EP3481893A1 - Durcissement accéléré de résines polymères insaturées - Google Patents

Durcissement accéléré de résines polymères insaturées

Info

Publication number
EP3481893A1
EP3481893A1 EP17735163.2A EP17735163A EP3481893A1 EP 3481893 A1 EP3481893 A1 EP 3481893A1 EP 17735163 A EP17735163 A EP 17735163A EP 3481893 A1 EP3481893 A1 EP 3481893A1
Authority
EP
European Patent Office
Prior art keywords
curing
free
mercaptans
resins
petmp
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17735163.2A
Other languages
German (de)
English (en)
Inventor
Martin Kunz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
United Initiators GmbH and Co KG
Original Assignee
United Initiators GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by United Initiators GmbH and Co KG filed Critical United Initiators GmbH and Co KG
Publication of EP3481893A1 publication Critical patent/EP3481893A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • the invention relates to the cold and hot curing of unsaturated polymer resins, such as polyester resins and methyl methacrylate resins using mercaptans as reaction accelerators.
  • Unsaturated polymer resins contain olefinic double bonds in the main chain which enable copolymerization reactions.
  • reaction resins For processing, they are prepared in a copolymerizable monomer, e.g. Styrene, ⁇ -methylstyrene or methyl methacrylate, dissolved.
  • a copolymerizable monomer e.g. Styrene, ⁇ -methylstyrene or methyl methacrylate
  • an initiator and accelerator hardened, three-dimensionally crosslinked thermosets are formed by free-radical polymerization.
  • the initiators used are generally organic peroxides together with accelerators. Typical examples are diacyl peroxides such as dibenzoyl peroxide in combination with a tertiary amine such as dimethylaniline or diethoxy-p-toluidine as accelerator. Other commonly used systems currently in use at room temperature (cold curing) include ketone peroxides together with a cobalt-containing accelerator (such as methyl ethyl ketone peroxide and cobalt octoate) and cobalt-amine combinations.
  • a hot and hot curing of unsaturated polyester resins (UP resins) is carried out in the temperature range of about 40 ° C to 150 ° C. In many cases no accelerator is added.
  • accelerators and optionally a promoter can also be added here (PH Seiden, Glasmaschineverbecke Kunststoffe, Springer-Verlag 1967, page 1 18). Promoters are compounds that are not used as accelerators alone, but Activate systems of peroxides and accelerators additionally.
  • the accelerators especially the compounds containing heavy metals, such as the cobalt salts, have recently come under fire because of their toxicity.
  • Mercaptans have also been used occasionally as accelerators, but only with a weak effect (Seiden, page 129).
  • mercaptans have hitherto generally been used in combination with metal salts.
  • metals and especially heavy metals and their salts are undesirable because of their toxicity.
  • the invention therefore relates, in a first aspect, to a process for curing an unsaturated polymer resin comprising free radical polymerization of the unsaturated polymer resin with one or more co-polymerizable monomers in the absence of heavy metals and heavy metal salts using an initiator system containing one or more organic peroxides and one or more mercaptans.
  • Unsaturated polymer resins in the context of the invention are in particular unsaturated polyester resins, methyl methacrylate resins and vinyl ester resins.
  • the curing of orthophthalic acid-based unsaturated polyester resins can be accelerated particularly well by mercaptans.
  • the curing of unsaturated polymer resins is carried out in the absence of heavy metals and heavy metal salts.
  • heavy metal in the context of the invention refers to a metal whose density is greater than 5.0 g / cm 2. These include, in particular, the noble metals and bismuth, iron, copper, lead, zinc, tin, cobalt, nickel, cadmium
  • the expression "in the absence of” is to be understood as meaning that no heavy metals or heavy metal salts, and preferably no metals and metal salts, are added to the reaction system.
  • the amount of heavy metals or heavy metal salts or of metals and metal salts as a whole in the reaction system is preferably less than 50 ppm, preferably less than 10 ppm or less than 5 ppm. Particularly preferred are amounts of less than 1 ppm or the complete absence of heavy metals or heavy metal salts, ie 0 ppm (in each case based on the total amount of solids in the reaction system). Particularly preferred is a total amount of metals and metal salts of less than 1 ppm or 0 ppm.
  • the inventive curing of unsaturated polymer resins preferably takes place in the absence of tertiary amines, more preferably in the absence of any amines. It has also been found that mercaptans alone, without the additional use of amines, are able to accelerate the free-radical polymerization with organic peroxides as initiators.
  • the amount of amines in the reaction system is preferably less than 50 ppm, more preferably less than 10 ppm or less than 5 ppm. Particularly preferred are amounts of less than 1 ppm or the complete absence of amines, ie 0 ppm (in each case based on the total amount of solids in the reaction system).
  • mercaptans are suitable both for the cold and for the hot curing of unsaturated polymer resins by free-radical Polymerization. It has been found that by using mercaptans as accelerators, the application temperatures of peroxides can be reduced both during cold curing and during hot curing.
  • a hot curing according to the invention is preferably carried out at a temperature in the range of about 40-150 ° C.
  • a cold curing is preferably carried out at a temperature of less than 40 ° C, in particular in the range of about 18-35 ° C, preferably about 20-30 ° C.
  • Low temperatures are particularly advantageous in applications such as sewer rehabilitation, manual lamination, and fully automated processes such as the production of plane plates. They lead to energy savings and to avoid losses of volatile monomer components such as e.g. Styrene.
  • the curing of an unsaturated polymer resin according to the invention comprises a free-radical polymerization using an initiator system which comprises one or more organic peroxides.
  • an initiator system which comprises one or more organic peroxides.
  • any peroxides can be accelerated by combination with one or more mercaptans.
  • organic peroxides and peroxide combinations are cumyl hydroperoxide (CUHP), dicumyl peroxide (DCUP), terf-butyl peroxy-2-ethylhexanoate (TBPEH), tert-butyl peroxy-3,5,5-trimethylhexanoate (TBPIN), also in solution with acetylacetone, terf Butyl peroxybenzoate (TBPB), also in solution with acetylacetone, dilauroyl peroxide (LP), bis (4-tert-butylcyclohexyl) peroxydicarbonate (BCHPC), dimyristyl peroxydicarbonate (MYPC), tert-butyl peroxy-2-ethylhexyl carbonate (TBPEHC) and 2, 5-dimethyl-2,5-di (terf-butylperoxy) -hexane (DHBP), methyl isobutyl ketone peroxide (MIKP)
  • Combinations of peroxides in particular combinations of two or more of the abovementioned organic peroxides can be accelerated, such as BCHPC and MYPC.
  • An advantage of the use of mercaptans in the context of the invention is their significantly lower toxicity in comparison to the previously frequently used cobalt compounds, in particular cobalt octoate.
  • the mercaptans are water-clear, non-discoloring mercaptans. This results in a significant reduction in additives of covering pigments such as titanium dioxide, which is particularly advantageous for white gel coats and white artificial stone.
  • Mercaptans are practically miscible with the other components of the radical polymerization system. In particular, the miscibility with various monomers such as methyl methacrylate, unsaturated polyester resins and vinyl ester resins or solvents such as esters, alcohols and aromatics is very good.
  • mercaptans glycol dimercaptoacetate GDMA
  • PTMP pentaerythritol tetrakis (3-mercaptopropionate)
  • PMTMA pentaerythritol tetrakis (2-mercaptoacetate)
  • IOTG isooctyl thioglycolate
  • an initiator system is used which comprises the mercaptan IOTG and the organic peroxide BCHPC or PETMP and MIKP.
  • any copolymerizable monomers can be used for the inventive curing of an unsaturated polymer resin.
  • co-polymerisable monomers are particularly suitable Styrene and allyl ester.
  • (meth) acrylic esters such as methyl methacrylate or substituted styrenes such as in particular tert-butylstyrene.
  • Mixtures of two or more of the abovementioned co-polymerisable monomers or mixtures with other comonomers are also possible.
  • the invention relates to the use of one or more mercaptans as accelerators for the curing of unsaturated polymer resins in a heavy metal salt-free reaction system.
  • one or more mercaptans as accelerators for the curing of unsaturated polymer resins in a heavy metal salt-free reaction system.
  • the invention also provides a composition comprising an unsaturated polymer resin, one or more mercaptans and one or more organic peroxides.
  • Heavy metals and heavy metal salts are not included in the composition.
  • no metals or metal salts are included as defined above.
  • the composition contains no tertiary amines, more preferably no amines, as defined above.
  • the composition according to the invention consists of one or more unsaturated polymer resins, one or more mercaptans and one or more organic peroxides.
  • the composition according to the invention consists of one or more mercaptans, one or more organic peroxides and one or more copolymerizable monomers.
  • the invention relates to a kit comprising
  • a heavy metal and heavy metal free initiator system comprising one or more organic peroxides and one or more mercaptans
  • kits of the invention may be part of the kit of the invention.
  • the kit according to the invention is free of heavy metals and heavy metal salts, preferably free of any metals and metal salts as defined above. More preferably, the kit of the invention also contains no tertiary amines, more preferably no amines as defined above.
  • unsaturated polymer resins, copolymerizable monomers, organic peroxides and mercaptans reference is made to the preceding part of the description.
  • the invention therefore further provides a pre-accelerated resin.
  • This is a composition comprising an unsaturated polymer resin and one or more mercaptans as defined above, but not peroxides.
  • the composition according to the invention preferably comprises no further solvents. Heavy metals and heavy metal salts are not included in the composition. Preferably, no metals or metal salts are included as defined above. Further preferably, the composition contains no tertiary amines, more preferably no amines, as defined above.
  • the composition according to the invention consists of one or more unsaturated polymer resins and one or more mercaptans.
  • the composition according to the invention consists of one or a plurality of unsaturated polymer resins, one or more mercaptans, and one or more co-polymerizable monomers.
  • Figure 1 shows the cure for the implementation of an ortho-phthalic acid-based unsaturated polyester resin (Palatal P4) with 1% BCHPC at a slightly elevated temperature of 40 ° C in the presence of various mercaptans.
  • Figure 2 shows the cure for the cold curing of Palatal P4 at a temperature of 25 ° C using the organic peroxide BCHPC (2%) in the presence of various mercaptans.
  • FIG. 3 shows the hardening course for the curing of Palatal P4 at a slightly elevated temperature of 40 ° C. using 1% CUROX® I-300 (MIKP) in the presence of various mercaptans and cobalt octoate as comparative example.
  • MIKP 1% CUROX® I-300
  • FIG. 4 shows the curing curve for the hot curing of Palatal P4 at 100 ° C. using 1% TBPB-HA-M3 in combination with the mercaptan PETMP or cobalt octoate as comparative example.
  • FIG. 5 shows the curing curve for the hot curing of Palatal P4 at 80 ° C. using 1.5% CUHP (80% strength solution) in combination with the mercaptan PETMP or with cobalt octoate and dimethylaniline (cobalt / amine) as comparative example.
  • FIG. 6 shows the curing curve for the hot curing of Palatal P4 at 100 ° C. using 1% TBPIN in combination with the mercaptan PETMP or 0.5% cobalt octoate as comparative example.
  • FIG. 7 shows a graph of the curing curve for the hot curing of Palatal P4 at 100 ° C.
  • FIG. 10 shows the heat curing of Palatal P4 at 100 ° C.
  • DHBP 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane
  • PETMP 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane
  • PETMP 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane
  • PETMP 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane
  • PETMP 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane
  • PETMP 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane
  • PETMP 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane
  • PETMP 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane
  • FIG. 11 shows the curing curve for the hot curing of Palatal P4 with BCHPC alone or in combination with MYPC at 60 ° C. Curing was investigated with and without the addition of 0.1% PETMP as accelerator.
  • FIG. 12 shows the course of cure for the methyl methacrylate resin Degadur 1008 when using 1% TBPEH alone or in combination with the mercaptans PETMP, IOTG or GDMA, in each case 1.0%.
  • FIG. 13 shows the curing curve for the thermosetting of the vinyl ester resin Derakane 41 1 -350 using BCHPC alone or in combination with the mercaptans PETMP, IOTG or GDMA.
  • FIG. 14 shows the cure for the cold curing of Palatal P6 at a temperature of 25 ° C. using the organic peroxide TAPEH in different concentrations (0.5%, 0.8%, 1, 0%, 1, 5% and 2, 0%) in the presence of the mercaptan PETMP (0.05% thiocure PETMP, 50% in Rhodiasolv).
  • Figure 15 shows the cure for the cure of Palatal P4 at a slightly elevated temperature of 40 ° C using 1% BCHPC in the presence of the mercaptan PETMP at a concentration of 0.2% or 0.5%.
  • the combination of 1% BCHPC with 0.2% or 0.5% cobalt octoate Co-1 is shown.
  • the alternative accelerators GDMA, PETMP and IOTG were used as 10% solutions in ethyl acetate to allow a more accurate dosage.
  • Thiocure PETMP was used as a 50% solution in Rhodiasolv.
  • the orthophthalic resin used was a medium-reactivity standard resin Palatal P4 or P6 from DSM.
  • the methyl methacrylate used was Degadur 1008 from Evonik and the vinyl ester resin used was Derakane 41 1 -350 from Ashland.
  • the percentages relate to weight ratios (w / w).
  • the quantity refers to the amount of peroxide added to the 100% resin.
  • the dosing also refers to the amount of accelerator solution added to the 100% resin. 1. Cold hardening or curing at slightly elevated temperatures (40 ° C) of orthophthalic resins
  • MIKP methyl isobutyl ketone peroxide
  • PETMP was used as a 50% solution in Rhodiasolv (methyl 5- (dimethylamino) -2-methyl-5-oxopentanoate).
  • Rhodiasolv methyl 5- (dimethylamino) -2-methyl-5-oxopentanoate. The example shows that as the amount of peroxide increases, the curing rate increases while the amount of PETMP remains the same. The results are shown in FIG.
  • PETMP was used as a 10% solution in ethyl acetate.
  • the example shows that the addition of the cobalt accelerator Co-1 hardly increases the curing rate when using BCHPC, while even small amounts of the mercaptan PETMP cause a significant increase in the curing rate.
  • the results are shown in FIG.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerization Catalysts (AREA)

Abstract

La présente invention concerne le durcissement à froid et à chaud de résines polyester insaturées telles que des résines polyester et des résines de méthylméthacrylate par utilisation de mercaptans en tant qu'accélérateurs de réaction.
EP17735163.2A 2016-07-08 2017-07-07 Durcissement accéléré de résines polymères insaturées Withdrawn EP3481893A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16178671 2016-07-08
PCT/EP2017/067060 WO2018007576A1 (fr) 2016-07-08 2017-07-07 Durcissement accéléré de résines polymères insaturées

Publications (1)

Publication Number Publication Date
EP3481893A1 true EP3481893A1 (fr) 2019-05-15

Family

ID=56408997

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17735163.2A Withdrawn EP3481893A1 (fr) 2016-07-08 2017-07-07 Durcissement accéléré de résines polymères insaturées

Country Status (4)

Country Link
US (1) US10858477B2 (fr)
EP (1) EP3481893A1 (fr)
IL (1) IL264135B (fr)
WO (1) WO2018007576A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11873381B2 (en) 2018-02-19 2024-01-16 Arkema Inc. Accelerated peroxide-cured resin compositions having extended open times

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1093374B (de) * 1955-07-18 1960-11-24 American Cyanamid Co Verfahren zur Herstellung von Hydroxylgruppen enthaltenden Benzophenonaethern
US3959103A (en) * 1971-02-24 1976-05-25 W. R. Grace & Co. Photocuring of unsaturated polyester/polythiol compositions
DE3620149A1 (de) 1986-06-14 1987-12-17 Roehm Gmbh Geruchsarmes wasserloesliches polymerisat oder copolymerisat, seine herstellung und verwendung
WO1990012826A1 (fr) * 1989-04-26 1990-11-01 Akzo N.V. Cocatalyseurs de polymerisation a base de composes thioliques
US5972272A (en) * 1994-06-30 1999-10-26 Nippon Zeon Co., Ltd. Unsaturated polyester resin composition and process for molding the composition
CA2266054A1 (fr) 1996-09-13 1998-03-19 Mohammad W. Katoot Nouveaux additifs polymeres pour la formation d'objets
KR100900138B1 (ko) 2007-02-08 2009-06-01 주식회사 엘지화학 알칼리 가용성 수지, 이의 제조방법 및 상기 알칼리 가용성수지를 포함하는 감광성 수지 조성물
CN103975031A (zh) * 2011-12-06 2014-08-06 帝斯曼知识产权资产管理有限公司 树脂组合物
EP2957577B1 (fr) 2014-06-19 2019-11-27 3M Innovative Properties Company Compositions d'adhésif autocollant durcissable

Also Published As

Publication number Publication date
IL264135B (en) 2022-04-01
WO2018007576A1 (fr) 2018-01-11
US20190202979A1 (en) 2019-07-04
IL264135A (en) 2019-02-28
US10858477B2 (en) 2020-12-08

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