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    • 专利摘要:
    The invention relates to an acrylate oligomer having a number-average acrylate functionality of> 0.0> 2.0, a branched structure resulting from the polyaddition reaction of at least one amine A) of functionality fA in NH groups of at least 2, on at least one multifunctional acrylate B) of functionality fe in acrylate groups of at least 2, with an average functionality per mole over all components A) + B) greater than 2 and with said oligomer comprising in its structure repeating unit at least one aminoacrylate group -O2C-CH2-CH2-N =, resulting from said polyaddition and with a nitrogen content derived from said amine A) greater than or equal to 0.35 mEq / g and an initial ratio r = acrylate / NH between rinf and 1.1 rsup with rinf = 0.90 * (fA-1) * (fB-1) and rsup = 2 * fA + 2 * fB-6 and the average number nmoy of repeating units per oligomer nmoy = 1 / [(r * fA / fB) + 1 - fA]. The invention also relates to a specific process for the preparation and the use of said oligomer in crosslinkable compositions, in particular as a UV synergist in crosslinkable coatings, such as inks, varnishes, paints, adhesives, gelled coatings or in molding compositions or in compositions for 3D objects by superposition of successive layers and finally the resulting crosslinked product.
    公开号:FR3022544A1
    申请号:FR1455789
    申请日:2014-06-23
    公开日:2015-12-25
    发明作者:Philippe Ciceron；Charles Bourrousse；Catherine Leroy
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to multifunctional acrylate oligomers of average functionality greater than 2, of branched structure, obtained by polyaddition reaction between a multifunctional amine of functionality -NH of at least 2 and a multifunctional functional acrylate of at least 2, with an average functionality on the amine and acrylate group greater than 2, said oligomers resulting from chain extension by said polyaddition and by formation in the repeating unit of at least one aminoacrylate group under conditions Acrylate / NH mole ratio specific. As a result, said oligomers have a controlled structure, obtained by a simple one-step process, having a high reactivity and a controlled viscosity for applications in the fields of coatings or 3D articles in superposed layers or the field of chemical sealing. . The invention also covers a specific process for obtaining said products, a crosslinkable composition comprising them, their uses in the cited applications and the finished products obtained. In particular, the oligomers according to the invention have, as advantages combined, both a density of acrylate groups per unit weight and an acrylate group functionality per mole which are higher and better controlled than comparable products of the state of the art. while having a nitrogen content and a sufficient aminoacrylate level, in particular for a synergistic effect activating crosslinking under UV and a low viscosity and suitable for the intended applications.
    [0002] Obtaining acrylated aminoacrylates in general, monomers or oligomers, comprising an aminoacrylate group is already known from the state of the art as well as their performance for a synergistic effect by the presence of the nitrogen atom in the aminoacrylate group. for compositions crosslinkable under UV. These groups are in fact known to accelerate said crosslinking by participating in a bimolecular priming mechanism, in the presence of photoinitiators such as benzophenone, by the electronic donor effect of the nitrogen atom which makes the hydrogen labile to a hydrogen. the tertiary amine function. US 6,172,129 describes in particular aminoacrylates resulting from the addition of cyclic secondary mono-amines to a multifunctional acrylate having at least 3 acrylate groups per molecule. These products have no possible chain extension and have a monomeric structure, with in particular a reduction in the functionality of the final product relative to the multifunctional acrylate starting and therefore they have a lower density of acrylate groups per unit weight. as said multifunctional acrylate starting, despite their low viscosity. These products, to achieve a high level of aminoacrylate groups, contain a high proportion of saturated species resulting from the addition of secondary monoamine on all the acrylate groups of the starting multifunctional acrylate. WO 2011/131501 discloses amino (meth) acrylates obtained by addition reaction of an amine with a mixture of urethane (meth) acrylates and a reactive diluent (meth) acrylate. These products have in their structure a chain extension per aminoacrylate group generated by polyaddition between a primary amine or a secondary diamine and said multifunctional urethane (meth) acrylate. However, they have the drawback of having high viscosities, even in the presence of reactive diluent, firstly by the nature of the multifunctional (meth) acrylic monomers which are urethanes and then by the lack of strict control of this extension. and the final structure. This without considering the fact that the methacrylate groups, cited as an alternative to acrylates, can not give a polyaddition reaction with an amine (lack of description with non-feasibility of part of the described structures). On the other hand, the density of residual acrylate groups is lower than that of the starting multifunctional acrylate with a higher final viscosity. The present invention overcomes the aforementioned drawbacks of the state of the art by providing novel multifunctional acrylated oligomers having both a higher acrylate group functionality than that of the starting multifunctional acrylate by the effect of the presence of the acrylate groups at the ends of the chain and in the main chain and by the effect of the branched structure. They are in fact oligomers comprising amino acrylate groups with a number average functionality per oligomer of> 2 acrylates / mole with a nitrogen content derived from the high amine tA (tA> 0.35 mEq / g ) while having a controlled viscosity and remaining <2000 25 mPa.s at 25 ° C according to the ISO 2555 method, without any added reactive diluent. The advantage of such low viscosity is to avoid the addition of large amounts of reactive diluents. In particular, such products have a high reactivity thanks to the combination of their high acrylate functionality and the synergistic effect of the amine functions, with type I and II priming possible in the presence of a bimolecular photoinitiator.
    [0003] In photocurable formulations, the compromise between crosslinking rate, flexibility, hardness and solvent resistance is improved by the use of such multifunctional acrylated aminoacrylate oligomers. These aminoacrylates are obtained by polyaddition reaction (called Michael addition or aza addition) of amine A) of functionality fA (fA: average in number if amine mixture) of at least 2, on an acrylate B) of function fB of at least 2 (fB 3022544 - 3 - number average if acrylate mixture) excluding the case where fA = fB = 2 in that the average functionality in number on all the components A) and B) must be greater than 2, thus allowing a controlled branched structure. "Branched" structure also means that the oligomer chain obtained comprises at least one chain branching or branching with the same repetitive unit. The control of the increase in molecular weight of these systems and therefore of their viscosity is ensured by the ratio r of the number of acrylate double bonds relative to the number of amine functions -NH (r = Acrylate / NH), the conversion x being greater than 95% with respect to reactive -NH functions which are in defect with respect to acrylate functions B). The viscosity of such systems remains controllable without leading to gelation of the reaction medium by the specific limitation of said ratio r which remains higher than a specifically defined value and dependent on the functionalities of the two components for a given conversion. Among the main advantages of the present invention compared with the state of the art, the following can be mentioned: For the process of obtaining: - Simple addition reaction (Aza or Michael) of the amine A) on acrylate B) with a reaction mixture and in a single process step. No gaseous effluents or by-products to be removed with a yield of 100% based on the weight of the reactants. - No solvent or catalyst required, with a reaction temperature of about 80 ° C and short reaction time with less impact on the environment. - Reproducibility and predictability of structures and final properties based on the criteria of the invention.
    [0004] For the product: - Controlled viscosity with a value <2000 mPa.s at 25 ° C according to ISO 2555. - High nitrogen content tA, from amine A) with tA greater than or equal to 0.35 mEq / boy Wut. Good compromise between number-average acrylate functionality per oligomer, fo and the density of acrylate groups per unit weight tau-, with respectively f,> 2 and tau-> 2.3 mEq / g. - Low migration rate with no saturated species completely (no complete saturation of acrylates due to the significant excess of acrylate functions compared to amine functions). Control of the chain extension by adjusting the ratio r = Acrylate / NH and control of the structure without risk of gelation, in spite of the branching of the chain. Compared to the intended applications in radiation-curable compositions and in particular UV or peroxide compositions comprising said oligomers of the invention, there are advantages of high reactivity of said oligomers with high flexibility, hardness and resistance to solvents of crosslinked products. obtained. The invention firstly covers the acrylated oligomer of branched structure, as defined according to the invention.
    [0005] Next, it relates to a specific process for preparing said oligomer. Another object relates to a crosslinkable composition comprising said oligomer. Also part of the invention is the use of said oligomer in crosslinkable compositions. Finally, the invention relates to the crosslinked end products obtained using said oligomer or a crosslinkable composition containing it. Thus, the first subject of the invention relates to an acrylated oligomer, which has a number average acrylate functionality (or average acrylate number functionality) that is strictly greater than 2.0 acrylates per mole, which oligomer has a branched structure and as a result of the polyaddition reaction of at least one amine A) of functionality fA to NH groups of at least 2, preferably 2 to 6, with said NH functionality signifying a number average functionality if it is is a mixture of amines, said amine A) carrying primary and / or secondary amine functions with optionally said amine A) being carrier in addition to at least one tertiary amine function (i.e. without NH), with said polyaddition on at least one multifunctional acrylate B) of functionality fB to acrylate groups of at least 2, preferably 2 to 6, with said functionality fB in acrylates meaning a mean functionality in terms of re if it is a mixture of acrylates, with a number average functionality per mole over all components A and B greater than 2 and with said oligomer comprising in its repeating unit structure at least one aminoacrylate group -OC-CH2-CH2-N = = resulting from said polyaddition and with a nitrogen content tA from said amine A) greater than or equal to 0.35 mEq / g and an initial ratio r = acrylate / NH included between rinf and 1.1 rsup and preferably r between rinf and rsup, with the values rinf and rsup being defined according to relation (1) and (2) below: rinf = 0.90 * (fA-1) * (fB (1) (r) = 2 * fA + 2 * fB-6 (2) 3022544 - 5 - and with a mean number nmoy of repeating units (or repeating units) per oligomer, defined according to the following relation (3) [0008] According to a particular preference, the sum fA + fB remains less than or equal to 8. According to a first preferred option, said amine A) in addition, at least one tertiary amine function, preferably said amine being selected from dimethylamino propylamine (DMAPA), dimethylamino propylamino propylamine (DMAPAPA) and 1,4 Bis (3-aminopropyl) piperazine (1,4-BAPP) and more preferentially from DMAPAPA and 1,4-BAPP and with a nitrogen level tA greater than or equal to 0.35 mEq / g. The nitrogen level, in this case, encompasses the nitrogen of all amine functions, including that of the tertiary amine functions present in this preferred case. The viscosity of said acrylate B) measured according to the ISO 2555 method at 23 ° C. is preferably less than 200 mPa.s under a shear of 100 s-1. Said acrylate B) is more particularly selected from: 131) optionally alkoxylated aliphatic or cycloaliphatic polyol acrylates, b2) oligoether acrylates, b3) alkoxylated phenolic acrylates or b4) acrylated aminoacrylates or mixtures thereof and preferably according to 131) or b4) or their mixtures. A mixture of acrylates B) can therefore be a mixture of acrylates B) of the same type, that is to say for example a mixture between at least two acrylates of type 131) or at least two acrylates of type b2) or at least two acrylates of type b3) or of at least two acrylates of type b4), in particular of at least two acrylates of type 131) or b2) and their mixtures between different types. Said amine A) is preferably chosen from: al) an aliphatic amine, a2) a cycloaliphatic amine or a3) an aralkylene amine with the amine function in a position other than the position in alpha (alpha meaning that N is linked directly to the nucleus ) or other than the position in beta (with N carried by a carbon alpha to the aromatic ring) of the aromatic ring or their mixtures, preferably al) aliphatic and / or a2) cycloaliphatic including polycyclic or mixtures thereof. More precisely, in the particular case a3), the amine function is neither in the alpha position nor in the beta position with respect to the aromatic nucleus. Said amine A) may be represented by a general formula (NH2) fA1R2 (NHR3) fA2, with R2 = R '(NR "R" IA3, R3, R', R "and R" 'being C1 to C3 alkyls same or different with fA1 being the number of primary amine functions per mole, fA2 being the number of secondary amine functions per mole and fA3 being the number of tertiary amine functions per mole and with fA = 2 * fA1-FfA2 3022544 - 6 Said acrylate B) can be represented by the general formula R 1 (X) fB with X being an acrylate group CH 2 = CH-OO 2 - and R 1 being the residue of said acrylate B) carrying f B acrylates per mole. The acrylated oligomer according to the invention has in particular a degree of acyl groups. 5 acrylates or a density of acryl groups tac [greater than 2.3 and preferably 3.5 to 10.0 mmol / g or milli equivalent / g (mEq / g). Said oligomer can be characterized by a calculated number average molecular weight Mn defined according to the following relation (4): Mn = MB (nmoy * Mu) (4) with M, being the molar mass of the repetitive unit defined according to following relationship (5): Mu = MA + (fA2 2 * fA1 1) * MB (5) nmoy being the average number of repeating units as defined in claim MB being the molar mass of acrylate B), MA being the molar mass of amine A), where fA1 is the number of -NH2 functions of primary amine, per amine A) and fA2 is the number of -NH- functions of secondary amine, per amine A). the amount of nitrogen tA in said oligomer of the invention, it can be defined according to the following relation (6): tA = 1000 * nmoy * (fAi fA2 fA3) / Mn (6) with Mn being the average molecular weight number as defined above and fAl being the number of -NH 2 primary amine functions, by amine A) and fA 2 being the number of -NH-secondary amine functions, by amine A) and fA3 being the number of functions -N = tertiary amine, by amine A). The functionality fo, expressed as the equivalent of double bonds per mole of said oligomer, may be defined according to the following equation (7): fo = fB nmoy * (fA2 * fB - fA2 - fB 2 * fA1 * fB - 2 * fA1) (7) The level of acrylate t -acr, expressed in milliequivalents (or mmol) of double bond per gram of said oligomer, can be defined according to the following relation (8): tau- = 1000 * fo / 1 Ari (8) Said acrylate B) can be alkoxylated and in this case preferably the number of alkoxy units per acrylate group does not exceed 3 if said alkoxy is ethoxy and does not exceed 1 if said alkoxy is propoxy. More particularly, with regard to the two reactants A) and B), said amine A) has a functionality fA greater than or equal to 2 and said acrylate B) has a functionality greater than or equal to 3 or conversely said amine A) has a functionality fA greater than or equal to 3 and that said acrylate B) has a functionality fB greater than or equal to 2 and more particularly fA + fB does not exceed 8. According to a particular option where there is absence of functions -NH2 primary amine In said amine A) (fAl = O in the general formula of amine A)), said oligomer can be defined in that: said amine A) is of general formula (NH2) fmR2 (NHR3) fA2, with R2 = R '(NR "R" IA 3, R 3, R', R "and R" 'being C 1 -C 3 alkyls which are identical or different with fAl being equal to 0 and being the number of primary amine functions per mole, fA 2 being greater than or equal to 2 and being the number of secondary amine functions per mole and fA3 being greater than or 0 and being the number of tertiary amine functions per mole and with fA = fA2 said acrylate B) has the general formula R1 (X) fB with X being an acrylate group CH2 = CH-OO2- and R1 being the residue said acrylate B) bearing acrylates per mole and said oligomer comprising the product of the following general formula (I): X (fB4) R1 [O2CCH2CH2NR3R2Y (fA2-2 »R3C H2C H2CO2R1 X03_21X (I) with Y = - (NR3CH2CH2COOR1X (3-1)) The more detailed and detailed formula of formula (I) can correspond to the following formula with all the parameters used being defined as above for said formula (I): R3 R3 X ON1 R2 R 0 (Y) O (X) fA-22 fB 2 -n 30 with: R3 7) X) f-1 O Y: 3022544 - 8 - According to another particular option with presence of primary and secondary amine functional groups, said oligomer can be defined by the fact that: said amine A) is of general formula (NH2) fmR2 (NHR3) fA2, with R2 = R '(NR "R" IA3, R3, R', R "and R" ' being of same or different C1 to C3 alkyls, fAl being greater than or equal to 1 and being the number of primary amine functions per mole, fA2 being greater than or equal to 0 and being the number of secondary amine functions per mole and fA3 being greater; or equal to 0 and being the number of tertiary amine functions per mole and with fA = 2 * fA1 fA2 10 - said acrylate B) is of general formula R1 (X) fB with X being an acrylate group CH2 = CH-OO2- and Wherein R1 is the residue of said acrylate B) carrying acrylates per mole and said oligomer comprises the product of the following general formula (11): X (O) R1 [O2CCI-12C1-12NR2YfA2Z (fAi-i) C1-12C1-12CO2R1X (fB_21X (II) with Y = - (NR3CH2CH2CO2R1X (34) and Z = - (N (CH2CH2COOR1X (3-1)) 2) - The more developed and detailed formula of formula (11) can correspond to the following formula with all the parameters used being defined as above for said formula (11): ## STR2 ## with Z: 35, (X) According to another possibility, said functionality fA of amine A) is equal to 3 and said amine A) is selected from one of the following groups: ## STR2 ## a diamine carrying a primary amine function and a secondary amine function or a triamine carrying secondary amine functions. According to another variant, said amine A) has a functionality fA equal to 2 and is a primary amine, that is to say carrier of a primary amine function -NH2 or is a diamine carrying 2 secondary amine functions and said acrylate B) is an optionally alkoxylated triacrylate with, in the case where said triacrylate is alkoxylated, a number of 10 alkoxy units per acrylate not exceeding 3 if said alkoxy is ethoxy and a number of alkoxy units per acrylate not exceeding 1 if said alkoxy is propoxy. According to another possible variant, said amine A) has a functionality fA equal to 3 and is a primary-secondary diamine, that is to say carrying a primary amine function and a secondary amine function or is a triamine carrier of 3 secondary amine functions and said acrylate B) is an optionally alkoxylated diacrylate, with in the case where said diacrylate is alkoxylated, a number of alkoxy units per acrylate not exceeding 2 if said alkoxy is ethoxy and a number of acrylate alkoxy units not exceeding 1 if said alkoxy is propoxy. According to another option, said functionality fA of amine A) is equal to 4 and said amine A) is selected from a diamine carrying 2 primary amine functions or a triamine carrying 1 primary amine function and 2 secondary amine functions or a tetra-amine carrying 4 secondary amine functions. Again according to a different option, said functionality fA is equal to 5 and said amine A) is selected from a triamine carrying two primary amine functions and a secondary amine function or a tetraamine carrying a primary amine function and of three secondary amine functions or a penta-amine carrying 5 secondary amine functions. According to another option, said functionality fA is equal to 6 and said amine A) is selected from a triamine carrying three primary amine functional groups or a tetra-amine carrying 2 primary amine functional groups and 2 secondary amine functional groups or a penta amine functional group. -amine carrying 1 primary amine function and 4 secondary amine functions or a 6-amine hexamine secondary amine functional. The oligomer of the invention, of branched structure, has a number average functionality in acrylates of from 2.1 to 6.0, preferably from 2.3 to 5.0 per oligomer, ie say per mole of oligomer. According to a particular option, said oligomer may result from the reaction between at least two amines A) and / or at least two acrylates B). This means that at least two amines A) can be reacted with at least one acrylate B) or an amine A) with at least two acrylates B) or at least two amines A) with at least two acrylates. B). Said oligomer according to the invention preferably has a number average molecular weight Mn calculated according to the relation (4) defined above, ranging from 275 to 5000 (in g / mol or Dalton) and preferably from 300 to 3000. L According to the invention, the oligomer comprises n repeating units with a molecular distribution as a function of n (number of repeating units), which means that it has a molecular distribution as a function of n and in particular it comprises at least the 4 products corresponding to: n = 0 and n = 1 and n = 2 and n = 3 and more particularly with at least 50% by weight of said distribution corresponding to n less than or equal to 3. More particularly, said molecular distribution in The function of n comprises at least 5 products corresponding to: n = 0 and n = 1 and n = 2 and n = 3 and n = 4 and even more particularly with at least 60% by weight of said distribution corresponding to n less than or equal to 4. The second The subject of the invention relates to a process for preparing said oligomer as defined according to the invention above, which process comprises a polyaddition reaction step (Michael addition) of said at least one amine A) on said less an acrylate B), in the presence of a radical polymerization inhibitor and in the absence of any solvent, catalyst and any other reactant except said amine A) and said acrylate B) and inhibitor, said method comprising the progressive and continuous addition of said amine A) to said acrylate B) already present in the reactor and (B) still in stoichiometric excess and with said reaction occurring at a temperature above 40 ° C and below 90 ° C, preferably from 60 to 80 ° C and with said reaction being stopped at a conversion rate of NH amine functions of at least 95% and with an initial ratio r of acrylate functions on said amine groups NH, r = ac the rylate / NH being between rinf and 1.1 rsup and preferably r between rinf and rsup, with the values rinf and rsup being defined according to the following relations (1) and (2): ria = 0.90 * (fA- Another object of the invention relates to a crosslinkable composition, which comprises at least one oligomer as defined above, or obtained by the process as defined according to the invention, optionally with the presence of a reactive diluent, in particular chosen from mono (and / or multifunctional) (meth) acrylic monomers and with said reagent diluent 3022544 which may be identical to said starting B) or said diluent may be different. In particular, said reactive diluent can be used for the highest viscosity values in the range <2000 mPa.s. Said diluent identical to B) is by definition multifunctional acrylic, as B). If different from B), it may be different by the nature of the (meth) acrylic functionality, that is to say carry methacrylate groups or be monofunctional acrylate or methacrylate or multifunctional (acrylate or methacrylate) of different nature or of functionality (acrylate or methacrylate groups per mole) different from that of B) (in acrylates). Said reactive diluent apart from its role as a reactive diluent for adjusting the viscosity to that intended for the end application can also be used to adjust the final performance of the crosslinked product obtained from said crosslinkable composition. More particularly, said (crosslinkable) composition is a radiation crosslinkable composition, preferably of UV, laser, LED or EB, which is a coating composition, in particular of inks, varnishes, gelled coatings (commonly called "coatings"). gel coats "), paints or adhesives, in particular structural adhesives, or is a composition for 3D articles by superposition of successive layers or is a molding composition. According to another variant, said composition is a peroxidically crosslinkable composition (commonly known as "P-cure") and in particular it is a coating composition more particularly of varnish, gel coatings ("gel coats"), of paints or adhesives, in particular structural adhesives, or is a chemical sealing composition or a molding composition. The molding compositions are crosslinkable compositions for moldings and in particular for structural materials, including composite materials reinforced with fibrous reinforcements. Another subject of the invention relates to the use of an oligomer as defined above as a binder in a crosslinkable composition. According to a first option of said use, said composition is crosslinkable by radiation preferably among UV, laser, LED or EB, said composition being a composition of coatings, in particular inks, varnishes, gelled coatings (commonly called "Gel coats"), paints or adhesives, in particular structural adhesives, or being a composition for 3D articles by superposition of successive layers or being a molding composition. According to another variant of said use, it is use in a peroxidically crosslinkable composition (commonly called "P-cure") which is in particular a coating composition more particularly of varnish, coatings 3022544 - 12- gels ("gel coats"), paints or adhesives, in particular structural adhesives or a chemical sealing composition or a molding composition. Finally, the invention relates to the final crosslinked product which results from the use of at least one oligomer as defined above or obtained by the method defined above or which results from the crosslinking of a composition such that defined above according to the invention and in particular which is a coating film, more particularly a film of ink, varnish, coating of gelled coatings, adhesive or which is a 3D article or a seal of chemical sealing or a molded part. The following examples are given by way of illustration of the invention and its performance and do not limit its scope in any way. Experimental part Raw materials: see table 1 below Table 1: raw materials 15 Name Chemical name Short name Supplier Function according to commercial function the invention (REF) SR341 3 Methyl 1,5 Pentane Diol 3M15PDDA SARTOMER Acrylate B) fB = 2 Diacrylate SR238 HexaneDiol Diacrylate HDDA SARTOMER Acrylate B) fB = 2 SR455LM TriMethylol Propane TMP4EOTA SARTOMER Acrylate B) fB = 3 Tetraethoxylated Triacrylate SR454 TriMethylol Propane TMP3EOTA SARTOMER Acrylate B) fB = 3 TriEthoxylated Triacrylate SR351 TriMethylol Propane TMPTA SARTOMER Acrylate B) fB = 3 TriAcrylate DMAPA 3- (DiMethylAmino) 1- DMAPA ALDRICH Amine A) fA = 2 Propyl Amine DMAPAPA Dimethyl Amino DMAPAPA ARKEMA Amine A) fA = 3 PropylAmino PropylAmine 1,3BAC 1,3Bis (AminomethylCyclo 1,3 BAC MITSUBISHI Amine A) fA = 4 hexane) 1,4BAPP 1,4Bis (3-AminoPropyl) 1,4 BAPP ALDRICH Amine A) fA = 4 3022544 -13- Piperazine EMHQ Ether Methyl EMHQ RHODIA Inhibitor hydroquinone Darocure® 2 Hydr oxy 2 Methyl Dar1173 CIBA Photoinitiator 1173 Phenyl Propane-1-one Benzophenone Diphenyl Methanone BzPh ARKEMA Photoinitiator Examples of preparation of oligomers according to the invention Example A1 In a 1-liter reactor equipped with an anchor stirrer and surmounted by a single refrigerant ascending, device allowing the atmosphere of the reaction medium, an air inlet (air sparge), a dropping funnel and a thermometric probe, to introduce: 178.4 g of hexanediol diacrylate (HDDA) (0.7895 mole) and 84.7 mg of hydroquinone methyl ether (EMHQ). Subsequently, 33.5 g of dimethylamino propylamino propylamine (DMAPAPA) (0.2105 mol) are introduced gradually into the reactor through the dropping funnel over a period of one hour while the reaction mixture is progressively brought to 80 ° C. and maintained. at this temperature up to a conversion greater than 95% of the primary and secondary reactive amine functions (Vire + 2aIre) and stabilization of the viscosity, ie 10 hours of reaction. After cooling to room temperature, a product having a clear, light yellow appearance is obtained. EXAMPLE A2 Carried out identically with respect to Example A1, except by replacing with equal weight for A) H DDA with 178.4 g of 3-methyl 1,5-pentanediol diacrylate (3M1, 5PDDA) ( 0.7895 moles). A product having a limpid, light yellow appearance is obtained. Example A3 Identical to Example A1, except that the reagents acrylate B) and amine A) are modified, as follows: for B), 188.49 g dipropylene glycol diacrylate (DPGDA) (0) , 7895 moles) and for A), 35.15 g of dimethylamino propylamino propylamine (DMAPAPA) (0.2105 moles). A product having a limpid, light yellow appearance is obtained. The molar compositions and characteristics of the 3 oligomers obtained A1, A2 and A3 are presented below in Table 2. Table 2: Molar composition and characteristics of the oligomers A1, A2 and A3 Oligomer reference, for example Al A2 A3 Reactive component (moles) A: 3M1.5PDDA 0.7895 B: DPGDA 0.7895 B: HDDA 0.7895 A: DMAPAPA 0.2105 0.2105 0.2105 Characteristics r 2.50 2.50 2.35 tA (mEq / g) 2.94 2.94 2.69 Viscosity at 25 ° C (mPa $) 255 250 590 tau- (mEq / g) 4.47 4.47 4.08 fo (mEq / mole) 2 , 57 2.57 2.57 nmoy 0.57 0.57 0.57 Mn calc 575 575 631 Example B1 5 Identical to that of Example A1, except that acrylate reagents B) are modified and amine A), as follows: for B), 303.45 g of trimethylol propane (4 ethoxy) triacrylate (TMP4EOTA) (0.6429 mol) and for A), 36.42 g of dimethylamino propylamine (DMAPA) (0, 3571 moles). A product having a limpid, light yellow appearance is obtained.
    [0006] Example B2 Exemplified in relation to Example A1, except that the reagents acrylate B) and amine A) are modified as follows: for B), 197.34 g of trimethylol propane triacrylate (TMPTA) ( 0.6667 mol) and for A), 34.00 g of dimethylamino propylamine (DMAPA) (0.3333 mol). A product having a limpid, light yellow appearance is obtained.
    [0007] The table below groups the molar compositions of the reactants A and B and the characteristics of the oligomers B1 and B2 as described above. Table 3: Molar Composition of Reagents A) and B) and Characteristics of Oligomers B1 and B2 Oligomeric reference B1 B2 Reactive component (moles) B: TMP4EOTA 0.6429 B: TMPTA 0.6667 A: DMAPA 0.3571 0.3333 Characteristics r 2.70 3.00 tA (mEq / g) 2.32 2.88 Viscosity at 25 ° C (mPa $) 2000 6400 tau- (mEq / g) 3.57 5.76 fo ( mEq / mole) 4.25 4.00 nmoy 1.25 1.00 Mn calc 1190 694 Example C1 Carried out identically with respect to Example A1, except that the reagents acrylate B) and amine A are modified ), as follows: for B), 193.71 g of hexanediol diacrylate (HDDA) (0.8571 mole) and for A), 28.58 g of 1,4 bis (3-aminopropyl) piperazine (1,4BAPP) ) (0.1499 moles). A product having a limpid, light yellow appearance is obtained.
    [0008] Example C2 Identical to Example A1, except that the acrylate B) and amine A) reactants are modified as follows: for B), 193.71 g of hexanediol diacrylate (HDDA) ( 0.8571 moles) and for A), 20.29 g of 1,3 bis (aminomethyl) cyclohexane (1,3BAC) (0.1499 moles). A product having a limpid, light yellow appearance is obtained. The molar composition of the reactants A) and B) and characteristics of the oligomers C1 and C2 are presented in Table 4 below. Table 4: Molar Composition of Reagents A) and B) and Characteristics of Oligomers C1 and C2 Oligomer Reference C1 C2 Reactive Component (moles) B: HDDA 0.8571 0.8571 A: 1.3BAC 0, 1429 A: 1,4BAPP 0.1499 Characteristics r 3.00 3.00 tA (mEq / g) 2.57 1.34 Viscosity at 25 ° C (mPa · $) 955 340 tau- (mEq / g) 5, 14 5.34 fo (mEq / mole) 2.67 2.67 nmoy 0.33 0.33 Mn calc 519 499 Example D1 Identical to that of Example A1, except that the reagents are modified acrylate B) and amine A), as follows: for B), 380.45 g of trimethylol propane (3 ethoxy) triacrylate (TMP3EOTA) (0.8889 mole) and for A), 22.22 g of 1,4 bis (3-aminopropyl) piperazine (1.4 BAPP) (0.1111 mole). A product having a clear, light yellow appearance is obtained. EXAMPLE D2 Identical to Example A1, except that the reagents acrylate B) and amine A) are modified, as follows: for B), 380.49 g of trimethylol propane (3 ethoxy) triacrylate (TMP3EOTA) (0.8889 mol) and for A), 15.78 g of 1,3 bis (aminomethyl) cyclohexane (1,3BAC) (0.1111 mol). A product having a limpid, light yellow appearance is obtained. Table 5: Molar composition and characteristics of oligomers D1 and D2 Oligomeric reference D1 D2 Reactive component (moles) TMP3EOTA 0.8889 0.8889 1.3BAC 0.1111 1.4BAPP 0.1111 Characteristics r 6.00 6 , 00 tA (mEq / g) 1.10 0.56 Viscosity at 25 ° C (mPa · $) 1740 1278 tau- (mEq / g) 5.52 5.61 fo (mEq / mole) 4.00 4, The oligomers prepared according to the examples described above were tested in crosslinkable formulations (application compositions) as described below. Formulations and Preparation The oligomers are formulated by mixing at room temperature according to the following compositions Fl to F18 with two types of formulations tested.
    [0009] Odd formulas (F1, F3, F5, ... F17) Acrylate oligomer (Al to D2): 96% by weight Darocure® 1173: 4% by weight Even Formulas (F2, F4, F6, ... F18) Acrylate oligomer (Al to D2): 96% by weight Darocure® 1173: 2% by weight Benzophenone: 2% by weight The compositions of the formulations carried out Fl to F18 and their performances are presented in the following tables 6 to 9. The characterization methods said oligomers and determining the performance of said formulations F1 to F18 and the conditions used are recalled below after these tables 6 to 9. Table 6: Formulations Fl to F6 based on oligomers A1 to A3 Reference Fl F2 F3 F4 F5 F6 formulation Components Al 96.0 96.0 A2 96.0 96.0 A3 96.0 96.0 Darocure® 1173 4.0 2.0 4.0 2.0 4.0 2.0 Benzophenone 2.0 2.0 2.0 Performance Speed 25 55 20 55 25 60 Crosslinking (mm / min) Hardness Persoz 91 139 84 114 59 75 Pencil hardness HH HB HB HB (5B - 5H) Flexibility (mm) 3 3 3 3 4 3 Resistance 300 300 300 300 54 126 solvent (s) Table 7: Formulations F7 to F10 based on oligomers B1 and B2 Reference F7 F8 F9 F10 formulation Components B1 96.0 96.0 B2 96.0 96.0 Darocure® 1173 4.0 2.0 4.0 2.0 Benzophenone 2.0 2.0 Performances Speed 40 65 100 Crosslinking (mm / min) Hardness Persoz 96 157 97 Pen hardness HB HB 4B 3022544 -19- (5B - 5H) Flexibility (mm) 4 4 20 Resistance 300 300 300 solvent (s) Table 8: Formulations F11 to F14 based on oligomers Cl and C2 Reference F11 F12 F13 F14 formulation Components Cl 96.0 96.0 C2 96, 0 96.0 Darocure® 4.0 2.0 4.0 2.0 1173 Benzophenone 2.0 2.0 Performance Speed 35 65 30 45 Cross-linking (mm / min) Hardness Persoz 94 93 113 91 Pencil hardness 2H H HB HB (5B-5H) Flexibility (mm) 6 4 8 6 Resistance 300 300 300 300 solvent (s) Table 9: Formulations F15 to F18 based on oligomers D1 and D2 Reference F15 F16 F17 F18 formulation Components D1 96.0 96.0 D2 96.0 96.0 Darocure® 4.0 2.0 4.0 2.0 11 73 3022544 -20- Benzophenone 2.0 2.0 Performance Speed 35 55 25 40 Cross-linking (mm / min) Hardness Persoz 160 124 186 170 Pencil hardness 3H B HB HB (5B - 5H) Flexibility (mm) 15 10 20 15 Resistance 300 300 300 300 solvent (s) Methods for determining oligomer characteristics and performance of formulations 1) Appearance 5 The product is visually observed in daylight through a 60 ml white glass vial and can be distinguished if the product is: - Clear: no turbidity, it is comparable to water, - Veiled: no longer allowing clear vision through the bottle, - Trouble: opaque bottle, no image can be seen through the bottle. 2) Viscosity: According to Noury viscosity The travel time, in the liquid to be characterized, of a steel ball subjected to its gravity is measured. The standard AFNOR XP.T51-213 specifies in particular the geometry of the container, the diameter of the ball (2 mm) and the path of the ball (104 mm). Under these conditions, the dynamic viscosity is proportional to the travel time of the ball with: 1 second corresponding to 0.1 Pa.s. 3) Amine level tA: Calculation according to equation (6) above defined in description 4) Functionality f 1: Calculation according to relation (7) above defined in the description 5) Acrylate content t - Calculation according to the relation (8) above defined in the description. 6) Reactivity by crosslinking rate Formulation F1 to F18 is applied to a 12 μm film on a contrast card ("Penoparc charts form 1B" ® Leneta), and is crosslinked using a UV lamp. , Fusion Hg at 120 W / cm. The minimum required passage rate (in m / min) is measured to obtain a dry film to the touch. The higher the speed, the more reactive the formulation is.
    [0010] For the hardness, flexibility and acetone resistance tests, the photocured films are left in the air-conditioned room at 23 ° C. for 24 hours after crosslinking and before the measurements. 7) Persoz hardness The formulation to be examined is applied in a 100 μm film on a glass plate and cross-linked by a UV lamp, Fusion Hg 120 W / cm at a speed of 8 m / min. The result is given in the number of oscillations before damping of the oscillations (passage of 12 ° to 4 ° of amplitude), of a pendulum in contact with the coated glass plate, according to the ISO 1522 standard. Flexibility The examined formulation is applied in a 100 μm film on a 25/10 mm thick smooth steel plate (D-46® Q-Panel), then crosslinked by a UV lamp, Fusion 20 Hg 120 W / cm at a speed of 8 m / min. The coated plate is bent on cylindrical mandrels in accordance with ISO 1519. The result is expressed as the value (in mm) of the smallest radius of curvature that can be applied to the coating without it cracking or takes off from the support. 9) Acetone Resistance (Chemical Resistance) The examined formulation is applied to a glass plate in a 12 μm film and then cross-linked by a UV lamp, Fusion Hg 120 W / cm at a speed of 8 m / min. The coating is rubbed with a cloth soaked with acetone. The result retained is the time (expressed in seconds) beyond which the film comes off and / or disintegrates. 10) Number average molecular weight Mn: Calculated according to (4) above defined in the description
    权利要求:
    Claims (32)
    [0001]
    REVENDICATIONS1. Acrylated oligomer, characterized in that it has an average acryl acrylate number function strictly greater than 2.0 acrylates per mole, that it has a branched structure and that it results from the polyaddition reaction of at least one amine A) of functionality fA in NH groups of at least 2, preferably from 2 to 6, with said NH functionality meaning a number-average functionality if it is a mixture of amines, said amine A ) having primary and / or secondary amine functions, with optionally said amine A) capable of being a carrier in addition to at least one tertiary amine function (without NH), on at least one multifunctional acrylate B) with functional groups in groups acrylates of at least 2, preferably 2 to 6, with said acrylate functionality meaning a number average functionality if it is a mixture of acrylates, with a number average functionality per mole on the set of components A) e B) greater than 2 and with said oligomer comprising in its repeating unit structure at least one aminoacrylate group -OC-CH 2 -CH 2 -N = resulting from said polyaddition and with a nitrogen content tA, derived from said amine A ), greater than or equal to 0.35 mEq / g and an initial ratio r = acrylate / NH, between rinf and 1.1 rsup and preferably r between ria and rsup, with the values ripf and rsup being defined according to the relationships (1) and (2): r, f = 0.90 * (fA-1) * (fB -1) (1) rsup = 2 * fA + 21B-6 (2) and with an average number nmoy of repeating units (repeating units) per oligomer defined according to the following equation (3): nmoy = 1 / [(r * fA / fB) + 1 - fA] (3)
    [0002]
    2. Oligomer according to claim 1, characterized in that said amine A) additionally carries, at least one tertiary amine function, preferably said amine being selected from: dimethylamino propylamine (DMAPA), dimethylamino propylamino propylamine (DMAPAPA) and 1 , 4 bis (3-aminopropyl) piperazine (1,4-BAPP) and more preferably from DMAPAPA and 1,4-BAPP and with a nitrogen content derived from the amine tA greater than or equal to 0.35 mEq / g .
    [0003]
    3. Oligomer according to one of claims 1 and 2, characterized in that the viscosity of said acrylate B) measured according to ISO 2555 method at 23 ° C is less than 200 mPa.s under a shear of 100 s-1.
    [0004]
    4. Oligomer according to one of claims 1 to 3, characterized in that said acrylate B) is selected from: b1) acrylates of aliphatic or cycloaliphatic polyols optionally alkoxylated, b2) oligoether acrylates, b3) alkoxylated phenolic acrylates or b4) acrylated aminoacrylates or mixtures thereof and preferably according to 131) or b4) or mixtures thereof.
    [0005]
    5. Oligomer according to one of claims 1 to 4, characterized in that said amine 5 A) is chosen from: al) an aliphatic amine, a2) a cycloaliphatic amine or a3) an aralkylene amine with the amine function in position other that the alpha or beta position of the aromatic ring, preferably al) aliphatic and / or a2) cycloaliphatic (including polycyclic) or mixtures thereof.
    [0006]
    6. Oligomer according to one of claims 1 to 5, characterized in that said functionalities fA and fB are selected so that the sum fA + fB does not exceed 8 and preferably is less than 8.
    [0007]
    7. Oligomer according to one of claims 1 to 6, characterized in that it has a rate _acr. of acryl acrylates [greater than 2.3 and preferably 3.5 to 10.0 mmol (or milli equivalents) per g. 15
    [0008]
    8. Oligomer according to one of claims 1 to 7, characterized in that it has a number average mass Mn defined according to the following relation (4): Mn = MB (nmoy * Mu) (4) with M, being the molar mass of the repeating unit defined according to the following equation (5): Mu = MA + (fA2 2 * fA1 1) * MB (5) where nmoy is the average number of repeating units as defined in claim 1 MB being the molar mass of the acrylate B), MA being the molar mass of the amine A), fAl being the number of functions -NH2 of primary amine, by amine A) and fA2 being the number of functions -NH secondary amine, by amine A). 25
    [0009]
    9. Oligomer according to one of claims 1 to 8, characterized in that it has a nitrogen content from the amine tA expressed in mEq / g, defined according to the following relationship (6): tA = 1000 * wherein M n is the number average molecular weight as defined in claim 7, wherein f A is the number of -NH 2 primary amine functions, per amine A) and f A 2 is the number of -NH- secondary amine functions, by amine A) fA3 being the number of functions -N = tertiary amine, by amine A).
    [0010]
    10. Oligomer according to one of claims 1 to 9, characterized in that said acrylate B) is alkoxylated with a number of alkoxy units per acrylate group not exceeding 3, if said alkoxy is ethoxy and not not exceeding 1, if said alkoxy is propoxy.
    [0011]
    11. Oligomer according to one of claims 1 to 10, characterized in that said amine A) has a functionality fA greater than or equal to 2 and that said acrylate B) has a functionality fB greater than or equal to 3 or conversely said amine A) has a functionality fA greater than or equal to 3 and that said acrylate B) has a functionality fB greater than or equal to 2.
    [0012]
    12. Oligomer according to one of claims 1 to 11, characterized in that: - said amine A) is of general formula (NH2) fm R2 (NHR4A2, with R2 = 10 R '(NR "R" IA3, R3, R ', R "and R"' being identical or different C1 to C3 alkyls with fAl being equal to 0 and being the number of primary amine functions per mole, fA2 being greater than or equal to 2 and being the number of amine functions secondary by mole and fA3 being greater than or equal to 0 and being the number of tertiary amine functions per mole and with fA = fA2 15 - said acrylate B) is of general formula R1 (X) fB with X being an acrylate group CH2 = CH And wherein R1 is the residue of said acrylate B) carrying acrylates per mole - said oligomer comprises the product of the following general formula (I): X (fB_i) R1 [O2CCH2CH2NR3R2Y (fA2-2) N R3CH2CH2CO2R1XO3_21X (I) with Y = - (NR3CH2CH2COOR1X (3-1))
    [0013]
    13. Oligomer according to one of claims 1 to 11, characterized in that: said amine A) is of general formula (NH2) fA1R2 (NHR3) fA2, with R2 R '(NR "R"') fA3, R3, R ', R "and R"' being C1 to C3 alkyls which are identical or different with fAi being greater than or equal to 1 and being the number of primary amine functions per mole, fA2 being greater than or equal to 0 and being the number of secondary amine functions per mole and fA3 being greater than or equal to 0 and being the number of tertiary amine functions per mole and with fA = 2 * fAi fA2 - said acrylate B) is of general formula R1 (X) fB with X being a acrylate group CH2 = CH-OO2- and R1 being the residue of said acrylate B) carrying acrylates per mole - said oligomer comprises the product of the following general formula (11): X (fg_i) R1 [02CCI-12C1-12NR2YfA2Z ( ## STR2 ## where Y = - (NR3CH2CH2CO2R1X (f34) and Z = - (N (CH2CH2COOR1X (3-1)) 2) 3022544 -25-
    [0014]
    14. Oligomer according to claim 11, characterized in that said functionality fA is equal to 3 and said amine A) is selected from a diamine carrying a primary amine function and a secondary amine function or a triamine carrying 3 secondary amine functions. 5
    [0015]
    15. Oligomer according to claim 11, characterized in that said amine A) has functionality fA equal to 2 and is a primary amine or a diamine carrying 2 secondary amine functions and that said acrylate B) is an optionally alkoxylated triacrylate, with in the case where said triacrylate is alkoxylated a number of alkoxy units per acrylate not exceeding 3 if said alkoxy is ethoxy and a number of alkoxy units per acrylate not exceeding 1 if said alkoxy is propoxy.
    [0016]
    16. Oligomer according to claim 11, characterized in that said amine A) has a functionality fA equal to 3, which is a primary-secondary diamine or a triamine bearing 3 secondary amine functions and that said acrylate B) is a diacrylate optionally alkoxylated, with in the case where said diacrylate is alkoxylated a number of alkoxy units per acrylate not exceeding 2 if said alkoxy is ethoxy and a number of alkoxy units per acrylate not exceeding 1 if said alkoxy is propoxy.
    [0017]
    17. Oligomer according to claim 11, characterized in that said functionality fA is equal to 4 and said amine A) is selected from a diamine carrying 2 primary amine functions or a triamine carrying 1 primary amine function and 2 amine functions secondary or a tetra-amine carrying 4 secondary amine functions.
    [0018]
    18. Oligomer according to claim 11, characterized in that said functionality fA is equal to 5 and said amine A) is selected from a triamine carrying two primary amine functions and a secondary amine function or a tetra-amine carrier of a primary amine function and three secondary amine functions or a penta-amine carrying 5 secondary amine functions.
    [0019]
    19. Oligomer according to claim 11, characterized in that said fA functionality is equal to 6 and said amine A) is selected from a triamine carrying three primary amine functions or a tetra-amine carrying 2 primary amine functions and 30 2 secondary amine functions or a penta-amine carrying 1 primary amine function and 4 secondary amine functions or a hexa-amine carrying 6 secondary amine functions.
    [0020]
    20. Oligomer according to one of claims 1 to 19, characterized in that it has a number average functionality in acrylates fo ranging from 2.1 to 6.0, preferably from 2.3 to 5.0 by oligomer. 3022544 -26-
    [0021]
    21. Oligomer according to one of claims 1 to 20, characterized in that it results from the reaction between at least two amines A) and / or at least two acrylates B).
    [0022]
    22. Oligomer according to one of claims 1 to 21, characterized in that it has a number average molecular weight Mn calculated according to the relation 4 ranging from 275 to 5000 and preferably from 300 to 3000.
    [0023]
    23. Oligomer according to one of claims 1 to 22, characterized in that it comprises n repetitive units with a molecular distribution as a function of n comprising at least the 4 products corresponding to: n = 0 and n = 1 and n = 2 and n = 3 and more particularly with at least 50% by weight of said distribution corresponding to n 10 less than or equal to 3.
    [0024]
    24. Oligomer according to one of claims 1 to 23, characterized in that it comprises n repetitive units with a molecular distribution as a function of n comprising at least the products corresponding to: n = 0 and n = 1 and n = 2 and n = 3 and n = 4 and more particularly with at least 60% by weight of said distribution corresponding to n less than or equal to 4.
    [0025]
    25. A process for preparing an oligomer as defined according to one of claims 1 to 24, characterized in that it comprises a polyaddition reaction step (Michael) of said at least one amine A) on said less an acrylate B), in the presence of a radical polymerization inhibitor and in the absence of any solvent, of any catalyst and of any other reactant except said amine A) and said acrylate B) and inhibitor, said process comprising progressive and continuous addition of said amine A) to said acrylate B) already present in the reactor and still in stoichiometric excess and with said reaction occurring at a temperature above 40 ° C and below 90 ° C, preferably 60 at 80 ° C. and with said reaction being stopped at a conversion ratio of the amine groups NH at least 95% and with an initial ratio r of acrylate functional groups on amine functional groups NH, where r = acrylate / NH is between 1 and 1, 1 rsup and preferably r between ria and rsup, with the values rinf and rsup being defined according to relations (1) and (2) below: rinf = 0,90 * (fA-1) * (fB -1) (1) Rsup = 2 * fA + 21B-6 (2)
    [0026]
    26. Crosslinkable composition, characterized in that it comprises at least one oligomer as defined according to one of claims 1 to 24 or obtained by the process as defined according to claim 25, optionally with the presence of a reactive diluent. , in particular chosen from mono and / or multifunctional (meth) acrylic monomers and which may be identical to said starting acrylate B). 3022544 -27-
    [0027]
    27. A composition according to claim 26, characterized in that it is a composition crosslinkable by radiation preferably among UV, laser, LED or EB, which is a composition of coatings, in particular inks, varnishes , gelled coatings, paints or adhesives, in particular structural adhesives, or is a composition for 3D articles by superposition of successive layers or is a molding composition.
    [0028]
    28. A composition according to claim 26, characterized in that it is a peroxidically crosslinkable composition (commonly called "P-cure") and in particular it is a coating composition more particularly varnish, 10 d gelled coatings, paints or adhesives, in particular structural adhesives or is a chemical sealing composition or a molding composition.
    [0029]
    29. Use of an oligomer as defined in one of claims 1 to 24 as a binder in crosslinkable compositions.
    [0030]
    30. Use according to claim 29, characterized in that said composition is crosslinkable by radiation preferably from UV, laser, LED or EB, said composition being a coating composition, in particular of inks, varnishes, coatings gels, paints or adhesives, in particular structural adhesives or being a composition for 3D articles by superposition of successive layers or being a molding composition. 20
    [0031]
    31. Use according to claim 30, characterized in that said composition is a peroxidically crosslinkable composition (commonly known as "P-cure") which in particular is a composition of coatings, more particularly varnishes, gelled coatings, paints or adhesives, in particular structural adhesives or a chemical sealing composition or a molding composition. 25
    [0032]
    32. Final crosslinked product, characterized in that it results from the use of at least one oligomer as defined in one of claims 1 to 24 or obtained by the process as defined in claim 25 or it results from the crosslinking of a composition as defined according to one of claims 26 to 28 and in particular that it is coating film, more particularly ink film, varnish, coating 30 gelled coatings, adhesive or a 3D article or a chemical seal or a molded part.
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    同族专利:
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    TW201604174A|2016-02-01|
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    TWI585068B|2017-06-01|
    US10125223B2|2018-11-13|
    US20170198097A1|2017-07-13|
    FR3022544B1|2018-01-05|
    CN106459271A|2017-02-22|
    JP2017527642A|2017-09-21|
    ES2779316T3|2020-08-14|
    DK3158008T3|2020-03-30|
    WO2015197941A1|2015-12-30|
    JP6594913B2|2019-10-23|
    EP3158008A1|2017-04-26|
    CN106459271B|2019-07-16|
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    EP3401370A1|2017-05-10|2018-11-14|Allnex Belgium S.A.|Amino acrylates|
    法律状态:
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    2015-12-25| PLSC| Publication of the preliminary search report|Effective date: 20151225 |
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    2021-05-13| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1455789A|FR3022544B1|2014-06-23|2014-06-23|MULTIFUNCTIONAL ACRYLIC OLIGOMERS OF BRANCHED STRUCTURE, BY POLYADDITION BETWEEN AMINES AND MULTIFUNCTIONAL ACRYLATES.|
    FR1455789|2014-06-23|FR1455789A| FR3022544B1|2014-06-23|2014-06-23|MULTIFUNCTIONAL ACRYLIC OLIGOMERS OF BRANCHED STRUCTURE, BY POLYADDITION BETWEEN AMINES AND MULTIFUNCTIONAL ACRYLATES.|
    JP2016575233A| JP6594913B2|2014-06-23|2015-06-15|Branched polyfunctional acrylic oligomers by polyaddition between polyfunctional amines and acrylates|
    CN201580030570.8A| CN106459271B|2014-06-23|2015-06-15|Pass through the multifunctional acrylic compounds oligomer of the branched structure of the addition polymerization between polyfunctional amine and acrylate|
    PCT/FR2015/051575| WO2015197941A1|2014-06-23|2015-06-15|Multifunctional acrylic oligomers of branched structure, by polyaddition between multifunctional amines and acrylates|
    ES15733833T| ES2779316T3|2014-06-23|2015-06-15|Multifunctional acrylated oligomers of branched structure by polyaddition between multifunctional amines and acrylates|
    DK15733833.6T| DK3158008T3|2014-06-23|2015-06-15|MULTIFUNCTIONAL ACRYLOLIGOMERS WITH A BRANCHED STRUCTURE BY POLY ADDITION BETWEEN AMINES AND MULTIFUNCTIONAL ACRYLATES|
    US15/321,023| US10125223B2|2014-06-23|2015-06-15|Multifunctional acrylic oligomers of branched structure, by polyaddition between multifunctional amines and acrylates|
    EP15733833.6A| EP3158008B1|2014-06-23|2015-06-15|Multifunctional acrylic oligomers of branched structure, by polyaddition between multifunctional amines and acrylates|
    TW104119419A| TWI585068B|2014-06-23|2015-06-16|Multifunctional acrylated oligomers of branched structure, by polyaddition between multifunctional amines and acrylates|
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