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 relatively 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 polymer powder comprising polymeric particles made by a multistage process comprising two stages and comprising internal a (meth)acrylic polymer or copolymer comprising lateral ester groups, its process of preparation, its use and compositions and articles comprising it.

Description

MULTISTAGE POLYMER, ITS METHOD OF PREPARATION, COMPOSITIONCOMPRISING IT AND ITS USE[Field of the invention]

[0001] The present invention relates to a composition comprising a multistage polymer, its process of preparation, composition comprising it and its use .

[0002] In particular the present invention relates to a composition in form of a polymer powder comprising a relatively simple multistage polymer in form of polymeric particles made by a multistage process .

[0003] More particularly the present invention relates to polymer composition in form of a polymer powder comprising polymeric particles made by a multistage process comprising two stages and comprising internal a (meth ) acrylic polymer or copolymer comprising lateral ester groups or polyester groups , its process of preparation, its use and compositions and articles comprising it .[Technical problem]

[0004] 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 .

[0005] One class of polymeric additives are processing aids , another one is polymeric impact modifiers .

[0006] Polymeric impact modifiers can be in form of block copolymers of polymeric particles , in order to form a dispersed elastomeric or rubber phase in a continuous phase .

[0007] These polymeric impact modifiers in form of polymeric particles are usually 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 .

[0008] Thermosetting polymers consist of crosslinked three- dimensional structures . The crosslinking is obtained by curing reactive groups inside the so-called prepolymer . Curing for examplecan be obtained by heating the polymer chains or prepolymer in order to crosslink and harden the material permanently .

[0009] 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 rapidly to disperse in all kinds of resins or polymers or precursors to polymers , especially for example in polyesters .

[0010] A good homogenous and rapid dispersion is necessary for having satisfying impact performance in the final polymeric composition . An easy a rapid process for making the dispersion and fast dispersion time is also required to reduce the process time and gain on an easier simpler process .[Oil ] This applies for virgin polymers but also recycled polymers . Latter might use another amount of impact modifier for enhancing properties .

[0012] An obj ective of the present invention is to propose a polymeric composition as impact modifier which is rapidly and easily dispersible , especially in thermoplastic polymers as for instance in polyesters , but also in monomers or precursors for polymers as for instances polyols .

[0013] An obj ective of the present invention is as well to propose a polymeric composition as impact modifier in form of a polymer powder which is rapidly and easily dispersible , especially in thermoplastic polymers as for instance in polyesters , and blends comprising polyesters .

[0014] An additional obj ective of the present invention is to propose a polymeric composition as impact modifier in form of a dry polymer powder , with reduced caking and good flowability which is easily dispersible , especially in thermoplastic polymers as for instance in polyesters and blends comprising polyesters .

[0015] An obj ective of the present invention is also to propose a polymer composition as impact modifier which is easily dispersible and comprises raw materials that are less harmful than some of today' s standard impact modifiers , especially impact modifier for thermoplastic polymers , and more especially for polyesters .

[0016] An additional obj ective of the present invention is to propose a polymer composition as impact modifier for polyesters .

[0017] An additional obj ective of the present invention is to propose a polymer composition as impact modifier for recycled polyesters , virgin polyesters , blends of recycled polyesters or a blend of virgin and recycled polyester .

[0018] Another obj ective of the present invention is to propose a simplified process for making a polymer composition in form of a polymer powder which is rapidly and easily dispersible in especially in thermoplastic polymers as for instance in polyesters .

[0019] Still another obj ective of the present invention is the use of a polymeric composition in form of a polymer powder for preparing impact modified thermoplastic polymers .

[0020] Still another obj ective is to propose impact modified polymeric articles , especially based on polyesters or polyester blends , including recycled polyesters .[BACKGROUND OF THE INVENTION] Prior art

[0021] The document WO2016 / 102666 discloses a composition comprising a multistage polymer and its method of preparation . The composition comprises as well a (meth) acrylic polymer that has a mass average molecular weight of less than 100 O OOg / mol . The (meth) acrylic polymer can comprise a functional monomer unit .

[0022] The document WO2016 / 102682 discloses a multistage polymer composition and its method of preparation . The multistage polymer comprises a last stage that comprises a (meth ) acrylic polymer that has a mass average molecular weight of less than 100 O O Og / mol . The (meth ) acrylic polymer can comprise a functional monomer unit .

[0023] The document W02019 / 012052 discloses a composition comprising a multistage polymer and its method of preparation . The composition comprises as well a (meth) acrylic polymer that has a mass average molecular weight between 100 000 g / mol and 1 000 000 g / mol . The (meth ) acrylic polymer can comprise a functional monomer unit .

[0024] The patent application EP3733727 discloses a rubber-containing graft polymer and a resin composition containing said rubbercontaining graft polymer . The rubber-containing graft polymer is grafted with a caprolactone .

[0025] The document EP0362855 discloses a core-shell polymer and compositions comprising it . The core-shell polymer comprises epoxy groups .

[0026] The document EP1104784 discloses thermoplastic polyester compositions having improved impact properties . The impact modifier comprises a core-shell polymer and a functional ethylene copolymer with carboxylic acid anhydride or epoxy functions .

[0027] The document EP1252234 discloses thermoplastic polyester compositions with improved impact properties and an impact modifying composition . The impact modifying composition comprises a core-shell polymer, a functional ethylene copolymer with carboxylic acid anhydride or epoxy functions and a copolymer selected from ethylenealkyl (meth) acrylate copolymers optionally neutralized ethylenemeth ) acrylic acid copolymers .

[0028] None of the prior art documents discloses a composition comprising a simple impact modifier as a multistage polymer having one shell above the rubber like polymer, said shell polymer is comprising monomer units with lateral polyester functions .[Brief description of the invention]

[0029] Surprisingly it has been found that a polymer composition ( PCI ) comprisin : 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 2wt% and at most 30wt% 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 ) , characterized in that the polymer (Al ) comprises between lwt% and up to 100wt% of polymerized monomer unit ( CLM) with following general formula CH2=CRICOO ( CH2)m(OCO (CH2)ni)n2OH , wherein Ri is H or CH3, m is integer number from 1 to 5 , nl is integer number from 1 to 10 and n2 is integer number from 1 to 10 , allows to provide a polymer composition suitable as an impact modifier , which is rapidly, easily and homogenously dispersible , especially in thermoplastic polymers as for instance in polyesters ,while polymer composition is having a reduced caking and good flowability.

[0030] Surprisingly it has also been found that a process for manufacturing the polymer composition (PCI) comprising the steps of: a) polymerizing by emulsion polymerization of a monomer or monomer mixture (Am) to obtain one layer in a 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 (Bm) to obtain a layer in a stage (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C, said polymer (Bl) represents at least 2wt% and at most 30wt% of the composition based on a) and b) only, characterized in that said monomer mixture (Am) comprises between lwt% and up to 100wt% of a monomer unit (CLM) with following general formula CH2=CRICOO (CH2)m(OCO (CH2)ni)n2OH, wherein Ri is H or CH3, m is integer number from 1 to 5, nl is integer number from 1 to 10 and n2 is integer number from 1 to 10, allows to provide a process for manufacturing rapidly a polymer composition suitable as an impact modifier, which is rapidly and easily dispersible, especially in thermoplastic polymers as for instance in polyesters, while using raw materials that are less toxic than today's standard impact modifiers for polyesters.

[0031] Surprisingly it has also been found that that a polymer composition (PC2) comprising: a) the polymer composition (PCI) according to the first aspect and b) a thermoplastic polymer (TP1) yields to polymer composition (PC2) possessing a better impact performance in comparison to an impact modifier composition not comprising polymerized monomer unit (CLM) .

[0032] Surprisingly it has also been found that 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 2wt% and at most 30wt% 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) , characterized in that the polymer (Al) comprises between lwt% and up to 100wt% of polymerized monomer unit (CLM) with following general formula CH2=CRICOO (CH2)m(OCO (CH2)ni) mOH, wherein Ri is H or CH3, m is integer number from 1 to 5 , nl is integer number from 1 to 10 and n2 is integer number from 1 to 10, can be used as impact modifier, which is rapidly, easily and homogenously dispersible, especially in thermoplastic polymers as for instance in polyesters.[Detailed description of the invention]

[0033] According to a first aspect, the present invention relates to 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 2wt% 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) , characterized in that the polymer (Al) comprises between lwt% and up to 100wt% of polymerized monomer unit (CLM) with following general formula CH2=CRICOO (CH2 )m(OCO (CH2 )ni) icOH, wherein Ri is H or CH3 , m is integer number from 1 to 5, nl is integer number from 1 to 10 and n2 is integer number from 1 to 10.

[0034] According to a second aspect, the present invention relates to a process for manufacturing the polymer composition (PCI) comprising the steps of :a) polymerizing by emulsion polymerization of a monomer or monomer mixture (Am) to obtain one layer in a 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 (Bm) to obtain a layer in a stage (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C, said polymer (Bl) represents at least 2wt% and at most 30wt% of the composition based on a) and b) only, characterized in that said monomer mixture (Am) comprises between lwt% and up to 100wt% of a monomer unit (CLM) with following general formula CH2=CRICOO (CH2)m(OCO (CH2)ni)n2OH, wherein Ri is H or CH3, m is integer number from 1 to 5 , nl is integer number from 1 to 10 and n2 is integer number from 1 to 10.

[0035] In a third aspect the present invention relates to a process for manufacturing the polymer composition (PCI) in form of a polymer powder comprising the steps of : a) polymerizing by emulsion polymerization of monomer or monomer mixture (Am) 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 (Bm) 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 monomer mixture (Am) comprises between lwt% and up to 100wt% of a monomer unit (CLM) with following general formula CH2=CRICOO (CH2)m(OCO (CH2)ni)n2OH, wherein Ri is H or CH3, m is integer number from 1 to 5 , nl is integer number from 1 to 10 and n2 is integer number from 1 to 10.

[0036] In a fourth aspect the present invention relates to the use of a polymer composition (PCI) as impact modifier.

[0037] In a fifth aspect the present invention relates to the use of a polymer composition (PCI) as a reduced dispersing time composition .

[0038] In a sixth aspect the present invention relates to a process to reduce the dispersing time of a polymer composition (PCI) in a thermoplastic polymer, preferably a polyester or a polymer blend comprising a polyester, by using the polymeric composition (PCI) in form of a polymer powder.

[0039] In a seventh aspect the present invention relates to a polymer composition (PC2) comprising the polymer composition (PCI) as impact modifier .

[0040] In an eighth aspect the present invention relates to a process to reduce the time of dispersing a polymeric composition (PCI) in a thermoplastic polymer (TP1) comprising the steps of: a) providing said polymeric composition (PCI) of first aspect in form of a porous polymer powder (POW1) having total intruded volume of at least 0.6 ml / g as measured by mercury porosimetry, b) blending the polymeric composition (PCI) with thermoplastic polymer (TP1 ) .

[0041] In a ninth aspect the present invention relates to a polymer composition (PC2) comprising: a) polymeric composition (PCI) of first aspect, and b) a thermoplastic polymer (TP1) , preferably chosen from a polyester .

[0042] By the term "polymer powder" as used is denoted a polymer in form of a powder comprising powder grains in the range of at least 1pm, said powder grains are obtained by agglomeration of primary polymer particles comprising polymer or polymers, said primary polymer particles are in the nanometer range.

[0043] By the term "primary particle" as used is denoted a spherical polymer particle comprising particle in the nanometer range. Preferably the primary particle has a weight average particle size between 20nm and 800nm.

[0044] By the term "particle size" as used is denoted the volume average diameter of a particle considered as spherical.

[0045] By the term "thermoplastic polymer" 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 pressure .

[0046] By the term "thermosetting polymer" as used is denoted a prepolymer in a soft , solid or viscous state that changes irreversibly into an infusible , insoluble polymer network by curing .

[0047] By the term "copolymer" as used is denoted that the polymer consists of at least two different monomer units .

[0048] By " multistage polymer" as used is denoted a polymer formed in sequential fashion by a multi-stage polymerization process . Preferred is a multi-stage emulsion polymerization process in which the first polymer is a first-stage polymer and the second polymer is a second-stage polymer, i . e . , the second polymer is formed by emulsion polymerization in the presence of the first emulsion polymer, with at least two stages that are different in composition .

[0049] By the term " (meth ) acrylic" as used is denoted all kind of acrylic and methacrylic monomers .

[0050] By the term " (meth ) acrylic polymer" as used is denoted that the (meth) acrylic ) polymer comprises essentially polymers comprising (meth ) acrylic monomers that make up 50wt% or more of the (meth ) acrylic polymer .

[0051] By the term "dry" as used is denoted that the ratio of residual water is less than 1 . 5wt and preferably less than 1 . 2wt% .

[0052] 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 .

[0053] 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 .

[0054] By the term "total intruded volume" as used is denoted the total volume intruded by liquid mercury according to ISO 15901- 1 : 2016 . This volume is cumulated and the analysis results show cumulated intruded volume in ml / g ( cm3 / g ) as function of the applied pressure or the pore diameter . The total intruded volume is the volume intruded at the maximal applied pressure , which corresponds also to the smallest pores .

[0055] By the term "incremental intrusion" as used is denoted the volume intruded in ml / g between two certain pressures or two pore sizes. This incremental intrusion can also be expressed relatively to the total intruded volume in volt .

[0056] With easily dispersed in liquid resins is meant that a homogenous dispersion is obtained. The distribution of the polymeric composition (PCI) is not homogenous if separation takes place after initial homogenization.

[0057] With rapidly dispersed it is meant that a homogeneous dispersion is obtained much faster than with a polymeric composition not having the specific composition with polymerized monomer unit (CLM) .

[0058] With regard to the polymer composition (PCI) according to the invention, it can be according to a first embodiment in form of a polymer powder, also referred to as polymer powder POW1, comprising a) the polymer (Al) having a glass transition temperature of less than 10°C, b) the polymer (Bl) having a glass transition temperature of at least 60°C, said polymer (Bl) represents at least 2wt% 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 (Al) comprises polymerized monomer units between lwt% and up to 100wt% of polymerized monomer unit (CLM) with following general formula CH2=CRICOO (CH2 )m(OCO (CH2 )ni) icOH, wherein Ri is H or CH3 , m is integer number from 1 to 5, nl is integer number from 1 to 10 and n2 is integer number from 1 to 10.

[0059] Preferably the component b) represents at least 3wt% of a composition based on a) and b) . More preferably the component b) represents at least 4wt% of the composition based on a) and b) and still more preferably at least 5wt%

[0060] Preferably the component b) represents at most 40wt% of a composition based on a) and b) . More preferably the component b) represents at most 35wt% of the composition based on a) and b) and still more preferably at most 30wt%.

[0061] In a first advantageously embodiment component b) represents less than 29wt% of a composition based on a) and b) .

[0062] In a second advantageously embodiment component b) represents less than 28wt% of a composition based on a) and b) .

[0063] In a third advantageously embodiment component b) represents less than 27wt% of a composition based on a) and b) .

[0064] Preferably the component b) represents more than 5wt% of a composition based on a) and b) . More preferably the component b) represents more than 6wt% of the composition based on a) and b) .

[0065] In a first advantageously embodiment component b) represents more than 7wt% of a composition based on a) and b) .

[0066] In a second advantageously embodiment component b) represents more than 8wt% of a composition based on a) and b) .

[0067] In a third advantageously embodiment component b) represents more than 9wt% of a composition based on a) and b) .

[0068] The respective upper and lower limits given in the previous paragraphs for the quantity of component b) , can be combined in any combinations of one upper and one lower limit .

[0069] Preferably the component b) represents between 5wt% and 30wt% of the composition based on a) and b) . More preferably the component b) represents between 6wt% and 25wt% of the composition based on a) and b) .

[0070] In a first advantageously embodiment component b) represents between 6wt% and 22wt% of a composition based on a) and b) .

[0071] In a second advantageously embodiment component c) represents between 8wt% and 20wt% of a composition based on a) and b) .

[0072] In a third advantageously embodiment component b) represents between 6wt% and 15wt% of a composition based on a) and b) .

[0073] The component a) and the component b) of composition (PCI) are part of a multistage polymer (MP1) .

[0074] At least the component a) and the component b) are obtained by a multistage process comprising at least two stages (A) and (B) respectively; and these two, polymer (Al) and polymer (Bl) form a multistage polymer (MP1) .

[0075] With regard to the polymer powder (POW1) , it has a volume median particle size D50 between 1 m and 700 m. Preferably the volume median particle size of the polymer powder is between 10pm and 600pm,more preferably between 15 m and 550pm and advantageously between 20pm and 500pm.

[0076] The DIO of the particle size distribution in volume is at least 10pm and preferably 15pm, more preferably 20pm.

[0077] The D90 of the particle size distribution in volume is at most 1000pm and preferably 950pm, more preferably at most 925pm and even more preferably at most 900pm.

[0078] In one embodiment the porosity of the polymer composition (PCI) in form of a polymer powder (POW1) is expressed as total intruded volume or total cumulative intrusion (cumulative intruded volume) in millilitre (ml) of mercury per mass (g) of said polymer powder POW1. This is measured according to the norm ISO 15901-1: Evaluation of pore size distribution and porosity of solid materials by mercury porosity and gas adsorption - Part 1: mercury porosity. Preferably the polymer powder (POW1) of the invention has a total intruded volume or total cumulative intrusion of at least 0.6ml / g, preferably 0.65 ml / g, more preferably 0.07 ml / g, even more preferably 0.75ml / g. The total cumulative intrusion is taken into account until a pore size diameter of 0.005pm. Preferably the total intruded volume or total cumulative intrusion is taken into account between a pore size diameter of 100pm and 0.005pm or a pressure between O.OIMPa and 400MPa.

[0079] The polymer powder (POW1) of the invention has a total intruded volume or total cumulative intrusion of at most lOml / g. Preferably the total intruded volume is at most 8ml / g, more preferably at most 7ml / g, even more preferably at most 6ml / g, advantageously at most 5ml / g, more advantageously at most 4ml / g and most advantageously at most 3.5ml / g.

[0080] The respective upper and lower limits given in the previous two paragraphs for total intruded volume or total cumulative intrusion of the porous polymer powder (POW1) of the invention, can be combined in any combinations of one upper and one lower limit.

[0081] Preferably the polymer powder (POW1) of the invention has a total intruded volume or total cumulative intrusion between 0.6ml / g and lOml / g, more preferably between ml / g and 8 ml / g, even more preferably between 0.65 ml / g and 7 ml / g, advantageously between 0.65 ml / g and 6 ml / g, more advantageously between 0.65ml / g and 5ml / g andmore advantageously between 0.7 ml / g and 4ml / g and most advantageously between 0.75 ml / g and 3.5ml / g.

[0082] The apparent bulk density of the polymer powder (POW1) is less than 0.60g / cm3. Preferably the apparent bulk density is less than 0.45g / cm3, more preferably less than 0.43g / cm3, and even more preferably less than 0.41g / cm3.

[0083] The apparent bulk density of the polymer powder (POW1) is more than 0.1g / cm3. Preferably the apparent bulk density is more than 0.11g / cm3, more preferably is more than 0.12g / cm3, even more preferably more than 0.13g / cm3.

[0084] The apparent bulk density of the polymer powder (POW1) is between 0.1g / cm3and 0.60g / cm3. Preferably the apparent bulk density of the polymer powder (POW1) is between 0.15g / cm3and 0.45g / cm3. Advantageously the apparent bulk density of the polymer powder POW1 is between 0.2g / cm3and 0.4g / cm3.

[0085] The respective preferred embodiment of all the different characteristics of the porous polymer powder (POW1) , can be combined in any combination.

[0086] With regard to the polymer composition (PCI) according to the invention, it can be according to a second embodiment be dispersed in a continuous phase, comprising a) the polymer (Al) having a glass transition temperature of less than 10°C, b) the polymer (Bl) having a glass transition temperature of at least 60°C; where the component a) and the component b) of composition (PCI) are part of a multistage polymer (MP1) and the polymer (Al) comprises between lwt% and up to 100wt% of polymerized monomer unit (CLM) ; and c) a thermoplastic polymer (TP1) . The thermoplastic polymer (TP1) can be a continuous phase wherein the polymer composition (PCI) is dispersed in.

[0087] The multistage polymer (MP1) of the composition (PCI) according to the invention has at least two stages (A) and (B) respectively; and these two, comprising polymer (Al) and polymer (Bl) respectively, are different in their polymer composition.

[0088] The multistage polymer (MP1) is preferably in form of polymer particles (PAR) . These particles (PAR) are also called core-shellparticles. For example, the first stage comprising polymer (Al) forms the core, the second or all following stages form the respective shells. Such a multistage polymer (MP1) , which is also called core-shell particle, is preferred. If the multistage polymer (MP1) comprises only the polymer (Al) and polymer (Bl) it is coreshell particle comprising one shell only.

[0089] In a first preferred embodiment the multistage polymer (MP1) of the composition (PCI) consists of the polymer (Al) forming the core and polymer (Bl) the shell, it is core-shell particle comprising one shell only.

[0090] In a second preferred embodiment the multistage polymer (MP1) of the composition (PCI) consists of a seed, the polymer (Al) , both together forming the core, and polymer (Bl) forming the shell, it is also considered a core-shell particle comprising one shell only.

[0091] In a third preferred embodiment the multistage polymer (MP1) consists of the polymer (Al) forming the core or an inner stage or shell and the polymer (Bl) is the shell covering the polymer (Al) or formed afterwards, it is core-shell particle comprising potentially several shells .

[0092] In a fourth preferred embodiment the multistage polymer (MP1) of the composition (PCI) consists of the polymer (Al) forming the core or an inner stage or shell and the polymer (Bl) forms a shell covering the polymer (Al) and a polymer (Cl) a shell covering the polymer (Bl) , wherein polymer (Cl) is the outer shell.

[0093] The particles (PAR) , comprised in the polymer composition (PCI) in form of a polymer powder (POW1) according to one embodiment or dispersed according to another embodiment are the primary particles .

[0094] The particles (PAR) have a weight average particle size between 15nm and 900nm. Preferably the weight average particle size of the polymer particle is between 20nm and 800nm, more preferably between, more preferably between 25nm and 600nm, still more preferably between 30nm and 550nm, again still more preferably between 35nm and 500nm, advantageously between 40nm and 400nm, even more advantageously between 75nm and 350nm and advantageously between 80nm and 300nm.

[0095] According to a first preferred embodiment, the primary polymer particles (PAR) are agglomerated and are giving the polymer composition (PCI) or a part of the polymer composition (PCI) . In that case the polymer composition (PCI) of the invention is in form of a polymer powder, as described previously.

[0096] The polymer composition (PCI) according to the invention comprises a multistage polymer (MP1) comprising at least a) one stage (A) comprising a polymer (Al) having a glass transition temperature below 10°C, and at least b) one stage (B) comprising a polymer (Bl) having a glass transition temperature over 60°C.

[0097] In a first preferred embodiment the stage (A) is the first stage of the at least two stages and the stage (B) comprising polymer (Bl) is covering stage (A) comprising polymer (Al) .

[0098] In a second preferred embodiment, there could also be a seed added before stage (A) , so that stage (A) and the seed together would be considered as first stage and the stage (B) comprising polymer (Bl) is covering stage (A) comprising seed and polymer (Al) .

[0099] In a third preferred embodiment the stage (A) is the first stage of the two stages and the stage (B) comprising polymer (Bl) is covering stage (A) comprising polymer (Al) and the multistage polymer (MP1) consist of stage (A) comprising polymer (Al) and the stage (B) comprising polymer (Bl) .

[0100] The stage (B) takes place after stage (A) . More preferably stage (B) is the last stage and the polymer (Bl) is the outer shell of the multistage polymer (MP1) .

[0101] With regard to the polymerized monomer unit (CLM) with following general formula CH2=CRICOO (CH2 )m(OCO (CH2 )ni) icOH, wherein Ri is H or CH3 , m is integer number from 1 to 5, nl is integer number from 1 to 10 and n2 is integer number from 1 to 10, it is part of the polymer (Al) between lwt% and up to 100wt%.

[0102] The polymer (Al) is a homopolymer or copolymer, comprising polymerized monomer unit (CLM) .

[0103] The monomer unit (CLM) has following general formula CH2=CRICOO (CH2)m(OCO (CH2) ni) n2OH, wherein Ri is H or CH3, m is integernumber from 1 to 5, nl is integer number from 1 to 10 and n2 is integer number from 1 to 10.

[0104] Preferably m is integer number from 1 to 4. In one embodiment m=2 in another embodiment m=4. In a first preferred embodiment m=2.

[0105] Preferably nl is integer number from 2 to 8, more preferably from 3 to 8. In one embodiment nl=5. In another embodiment nl=4. In still another embodiment nl=3.

[0106] In a first preferred embodiment nl=5.

[0107] Preferably n2 is integer number from 1 to 8 , more preferably from 1 to 6. In one embodiment n2 from 1 to 5.

[0108] In a first preferred embodiment the monomer unit (CLM) has formula (1)wherein Ri is H or CH3 and n2 is from 1 to 5.

[0109] In a second preferred embodiment the monomer unit (CLM) has formula (2)wherein Ri is H or CH3 and n2 is from 3 to 5.

[0110] In a third more preferred embodiment the monomer unit (CLM) is according to formula (1) wherein Ri is H, the polymerizable group is chosen from an acrylate.

[0111] In a fourth more preferred embodiment the monomer unit (CLM) is according to formula (1) wherein Ri is CH3 the polymerizable group is chosen from a methacrylate.

[0112] The polymer (Al) comprises from 2wt% up to 100wt% of polymerized monomer unit (CLM)

[0113] In a first embodiment the polymer (Al) having a glass transition temperature below 10°C comprises at least 50wt% of polymeric units coming from alkyl acrylate or alkyl acrylates andthe stage (A) is the most inner layer of the polymer particle having the multilayer structure . In other words , the stage (A) comprising the polymer (Al ) is the core of the polymer particle .

[0114] In a second embodiment the polymer (Al ) having a glass transition temperature below 10 ° C comprises at least 50wt% of polymeric units coming from alkyl acrylate or alkyl acrylates and the stage (A) is an inner layer of the polymer particle having the multilayer structure . In other words , the stage (A) comprising the polymer (Al ) is not the outer layer and is considered as part of the core of the polymer particle , especially in the case when a seed is used in the process .

[0115] With regard to the polymer (Al ) of the first and second j ust mentioned embodiment , it is a (meth ) acrylic polymer comprising at least 50wt% of polymeric units coming from (meth) acrylic monomers , including the monomer unit (CLM) . Preferably 60wt% and more preferably 70wt% of the polymer (Al ) are (meth) acrylic monomers .

[0116] In a first preferred embodiment the polymer (Al ) comprises least 80wt% of polymeric units coming from (meth) acrylic monomers , including the monomer unit (CLM) .

[0117] In a second preferred embodiment the polymer (Al ) comprises least 90wt% of polymeric units coming from (meth) acrylic monomers , including the monomer unit (CLM) .

[0118] In a third preferred embodiment the polymer (Al ) comprises from 80wt% to 100wt% of polymeric units coming from (meth) acrylic monomers , including the monomer unit (CLM) .

[0119] The acrylic mononomer in polymer (Al ) can comprises beside the monomer unit (CLM) monomers chosen from Cl to C18 alkyl acrylates or mixtures thereof . More preferably the acrylic monomer in polymer (Al ) comprises beside the monomer unit ( CLM) monomers of C2 to C12 alkyl acrylic monomers or mixtures thereof . Still more preferably the acrylic monomer in polymer (Al ) comprises beside the monomer unit ( CLM) monomers of C2 to C8 alkyl acrylic monomers or mixtures thereof .

[0120] The polymer (Al ) comprises as comonomer the monomer unit ( CLM) which are copolymerizable with the acrylic monomer or monomers , as long as polymer (Al ) is having a glass transition temperature of less than 10 ° C .

[0121] Most preferably the other acrylic or methacrylic comonomers beside the monomer unit (CLM) of the polymer (Al) are chosen from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as polymer (Al) is having a glass transition temperature of less than 10°C.

[0122] Preferably the polymer (Al) comprises between 2wt% and 70wt% of polymerized monomer unit (CLM) and more preferably between 3wt% and 50wt%.

[0123] In one embodiment the polymer (Al) comprises from 5wt% to 20wt% of polymerized monomer unit (CLM) .

[0124] In another embodiment the polymer (Al) comprises from 5wt% to 25wt% of polymerized monomer unit (CLM) .

[0125] In another embodiment the polymer (Al) comprises from 10wt% to 50wt% of polymerized monomer unit (CLM) .

[0126] In another embodiment the polymer (Al) comprises from 10wt% to 40wt% of polymerized monomer unit (CLM) .

[0127] The polymer (Al) can comprise a crosslinker or graft crosslinker .

[0128] In a specific embodiment polymer (Al) is a copolymer comprising butyl acrylate and monomer unit (CLM) .

[0129] In another specific embodiment polymer (Al) is a copolymer of butyl acrylate, monomer unit (CLM) and another preferred acrylic or methacrylic comonomer.

[0130] In still another specific embodiment polymer (Al) is a copolymer of butyl acrylate, monomer unit (CLM) and allyl methacrylate .

[0131] More preferably the glass transition temperature Tg of the polymer (Al) comprising at least 70wt% of polymeric units coming from monomer unit (CLM) and C2 to C8 alkyl acrylate is between - 100°C and 10°C, even more preferably between -80°C and 0°C and advantageously between -80 °C and -20 °C and more advantageously between -70°C and -20°C.

[0132] The polymer (Al) having a glass transition temperature below 10°C comprises monomer units, that have been polymerized. The polymer (Al) in general and respective polymers (Al) of the first,preferred embodiment are prepared from the respective monomer mixture (Am) yielding after polymerization to the monomer units comprised polymer (Al) .

[0133] With regard to the polymer (Bl) , mention may be made of homopolymers and copolymers comprising monomers with double bonds and / or vinyl monomers. Preferably the polymer (Bl) is a (meth) acrylic polymer.

[0134] Preferably the polymer (Bl) is a (meth) acrylic polymer, meaning that at least 50wt% of the monomer units of the polymer (Bl) are (meth) acrylic monomers.

[0135] Preferably the polymer (Bl) comprises at least 70wt% monomers chosen from Cl to C12 alkyl (meth) acrylates . Still more preferably the polymer (Bl) comprises at least 80 wt% of monomers chosen from Cl to C4 alkyl methacrylate and / or Cl to C8 alkyl acrylate monomers. Even still more preferably the polymer (Bl) comprises at least 80 wt% of monomers chosen from Cl to C4 alkyl methacrylate and Cl to C8 alkyl acrylate monomers.

[0136] Most preferably the acrylic or methacrylic monomers of the polymer (Bl) are chosen from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as polymer (Bl) is having a glass transition temperature of at least 60 °C.

[0137] Advantageously the polymer (Bl) comprises at least 30wt% of monomer units coming from methyl methacrylate.

[0138] In a first advantageous embodiment the polymer (Bl) comprises at least 70wt% of monomer units coming from methyl methacrylate .

[0139] In a second advantageous embodiment the polymer (Bl) comprises at least 80wt% of monomer units coming from methyl methacrylate .

[0140] In a third advantageous embodiment the polymer (Bl) comprises from 70wt% to 100wt% of monomer units coming from methyl methacrylate .

[0141] In a fourth advantageous embodiment the polymer (Bl) comprises at least 50wt% of monomer units coming from methyl methacrylate .

[0142] In a fifth advantageous embodiment the polymer (Bl) comprises from 50wt% to 100wt% of monomer units coming from methyl methacrylate .

[0143] In a variation the polymer (Bl) can be a copolymer. In that case the respective monomers come from monomer mixture (Bm) comprising at least two monomers from the preferred list.

[0144] Preferably the glass transition temperature Tg of the polymer (Bl) is between 60°C and 150°C. The glass transition temperature of the polymer (Bl) is more preferably between 70°C and 140°C, advantageously between 80 °C and 130 °C and more advantageously between 85°C and 125°C.

[0145] Preferably a part of the polymer (Bl) is grafted on the polymer made in the previous stage.

[0146] Preferably the polymer (Bl) is not completely grafted. By not completely grafted is meant that at least 5wt% of the polymer (Bl) in the multistage polymer (MP1) can be solubilized in a solvent of the polymer (Bl) and extracted. Preferably at least 10wt% of the copolymer (Bl) in the multistage polymer (MP1) can be solubilized in a solvent of the copolymer (Bl) and extracted.

[0147] The polymer (Bl) having a glass transition temperature of at least 60°C comprises monomer units, that have been polymerized. The polymer (Bl) in general and in the respective embodiments is prepared from the respective monomer or monomer mixtures (Bm) , yielding after polymerization to the polymer (Bl) with polymerized monomer units comprised in copolymer (Bl) .

[0148] With further regard to the polymer (Bl) or more specifically the extractible part of the polymer (Bl) , it can have a mass average molecular weight Mw of between 10 OOOg / mol and 500 OOOg / mol.

[0149] The polymer (Bl) , it can have a mass average molecular weight Mw of more than 10 OOOg / mol, preferably more than 10 500g / mol, more preferably more than 11 OOOg / mol, still more preferably more than 12 OOOg / mol, advantageously more than 13 000 g / mol, more advantageously more than 14 000 g / mol and still more advantageously more than 15 000 g / mol.

[0150] The polymer (Bl) or more specifically the extractible part of the polymer (Bl) , it can have a mass average molecular weight Mwbelow 500 OOOg / mol, preferably below 450 OOOg / mol, more preferably below 400 OOOg / mol, still more preferably below 400 OOOg / mol, advantageously below 350 000 g / mol, more advantageously below 300 000 g / mol and still more advantageously below 250 000 g / mol and most advantageously below 200 000 g / mol.

[0151] Preferably the mass average molecular weight Mw of polymer (Bl) or more specifically the extractible part of the polymer (Bl) can be between 10 500g / mol and 450 OOOg / mol, more preferable between11 000 g / mol and 400 000 g / mol and even more preferably between12 OOOg / mol and 350 OOOg / mol advantageously between 13 OOOg / mol and 300 OOOg / mol, more advantageously between 14 OOOg / mol and 250 OOOg / mol and most advantageously between 15 OOOg / mol and 200 OOOg / mol.

[0152] In a first advantageously embodiment the mass average molecular weight Mw of the (meth) acrylic polymer (Bl) or more specifically the extractible part of the polymer (Bl) can be between 10 500g / mol and 200 OOOg / mol, more preferable between 11 000 g / mol and 190 000 g / mol and even more preferably between 12 OOOg / mol and 180 OOOg / mol advantageously between 13 OOOg / mol and 150 OOOg / mol, more advantageously between 14 OOOg / mol and 135 OOOg / mol and most advantageously between 15 OOOg / mol and 120 OOOg / mol.

[0153] In a second advantageously embodiment the mass average molecular weight Mw of the (meth) acrylic polymer (Bl) or more specifically the extractible part of the polymer (Bl) can be between 15 OOOg / mol and 450 OOOg / mol, more preferable between 15 500 g / mol and 400 000 g / mol and even more preferably between 16 OOOg / mol and 350 OOOg / mol advantageously between 16 500g / mol and 300 OOOg / mol, more advantageously between 17 OOOg / mol and 250 OOOg / mol and most advantageously between 17 500g / mol and 200 OOOg / mol.

[0154] The respective preferred and advantageous embodiments of all the different characteristics of the polymers (Al) and (Bl) and its respective monomers, can be combined in any combination.

[0155] The multistage polymer (MP1) is obtained by a multistage process comprising at least two stages. The component a) and thecomponent b) of composition (PCI) are part of a multistage polymer (MP1) .

[0156] Preferably the polymer (Al) having a glass transition temperature below 10°C made during the stage (A) , is made before stage (B) or is the first stage of the multistage process.

[0157] The copolymer (Bl) having a glass transition temperature of at least 60°C made during the stage (B) is made after the stage (A) of the multistage process.

[0158] More preferably the copolymer (Bl) having a glass transition temperature of at least 60°C made during the stage (B) is the external layer of the multistage polymer (MP1) .

[0159] There could be additional intermediate stages, between stage(A) and stage (B) .

[0160] The weight ratio r of the copolymer (Bl) of the external layer comprised in stage (B) in relation to the complete polymer particle or the multistage polymer (MP1) is at least 2wt%, more preferably at least 5wt% and still more preferably at least 8wt% .

[0161] According to the invention the ratio r of the external stage(B) comprising copolymer (Bl) in relation to the complete polymer particle or the multistage polymer (MP1) is at most 40w%.

[0162] Preferably the ratio of polymer (Bl) in view of the polymer particle or the multistage polymer (MP1) is between 2wt% and 30wt% and preferably between 5wt% and 25wt%.

[0163] In preferred embodiment the polymer (Bl) having a glass transition temperature of at least 60 °C is the external layer of the primary polymer particle having the multilayer structure in other words the multistage polymer (MP1) .

[0164] Preferably at least a part of the copolymer (Bl) of layer (B) is grafted on the polymer made in the previous layer. If there are only two stages (A) and (B) comprising polymer (Al) and (Bl) respectively, a part of copolymer (Bl) is grafted on polymer (Al) . More preferably at least 25wt% of polymer (Bl) is grafted. The ratio of grafting can be determined by extraction with a solvent for the copolymer (Bl) and gravimetric measurement before and after extraction to determine the non-grafted quantity.

[0165] In a first more preferred embodiment at least 30wt% of polymer(Bl) is grafted.

[0166] In a second more preferred embodiment at least 40wt% of polymer (Bl) is grafted.

[0167] In a third more preferred embodiment at least 50wt% of polymer (Bl) is grafted.

[0168] Preferably at least a part of the copolymer (Bl) of layer (B) is extractible. More preferably at least 3wt% of polymer (Bl) is extractible .

[0169] In a first more preferred embodiment at least 5wt% of polymer (Bl) is extractible.

[0170] In a second more preferred embodiment at least 10 wt% of polymer (Bl) is extractible.

[0171] In a third more preferred embodiment at least 15 wt% of polymer (Bl) is extractible.

[0172] The glass transition temperature Tg of the respective polymers can be estimated for example by dynamic methods as thermo mechanical analysis .

[0173] In order to obtain a sample of the respective polymers (Al) and (Bl) they can be prepared alone, and not by a multistage process, for estimating and measuring more easily the glass transition temperature Tg individually of the respective polymers of the respective stages. The copolymer (Bl) can be extracted for estimating and measuring the glass transition temperature Tg and or the molecular weight .

[0174] Preferably the polymer composition of the invention if in form of a powder comprises no solvents . By no solvents is meant that eventually present solvent makes up less than lwt% of the composition. The monomers of the synthesis of the respective polymers are not considered as solvents. The residual monomers in the composition present less than 2wt% of the composition.

[0175] Preferably the polymer composition according to the invention if in form of a powder is dry. By dry is meant that the polymer composition according to the present invention comprises less than 3wt% humidity and preferably less than 1.5wt% humidity and more preferably less than 1.2wt% humidity.

[0176] The humidity can be measured by a thermo balance that heats the polymer composition and measures the weight loss .

[0177] The composition according to the invention in form of a powder does not comprise any voluntary added solvent. Eventually residual monomer from the polymerization of the respective monomers and water are not considered as solvents.

[0178] With regard to a first preferred process for manufacturing the polymer composition (PCI) according to the invention it comprises the steps of a) polymerizing by emulsion polymerization of a monomer mixture (Am) 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 (Bm) to obtain layer in stage (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C.

[0179] Preferably the step a) is made before step b) .

[0180] More preferably step b) is performed in presence of the polymer (Al) obtained in step a) .

[0181] With regard to a second preferred process for manufacturing the polymer composition (PCI) according to the invention form of a polymer powder it comprises the steps of a) polymerizing by emulsion polymerization of a monomer or monomer mixture (Am) to obtain one layer in stage (A) comprising polymer (Al) having a glass transition temperature of less than 10°C, said monomer mixture (Am) comprises a monomer unit (CLM) with following general formula CH2=CRICOO (CH2 )m(OCO (CH2 )ni) icOH, wherein Ri is H or CH3 , m is integer number from 1 to 5, nl is integer number from 1 to 10 and n2 is integer number from 1 to 10; b) polymerizing by emulsion polymerization of a monomer or monomer mixture (Bm) 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 c) .

[0182] Preferably the step a) is made before step b) and step b) before step c) .

[0183] More preferably step b) is performed in presence of the polymer (Al) obtained in step a) .

[0184] Preferably during step b) no chain transfer agent is used, especially mercaptan based chain transfer agents.

[0185] With regard to a third preferred process for manufacturing the polymer composition (PCI) according to the invention form of a polymer powder it comprises the steps of a) providing or preparing a seed; b) polymerizing by emulsion polymerization of a monomer or monomer mixture (Am) to obtain one layer in stage (A) comprising polymer (Al) having a glass transition temperature of less than 10°C, said monomer mixture (Am) comprises a monomer unit (CLM) with following general formula CH2=CRICOO (CH2 )m(0C0 (CH2 )ni) icOH, wherein Ri is H or CH3 , m is integer number from 1 to 5, nl is integer number from 1 to 10 and n2 is integer number from 1 to 10; c) polymerizing by emulsion polymerization of a monomer or monomer mixture (Bm) to obtain layer in stage (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C; d) agglomerating the composition obtained in steps a) to c) .

[0186] Preferably the step a) is made before step b) and step b) before step c) and step c) before step d) .

[0187] More preferably step b) is performed in presence of the polymer (Al) obtained in step a) .

[0188] Advantageously the first preferred process for manufacturing the polymer composition (PCI) according to the invention is a multistep process comprises the steps one after the other of: a) polymerizing by emulsion polymerization of a monomer or monomer mixture (Am) to obtain one layer in stage (A) comprising polymer (Al) having a glass transition temperature of less than 10°C, said monomer mixture (Am) comprises a monomer unit (CLM) with following general formula CH2=CRICOO (CH2 ) m (OCO (CH2 )ni) 112OH, wherein Ri is H or CH3 , m is integer number from 1 to 5 , nl isinteger number from 1 to 10 and n2 is integer number from 1 to 10, b) polymerizing by emulsion polymerization of a monomer or monomer mixture (Bm) 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) .

[0189] Preferably the steps a) , b) and c) are performed in that order. As emulsion polymerization is used, the polymer composition at the end of the polymerization is obtained as an aqueous dispersion .

[0190] Preferably during step b) no chain transfer agent is used, especially mercaptan based chain transfer agents.

[0191] dvantageously the second preferred process for manufacturing the polymer composition (PCI) according to the invention is a multistep process comprises the steps one after the other of: a) providing or preparing a seed; b) polymerizing by emulsion polymerization of a monomer or monomer mixture (Am) to obtain one layer in stage (A) comprising polymer (Al) having a glass transition temperature of less than 10°C, said monomer mixture (Am) comprises a monomer unit (CLM) with following general formula CH2=CRICOO (CH2 ) m (OCO (CH2 )ni) icOH, wherein Ri is H or CH3 , m is integer number from 1 to 5, nl is integer number from 1 to 10 and n2 is integer number from 1 to 10; c) polymerizing by emulsion polymerization of a monomer or monomer mixture (Bm) to obtain layer in stage (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C; d) agglomerating the composition obtained in steps a) to c) .

[0192] The respective monomers or monomer mixtures (Am) and (Bm) for forming the layers in the stages (A) and (B) respectively comprising the polymers (Al) and (Bl) respectively, of preferred and advantageous process, are the same as defined before. The monomers or monomer mixtures (Am) and (Bm) comprise the respective monomersthat are as polymerized monomer units in the polymer chain of the respective polymers (Al) and (Bl) . The characteristics of the polymers (Al) and (Cl) respectively, are the same as defined before.

[0193] The preferred and advantageous processes for manufacturing the polymer composition (PCI) comprising the multi stage polymer (MP1) yields to the polymer powder POW1. The polymer powder POW1 is in form of grains (large particles) . The polymer powder grain or particle comprises agglomerated primary polymer particles made by multistage process comprising the multistage polymer (MP1) or agglomerated primary polymer particles comprising the multistage polymer (MP1 ) .

[0194] The agglomeration step can be made by coagulation or by flash drying .

[0195] For the preferred processes flash drying is preferred in agglomerating step.

[0196] The process for manufacturing the polymer composition (PCI) according to the invention can comprise optionally the additional step d)of drying of the polymer composition.

[0197] Preferably after the drying step d) the polymer composition comprises less than 3wt%, more preferably less than 1.5wt% advantageously less than 1.2% of humidity or water.

[0198] The humidity of a polymer composition can be measure with a thermo balance.

[0199] The drying of the polymer can be made for example in an oven or vacuum oven with heating of the composition for 48hours at 50°C.

[0200] One additional aspect of the present invention is the use of the polymer composition (PCI) as an impact modifier.

[0201] Preferably the use of the polymer composition (PCI) as an impact modifier is for a thermoplastic polymer (TP1) .

[0202] Another additional aspect of the present invention is a polymer composition (PC2) comprising the polymer composition (PCI) . Preferably the thermoplastic polymer composition (PC2) is comprising a thermoplastic polymer (TP1) .

[0203] The thermoplastic polymer (TP1) can be chosen from poly (vinyl chloride) (PVC) , chlorinated poly(vinyl chloride) (C-PVC) ,polyesters as for example poly (ethylene terephtalate ) (PET) or poly (butylene terephtalate) (PBT) polyhydroxyalkanoates (PHA) or polylactic acid (PLA) , cellulose acetate, polycarbonates (PC) , poly (methyl methacrylate ) s (PMMA) , (meth) acrylic copolymers, thermoplastic poly (methyl methacrylate-co-ethylacrylates ) , poly ( alkylene-terephtalates ) , poly vinylidene fluoride , poly ( vinylidenchloride ) , polyoxymethylen (POM) , semi-crystalline polyamides, amorphous polyamides, semi-crystalline copolyamides, amorphous copolyamides, polyetheramides, polyesteramides, copolymers of styrene and acrylonitrile (SAN) , and their respective mixtures or alloys or blends .

[0204] In a first preferred embodiment the thermoplastic polymer (TP1) is chosen from a polyesters or blends of polyesters or blends comprising polyesters.

[0205] In one more preferred embodiment the polyester is polyethylene terephthalate .

[0206] In another more preferred embodiment the polyester is polybutylene terephthalate .

[0207] In still another more preferred embodiment the polyester is polylactic acid.

[0208] In still another more preferred embodiment the polyester is a polyhydroxyalkanoate.

[0209] In still another more preferred embodiment the polyester is an alloy comprising at least on polyester chosen from polyethylene terephthalate, polybutylene terephthalate, polylactic acid and polyhydroxyalkanoate .

[0210] In one embodiment the polymer composition (PC2) is comprising: a) the polymer composition (PCI) and b) a thermoplastic polymer (TP1) wherein the polymer composition (PCI) to a thermoplastic polymer (TP1) ratio by weight in the polymer composition (PC2) is between 1 / 99 and 99 / 1 or between 2 / 99 and 80 / 20.

[0211] Preferably the ratio of the polymer composition (PCI) to a thermoplastic polymer (TP1) by weight in the polymer composition (PC2) is between 2 / 99 and 80 / 20.

[0212] In a first more preferred embodiment, the ratio of the polymer composition (PCI) to a thermoplastic polymer (TP1) by weight in the polymer composition (PC2) is between 3 / 97 and 75 / 25.

[0213] In a second more preferred embodiment, the ratio of the polymer composition (PCI) to a thermoplastic polymer (TP1) by weight in the polymer composition (PC2) is between 4 / 96 and 25 / 75.

[0214] In a third more preferred embodiment, the ratio of the polymer composition (PCI) to a thermoplastic polymer (TP1) by weight in the polymer composition (PC2) is between 5 / 95 and 50 / 50.

[0215] In a fourth more preferred embodiment, the ratio of the polymer composition (PCI) to a thermoplastic polymer (TP1) by weight in the polymer composition (PC2) is between 50 / 50 and 80 / 20.

[0216] The polymer composition (PC2) can be injection molded or extruded .

[0217] The polymer composition (PC2) can also be blended with still other polymers, preferably thermoplastic polymers.

[0218] When the ratio of the polymer composition (PCI) to a thermoplastic polymer (TP1) by weight in the polymer composition (PC2) is high, the polymer composition (PC2) can be used as masterbatch. By high is meant a ratio of the polymer composition (PCI) to a thermoplastic polymer (TP1) by weight above 50 / 50.

[0219] The present invention relates also to the use of the polymer composition (PCI) in form of the polymer powder according to the invention as an impact modifier in polymers, in order to obtain an impact modified polymer composition. Preferably the polymers are thermoplastic polymers .

[0220] The present invention relates also to the use of the polymer composition (PC2) in the field of compositions for alimentary, packaging, electrical and electronics applications, automotive, textile, 3D printing and toys.

[0221] The present invention relates also to an article comprising the polymer composition (PCI) or the polymer composition (PC2) .

[0222] The article can be a bottle, a container, a 3D printed object, film, fiber or textile fiber.[Methods of evaluation]

[0223] Glass transition Temperature

[0224] The glass transitions (Tg) of the polymers are measured with equipment able to realize a thermo mechanical analysis. A RDAII "RHEOMETRICS DYNAMIC ANALYSER" proposed by the Rheometrics Company has been used. The thermo mechanical analysis measures precisely the visco-elastics changes of a sample in function of the temperature, the strain or the deformation applied. The apparatus records continuously, the sample deformation, keeping the stain fixed, during a controlled program of temperature variation.

[0225] The results are obtained by drawing, as a function of the temperature, the elastic modulus (G' ) , the loss modulus and the tan delta. The Tg is highest temperature value read in the tan delta curve, when the derived of tan delta is equal to zero.

[0226] Molecular Weight

[0227] The mass average molecular weight (Mw) of the polymers is measured with by size exclusion chromatography (SEC) . Polystyrene standards are used for calibration. The polymer is dissolved in THE at a concentration of Ig / L. The chromatography column uses modified silica. The flow is Iml / min and a detector for refractive index is used .

[0228] Extraction

[0229] The extractible part of the polymer composition is measured by gravimetrically . The sample is treated under agitation for 4 hours at 20°C in THE at lOg / L. The solution is filtrated and after evaporation of the solvent of the filtrated solution the recovered polymer is weighted and its ratio calculated.

[0230] Particle size analysisThe particle size of the primary particles after the multistage polymerization is measured with a Zetasizer from Malvern using dynamic light scattering. As result the volume average particle size (diameter) is taken.The particle size of the polymer powder after recovering is measured with Malvern Mastersizer 3000 from MALVERN with laser diffraction.For the estimation of volume average powder particle size, particle size distribution and ratio of fine particles a Malvern Mastersizer 3000 apparatus with a 300mm lenses, measuring a range from 0,5-880pm is used.

[0231] Apparent Density

[0232] The norm ISO 60:1977 is used. The sample is pured through a specified funnel into a measuring cylinder of 100 cubic centimeter capacity, the excess is removed with a straightedge and the mass of the contents is determined by weighing.

[0233] Impact Strength

[0234] The norm ISO179 type leA is applied.

[0235] [Examples]

[0236] A polymer composition (PCI) in form of a core-shell multistage polymer comprising a core and a shell layer is prepared according to the process as described.

[0237] ALMA - allyl methacrylate

[0238] BA - butyl acrylate

[0239] MMA - methyl methacrylate

[0240] CLA - caprolactone acrylate

[0241] CLM - caprolactone methacrylate

[0242] As example 1 following product is made:

[0243] First stage to prepare the core comprising polymer (Al) . To a 20 litres reactor with stirrer was charged: 2931g de-ionized water and 18.9g sodium hydrogen phosphate. The reactor is flushed three times by applying vacuum and refilled with nitrogen. The solution was heated to 80°C with agitation at 150 round / min. A pre-emulsion of 458.54g butylacrylate, 3.47 g allyl methacrylate, 18.6g sodium dodecylbenzensulf onate (30wt% in water) and 320g of de-ionized water is introduced into the reactor. Solutions 2.31g potassium persulfate in 37.7g water and 1.62g sodium metabisulfite in 14.58g water are injected into the reactor. The temperature of the reactor is maintained at 80°C for 30min. A pre-emulsion of 5093.66g butyl acrylate, 700.56g caprolactone acrylate, 43.79g allyl methacrylate, 235.01g sodium dodecylbenzensulf onate (30wt% in water) and 2271.1g of de-ionized water is introduced into the reactor over 210 minutes. At the same time, a solution of 8.76g potassium persulfate in 487.7g of water is introduced into the reactor over 210 minutes as well. After the introduction of the parallel introduction pre-emulsion and solution it is continued to stir during 80min at 80°C.

[0244] Second stage to prepare the shell comprising polymer (Bl) . Then the temperature is still maintained at 80°C, but the stirring speed is increased to 160rounds / min. A solution of 1.24g sodium formaldehyde sulfoxolate in 38.76g of water are added into the reactor, and at the same time an emulsion of 689g methyl methacrylate and 27.74g sodium dodecylbenzensulf onate and 206.2g of water and as well as a solution of 3.44g potassium persulfate in 116.6g water during 30min at 80 °C. Afterwards 1.31g of sodium metabisulfite in 31.78g water are injected into the reactor. The temperature is still maintained 30min at 80°C. it is cooled dawn to ambient temperature. Final conversion is 99%. The product, a core shell particle, is recovered with a flash dryer.

[0245] In examples 2 and 3 the synthesis of example 1 is repeated, only the quantity of the caprolactone acrylate is adapted in the first stage, in order to arrive at the quantities as indicated in table 1.

[0246] In example 4 the synthesis of example 1 is repeated, the quantity of the outer shell is reduced in the second stage, in order to arrive at the ratio as indicated in table 1.

[0247] In example 5 the synthesis of example 1 is repeated, only the caprolactone acrylate is substituted by caprolactone methacrylate in the first stage, in order to arrive at the quantities as indicated in table 1.

[0248] In comparative example 1 the synthesis of example 1 is repeated, only no caprolactone acrylate is used in the first stage and it is substituted by butyl acrylate.

[0249] In comparative example 2 the synthesis of example 1 is repeated, only no caprolactone acrylate is used in the first stage and it is substituted by butyl acrylate, however in the second stage 206.7g of methyl methacrylate is substituted by caprolactone acrylate .

[0250] In comparative example 3 the synthesis of example 1 is repeated, only no caprolactone acrylate is used in the first stage and it is substituted by butyl acrylate, however in the second stage 137.8g of methyl methacrylate is substituted by caprolactone acrylate .

[0251] In comparative example 4 the synthesis of example 1 is repeated, only no caprolactone acrylate is used in the first stage and it is substituted by butyl acrylate , however in the second stage 137 . 8g of methyl methacrylate is substituted by caprolactone methacrylate .

[0252] The respective global compositions of examples 1 to 4 and comparative examples 1 to 4 are summarized in table 1 with other characteristics .

[0253] Table 1 - Characteristics

[0254] Table 2 - Powder properties

[0255] The compositions according to the invention have a better powder usability . By powder usability is meant that

[0256] +++ good flowable powder

[0257] - heavy caking which degrades flowability of powder

[0258] - some caking during drying step of powder particle

[0259] The compositions are blended with PET and the ISO notched charpy impact resistance is evaluated . Results are shown in table 3 .

[0260] Table 3 - Impact Properties

[0261] The composition according to the invention and obtained according to the process of the invention yields to a significant increase of impact resistance .

Claims

CLAIMS1. 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 2wt% and at most 30wt% 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) , characterized in that the polymer (Al) comprises between lwt% and up to 100wt% of polymerized monomer unit (CLM) with following general formula CH2=CRICOO (CH2 )m(0C0 (CH2 )ni) icOH, wherein Ri is H or CH3 , m is integer number from 1 to 5, nl is integer number from 1 to 10 and n2 is integer number from 1 to 10.

2. The polymer composition (PCI) according to claim 1, characterized in that the polymer composition (PCI) comprises a multistage polymer (MP1) comprising at least a) one stage (A) comprising the polymer (Al) having a glass transition temperature below 10°C, and at least b) one stage (B) comprising the polymer (Bl) having a glass transition temperature over 60°C.

3. The polymer composition (PCI) according to claim 1 or 2 characterized in that polymer composition (PCI) is in form of a polymer powder.

4. The polymer composition (PCI) according to any of claims 1 to 3, characterized in that the polymer (Al) comprises between 2wt% and 70wt% of polymerized monomer unit (CLM) and more preferably between 3wt% and 50wt%.

5. The polymer composition (PCI) according to any of claims 1 to3, characterized in that the polymer (Al) comprises from 5wt% to 25wt% of polymerized monomer unit (CLM) .

6. The polymer composition PCI according to any of claims 1 to 5 characterized in that the polymer (Al) is a copolymer comprising butyl acrylate and monomer unit (CLM) .

7. The polymer composition PCI according to any of claims 1 to 6, characterized in that the polymerized monomer unit (CLM) has formula (1)wherein Ri is H or CH3 and n2 is from 1 to 5.

8. A process for manufacturing a polymer composition (PCI) according to any of claims 1 to 8 comprising a multistage polymer comprising the steps of a) polymerizing by emulsion polymerization of a monomer or monomer mixture (Am) to obtain during this stage one layer (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 (Bm) to obtain a layer in a stage (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C, characterized in that said monomer mixture (Am) comprises a monomer unit (CLM) with following general formula CH2=CRICOO (CH2)m(OCO (CH2) ni) n2OH, wherein Ri is H or CH3, m is integer number from 1 to 5, nl is integer number from 1 to 10 and n2 is integer number from 1 to 10.

9. The process according to claim 8, characterized in that the process comprises the additional step c) agglomerating the multistage polymer.

10. The process according to claim 8 or 9, characterized in that the process comprises the additional step d) drying the polymer composition .

11. Use of the polymer composition (PCI) according to any of claims 1 to 7 or obtained by the method according to any of claims 8 to 10 as impact modifier.

12. The use according to claim 11 for a thermoplastic polymer(TP1) .

13. The use of the polymer composition (PCI) according to claim 12 characterized that the thermoplastic polymer (TP1) is chosen from poly(vinyl chloride) (PVC) , chlorinated poly(vinyl chloride) (C-PVC) , polyesters as for example poly (ethylene terephtalate ) (PET) or poly(butylen terephtalate ) (PBT) polyhydroxyalkanoates (PHA) or polylactic acid (PLA) , cellulose acetate, polycarbonates (PC) , poly (methyl methacrylate ) s (PMMA) , (meth) acrylic copolymers, thermoplastic poly(methyl methacrylate-co-ethylacrylates ) , poly ( alkylene- terephtalates ) , poly vinylidene fluoride , poly ( vinylidenchloride ) , polyoxymethylen (POM) , semicrystalline polyamides, amorphous polyamides, semicrystalline copolyamides, amorphous copolyamides, polyetheramides, polyesteramides, copolymers of styrene and acrylonitrile (SAN) , and their respective mixtures or alloys.

14. The use according to claim 12 characterized in that said thermoplastic polymer (TP1) is a polyester or blend comprising polyester .

15. A thermoplastic polymer composition (PC2) comprising the polymer composition (PCI) according to any of claims 1 to 7 or obtained by the process according to any of claims 8 to 10.

16. The thermoplastic polymer composition (PC2) comprising a thermoplastic polymer (TP1) , preferably chosen from a polyester .

17. Use of the polymer composition (PC2) according to claim 15 or 16 in the field of compositions for alimentary, packaging, electrical and electronics applications, automotive, textile, 3D printing or toys.

18. An article comprising the polymer composition (PCI) according to any of claims 1 to 7 or the polymer composition (PC2) according to claim 15 or 16.

19. The article according to claim 18 being a bottle, a container a 3D printed object film, fiber or textile fiber.

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