# US 10,500,339 B2 · Impregnation process for a fibrous substrate, a liquid monomer syrup for the impregnation process, its method of polymerization and structured article obtained thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,500,339 B2 - Document ID: US10500339B2 - Status: Granted - Kind: B2 - Application number: 15/113,206 - Filed: 2015-01-22 - Published: 2017-01-12 - Granted: 2019-12-10 - Earliest claimed: 2014-01-22 - Assignees: Arkema France - Applicants: Arkema France - Inventors: Pierre Gerard; Michel Glotin; Sebastien Taillemite - Web page: https://patentgrep.com/patent/US10500339B2 ## CPC - A61M 5/282: {by compression of deformable ampoule or carpule wall} - C08J 5/042: {with carbon fibres} - A61J 1/067: {Flexible ampoules, the contents of which are expelled by squeezing} - A61J 1/1468: {Containers characterised by specific material properties} - B29C 45/02: Transfer moulding, i.e. transferring the required volume of moulding material by a plunger from a "shot" cavity into a mould cavity - B29C 45/14: incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles {(B29C45/1671 takes precedence)} - B29C 70/305: {Spray-up of reinforcing fibres with or without matrix to form a non-coherent mat in or on a mould (B29C41/365, B29C70/32, B29C70/34, B29C70/502, B29C70/508 take precedence; coating a former by spraying plastics B29C41/08)} - B29C 70/52: Pultrusion, i.e. forming and compressing by continuously pulling through a die - B65D 1/0215: {multilayered (B65D81/3837 takes precedence)} - B65D 1/0292: {Foldable bottles} - B65D 83/0094: {Containers having an external wall formed as, or with, a diaphragm or the like which is deformed to expel the contents (B65D1/32 takes precedence)} - C08F 220/14: Methyl esters {, e.g. methyl (meth)acrylate} - C08F 220/1806: {C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate} - C08F 265/04: on to polymers of esters - C08F 265/06: Polymerisation of acrylate or methacrylate esters on to polymers thereof - C08J 5/06: using pretreated fibrous materials - C08J 5/24: Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs - D06M 15/263: of unsaturated carboxylic acids; Salts or esters thereof - A61J 1/1475: {Inlet or outlet ports} - B29K 2033/12: {Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate} - B29K 2105/08: of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns - C08J 2333/10: Homopolymers or copolymers of methacrylic acid esters - C08J 2333/12: Homopolymers or copolymers of methyl methacrylate - A61M: DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY (introducing media into or onto the bodies of animals A61D7/00; means for inserting tampons A61F13/26; devices for administering food or medicines orally A61J; containers for collecting, storing or administering blood or medical fluids A61J1/05); DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY (surgery A61B; chemical aspects of surgical articles A61L); DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR {(Electrotherapy, e.g. producing anaesthesia by the use of alternating or intermittent currents A61N1/36021)} - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - A61J: CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE - B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - B65D: CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - D06M: TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS - B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS ## Abstract The present invention relates to an impregnation process for a fibrous substrate, a liquid composition for implementing this process and the obtained impregnated fibrous substrate. The impregnated fibrous substrate is suitable for manufacturing mechanical or structured parts or articles. In particular the present invention deals with an industrial process for impregnating a fibrous substrate or long fibers with a viscous liquid composition containing mainly methacrylic, vinylic or acrylic components either in form of monomers or polymers. This viscous composition is called hereafter liquid monomer syrup. The invention concerns also a fibrous substrate pre-impregnated with said syrup which is useful for manufacturing mechanical or structured parts or articles. More particular the impregnation of fibrous substrate with the monomer syrup is achieved in a mould. The present invention concerns also manufacturing process for manufacturing mechanical or structured parts or articles and three-dimensional mechanical or structured parts obtained by this process. ## Claims ### Claim 1 An impregnation process for impregnating a fibrous substrate, wherein said fibrous substrate is made of long fibres having an aspect ratio of at least 1000, said fibers having a diameter between 0.005 micrometers and 100 micrometers, and said process comprises a step of impregnating said fibrous substrate with a liquid monomer syrup comprising: a) a (meth)acrylic polymer, b) at least one monomer (A) chosen from a (meth) acrylic monomer or a vinyl monomer or mixture thereof, c) at least one initiator or initiating system for starting the polymerization of the (meth) acrylic monomer, d) optionally another (meth) acrylic monomer (B) wherein the at least one monomer (A) chosen from (meth) acrylic monomer or vinylic monomers has a boiling point of at least 115° C. at 1013 mbar and/or a vapour pressure of less than 25 mbar at 20° C. and wherein the other (meth)acrylic monomer B has a boiling point less than 115° C. at 1013 mbar and/or a vapour pressure of more than 25 mbar at 20° C., and wherein said liquid monomer syrup has a dynamic viscosity of a value in the range from 10 mPa*s to 10000 mPa*s, wherein monomer (A) is present at more than 50 wt % and (meth)acrylic monomer (B) presents less than 50 wt % of the total sum of monomers (A) and (B) present in the liquid monomer syrup, and wherein monomer (A) is selected from the group consisting of cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, heptyl methacrylate, n-octyl acrylate, 2-octyl acrylate, iso-octyl acrylate, 2-ethylhexyl methacrylate, butyl diglycol methacrylate, dicyclopentenyloxyethyl methacrylate, ethoxy ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, hydroxyl propyl methacrylate, styrene, alpha methyl styrene, ortho-, beta- or para-methyl styrene, tert-butyl styrene, nitro styrene, N-vinylpyrrolidone, and mixtures thereof. ### Claim 2 (depends on 1) The impregnation process according to claim 1, wherein monomer (A) has vapour pressure of less than 10 mbar at 20° C. ### Claim 3 (depends on 1) The impregnation process according to claim 1, wherein monomer (A) has boiling point of at least 135° C. at 1013 mbar. ### Claim 4 (depends on 1) The impregnation process according to claim 1, wherein the monomer syrup comprises the (meth) acrylic monomer (B). ### Claim 5 (depends on 4) The impregnation process according to claim 4, wherein the (meth)acrylic monomer (B) is chosen from alkyl acrylic monomers the alkyl group having from 1 to 4 carbons either linear or branched, methyl methacrylate and mixtures thereof. ### Claim 6 (depends on 4) The impregnation process according to claim 4, wherein the (meth)acrylic monomer (B) is chosen from methyl methacrylate, methyl acrylate, ethyl acrylate and mixtures thereof. ### Claim 7 (depends on 1) The impregnation process according to claim 1, wherein the (meth)acrylic polymer is a homo- or copolymer of methyl methacrylate (MMA) or a mixture thereof. ### Claim 8 (depends on 7) The impregnation process according to claim 7, wherein the copolymer of methyl methacrylate (MMA) comprises at least 70% by weight of methyl methacrylate (MMA). ### Claim 9 (depends on 1) The impregnation process according to claim 1, wherein the copolymer of methyl methacrylate (MMA) comprises from 70% to 99.7% by weight of methyl methacrylate and from 0.3 to 30% by weight of at least one monomer having at least one ethylenic unsaturation that can copolymerize with methyl methacrylate. ### Claim 10 (depends on 9) The impregnation process according to claim 9, wherein the comonomer is chosen from methyl acrylate or ethyl acrylate and a mixture thereof. ### Claim 11 (depends on 1) The impregnation process according to claim 1, wherein said initiator or initiating system for starting the polymerization of monomer (A) and the (meth) acrylic monomer (B) is generating radicals. ### Claim 12 (depends on 1) The impregnation process according to claim 1, wherein said initiator or initiating system for starting the polymerization of monomer (A) and the (meth) acrylic monomer (B) is chosen from diacyl peroxides, peroxy esters, dialkyl peroxides, peroxyacetals, hydroperoxides, azo compounds and mixtures thereof. ### Claim 13 (depends on 1) The impregnation process according to claim 1, wherein the (meth)acrylic polymer in the liquid monomer syrup present at least 5% by weight of total weight of compounds a)+b)+c)+d) of the liquid monomer syrup. ### Claim 14 (depends on 1) The impregnation process according to claim 1, wherein the (meth)acrylic polymer in the liquid (meth) acrylic syrup present at most 60% by weight of total weight of compounds a)+b)+c)+d) of the liquid monomer syrup. ### Claim 15 (depends on 1) The impregnation process according to claim 1, wherein the monomer (A) and the monomer (B) in the liquid monomer syrup present at least 30% by weight of total weight of compounds a)+b)+c)+d) of the liquid monomer syrup. ### Claim 16 (depends on 1) The impregnation process according to claim 1, wherein the liquid monomer syrup comprises: a) from 5 wt % to 59.99 wt % (meth)acrylic polymer, b) from 30 wt % to 89.99 wt % sum of monomer (A) and monomer (B), c) from 0.01 wt % to 5 wt % one initiator or initiating system for starting the polymerization of the monomer or monomers, d) from 0 wt % to 1 wt % activator, e) from 0 wt % to 60 wt % filler, and f) from 0 wt to 20 wt % additives. ### Claim 17 (depends on 1) A manufacturing process for manufacturing mechanical or structured parts or articles comprising following steps: a) impregnating a fibrous substrate with a liquid monomer syrup according to claim 1, and b) polymerising the liquid monomer syrup impregnating said fibrous substrate. ### Claim 18 (depends on 17) The process according to claim 17, wherein the impregnation of the fibrous substrate in step a) is made in a mold. ### Claim 19 (depends on 17) The process according to claim 17, wherein in step a) and step b) are made in the same mold. ### Claim 20 (depends on 17) The process according to claim 17, wherein the process is chosen from pultrusion, hand lay up, spray-up, resin transfer molding and infusion. ### Claim 21 (depends on 17) The process according to claim 17 wherein the temperature of the polymerization is step b) is below 120° C.