3c1) or (3c2):

[0015] [ka]

[0016] where: R 1 is H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms, or C6H5(CR 18 R19 ) o -Z-, preferably H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms; R 2 ,R 4 ,R 6 ,R 7 ,R 8 , R 9 ,R 11 and R 12 are each independently H or alkyl having 1 to 5 carbon atoms, R 3 and R 5 is H, OH, NO, halogen, alkyl having 1 to 5 carbon atoms, or oxyalkyl having 1 to 5 carbon atoms, R 10 and R 13 is alkyl having 1 to 5 carbon atoms or cycloalkyl having 5 to 6 carbon atoms, R 14 is a cycloalkyl having 5 to 12 carbon atoms, optionally substituted with a methyl or ethyl group; R 15 ,R 16 and R 17 are each independently H or alkyl having 1 to 5 carbon atoms, preferably —CH3; R 18 and R 19 are each independently H or CH3; Z is a covalent bond or —O—; o is 1 or 0, m is an integer from 1 to 7, n is an integer from 2 to 21.

[0017] The present invention further comprises: A phenolic polymer comprising a phenolic compound, a linker group L, and a terminal group E, and having a number average molar mass (Mn) of 200 to 1,500 g / mol, the phenolic polymer having a structure represented by the following formula (1): Use as accelerators for the curing of epoxy resins, especially in the presence of curing agents containing amine functional groups; Or, It is intended for use as a curing agent for epoxy resins, particularly in the presence of a co-curing agent containing amine functionality.

[0018] [ka]

[0019] wherein the linker group L has the meaning of the following formula (2), (3), (4), (5) or (6):

[0020] [ka]

[0021] The end group E has the meaning of H or is a group of the formula (2), (3), (4), (5) or (6) which has only one bond to the phenolic compound of the formula (1), or has the meaning of the following formula (2c1), (2c2), (3c1) or (3c2):

[0022] [ka]

[0023] where: R 1 is H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms, or C6H5(CR 18 R 19 ) o -Z-, preferably H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms; R 2 ,R 4 ,R 6 ,R 7 ,R 8 , R 9 ,R 11 and R 12 are each independently H or alkyl having 1 to 5 carbon atoms, R 3 and R 5is H, OH, NO, halogen, alkyl having 1 to 5 carbon atoms, or oxyalkyl having 1 to 5 carbon atoms, R 10 and R 13 is alkyl having 1 to 5 carbon atoms or cycloalkyl having 5 to 6 carbon atoms, R 14 is a cycloalkyl having 5 to 12 carbon atoms, optionally substituted with a methyl or ethyl group; R 15 ,R 16 and R 17 are each independently H or alkyl having 1 to 5 carbon atoms, preferably —CH3; R 18 and R 19 are each independently H or CH3; Z is a covalent bond or —O—; o is 1 or 0, m is an integer from 1 to 7, n is an integer from 2 to 21.

[0024] The present invention further comprises: Epoxy resin, a phenolic polymer comprising a phenolic compound, a linker group L, and a terminal group E, and having a number average molar mass (Mn) of 200 to 1,500 g / mol, the phenolic polymer having a structure represented by the following formula (1): and a curing agent containing amine, anhydride, phenol and / or thiol functional groups, particularly amine functional groups.

[0025] [ka]

[0026] wherein the linker group L has the meaning of the following formula (2), (3), (4), (5) or (6):

[0027] [ka]

[0028] The end group E has the meaning of H or is a group of the formula (2), (3), (4), (5) or (6) which has only one bond to the phenolic compound of the formula (1), or has the meaning of the following formula (2c1), (2c2), (3c1) or (3c2):

[0029] [ka]

[0030] where: R 1 is H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms, or C6H5(CR 18 R 19 ) o -Z-, preferably H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms; R 2 ,R 4 ,R 6 ,R 7 ,R 8 , R 9 ,R 11 and R 12 are each independently H or alkyl having 1 to 5 carbon atoms, R 3 and R 5 is H, OH, NO, halogen, alkyl having 1 to 5 carbon atoms, or oxyalkyl having 1 to 5 carbon atoms, R 10 and R 13 is alkyl having 1 to 5 carbon atoms or cycloalkyl having 5 to 6 carbon atoms, R 14 is a cycloalkyl having 5 to 12 carbon atoms, optionally substituted with a methyl or ethyl group; R 15 ,R 16 and R 17 are each independently H or alkyl having 1 to 5 carbon atoms, preferably —CH3; R 18 and R 19are each independently H or CH3; Z is a covalent bond or —O—; o is 1 or 0, m is an integer from 1 to 7, n is an integer from 2 to 21.

[0031] The phenolic polymers according to the invention accelerate the curing of epoxy resins, for example in adhesive systems or in coatings, and the cured epoxy resins have good mechanical properties and also good chemical resistance.

[0032] Furthermore, it has been found that the use of the phenolic polymer according to the present invention in an epoxy system or component kit according to the present invention, or as an accelerator, can impart controlled acceleration properties to the epoxy resin. At the same time, the phenolic polymer according to the present invention can prevent a decrease in the mechanical strength of the epoxy system. Moreover, it has been found that an epoxy resin or epoxy system comprising the phenolic polymer according to the present invention can have high mechanical resistance. Furthermore, an epoxy resin or epoxy system comprising the phenolic polymer according to the present invention can have high chemical resistance.

[0033] Epoxy resins or epoxy systems, particularly cured epoxy systems, comprising the phenolic polymers of the present invention may also have a high glass transition temperature (Tg). Epoxy resins or epoxy systems, particularly cured epoxy systems, comprising the phenolic polymers of the present invention may also have high thermal stability. Finally, epoxy resins or epoxy systems, particularly cured epoxy systems, comprising the phenolic polymers of the present invention may have improved adhesion to metal and mineral surfaces and / or higher corrosion resistance. [Brief explanation of the drawings]

[0034] [Figure 1] FIG. 1 shows the time-dependent results of the rheological analysis, illustrating the increase in viscosity over time. DETAILED DESCRIPTION OF THE INVENTION

[0035] The phenolic polymers according to the present invention are also called terpolymers.

[0036] First, the components of the phenolic polymer and their properties will be described in detail below.

[0037] According to a preferred embodiment of the present invention, R 1 is H, alkyl having 1 to 10 carbon atoms, particularly alkyl having 1 to 8 carbon atoms, more particularly alkyl having 1 to 5 carbon atoms, or oxyalkyl having 1 to 10 carbon atoms, particularly oxyalkyl having 1 to 8 carbon atoms, more particularly oxyalkyl having 1 to 5 carbon atoms.

[0038] According to a preferred embodiment, the phenolic polymer has a structure represented by formula (1):

[0039] [ka]

[0040] (wherein the linker group L has the meaning of the following formula (2), (3), (4), (5) or (6),

[0041] [ka]

[0042] the terminal group E each has the meaning H or is a group of formula (2), (3), (4), (5) or (6) which has only one bond to the phenolic compound of formula (1),

[0043] where: R 1 is H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms, R 2 ,R 4 ,R 6 ,R 7 ,R 8 , R 9 ,R 11 and R12 are each independently H or alkyl having 1 to 5 carbon atoms, R 3 and R 5 is H, OH, NO, halogen, alkyl having 1 to 5 carbon atoms, or oxyalkyl having 1 to 5 carbon atoms, R 10 and R 13 is alkyl having 1 to 5 carbon atoms or cycloalkyl having 5 to 6 carbon atoms, R 14 is a cycloalkyl having 5 to 12 carbon atoms, optionally substituted with a methyl or ethyl group; n is an integer from 2 to 21.

[0044] According to a preferred embodiment, the phenolic polymer has a structure represented by formula (1):

[0045] [ka]

[0046] (wherein the linker group L has the meaning of the following formula (2), (3), (4), (5) or (6),

[0047] [ka]

[0048] The terminal group E has the meaning of H or is a group of the formula (2), (3), (4), (5) or (6) which has only one bond to the phenolic compound of the formula (1), or has the meaning of the formula (2c1) or (2c2) below:

[0049] [ka]

[0050] where: R 1is H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms, or C6H5(CR 18 R 19 ) o -Z-, preferably H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms; R 2 ,R 4 ,R 6 ,R 7 ,R 8 , R 9 ,R 11 and R 12 are each independently H or alkyl having 1 to 5 carbon atoms, R 3 and R 5 is H, OH, NO, halogen, alkyl having 1 to 5 carbon atoms, or oxyalkyl having 1 to 5 carbon atoms, R 10 and R 13 is alkyl having 1 to 5 carbon atoms or cycloalkyl having 5 to 6 carbon atoms, R 14 is a cycloalkyl having 5 to 12 carbon atoms, optionally substituted with a methyl or ethyl group; R 18 and R 19 are each independently H or CH3; Z is a covalent bond or —O—; o is 1 or 0, n is an integer from 2 to 21.

[0051] According to a preferred embodiment, the phenolic polymer comprises a phenolic compound, a linker group L and a terminal group E, has a number average molar mass (Mn) of 200 to 1,500 g / mol, and has a structure represented by the following formula (1):

[0052] [ka]

[0053] (wherein the linker group L has the meaning of the following formula (2), (3), (4), (5) or (6),

[0054] [ka]

[0055] The terminal group E is a group of formula (2), (3), (4), (5) or (6) having only one bond to the phenolic compound of formula (1) or has the meaning of formula (2c1), (2c2), (3c1) or (3c2) below, respectively.

[0056] [ka]

[0057] where: R 1 is H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms, or C6H5(CR 18 R 19 ) o -Z-, preferably H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms; R 2 ,R 4 ,R 6 ,R 7 ,R 8 , R 9 ,R 11 and R 12 are each independently H or alkyl having 1 to 5 carbon atoms, R 3 and R 5 is H, OH, NO, halogen, alkyl having 1 to 5 carbon atoms, or oxyalkyl having 1 to 5 carbon atoms, R 10 and R 13 is alkyl having 1 to 5 carbon atoms or cycloalkyl having 5 to 6 carbon atoms, R 14 is a cycloalkyl having 5 to 12 carbon atoms, optionally substituted with a methyl or ethyl group; R 15 ,R 16 and R 17are each independently H or alkyl having 1 to 5 carbon atoms, preferably —CH3; R 18 and R 19 are each independently H or CH3; Z is a covalent bond or —O—; o is 1 or 0, m is an integer from 1 to 7, n is an integer from 2 to 21.

[0058] According to a preferred embodiment, the linker group L has the meaning of formula (2) below:

[0059] [ka]

[0060] (In the formula, R 2 ,R 3 and R 4 are each independently H or alkyl having 1 to 5 carbon atoms; preferably, are each independently R 3 is H and R 2 is H or CH3, and R 4 is H or CH; more preferably, R 3 is H, R 2 and R 4 is H, or R 3 is H, R 2 and R 4 is CH3.)

[0061] According to a preferred embodiment, the linker group L has the meaning of formula (2) below:

[0062] [ka]

[0063] (In the formula, R 2 ,R 3 and R 4is as defined herein in formula (2), in particular H.) The linker group L has the above-mentioned meaning, in particular R 2 , R 3 and R 4 Phenolic polymers in which H have been found to have good properties. In particular, phenolic polymers with lower softening points can be achieved. Lower softening points can improve processability and / or miscibility with other compounds, such as epoxide resins.

[0064] The phenolic polymer is optionally R 1 Substituted phenolic compounds, R 1 can be prepared by polymerizing a phenolic compound, wherein R is as defined herein, with one of the monomers of formulae (2a) to (5a) or with a substituted or unsubstituted cycloolefin compound having 5 to 12 carbon atoms and at least two double bonds in a series of Friedel-Crafts alkylation reactions. Instead of the monomers of formulas (2a) to (5a), a monomer of formula (2b) may be used. This reaction is carried out by the Friedel-Crafts alkylation reaction, which is a known synthesis method. The structure of the monomers of formulas (2a) to (5a) or the cycloolefin compound having 5 to 12 carbon atoms used as the linker group L in the polymerization reaction is represented by the following formulas (2a), (3a), (4a), (5a),

[0065] [ka]

[0066] Alternatively, it is selected from cycloolefin compounds having 5 to 12 carbon atoms, which are optionally substituted with a methyl group or an ethyl group, and preferably contain two non-conjugated double bonds.

[0067] (In the formula, R 2 ~R 13 has the meaning as explained above for the residues of formulae (2), (3), (4) and (5), X is a hydroxyl group or a halogen selected from chlorine, bromine and iodine.

[0068] The structure of formula (2b) is as follows:

[0069] [ka]

[0070] (In the formula, R 2 , R 3 , and R 4 is as described above for the residue of formula (2), and R 15 and R 16 are each independently H or alkyl having 1 to 5 carbon atoms, and X is a hydroxyl group or a halogen selected from chlorine, bromine and iodine. Preferably, the residue R 2 , R 4 , R 15 and R 16 has the meaning of H and / or alkyl having 1 to 2 carbon atoms. In a particularly preferred embodiment, the residue R 2 and R 4 has the meaning of H, and residue R 15 and R 16 has the meaning -CH3. Most preferably, the residue R 15 and R 16 has the meaning of -CH3.)

[0071] According to a preferred embodiment of the present invention, the residues R of the phenolic polymers of formula (1) and therefore of the monomers according to formulae (2a), (3a), (4a) and (5a) 2 , R 4 , R 6 , R 7 , R 8 , R 9 , R 11 and R 12 has the meaning of H and / or alkyl having 1 to 2 carbon atoms. In a particularly preferred embodiment, the residue R 2 , R 4 , R 6 , R 7 , R 8 , R 9 , R 11 and R 12has the meaning of H.

[0072] The above formulae (2a), (2b), (3a), (4a), (5a) or optionally methyl- or ethyl-substituted cycloolefin compounds having 5 to 12 carbon atoms represent starting compounds for the polymerization of phenolic polymers, while the groups of formulae (2), (3), (4), (5) and (6) represent the corresponding units L that result in the phenolic polymers upon polymerization.

[0073] The starting compounds of formulae (2a), (2b), (3a), (4a), (5a), and optionally methyl- or ethyl-substituted cycloolefin compounds having 5 to 12 carbon atoms can be used as purified materials, or alternatively, a particular starting compound can be used as part of a mixture of compounds. This is particularly true when divinylbenzene is used as the starting compound for the polymerization of phenolic polymers. When such a mixture of compounds is used, the starting compound, particularly the starting monomer of the linker group L, should be present in the mixture in an amount of at least 50% to 100% by weight, preferably 50% to 80% by weight, based on the weight of the compounds in the mixture.

[0074] Compounds of formulas (2a) to (5a) and optionally methyl- or ethyl-substituted cycloolefin compounds R having 5 to 12 carbon atoms 14The phenolic compound for polymerizing with (α,α-dimethylbenzyl)phenol to form the phenolic polymer of formula (1) can be selected from phenol, benzylphenol, (α-methylbenzyl)phenol, (α,α-dimethylbenzyl)phenol, benzyloxyphenol, (α-methylbenzyloxy)phenol, (α,α-dimethylbenzyloxy)phenol, phenylphenol, phenoxyphenol, alkylphenols having 1 to 15 carbon atoms, particularly alkylphenols having 1 to 10 carbon atoms, more particularly alkylphenols having 1 to 8 carbon atoms, even more particularly alkylphenols having 1 to 5 carbon atoms, and oxyalkylphenols having 1 to 15 carbon atoms, particularly oxyalkylphenols having 1 to 10 carbon atoms, more particularly oxyalkylphenols having 1 to 8 carbon atoms, even more particularly oxyalkylphenols having 1 to 5 carbon atoms, such as o-cresol, m-cresol, p-cresol, ethylphenol, and isopropylphenol.

[0075] The catalyst for polymerization can be a Lewis acid or a Bronsted acid. Preferably, the catalyst is selected from AlCl3, BF3, ZnCl2, H2SO4, TiCl4, or a mixture thereof. The catalyst can be used in an amount of 0.1 to 1 mol %. The catalyst is added after the phenolic compound is dissolved by heating at a temperature of 25°C to 180°C, preferably 35°C to 100°C, or after dissolving in a suitable solvent (e.g., toluene). Then, a monomer compound selected from formulas (2a) to (5a) or a cycloolefin compound having 5 to 12 carbon atoms and optionally substituted with methyl or ethyl is added dropwise to the phenolic compound. Alternatively, the catalyst is added to a mixture of the phenol compound and the monomer compound of formula (2a) to (5a) or the cycloolefin compound having 5 to 12 carbon atoms and optionally substituted with methyl or ethyl. The reaction mixture may be cooled, for example, to -10 to 10°C when adding the catalyst. The addition time of the compound of formula (2a), (3a), (4a), or (5a) or the cycloolefin compound having 5 to 12 carbon atoms and optionally substituted with methyl or ethyl may be selected from the range of 10 minutes to 2 hours. The reaction may be allowed to continue for 1.5 to 2.5 hours. The polymerization reaction may be carried out at a temperature of 40 to 200°C, preferably 60 to 150°C, more preferably 60 to 100°C. Preferably, the polymerization is carried out under ambient pressure. The polymerization may be terminated by the addition of a suitable additive, preferably lime. The resulting polymer may be purified by filtration and / or steam distillation.

[0076] The molar mass (Mn) of the phenolic polymer is in the range of 200 to 1,500 g / mol, preferably in the range of 350 or 400 to 800 g / mol.

[0077] The mass average molecular weight (Mw) of the phenolic polymer is preferably 500 to 12,000 g / mol, more preferably 600 to 10,000 g / mol, and even more preferably 700 to 9,000 g / mol.

[0078] The z-average molecular weight (Mz) of the phenolic polymer is preferably 800 to 35,000 g / mol, more preferably 900 to 25,000 g / mol, and even more preferably 1,000 to 20,000 g / mol.

[0079] The number average molecular weight (Mn), weight average molecular weight (Mw) and z-average molecular weight (Mz) may be measured, inter alia, by gel permeation chromatography (GPC). In GPC, a styrene-divinylbenzene copolymer may be used as the column material. One 3 μm pre-column and three 3 μm, 1000 Å main columns may be used. SECcurity from PSS-Polymers 2The HPLC-MS System may be used. The substance may be detected using an RI detector. Stabilizer-free ULC / MS grade THF is preferably used as the eluent. The measurement is preferably carried out isothermally at 40°C. For the calibration curve, the ReadyCal-Kit Poly(styrene) low (Mp 266-66,000 Da) from PSS-Polymers may be used as an external standard.

[0080] Phenolic polymers with low molecular weights in the ranges mentioned above have been found to have improved properties, particularly miscibility and compatibility with epoxy resins, which results in accelerated cure and, in some cases, improved mechanical properties and / or chemical resistance.

[0081] The glass transition temperature (Tg) of the phenolic polymer is advantageously between −10° C. and 90° C., preferably between −10° C. and 70° C., more preferably between −5° C. and 50° C., and most preferably between 0° C. and 40° C. It has been found that phenolic polymers having a glass transition temperature in the above range exhibit good processability and / or good solubility in other compounds such as epoxy resins.

[0082] The glass transition temperature is preferably measured using differential scanning calorimetry (DSC). A Mettler Toledo DSC 2 / 400 equipped with an intracooler may be used. An aluminum crucible with a pinhole, in particular an ME-26763 AL crucible, may be used for the measurement. A heating-cooling-heating-cooling sequence with a heating / cooling rate of 10 K per minute within a measurement window of -40°C to 150°C may be used to evaluate the glass transition temperature. The Tg is evaluated in accordance with DIN 53765, in particular DIN 53765:1994-03.

[0083] The phenolic polymer may comprise 50% to 70% by weight of the phenolic compound. The phenolic polymer may comprise 20% to 50% by weight of a linker group L, in particular a bifunctional monomer (linker L) selected from a divinylbenzene compound, a dicyclopentadiene compound, or a compound of formula (4), (5), or (6), based on the weight (mass) of the phenolic polymer. The divinylbenzene compound is preferably a compound of formula (2), more preferably R 2 , R 3 and R 4 is as defined herein, most preferably a compound of formula (2) wherein R 2 , R 3 and R 4 is a compound of formula (2) in which ⁢ ... According to another embodiment, the end group E is a mixture of H and at least one further end group E that is not H as defined herein.

[0084] According to a preferred embodiment, the end group E may have the meaning of formula (2c1), (2c2), (2c3), (2c4), (2c5), (2c6), (4c1), (4c2), (5c1), (5c2), (3c1) or (3c2).

[0085] [ka]

[0086] (In the formula, R 2 ~R 13 has the meaning as explained above for the residues of formulae (2), (3), (4) and (5), m is an integer from 1 to 7, R 15 ,R 16 and R 17 are each independently H or alkyl having 1 to 5 carbon atoms, preferably —CH3.

[0087] The use of end groups E different from H, in particular end groups E having the meaning of the formula above, allows the acceleration properties of the phenolic polymer to be adjusted. It has been found that when the end groups E described above are incorporated into the phenolic polymer, the acceleration can be increased. Furthermore, the miscibility of the phenolic polymer with other compounds, in particular epoxy resins, can be improved.

[0088] The terminal group E may also have the meaning of a cycloalkyl group having 5 to 12 carbon atoms, optionally substituted with a methyl or ethyl group.

[0089] Thus, the end group E may advantageously be obtained from a monofunctional monomer having the meaning of the following formula (2d1), (2d2), (2d3), (2d4), (2d5), (2d6), (2d7), (2d8), (4d1), (4d2), (5d1), (5d2), (3d1) or (3d2):

[0090] [ka]

[0091] (In the formula, R 2 ~R 13 has the meaning as explained above for the residues of formulae (2), (3), (4) and (5), R 15 , R16 and R 17 are each independently H or alkyl having 1 to 5 carbon atoms, m is an integer from 1 to 7, X is a hydroxyl group or a halogen selected from chlorine, bromine and iodine.

[0092] The end group E may also result from a monomer having the meaning of a cycloolefin compound having 5 to 12 carbon atoms and only one double bond, optionally substituted with a methyl or ethyl group.

[0093] According to one embodiment, the terminal group E has the meaning of the following formula (2c1), (2c2), (2c3), (2c4), (2c5) or (2c6):

[0094] [ka]

[0095] (In the formula, R 2 , R 3 , R 4 , R 15 and R 16 are each independently H or alkyl having 1 to 5 carbon atoms, and preferably, in the formula, R 3 is H and R 2 is H or CH3, and R 4 is H or CH3, and R 15 is alkyl having 1 to 5 carbon atoms, and R 16 is alkyl having 1 to 5 carbon atoms.) Preferably, the terminal group E has the meaning of formula (2c1), (2c3) or (2c5) above, in which R 2 , R 3 , R 4 , R 15 and R 16 are each independently H or alkyl having 1 to 5 carbon atoms, and more preferably, in the formula, R 3 is H and R 2 is H or CH3, and R 4 is H or CH3, and R 15is alkyl having 1 to 5 carbon atoms, and R 16 is alkyl having 1 to 5 carbon atoms.

[0096] According to a preferred embodiment, the terminal group E has the meaning of formula (2c5) or (2c6) below:

[0097] [ka]

[0098] (In the formula, R 2 , R 3 and R 4 are each independently H or alkyl having 1 to 5 carbon atoms, and preferably H.

[0099] According to a preferred embodiment, the linker group L has the meaning of formula (2) below:

[0100] [ka]

[0101] The terminal group E has the meaning of the following formula (2c5) or (2c6):

[0102] [ka]

[0103] (In the formula, R 2 , R 3 and R 4 are each independently H or alkyl having 1 to 5 carbon atoms, and preferably H.

[0104] The phenolic polymer may have a high OH content, preferably 5 to 13 wt. %, particularly preferably 6 to 9 wt. %, based on the weight of the phenolic polymer. The softening point of the phenolic polymer according to ASTM 3461 is up to 170°C, more preferably 40 to 120°C, and most preferably 50 to 100°C. The hydroxyl content of the phenolic polymer can be influenced by incorporating end groups E other than H. A high hydroxyl content allows for improved acceleration or curing of the phenolic polymer. The softening point of the phenolic polymer can also be influenced by incorporating end groups E other than H. A lower softening point reduces the viscosity of the aqueous solution, allowing for a reduction in the amount of thinner or diluent used to provide the epoxy-based phenolic polymer to customers. The solvent may be released or already completely released from the cured product. The thinner may remain in the cured product. The low-boiling thinner may in particular be partially released from the cured product, for example up to 30% by weight, or up to 20% by weight, or up to 10% by weight of the low-boiling thinner, based on the total mass of the low-boiling thinner.

[0105] The softening point can also be adjusted by the reaction temperature used to prepare the phenolic polymer, but higher temperatures are not preferred because they also increase the Gardner color index. According to one embodiment, the phenolic polymer has a Gardner color index of 0 to 5, preferably 0 to 2, more preferably 0 to 1, determined according to DIN EN ISO 4630:2016-05 using acetone instead of toluene. Epoxy systems containing phenolic polymers with low Gardner color indexes allow the preparation of coatings that are nearly colorless or colorless.

[0106] Further properties of the epoxy system according to the present invention are described below.

[0107] The epoxy system of the present invention may be a one-part or two-part epoxy system. In a one-part epoxy system, the epoxy resin, curing agent, accelerator, and other components are typically contained in the same mixture, i.e., one part. In a one-part epoxy system, the curing agent is latent at ambient temperature and becomes active at elevated temperatures. In a one-part epoxy system, the curing agent preferably contains anhydride, thiol, and / or phenolic functional groups. Latent curing agents include, for example, dicynamide, BF3 complexes such as BF3 monoethylamine complex, aromatic amines, and imidazoles such as 2-ethyl-4-methylimidazole. However, curing agents containing carboxylic acid and / or isocyanate functional groups can also be used in one-part epoxy systems. The accelerator or optional additional accelerator in a one-part epoxy system can be, specifically, amines that exhibit catalytic activity at the curing temperature. In a two-part epoxy system, the epoxy resin and curing agent are separate. The epoxy resin and curing agent are combined to crosslink the epoxy resin and curing agent. The curing agent for a two-part epoxy system is preferably an amine or a derivative thereof. The accelerator for a two-part epoxy system may particularly be incorporated into the part containing the curing agent. The accelerator or optional additional accelerator for a two-part epoxy system may particularly be a compound containing an amine, phenol, alcohol, thiol or carboxylic acid functional group. In both one-part and two-part epoxy systems, the epoxy resin may be present in a crosslinked state with the curing agent.

[0108] The epoxy system may also contain a curing agent containing amine, anhydride, phenol, and / or thiol functional groups, especially amine functional groups. When the phenolic polymer according to the present invention is used as an accelerator, the epoxy system preferably contains a curing agent. When the phenolic polymer according to the present invention is used as a curing agent, the epoxy system may contain a curing agent containing amine, anhydride, phenol, and / or thiol functional groups, especially amine functional groups, as a co-curing agent. In the epoxy system, the epoxy resin may be present in a crosslinked state with the curing agent.

[0109] The curing agent or co-curing agent containing an amine functionality may be selected from, for example, but not limited to, aliphatic amines, dicyandiamide, substituted guanidines, phenolic, amino, benzoxazine, anhydrides, amidoamines, polyamides, polyamines, carbodiimides, urea formaldehyde resins, melamine formaldehyde resins, ethanolamine, ethylenediamine, diethylenetriamine (DETA), triethyleneaminetetramine (TETA), 1-(o-tolyl)-biguanide, amine-terminated polyols, aromatic amines such as methylenedianiline (MDA), toluenediamine (TDA), diethyltoluenediamine (DETDA), diaminodiphenylsulfone (DADS), and mixtures thereof.

[0110] Examples of curing agents or co-curing agents containing anhydride functionality include phthalic anhydride, trimellitic anhydride, nadic methyl anhydride (also known as methyl-5-norbornene-2,3-dicarboxylic anhydride), methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and mixtures thereof.

[0111] Examples of curing agents or co-curing agents containing a phenol functional group include novolaks such as bisphenol A, bisphenol F, 1,1-bis(4-hydroxyphenyl)-ethane, hydroquinone, resorcinol, catechol, tetrabromobisphenol A, phenol novolak, bisphenol A novolak, hydroquinone novolak, resorcinol novolak, and naphthol novolak, and mixtures thereof.

[0112] Examples of curing agents or co-curing agents containing thiol functional groups include methanedithiol, propanedithiol, cyclohexanedithiol, 2-mercaptoethyl-2,3-dimercaptosuccinate, 2,3-dimercapto-1-propanol(2-mercaptoacetic acid), diethylene glycol bis(2-mercaptoacetic acid), 1,2-dimercaptopropyl methyl ether, bis(2-mercaptoethyl)ether, trimethylolpropane tris(thioglycolate), pentaerythritol tetra(mercaptopropionate), pentaerythritol tetra(thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris(β-thiopropionate), triglycidyl ethers of propoxylated alkanes, and the like. aliphatic thiols such as mercaptan derivatives and dipentaerythritol poly(β-thiopropionate); halogen-substituted derivatives of aliphatic thiols; aromatic thiols such as di-, tris-, or tetra-mercaptobenzene, bis-, tris-, or tetra-(mercaptoalkyl)benzene, dimercaptobiphenyl, toluenedithiol, and naphthalenedithiol; halogen-substituted derivatives of aromatic thiols; heterocyclic ring-containing thiols such as amino-4,6-dithiol-sym-triazine, alkoxy-4,6-dithiol-sym-triazine, aryloxy-4,6-dithiol-sym-triazine, and 1,3,5-tris(3-mercaptopropyl)isocyanurate; halogen-substituted derivatives of heterocyclic ring-containing thiols;Examples of the thiol compounds include thiol compounds having at least two mercapto groups and containing a sulfur atom in addition to the mercapto groups, such as bis-, tris-, or tetra(mercaptoalkylthio)benzene, bis-, tris-, or tetra(mercaptoalkylthio)alkane, bis(mercaptoalkyl)disulfide, hydroxyalkyl sulfide bis(mercaptopropionate), hydroxyalkyl sulfide bis(mercaptoacetate), mercaptoethyl ether bis(mercaptopropionate), 1,4-dithiane-2,5-diol bis(mercaptoacetate), thiodiglycolic acid bis(mercaptoalkyl ester), thiodipropionic acid bis(2-mercaptoalkyl ester), 4,4-thiobutyric acid bis(2-mercaptoalkyl ester), 3,4-thiophenedithiol, bismuth thiol, and 2,5-dimercapto-1,3,4-thiadiazole, and mixtures thereof;

[0113] Examples of epoxy resins may include at least one epoxy resin based on bisphenol A, bisphenol F, novolac, phenolic resin, epoxidized natural oil, and polyhydric alcohol. These compounds may also be reacted with, for example, epichlorohydrin. Other examples of epoxy resins are described in U.S. Pat. No. 9,074,041, column 4, lines 24-46.

[0114] The epoxy resins described herein may be colored and filled systems using pigments and / or fillers such as, for example, iron oxide, titanium dioxide, organic pigments, calcium carbonate, talc, barium sulfonate, silica, mica, glass pearls, sand, alumina trioxide, magnesium oxide, or zinc phosphate.

[0115] The epoxy resins described herein may contain a reactive or non-reactive diluent. The diluent may also be referred to as a thinner. The epoxy systems and / or epoxy resins described herein may contain, in particular, a non-reactive solvent. As already explained above, the solvent may be completely or already completely released from the cured product. The thinner may particularly remain in the cured product. The low-boiling thinner may particularly be partially released from the cured product, for example, up to 30 wt. %, up to 20 wt. %, or up to 10 wt. % of the low-boiling thinner, based on the total mass of the low-boiling thinner. Reactive diluents include, for example, low-molecular-weight compounds having a linear or cyclic skeleton, or an ether or ester skeleton, with 2 to 20 carbon units and 1 to 5 glycidyl functional groups. Non-reactive solvents and / or diluents include, for example, acetone, ketones, esters, ethers, aromatic solvents, or mixtures thereof.

[0116] Thus, the epoxy system may also contain pigments and / or fillers and / or reactive diluents and / or non-reactive diluents as described above.

[0117] The epoxy resins and epoxy systems described herein may be used in coatings, such as floor coatings, architectural coatings, metal coatings, adhesives, sealants, especially structural adhesives in metal, wood and concrete construction, laminates, especially laminates for electronic circuits and devices, composite and casting applications, chemical dowels, and electrical encapsulation. The same applies to the epoxy systems described herein.

[0118] The phenolic polymers described herein as part of the epoxy system according to the present invention may also be used as accelerators for the curing of epoxy resins. When the phenolic polymers of the present invention are used as accelerators for the curing of epoxy resins, it is preferred that a curing agent containing amine, anhydride, phenol, and / or thiol functionality is present. More preferably, a curing agent containing amine functionality is present.

[0119] The phenolic polymers described herein as part of an epoxy system according to the present invention may also be used as curing agents for epoxy resins. When the phenolic polymers of the present invention are used as curing agents for the curing of epoxy resins, a co-curing agent containing amine, anhydride, phenol, and / or thiol functionality, especially amine functionality, may also be present.

[0120] All of the details regarding the phenolic polymer, epoxy resin, hardener, accelerator, optional additional accelerator, and optional additional compounds described above in the context of epoxy systems also apply to the use of phenolic polymers.

[0121] In particular, the phenolic polymers described herein as part of the epoxy system according to the present invention may function as accelerators at or below room temperature. At higher temperatures, the phenolic polymers of the present invention may also function as curing agents. It has been found that phenolic polymers provide particularly good results as curing agents for epoxy resins at temperatures between 50 and 200°C, preferably between 100 and 170°C, and more preferably between 120 and 160°C.

[0122] The phenolic polymers described herein as part of the epoxy system according to the present invention are used as accelerators for epoxy resins, preferably at temperatures below room temperature, particularly between -10°C and 40°C, and more particularly between 15°C and 25°C.

[0123] When the phenolic polymer is used as an accelerator or hardener for epoxy resins, the phenolic polymer is preferably part of an epoxy system, preferably an epoxy system according to the present invention.

[0124] As a curing agent, a phenolic polymer may be used in various amounts depending on the desired degree of crosslinking. As a curing agent, the phenolic polymer is preferably used in an OH:epoxy group ratio of 0.5:1 to 10:1, preferably 1:1 to 10:1, based on the total weight of the epoxy system, especially in casting, laminating, and adhesive applications. As an accelerator, the phenolic polymer is preferably used in an amount of 0.5 to 20 wt%, more preferably 5 to 15 wt%, even more preferably 8 to 12 wt%, or 0.5 to 30 wt%, more preferably 0.5 to 25 wt%, even more preferably 0.5 to 20 wt%, 0.5 to 15 wt%, and most preferably 0.5 to 12 wt%, based on the total weight of the epoxy system. As an accelerator, the phenolic polymer is used in an amount of, based on the total mass of the epoxy resin, more preferably 0.5 to 20 wt%, more preferably 5 to 15 wt%, even more preferably 8 to 12 wt%, or 0.5 to 30 wt%, more preferably 0.5 to 25 wt%, even more preferably 0.5 to 20 wt%, 0.5 to 15 wt%, and most preferably 0.5 to 12 wt%. Preferably, the phenolic polymer is used as an accelerator.

[0125] Additionally, the present invention also provides a kit of components comprising an epoxy resin; a phenolic polymer as described herein as part of an epoxy system according to the present invention; and a curing agent comprising amine, anhydride, phenolic and / or thiol functional groups, particularly amine functional groups. The kit of components according to the present invention is preferably a two-part epoxy system.

[0126] All of the details regarding the phenolic polymer, epoxy resin, hardener, accelerator, optional additional accelerators, and optional additional compounds described above in the context of epoxy systems also apply to the component kit.

[0127] In the component kit, the phenolic polymer and curing agent are preferably present as a mixture, optionally containing a solvent and / or thinner.

[0128] The present invention is further illustrated by the following examples. [Example]

[0129] Abbreviation SP=softening point DVB = Divinylbenzene EVB = ethyl vinyl benzene DIPB = diisopropenylbenzene DVBP = Divinylbenzene-phenol DCPD = dicyclopentadiene

[0130] [Table 1]

[0131] Example 1 Phenol (282 g) was dissolved in toluene (138 g) at 70°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3* (OEt2) (2.01 mL) was added. Divinylbenzene (195 g, purity 62%) was added dropwise to the reaction mixture over 30 minutes from the dropping funnel. After the dropwise addition, the solution was stirred at a reaction temperature of 90°C for 2 hours. The polymerization was terminated by adding chalk. The crude product was filtered and purified by steam distillation at 230°C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0132] [Table 2]

[0133] Example 1a Phenol (282 g) was dissolved in xylene (138 g) at 70°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3*(OEt2) (2.01 mL) was added. Divinylbenzene (195 g, purity 62%) was added dropwise to the reaction mixture over 30 minutes from the dropping funnel. After the dropwise addition, the solution was stirred at a reaction temperature of 120°C for 2 hours. The polymerization was terminated by adding chalk. The crude product was filtered and purified by steam distillation at 230°C to obtain a yellowish solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0134] [Table 3]

[0135] Example 1b Phenol (282 g) was dissolved in xylene (138 g) at 70°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3* (OEt2) (2.01 mL) was added. Divinylbenzene (195 g, purity 62%) was added dropwise to the reaction mixture over 30 minutes via the dropping funnel. After the dropwise addition, the solution was stirred at a reaction temperature of 140°C for 2 hours. The polymerization was terminated by adding chalk. The crude product was filtered and purified by steam distillation at 230°C to obtain a yellowish solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0136] [Table 4]

[0137] Example 2 Phenol (254 g) was dissolved in toluene (138 g) at 70°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3*(OEt2) (2.01 mL) was added. Divinylbenzene (195 g, purity 62%) was added dropwise to the reaction mixture over 30 minutes from the dropping funnel. After the dropwise addition, the solution was stirred at a reaction temperature of 90°C for 2 hours. The polymerization was terminated by adding chalk. The crude product was filtered and purified by steam distillation at 230°C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0138] [Table 5]

[0139] [Table 6]

[0140] Example 3 Phenol (94 g) was dissolved in toluene (61 g) in a three-neck flask equipped with a Dimroth coil condenser and a dropping funnel at 40 °C, and then BF3*(OEt2) (0.88 mL) was added. Dicyclopentadiene (44 g, 80% purity, 5% vinyl aromatics (indene, methylstyrene isomers), Braskem) was added dropwise to the reaction mixture over 30 min via the dropping funnel. After the addition, the solution was stirred at a reaction temperature of 120 °C for 3 h. The polymerization was terminated by the addition of chalk. The crude product was filtered and purified by steam distillation at 250 °C to yield a red solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0141] [Table 7]

[0142] Example 4 Phenol (282 g) was dissolved in toluene (92 g) at 40°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3*(OEt2) (2.70 mL) was added. Dicyclopentadiene (132 g, 80% purity, 5% vinyl aromatics (indene, methylstyrene isomers), Braskem) was added dropwise to the reaction mixture via the addition funnel over 30 minutes. After the addition, the solution was stirred for 3 hours at a reaction temperature of 120 °C. The polymerization was terminated by the addition of chalk. The crude product was filtered and purified by steam distillation at 250 °C to give a red solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0143] [Table 8]

[0144] Example 5 4-Tert-octylphenol (255 g) was dissolved in xylene (255 g) at 70°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3* (OEt2) (0.921 mL) was added. Divinylbenzene (195 g, 62% purity, divinylbenzene:ethylvinylbenzene = 62:38) was added dropwise to the reaction mixture through a dropping funnel over 14 minutes. After the dropwise addition, the solution was stirred at a reaction temperature of 90 °C for 2 hours. The polymerization was terminated by adding chalk. The crude product was filtered and purified by steam distillation at 230 °C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0145] [Table 9]

[0146] Example 6 Phenol (254 g) and divinylbenzene (195 g, purity 62%, divinylbenzene:ethylvinylbenzene = 62:38) were dissolved in xylene (138 g) at 30°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3*(OEt2) (0.624 mL) was added portionwise. The reaction mixture was cooled in an ice bath. After the addition, the solution was stirred at a reaction temperature of 70°C for 1 hour. The polymerization was stopped by adding chalk. The crude product was filtered and purified by steam distillation at 230°C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0147] [Table 10]

[0148] Example 7 Phenol (203 g) and divinylbenzene (195 g, purity 62%, divinylbenzene:ethylvinylbenzene = 62:38) were dissolved in xylene (138 g) at 30°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3* (OEt2) (0.624 mL) was added portionwise. The reaction mixture was cooled in an ice bath. After the addition, the solution was stirred at a reaction temperature of 70°C for 1 hour. The polymerization was stopped by adding chalk. The crude product was filtered and purified by steam distillation at 230°C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0149] [Table 11]

[0150] Example 8 Phenol (177 g) and divinylbenzene (195 g, purity 62%, divinylbenzene:ethylvinylbenzene = 62:38) were dissolved in xylene (138 g) at 30°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3*(OEt2) (0.624 mL) was added portionwise. The reaction mixture was cooled in an ice bath. After the addition, the solution was stirred at a reaction temperature of 70°C for 1 hour. The polymerization was stopped by adding chalk. The crude product was filtered and purified by steam distillation at 230°C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0151] [Table 12]

[0152] Example 9 Phenol (141 g) and divinylbenzene (195 g, purity 62%, divinylbenzene:ethylvinylbenzene = 62:38) were dissolved in xylene (138 g) at 30°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3* (OEt2) (0.624 mL) was added portionwise. The reaction mixture was cooled in an ice bath. After the addition, the solution was stirred at a reaction temperature of 70°C for 1 hour. The polymerization was stopped by adding chalk. The crude product was filtered and purified by steam distillation at 230°C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0153] [Table 13]

[0154] Example 10 Phenol (141 g) and divinylbenzene (215 g, purity 62%, divinylbenzene:ethylvinylbenzene = 62:38) were dissolved in xylene (138 g) at 30°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3*(OEt2) (0.624 mL) was added portionwise. The reaction mixture was cooled in an ice bath. After the addition, the solution was stirred at a reaction temperature of 70°C for 1 hour. The polymerization was stopped by adding chalk. The crude product was filtered and purified by steam distillation at 230°C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0155] [Table 14]

[0156] [Table 15]

[0157] Example 11 Phenol (254 g) and divinylbenzene (195 g, purity 80%, divinylbenzene:ethylvinylbenzene = 80:20) were dissolved in xylene (138 g) at 30°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3* (OEt2) (0.234 mL) was added in small portions. The reaction mixture was cooled in an ice bath. After the addition, the solution was stirred at a reaction temperature of 70 °C for 1 hour. The polymerization was stopped by adding chalk. The crude product was filtered and purified by steam distillation at 230 °C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0158] [Table 16]

[0159] Example 12 Phenol (207 g) and divinylbenzene (195 g, purity 80%, divinylbenzene:ethylvinylbenzene = 80:20) were dissolved in xylene (138 g) at 30°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3*(OEt2) (0.234 mL) was added in small portions. The reaction mixture was cooled in an ice bath. After the addition, the solution was stirred at a reaction temperature of 70 °C for 1 hour. The polymerization was stopped by adding chalk. The crude product was filtered and purified by steam distillation at 230 °C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0160] [Table 17]

[0161] [Table 18]

[0162] Example 13 Phenol (141 g) and diisopropenylbenzene (158 g) were dissolved in xylene (138 g) at 30°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3* (OEt2) (0.234 mL) was added in small portions. The reaction mixture was cooled in an ice bath. After the addition, the solution was stirred at a reaction temperature of 70 °C for 1 hour. The polymerization was stopped by adding chalk. The crude product was filtered and purified by steam distillation at 230 °C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0163] [Table 19]

[0164] Example 14 Phenol (141 g), styrene (52 g), and diisopropenylbenzene (79 g) were dissolved in xylene (138 g) at 30°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3*(OEt2) (0.234 mL) was added in small portions. The reaction mixture was cooled in an ice bath. After the addition, the solution was stirred at a reaction temperature of 70 °C for 1 hour. The polymerization was stopped by adding chalk. The crude product was filtered and purified by steam distillation at 230 °C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0165] [Table 20]

[0166] Example 15 Phenol (141 g), styrene (73 g), and diisopropenylbenzene (48 g) were dissolved in xylene (138 g) at 30°C in a three-necked flask equipped with a Dimroth coil condenser and a dropping funnel, and then BF 3* (OEt2) (0.234 mL) was added in small portions. The reaction mixture was cooled in an ice bath. After the addition, the solution was stirred at a reaction temperature of 70 °C for 1 hour. The polymerization was stopped by adding chalk. The crude product was filtered and purified by steam distillation at 230 °C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0167] [Table 21]

[0168] [Table 22]

[0169] Example 16 Phenol (141 g), α-methylstyrene (59 g), and diisopropenylbenzene (79 g) were dissolved in xylene (138 g) in a three-neck flask equipped with a Dimroth coil condenser and a dropping funnel at 30°C, and then BF3*(OEt2) (0.234 mL) was added portionwise. The reaction mixture was cooled in an ice bath. After the addition, the solution was stirred at a reaction temperature of 70°C for 1 hour. The polymerization was terminated by the addition of chalk. The crude product was filtered and purified by steam distillation at 230°C to obtain a colorless solid resin. The characterization results of the phenolic polymer are shown in the table below.

[0170] [Table 23]

[0171] As can be seen from the synthesis examples given above, the properties of high molecular weight phenolic polymers can vary widely.

[0172] As can be seen from the above results, the material properties can be affected by the end-capping agent (end group E). Further experiments on the effect of the end-capping agent are shown below.

[0173] Effect of end-capping agent content on material properties and processability Epoxy systems are typically cured by mixing two liquid materials (epoxy prepolymer and hardener) and modifying them with various additives and fillers. The viscosity of both the prepolymer and hardener typically significantly impacts the handling and curing process, and consequently, the final properties of the cured resin. The viscosity of a single component and final composition is related to the physical and chemical properties (e.g., softening point, Tg, polarity, and functional groups) of a single material, such as the compounds synthesized herein. Other aspects directly affected by these physical and chemical properties include the solubility and dissolution behavior at a given temperature in the hardener or in common thinners. The dissolution temperature, in particular, is often crucial due to the temperature sensitivity of various hardeners. Therefore, controlling the softening point of the accelerators presented in this invention dramatically impacts their applicability.

[0174] [Table 24]

[0175] As shown in Table 20b (Examples 13-15) and Table 20a (Examples 6 vs. 11 and 7 vs. 12), the ratio of monovinyl (EVB and styrene) compounds to divinyl (DVB and DIPB) compounds has a significant effect on the molecular weight distribution and on the softening point and Tg of the resulting resin.

[0176] [Table 25]

[0177] Under the same reaction conditions and at a constant phenol content, as the monovinyl compound content increases, the molecular weight, softening point, and Tg decrease. Furthermore, this change, unlike a change in phenol content, has only a small effect on the OH content of the final resin (see Table 12 above). As the ratio of phenol to the sum of monovinyl and divinyl compounds increases, the OH content increases and the softening point, Tg, and molecular weight decrease, just as when using monovinyl compounds.

[0178] In contrast to the monomer ratio (monovinylaromatic to divinylaromatic to phenol), the reaction temperature shows little or no effect on the product properties, with the exception of color (Table 20c). The higher the reaction temperature, the more yellow the product becomes. These results reaffirm the need for molecular weight control by endcapping, since molecular weight cannot be controlled by reaction temperature as in, for example, a typical cationic polymerization reaction.

[0179] [Table 26]

[0180] As mentioned above, softening point and molecular weight have a significant impact on resin solubility and processability, as well as formulation viscosity in epoxy applications. This effect and its correlation with endcapping agent content are shown in Tables 20d, 20f, and 20g. Resins prepared under identical reaction conditions and identical phenolic content (Examples 6 vs. 11; Examples 13 vs. 14 vs. 15) were dissolved in various solvents and thinners commonly used in the coatings industry, as well as in hardeners.

[0181] General Procedure: Dissolving Resin 50 g of resin and 100 g of thinner / solvent were placed in a 300 mL three-neck round-bottom flask equipped with a Dimroth coil condenser and overhead stirrer. The mixture was stirred at room temperature for 1 hour. If complete dissolution was not achieved, the temperature of the mixture was then increased in 10°C increments over 5 minutes until the resin was completely dissolved. While it is believed that for at least some resins, a smaller amount of thinner would have been sufficient to dissolve the resin upon heating, especially when heated above its softening point, 100 mL of solvent / thinner was employed according to the above protocol.

[0182] [Table 27]

[0183] The low viscosity solvents butan-2-one and xylene were already able to dissolve all resins at room temperature, however, as the solvent power decreased (benzyl alcohol, L40, Epikure® 548), the influence of the softening point and therefore the end-capping agent content became more significant.

[0184] [Table 28]

[0185] The above results show that as the endcapping agent content decreased and the softening point increased, the dissolution process became more difficult and the dissolution temperature had to be increased accordingly. Importantly, in the case of Example 13 (Dissolution Example 3), which was prepared without additional endcapping agent, complete dissolution of L40 and the hardener Epikure 548 was not achieved.

[0186] [Table 29]

[0187] Viscosity measurements show a similar trend. The effect of the resin softening point on the viscosity of the resin-thinner mixture increases dramatically with increasing thinner / solvent viscosity (Table 20f). Increasing the softening point results in a much more pronounced increase in resin / thinner viscosity (Dissolution Examples 1 and 2; Dissolution Examples 3-5, Tables 20f and 20g).

[0188] [Table 30]

[0189] Effect of softening point on resin dosage when viscosity of mixture is constant Generally, industry requires that each coating formulation has a well-defined viscosity or viscosity range, and therefore the dosable amount of an additive, such as the accelerator disclosed in this invention, is directly related to the effect of that additive on viscosity. To demonstrate the effect of softening point, and therefore endcapping agent content, on accelerator dosage, the resins of Examples 6 and 11 were dissolved in thinner L40. The viscosity of both mixtures was adjusted to the same level by adding more L40 (Table 20h). The details are as follows:

[0190] 50 g of resin and 50 g of L40 were placed in a 300 mL three-neck round-bottom flask equipped with a Dimroth coil condenser and overhead stirrer. The mixture was heated to the temperature established in the dissolution examples above (see Table 20d; dissolution temperature of 80°C for the resin in Example 6 and 130°C for the resin in Example 11) until complete dissolution was achieved. The viscosities of both mixtures were then measured. The viscosity of Dissolution Example 7 was then targeted, and the viscosity of Dissolution Example 6 was adjusted to the same value by adding 26.6 g of L40.

[0191] [Table 31]

[0192] The results of the dosing experiments demonstrated that precise control of molecular weight and softening point allowed for improved formulation dosing. In particular, the difference in OH content, a key indicator of the solution's accelerator activity, indicated that this beneficial effect was induced by the difference in EVB content. Furthermore, by adjusting the end-group content and thus the softening point, it is possible to obtain so-called "high-solids" systems containing, for example, up to 80% solids by weight, or "solventless" systems that do not contain solvents and / or thinners. This is interesting because the amount of thinner can be reduced to such low levels that final removal is not necessary, or even the use of thinners or solvents can be completely avoided. High-solids systems are primarily prepared using diluents or thinners. As already mentioned, the solvent is usually released or has already been released from the cured product. The thinner usually remains in the cured product.

[0193] Explanation of analysis method Molar mass distribution by GPC Molar mass distribution (Mn, Mw, Mz) was measured using SECcurity polymers supplied by PSS-Polymers. 2The chromatographic analysis was performed by gel permeation chromatography (GPC) using a HPLC-System. The column system used consisted of one 3 μm pre-column and three 3 μm, 1000 Å main columns, packed with styrene-divinylbenzene copolymer. A refractive index (RI) detector was used to detect the substance. The eluent used was stabilizer-free ULC / MS-grade THF supplied by Biosolve. Each measurement was performed isothermally at 40°C. The external standard used was "ReadyCal-Kit Poly(styrene) low" (Mp 266-66 000 Da) supplied by PSS-Polymers.

[0194] Glass transition temperature by DSC The glass transition temperature (Tg) was estimated using a DSC 2 / 400 equipped with an intracooler supplied by Mettler Toledo. A 40 μl pinhole-equipped aluminum crucible (ME-26763 AL crucible) was used as the sample container. The sample weight was 10–20 mg. To evaluate the thermal properties, a heating-cooling-heating-cooling sequence with a heating / cooling rate of 10 K per minute within the measurement window of -40 °C to 150 °C was selected as the analytical method. The Tg evaluation was performed in accordance with DIN 53765.

[0195] Softening point (SP) by Mettler Ring & Ball The softening point was estimated by the "Ring and Ball" method in accordance with ASTM D 3461 "Softening Point of Asphalt and Pitch - Mettler Cup and Ball Method." The test equipment used was a combination of an FP 90 Central Processor and an FP 83 HT Dropping Point Cell supplied by Mettler Toledo.

[0196] Hydroxyl group content The hydroxyl content was estimated by potentiometric titration according to DIN 53240-2 (acetylation of free OH groups with acetic anhydride using 1-methylimidazole as catalyst, followed by titration with 0.5 M sodium hydroxide). The measurements were carried out using an automatic titrator (Titrando in combination with Titroprozessor 840 Touch Control and Dosimate 6.2061.010) supplied by Deutsche METROHM GmbH & Co. KG.

[0197] Viscosity measurement with a rheometer The viscosity of the resin thinner / solvent mixtures was measured with an Anton Paar MCR301 rheometer. Either a double gap geometry (DG26.7) for viscosities below 250 mPas or a concentric cylinder geometry (CC27) for viscosities above 250 mPas was used. Measurements were performed at a shear rate of 25 s -1 The experiments were carried out in rotation mode at 25°C or 30°C isothermally.

[0198] Application of accelerators in epoxy systems. Phenolic polymers, such as the DVBP resins prepared in the above examples, are suitable as modifiers for coatings, adhesives, and composite formulations, particularly as accelerators and chemical resistance enhancers in epoxy-based systems.

[0199] To investigate its effect in epoxy systems, the divinylbenzenephenol (DVBP) resin from Synthesis Example 2 was tested by curing the commercial epoxy resin Epikote 828 with the hardener Epikure 548. For comparison, an epoxy system without additional accelerator (standard) and without the influence of styrenated phenol, the accelerator Novares LS500, commonly applied in the curing of epoxy resins, was tested with the epoxy resin Epikote 828 and the hardener Epikure 548. Furthermore, its effect on the mechanical properties and chemical resistance of the cured epoxy resin was investigated.

[0200] General Procedure for Curing Epoxy Resins Mixtures of Epikote 828, Epikure 548 and the corresponding accelerators shown in Table 21 were placed in 100 mL plastic cups at room temperature and mixed in a high speed mixer at 2500 rpm for 1 minute.

[0201] [Table 32]

[0202] Corresponding amounts of samples were then extracted for various application tests. Curing was carried out at room temperature.

[0203] Promotion effect 20 g of the mixture was extracted for rheological analysis. Extraction started directly after mixing the materials and transferred to the rheometer. The curing process was analyzed by rheometer at 40°C according to the general procedure described above. The time-dependent results of the rheological analysis are shown in Table 22 and Figure 1. Table 22 shows typical time points in the relationship between time and viscosity during the rheological measurements. Figure 1 shows the viscosity increase over time.

[0204] [Table 33-1]

[0205] [Table 33-2]

[0206] [Table 33-3]

[0207] Thus, in each experiment, the viscosity increased exponentially after a defined period of time. The viscosity of the epoxy system in Cure Example 2 using styrenated phenol and the epoxy system in Cure Example 1 both increased faster than the control system in Cure Example 3 without any additional additives, indicating an accelerating effect. Furthermore, the impact of the phenolic polymer exemplified by Synthesis Example 2 on accelerating the curing process in Cure Example 1 exceeds that of styrenated phenol in Cure Example 2.

[0208] Complex viscosity measured by a rheometer The complex viscosity of the cured epoxy was measured using an Anton Paar MCR302 rheometer. An aluminum plate (PP15 shape) was used. The measurement was performed at an isothermal temperature of 40°C with a frequency of 10 rads. -1 Measurements were performed in vibration mode with a shear gap of 1 mm. The deformation started at 10% and was reduced to 1% by 0.2% per minute. After the deformation was reduced to 1%, the remaining measurements were performed at this deformation level until the torque reached 100 mNm.

[0209] Influence on the mechanical properties of epoxy systems Pendulum hardness measured by a pendulum hardness tester The pendulum hardness of the cured epoxy resins was measured using a König pendulum hardness tester (DIN 53 157) supplied by BYK-Gardner. 10 g of each of the various mixtures was poured into a specified mold and stored at room temperature for one day before the first measurement. The prepared sample was clamped into the tester and the pendulum was fixed in the starting position. The measurement was started by releasing the pendulum. Measurements were repeated after storage periods of 1, 2, 6, and 13 weeks. The results are shown in Table 23.

[0210] [Table 34]

[0211] As can be seen from Table 23, the epoxy system containing the phenolic polymer accelerator of Cure Example 1 reached high pendulum hardness values ​​already at the beginning of the measurement (week 0). In contrast, the epoxy system without an accelerator had a lower pendulum hardness at the start of the measurement, and the epoxy system containing the styrenated phenol accelerator showed an even lower initial pendulum hardness. After the first week, all cured examples showed higher pendulum hardness values. Thereafter, the pendulum hardness of Cure Example 1, containing the phenolic polymer accelerator of Synthesis Example 2, remained fairly constant, while the pendulum hardness of Cure Example 3, containing no accelerator, increased significantly after the first week. In contrast, the epoxy system containing the styrenated phenol accelerator showed a significant increase in pendulum hardness from week 2 through week 13.

[0212] Tensile strength and maximum elongation by tensile test The tensile strength and elongation at break of the cured epoxy resins were measured using a Shimadzu AGS-X tensile testing machine. Each of the various mixtures was poured into a specified bone-shaped mold and stored at room temperature for two weeks. The dimensions of the samples were measured before the measurements. Measurements were performed at room temperature with a starting gauge length of 130.0 mm and a speed of 10 mm / min. The measurement results and calculated average values ​​are shown in Table 24.

[0213] [Table 35]

[0214] Low molecular weight accelerators such as styrenated phenols as well as benzyl alcohol or nonylphenol often cause softening of the epoxy system, exemplified by high elongation at break. As shown in the tensile tests (Table 24), the phenolic polymer of Synthesis Example 2 has only a small effect on the mechanical properties compared to the epoxy system without accelerator.

[0215] Impact on chemical resistance General Procedure for Chemical Resistance Testing Ten grams of each of the various mixtures were poured into five standard molds and stored at room temperature for two weeks. The samples were then weighed and each sample was immersed in a 100 mL sealed glass bottle filled with 90 mL of a separate test medium. The test medium used was as follows: 1. Acetic acid aqueous solution (10w%) 2. Sodium hydroxide aqueous solution (5w%) 3. Xylene 4.Water

[0216] Each week, the samples were removed from the vials, the remaining test medium was removed, and the samples were weighed. After weighing, the samples were returned to the vials. This process was repeated for 6 weeks.

[0217] [Table 36]

[0218] Both Curing Examples 2 and 3 demonstrate improved storage stability of the cured epoxy resins under aqueous conditions (Table 25). This is reflected in the reduced weight gain due to swelling. When an accelerator is used, the weight gain is reduced to 0.96 wt% (Curing Example 1) and 1.11 wt% (Curing Example 2), as opposed to 1.30 wt% (Curing Example 3).

[0219] [Table 37]

[0220] The hydrophilic properties of the accelerator of Synthesis Example 2 were evident under both acidic (Table 26) and basic (Table 27) conditions. Swelling was reduced from 5.63 wt% (Cured Example 3) to 2.67 wt% (Cured Example 1) under acidic conditions, and from 1.06 wt% (Cured Example 3) to 0.83 wt% (Cured Example 1) under basic conditions. In both cases, this effect was comparable to that of the styrenated phenol of Cured Example 2 (acidic 1.96 wt%; basic 0.90 wt%).

[0221] [Table 38]

[0222] [Table 39]

[0223] Both the cured epoxy system of Cure Example 1 (using the phenolic polymer of Synthesis Example 2 as an accelerator) and the cured epoxy system of Cure Example 3 (without accelerator) exhibited very high chemical resistance to xylene. Little swelling effect was observed over the test period (0.11 wt. % for Cure Example 3; 0.08 wt. % for Cure Example 1) (Table 28). In comparison, the styrenated phenol accelerator of Cure Example 2 significantly reduced chemical resistance. After 6 weeks, a weight gain of 2.43 wt. % was detected for Cure Example 2.

[0224] The chemical resistance tests described above demonstrate that DVBP resins are modifiers for coating systems that are completely improved against aqueous and organic influences.

Claims

1. Epoxy resin, a phenolic polymer comprising a phenolic compound, a linker group L, and a terminal group E, and having a number average molar mass (Mn) of 200 to 1,500 g / mol, the phenolic polymer having a structure represented by the following formula (1):

1. An epoxy resin composition comprising: 【Chemistry 1】 wherein the linker group L has the meaning of the following formula (2), (3), (4), (5) or (6): 【Chemistry 2】 The end group E has any one of the meanings of the formulae (2c1), (2c2), (2c3), (2c4), (2c5), (2c6), (4c1), (4c2), (5c1), (5c2), (3c1) and (3c2). 【Transformation 3】 where: R １ is H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms, or C ６ H ５ (CR １８ R １９ ) ｏ -Z-, R ２ , R ４ , R ６ , R ７ , R ８ , R ９ , R １１ and R １２ are each independently H or alkyl having 1 to 5 carbon atoms, R ３ and R ５ H, OH, NO ２ , halogen, alkyl having 1 to 5 carbon atoms, or oxyalkyl having 1 to 5 carbon atoms; R １０ and R １３ is an alkylene having 1 to 5 carbon atoms or a cycloalkylene having 5 to 6 carbon atoms, R １４ is a cycloalkylene having 5 to 12 carbon atoms, optionally substituted with a methyl or ethyl group; R １５ , R １６ and R １７ are each independently H or alkyl having 1 to 5 carbon atoms, R １８ and R １９ are each independently H or CH ３ and Z is a covalent bond or —O—; o is 1 or 0; m is an integer from 1 to 7, n is an integer from 2 to 21.

2. R １５ , R １６ and R １７ Ha-CH ３ 2. The epoxy resin composition according to claim 1, wherein

3. The phenolic polymer may comprise, based on the mass of the phenolic polymer:

3. The epoxy resin composition according to claim 1, comprising 50% by weight to 70% by weight of the phenol compound.

4. The phenolic polymer comprises, based on the mass of the phenolic polymer, 3. The epoxy resin composition according to claim 1, comprising 20% ​​by weight to 50% by weight of the linker group L.

5. The phenolic polymer comprises, based on the mass of the phenolic polymer, 3. The epoxy resin composition according to claim 1, wherein the terminal group E is present in an amount of 5% by weight to 40% by weight.

6. 6. The epoxy resin composition according to claim 1, wherein the phenolic polymer comprises 10% by weight to 40% by weight of end groups E, based on the mass of the phenolic polymer.

7. In the phenolic polymer, R １ The epoxy resin composition according to any one of claims 1 to 6, wherein is H, alkyl having 1 to 10 carbon atoms, or oxyalkyl having 1 to 10 carbon atoms.

8. In the phenolic polymer, R １ The epoxy resin composition according to any one of claims 1 to 6, wherein is H, alkyl having 1 to 5 carbon atoms, or oxyalkyl having 1 to 5 carbon atoms.

9. Epoxy resin composition according to any one of claims 1 to 8, wherein in the phenolic polymer, the linker group L has the meaning of formula (2). 【Chemistry 4】 (In the formula, R ２ , R ３ and R ４ is as defined in claim 1.

10. 10. The epoxy resin composition according to claim 1, wherein in the phenolic polymer, the end group E has the meaning of formula (2c5) or (2c6). 【Transformation 5】 (In the formula, R ２ , R ３ and R ４ is as defined in claim 1.

11. R ２ , R ３ and R ４ The epoxy resin composition according to claim 9 or 10, wherein is H.

12. 12. The epoxy resin composition according to claim 1, wherein the phenolic polymer has an OH content of 5 to 13 mass % based on the mass of the phenolic polymer.

13. 13. The epoxy resin composition according to claim 1, wherein the phenolic polymer has an OH content of 6 to 9 mass % based on the mass of the phenolic polymer.

14. Epoxy resin composition according to any one of claims 1 to 13, wherein the phenolic polymer has a softening point according to ASTM 3461 of up to 170°C and / or a Gardner colour scale of 0 to 5, determined according to DIN EN ISO 4630:2016-05 using acetone instead of toluene for the measurement.

15. Epoxy resin composition according to any one of claims 1 to 13, wherein the phenolic polymer has a softening point according to ASTM 3461 of 50°C to 100°C and / or a Gardner color index of 0 to 1, determined according to DIN EN ISO 4630:2016-05 using acetone instead of toluene for the measurement.

16. 16. The epoxy resin composition of claim 1, wherein the epoxy resin composition comprises a curing agent comprising amine, anhydride, phenol and / or thiol functional groups.

17. A phenolic polymer comprising a phenolic compound, a linker group L and a terminal group E, and having a number average molar mass (Mn) of 200 to 1,500 g / mol, the phenolic polymer having a structure represented by the following formula (1): Use as an accelerator for the curing of epoxy resins, Or, Used as a hardener for epoxy resins. 【Transformation 6】 wherein the linker group L has the meaning of the following formula (2), (3), (4), (5) or (6): 【Transformation 7】 The terminal group E has any one of the meanings of formulae (2c1), (2c2), (2c3), (2c4), (2c5), (2c6), (4c1), (4c2), (5c1), (5c2), (3c1) and (3c2). 【Transformation 8】 where: R １ is H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms, or C ６ H ５ (CR １８ R １９ ) ｏ -Z-, R ２ , R ４ , R ６ , R ７ , R ８ , R ９ , R １１ and R １２ are each independently H or alkyl having 1 to 5 carbon atoms, R ３ and R ５ H, OH, NO ２ , halogen, alkyl having 1 to 5 carbon atoms, or oxyalkyl having 1 to 5 carbon atoms; R １０ and R １３ is an alkylene having 1 to 5 carbon atoms or a cycloalkylene having 5 to 6 carbon atoms, R １４ is a cycloalkylene having 5 to 12 carbon atoms, optionally substituted with a methyl or ethyl group; R １５ , R １６ and R １７ are each independently H or alkyl having 1 to 5 carbon atoms, R １８ and R １９ are each independently H or CH ３ and Z is a covalent bond or —O—; o is 1 or 0; m is an integer from 1 to 7, n is an integer from 2 to 21.

18. 20. Use of the phenolic polymer of claim 17 as an accelerator for the curing of epoxy resins in the presence of a curing agent containing amine functional groups.

19. 20. Use of the phenolic polymer of claim 17 as a curing agent for epoxy resins in the presence of a co-curing agent containing an amine functionality.

20. Use of a phenolic polymer according to any one of claims 17 to 19, wherein said phenolic polymer is further characterized by at least one of the features according to any one of claims 2 to 15.

21. Epoxy resin, a phenolic polymer comprising a phenolic compound, a linker group L, and a terminal group E, and having a number average molar mass (Mn) of 200 to 1,500 g / mol, the phenolic polymer having a structure represented by the following formula (1): and a curing agent comprising amine, anhydride, phenol and / or thiol functional groups. 【Chemistry 9】 wherein the linker group L has the meaning of the following formula (2), (3), (4), (5) or (6): 【Chemistry 10】 The end group E has any one of the meanings of the formulae (2c1), (2c2), (2c3), (2c4), (2c5), (2c6), (4c1), (4c2), (5c1), (5c2), (3c1) and (3c2). 【Chemistry 11】 where: R １ is H, alkyl having 1 to 15 carbon atoms, or oxyalkyl having 1 to 15 carbon atoms, or C ６ H ５ (CR １８ R １９ ) ｏ -Z-, R ２ , R ４ , R ６ , R ７ , R ８ , R ９ , R １１ and R １２ are each independently H or alkyl having 1 to 5 carbon atoms, R ３ and R ５ H, OH, NO ２ , halogen, alkyl having 1 to 5 carbon atoms, or oxyalkyl having 1 to 5 carbon atoms; R １０ and R １３ is an alkylene having 1 to 5 carbon atoms or a cycloalkylene having 5 to 6 carbon atoms, R １４ is a cycloalkylene having 5 to 12 carbon atoms, optionally substituted with a methyl or ethyl group; R １５ , R １６ and R １７ are each independently H or alkyl having 1 to 5 carbon atoms, R １８ and R １９ are each independently H or CH ３ and Z is a covalent bond or —O—; o is 1 or 0; m is an integer from 1 to 7, n is an integer from 2 to 21.

22. R １５ , R １６ and R １７ Ha-CH ３ 22. The kit of components of claim 21, wherein:

23. 23. The kit of components of claim 21 or 22, wherein the phenolic polymer and the curing agent are present as a mixture, optionally containing a solvent and / or thinner.

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