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US-12617886-B2 - Liquid composition comprising a wax compound, its process of polymerization, use and material or composition obtained following polymerization of composition

US12617886B2US 12617886 B2US12617886 B2US 12617886B2US-12617886-B2

Abstract

A liquid composition including a monomer, a (meth)acrylic polymer and a wax compound. The liquid composition can be used as a syrup and especially as a syrup for impregnation of fibres or fibrous material. Also, a thermoplastic material obtained after polymerization of the liquid composition. Also, a process for manufacturing such a liquid composition. Also, a process for impregnating a fibrous substrate of long or continuous fibres with such a liquid composition. Also, a fibrous substrate impregnated with such a liquid composition which is useful for manufacturing composite parts. Also, a process for manufacturing mechanical parts or structural elements made of composite material and mechanical parts or structural elements made of composite material obtained via a process using such a liquid composition.

Inventors

  • Pierre Gerard

Assignees

  • ARKEMA FRANCE

Dates

Publication Date
20260505
Application Date
20200311
Priority Date
20190311

Claims (20)

  1. 1 . A liquid composition LC1 comprising, a) a (meth)acrylic polymer (P1) having a weight-average molecular mass greater than 100,000 g/mol and comprising at least 90% by weight of methyl methacrylate, b) a (meth)acrylic monomer (M1), wherein at least 80% by weight of the (meth)acrylic monomer (M1) is methyl methacrylate, and c) between 0.45 phr and 1.4 phr relative to the sum of (meth)acrylic monomer (M1) and (meth)acrylic polymer (P1) of a wax compound (W) having a congealing point below 60° C., said liquid composition having a dynamic viscosity of between 25 mPa*s and 10,000 mPa*s at 25° C., wherein the (meth)acrylic polymer (P1) is present in a proportion not more than 30% by weight relative to the total weight of (meth)acrylic monomer (M1) and (meth)acrylic polymer (P1), and wherein less than 5 wt % of the (meth)acrylic monomer (M1) evaporates at 23° C. for a duration of 20 minutes.
  2. 2 . The liquid composition LC1 as claimed in claim 1 , wherein the quantity of the wax compound (W) in the composition is between 0.5 phr and 1.3 phr relative to the sum of (meth)acrylic monomer (M1) and (meth)acrylic polymer (P1).
  3. 3 . The liquid composition LC1 according to claim 1 , wherein the density of the wax compound (W) is less than the density of the (meth)acrylic monomer (M1) and (meth)acrylic polymer (P1) together.
  4. 4 . The liquid composition LC1 according to claim 1 , wherein the density of the wax compound (W) is less than 1.1 g/cm 3 .
  5. 5 . The liquid composition LC1 according to claim 1 , wherein the density of the wax compound (W) is between 0.7 g/cm 3 and 1.1 g/cm 3 .
  6. 6 . The liquid composition LC1 according to claim 1 , wherein the liquid composition comprises additionally d) an initiator (Ini).
  7. 7 . The liquid composition LC1 according to claim 6 , wherein quantity the initiator (Ini) in the composition is between 0.75 phr and 8 phr relative to the sum of (meth)acrylic monomer (M1) and (meth)acrylic polymer (P1).
  8. 8 . The liquid composition LC1 according to claim 6 , wherein the initiator (Ini) 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) peroxydicarbonate, 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-tert-butyl-peroxyisopropyl)-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-1,4,7-triperoxonane, 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azodi-(2-methylbutyronitrile), azobisisobutyramide, 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-Azodi(hexahydrobenzonitrile), or 4,4′-azobis (4-cyanopentanoic) and mixtures thereof.
  9. 9 . The liquid composition LC1 according to claim 1 , wherein the wax compound (W) has a congealing point is between 15° C. and 60° C.
  10. 10 . The liquid composition LC1 according to claim 1 , wherein the liquid composition LC1 comprises a monomer (M2) between 0.01 and 10 phr by weight relative to the sum of (meth)acrylic monomer (M1) and (meth)acrylic polymer (P1), said (meth)acrylic monomer (M2) comprises at least two (meth)acrylic functions.
  11. 11 . The liquid composition LC1 according to claim 1 , wherein the (meth)acrylic monomer(s) (M1) in the liquid composition LC1 or (meth)acrylic syrup are present in proportions of between 40% and 90% by weight of the composition comprising (meth)acrylic monomer(s) (M1) and (meth)acrylic polymer (P1).
  12. 12 . Process for preparing the liquid composition LC1 according to claim 1 , said process comprising the following steps: i) preparing a mixture of (meth)acrylic polymer (P1) and (meth)acrylic monomer (M1); ii) adding a wax compound (W) to the mixture prepared in previous step.
  13. 13 . The process according to claim 12 , wherein the (meth)acrylic polymer (P1) in the liquid composition LC1 or (meth)acrylic syrup is present in proportions of between 15% and 35% by weight and the (meth)acrylic monomer (M1) in the liquid composition LC1 or (meth)acrylic syrup is present in proportions of between 65% and 85% by weight of the composition comprising (meth)acrylic monomer (M1) and (meth)acrylic polymer (P1).
  14. 14 . The process according to claim 12 , wherein an initiator (Ini) is added to the the liquid composition LC1.
  15. 15 . The process according to claim 12 , wherein the in that the wax compound (W) has a congealing point is between 25° C. and 60° C.
  16. 16 . Process for manufacturing thermoplastic parts by a process comprising the following steps: i) preparing a liquid mixture of (meth)acrylic polymer (P1) and (meth)acrylic monomer (M1) ii) adding a wax compound (W) to the mixture prepared in previous step, iii) putting the liquid (meth)acrylic composition prepared in i) and ii) in means for polymerization, said composition comprises additionally: d) a initiator (Ini); said liquid (meth)acrylic syrup having a dynamic viscosity of between 10 mPa*s and 10 000 mPa*s at 25° C., according to claim 1 , iv) polymerizing.
  17. 17 . The process according to claim 16 made by open molding, pultrusion, hand lay-up and filament winding.
  18. 18 . The process according to claim 16 , wherein the polymerizing step takes place at temperature between 40° C. and 140° C.
  19. 19 . The process according to claim 16 , wherein the process further comprises a step of post forming.
  20. 20 . The process according to claim 16 , wherein the process further comprises a step of welding or gluing or laminating.

Description

FIELD OF THE INVENTION The present invention relates to a liquid composition comprising a monomer, a (meth)acrylic polymer and at a wax compound. In particular the present invention relates to a liquid composition comprising a monomer, a (meth)acrylic polymer and a wax compound. That liquid composition can be used as a syrup and especially as a syrup for impregnation of fibres or fibrous material. Also concerned is a thermoplastic material obtained after polymerization of the liquid composition. The invention also relates to a process for manufacturing such a liquid composition. The invention also relates to a process for impregnating a fibrous substrate of long or continuous fibres with said liquid composition. The invention also relates to a fibrous substrate impregnated with said liquid composition which is useful for manufacturing composite parts. The present invention also relates to a process for manufacturing mechanical parts or structural elements made of composite material and to mechanical parts or structural elements made of composite material obtained via a process using such a liquid composition. PRIOR ART Thermoplastic polymers are materials that are widely used today in several fields and applications, for example in the construction, aeronautic, automobile or railway sectors, where they are part of mechanical parts. These mechanical parts that have to withstand high stresses during their use are widely manufactured from composite materials. A composite material is a macroscopic combination of two or more immiscible materials. The composite material consists of at least one material which forms the matrix, i.e. a continuous phase that ensures the cohesion of the structure, and a reinforcing material. The purpose of using a composite material is to obtain performance qualities that are not available from each of its constituents when they are used separately. Consequently, composite materials are widely used in several industrial sectors, for instance building, automotive, aerospace, transport, leisure, electronics, and sports notably due to their better mechanical performance (higher tensile strength, higher tensile modulus, higher fracture toughness) and their low density, in comparison with homogeneous materials. To allow thermoforming and recycling, it is preferred to use thermoplastic polymers also in composite materials, contrary to thermoset polymers. Thermoplastic polymers consist of linear or branched polymers, which are usually not crosslinked. The thermoplastic polymers are heated in order to mix the constituents necessary for manufacturing the composite material and are cooled to set the final form. The problem of these molten thermoplastic polymers is their very high viscosity in the molten state in order to homogenously impregnating for example a fibrous substrate. The wetting or correct impregnation of the fibers by the thermoplastic polymer can only be achieved, if the thermoplastic resin is sufficiently fluid. In order to have a low viscosity or sufficient fluidity of the thermoplastic polymer the chain length or molecular mass shall be reduced. However a too low molecular weight has a negative impact on the performance of the composite material and on the mechanical or structured parts especially their mechanical properties as the deformation modulus. In order to prepare a polymeric composite material based on thermoplastic polymer, a thermoplastic polymer resin, commonly known as a “syrup”, is used to impregnate the reinforcing material, for example a fibrous substrate. Once polymerized, the thermoplastic polymeric syrup constitutes the matrix of the composite material. Another way to reduce the viscosity in an important way of the thermoplastic polymer is to increase the temperature. Consequently the continuous working temperature is relatively high, above 200° C., increasing the economics costs of the composite material and mechanical or structured parts due to implication of high energy costs. Additionally thermoplastic polymers tend to degrade if the temperature is too high, which is especially true for semicrystalline thermoplastic polymers that have high melting points as for example polyamides such as PA6.6, polyethersulfon (PES), polyetherimid (PEI), polyetheretherketon (PEEK) or polyphenylene sulfide (PPS). This thermoinduced degradation yields to a decreasing molecular weight of the polymer matrix on the fibrous substrate important for the cohesion of the composite material and the mechanical or structured parts. Another way for impregnating the fibrous substrate is to dissolve the thermoplastic polymer in an organic solvent. However this method requires a lot of solvent that has to be evaporated. There are environmental issues in using large quantities of solvent in term of energy and pollution. Still another way is for impregnating the fibrous substrate is to use the respective monomers for the impregnation and polymerize to form the thermoplastic polymer after t