EP-4735493-A1 - MULTISTAGE POLYMER, ITS METHOD OF PREPARATION, COMPOSITION COMPRISING IT AND ITS USE

Abstract

The present invention relates to a composition comprising a multistage polymer, its process of preparation, composition comprising it and its use. In particular the present invention relates to a composition in form of a polymer powder comprising a simple multistage polymer in form of polymeric particles made by a multistage process. More particularly the present invention relates to polymer composition in form of a porous polymer powder comprising polymeric particles made by a multistage process comprising two stages and comprising as external shell a (meth)acrylic copolymer comprising alicyclic hydrocarbon groups, its process of preparation, its use and compositions and articles comprising it.

Inventors

• COUFFIN, Aline
• INOUBLI, RABI

Assignees

• ARKEMA France

Dates

Publication Date

20260506

Application Date

20240625

Claims (20)

1. 1. A polymer composition (PCI) comprising a) a polymer (Al) having a glass transition temperature of less than 10°C, b) a polymer (Bl) having a glass transition temperature of at least 60°C, said polymer (Bl) represents at least 10wt% and at most 40wt% of the composition based on a) and b) only, the component a) and the component b) of composition (PCI) are part of a multistage polymer (MP1) and the polymer (Bl) has a mass average molecular weight Mw between 10 OOOg/mol and 500 OOOg/mol, characterized in that the polymer (Bl) comprise polymerized monomer units comprising an alicyclic hydrocarbon group with a carbon number from 3 to 20.
2. 2. The polymer composition (PCI) according to claim 1, characterized in that part of polymer (Bl) is grafted on polymer (Al) .
3. 3. The polymer composition (PCI) according to claim 2, characterized in that at least 25wt% of polymer (Bl) is grafted.
4. 4. The polymer composition (PCI) according to claim 1, characterized in that at least 3wt% of the polymer (Bl) in the multistage polymer (MP1) can be solubilized in a solvent of the copolymer (Bl) and extracted.
5. 5. The polymeric composition according to claim 1 to 4, characterized in that each of the polymer (Bl) does not comprise moieties coming from chain transfer agents, especially mercaptan based chain transfer agents.
6. 6. The polymer composition (PCI) according to any of claims 1 to 5, characterized in that the polymer composition (PCI) comprises less than lOOOppm of sulphur.
7. 7. The polymeric composition according any of claims 1 to 7, characterized in that the each of the polymer (Bl) comprises between 25wt% and 35wt% monomer units comprising the alicyclic hydrocarbon group with a carbon number from 3 to 20.
8. 8. The polymeric composition (PCI) according to any of claims 1 to 7, characterized in that the monomer units comprising an alicyclic hydrocarbon group with a carbon number from 3 to 20 is chosen from cyclohexyl acrylate, cyclohexyl methacrylate, 4- tertbutyl cyclohexyl acrylate, trimethyl cyclohexyl acrylate, norbornyl acylate, norbornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, fenchyl acrylate, fenchyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, adamantyl acrylate, adamantyl methacrylate, dimethyl admantyl acrylate, dimethyl admantyl methacrylate, cyclodecyl acrylate, cyclodecyl methacrylate.
9. 9. The polymeric composition (PCI) according to any of claims 1 to 8, characterized in that the polymeric composition (PCI) in form of a porous polymer powder (POW1) is having total intruded volume of at least 1.2 ml/g, as measured by mercury porosimetry.
10. 10. The polymeric composition (PCI) according to any of claims 1 to 9, characterized in that the polymeric composition (PCI) in form of a porous polymer powder (POW1) is having a total intruded volume or total cumulative intrusion between 1.2ml/g and lOml/g, as measured by mercury porosimetry.
11. 11. The polymeric composition (PCI) according to any of claims 1 to 10, characterized in that the polymeric composition (PCI) in form of a porous polymer powder (POW1) is having a cumulative intrusion for a pore size above 10pm of at least 0.9ml/g, as measured by mercury porosimetry.
12. 12. The polymeric composition (PCI) according to any of claims 1 to 11, characterized in that the polymeric composition (PCI) in form of a porous polymer powder (POW1) is having an incremental intrusion between a pore size from 10pm to 1pm of at least O.lml/g, as measured by mercury porosimetry.
13. 13. The polymeric composition (PCI) according to any of claims 1 to 12, characterized in that the polymeric composition (PCI) in form of a porous polymer powder (POW1) is having an apparent bulk density between 0.1g/cm 3 and 0.60g/cm 3 .
14. 14. The polymeric composition (PCI) according to any of claims 1 to 13, characterized in that the polymer (Bl) is a copolymer comprising a comonomer (MCbi) , said comonomer (MCbi) is comprising an alicyclic hydrocarbon group with a carbon number from 3 to 20.
15. 15. The polymeric composition (PCI) according to claim 14, characterized in that the the comonomer (MCbi) in the copolymer (Bl) is present between 5wt% and 50wt%, preferably between 10wt% and 40wt% and more preferably between 20wt% and 40wt%.
16. 16. A process for manufacturing the polymer composition according to any of claims 1 to 15 comprising the steps of a) polymerizing by emulsion polymerization of a monomer or monomer mixture (A m ) to obtain one layer in stage (A) comprising polymer (Al) having a glass transition temperature of less than 10°C; b) polymerizing by emulsion polymerization of a monomer or monomer mixture (B m ) to obtain layer in stage (B) comprising a polymer (Bl) having a glass transition temperature of at least 60 °C; characterized in that said polymer (Bl) represents at least 10wt% and at most 40wt% of the composition based on a) and b) only, and that the polymer (Bl) has a mass average molecular weight Mw between 10 OOOg/mol and 500 OOOg/mol and the monomer or monomer mixture (B m ) comprise a comonomer (MCbi) said comonomer (MCbi) comprises an alicyclic hydrocarbon group with a carbon number from 3 to 20.
17. 17. A process for manufacturing the polymer composition according to any of claims 1 to 15 comprising the steps of a) polymerizing by emulsion polymerization of a monomer or monomer mixture (A m ) to obtain one layer in stage (A) comprising polymer (Al) having a glass transition temperature of less than 10°C; b) polymerizing by emulsion polymerization of a monomer or monomer mixture (B m ) to obtain layer in stage (B) comprising a polymer (Bl) having a glass transition temperature of at least 60 °C; c) agglomerating the composition obtained in steps a) to b) ; characterized in that said polymer (Bl) represents at least 10wt% and at most 40wt% of the composition based on a) and b) only, and that the polymer (Bl) has a mass average molecular weight Mw between 10 OOOg/mol and 500 OOOg/mol and the monomer or monomer mixture (B m ) comprise a comonomer (MCbi) said comonomer (MCbi) comprises an alicyclic hydrocarbon group with a carbon number from 3 to 20.
18. 18. The process according to claim 16 or 17, characterized in that the agglomeration step is made by coagulation.
19. 19. The process according to claim 16 or 17, characterized in that the agglomeration step is made by spray drying.
20. 20. The process according to claim 16 or 17, characterized in that the during step b) no chain transfer agent is used, especially mercaptan based chain transfer agents.

Description

MULTISTAGE POLYMER, ITS METHOD OF PREPARATION, COMPOSITION COMPRISING IT AND ITS USE [Field of the invention] [001 ] The present invention relates to a composition comprising a multistage polymer , its process of preparation, composition comprising it and its use . [002 ] In particular the present invention relates to a composition in form of a polymer powder comprising a simple multistage polymer in form of polymeric particles made by a multistage process . [003 ] More particularly the present invention relates to polymer composition in form of a porous polymer powder comprising polymeric particles made by a multistage process comprising two stages and comprising as external shell a (meth ) acrylic copolymer comprising alicyclic hydrocarbon groups , its process of preparation, its use and compositions and articles comprising it . [Technical problem] [004 ] Polymers are widely used also as additives in polymer compositions . These so-called polymer additives are usually added as granulate or also as powder , either to solid polymers , or to molten polymers or to liquid resins or to liquid compositions . [005 ] One class of polymeric additives are processing aids , another one is polymeric impact modifiers . [006 ] Polymeric impact modifiers can be in form of polymeric particles . Usually, these polymeric impact modifiers are in form of core-shell particles that are made by a multistage process , with at least one stage comprising a rubber like polymer . Afterwards these particles are incorporated in the polymers or polymer compositions , in order to increase their impact resistance . The polymers or polymer compositions can be thermoset ones or thermoplastic ones . [007 ] Thermosetting polymers consist of crosslinked three- dimensional structures . The crosslinking is obtained by curing reactive groups inside the so-called prepolymer . Curing for example can be obtained by heating the polymer chains or prepolymer in order to crosslink and harden the material permanently . [008 ] Thermoplastic polymers consist of linear or branched polymers , which are usually not cross-linked . They might be slightly crosslinked as long as they can be deformed by heat . However , these before mentioned core-shell particles are not easy to disperse or fast to disperse in all kind of resins or polymers or precursors to polymers , especially for example in liquid epoxy resins or liquid monomers or other liquid polymeric precursors . [009 ] A good homogenous and fast dispersion is necessary for having satisfying impact performance in the final polymeric composition . An easy dispersion making and fast dispersion time is also required to reduce the process time and gain on an easier simpler process . [010 ] An obj ective of the present invention is to propose a polymeric composition which is rapidly and easily dispersible , especially in liquid resins as for example precursors for thermoset polymers or thermoplastic polymers as respectively for instance in epoxy resins or in (meth) acrylic monomers . [Oil ] An obj ective of the present invention is to propose a polymeric composition in form of a polymer powder which is rapidly and easily dispersible , especially in liquid resins as for example precursors for thermoset polymers or thermoplastic polymers as respectively for instance in epoxy resins or in (meth ) acrylic monomers . [012 ] An additional obj ective of the present invention is to propose a polymeric composition in form of a dry polymer powder which is easily dispersible , especially in low polar liquid resins or low polar (meth) acrylic monomers . [013 ] An obj ective of the present invention is also to propose a multistage polymer composition in form of a dry polymer powder which is easily dispersible , especially in low polar liquid resins or low polar (meth) acrylic monomers . [014 ] An additional obj ective of the present invention is to propose a multistage polymer composition in form of a dry polymer powder which is easily dispersible in reactive epoxy resins , polyester resins or (meth) acrylic resins /polymers or liquid monomers or resins . [015 ] Another obj ective of the present invention is to propose a simplified process for making a multistage polymer composition in form of a polymer powder which is easily dispersible in in reactive epoxy resins , polyester resins or (meth) acrylic resins /polymers or liquid monomers or resins , especially in low polar liquid resins or low polar (meth) acrylic monomers . [016 ] Still another obj ective of the present invention is the use of a polymeric composition in form of a polymer powder for preparing a liquid composition comprising precursors for thermoset polymers or thermoplastic polymers . [017 ] Still another obj ective is to reduce the time of dispersing a polymer powder in such a liquid composition . [BACKGROUND OF THE INVENTION] Prior art [018 ] The document WO2016/ 102666 discloses a composition comprising a multistage polymer and its method of preparatio