Impregnation process for a fibrous substrate, a liquid (meth) acrylic syrup for the impregnation process, its method of polymerization and structured article obtained thereof

Patent metadata

Field	Value
Publication number	US-11773247-B2
Application number	US-201916383704-A
Country	US
Kind code	B2
Filing date	Apr 15, 2019
Priority date	Jul 18, 2012
Publication date	Oct 3, 2023
Grant date	Oct 3, 2023

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 or acrylic components. This viscous composition is called hereafter liquid (meth) acrylic 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 (meth) acrylic syrup is achieved in a closed 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.

First claim

What is claimed is:

1. An impregnation liquid (meth) acrylic syrup for implementing an impregnation process of a fibrous substrate, wherein said fibrous substrate is made of long fibres having an aspect ratio of at least 1000, said liquid (meth) acrylic syrup comprises:
a) a (meth)acrylic polymer comprising at least 90 percent by weight of methyl methacrylate monomer units and having a weight average molecular weight larger than 50,000 g/mol,
b) a (meth) acrylic monomer comprising an inhibitor, wherein said (meth)acrylic monomer is two or more selected from the group consisting of acrylic acid, methacrylic acid, alkyl acrylic monomers wherein said alkyl has 1 to 22 carbons, either linear, branched or cyclic; alkyl methacrylic monomers wherein said alkyl has 1 to 22 carbons, either linear, branched or cyclic; methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, n-butyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate and mixtures thereof
c) at least one initiator or initiating system for starting the polymerization of the (meth) acrylic monomer, and
d) from 300 ppm to 4000 ppm by weight of an activator, based on the weight of the (meth) acrylic monomer
said liquid (meth)acrylic syrup has a dynamic viscosity of a value in the range from 50 mPa*s to 1000 mPa*s,
and wherein said syrup contains no metal based catalysts.

2. The impregnation liquid (meth) acrylic syrup according to claim 1 , wherein said syrup comprises:
a) from 10 weight percent to 59.99 weight percent (meth)acrylic polymer, based on the sum of the (meth)acrylic monomer plus (meth)acrylic polymer,
b) from 40 weight percent to 89.99 weight percent (meth)acrylic monomer,
c) from 0.01 weight percent to 5 weight percent one initiator or initiating system for starting the polymerization of the (meth) acrylic monomer, based on the weight of the (meth)acrylic monomer,
d) from 300 ppm to 4000 ppm by weight of an activator, based on the weight of the (meth) acrylic monomer
e) from 0 weight percent to 20 weight percent fillers, based on the weight of the liquid (meth)acrylic syrup,
f) from 0 weight percent to 20 weight percent additives based on the weight of the liquid (meth)acrylic syrup.

3. The impregnation liquid (meth) acrylic syrup according to claim 1 , wherein the (meth)acrylic polymer is a homopolymer or copolymer of methyl methacrylate (MMA) units or a mixture thereof.

4. The impregnation liquid (meth) acrylic syrup according to claim 1 , wherein the (meth)acrylic polymer comprises at least 95 percent by weight of methyl methacrylate (MMA) units.

5. The impregnation liquid (meth) acrylic syrup according to claim 1 , wherein the (meth)acrylic polymer comprises from 90 percent to 99.7 percent by weight of methyl methacrylate units, and from 0.3 to 10 percent by weight of at least one monomer unit derived from at least one ethylenic unsaturation that can copolymerize with methyl methacrylate.

6. The impregnation liquid (meth) acrylic syrup according to claim 1 , wherein the (meth)acrylic polymer further comprises comonomer units, wherein said comonomer units are an alkyl acrylate having an alkyl group from 1 to 12 carbon atoms.

7. The impregnation liquid (meth) acrylic syrup according to claim 6 , wherein said comonomer units are chosen from methyl acrylate, ethyl acrylate, and a mixture thereof.

8. The impregnation liquid (meth) acrylic syrup according to claim 1 , wherein the (meth)acrylic polymer has polymer weight average molecular weight larger than 100,000 g/mol.

9. The impregnation liquid (meth) acrylic syrup according to claim 1 , wherein at least 50 weight percent of the (meth)acrylic monomer is methyl methacrylate.

10. The impregnation liquid (meth) acrylic syrup according to claim 1 , wherein the initiator or initiating system for starting the polymerization of the (meth) acrylic monomer generates radicals.

11. The impregnation liquid (meth) acrylic syrup according to claim 10 , wherein the initiator or initiating system for starting the polymerization of the (meth) acrylic monomer is selected from the group consisting of diacyl peroxides, peroxy esters, dialkyl peroxides, peroxyacetals, azo compounds, isopropyl carbonate, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, dicumyl peroxide, tert-butyl perbenzoate, tert-butyl per(2-ethylhexanoate), cumyl hydroperoxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxyisobutyrate, tert-butyl peracetate, tert-butyl perpivalate, amyl perpivalate, tert-butyl peroctoate, azobisisobutyronitrile (AIBN), azobisisobutyramide, 2,2′-azobis(2,4-dimethylvaleronitrile) or 4,4′-azobis(4-cyanopentanoic) and mixtures thereof.

12. The impregnation liquid (meth) acrylic syrup according to claim 11 , wherein the initiator or initiating system for starting the polymerization of the (meth) acrylic monomer is chosen from peroxides having 2 to 20 carbon atoms.

13. The impregnation liquid (meth) acrylic syrup according to claim 11 , wherein the amount of the initiator or initiating system for starting the polymerization of the (meth) acrylic monomer is from 100 to 50000 ppm by weight, based on the (meth)acrylic monomer.

14. The impregnation liquid (meth) acrylic syrup according to claim 2 , wherein the liquid (meth) acrylic syrup comprises 300 to 4,000 ppm by weight based on the weight of (meth)acrylic monomer, of an activator, said activator being selected from the group consisting of tertiary amines, N,N-dimethyl-p-toluidine (DMPT), N,N-dihydroxyethyl-p-toluidine (DHEPT), and mixtures thereof.

15. The impregnation liquid (meth) acrylic syrup according to claim 1 , wherein the (meth)acrylic polymer in the liquid (meth) acrylic syrup is present at from 15 weight percent to 50 weight percent, based on the total liquid (meth) acrylic syrup.

16. The impregnation liquid (meth) acrylic syrup according to claim 2 , wherein said additive is selected from the group consisting of impact modifiers, block copolymers, thermal stabilizers, UV stabilizers, flame retardants, lubricants and mixtures thereof.

17. A manufacturing process for manufacturing mechanical or structured parts or articles comprising following steps:
a) impregnating a fibrous substrate with the impregnation liquid (meth) acrylic syrup according claim 1 ,
b) polymerizing the liquid (meth) acrylic syrup impregnating said fibrous substrate.

18. The process according to claim 17 , wherein said fibrous substrate consists of fibers have an aspect ratio of at least 1000.

19. The process according to claim 17 , wherein the fibrous substrate is in form of fibrous mats, non-woven reinforcements, woven roving or bundles of fibers.

20. The process according to claim 17 , wherein the impregnation of the fibrous substrate in step a) is made in a closed mold.

21. The process according to claim 17 , wherein step a) and step b) occur in the same closed mold.

22. The process according to claim 17 , wherein the process is chosen from resin transfer molding and infusion.

23. The process according to claim 17 , wherein the temperature of the polymerization is step b) is below 40° C.

24. A three-dimensional mechanical or structured parts obtained by the manufacturing process according to claim 17 .

25. The three-dimensional mechanical or structured parts according to claim 24 , wherein said part is selected from the group c

Assignees

• Arkema France

Inventors

• Gerard Pierre
• Cauchois Jean-Pierre
• Hochstetter Gilles
• Glotin Michel
• Perrin Camille
• Francois Gilles Raymond

Classifications

• C08L33/12 Primary

  Homopolymers or copolymers of methyl methacrylate · CPC title

• B29C70/48

  and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM] {, e.g. by vacuum} · CPC title

• C08F265/06 Primary

  Polymerisation of acrylate or methacrylate esters on to polymers thereof · CPC title

• C08J5/244 Primary

  using glass fibres · CPC title

• C08J5/249

  characterised by the additives used in the prepolymer mixture · CPC title