(METH)acrylic multi part composition, method for producing said composition and uses thereof
A (meth) acrylic composition with a multi-part structure, including a liquid syrup, transition metal, and initiator, addresses the need for extended pot-life and polymerization time, facilitating the production of large or thick parts with controlled polymerization and recyclability.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- ARKEMA FRANCE SA
- Filing Date
- 2025-12-20
- Publication Date
- 2026-06-25
AI Technical Summary
Existing (meth) acrylic compositions lack sufficient pot-life for preparing large or thick parts, and there is a need for compositions and processes that provide a medium to long polymerization time without significant viscosity increase or temperature rise, while being easily recyclable.
A (meth) acrylic composition comprising a first part with a liquid (meth) acrylic syrup, a second part with a transition metal and reducing agent, and a third part with a polymerization initiator, allowing for a composition with adjustable pot-life and suitable for large parts, achieved by mixing these parts.
The composition provides a sufficient pot-life of at least 1 hour to 3 hours at 25°C, enabling the preparation of large or thick parts with controlled polymerization, and is recyclable.
Smart Images
Figure IMGF000022_0001 
Figure IMGF000032_0001
Abstract
Description
(METH) CRYLIC MULTI PART COMPOSITION , METHOD FOR PRODUCING SAID COMPOSITION AND USES THEREOF[Field of the invention]
[0001] The present invention relates to a (meth) acrylic composition, a process for preparing the (meth) acrylic composition and uses of such a (meth) acrylic composition .
[0002] In particular the present invention relates to a (meth ) acrylic composition comprising several parts , a process for preparing the (meth ) acrylic composition and uses of such a (meth ) acrylic composition .
[0003] The invention also relates also to a (meth ) acrylic polymeric composite material , made of a (meth) acrylic composition comprising several parts , a method for preparing such (meth) acrylic composite material made of a (meth) acrylic composition comprising several parts and an obj ect comprising such a (meth ) acrylic polymeric composite material made of a (meth) acrylic composition comprising several parts .[Technical problem]
[0004] Many materials used today are not pure materials based on one compound but are a blend of several components or a composite materials .
[0005] A composite material is a macroscopic combination of two or more non-miscible materials . The composite material constitutes at least of a matrix material , for example a polymeric material , that forms a continuous phase for the cohesion of the structure and a reinforcing material with various architectures for the mechanical properties .
[0006] The aim in using composite materials is to achieve a performance from the composite material that is not available from its separate constituents if used alone . Consequently, composite materials are widely used in several industrial sectors as for example building, automotive , nautical or marine , aerospace , transport , leisure , electronics , and sport notably due to their better mechanical performance ( higher tensile strength, highertensile modulus , and higher fracture toughness ) in comparison with homogenous materials and their low density .
[0007] The most important class in view of volume in commercial industrial scale , are composites with organic matrices , where the matrix material is generally a polymer . The principal matrix or continuous phase of a polymeric composite material is either a thermoplastic polymer or a thermosetting polymer .
[0008] One way for preparing a polymeric composite material based on thermoplastic polymers is by using a liquid polymer composition comprising a monomer, commonly known as a "syrup" . Such a syrup is used for blending with a mineral filler or for impregnating the reinforcing material , for example a fibrous substrate ; followed by polymerization .
[0009] Before using such a liquid polymer composition, it might have to be stocked and transported after preparation to the place where the polymerization takes place . So , a certain shelf-life is required . Even if the composition of prepared at the place where the polymerization takes place , a certain pot-life is required . For example , for the purpose of preparing large parts , as filling up large moulds by inj ection or for the impregnation of large quantities of a reinforcing material as for example by an infusion process for preparing large wind blades or large boat parts , but also thick parts . This pot-life is required in order to ensure medium to long polymerization time for keeping the liquid polymer composition still liquid enough for time it takes to inj ect or infuse the large quantities of liquid polymer composition over a certain time .
[0010] At the end of the use of obj ect or article comprising the composite material , said obj ect or article should be easily recyclable .[Oil ] There is a need for (meth) acrylic compositions that have a medium to long pot life .
[0012] There is a need for (meth) acrylic compositions that can be used for the inj ection in large moulds or the preparation large composite parts .
[0013] There is also a need to propose a process for making (meth) acrylic compositions that have a medium to long pot life .
[0014] There is also a need to propose (meth ) acrylic compositions that have an adj ustable pot life .
[0015] There is also a composition and a process to prepare a composition for preparing large or thick obj ects . By large is meant in one dimension of at least 4m, even 5m or even 10m. By thick is meant an obj ect that at least at one point has a thickness of at least 1cm, preferably 2 cm, or even 5cm.
[0016] There is also a need of process to prepare (meth ) acrylic composite materials that have large dimensions , preferably a length in one dimension of at least than 4m, even 5m or even 10m or an obj ect that at least at one point has a thickness of at least 1cm, preferably 2cm, or even 5 cm .
[0017] Another aim of the present invention is to propose a process for manufacturing a polymeric (meth ) acrylic composite material that have a medium to long polymerization time .
[0018] By long pot life is meant at least 1 hour at 25 ° C preferably up to at least 2 hours at 25 ° C and more preferably up to at least 3 hours without significant polymerization, meaning no significant increase of viscosity and / or temperature .
[0019] An adj ustable pot life of the composition signifies by adj usting j ust one component of the composition, the pot life is changed significantly .[BACKGROUND OF THE INVENTION] Prior art
[0020] The document WO2013 / 056845 discloses a composite material via in-situ polymerization of thermoplastic (meth) acrylic resins . The polymeric composite material obtained by in-situ polymerization of a thermoplastic (meth) acrylic resin and a fibrous material containing long fibers and its use , a process for making such a composite material and manufactured mechanical or structured part or article comprising this polymeric composite material . The document does not disclose anything about pot life .
[0021] The document W02014 / 013028 an impregnation process for a fibrous substrate , a liquid (meth ) acrylic syrup for the impregnation process , its method of polymerization and structured article obtained thereof . The liquid (meth ) acrylic syrup comprises a (meth ) acrylic polymer, a (meth) acrylic monomer and at least oneinitiator or initiating system for starting the polymerization of the (meth) acrylic monomer. The document does not disclose anything about pot life.
[0022] The document WO2014 / 174098 discloses a liquid (meth) acrylic syrup and its method of polymerization. The initiating system of said syrup comprises at least one accelerator, at least one organic aldehyde and a peroxy compound and organic peracid.
[0023] The document W003 / 008463 discloses a method for polymerising vinyl monomers and / or oligomers comprising at least a vinyl radical. Additionally, the composition comprises compound giving a dioxygen as a peroxide, an aldehyde and an accelerator.
[0024] The document WO2020 / 247549 discloses a thermoplastic gel coat. The gel coat is based on liquid thermoplastic (meth) acrylic resin comprising a blend of (meth) acrylic polymer(s) , (meth) acrylic monomer (s) , and initiator. The liquid thermoplastic (meth) acrylic resin can optionally comprise other additives .
[0025] The document W02020 / 078991 discloses a (meth) acrylic composition suitable for (meth) acrylic polymeric compositions and composites, its method of preparation and its use. The (meth) acrylic composition comprises a blend of (meth) acrylic polymer (s) , two different (meth) acrylic monomer (s) and initiator and some optional additives .
[0026] None of the cited prior art discloses a (meth) acrylic composition having a sufficient pot-life.[Brief description of the invention]
[0027] Surprisingly it has been found that a (meth) acrylic composition (MCI) comprising: a first part composition (A) comprising:(Aa) 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) comprising :(Aai) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (Pl) , and(Aa2) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (Ml) , each monomer (Ml) comprising only one (meth) acrylic function per monomer,(Ab) at least one organic aldehyde(Ac) an inhibitor; a second part composition (B) comprising:(Ba) a transition metal,(Bb) a reducing agent,(Be) optionally an inhibitor,(Bd) optionally one or more (meth) acrylic monomers (M2) and / or optionally one or more (meth) acrylic polymers (P2) ; and a third part composition (C) comprising:(Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator, allows to provide a composition that possesses a sufficient potlife and a sufficient pot-life for preparing for large parts and for the preparation of (meth) acrylic polymeric compositions (MPC1) and (meth) acrylic composite materials (MPCM1) .
[0028] Surprisingly it has also been found that a (meth) acrylic composition MCI comprising: a first part composition (A) comprising:(Aa) 100-n parts by weight of a liquid (meth) acrylic syrup (LMS1) comprising :(Aai) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (Pl) , and(Aa2) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (Ml) , each monomer (Ml) comprising only one (meth) acrylic function per monomer,(Ab) at least one organic aldehyde(Ac) an inhibitor; a second part composition (B) comprising:(Ba) a transition metal,(Bb) a reducing agent,(Be) optionally an inhibitor,(Bd) n parts by weight of a liquid (meth) acrylic syrup (LMS2) comprising :(Bdi) from 1% by weight to 50% by weight of one or more(meth) acrylic polymers (P2) , and(Bd2) from 50% by weight to 99% by weight of one or more(meth) acrylic monomers (M2) , and a third part composition (C) comprising:(Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator, with n being from 0 to 100, allows to provide a composition that possesses a sufficient pot-life and a sufficient pot-life for preparing for large parts and for the preparation of a (meth) acrylic polymeric composition (MPC1) and (meth) acrylic polymeric composite material (MPCM1) .
[0029] Surprisingly it has also been found that a (meth) acrylic composition (MCI) comprising: a first part composition (A) comprising:(Aa) 100-n parts by weight of a liquid (meth) acrylic syrup (LMS1) comprising :(Aai) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (Pl) , and(Aa2) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (Ml) , each monomer (Ml) comprising only one (meth) acrylic function per monomer,(Ab) at least one organic aldehyde(Ac) an inhibitor; a second part composition (B) comprising:(Ba) a transition metal,(Bb) a reducing agent,(Be) optionally an inhibitor,(Bd) n parts by weight of a liquid (meth) acrylic syrup (LMS2) comprising :(Bdi) from 1% by weight to 50% by weight of one or more(meth) acrylic polymers (P2) , and(Bd2) from 50% by weight to 99% by weight of one or more(meth) acrylic monomers (M2) , and a third part composition (C) comprising:(Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator, with n being from 0 to 100, can be used for preparing for large parts comprising a (meth) acrylic polymeric composition (MPC1) and (meth) acrylic polymeric composite material (MPCM1) .
[0030] Surprisingly it has been found that a process for preparing a (meth) acrylic composition (MCI) , said process is comprising the following steps :(i) providing a first part composition (A) comprising:(Aa) 100-n parts by weight of a liquid (meth) acrylic syrup (LMS1) comprising :(Aai) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (Pl) , and(Aa2) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (Ml) , each monomer (Ml) comprising only one (meth) acrylic function per monomer, (Ab) at least one organic aldehyde (Ac) an inhibitor;(ii) providing a second part composition (B) comprising:(Ba) a transition metal,(Bb) a reducing agent,(Be) optionally an inhibitor,(Bd) n parts by weight of a liquid (meth) acrylic syrup (LMS2) comprising :(Bdi) from 1% by weight to 50% by weight of one or more(meth) acrylic polymers (P2) , and(Bd2) from 50% by weight to 99% by weight of one or more(meth) acrylic monomers (M2) , and iii) providing a third part composition (C) comprising:(Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator, iv) mixing the three provided compositions; with n being from 0 to 100, allows to prepare a composition that possesses a sufficient pot-life and a sufficient pot-life for preparing for large parts and for the preparation of a (meth) acrylic polymeric composition (MPC1) and (meth) acrylic polymeric composite material (MPCM1) .[Detailed description of the invention]
[0031] According to a first aspect, the present invention relates to a (meth) acrylic composition (MCI) , said composition is comprising: a first part composition (A) comprising:(Aa) 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) comprising :(Aai) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (Pl) , and(Aai) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (Ml) , each monomer (Ml) comprising only one (meth) acrylic function per monomer,(Ab) at least one organic aldehyde(Ac) an inhibitor; a second part composition (B) comprising:(Ba) a transition metal,(Bb) a reducing agent,(Be) optionally an inhibitor,(Bd) optionally one or more (meth) acrylic monomers (M2) and / or optionally one or more (meth) acrylic polymers (P2) ; and a third part composition (C) comprising:(Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator.
[0032] According to a second aspect, the present invention relates to a (meth) acrylic composition (MCI) , said composition is comprising: a first part composition (A) comprising:(Aa) 100-n parts by weight of a liquid (meth) acrylic syrup (LMS1) comprising :(Aai) from 1% by weight to 50% by weight of one or more(meth) acrylic polymers (Pl) , and(Aa2) from 50% by weight to 99% by weight of one or more(meth) acrylic monomers (Ml) , each monomer (Ml) comprising only one (meth) acrylic function per monomer,(Ab) at least one organic aldehyde(Ac) an inhibitor; a second part composition (B) comprising:(Ba) a transition metal,(Bb) a reducing agent,(Be) optionally an inhibitor,(Bd) n parts by weight of a liquid (meth) acrylic syrup (LMS2) comprising :(Bdi) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (P2) , and(Bd2) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (M2) , a third part composition (C) comprising:(Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator; characterized in that O^n^lOO.
[0033] According to a third aspect, the present invention relates to a process for preparing a (meth) acrylic composition (MCI) comprising following steps :(i) providing a first part composition (A) comprising:(Aa) 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) comprising :(Aai) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (Pl) , and(Aa2) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (Ml) , each monomer (Ml) comprising only one (meth) acrylic function per monomer,(Ab) at least one organic aldehyde(Ac) an inhibitor;(ii) providing a second part composition (B) comprising:(Ba) a transition metal,(Bb) a reducing agent,(Be) optionally an inhibitor,(Bd) optionally one or more (meth) acrylic monomers (M2) and / or optionally one or more (meth) acrylic polymers (P2) ; and(iii) providing a third part composition (C) comprising:(Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator,(iv)mixing the three provided compositions.
[0034] According to a fourth aspect, the present invention relates to a process for preparing a (meth) acrylic composition (MCI) , process is comprising following steps :(i) providing a first part composition (A) comprising:(Aa) 100-n parts by weight of a liquid (meth) acrylic syrup (LMS1) comprising:(Aai) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (Pl) , and(Aa2) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (Ml) , each monomer (Ml) comprising only one (meth) acrylic function per monomer,(Ab) at least one organic aldehyde(Ac) an inhibitor;(ii) providing a second part composition (B) comprising:(Ba) a transition metal,(Bb) a reducing agent,(Be) optionally an inhibitor,(Bd) n parts by weight of a liquid (meth) acrylic syrup (LMS2) comprising :(Bdi) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (P2) , and(Bd2) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (M2) , and(iii) providing a third part composition (C) comprising:(Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator,(iv)mixing the three provided compositions; with n being from 0 to 100.
[0035] According to a fifth aspect the present invention relates to the use of a (meth) acrylic composition (MCI) according to the first aspect or the second aspect to prepare a (meth) acrylic polymeric material (MPC1) or (meth) acrylic polymeric composite material (MPCM1) .
[0036] According to a sixth aspect the present invention relates to a (meth) acrylic polymeric material (MPC1) or (meth) acrylic polymeric composite material (MPCM1) prepared by polymerization of the (meth) acrylic composition (MCI) according to the first aspect or the second aspect.
[0037] According to a seventh aspect the present invention relates to a process for preparing a (meth ) acrylic polymeric material (MPC1 ) , said process comprises the following steps :( i ) providing a (meth) acrylic composition (MCI ) according to first or second aspect ,( ii ) polymerizing the (meth) acrylic composition (MCI ) .
[0038] According to an eight aspect the present invention relates to a process for preparing a (meth) acrylic polymeric composite material (MPCM1 ) , said process comprises the following steps :( i ) providing a (meth) acrylic composition (MCI ) according to first or second aspect ,( ii ) bringing the (meth ) acrylic composition (MCI ) in contact with a reinforcing material ,( iii ) polymerizing the (meth ) acrylic composition (MCI ) .
[0039] The term " (meth) acrylic monomer" covers both an acrylic monomer and a methacrylic monomer . Similarly, the term " (meth) acrylic polymer" covers not only an acrylic homopolymer but also a methacrylic homopolymer , an acrylic copolymer and a methacrylic copolymer .
[0040] By the term "PMMA" as used are denoted homo- and copolymers of methylmethacrylate (MMA) , for the copolymer of MMA the weight ratio of MMA inside the PMMA is at least 50 wt% .
[0041] By the term "initiator" as used is denoted a chemical species that forms compound or an intermediate compound that starts the polymerization of a monomer , that to capable of linking successively with a large number of other monomers into a polymeric compound .
[0042] By the term "polymer composite" as used is denoted a multicomponent material comprising multiple different phase domains in which at least one type of phase domain is a continuous phase and in which at least one component is a polymer .
[0043] By the term "thermoplastic" as used is denoted a polymer that turns to a liquid or becomes more liquid or less viscous when heated and that can take on new shapes by the application of heat and optionally pressure . This applies also for slightly crosslinkedthermoplastic polymers that can be thermoformed when heated above the softening temperature.
[0044] By saying that a range from x to y in the present invention, it is meant that the upper and lower limit of this range are included, equivalent to at least x and up to y.
[0045] By saying that a range is between x and y in the present invention, it is meant that the upper and lower limit of this range are excluded, equivalent to more than x and less than y.
[0046] The (meth) acrylic composition (MCI) comprises a first part composition (A) , second part composition (B) and third part composition (C ) . Each partly composition it its respective components are detailed in the following. The quantity of each respective component of the respective compositions is given by weight parts relative to the weight of the liquid (meth) acrylic syrup (LMS1) or to the sum of the liquid (meth) acrylic syrups (LMS1) and (LSM2) , which is 100 parts by weight.
[0047] The first part composition (A) according to the invention comprises components (Aa) a liquid (meth) acrylic syrup, (Ab) at least one organic aldehyde and (Ac) optionally an inhibitor. The liquid (meth) acrylic syrup (LSM1) of the composition (Aa) comprises (Aai) a (meth) acrylic polymer (Pl) and (Aa2) a (meth) acrylic monomer (Ml) .
[0048] The liquid (meth) acrylic syrup (LSM1) of the first part composition (A) according to the (meth) acrylic composition (MCI) of invention comprises between lwt% and 50wt% of at least a (meth) acrylic polymer (Pl) and between 50wt% and 99wt% of at least a (meth) acrylic monomer (Ml) .
[0049] Preferably the liquid (meth) acrylic syrup (LSM1) comprises between 2wt% and 50wt% of a (meth) acrylic polymer (Pl) and between 50wt% and 98wt% of a (meth) acrylic monomer (Ml) , more preferably between 2wt% and 40wt% of a (meth) acrylic polymer (Pl) and between 60wt% and 98wt% of a (meth) acrylic monomer (Ml) , still more preferably between 3wt% and 40wt% of a (meth) acrylic polymer (Pl) and between 60wt% and 97wt% of a (meth) acrylic monomer (Ml) , advantageously between 3wt% and 35wt% of a (meth) acrylic polymer(Pl) and between 65wt% and 97wt% of a (meth) acrylic monomer (Ml) and more advantageously between 3wt% and 30wt% of a (meth) acrylic polymer (Pl) and between 70wt% and 97wt% of a (meth) acrylic monomer (Ml) .
[0050] The dynamic viscosity of the liquid (meth) acrylic syrup (LMS1) is in a range from 10 mPa*s to 10000 mPa*s, preferably from 20 mPa*s to 7000 mPa*s and advantageously from 20 mPa*s to 5000 mPa*s and more advantageously from 20 mPa*s to 2000 mPa*s and even more advantageously between 20mPa*s and 1000 mPa*s. The viscosity of the syrup can be easily measured with a Rheometer or viscosimeter. The dynamic viscosity is measured at 23°C. If the liquid (meth) acrylic syrup has a Newtonian behaviour, meaning no shear thinning, the dynamic viscosity is independent of the shearing in a rheometer or the speed of the mobile in a viscometer. If the liquid composition has a non-Newtonian behaviour, meaning shear thinning, the dynamic viscosity is measured at a shear rate of Is-1at 23°C.
[0051] As regards the liquid (meth) acrylic syrup (LSM1) , it comprises ( a2) the (meth) acrylic monomer (Ml) and ( ai) the (meth) acrylic polymer (Pl) . Once the (meth) acrylic composition (MCI) has been polymerized, the (meth) acrylic monomer (Ml) polymerizes eventually with other (meth) acrylic monomers and is transformed to a (meth) acrylic polymer (P2) comprising the monomeric units of (meth) acrylic monomer (Ml) and other possible comonomers.
[0052] The liquid (meth) acrylic syrup (LSM1) of the first part composition (A) of the (meth) acrylic composition (MCI) according to the invention may comprise only one (meth) acrylic polymer (Pl) , but may equally comprise a mixture of two, three or even more (meth) acrylic polymers (Pl) . If there is a mixture of different (meth) acrylic polymer (Pl) , the difference is the composition of the respective (meth) acrylic polymer (Pl) or the molecular weight of the respective (meth) acrylic polymer (Pl) or both.
[0053] The or each (meth) acrylic polymer Pl included in the liquid (meth) acrylic syrup may in particular be chosen from:. polyalkyl acrylates which comprise alkyl acrylate homopolymers and alkyl acrylate copolymers, and. polyalkyl methacrylates which comprise alkyl methacrylate homopolymers and alkyl methacrylate copolymers.
[0054] According to a preferred embodiment, the or each (meth) acrylic polymer (Pl) is a polymethyl methacrylate (PMMA) , it being understood that, as indicated above, the polymethyl methacrylate (PMMA) may denote a methyl methacrylate (MMA) homopolymer or an MMA copolymer .
[0055] In particular, in the case where the liquid (meth) acrylic syrup (LMS1) comprises a mixture of two or more polymethyl methacrylates (Pl) , this mixture may be formed by mixing at least two MMA homopolymers having a different molecular weight, by mixing at least two MMA copolymers having an identical monomer composition and a different molecular weight, by mixing at least two MMA copolymers having a different monomer composition or by mixing at least one MMA homopolymer and at least one MMA copolymer.
[0056] According to a first preferred embodiment the (meth) acrylic polymer (Pl) is chosen from a methyl methacrylate homopolymer or a methyl methacrylate copolymer or a mixture thereof, methyl methacrylate advantageously representing at least 50% by weight of the or of each (meth) acrylic polymer (Pl) .
[0057] According to one embodiment of the invention, methyl methacrylate represents at least 55% by weight of the or each (meth) acrylic polymer (Pl) .
[0058] According to another particular embodiment, the or each (meth) acrylic polymer (Pl) comprises at least 70%, advantageously at least 80%, preferentially at least 90% and more preferentially at least 95% by weight of methyl methacrylate.
[0059] When the or each (meth) acrylic polymer (Pl) is a methyl methacrylate (MMA) copolymer, it may comprise at least one comonomer containing at least one ethylenic unsaturation and which is capable of copolymerizing with methyl methacrylate. Among these comonomers, mention may notably be made of acrylic and methacrylic acids and alkyl (meth) acrylates in which the alkyl group contains from 1 to 12 carbon atoms. Alkyl (meth) acrylates means an alkyl ester of acrylic acid or methacrylic acid. As examples of comonomers, mention may be made of methyl acrylate and ethyl, butyl or 2-ethylhexyl (meth) acrylate .
[0060] Advantageously, the or each (meth) acrylic polymer (Pl) is a homopolymer of methyl methacrylate or a copolymer of methylmethacrylate and of an alkyl acrylate or an alkyl methacrylate in which the alkyl group contains from 1 to 12 carbon atoms, advantageously from 1 to 6 carbon atoms and preferentially from 1 to 4 carbon atoms .
[0061] According to a first preferred embodiment, when the or each (meth) acrylic polymer (Pl) is a methyl methacrylate (MMA) copolymer, this methyl methacrylate (MMA) copolymer comprises from 70% to 99.9%, advantageously from 80% to 99.9%, preferentially from 90% to 99.9% and more preferentially from 95% to 99.9% by weight of methyl methacrylate and from 0.1% to 30%, advantageously from 0.1% to 20%, preferentially from 0.1% to 10% and more preferentially from 0.1% to 5% by weight of at least one comonomer containing at least one ethylenic unsaturation that can copolymerize with methyl methacrylate. Preferably, the or each comonomer is chosen from methyl acrylate and ethyl acrylate.
[0062] In an advantageous variant of the first preferred embodiment, when the or each (meth) acrylic polymer (Pl) is a methyl methacrylate (MMA) copolymer, the (meth) acrylic polymer (Pl) is a copolymer of methyl methacrylate and of alkyl acrylate.
[0063] In a preferred variant of the first preferred embodiment, when the or each (meth) acrylic polymer (Pl) is a methyl methacrylate (MMA) copolymer, the (meth) acrylic polymer Pl is a copolymer of methyl methacrylate and of methyl acrylate or ethylacrylate.
[0064] According to a second preferred embodiment, when the or each (meth) acrylic polymer (Pl) is a methyl methacrylate (MMA) copolymer, this methyl methacrylate (MMA) copolymer comprises from 50% to 99.9%, advantageously from 52% to 99.9%, preferentially from 53% to 99.9% and more preferentially from 55% to 99.9% by weight of methyl methacrylate and from 0.1% to 50%, advantageously from 0.1% to 48%, preferentially from 0.1% to 47% and more preferentially from 0.1% to 45% by weight of at least one comonomer containing at least one ethylenic unsaturation that can copolymerize with methyl methacrylate. Preferably, the or each comonomer is chosen from methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate or butyl methacrylate.
[0065] The weight-average molecular weight, noted as Mw, of the or each (meth) acrylic polymer Pl is generally high and may consequentlybe greater than 40 000 g / mol, advantageously greater than 45 000 g / mol and preferentially greater than 50 000 g / mol. The weightaverage molecular weight may be measured by size exclusion chromatography (SEC) .
[0066] The (meth) acrylic polymer (Pl) , if not crosslinked, usually has a melt mass-flow rate (MFR) ISO 1133-2:2011 (230°C / 3.8 kg) of between 0.1 g / 10 min and 20 g / 10 min or the melt mass-flow rate is between 0.2 g / 10 min and 18 g / 10 min, or between 0.3 g / 10 min and 16 g / 10 min or between 0.4 g / 10 min and 13 g / 10 min.
[0067] The liquid (meth) acrylic syrup (LSM1) of the first part composition (A) of the (meth) acrylic composition (MCI) according to the invention may comprise only one (meth) acrylic monomer (Ml) , but may equally comprise a mixture of two, three or even more (meth) acrylic monomers (Ml) . This would be (meth) acrylic monomer (Mia) , (meth) acrylic monomer (Mlb) , (meth) acrylic monomers (Mlc) and so on .
[0068] Whether the liquid (meth) acrylic syrup comprises one or more (meth) acrylic monomers (Ml) , the or each (meth) acrylic monomer (Ml) comprises only one (meth) acrylic function per monomer.
[0069] As regards the (meth) acrylic monomer (Ml) , the monomer is chosen from alkyl acrylic monomers, alkyl methacrylic monomers, hydroxyalkyl acrylic monomers and hydroxyalkyl methacrylic monomers, and mixtures thereof. Alkyl acrylic monomer or alkyl methacrylic monomer means an alkyl ester of acrylic acid or methacrylic acid.
[0070] Preferably, the (meth) acrylic monomer (Ml) is chosen from hydroxyalkyl acrylic monomers, hydroxyalkyl methacrylic monomers, alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof, the alkyl group containing from 1 to 22 linear, branched or cyclic carbons; the alkyl group preferably containing from 1 to 12 linear, branched or cyclic carbons.
[0071] Advantageously, the (meth) acrylic monomer (Ml) is chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl acrylate,cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate, and mixtures thereof.
[0072] According to a preferred embodiment, at least 50% by weight and preferably at least 60% by weight of the (meth) acrylic monomer (Ml) is methyl methacrylate.
[0073] According to a first more preferred embodiment, at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, advantageously at least 80% by weight and even more advantageously 90% by weight of the monomer (Ml) is methyl methacrylate or a mixture of methyl methacrylate with optionally at least one other monomer.
[0074] According to a second more preferred embodiment the monomer(Ml) is methyl methacrylate.
[0075] In a first variant of the invention, the liquid (meth) acrylic syrup (LSM1) comprises:(Aai) from 3% by weight to 45% by weight and preferentially from 3% by weight to 40% by weight of the (meth) acrylic polymer (s) (Pl) , and(Aai) from 55% by weight to 97% by weight and preferentially from 60% by weight to 97% by weight of the (meth) acrylic monomer (s) (Ml) .
[0076] In a second variant of the invention, the liquid (meth) acrylic syrup (SLM1) comprises:(Aai) from 10% by weight to 35% by weight and preferentially from 12% by weight to 35% by weight and more preferentially from 15% by weight to 30% by weight and even more preferentially from 17% by weight to 30% by weight of the (meth) acrylic polymer (s) (Pl) , and(Aai) from 65% by weight to 90% by weight and preferentially from 65% by weight to 88% by weight and more preferentially from 70% by weight to 85% by weight and even more preferentially from 70% by weight to 83% by weight of the (meth) acrylic monomer(s) (Ml) .
[0077] In an advantageous variant, the or each (meth) acrylic polymer (Pl) and the or each (meth) acrylic monomer (Ml) of the liquid(meth) acrylic syrup comprise at least one same (meth) acrylic unit, such a variant making it possible to optimize the solubility of the (meth) acrylic polymer(s) (Pl) in the (meth) acrylic monomer(s) (Ml) .
[0078] Preferentially, the or each (meth) acrylic polymer (Pl) is chosen from a homopolymer of methyl methacrylate or copolymer of methyl methacrylate and of methyl acrylate and a copolymer of methyl methacrylate and of ethyl acrylate or a copolymer of methyl methacrylate and of butyl acrylate or a copolymer of methyl methacrylate and of butyl methacrylate, the respective comonomer being present at most at 45wt% in the copolymer.
[0079] In a first advantageous variant, the liquid (meth) acrylic syrup comprises a (meth) acrylic polymer (Pl) , rather than a mixture of (meth) acrylic polymers (Pl) .
[0080] In a second advantageous variant, the liquid (meth) acrylic syrup comprises a mixture of two (meth) acrylic polymers (Pl) .
[0081] Stabilizers may also be present in the liquid (meth) acrylic syrup (LSM1) to prevent spontaneous polymerization of the (meth) acrylic monomer(s) (Ml) .
[0082] These stabilizers may notably be chosen from hydroquinone (HQ) , hydroquinone monomethyl ether (HQME) , 2 , 6-di-tert-butyl-4- methylphenol (BHT) , 2 , 6-di-tert-butyl-4-methoxyphenol (Topanol O) and 2 , 4-dimethyl-6-tert-butylphenol (Topanol A) .
[0083] These stabilizers may be present, in the liquid (meth) acrylic syrup (LSM1) , in a proportion of not more than 3 parts by weight, advantageously not more than 2 parts by weight and preferentially in a proportion of between 0.005 and 1 parts by weight, per 100 parts by weight of the sum of the (meth) acrylic polymer (s) (Pl) and of the (meth) acrylic monomer (s) (Ml) of the liquid (meth) acrylic syrup (LMS1 ) .
[0084] The component (Ab) the at least one organic aldehyde of the first part composition (A) can be aliphatic or aromatic.
[0085] The aliphatic part organic aldehyde can be linear, cyclic or branched, but also be saturated or unsaturated.
[0086] The organic aldehyde comprises between 3 and 30 carbon atoms.It has a general formula R-CH=O, in which R represents a cyclichydrocarbon-based chain or a linear or branched hydrocarbon-based chain, R comprising from 2 to 29 carbon atoms, preferably from 3 to 15, optionally comprising one or more unsaturation ( s ) in the form of double bonds and being optionally substituted with one or more hydroxyl groups .
[0087] Mention may be made of propionaldehyde, butyraldehyde, valeraldehyde, capraldehyde , benzaldehyde, geranial, neral, citronellal and in general, aldehydes containing hydrocarbon-based groups comprising one or more unsaturations of olefinic type and also mixtures of two or more thereof in all proportions .
[0088] In one embodiment the organic aldehyde chosen from propionaldehyde, butyraldehyde, valeraldehyde, capraldehyde, benzaldehyde, geranial, neral, citronellal.
[0089] In one embodiment the organic aldehyde chosen from 3,7- dimethylocta-2 , 6-dienal .
[0090] The component (Ab) the at least one organic aldehyde of the first part composition (A) is present between 0.5 part and 10 parts by weight for 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth) acrylic syrup (LMS1) and (LSM2) , preferably between 0.5 part and 8 parts by weight, more preferably between 0.5 part and 6 parts by weight .
[0091] The component (Ac) an inhibitor is also part of the first part composition (A) .
[0092] The inhibitor is preferably chosen from 4-hydroxy-2 , 2 , 6, 6- tetramethylpiperidin-l-oxyl ( 4-Hydroxy-TEMPO or TEMPOL) or ( 2 , 2 , 6, 6-Tetramethylpiperidin-l-yl ) oxyl (TEMPO) .
[0093] The component (Ac) the inhibitor of the first part composition (A) , presents between 0.005 part and 1 parts by weight for 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth) acrylic syrup (LMS1) and (LSM2) , preferably between 0.005 part and 0.5 parts by weight.
[0094] The second part composition (B) according to the invention comprises components (Ba) a transition metal, (Bb) a reducing agent, (Be) optionally an inhibitor and optionally or not component (Bd) . The component (Bd) is either according to a first embodimentoptionally one or more (meth) acrylic monomers (M2) and / or optionally one or more (meth) acrylic polymers (P2) or according to a second embodiment a liquid (meth) acrylic syrup (LMS2) . The liquid (meth) acrylic syrup (LSM2) according to the second embodiment comprises (Bdi) a (meth) acrylic polymer (P2) and (Bd2) a (meth) acrylic monomer (M2) . The (meth) acrylic monomers (M2) and the one or more (meth) acrylic polymers (P2) are chosen according to all embodiments described before for the choice of the (meth) acrylic polymer (Pl) and the (meth) acrylic monomer (Ml) .
[0095] In a first preferred embodiment the one or more (meth) acrylic monomers (M2) and the one or more (meth) acrylic polymers (P2) if present are the same as the (meth) acrylic polymer (Pl) and the (meth) acrylic monomer (Ml) .
[0096] In a second preferred embodiment either the one or more (meth) acrylic monomers (M2) or the one or more (meth) acrylic polymers (P2) if present is the same as the (meth) acrylic monomer (Ml) or (meth) acrylic polymer (Pl) . Nevertheless the (meth) acrylic monomers (M2) and the one or more (meth) acrylic polymers (P2) are chosen according to all embodiments described before for the choice of the (meth) acrylic polymer (Pl) and the (meth) acrylic monomer (Ml) , but only one is the same.
[0097] In a third preferred embodiment the one or more (meth) acrylic monomers (M2) and the one or more (meth) acrylic polymers (P2) of the liquid (meth) acrylic syrup (LMS2) are the same as the (meth) acrylic polymer (Pl) and the (meth) acrylic monomer (Ml) of liquid (meth) acrylic syrup (LMS1) .
[0098] In a fourth preferred embodiment either the one or more (meth) acrylic monomers (M2) or the one or more (meth) acrylic polymers (P2) of the liquid (meth) acrylic syrup (LMS2) is the same as the (meth) acrylic polymer (Pl) or the (meth) acrylic monomer (Ml) of liquid (meth) acrylic syrup (LMS1) . Nevertheless the (meth) acrylic monomers (M2) and the one or more (meth) acrylic polymers (P2) are chosen according to all embodiments described before for the choice of the (meth) acrylic polymer (Pl) and the (meth) acrylic monomer (Ml) , but only one is the same.
[0099] The quantity of each respective component of the respective part compositions is given by weight parts relative to the weightof the liquid (meth) acrylic syrup (LMS1) or to the sum of the liquid (meth) acrylic syrups (LMS1) and (LSM2) , which is 100 parts by weight.
[0100] If the second part composition (B) according to the invention does not comprises any (meth) acrylic monomers (M2) , any (meth) acrylic polymers (P2) nor the liquid (meth) acrylic syrups (LSM2) , the first part composition is taken that is comprises 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) .
[0101] If the second part composition (B) according to the invention comprises the liquid (meth) acrylic syrups (LSM2) it is expressed by 100-n parts by weight of a liquid (meth) acrylic syrup (LMS1) first part composition (A) and n parts by weight of a liquid (meth) acrylic syrup (LMS2) so that the overall parts for the respective monomers and polymers is constant at 100 parts by weight and the quantities of all the other compounds are given relative to that. The variable n defines a kind of weight ratio of liquid (meth) acrylic syrup (LMS1) in the first part composition (A) to the liquid (meth) acrylic syrupm the second part composition (B) .
[0102] In a first preferred embodiment n is from 0 to 99, corresponding to 0^n^99.
[0103] In a second preferred embodiment n is from 10 to 90, corresponding to 10^n^90.
[0104] In a third preferred embodiment n is from 20 to 80, corresponding to 20^n^80.
[0105] In a fourth preferred embodiment n is from 30 to 70, corresponding to 30^n^70.
[0106] In a fifth preferred embodiment n is from 40 to 60, corresponding to 40^n^60.
[0107] In a sixth preferred embodiment n is from 45 to 55, corresponding to 45^n^55.
[0108] In a seventh preferred embodiment n is from 25 to 60, corresponding to 25^n^60.
[0109] The component (Ba) the transition metal of the second part composition (B) it can be chosen from the 4thperiod of the periodic system of elements.
[0110] Advantageously the transition metal is chosen from Manganese, Cobalt, Iron or Copper and more advantageously Manganese, Iron, Copper or mixtures thereof.
[0111] The transition metal can be in form a metal salt or a mixture of metal salts or an organic complex comprising the transition metal.
[0112] The component (Ba) the transition metal of the second part composition (B) is present between 0.01 part and 4 parts by weight for 100 parts by weight of the liquid (meth) acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth) acrylic syrup (LMS1) and (LSM2) . The quantity of the component (Ba) the transition metal is calculated in the transition metal part only.
[0113] The component (Bb) the reducing agent of the second part composition (B) it can preferably be chosen from ascorbic acid, a- hydroxy sulfones, thioureas and saccharin (also known as benzoic sulf inide ) .
[0114] In a first more preferably embodiment the reducing agent is saccharin .
[0115] The reducing agent is advantageously soluble in a polar aprotic solvent at 20°C. Preferably, the polar aprotic solvent is dimethyl sulfoxide (DMSO) .
[0116] The amount of reducing agent in the composition is advantageously between 0.1 part by weight and 2 parts by weight and even more preferably it is less than or equal to 1 part by weight, for 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth) acrylic syrup (LMS1) and (LSM2) .
[0117] The component (Be) optionally an inhibitor can be also part of the first part composition (B) .
[0118] In one embodiment the inhibitor of component (Be) is the same as the inhibitor of component (Ac) of first part composition (A) .
[0119] The inhibitor of component (Be) is preferably chosen from 4- hydroxy-2 , 2 , 6 , 6-tetramethylpiperidin-l-oxyl ( 4-Hydroxy-TEMPO or TEMPOL) or ( 2 , 2 , 6 , 6-Tetramethylpiperidin-l-yl ) oxyl (TEMPO) .
[0120] The component (Be) the optional inhibitor of the second part composition (B) , if present presents between 0.005 part and 1 partsby weight for 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth) acrylic syrup (LMS1) and (LSM2) , preferably between 0.01 part and 0.5 parts by weight.
[0121] The third part composition (C) according to the invention comprises component (Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator (INI1) . The function of which is to ensure the start of polymerization of the (meth) acrylic monomers (Ml) and (M2) , it is advantageously a radical initiator.
[0122] The polymerization initiator is chosen from diacyl peroxides, peroxy esters, peroxydicarbonates, dialkyl peroxides, peroxyacetals, hydroperoxide or peroxyketale .
[0123] In one embodiment, the polymerization initiator is chosen from a liquid component. This means that either the initiator itself is liquid or it is a solution or dispersion, at least within a temperature range of between 0°C and 50°C.
[0124] In a first preferred embodiment the polymerization initiator is an organic peroxide comprising 2 to 30 carbon atoms, such as methyl ethyl ketone peroxide (MEKP) , methyl isopropyl ketone peroxide (MIKP) or a hydroperoxide (HP) .
[0125] In a second preferred embodiment is a hydroperoxide or a peroxide comprising at least one hydroperoxide function chosen from tert-butyl hydroperoxide, monohydroperoxide, para-methane hydroperoxide, tert-amyl hydroperoxide, methyl ethyl ketone peroxide, methyl isopropyl ketone peroxide and cumene hydroperoxide or mixtures thereof.
[0126] In a third preferred embodiment it is monohydroperoxide, methyl ethyl ketone peroxide, methyl isopropyl ketone peroxide or para-methane hydroperoxide.
[0127] In a fourth preferred embodiment the polymerization initiator is chosen from diisobutyryl peroxide, cumyl peroxyneodecanoate , di ( 3 -methoxybutyl ) peroxydicarbonate , 1 , 1 , 3 , 3-Tetramethylbutyl peroxyneodecanoate, cumyl peroxyneoheptanoate , di-n-propyl peroxydicarbonate, tert-amyl peroxyneodecanoate, , di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di(4-tert- butylcyclohexyl ) per oxydi carbonate, di- ( 2-ethylhexyl ) -peroxydicarbonate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, di-n-butyl peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 1, 1,3,3- tetramethylbutylperoxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, di- (3,5,5- trimethylhexanoyl ) -peroxide , dilauroyl peroxide, didecanoyl peroxide, 2 , 5-dimethyl-2 , 5-di ( 2-ethylhexanoylperoxy) -hexane,1 , 1 , 3 , 3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy- 2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2- ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxyisobutyrate, 1, 1-di- ( tert-butylperoxy ) -3,3,5- trimethylcyclohexane, 1, 1-di (tert-amylperoxy) cyclohexane, 1, 1-di- (tert-butylperoxy) -cyclohexane, tert-amyl peroxy-2- ethylhexylcarbonate , , tert-amyl peroxyacetate, tert-butyl peroxy- 3,5, 5-trimethylhexanoate, 2 , 2 -di- ( tert-butylperoxy) -butane , tert- butyl peroxyisopropylcarbonate, tert-butyl peroxy-2- ethylhexylcarbonate , tert-amyl peroxybenzoate, tert-butyl peroxyacetate, butyl 4, 4-di (tert-butylperoxy) valerate, tert-butyl peroxybenzoate, di-tert-amylperoxide , dicumyl peroxide, di- (2- t er t -butyl -per oxy isopropyl ) -benzene , 2 , 5 -dimethyl -2 ,5-di- (tert- butylperoxy ) -hexane , tert-butylcumyl peroxide, 2 , 5-dimethyl-2 ,5- di ( tert-butylperoxy ) hexyne-3 , di-tert-butyl peroxide, 3, 6, 9- triethyl-3, 6, 9-trimethyl-l, 4, 7-triperoxonane, ) and mixtures thereof .
[0128] The (meth) acrylic composition (MCI) according to the invention may comprise from 0.01 part by weight to 5 parts by weight of polymerization initiator.
[0129] According to a particular embodiment, the (meth) acrylic composition (MCI) according to the invention comprises from 0.02 part by weight to 4.5 parts by weight and advantageously 0.03 part by weight to 4 parts by weight of polymerization initiator per 100 parts by weight of the liquid (meth) acrylic syrup.
[0130] The (meth) acrylic composition (MCI) according to the invention may also effectively further according to additional aspects comprise a polymerization activator or accelerator.
[0131] According to a particular embodiment, the (meth) acrylic composition (MCI) according to the invention comprises between lOOppm and 10 OOOppm, advantageously between lOOppm and 7 OOOpmm and preferably between 200ppm and 5 OOOppm of polymerization activator or accelerator 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth) acrylic syrup (LMS1) and (LSM2) .
[0132] If the (meth) acrylic composition (MCI) comprises a polymerization activator or accelerator, it is a component of the first part composition (A) or second part composition (B) .
[0133] The polymerization activator or accelerator is preferably a tertiary amine. The tertiary amine is advantageously chosen from N, N-dimethyl-p-toluidine (DMPT) , N, N-dihydroxyethyl-p-toluidine (DHEPT) , N, N-diethyl-p-toluidine (DEPT) and para-toluidine ethoxylate (PTE) .
[0134] The present invention relates also to a process for preparing the (meth) acrylic composition (MCI) according to the first aspect and the second aspect of the invention.
[0135] According to the third and fourth aspect of the invention, this process comprises the steps: providing the respective part compositions (A) , (B) and (C) with its respective components and iv) mixing the provided part compositions.
[0136] The respective part compositions (A) , (B) and (C) to be provided are prepared by providing the respective components for each part composition and mix them accordingly.
[0137] If a monomer or liquid (meth) acrylic syrup is present in a part composition it is taken or prepared first, and the other components are added. The components are mixed. This mixing may be manual or may be performed using mixing means. In one embodiment the mixing is done at a temperature between 10°C and 30°C.
[0138] Preferably the mixing of the respective part compositions is done in a certain order.
[0139] Preferably the first part composition (A) and third part composition (C) are mixed first in a first submixing step (iva) . In a second submixing step (ivb) the second part composition (B) isadded and mixed with the mixture obtained in first submixing step (iva) .
[0140] Optionally, the mixing is performed by stirring, and for a time of between 1 minutes and 36 hours, advantageously between 2 minutes and 24 hours, more advantageously between 3 minutes and 24 hours and preferentially between 4 minutes and 24 hours.
[0141] The (meth) acrylic composition (MCI) comprising the three part compositions (A) , (B) and (C) and any of the optionally other added components has a viscosity between 10mPa*s and 10 000 mPa*s at 23°C.
[0142] Preferably the viscosity of (meth) acrylic composition (MCI) at 23°C is in a range from 50 mPa*s to 10 000 mPa*s, more preferably from 50 mPa*s to 9 000 mPa*s, still more preferably from 50 mPa*s to 8 000 mPa*s, even still more preferably from 50 mPa*s to 7 500 Pa*s, even still more preferably between 50mPa*s and 7 000 mPa*s, advantageously between 50mPa*s and 6 000mPa*s and more advantageously between 50mPa*s and 5 000mPa*s.
[0143] The (meth) acrylic composition (MCI) according to the first aspect or the second aspect is used to prepare a (meth) acrylic polymeric material (MPC1) or (meth) acrylic polymeric composite material (MPCM1) .
[0144] The (meth) acrylic polymeric material (MPC1) or the (meth) acrylic polymeric composite material (MPCM1) is prepared by polymerization of the (meth) acrylic composition (MCI) according to the first aspect or the second aspect.
[0145] The invention relates to a process for preparing a (meth) acrylic polymeric material (MPC1) , said process comprises the following steps :(i) providing a (meth) acrylic composition (MCI) according to first or second aspect,(ii) polymerizing the (meth) acrylic composition (MCI) .
[0146] The invention relates to a process for preparing a (meth) acrylic polymeric composite material (MPCM1) , said process comprises the following steps :(i)providing a (meth) acrylic composition (MCI) according to first or second aspect,(ii) bringing the (meth) acrylic composition (MCI) in contact with a reinforcing material,(iii) polymerizing the (meth) acrylic composition (MCI) .
[0147] In one embodiment, the reinforcing material is a fibrous substrate. The fibers of the fibrous substrate in the present invention are long fibers or continuous fibers. The fibrous substrate comprises preferably fibers having an aspect ratio of at least 1000, preferably at least 2000, more preferably at least 4000, advantageously at least 7000 and most advantageously at least 10 000 or continuous fibers. A fiber is defined by its aspect ratio, which is the ratio between the length and diameter of the fiber.
[0148] The fibrous substrate of the present invention is chosen from plant fibers, wood fibers, animal fibers, mineral fibers, synthetic polymeric fibers, glass fibers and carbon fibers, and mixtures thereof .
[0149] The fibers of the fibrous material have a diameter between 0.005 pm and 100 pm, preferably between 1 pm and 50 pm, more preferably between 5 pm and 30 pm and advantageously between 10 pm and 25 pm.
[0150] In another embodiment, the reinforcing material is a mineral filler. The mineral filler C may notably comprise a filler Cl chosen from quartz, granite, marble, feldspar, clay, glass, ceramics, mica, graphite, silicates, carbonates, carbides, sulfates, silicates, hydroxides, metal oxides, metals and mixtures thereof.
[0151] The step of bringing the (meth) acrylic composition (MCI) in contact with a reinforcing material
[0152] With regard to the process for preparing a (meth) acrylic polymeric composite material (MPCM1) several methods could be used, notably including the step bringing the (meth) acrylic composition (MCI) in contact with a reinforcing material for a fibrous substrate.
[0153] Mention may be made of infusion, vacuum assisted resin infusion (VARI) , pultrusion, vacuum bag molding, pressure bag molding, autoclave molding, resin transfer molding (RTM) and variations thereof as (HP-RTM, C-RTM, I-RTM) , reaction injection molding (RIM) , reinforced reaction injection molding (R-RIM) andvariants thereof, press molding, compression molding, liquid compression molding (LCM) or sheet molding compound (SMC) or bulk molding compound (BMC) and filament winding.
[0154] A first preferred manufacturing process for a (meth) acrylic polymeric composite material (MPCM1) is infusion.
[0150] A second preferred manufacturing process for a (meth) acrylic polymeric composite material (MPCM1) is filament winding.
[0152] A third preferred manufacturing process is vacuum assisted resin infusion (VARI) .
[0153] A fourth preferred manufacturing process is resin transfer molding (RTM) and variations thereof as (HP-RTM, C-RTM, I-RTM) and more preferred compression resin transfer molding (C-RTM) .
[0155] A fifth preferred manufacturing process for a (meth) acrylic polymeric composite material (MPCM1) is vacuum bag molding, pressure bag molding.
[0156] The present invention relates in an additional aspect to a moulded part (MP1) comprising the (meth) acrylic polymeric material (MCP1) or a (meth) acrylic polymeric composite material (MPCM1) .
[0157] The moulded part (MP1) has preferably a length in one dimension of at least than 5m or at least at one point has a thickness of at least 1cm, preferably 2cm.
[0158] In one embodiment the moulded part (MP1) has a length in one dimension of at least than 10m.
[0159] In another embodiment the moulded part (MP1) has a length in one dimension of at least than 20m.
[0160] In still another embodiment has at one point has a thickness of more than 3cm.
[0161] In a first preferred embodiment the (meth) acrylic polymeric composite material (MPCM1) is a fiber reinforced (meth) acrylic polymeric composite material.
[0162] In a second preferred embodiment the (meth) acrylic polymeric composite material (MPCM1) is a particle reinforced (meth) acrylic polymeric composite material.
[0163] The fiber reinforced (meth) acrylic polymeric composite material can be motor vehicle part, boat part, bus part, train part, sport article, plane or helicopter part, space ship or rocket part, photovoltaic module part, a pressure vessel, a material forconstruction or building, wind turbine part for example spar cap of girder of wind turbine blade, furniture part, construction or building part.
[0164] With regard to the use of (meth) acrylic polymeric composite material (MPCM1) , one can mention automotive and motorsports applications as for example pressure vessel, ballistic & defense applications, marine applications, railroad and transport applications, sport, leisure and recreational applications, arts and entertainments applications, aeronautic and aerospace applications, construction and civil engineering applications, oil & gas applications, renewable applications such as photovoltaic applications and wind energy applications .
[0165] As regards the use of mechanical parts made of (meth) acrylic polymeric composite material (MPCM1) , mention may be also be made of automotive applications, transport applications such as buses or lorries, marine applications, railroad applications, sport, aeronautic and aerospace applications, photovoltaic applications, computer-related applications, construction and building applications, telecommunication applications and wind energy applications .
[0166] The (meth) acrylic polymeric composite material (MPCM1) has preferably a length in one dimension of at least than 5m or at least at one point has a thickness of at least 1cm, preferably 2cm.
[0167] In one embodiment the (meth) acrylic polymeric composite material (MPCM1) has a length in one dimension of at least than 10m.
[0168] In another embodiment the (meth) acrylic polymeric composite material (MPCM1) has a length in one dimension of at least than 20m.
[0169] In still another embodiment the (meth) acrylic polymeric composite material (MPCM1) has at one point has a thickness of more than 3cm.
[0170] In one specific embodiment the (meth) acrylic polymeric composite material (MPCM1) is part of a wind blade.
[0171] In another specific embodiment the (meth) acrylic polymeric composite material (MPCM1) is part of a nautical vessel.
[0172] In still another specific embodiment the (meth) acrylic polymeric composite material (MPCM1) is part of a pressure vessel.[Methods]
[0173] The weight-average molecular weight may be measured by size exclusion chromatography (SEC) . The chromatography column is calibrated with PMMA standards having a molecular weight between 402g / mol and 1 900 000 g / mol. The average molecular weight is expressed in g / mol for the number and average molecular weight Mn and Mw respectively. For the measurement, the concentration is Ig / L.
[0174] The viscosity of the (meth) acrylic compositions comprising at least the components (Aal) and (Aa2 ) is measured with a Brookfield viscosimeter at 23°C, according to ISO 2555:2018 "Plastics — Resins in the liquid state or as emulsions or dispersions — Determination of apparent viscosity using a single cylinder type rotational viscometer method".
[0175] Stability is measured with following method. Temper the samples at 25°C. Pour 200 g of the liquid resin in a bottle and continue to keep it at 25°C. Check periodically sample. A thermocouple can be used in order to follow the temperature inside of the sample along the stability test. Sample is considered "conform", meaning stable, if the resin remains liquid at 25°C and if no exothermic peak is observed during a time of at least 3 hours, preferably at least 4 hours and more preferably even longer. By remaining liquid is meant that the viscosity does no pass 20Pa*s at 25°C.
[0176] Reactivity is measured with following method. A 20x180mm test tube is filled to a height of 7.5cm with liquid syrup and added initiator and accelerator. A thermocouple is placed in the syrup. Tube is immersed at least 140 mm in a water bath at 25 °C. Temperature is continuously measured and the time to temperature peak is taken.[Examples]
[0177] The compounds used for the preparation of the various parts of (meth) acrylic compositions are the following: in the first part composition (A) and second part composition (B)- as (meth) acrylic polymer (Pl) and (P2) : a PMMA formed by a copolymer of methyl methacrylate and of ethyl acrylate, from company Altuglas under the name Altuglas® BS 520B,- as (meth) acrylic monomer (Ml) and (M2) : a methyl methacrylate stabilized with hydroquinone monomethyl ether is used, in the first part composition (A)- as organic aldehyde (Ab) 3 , 7-demethylocta-2 , 6-dienal is used as inhibitor (Ac) 4 -hydroxy-2 , 2 , 6, 6-tetramethylpiperidin-l- oxyl is used- as accelerator if present DMPT (N, N-dimethyl-p-toluidine ) is used . in the second part composition (B)- as transition metal (Ba) metal containing Borchi® OXY-Coat 1101 from BORCHERS is used- as reducing agent (Bb) saccharine is used as inhibitor (Be) if present 4-hydroxy-2 , 2 , 6 , 6- tetramethylpiperidin-l-oxyl is used in the third part composition (C)- as initiator Trigonox® 249VR from Nouryon is used,
[0178] A liquid (meth) acrylic syrup LSM is prepared by first dissolving 20 parts by weight of the (meth) acrylic polymer (Pl) in 80 parts by weight of e (meth) acrylic monomer (Ml) . This syrup LSM is used to prepare the first part composition (A) and second part composition (B) , in other word it serves as (LSM1) for component (Aa) and (LSM2) for component (Bd) respectively.
[0179] Table 1 - compositions of first part composition (A) and second part composition (B) for methacrylic composition (MCI) according to the invention in parts by weight
[0180] The first part composition (A) and the second part composition (B) stay liquid without significant change for several days.
[0181] As the third part composition (C) Trigonox® 249VR from Nouryon is used. As a stability test it is added at 3 parts by weight to first part composition (A) and at 3 parts by weight to second part composition (B) . The compositions are kept at 23°C.
[0182] The first part composition (A) with added third part composition (C) stays stable and liquid for several hours and up to two weeks.
[0183] The second part composition (B) with added third part composition (C) stays stable and liquid for two to three hours than the temperature begins to increase slightly after three hours indicating slow polymerization, then yielding to a peak at 85 °C after 6 hours .
[0184] The first part composition (A) and the second part composition(B) itself are stable, also when mixed with third part composition(C) .
[0185] Afterwards 3 parts by weight third part composition (C) is added to 50 parts of first part composition (A) . After mixing 50 parts of second part composition (B) is added. The temperature begins to increase slightly at the beginning after three hours the increase is faster indicating beginning polymerization, then yielding to a peak at 100°C after 4 hours.
[0186] The three part composition according to the invention leaves has sufficient pot-life and leaves enough time to prepare large and or thick parts. The composition stays liquid enough for a sufficient time in order to fill a mould or impregnate a fibrous substrate or both .
Claims
CLAIMS1. A (meth) acrylic composition (MCI) comprising: a first part composition (A) comprising:(Aa) 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) comprising :(Aai) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (Pl) , and(Aa2) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (Ml) , each monomer (Ml) comprising only one (meth) acrylic function per monomer,(Ab) at least one organic aldehyde(Ac) an inhibitor; a second part composition (B) comprising:(Ba) a transition metal,(Bb) a reducing agent,(Be) optionally an inhibitor,(Bd) optionally one or more (meth) acrylic monomers (M2) and / or optionally one or more (meth) acrylic polymers (P2) ; and a third part composition (C) comprising:(Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator.
2. A (meth) acrylic composition (MCI) comprising: a first part composition (A) comprising:(Aa) 100-n parts by weight of a liquid (meth) acrylic syrup (LMS1) comprising:(Aai) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (Pl) , and(Aai) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (Ml) , each monomer (Ml) comprising only one (meth) acrylic function per monomer,(Ab) at least one organic aldehyde(Ac) an inhibitor; a second part composition (B) comprising:(Ba) a transition metal,(Bb) a reducing agent,(Be) optionally an inhibitor,(Bd) n parts by weight of a liquid (meth) acrylic syrup (LMS2) comprising :(Bdi) from 1% by weight to 50% by weight of one or more(meth) acrylic polymers (P2) , and(Bd2) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (M2) , a third part composition (C) comprising:(Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator; characterized in that O^n^lOO.
3. The (meth) acrylic composition (MCI) according to claim 1 or 2, characterized in that the liquid (meth) acrylic syrup (LSM1) comprises :( ai) from 10% by weight to 35% by weight of one or more (meth) acrylic polymers (Pl) , and( a2) from 650% by weight to 90% by weight of one or more (meth) acrylic monomers (Ml) , each monomer Ml comprising only one (meth) acrylic function per monomer.
4. The (meth) acrylic composition (MCI) according to claim 2, characterized in that the liquid (meth) acrylic syrup (LSM2) comprises :(Bdi) from 10% by weight to 35% by weight of one or more(meth) acrylic polymers (P2) , and(Bd2) from 65% by weight to 90% by weight of one or more(meth) acrylic monomers (M2) .
5. The (meth) acrylic composition (MCI) according to any of claims 1 to 4, characterized in that the organic aldehyde is chosen from propionaldehyde, butyraldehyde, valeraldehyde, capraldehyde, benzaldehyde, geranial, neral, citronellal and also mixtures of two or more thereof in all proportions .
6. The (meth) acrylic composition (MCI) according to any of claims1 to 5 , characterized in that the organic aldehyde is present between 0.5 part and 10 parts by weight for 100 parts by weightof a liquid (meth) acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth) acrylic syrup (LMS1) and (LSM2).
7. The (meth) acrylic composition (MCI) according to any of claims 1 to 5, characterized in that the transition metal is chosen from Manganese, Cobalt, Iron or Copper and more advantageously Manganese, Iron, Copper or mixtures thereof.
8. The (meth) acrylic composition (MCI) according to any of claims 1 to 5 , characterized in that the transition metal is present between 0.01 part and 4 parts by weight for 100 parts by weight of the liquid (meth) acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth) acrylic syrup (LMS1) and (LSM2 ) .
9. The (meth) acrylic composition (MCI) according to any of claims1 to 5, characterized in that the reducing agent is chosen from ascorbic acid, o-hydroxy sulfones, thioureas and saccharin.
10. The (meth) acrylic composition (MCI) according to any of claims 1 to 5, characterized in that the reducing agent is present between 0.1 part by weight and 2 parts by weight for 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth) acrylic syrup (LMS1) and (LSM2 ) .
11. The (meth) acrylic composition (MCI) according to any of claims1 to 5, characterized in that the inhibitor is chosen from 4- hydroxy-2 , 2 , 6 , 6-tetramethylpiperidin-l-oxyl or (2, 2, 6, 6-Tetramethylpiperidin-l-yl ) oxyl .
12. The (meth) acrylic composition (MCI) according to any of claims 1 to 5, characterized in that the inhibitor is presents between 0.005 part and 1 parts by weight for 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth) acrylic syrup (LMS1) and (LSM2) .
13. The (meth) acrylic composition (MCI) according to any of claims 1 to 10, characterized in that the inhibitor is chosen from 4- hydroxy-2 , 2 , 6 , 6-tetramethylpiperidin-l-oxyl or (2, 2, 6, 6-Tetramethylpiperidin-l-yl ) oxyl and is present between 0.005 part and 1 parts by weight for 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth) acrylic syrup (LMS1) and (LSM2) .
14. The (meth) acrylic composition MCI according to any of claims 1 to 4, characterized in that it comprises:(Ab) between 0.5 part and 10 parts by weight at least one organic aldehyde chosen from propionaldehyde, butyraldehyde, valeraldehyde, capraldehyde, benzaldehyde, geranial, neral, citronellal and also mixtures of two or more thereof in all proportions ,(Ac) between 0.005 part and 1 parts by weight of an inhibitor chosen from 4 -hydroxy-2 , 2 , 6, 6-tetramethylpiperidin-l-oxyl or (2,2, 6 , 6-Tetramethylpiperidin-l-yl ) oxyl;(Ba) between 0.01 part and 4 parts by weight of a transition metal chosen from Manganese, Iron, Copper or mixtures thereof, (Bb) between 0.1 part by weight and 2 parts by weight a reducing agent chosen from ascorbic acid, o-hydroxy sulfones, thioureas and saccharin, all for 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth) acrylic syrup (LMS1) and (LSM2) .
15. The (meth) acrylic composition MCI according to claim 1 or 2 , characterized in that the polymerization initiator is chosen from diacyl peroxides, peroxy esters, peroxydicarbonates, dialkyl peroxides, peroxyacetals, hydroperoxide or peroxyketale .
16. The composition according to any of claims 2 to 15, characterized in that the parameter n is from 0 to 99, corresponding to 0^n^99.
17. The composition according to any of claims 2 to 15, characterized in that the parameter n is from 40 to 60, corresponding to 40<n<60.
18. A process to prepare the (meth) acrylic composition (MCI) according to any of claims 1 to 17, comprising the steps:(i) providing a first part composition (A) comprising:(Aa) 100 parts by weight of a liquid (meth) acrylic syrup (LMS1) comprising :(Aai) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (Pl) , and(Aa2) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (Ml) , each monomer (Ml) comprising only one (meth) acrylic function per monomer,(Ab) at least one organic aldehyde(Ac) optionally an inhibitor;(ii) providing a second part composition (B) comprising:(Ba) a transition metal,(Bb) a reducing agent,(Be) optionally an inhibitor,(Bd) optionally one or more (meth) acrylic monomers (M2) and / or optionally one or more (meth) acrylic polymers (P2) ; and(iii) providing a third part composition (C) comprising:(Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator,(iv) mixing the three provided compositions.
19. A process to prepare the (meth) acrylic composition (MCI) according to any of claims 1 to 17, comprising the following steps :(i) providing a first part composition (A) comprising:(Aa) 100-n parts by weight of a liquid (meth) acrylic syrup (LMS1) comprising:(Aai) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (Pl) , and(Aab) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (Ml) , each monomer (Ml) comprising only one (meth) acrylic function per monomer,(Ab) at least one organic aldehyde(Ac) optionally an inhibitor;(ii) providing a second part composition (B) comprising:(Ba) a transition metal,(Bb) a reducing agent,(Be) optionally an inhibitor,(Bd) n parts by weight of a liquid (meth) acrylic syrup (LMS2) comprising :(Bdi) from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (P2) , and(Bdb) from 50% by weight to 99% by weight of one or more (meth) acrylic monomers (M2) , and(iii) providing a third part composition (C) comprising:(Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator,(iv)mixing the three provided compositions; with n being from 0 to 100.
20. The process according to any of claims 18 or 19, characterized in that the mixing step (iv) comprises two submixing steps:(iva) mixing the first part composition (A) and third part composition (C) and(ivb) adding and mixing the second part composition (B) with the mixture obtained in first submixing step (iva) .
21. Use of the (meth) acrylic composition (MCI) according to any of claims 1 to 17 to prepare a (meth) acrylic polymeric material (MCP1) or (meth) acrylic polymeric composite material (MPCM1) .
22. A (meth) acrylic polymeric material (MCP1) prepared by polymerization of the (meth) acrylic composition MCI according to any of claims 1 to 17.
23. A (meth) acrylic polymeric composite material (MPCM1) prepared by polymerization of the (meth) acrylic composition (MCI) according to any of claims 1 to 17.
24. The (meth) acrylic polymeric composite material (MPCM1) according to claim 23, being part of a wind blade or part of a nautical vessel or part of a pressure vessel.
25. The (meth) acrylic polymeric composite material (MPCM1) according to claim 23, having length in one dimension of at least than 5m or at least at one point has a thickness of at least 1cm, preferably 2cm.
26. A process to prepare a (meth) acrylic polymeric material (MCP1) comprising the following steps:(i) providing a (meth) acrylic composition (MCI) according to any of claims 1 to 17,(ii) polymerizing the (meth) acrylic composition (MCI) .
27. A process to prepare a (meth) acrylic polymeric composite material (MCPM1) comprising the following steps:(i) providing a (meth) acrylic composition (MCI) according to any of claims 1 to 17,(ii)bringing the (meth) acrylic composition (MCI) in contact with a reinforcing material,( iii ) polymerizing the (meth) acrylic composition (MCI) .
28. The process according to claim 27, comprising infusion, vacuum assisted resin infusion (VARI) , pultrusion, vacuum bag molding, pressure bag molding, autoclave molding, resin transfer molding (RTM) and variations thereof as (HP-RTM, C-RTM, I-RTM) , reaction injection molding (RIM) , reinforced reaction injection molding (R-RIM) and variants thereof, press molding, compression molding, liquid compression molding (LCM) or sheet molding compound (SMC) or bulk molding compound (BMC) and filament winding .