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    • 专利摘要:
    The present invention relates to a curable composition comprising (a) at least one ethylene polymer, (b) less than 2 parts by weight of at least one monoperoxycarbonate per 100 parts by weight of component (a), (c) of 0 4 to less than 4 parts by weight of at least one t-alkyl hydroperoxide per 100 parts by weight of component (b). It further relates to a method of preventing roasting of a curable composition comprising an ethylene polymer, by adding a specific amount of t-alkyl hydroperoxide thereto and a method of making a protected material against the fence.
    公开号:FR3055629A1
    申请号:FR1658362
    申请日:2016-09-08
    公开日:2018-03-09
    发明作者:Chao Lu
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    © Publication no .: 3,055,629 (to be used only for reproduction orders)
    ©) National registration number: 16 58362 ® FRENCH REPUBLIC
    NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY
    COURBEVOIE © Int Cl 8 : C 08 K5 / 14 (2017.01), C 08 L 29/04, 23/04, H 01 L 31/048
    A1 PATENT APPLICATION
    ©) Date of filing: 08.09.16.(© Priority: (© Applicant (s): ARKEMA FRANCE Public limited company - FR. @ Inventor (s): LU CHAO. ©) Date of public availability of the request: 09.03.18 Bulletin 18/10. ©) List of documents cited in the preliminary search report: See the end of this booklet (© References to other related national documents: ©) Holder (s): ARKEMA FRANCE Société anonyme. ©) Extension request (s): (© Agent (s): ARKEMA FRANCE Public limited company.
    CURABLE COMPOSITION COMPRISING AN ETHYLENE POLYMER, A MONOPEROXYCARBONATE AND A T-ALKYL HYDROPEROXIDE.
    FR 3 055 629 - A1
    The present invention relates to a curable composition comprising (a) at least one ethylene polymer, (b) less than 2 parts by weight of at least one monoperoxycarbonate per 100 parts by weight of component (a), (c) of 0 , 4 to less than 4 parts by weight of at least one t-alkyl hydroperoxide per 100 parts by weight of component (b). It further relates to a process for preventing the toasting of a curable composition comprising an ethylene polymer, by adding a specific amount of t-alkyl hydroperoxide to it and a process for manufacturing a protected material. against the grill.
    CURABLE COMPOSITION COMPRISING AN ETHYLENE POLYMER, A MONOPEROXYCARBONATE AND A t-ALKYL HYDROPEROXIDE
    The present invention relates to a curable composition comprising an ethylene polymer, such as an ethylene / vinyl acetate copolymer. It further relates to a process for preventing the toasting of a curable composition comprising such an ethylene polymer.
    Ethylene vinyl acetate (EVA) is a copolymer widely used, among others, in solar panels, as an encapsulation material to protect solar cells (and particularly the semiconductors contained therein) against external environmental elements, in particular humidity and UV radiation, and to produce electrical insulation. EVA does indeed have good transparency and adhesion to the substrates of the photovoltaic module (PV), together with a high resistivity and a good barrier effect against humidity. These properties can, as a variant, be used in the manufacture of laminated glass.
    It is common practice to crosslink these EVA copolymers in order to improve their thermal stability, in particular their creep resistance, their adhesion to substrates and their resistance to degradation by weathering. To this end, various crosslinking agents have been used to date in the formulation of EVA, which are typically peroxides such as dicumyl peroxide (DCP), peroxyesters, peroxyketals, peroxycarbonates and mixtures thereof. this. An example of a monoperoxycarbonate used for this purpose is OO-t-butylO-2-ethylhexyl monoperoxycarbonate (TBEC). This peroxide has been shown to require a lower operating temperature than DCP, without leading to a resulting product with a yellowing coloration. Therefore, it is used in the manufacture of photo voltaic modules (see, for example, K. Thawom et al., Open Journal of Polymer Chemistry, 2012, 2, 77-85). The applicant has further demonstrated that the addition of OO-t-amyl-O-2-ethylhexyl monoperoxycarbonate (TAEC) to TBEC decreases the reaction time and improves the crosslinking density of EVA, which leads to resistance with increased traction and a high modulus of elasticity of the products made of crosslinked EVA (WO 2010/007315).
    During the laminating process of the PV module, the EVA composition is first deposited on the front sheet, then covered by the solar cells and again deposited on them, before applying the sheet. support, so as to obtain a PV module which is then heated to a certain high temperature for a certain time and pressed into place, so that the EVA composition is cured.
    It has been observed that the EVA composition is susceptible to premature crosslinking in the barrel or die head of the extruder in which it is processed, prior to the formation of the above laminate. This phenomenon, which is called "roasting", leads to irregularities in the EVA sheet thus formed, which in turn alters the appearance and properties of the PV module. In some cases, pressure can also build up in the extruder, necessitating the interruption of the extrusion process. This has been observed, in particular, in the case of EVA having a relatively low creep index and / or a relatively narrow molecular weight distribution (source: US-4,015,058). However, on the other hand, in order to obtain commercially practicable processing speeds, it is necessary that once the EVA sheets have been formed and then heated above the thermal decomposition temperature of the peroxides, the crosslinking is carried out as quickly as possible in order to increase the economy of the process and also to minimize possible side reactions.
    Various solutions have been proposed to date to prevent toasting of EVA compositions. For example, it has been suggested that polymerization inhibitors be added to the EVA composition. However, undesirable yellowing has been observed. Alternatively, it has been proposed in US-4,015,058 to add at least 1% by weight of cumene hydroperoxide and / or tert-butyl hydroperoxide to dicumyl peroxide (DCP). However, the crosslinking rate obtained with this system is not high enough for industrial applications, in particular in the manufacture of PV modules, due to the presence of DCP. Due to the aromatic structure of DCP, yellowing problems still persist.
    Another solution has been proposed in JP2011-140588, which is said to be suitable for the manufacture of PV modules. It consists in adding from 4 to 50 parts by weight of a hydroperoxide, such as t-butyl hydroperoxide, to 100 parts by weight of an organic peroxide chosen from a monoperoxycarbonate, a dialkyl peroxide, a peroxyketal and a peroxyester. Although this solution overcomes the disadvantages associated with the use of DCP, it has been described in JP2011-140588 that the above amounts of hydroperoxide adversely affect the crosslinking density of EVA. In this context, it was suggested in this document increasing the total amount of monoperoxycarbonate and hydroperoxide while keeping the ratio of hydroperoxide to monoperoxycarbonate constant, that is to say about 20% (see Table 1) .
    Unexpectedly, the inventor discovered that the crosslinking density of EVA can be improved by a specific weight ratio of hydroperoxide to monoperoxycarbonate, namely from 0.4 to less than 4%. In addition, he observed a marked increase in the prevention effect of roasting of the hydroperoxide at these low weight ratios, contrary to what was expected in JP2011-140588, without altering the kinetics of the crosslinking reaction, even with a small amount of the crosslinking agent. In addition, it has been observed that the homogeneity of the film is satisfactory with practically no bubbles. In this regard, it should be noted that the bubbles formed by the evaporation of water trapped in the film at extrusion temperatures above 100 ° C are responsible for surface defects which negatively affect the resistivity of the film. This is particularly damaging if the film is to be used as an encapsulation material in PV modules.
    Compositions comprising an ethylene polymer such as EVA and the above peroxides can thus be processed in extrusion devices at a rapid rate without undergoing toasting.
    It should be noted that the monoperoxycarbonates are also useful for crosslinking other ethylene polymers such as polydiene elastomers, including ethylene-propylene-diene elastomers (EPDM) and also polyethylene, including a low density polyethylene and with high density, which are used, inter alia, in the manufacture of wire and cable insulation, pipes and flexible pipes (including pipes for automobile radiators, potable water and underfloor heating , for example), roller liners, rotational molding, and cellular articles. The composition of this invention is therefore also useful in these applications, for example, to prevent toasting during the extrusion of the composition in the form of an insulation sheath on an electrical conductor.
    More specifically, this invention relates to a curable composition comprising:
    (a) at least one ethylene polymer, (b) less than 2 parts by weight of at least one monoperoxycarbonate per 100 parts by weight of component (a), (c) from 0.4 to less than 4 parts by weight of at least one t-alkyl hydroperoxide per 100 parts by weight of component (b).
    The ethylene polymer used as component (a) in this invention can be an ethylene homopolymer or preferably an ethylene copolymer. Examples of ethylene copolymers are those produced from ethylene monomers and at least one other monomer chosen from hydrocarbons having at least one unsaturation such as methylene, propylene, butene, pentene, hexene, heptene, octene, butadiene, isoprene and styrene; acrylic monomers such as acrylic acid, methacrylic acid, alkyl methacrylate and alkyl acrylate, in which the alkyl group can be chosen from methyl, ethyl, propyl or butyl, for example; and vinyl monomers such as vinyl acetate. Generally, these copolymers comprise at least 30 percent by weight of ethylene and at most 70 percent by weight of the other monomer (s).
    According to a preferred embodiment, the ethylene copolymer is an ethylene / vinyl acetate (EVA) copolymer. The EVA copolymer can comprise 15 to 60% by weight, and preferably 25 to 45% by weight, of vinyl acetate (VA) monomer. Examples of such EVA copolymers are marketed under the trade name "Evatane® 18-150" and "Evatane® 40-55" by ARKEMA.
    Other ethylene polymers which can be used in the invention have been described, for example, in EP 2 242 647. They comprise a functionalized polyolefin, such as a homopolymer of ethylene or a copolymer of ethylene with a alkyl (meth) acrylate or vinyl acetate, which can be functionalized by grafting by copolymerization with maleic anhydride or glycidyl methacrylate. This functionalized polyolefin can optionally be mixed with an ethylene / vinyl ester copolymer of carboxylic acid such as EVA.
    The ethylene polymer is mixed with at least one monoperoxycarbonate. This peroxide compound can be an OO-t-alkyl-O-alkyl monoperoxycarbonate, preferably chosen from the group consisting of: OO-t-butylO-2-ethylhexyl monoperoxycarbonate (TBEC), OO-t-butyl monoperoxycarbonate O-2-isopropyl (TBIC), OO-t-amyl-O-2-ethylhexyl monoperoxycarbonate (TAEC), OO-t-amyl-O-2-isopropyl monoperoxycarbonate (TAIC) and mixtures thereof. These monoperoxycarbonates are available under the trade name Luperox® or Lupersol® supplied by ARKEMA.
    Preferred monoperoxycarbonates are TAEC and TBEC and a mixture thereof. According to an embodiment of the invention, a mixture of TBEC and TAEC is used as component (b).
    Preferably, when a mixture of O, O-tert-butyl-O- (2ethylhexyl) monoperoxycarbonate (TBEC) and O, O-tert-amyl-O- (2-ethylhexyl) monoperoxycarbonate (TAEC) is used , the mass ratio of O, O-tert-butyl-O (2-ethylhexyl) monoperoxycarbonate (TBEC) to O, O-tert-amyl-O- (2ethylhexyl) monoperoxycarbonate (TAEC) is in the range of 0 , 1: 99.9 at 60:40, more preferably from
    1:99 to 50:50, more preferably from 10:90 to 30:70 and even more preferably from 15:85 to 25:75 and even more preferably is about 20:80 respectively.
    Alternatively, said ratio is approximately 50:50.
    Preferably, the amount of component (b) in the composition of the invention can be in the range from 0.1 to less than 2 parts by weight, preferably from 0.2 to 1.5, more preferably from 0, 3 to 1, more preferably 0.4 to 1, more preferably 0.4 to 0.7 and even more preferably about 0.5 parts by weight, per 100 parts by weight of component (a).
    The third component of the composition according to this invention is a t-alkyl hydroperoxide, which can be chosen from the group consisting of: t-butyl hydroperoxide (TBHP), t-amyl hydroperoxide (TAHP), t-hexyl hydroperoxide (TH HP), 1,1,3,3-tetramethylbutyl hydroperoxide (TOHP), paramenthane hydroperoxide (PMHP), 2,5-dimethyl-2,5-di-hydroperoxide (2,5-2,5) and mixtures of these. Preferably, the t-alkyl hydroperoxide is TAHP.
    The amount of component (c) in the composition of this invention is preferably in the range of 0.4 to less than 4 parts by weight, preferably 0.5 to 3.5, preferably 0.5 to 3 , more preferably 0.5 to 2 and even more preferably approximately 1 part by weight of at least one t-alkyl hydroperoxide per 100 parts by weight of component (b).
    The composition of the invention may further comprise a co-agent, which is not an organic peroxide.
    Advantageously, said co-agent comprises at least one carbamate, maleimide, acrylate, methacrylate or allyl functional group. Allyl carboxylates can be used, which can be selected from the group consisting of allyl, diallyl and triallyl types.
    Said co-agent can be chosen from the group consisting of divinylbenzene, diisopropenylbenzene, alpha-methylstyrene, alpha-methylstyrene dimer, ethylene glycol dimethacrylate, phenylene dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol dimethacrylate glycol, polyethylene glycol dimethacrylate 200, polyethylene glycol 400 dimethacrylate, 1,3-butanediol dimethacrylate, 1,4butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,12-dodecanediol dimethacrylate, 1,3-dimethacrylate glycerol, diurethane dimethacrylate, trimethylolpropane trimethacrylate, epoxy bisphenol A diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol 600 diacrylate, ethylene glycol diacrylate diethylene glycol diacrylate diacrylate diacrylate tetraethylene glycol, diacrylate neopentyl glycol ethoxylate, butanediol diacrylate, hexanediol diacrylate, aliphatic urethane diacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxylate triacrylate, propoxylate triacrylate triacrylacrylate triacrylacrylate aliphatic, trimethylolpropane triacrylate and dipentaerythritol pentaacrylate, triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), N, N'-m-phenylenedimaleimide, butadiene, chloroprene and isoprene.
    More preferably, the co-agent is chosen from the group consisting of: triallyl cyanurate, triallyl isocyanurate, N, N'-m-phenylenedimaleimide, triallyl trimellitate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, preferably is chosen from group consisting of: triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethylolpropane triacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA) and even more preferably is trimethylolpropane triacrylate (TMPTA).
    Said co-agent may be present from 0.05% to 30%, preferably from 0.1% to 10% by weight relative to the total weight of the composition.
    The main objective of using a co-agent in the composition of the present invention is to increase the rate of crosslinking. This co-agent also makes it possible to reduce the emission of residual gas during the decomposition of these same peroxides, and ultimately to reduce the number of bubbles in the encapsulation film.
    Preferably, the mass ratio of the organic peroxide and the crosslinking co-agent is in the range from: 10 to 10: 1, most preferably from 1: 3 to 3: 1.
    The composition of this invention may further include additives such as coupling agents, UV stabilizers, UV absorbers, fillers, plasticizers, flame retardants, antioxidants, dyes and mixtures thereof. Examples of coupling agents are monoalkyl titanates, (vinyl) trichlorosilanes and (vinyl) trialkoxysilanes. They can represent from 0.01 to 5% by weight relative to the weight of ethylene polymer. UV stabilizers can be selected from optical masked amine stabilizers (HALS), while UV absorbers can be selected, for example, from benzophenones, triazines and benzotriazoles. These compounds can represent from 0.01 to 3% by weight relative to the weight of ethylene polymer. Inorganic fillers such as silicon dioxide, alumina, talc, calcium carbonate can be added to increase mechanical strength, although nanoscale clays are preferred because of the transparency they impart. Examples of plasticizers are paraffinic or aromatic mineral oils, phthalates, azelates, adipates and the like. The antioxidants can be phenolic, phosphate or sulfur antioxidants. Alternatively, quinolines, such as 1,2dihydro-2,2,4-trimethylquinoline, can be used as an antioxidant.
    According to a preferred embodiment, the composition of this invention does not include any aromatic peroxide such as dicumyl peroxide.
    According to a preferred embodiment, the composition of the invention does not include any other peroxide than at least one monoperoxycarbonate (b) and at least one t-alkyl hydroperoxide (c).
    According to a preferred embodiment, the total amount of peroxide in the composition is less than 2 parts by weight per 100 parts by weight of component (a), more preferably less than 1.5 parts by weight per 100 parts by weight of component (at).
    More preferably, this composition consists of the constituents (a), (b) and (c) above and optionally at least one of the following additives: a coupling agent, a UV stabilizer, a UV absorber, a filler, a plasticizer, flame retardant, antioxidant, colorant, co-agent and mixtures thereof.
    According to another aspect, the description relates to a process for preparing the composition as defined above, said process comprising a step of mixing the above constituents (a), (b) and (c). Advantageously, said step is carried out in conventional devices such as continuous mixers and mixer-extruders, preferably at a temperature below the degradation temperature of the peroxides of the invention.
    It further relates to the use of a t-alkyl hydroperoxide to prevent the roasting of a curable composition comprising (a) at least one ethylene polymer, and (b) at least one monoperoxycarbonate, t hydroperoxide. -alkyl representing from 0.4 to less than 4 parts by weight per 100 parts by weight of component φ), preferably from 0.5 to 3.5, preferably from 0.5 to 3, more preferably from 0.5 to 2 and even more preferably approximately 1 part by weight of component (c) per 100 parts by weight of component (b).
    This invention further relates to a method of preventing roasting of a curable composition comprising (a) at least one ethylene polymer, and (b) at least one monoperoxycarbonate, comprising the step of adding at least one hydroperoxide. of t-alkyl in the composition, in an amount of 0.4 to less than 4 parts by weight per 100 parts by weight of component (b), preferably from 0.5 to 3.5, preferably from 0.5 to 3, more preferably from 0.5 to 2 and even more preferably approximately 1 part by weight of at least one t-alkyl hydroperoxide per 100 parts by weight of component (b).
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    In another aspect, the present invention relates to a method for manufacturing a material protected against roasting comprising an ethylene polymer, in particular for manufacturing a material protected against roasting chosen from the group consisting of: an encapsulation material or a sealing agent, in particular an encapsulating material or a solar cell sealing agent, wire and cable insulation, pipes and flexible pipes (including pipes for automobile radiators, potable water and underfloor heating, for example), roller coatings, rotary moldings and cellular articles, said method comprising a step a) of curing a composition as defined above. Preferably, said product is an encapsulation material or a solar cell sealant.
    Preferably, said curing step a) consists of a stratification step.
    Preferably, step a) is carried out at a temperature of 130 to 180 ° C., more preferably from 140 to 165 ° C.
    Preferably, said step a) lasts from 8 to 30 minutes, more preferably from 12 to 25 minutes.
    Preferably, said method comprises a preceding and / or simultaneous step a ’) chosen from the group consisting of molding, extrusion and injection of the composition as defined above. When the product is an encapsulation material or a solar cell sealant, said step is preferably an extrusion step.
    Step a ’) can be carried out so as to obtain a sheet having a thickness of 50 to 2000 μm, preferably from 100 to 1000 μm, for example.
    Said step a ’) can be carried out with a T-die extruder or alternatively a twin-screw extruder coupled to a two-roller mill.
    Preferably, step a ’) is carried out at a temperature of 80 to 150 ° C., more preferably from 90 to 120 ° C.
    Preferably, no crosslinking is obtained during step a ’).
    In a particular embodiment, steps a ’) and a) are carried out in a single step.
    According to another embodiment, the present invention relates to a method for manufacturing a photovoltaic module, said method comprising the step of pressing a laminate successively comprising:
    a front sheet (such as a glass sheet or a PMMA sheet), a sheet comprising the composition of the invention, at least one solar cell (preferably made of crystalline silicon or organic photovoltaic substances),
    - another sheet comprising the composition of the invention, and a support sheet (such as a multilayer PVDF / PET film or a glass sheet or a PMMA sheet).
    This laminate can then be pressed by conventional techniques, under heating and / or under vacuum, for example at a temperature of 130 to 180 ° C, more preferably from 140 to 165 ° C under vacuum, for a curing time which can be in the range of 8 to 30 minutes, for example 8 to 25 minutes. The composition of the invention can be crosslinked during this pressing step or thereafter. Preferably, the method comprises a single simultaneous step of pressing and hardening.
    In another aspect, the present invention relates to a material protected against roasting comprising an ethylene polymer obtainable by the process as defined above.
    Preferably, said material protected against roasting comprising an ethylene polymer is chosen from the group consisting of: an encapsulation material or a sealing agent, in particular an encapsulation material or a cell sealing agent solar, wire and cable insulation, pipes and hoses (including pipes for car radiators, potable water and underfloor heating, for example), roller coverings, rotational molding and cellular articles.
    More preferably, said screen-protected material comprising an ethylene polymer is a film, preferably an EVA film, and is more preferably an encapsulation material or a sealant, and even more preferably is a material encapsulation or a solar cell sealant.
    The material protected against roasting comprising an ethylene polymer of the invention has an improved crosslinking density of the ethylene polymer as well as a marked reduction, or even the absence, of roasting problems. This therefore makes it possible to obtain films without surface defect and which have good resistivity.
    According to another aspect, the invention relates to a photovoltaic module comprising the material protected against roasting, preferably the encapsulation material of solar cell, as defined above.
    This invention will appear more clearly on reading the following examples which are presented by way of illustration only and are not intended to limit the scope of the invention, which is defined by the appended claims.
    EXAMPLES
    Example 1: protective effect against toasting
    The compositions according to this invention are prepared by mixing an ethylene / vinyl acetate copolymer (EVA) (Cosmothene® EVA KA-40 containing 28% VA, supplied by SUMITOMO) with OO-t-amyl-O monoperoxycarbonate -2ethylhexyl (Luperox® TAEC marketed by Arkema) and tamyl hydroperoxide (Luperox® TAHP marketed by Arkema) in an internal Haake mixer at 35 ° C for 12 minutes, using a stirring speed of 50 rpm . The polymer mixture is then passed through an open mill set at 60 ° C to produce sheets about 2mm thick.
    Samples of about 2 to 3 g of the above compositions are deposited in a plate on a mobile die rheometer (MDR) supplied by GOTECH, which is capable of measuring the curing properties of the samples and includes software to analyze the results. Each of the samples is placed in a temperature-controlled cavity between two dies, the lower of which oscillates so as to apply a cyclic stress or deformation to the sample while the upper die is connected to a torque sensor to measure the response of sample torque at deformation. The stiffness is recorded continuously as a function of time. The rigidity of the sample increases as vulcanization occurs.
    This device is capable of providing, among other things, calculated values of ML (minimum torque), MH (maximum torque), te 10 (time before 10% hardening state) and tc90 (time before 90% hardening state) hardening) as defined by international standards (ASTM D5289 and ISO 6502).
    The MDR is operated at 115 ° C and 145 ° C with an oscillation amplitude (degree of deformation) of 0.5 ° applied to the sample for 30 min. The roasting time is defined as the time necessary to reach 10% of the total hardening, i.e. tclO.
    This test is carried out on the following samples, in which the amounts of monoperoxycarbonate are indicated in parts per hundred parts of EVA resin (phr) and the quantities of TAHP in parts by weight per 100 parts by weight of monoperoxycarbonate:
    TAEC TAHP/ TAEC(m / m) MH (dN, m) to115 ° C MH-ML(dN, m) to145 ° C tclO (m: s) to145 ° C tc90 (m: s)at 145 ° C 0.5 phr 0.02% 1.27 1.8 1:03 8:52 0.5 phr 0.4% 1.17 1.82 1:05 8:58 0.5 phr 0.98% 1.15 1.86 1:07 9:21 0.5 phr 1.38% 1.06 1.82 1:09 9:27 0.5 phr 2% 0.63 1.8 1:17 9:31 0.5 phr 4% 0.35 1.74 1:43 9:43 0.5 phr 5% 0.32 1.60 2:31 10:58 0.7 phr 0.02% 1.45 2.02 0:56 9:50 a.m. 0.7 phr 0.2% 1.41 1.99 1:00 10:00 0.7 phr 0.98% 1.31 1.96 1:05 10:10 0.7 phr 2% 1 1.96 1:12 10:18 0.7 phr 4% 0.37 1.91 1:40 10:42 1 phr 0.02% 1.68 2.22 0:55 10:48 lphr 0.2% 1.63 2.24 0:56 10:56 lphr 0.98% 1.53 2.19 1:00 10:48 1 phr 2% 1.24 2.21 1:09 11:24 1 phr 4% 0.43 2.13 1:33 11:45 am 1 phr 5% 0.42 1.85 1:45 1:30 p.m.
    Table 1
    From this table, it can be observed that TAHP acts as a protective agent against roasting since the roasting time (tclO) increases with the amount of TAHP. When the amount of TAHP is less than 0.4% by weight relative to TAEC, crosslinking even begins at 115 ° C (see MH values), which is not desired. However, a strong increase in the crosslinking time (tc90) is observed, and therefore a lower crosslinking speed, when the amount of TAHP reaches 4% by weight relative to TAEC and also a crosslinking density (HD) weaker. At TAHP values of less than 4% by weight relative to TAEC, the mesh is effectively prevented while maintaining a high crosslinking rate (tc90) and a good crosslinking density (MH-ML).
    Example 2:
    The test is carried out under the same conditions as for Example 1, except that a mixture of 20% of O, O-tert-butyl-O- (2ethylhexyl) monoperoxycarbonate (TBEC) and 80% of O, O-tert-amyl-O- (2ethylhexyl) monoperoxycarbonate (TAEC) is used in place of TAEC alone. The results are presented in Table 2 below:
    TAEC +TBEC TAHP/ (TAEC +TBEC)(m / m) MH (dN-m)at 115 ° C MH-ML(dN-m) to145 ° C tclO (m: s) to145 ° C tc90 (m: s) to145 ° C 0.5 phr 0.2% 1.35 1.87 0:58 9:57 0.5 phr 0.6% 1.15 1.88 1:08 10:06 0.5 phr 1% 0.96 1.89 1:14 10:19 0.5 phr 2% 0.56 1.88 1:22 10:18 0.5 phr 4% 0.36 1.84 1:48 11:06 0.7 phr 0% 1.65 2.1 0:58 10:31 0.7 phr 0.2% 1.6 2.03 1:04 10:42 0.7 phr 0.6% 1.38 1.99 1:07 10:55 0.7 phr 1% 1.07 1.98 1:12 11:12 0.7 phr 2% 0.65 1.97 1:21 11:26 0.7 phr 4% 0.41 1.95 1:44 12:14 1 phr 0% 1.6 2.28 0:55 11:36 1 phr 0.2% 1.58 2.26 0:58 11:45 am 1 phr 0.6% 1.37 2.25 1:01 11:57 1 phr 1% 1.24 2.24 1:05 12:12 1 phr 2% 0.81 2.22 1:16 12:25 1 phr 4% 0.38 2.19 1:41 13:10
    Table 2
    As in the previous example, there is a sharp increase in the crosslinking time (tc90), when the latter reaches 4% by weight compared to TAEC + TBEC.
    Example 3:
    The test is carried out under the same conditions as for example 1, with the exception that a mixture of 50% of monoperoxycarbonate of O, O-tert-butyl-O- (2ethylhexyl) (TBEC) and 50 % O, O-tert-amyl-O- (210 ethylhexyl) monoperoxycarbonate (TAEC) is used in place of TAEC alone. The results are presented in Table 3 below:
    TAEC +TBEC TAHP /(TAEC +TBEC)(m / m) MH (dN, m) to115 ° C MH-ML ·(dN, m) to145 ° C tclO (m: s) to145 ° C tc90 (m: s) to145 ° C 0.5 phr 0% 1.30 1.83 0:58 9:16 0.5 phr 1% 1.02 1.87 1:10 9:36 0.5 phr 4% 0.36 1.81 1:40 10:21 0.7 phr 0% 1.45 1.99 0:58 9:55 a.m. 0.7 phr 0.6% 1.29 1.97 1:03 10:03 0.7 phr 1% 1.19 1.92 1:15 10:17 0.7 phr 4% 0.36 1.88 1:42 10:47 1 phr 0% 1.65 2.28 0:58 11:12 1 phr 0.6% 1.49 2.23 1:02 11:18 1 phr 1% 1.4 2.22 1:08 11:21 1 phr 4% 0.41 2.13 1:33 11:56
    Table 3
    As for the previous examples, a strong increase in the crosslinking time (tc90) is observed, when the latter reaches 4% by weight relative to TAEC + TBEC.
    Example 4:
    The test is carried out under the same conditions as for Example 1, with the exception that Lup @ TBHP (tert-butyl hydroperoxide) is used in place of TAHP. The results are presented in Table 4 below:
    TAEC TBHP/ TAEC(m / m) MH (dN, m) to115 ° C MH-ML(dN, m) to145 ° C tclO (m: s) to145 ° C tc90 (m: s)at 145 ° C 0.5 phr 0.02% 1.25 1.79 1:02 8:50 am 0.5 phr 0.4% 1.18 1.83 1:06 8:55 0.5 phr 1% 1.17 1.86 1:07 9:21 0.5 phr 2% 0.62 1.81 1:19 9:35 0.5 phr 4% 0.37 1.75 1:45 9:59 0.5 phr 5% 0.31 1.59 2:35 10:59 0.7 phr 0.02% 1.44 2.01 0:57 9:52 0.7 phr 0.2% 1.40 1.97 1:02 10:05 0.7 phr 1% 1.30 1.96 1:06 10:10 0.7 phr 2% 1.02 1.95 1:15 10:20 0.7 phr 4% 0.36 1.93 1:45 10:45 am 1 phr 0.02% 1.65 2.21 0:55 10:45 am 1 phr 0.2% 1.62 2.25 0:57 10:58 1 phr 1% 1.53 2.18 1:02 10:46 1 phr 2% 1.25 2.20 1:08 11:25 1 phr 4% 0.42 2.14 1:32 11:42 1 phr 5% 0.40 1.82 1:43 13:28
    Table 4
    As for the previous examples, a strong increase in the crosslinking time (tc90) is observed, when the amount of TBHP reaches 4% by weight relative to pure TAEC.
    Example 5:
    The test is carried out under the same conditions as for Example 4, except that a mixture of 20% of monoperoxycarbonate of O, O-tert-butyl-O- (2ethylhexyl) (TBEC) and 80 % of O, O-tert-amyl-O- (2ethylhexyl) monoperoxycarbonate (TAEC) is used in place of TAEC alone. The results are presented in Table 5 below:
    TAEC +TBEC TBHP/ (TAEC +TBEC)(m / m) MH (dN-m)at 115 ° C MH-ML(dN-m) to145 ° C tclO (m: s) to145 ° C tc90 (m: s) to145 ° C 0.5 phr 0.2% 1.32 1.89 0:57 9:56 0.5 phr 0.6% 1.16 1.88 1:05 10:05 0.5 phr 1% 0.95 1.88 1:12 10:12 0.5 phr 2% 0.55 1.88 1:23 10:15 am 0.5 phr 4% 0.37 1.85 1:47 11:08 0.7 phr 0% 1.62 2.1 0:58 10:31 0.7 phr 0.2% 1.61 2.01 1:02 10:40 0.7 phr 0.6% 1.42 1.99 1:09 10:54 0.7 phr 1% 1.12 1.98 1:15 11:13 0.7 phr 2% 0.7 1.98 1:20 11:25 0.7 phr 4% 0.45 1.94 1:41 12:12 1 phr 0% 1.61 2.27 0:54 11:36 1 phr 0.2% 1.59 2.25 0:59 11:47 1 phr 0.6% 1.38 2.26 1:02 11:55 1 phr 1% 1.26 2.23 1:04 12:13 lphr 2% 0.85 2.23 1:15 12:24 1 phr 4% 0.40 2.20 1:42 1:15 p.m.
    Table 5
    As for the previous examples, a strong increase in the crosslinking time (tc90) is observed, when the amount of TBHP reaches 4% by weight relative to
    TAEC + TBEC.
    Example 6:
    The test is carried out under the same conditions as for Example 4, except that a mixture of 50% of O, O-tert-butyl-O- (2ethylhexyl) monoperoxycarbonate (TBEC) and 50% of O, O-tert-amyl-O- (2ethylhexyl) monoperoxycarbonate (TAEC) is used in place of TAEC alone. The results are presented in Table 6 below:
    TAEC +TBEC TBHP /(TAEC +TBEC)(m / m) MH (dN, m) to115 ° C MH-ML(dN, m) to145 ° C tclO (m: s) to145 ° C tc90 (m: s) to145 ° C 0.5 phr 0% 1.25 1.85 0:55 9:15 a.m. 0.5 phr 1% 1.05 1.82 1:12 9:38 0.5 phr 4% 0.35 1.78 1:41 10:22 0.7 phr 0% 1.41 1.98 0:57 9:51 a.m. 0.7 phr 0.6% 1.32 1.96 1:05 10:00 0.7 phr 1% 1.21 1.93 1:16 10:16 0.7 phr 4% 0.39 1.87 1:45 10:52 1 phr 0% 1.66 2.27 0:57 11:10 1 phr 0.6% 1.48 2.24 1:02 11:18 1 phr 1% 1.37 2.23 1:09 11:20 1 phr 4% 0.42 2.10 1:35 11:59
    Table 6
    As for the previous examples, a strong increase in the crosslinking time (tc90) is observed, when the amount of TBHP reaches 4% by weight relative to TAEC + TBEC.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. Curable composition comprising:
    (a) at least one ethylene polymer, (b) less than 2 parts by weight of at least one monoperoxycarbonate per 100 parts by weight of component (a), (c) from 0.4 to less than 4 parts by weight of at least one t-alkyl hydroperoxide per 100 parts by weight of component (b).
    [2" id="c-fr-0002]
    2. Composition according to claim 1, in which the ethylene copolymer is an ethylene / vinyl acetate copolymer.
    [3" id="c-fr-0003]
    3. Composition according to any one of claims 1 and 2, in which the monoperoxycarbonate is an OO-t-alkyl-O-alkyl monoperoxycarbonate.
    [4" id="c-fr-0004]
    4. Composition according to claim 3, in which the OO-t-alkyl-O-alkyl monoperoxycarbonate is chosen from the group consisting of: OO-t-butyl-O-2-ethylhexyl monoperoxycarbonate (TBEC), OO monoperoxycarbonate -t-butyl-O-2isopropyl (TBIC), OO-t-amyl-O-2-ethylhexyl monoperoxycarbonate (TAEC), OO-t-amyl-O-2-isopropyl monoperoxycarbonate (TAIC) and mixtures thereof , preferably is chosen from the group consisting of: TAEC, TBEC and a mixture thereof.
    [5" id="c-fr-0005]
    5. Composition according to any one of the preceding claims, in which the monoperoxycarbonate is from 0.1 to less than 2 parts by weight, preferably from 0.2 to 1.5, more preferably from 0.3 to 1, more preferably from 0.4 to 0.8, more preferably 0.4 to 0.7 and even more preferably about 0.5 parts by weight, per 100 parts by weight of component (a).
    [6" id="c-fr-0006]
    6. Composition according to any one of the preceding claims, in which T t-alkyl hydroperoxide is chosen from the group consisting of:
    t-butyl hydroperoxide (TBHP), t-amyl hydroperoxide (TAHP), t-hexyl hydroperoxide (THHP), 1,1,3,3-tetramethylbutyl hydroperoxide (TOHP), paramenthane hydroperoxide (PMHP), 2 , 5-dimethyl-2,5dihydroperoxide (2,5-2,5) and mixtures thereof, preferably said t-alkyl hydroperoxide being TAHP.
    [7" id="c-fr-0007]
    7. Composition according to any one of the preceding claims, which comprises from 0.5 to 3.5, preferably from 0.5 to 3, more preferably from 0.5 to 2 and even more preferably approximately 1 part by weight of component (c) per 100 parts by weight of component (b).
    [8" id="c-fr-0008]
    8. Composition according to any one of the preceding claims, which further comprises a co-agent, preferably chosen from the group consisting of: triallyl cyanurate, triallyl isocyanurate, N, N'-m-phenylenedimaleimide, triallyl trimellitate , trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, preferably chosen from the group consisting of: triallyl cyanurate, triallyl isocyanurate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, and even more preferably is trimethylolpropane triacrylate.
    [9" id="c-fr-0009]
    9. Use of a t-alkyl hydroperoxide to prevent roasting of a curable composition comprising (a) at least one ethylene polymer, and (b) at least one monoperoxycarbonate, in which t-alkyl hydroperoxide represents from 0.4 to less than 4 parts by weight per 100 parts by weight of component (b), preferably from 0.5 to 3.5, preferably from 0.5 to 3, more preferably from 0.5 to 2 and even more preferably approximately 1 part by weight of component (c) per 100 parts by weight of component (b).
    [10" id="c-fr-0010]
    10. A method of preventing the roasting of a curable composition comprising (a) at least one ethylene polymer, and (b) at least one monoperoxycarbonate, comprising the step of adding at least one t-alkyl hydroperoxide in the composition, in an amount of 0.4 to less than 4 parts by weight per 100 parts by weight of component (b), preferably from 0.5 to 3.5, preferably from 0.5 to 3, more preferably from 0.5 to 2 and even more preferably approximately 1 part by weight of component (c) per 100 parts by weight of component (b).
    [11" id="c-fr-0011]
    11. Method for manufacturing a material protected against roasting comprising an ethylene polymer, in particular for manufacturing a material protected against roasting chosen from the group consisting of: an encapsulation material or a sealing agent, especially encapsulating material or sealant for solar cell, wire and cable insulation, pipes and flexible pipes (including pipes for automobile radiators, potable water and underfloor heating, for example), roller coatings, rotational molding and cellular articles, said method comprising a step a) of curing a composition as defined according to any one of claims 1 to 8.
    [12" id="c-fr-0012]
    12. The method of claim 11, which comprises a preceding and / or simultaneous step a ’) chosen from the group consisting of: molding, extrusion and injection of the composition as defined in any one of claims 1 to 8.
    [13" id="c-fr-0013]
    13. The method of claim 12, wherein step a ’) is carried out at a temperature of 80 to 150 ° C, more preferably 90 to 120 ° C.
    [14" id="c-fr-0014]
    14. Material protected against roasting comprising an ethylene polymer obtainable by the process as defined in any one of claims 10 to 13.
    [15" id="c-fr-0015]
    15. Photovoltaic module comprising the material protected against roasting, preferably the solar cell encapsulation material, as defined in claim 14.
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    同族专利:
    公开号 | 公开日
    ES2744082T3|2020-02-21|
    US10597521B2|2020-03-24|
    JP2019529630A|2019-10-17|
    WO2018046700A1|2018-03-15|
    EP3448925A1|2019-03-06|
    FR3055629B1|2018-08-17|
    EP3587483A1|2020-01-01|
    EP3448925B1|2019-08-07|
    CN109642064A|2019-04-16|
    US20190194434A1|2019-06-27|
    KR20190054063A|2019-05-21|
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    法律状态:
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    2018-03-09| PLSC| Publication of the preliminary search report|Effective date: 20180309 |
    2018-08-13| PLFP| Fee payment|Year of fee payment: 3 |
    2019-08-15| PLFP| Fee payment|Year of fee payment: 4 |
    2021-06-11| ST| Notification of lapse|Effective date: 20210506 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1658362|2016-09-08|
    FR1658362A|FR3055629B1|2016-09-08|2016-09-08|CURABLE COMPOSITION COMPRISING ETHYLENE POLYMER, MONOPEROXYCARBONATE AND T-ALKYL HYDROPEROXIDE|FR1658362A| FR3055629B1|2016-09-08|2016-09-08|CURABLE COMPOSITION COMPRISING ETHYLENE POLYMER, MONOPEROXYCARBONATE AND T-ALKYL HYDROPEROXIDE|
    US16/330,804| US10597521B2|2016-09-08|2017-09-08|Curable composition comprising an ethylene polymer, a monoperoxycarbonate and a t-alkyl hydroperoxide|
    PCT/EP2017/072659| WO2018046700A1|2016-09-08|2017-09-08|CURABLE COMPOSITION COMPRISING AN ETHYLENE POLYMER, A MONOPEROXYCARBONATE AND A t-ALKYL HYDROPEROXIDE|
    ES17761547T| ES2744082T3|2016-09-08|2017-09-08|Curable composition comprising an ethylene polymer, a monoperoxycarbonate and a t-alkyl hydroperoxide|
    EP17761547.3A| EP3448925B1|2016-09-08|2017-09-08|Curable composition comprising an ethylene polymer, a monoperoxycarbonate and a t-alkyl hydroperoxide|
    KR1020197006735A| KR20190054063A|2016-09-08|2017-09-08|A curable composition comprising an ethylene polymer, monoperoxycarbonate and t-alkyl hydroperoxide|
    CN201780054981.XA| CN109642064A|2016-09-08|2017-09-08|Curable compositions comprising ethene polymers, single peroxy carbonates and tert-alkyl peroxy hydrogen|
    EP19188377.6A| EP3587483A1|2016-09-08|2017-09-08|Curable composition comprising an ethylene polymer, a monoperoxycarbonate and a t-alkyl hydroperoxide|
    JP2019513374A| JP2019529630A|2016-09-08|2017-09-08|Curable composition comprising ethylene polymer, monoperoxycarbonate, and t-alkyl hydroperoxide|
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