WO2016101139A1

WO2016101139A1 - Fiber reinforced polypropylene composite

Info

Publication number: WO2016101139A1
Application number: PCT/CN2014/094640
Authority: WO
Inventors: Jianglei ZHU; Jiandong ZHANG; Shih Ping Cheng
Original assignee: Borouge Compounding Shanghai Co., Ltd.
Priority date: 2014-12-23
Filing date: 2014-12-23
Publication date: 2016-06-30
Also published as: CN107001741B; CN107001741A

Abstract

Fiber reinforced composite comprising polypropylene, fibers and a hindered amine light stabilizer, wherein said stabilizer is used as heat stabilizer.

Description

Fiber reinforced polypropylene composite

The present invention is directed to a fiber reinforce composite comprising polypropylene, fibres and a hindered amine light stabilizer as well as to the use of said hindered amine light stabilizer in said fiber reinforce composite as a heat stabilizer.

Fiber reinforced composite is widely used. Nowadays it comes more and more important in the automobile interior. However in addition to the requirements of stiffness and impact resistance, odour is an important requirement in the interior of a car. Another important issue is the long term heat resistance of the material used in the interior. Normally sulphur containing antioxidants are used to achieve good long term heat resistance. Unfortunately such type of antioxidants causes unpleasant odour not accepted by the passengers. Accordingly the automobile industries seeks for a composite fulfilling the demanding requirements of mechanical properties, including long term heat stability but are not affected by unpleasant odour.

The finding of the present invention is to use fiber reinforced material comprising hindered amine light stabilizer. Another finding is to use additionally a lubricant which helps to decrease decomposition of the polymer resin in the preparation process and thus reduces the formation of aldehyde and ketone that cause bad odour.

Accordingly the present invention is directed to a fibre reinforced composite comprising

(a) at least 10 wt. -％, based on the total weight of the fiber reinforced composite, of a propylene homopolymer (H-PP2) having melt flow rate MFR₂ (230 ℃, 2.16 kg) measured according to ISO 1133 of not more than 30 g/10 min, preferably in the range of 2 to 20 g/10 min；

(b) at least 5 wt. -％, based on the total weight of the fiber reinforced composite, of a heterophasic propylene copolymer (HECO) comprising

(b1) a matrix (M) being a propylene homopolymer (H-PP1) having melt flow rate MFR₂ (230 ℃, 2.16 kg) measured according to ISO 1133 of at least40 g/10 min, preferably in the range of 45 to 150 g/10 min, and

(b2) an elastomeric propylene copolymer (EC) ；

(c) at least 15 wt. -％, based on the total weight of the fiber reinforced composite, of fibres (F) ；

(d) optionally at least 0.6 wt. -％, based on the total weight of the fiber reinforced composite, of a polar modified polypropylene (PMP) as adhesion promoter (AP) ； and

(e) at least 0.1 wt. -％, based on the total weight of the fiber reinforced composite, of a hindered amine light stabilizer (HALS) .

In a preferred embodiment the fibre reinforced composite additionally comprises

(a) at least 20 wt. -％, based on the total weight of the fiber reinforced composite, of a propylene homopolymer (H-PP3) having a melt flow rate MFR₂ (230 ℃, 2.16 kg) measured according to ISO 1133 of at least 40 g/10 min, preferably in the range of 50 to 150 g/10 min；

and/or

(b) at least 0.1 wt. -％, based on the total weight of the fiber reinforced composite, of a lubricant (L) ；

and/or

(c) at least 0.1 wt. -％, based on the total weight of the fiber reinforced composite, of a phenolic antioxidant (AO) .

Preferably, the fiber reinforced composite has a melt flow rate MFR₂ (230 ℃, 2.16 kg) measured according to ISO 1133 in the range of 3 to 20 g/10min.

It is especially preferred that fibers (F) of the fiber reinforced composite are selected from the group consisting of glass fibers, metal fibers, ceramic fibers and graphite fibers.

In one preferred embodiment the melting temperature T_m of the propylene homopolymer (H-PP2) is in the range of 160 to 170 ℃ and/or of the propylene homopolymer (H-PP3) is in the range of 155 to 170 ℃.

Preferably the heterophasic propylene copolymer (HECO) of the fibre reinforced composite has a comonomer content, preferably ethylene content, in the range of 7 to 25 mol-％and/or a xylene soluble fraction (XCS) in the range of 20 to 40 wt. -％.

Still more preferably the xylene soluble fraction (XCS) of the heterophasic propylene copolymer (HECO) has a comonomer content, preferably ethylene content, in the range of 40 to 55 mol-％and/or an intrinsic viscosity (IV) in the range of 2.0 to 4.0 dl/g.

In a particular preferred embodiment, the antioxidant (AO) is a sterically hindered phenol (SHP) , like 1, 3, 5-tris (3’ , 5’ -di-tert. butyl-4’ -hydroxybenzyl) -isocyanurate, or pentaerythrityl-tetrakis (3- (3’ , 5’ -di-tert. butyl-4-hydroxyphenyl) -propionate.

Especially good results are achieved in case the hindered amine light stabilizer (HALS) of the fibre reinforced composite is selected from the group consisting of poly ( (6-morpholino-s-triazine-2, 4-diyl) (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) hexamethylene (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino)) (CAS-NO. 193098-40-7) , 1, 3, 5-triazine-2, 4, 6-triamine, N, N” ’ - (1, 2-ethane-diylbis ( ( (4, 6-bis(butyl (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) amino) -1, 3, 5-triazine-2-yl) imino) -3, 1-propanediyl) ) -bis- (N’ , N” -dibutyl-N’ , N” -bis- (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) (CAS-no.106990-43-6) , dimethyl succinate polymer with 4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidine ethanol (CAS-no. 65447-77-0) , and poly ( (6- ( (1, 1, 3, 3-tetramethylbutyl) amino) -1,3, 5-triazine-2, 4-diyl) (2, 2, 6, 6-tetramethyl-4-piperidyl) imino) -1, 6-hexanediyl ( (2, 2, 6, 6-tetramethyl-4-piperidyl) imino) ) (CAS-no. 71878-19-8) ；

or more preferably is poly ( (6-morpholino-s-triazine-2, 4-diyl) (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) hexamethylene (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) ) (CAS-NO. 193098-40-7) and/or 1, 3, 5-triazine-2, 4, 6-triamine, N, N” ’ - (1, 2-ethane-diylbis ( ( (4, 6-bis(butyl (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) amino) -1, 3, 5-triazine-2-yl) imino) -3, 1-propanediyl) ) -bis- (N’ , N” -dibutyl-N’ , N” -bis- (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) (CAS-no.106990-43-6) .

Additionally it is preferred that the lubricant (L) optionally present in the fiber reinforced composite is erucamide (CAS-no. 112-84-5) and/or oleamide (CAS-no. 301-02-0) .

The present invention is further directed to an automotive article comprising the fiber reinforced composite as defined in the present invention. Preferably the automotive article is an automotive interior article.

In another aspect the present invention is directed to the use of a hindered amine light stabilizer (HALS) in a fiber reinforced composite as a heat stabilizer, wherein the fiber reinforced composite comprises, in addition to the hindered amine light stabilizer (HALS) , polypropylene (PP) and fibers (F) .

More preferably the hindered amine light stabilizer (HALS) used in the fiber reinforced composite increases the heat resistance in said fiber reinforced composite, especially at a temperature above 120℃, wherein the heat resistance is increased in case the odor measured according to PV3900 of the fiber reinforced composite comprising the hindered amine light stabilizer (HALS) is lower compared to the odor measured according to PV3900 of the same fiber reinforced composite without said hindered amine light stabilizer (HALS) .

Preferably the fiber reinforced composite as well as its components are the same as defined in the present invention.

In the following the invention is defined in more detail.

The fiber reinforced composite

The fiber reinforced composite according to this invention comprises a propylene homopolymer (H-PP2) , a heterophasic propylene copolymer (HECO) , fibres (F) , a polar modified polypropylene (PMP) , a phenolic antioxidant (AO) and a hindered amine light stabilizer (HALS) . Additionally the fiber reinforced composite may comprise a propylene homopolymer (H-PP3) and/or a lubricant (L) .

Accordingly it is preferred that the fibre reinforced composite comprises

(a) at least 10 wt. -％, more preferably in the range of 15 to 35 wt. -％, more preferably in the range of 17 to 30 wt. -％, like in the range of 18 to 25 wt. -％, based on the total weight of the fiber reinforced composite, of the propylene homopolymer (H-PP2) ； (b) at least 5 wt. -％, more preferably in the range of 7 to 20 wt. -％, more preferably in the range of 8 to 15 wt. -％, like in the range of 9 to 12 wt. -％, based on the total weight of the fiber reinforced composite, of the heterophasic propylene copolymer (HECO) ；

(c) at least 15 wt. -％, more preferably in the range of 20 to 50 wt. -％, more preferably in the range of 25 to 40 wt. -％, like in the range of 28 to 35 wt. -％, based on the total weight of the fiber reinforced composite, of fibres (F) ；

(d) at least 0.1 wt. -％, more preferably in the range of 0.1 to 2.0 wt. -％, more preferably in the range of 0.2 to 1.5 wt. -％, like in the range of 0.2 to 0.8 wt. -％, based on the total weight of the fiber reinforced composite, of the phenolic antioxidant (AO) ； and

(e) at least 0.1 wt. -％, more preferably in the range of 0.1 to 2.0 wt. -％, more preferably in the range of 0.2 to 1.5 wt. -％, like in the range of 0.2 to 0.8 wt. -％, based on the total weight of the fiber reinforced composite, of the hindered amine light stabilizer (HALS) ；

preferably with the proviso that the fibre reinforced composite comprises is free of sulphur containing antioxidant.

The present invention is especially directed to a fibre reinforced composite comprising

(a) at least 10 wt. -％, more preferably in the range of 15 to 35 wt. -％, more preferably in the range of 17 to 30 wt. -％, like in the range of 18 to 25 wt. -％, based on the total weight of the fiber reinforced composite, of the propylene homopolymer (H-PP2) ；

(b) at least 20 wt. -％, more preferably in the range of 25 to 45 wt. -％, more preferably in the range of 28 to 40 wt. -％, like in the range of 30 to 38 wt. -％, based on the total weight of the fiber reinforced composite, of the propylene homopolymer (H-PP3) ；

(c) at least 5 wt. -％, more preferably in the range of 7 to 20 wt. -％, more preferably in the range of 8 to 15 wt. -％, like in the range of 9 to 12 wt. -％, based on the total weight of the fiber reinforced composite, of the heterophasic propylene copolymer (HECO) ；

(d) at least 15 wt. -％, more preferably in the range of 20 to 45 wt. -％, more preferably in the range of 25 to 40 wt. -％, like in the range of 28 to 35 wt. -％, based on the total weight of the fiber reinforced composite, of fibres (F) ；

(e) optionally at least 0.6 wt. -％, more preferably in the range of 0.6 to 2.0 wt. -％, more preferably in the range of 0.7 to 1.5 wt. -％, like in the range of 0.8 to 1.3 wt. -％, based on the total weight of the fiber reinforced composite, of the polar modified polypropylene (PMP) ；

(f) at least 0.1 wt. -％, more preferably in the range of 0.1 to 2.0 wt. -％, more preferably in the range of 0.2 to 1.5 wt. -％, like in the range of 0.2 to 0.8 wt. -％, based on the total weight of the fiber reinforced composite, of the phenolic antioxidant (AO) ；

(g) at least 0.1 wt. -％, more preferably in the range of 0.1 to 2.0 wt. -％, more preferably in the range of 0.2 to 1.5 wt. -％, like in the range of 0.2 to 0.8 wt. -％, based on the total weight of the fiber reinforced composite, of the hindered amine light stabilizer (HALS) ； and

(h) at least 0.1 wt. -％, more preferably in the range of 0.1 to 2.0 wt. -％, more preferably in the range of 0.2 to 1.5 wt. -％, like in the range of 0.3 to 0.9 wt. -％, based on the total weight of the fiber reinforced composite, of a lubricant (L) ；

In another preferred embodiment, the fiber reinforced composite according to this invention does not comprise (a) further polymer (s) different to the polymers present in the fiber reinforced composite, i.e. different to the propylene homopolymer (H-PP2) , the heterophasic propylene copolymer (HECO) , the propylene homopolymer (H-PP3) and the polar modified polypropylene (PMP) , in an amount exceeding in total 10 wt. -％, preferably exceeding in total 5 wt. -％, based on the total weight of the fiber reinforced composite. Typically if an additional polymer is present, such a polymer is a carrier polymer for additives and thus does not contribute to the improved properties of the claimed fiber reinforced composite.

Accordingly in one specific embodiment the fiber reinforced composite consists of the propylene homopolymer (H-PP2) , the heterophasic propylene copolymer (HECO) , the propylene homopolymer (H-PP3) , the polar modified polypropylene (PMP) , the fibers (F) , the phenolic antioxidant (AO) , the hindered amine light stabilizer (HALS) , the lubricant (L)and additional other additives, which might contain in low amounts of polymeric carrier material. However this polymeric carrier material is not more than 10 wt. -％, preferably not more than 5 wt. -％, based on the total weight of the fiber reinforced composite, present in said fiber reinforced composite.

Therefore the present invention is especially directed to a fibre reinforced composite comprising

(e) at least 0.6 wt. -％, more preferably in the range of 0.6 to 2.0 wt. -％, more preferably in the range of 0.7 to 1.5 wt. -％, like in the range of 0.8 to 1.3 wt. -％, based on the total weight of the fiber reinforced composite, of the polar modified polypropylene (PMP) ；

preferably with the proviso that the fibre reinforced composite comprises is free of sulphur containing antioxidant

and/or

preferably with the proviso that the fiber reinforced composite does not comprise further polymers except a polymeric carrier material as defined above. If a polymeric carrier material is present in the the fibre reinforced composite the amount is not more than 10 wt. -％, preferably not more than 5 wt. -％, like not more than 2 wt. -％, based on the total weight of the the fibre reinforced composite.

In an especially preferred embodiment the fibre reinforced composite consists of

(g) at least 0.1 wt. -％, more preferably in the range of 0.1 to 2.0 wt. -％, more preferably in the range of 0.2 to 1.5 wt. -％, like in the range of 0.2 to 0.8 wt. -％, based on the total weight of the fiber reinforced composite, of the hindered amine light stabilizer (HALS) ；

(h) at least 0.1 wt. -％, more preferably in the range of 0.1 to 2.0 wt. -％, more preferably in the range of 0.2 to 1.5 wt. -％, like in the range of 0.3 to 0.9 wt. -％, based on the total weight of the fiber reinforced composite, of a lubricant (L) ； and

(i) more than 0 to 8.0 wt. -％, more preferably in the range of 0.05 to 5.0 wt. -％, still more preferably in the range of 0.1 to 3.0 wt. -％, yet more preferably in the range of 0.1 to 2.0 wt. -％, like in the range of 0.1 to 1.0 wt. -％, based on the total weight of the fiber reinforced composite, of nucleating agents and/or additives (A) different to the phenolic antioxidant (AO) , the polar modified polypropylene (PMP) , the hindered amine light stabilizer (HALS) and the lubricant (L) ；

preferably with the proviso that the fibre reinforced composite is free of sulphur containing antioxidant.

The term “additives” covers also additives which are provided as a masterbatch containing the polymeric carrier material as discussed above. However the term “additive” does not cover nucleating agents, e.g. α-nucleating agents. Typical additives (A) are acid scavengers, antioxidants (different to phenolic antioxidant (AO) and the hindered amine light stabilizer (HALS) ) , colorants, pigments, anti-scratch agents, dispersing agents and carriers.

In addition the fiber reinforced composite contains preferably a α-nucleating agent. Even more preferred the present invention is free of β-nucleating agents. Accordingly, the nucleating agent is preferably selected from the group consisting of

(i) salts of monocarboxylic acids and polycarboxylic acids, e.g. sodium benzoate or aluminum tert-butylbenzoate, and

(ii) dibenzylidenesorbitol (e.g. 1, 3 : 2, 4 dibenzylidenesorbitol) and C₁-C₈-alkyl-substituted dibenzylidenesorbitol derivatives, such as methyldibenzylidenesorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol (e.g. 1, 3 : 2, 4 di(methylbenzylidene) sorbitol) , or substituted nonitol-derivatives, such as 1, 2, 3, -trideoxy-4, 6: 5, 7-bis-O- [ (4-propylphenyl) methylene] -nonitol, and

(iii) salts of diesters of phosphoric acid, e.g. sodium 2, 2'-methylenebis (4, 6, -di-tert-butylphenyl) phosphate or aluminium-hydroxy-bis [2, 2'-methylene-bis (4, 6-di-t-butylphenyl) phosphate] , and

(iv) vinylcycloalkane polymer and vinylalkane polymer, and

(v) mixtures thereof.

Preferably the fiber reinforced composite contains as α-nucleating agent a vinylcycloalkane polymer and/or a vinylalkane polymer. This nucleating agent is preferably included due to the preparation of the heterophasic propylene copolymer (HECO) .

Such additives and nucleating agents are generally commercially available and are described, for example, in "Plastic Additives Handbook", 5th edition, 2001 of Hans Zweifel.

Preferably the fiber reinforced composite has melt flow rate MFR₂ (230 ℃, 2.16 kg) measured according to ISO 1133 in the range of 3 to 20 g/10 min, more preferably in the range of 3 to 15 g/10min, like in the range of 5 to 12 g/10min.

In a preferred embodiment the fiber reinforced composite has

(a) a flexural modulus measured according to ISO 178 of at least 6,500 MPa, more preferably of at least 6,900 MPa, yet more preferably in the range of 6,800 to 7,600 MPa, like in the range of 7,000 to 7,400 MPa；

and/or

(b) a notched Charpy strength measured according to ISO 179 (23 ℃) of at least 7 kJ/m², more preferably in the range of 7.0 to 16 kJ/m², yet more preferably in the range of 7.0 to 14 kJ/m².

In addition, the present invention also relates to a process for the preparation of the fiber reinforced composite as described above and in more detail below, comprising the steps of adding

(a) the propylene homopolymer (H-PP2) and the heterophasic propylene copolymer (HECO) ；

(b) optionally the propylene homopolymer (H-PP3) and the polar modified polypropylene (PMP)

(c) the fibres (F) ；

(d) the hindered amine light stabilizer (HALS) ； and

(e) optionally the phenolic antioxidant (AO) and the lubricant (L) ；

to an extruder and extruding the same obtaining said fiber reinforced composite.

The fiber reinforced composite according to the invention may be compounded and pelletized using any of the variety of compounding and blending machines and methods well known and commonly used in the resin compounding art.

For blending the individual components of the instant composition a conventional compounding or blending apparatus, e.g. a Banbury mixer, a 2-roll rubber mill, Buss-co-kneader or a twin screw extruder may be used. The polymer materials recovered from the extruder/mixer are usually in the form of pellets. These pellets are then preferably further processed, e.g. by injection molding to generate articles and products of the inventive composition.

In the following the individual components of the fiber reinforced composite are described in more detail.

The propylene homopolymer (H-PP2)

The fiber reinforced composite must comprise several polymer components. To achieve the good balanced mechanical properties the polymer must contain two different polypropylenes. One must especially contribute to the impact and the other to the stiffness of the final product. Good stiffness can be achieved due to the presence of a propylene homopolymer with high molecular weight. Accordingly it is preferred that the propylene homopolymer (H-PP2) has a melt flow rate MFR₂ (230 ℃, 2.16 kg) measured according to ISO 1133 of not more than 30 g/10 min, more preferably in the range of 2 to 20 g/10min, still more preferably in the range of 5 to 15 g/10min, like in the range of 7 to 12 g/10min.

More preferably the propylene homopolymer (H-PP2) has a melting temperature T_m in the range of 160 to 170 ℃, like in the range of 164 to 170 ℃.

The term “propylene homopolymer” used in the present invention relates to a polypropylene that consists substantially, i.e. of more than 99.7 wt. -％, still more preferably of at least 99.8 wt.-％, of propylene units. In a preferred embodiment only propylene units in the propylene homopolymer are detectable.

The propylene homopolymer (H-PP2) is state of the art and commercial available. A suitable propylene homopolymer is for instance Bormed HD915CF of Borealis AG.

The heterophasic propylene copolymer (HECO)

A further important polymer component is the heterophasic propylene copolymer (HECO) . The heterophasic propylene copolymer (HECO) according to this invention comprises a propylene homopolymer (H-PP1) as matrix (M) and an elastomeric propylene copolymer (EC) .

The term ″heterophasic″ indicates that the elastomeric propylene copolymer (EC) is (finely) dispersed in a polypropylene matrix. In other words, the elastomeric propylene copolymer (EC) forms inclusions in the matrix (M) formed by the propylene homopolymer (H-PP1) . Thus, the matrix contains (finely) dispersed inclusions being not part of the matrix (M) and said inclusions contain the elastomeric propylene copolymer (EC) .

The term ″inclusion″ according to this invention shall preferably indicate that the matrix (M) and the inclusions form different phases within the heterophasic propylene copolymer (HECO) , said inclusions are for instance visible by high resolution microscopy, like electron microscopy or scanning force microscopy.

The amount of propylene homopolymer (H-PP1) in the heterophasic propylene copolymer (HECO) is preferably at least 55wt. -％, more preferably in the range of 55 to 80 wt. -％, even more preferably in the range of 60 to 75 wt. -％, yet even more preferably in the range of 65 to 71 wt. -％. The remaining part of the heterophasic propylene copolymer (HECO) constitutes the elastomeric propylene copolymer (EC) .

Preferably the heterophasic propylene copolymer (HECO) has a melt flow rate MFR₂ (230 ℃) in the range of 2 to 20 g/10min, more preferably in the range of 5 to 18 g/10min, like in the range of 8 to 15 g/10min.

The heterophasic propylene copolymer (HECO) according to this invention comprises, more preferably consists of units derived from

(a) propylene,

and as comonomer

(b) ethylene and/or a C₄ to C₁₂ α-olefin.

Preferably the heterophasic propylene copolymer (HECO) comprises propylene and comonomers copolymerizable with propylene, for example comonomers such as ethylene and/or C₄ to C₁₀ α-olefins, e.g. 1-butene and/or 1-hexene. Preferably the heterophasic propylene copolymer (HECO) comprises, especially consists of, -apart from propylene –of commoners selected from the group consisting of ethylene, 1-butene and 1-hexene. More specifically the heterophasic propylene copolymer (HECO) comprises -apart from propylene -units derivable from ethylene and/or 1-butene. In a preferred embodiment the heterophasic propylene copolymer (HECO) consist of units derivable from ethylene and propylene.

Preferably the comonomer, like ethylene, content in the heterophasic propylene copolymer (HECO) is in the range of 7 to 25 mol-％, more preferably in the range of 10 to 22 mol-％, still more preferably in the range of 12 to 21 mol-％, more preferably in the range of 15 to 20 mol.

As stated above the matrix (M) of the heterophasic propylene copolymer (HECO) is the propylene homopolymer (H-PP1) .

It is important that the propylene homopolymer (H-PP1) has a rather high melt flow rate to improve the processability. Accordingly it is preferred that the melt flow rate of the propylene homopolymer (H-PP1) is higher than the melt flow rate of the propylene homopolymer (H-PP2) . Thus it is preferred that the propylene homopolymer (H-PP1) has a melt flow rate MFR₂ (230 ℃) of at least 40 g/10min, more preferably in the range of 45 to 150 g/10min, more preferably in the range of 50 to 100 g/10min, like in the range of 52 to 80 g/10min.

Accordingly it is preferred that the propylene homopolymer (H-PP1) and the propylene homopolymer (HPP-2) fulfil together the inequation (Ia) , preferably inequation (Ib) , even more preferably inequation (Ic) , yet more preferably inequation (Id)

wherein

MFR (HPP-1) is the melt flow rate MFR₂ (230 ℃) [g/10 min] of the polypropylene (H-PP1) and

MFR (HPP-2) is the melt flow rate MFR₂ (230 ℃) [g/10 min] of the propylene homopolymer (H-PP2) .

The propylene copolymer (M) can have a xylene cold soluble content (XCS) in a broad range, i.e. up to 5.0 wt. -％. However it is preferred that the propylene copolymer (M) has a xylene cold soluble content (XCS) in the range of 0.3 to 4.0 wt. -％, more preferably in the range of 0.5 to 3.5 wt. -％, like in the range of 1.0 to 3.0 wt. -％.

One further essential component of the heterophasic propylene copolymer (HECO) is its elastomeric propylene copolymer (EC) .

Preferably, the elastomeric propylene copolymer (EC) according to this invention comprises, more preferably consists of units derived from

(a) propylene,

and as comonomer

(b) ethylene and/or a C₄ to C₁₂ α-olefin.

Preferably the elastomeric propylene copolymer (EC) comprises propylene and comonomers copolymerizable with propylene, for example comonomers such as ethylene and/or C₄ to C₁₀ α-olefins, e.g. 1-butene and/or 1-hexene. Preferably the elastomeric propylene copolymer (EC) comprises, especially consists of, -apart from propylene –of commoners selected from the group consisting of ethylene, 1-butene and 1-hexene. More specifically the elastomeric propylene copolymer (EC) comprises -apart from propylene -units derivable from ethylene and/or 1-butene. In a preferred embodiment the elastomeric propylene copolymer (EC) consist of units derivable from ethylene and propylene.

Preferably the comonomer, like ethylene, content of the elastomeric propylene copolymer (EC) is in the range of 35 to 65 mol-％, more preferably in the range of 40 to 60 mol-％, still more preferably in the range of 45 to 55 mol-％.

The properties of the elastomeric propylene copolymer (EC) mainly influence the xylene cold soluble (XCS) content of the heterophasic propylene copolymer (HECO) .

Thus it is preferred that the heterophasic propylene copolymer (HECO) has a xylene cold soluble content (XCS) in the range of 20 to 45 wt. -％, more preferably in the range of 25 to 40 wt. -％, yet more preferably in the range of 25 to 35 wt. -％, like in the range of 28 to 33 wt.-％.

Further it is preferred that the elastomeric propylene copolymer (EC) has a moderate weight average molecular weight. High intrinsic viscosity (IV) values reflect a high weight average molecular weight. Thus it is appreciated that the xylene cold soluble fraction (XCS) of the heterophasic propylene copolymer (HECO) has an intrinsic viscosity (IV) of equal or higher than 2.0 dl/g, more preferably in the range of 2.0 to 3.0 dl/g, more preferably in the range of 2.0 to 2.8 dl/g.

Preferably the α-nucleating agent as discussed above is part of the heterophasic propylene copolymer (HECO) . Accordingly the α-nucleating agent content of the heterophasic propylene copolymer (HECO) is preferably up to 5.0 wt. -％. In a preferred embodiment, the heterophasic propylene copolymer (HECO) contain (s) not more than 3, 000 ppm, more preferably of 1 to 2,000 ppm of a α-nucleating agent, in particular selected from the group consisting of dibenzylidenesorbitol (e.g. 1, 3 : 2, 4 dibenzylidene sorbitol) , dibenzylidenesorbitol derivative, preferably dimethyldibenzylidenesorbitol (e.g. 1, 3 : 2, 4 di(methylbenzylidene) sorbitol) , or substituted nonitol-derivatives, such as 1, 2, 3, -trideoxy-4,6: 5, 7-bis-O- [ (4-propylphenyl) methylene] -nonitol, vinylcycloalkane polymer, vinylalkane polymer, and mixtures thereof.

In a preferred embodiment the heterophasic propylene copolymer (HECO) contains a vinylcycloalkane, like vinylcyclohexane (VCH) , polymer and/or vinylalkane polymer, as the α-nucleating agent. Preferably in this embodiment, the heterophasic propylene copolymer (HECO) contains a vinylcycloalkane, like vinylcyclohexane (VCH) , polymer and/or vinylalkane polymer, preferably vinylcyclohexane (VCH) . Preferably the vinylcycloalkane is vinylcyclohexane (VCH) polymer which is optionally introduced into the heterophasic propylene copolymer (HECO) by the BNT technology. More preferably in this preferred embodiment, the amount of vinylcycloalkane, like vinylcyclohexane (VCH) , polymer and/or vinylalkane polymer, more preferably of vinylcyclohexane (VCH) polymer, in the heterophasic propylene copolymer (HECO) is not more than 500 ppm, more preferably of 0.5 to 200 ppm, most preferably 1 to 100 ppm.

With regard to the BNT-technology reference is made to the international applications WO 99/24478, WO 99/24479 and particularly WO 00/68315. According to this technology a catalyst system, preferably a Ziegler-Natta procatalyst, can be modified by polymerizing a vinyl compound in the presence of the catalyst system, comprising in particular the special Ziegler-Natta procatalyst, an external donor and a cocatalyst, which vinyl compound has the formula:

CH₂＝CH-CHR³R⁴

wherein R³ and R⁴ together form a 5-or 6-membered saturated, unsaturated or aromatic ring or independently represent an alkyl group comprising 1 to 4 carbon atoms, and the modified catalyst is used for the preparation of the heterophasic polypropylene according to this invention, i.e. of the heterophasic propylene copolymer (HECO) . The polymerized vinyl compound acts as an α-nucleating agent. The weight ratio of vinyl compound to solid catalyst component in the modification step of the catalyst is preferably of up to 5 (5: 1) , preferably up to 3 (3: 1) most preferably from 0.5 (1: 2) to 2 (2: 1) . The most preferred vinyl compound is vinylcyclohexane (VCH) .

Further it is preferred that the heterophasic propylene copolymer (HECO) is produced in a sequential polymerization process comprising the steps of

(a1) polymerizing propylene in a first reactor (R1) obtaining the propylene homopolymer (H-PP1) ,

(b2) transferring the propylene homopolymer (H-PP1) of step (a) into a second reactor (R2) ,

(c2) polymerizing in the second reactor (R2) and in the presence of the propylene homopolymer (H-PP1) obtained in step (a) propylene and at least one of ethylene and/or C₄ to C₁₂ α-olefin, obtaining thereby the elastomeric propylene copolymer (EC) , the propylene homopolymer (H-PP1) and the elastomeric propylene copolymer (EC) form the heterophasic propylene copolymer (HECO) .

or

(a2) polymerizing propylene in a first reactor (R1) obtaining the first propylene homopolymer fraction of the propylene homopolymer (H-PP1) ,

(b2) transferring the the first propylene homopolymer fraction into a second reactor (R2) ,

(c2) polymerizing in the second reactor (R2) and in the presence of said the first propylene homopolymer fraction propylene, obtaining thereby the second propylene homopolymer fraction, said the first propylene homopolymer fraction and said second propylene homopolymer fraction form the propylene homopolymer (H-PP1) , i.e. the matrix of the heterophasic propylene copolymer (HECO) ,

(d2) transferring the propylene homopolymer (H-PP1) of step (c) into a third reactor (R3) ,

(e2) polymerizing in the third reactor (R3) and in the presence of the propylene homopolymer (H-PP1) obtained in step (c) propylene and at least one of ethylene and/or C₄ to C₁₂ α-olefin, obtaining thereby the first elastomeric propylene copolymer fraction, .

(f2) transferring the product of step (e) (propylene homopolymer (H-PP1) and the first elastomeric propylene copolymer) into a fourth reactor (R4) ,

(g2) polymerizing in the fourth reactor (R4) and in the presence of the product of step (e) propylene and at least one of ethylene and/or C₄ to C₁₂ α-olefin, obtaining thereby the second elastomeric propylene copolymer fraction, the first and second elastomeric propylene copolymer fractions form the elastomeric propylene copolymer (EC) , and the propylene homopolymer (H-PP1) and the elastomeric propylene copolymer (EC) form the heterophasic propylene copolymer (RAHECO) .

Of course, in the first reactor (R1) the second propylene homopolymer fraction can be produced and in the second reactor (R2) the first propylene homopolymer fraction can be obtained.

Preferably between the second reactor (R2) and the third reactor (R3) , and between the third reactor (R3) and the fourth reactor (R4) , the monomers are flashed out.

The term “sequential polymerization process” indicates that the heterophasic propylene copolymer (HECO) is produced in at least two, like three or four reactors connected in series. Accordingly the present process comprises at least a first reactor (R1) and a second reactor (R2) , more preferably a first reactor (R1) , a second reactor (R2) , and a third reactor (R3) , and a fourth reactor (R4) . The term “polymerization reactor” shall indicate that the main polymerization takes place. Thus in case the process consists of four polymerization reactors, this definition does not exclude the option that the overall process comprises for instance a pre-polymerization step in a pre-polymerization reactor. The term “consist of” is only a closing formulation in view of the main polymerization reactors.

The first reactor (R1) is preferably a slurry reactor (SR) and can be any continuous or simple stirred batch tank reactor or loop reactor operating in bulk or slurry. Bulk means a polymerization in a reaction medium that comprises of at least 60 ％ (w/w) monomer. According to the present invention the slurry reactor (SR) is preferably a (bulk) loop reactor (LR) .

The second reactor (R2) and the third reactor (R3) and the fourth reactor (R4) are preferably gas phase reactors (GPR) . Such gas phase reactors (GPR) can be any mechanically mixed or fluid bed reactors. Preferably the gas phase reactors (GPR) comprise a mechanically agitated fluid bed reactor with gas velocities of at least 0.2 m/sec. Thus it is appreciated that the gas phase reactor is a fluidized bed type reactor preferably with a mechanical stirrer.

Thus in a preferred embodiment the first reactor (R1) is a slurry reactor (SR) , like a loop reactor (LR) , whereas the second reactor (R2) and the third reactor (R3) and the fourth reactor (R4) are gas phase reactors (GPR) . Accordingly for the instant process at least three, preferably four polymerization reactors, namely a slurry reactor (SR) , like a loop reactor (LR) , a first gas phase reactor (GPR-1) , and a second gas phase reactor (GPR-2) , and a third gas phase reactor (GRP-3) , connected in series are used. If needed prior to the slurry reactor (SR) a pre-polymerization reactor is placed.

A preferred multistage process is a “loop-gas phase” -process, such as developed by Borealis A/S, Denmark (known as

technology) described e.g. in patent literature, such as in EP 0 887 379, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.

A further suitable slurry-gas phase process is the

process of Basell.

Preferably, in the instant process for producing the heterophasic propylene copolymer (HECO) as defined above the conditions for the first reactor (R1) , i.e. the slurry reactor (SR) , like a loop reactor (LR) , of step (a) may be as follows:

-the temperature is within the range of 50 ℃ to 110 ℃, preferably between 60 ℃ and 100 ℃, more preferably between 68 and 95 ℃,

-the pressure is within the range of 20 bar to 80 bar, preferably between 40 bar to 70 bar,

-hydrogen can be added for controlling the molar mass in a manner known per se.

Subsequently, the reaction mixture from step (a) is transferred to the second reactor (R2) , i.e. gas phase reactor (GPR-1) , whereby the conditions are preferably as follows:

-the temperature is within the range of 50 ℃ to 130 ℃, preferably between 60 ℃ and 100 ℃,

-the pressure is within the range of 5 bar to 50 bar, preferably between 15 bar to 35 bar,

-hydrogen can be added for controlling the molar mass in a manner known per se.

The condition in the third reactor (R3) , preferably in the second gas phase reactor (GPR-2) , is similar to the second reactor (R2) . The condition in the fourth reactor (R4) , preferably in the third gas phase reactor (GPR-3) , is similar to the third reactor (R3) .

The residence time can vary in the four reactor zones.

In one embodiment of the process for producing the polypropylene the residence time in bulk reactor, e.g. loop is in the range 0.1 to 2.5 hours, e.g. 0.15 to 1.5 hours and the residence time in gas phase reactor will generally be 0.2 to 6.0 hours, like 0.5 to 4.0 hours.

If desired, the polymerization may be effected in a known manner under supercritical conditions in the first reactor (R1) , i.e. in the slurry reactor (SR) , like in the loop reactor (LR) , and/or as a condensed mode in the gas phase reactors (GPR) .

Preferably the process comprises also a prepolymerization with the catalyst system, as described in detail below, comprising a Ziegler-Natta procatalyst, an external donor and optionally a cocatalyst.

In a preferred embodiment, the prepolymerization is conducted as bulk slurry polymerization in liquid propylene, i.e. the liquid phase mainly comprises propylene, with minor amount of other reactants and optionally inert components dissolved therein.

The prepolymerization reaction is typically conducted at a temperature of 10 to 60 ℃, preferably from 15 to 50 ℃, and more preferably from 20 to 45 ℃.

The pressure in the prepolymerization reactor is not critical but must be sufficiently high to maintain the reaction mixture in liquid phase. Thus, the pressure may be from 20 to 100 bar, for example 30 to 70 bar.

The catalyst components are preferably all introduced to the prepolymerization step. However, where the solid catalyst component (i) and the cocatalyst (ii) can be fed separately it is possible that only a part of the cocatalyst is introduced into the prepolymerization stage and the remaining part into subsequent polymerization stages. Also in such cases it is necessary to introduce so much cocatalyst into the prepolymerization stage that a sufficient polymerization reaction is obtained therein.

It is possible to add other components also to the prepolymerization stage. Thus, hydrogen may be added into the prepolymerization stage to control the molecular weight of the prepolymer as is known in the art. Further, antistatic additive may be used to prevent the particles from adhering to each other or to the walls of the reactor.

The precise control of the prepolymerization conditions and reaction parameters is within the skill of the art.

According to the present invention the heterophasic propylene copolymer (HECO) is obtained by a multistage polymerization process, as described above, in the presence of a catalyst system comprising as component (i) a Ziegler-Natta procatalyst which contains a trans-esterification product of a lower alcohol and a phthalic ester.

The procatalyst used according to the invention for preparing the heterophasic propylene copolymer (HECO) is prepared by

a) reacting a spray crystallized or emulsion solidified adduct of MgCl₂ and a C₁-C₂ alcohol with TiCl₄

b) reacting the product of stage a) with a dialkylphthalate of formula (I)

wherein R^1’a nd R^2’a re independently at least a C₅ alkyl under conditions where a transesterification between said C₁ to C₂ alcohol and said dialkylphthalate of formula (I) takes place to form the internal donor

c) washing the product of stage b) or

d) optionally reacting the product of step c) with additional TiCl₄.

The procatalyst is produced as defined for example in the patent applications WO 87/07620, WO 92/19653, WO 92/19658 and EP 0 491 566. The content of these documents is herein included by reference.

First an adduct of MgCl₂ and a C₁-C₂ alcohol of the formula MgCl₂*nROH, wherein R is methyl or ethyl and n is 1 to 6, is formed. Ethanol is preferably used as alcohol.

The adduct, which is first melted and then spray crystallized or emulsion solidified, is used as catalyst carrier.

In the next step the spray crystallized or emulsion solidified adduct of the formula MgCl₂*nROH, wherein R is methyl or ethyl, preferably ethyl and n is 1 to 6, is contacting with TiCl₄ to form a titanized carrier, followed by the steps of

·adding to said titanised carrier

(i) a dialkylphthalate of formula (I) with R^1’a nd R^2’ being independently at least a C₅-alkyl, like at least a C₈-alkyl,

or preferably

(ii) a dialkylphthalate of formula (I) with R^1’a nd R^2’ being the same and being at least a C₅-alkyl, like at least a C₈-alkyl,

or more preferably

(iii) a dialkylphthalate of formula (I) selected from the group consisting of propylhexylphthalate (PrHP) , dioctylphthalate (DOP) , di-iso-decylphthalate (DIDP) , and ditridecylphthalate (DTDP) , yet more preferably the dialkylphthalate of formula (I) is a dioctylphthalate (DOP) , like di-iso-octylphthalate or diethylhexylphthalate, in particular diethylhexylphthalate,

to form a first product,

·subjecting said first product to suitable transesterification conditions, i.e. to a temperature above 100 ℃, preferably between 100 to 150 ℃, more preferably between 130 to 150 ℃, such that said methanol or ethanol is transesterified with said ester groups of said dialkylphthalate of formula (I) to form preferably at least 80 mol-％, more preferably 90 mol-％, most preferably 95 mol. -％, of a dialkylphthalate of formula (II)

with R¹ and R² being methyl or ethyl, preferably ethyl, the dialkylphthalat of formula (II) being the internal donor and

·recovering said transesterification product as the procatalyst composition (component (i)) .

The adduct of the formula MgCl₂*nROH, wherein R is methyl or ethyl and n is 1 to 6, is in a preferred embodiment melted and then the melt is preferably injected by a gas into a cooled solvent or a cooled gas, whereby the adduct is crystallized into a morphologically advantageous form, as for example described in WO 87/07620.

This crystallized adduct is preferably used as the catalyst carrier and reacted to the procatalyst useful in the present invention as described in WO 92/19658 and WO 92/19653.

As the catalyst residue is removed by extracting, an adduct of the titanised carrier and the internal donor is obtained, in which the group deriving from the ester alcohol has changed.

In case sufficient titanium remains on the carrier, it will act as an active element of the procatalyst.

Otherwise the titanization is repeated after the above treatment in order to ensure a sufficient titanium concentration and thus activity.

Preferably the procatalyst used according to the present invention contains 2.5 wt. -％of titanium at the most, preferably 2.2％wt. -％at the most and more preferably 2.0 wt. -％at the most. Its donor content is preferably between 4 to 12 wt. -％and more preferably between 6 and 10 wt. -％.

More preferably the procatalyst used according to the present invention has been produced by using ethanol as the alcohol and dioctylphthalate (DOP) as dialkylphthalate of formula (I), yielding diethyl phthalate (DEP) as the internal donor compound.

Still more preferably the catalyst used according to the present invention is the catalyst as described in the example section； especially with the use of dioctylphthalate as dialkylphthalate of formula (I) .

For the production of the heterophasic propylene copolymer (HECO) according to the present invention the catalyst system used preferably comprises in addition to the special Ziegler-Natta procatalyst an organometallic cocatalyst as component (ii) .

Accordingly it is preferred to select the cocatalyst from the group consisting of trialkylaluminium, like triethylaluminium (TEA) , dialkyl aluminium chloride and alkyl aluminium sesquichloride.

Component (iii) of the catalysts system used is an external donor represented by formula (IIIa) or (IIIb) . Formula (IIIa) is defined by

Si(OCH₃) ₂R₂ ⁵ (IIIa)

wherein R⁵ represents a branched-alkyl group having 3 to 12 carbon atoms, preferably a branched-alkyl group having 3 to 6 carbon atoms, or a cyclo-alkyl having 4 to 12 carbon atoms, preferably a cyclo-alkyl having 5 to 8 carbon atoms.

It is in particular preferred that R⁵ is selected from the group consisting of iso-propyl, iso-butyl, iso-pentyl, tert. -butyl, tert. -amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.

Formula (IIIb) is defined by

Si(OCH₂CH₃) ₃ (NR^xR^y) (IIIb)

wherein R^x and R^y can be the same or different a represent a hydrocarbon group having 1 to 12 carbon atoms.

R^x and R^y are independently selected from the group consisting of linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, branched aliphatic hydrocarbon group having 1 to 12 carbon atoms and cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms. It is in particular preferred that R^x and R^y are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, iso-propyl, iso-butyl, iso-pentyl, tert. -butyl, tert. -amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.

More preferably both R^x and R^y are the same, yet more preferably both R^x and R^y are an ethyl group.

More preferably the external donor is of formula (IIIa) , like dicyclopentyl dimethoxy silane [Si(OCH₃) ₂ (cyclo-pentyl) ₂] or diisopropyl dimethoxy silane [Si (OCH₃) ₂ (CH (CH₃) ₂) ₂] .

In a further embodiment, the Ziegler-Natta procatalyst can be modified by polymerising a vinyl compound in the presence of the catalyst system, comprising the special Ziegler-Natta procatalyst (component (i) ) , an external donor (component (iii) and optionally a cocatalyst (component (iii) ) , which vinyl compound has the formula:

CH₂＝CH-CHR³R⁴

wherein R³ and R⁴ together form a 5-or 6-membered saturated, unsaturated or aromatic ring or independently represent an alkyl group comprising 1 to 4 carbon atoms, and the modified catalyst is used for the preparation of the heterophasic propylene copolymer (HECO) according to the present invention. The polymerized vinyl compound can act as an α-nucleating agent.

Concerning the modification of catalyst reference is made to the international applications WO 99/24478, WO 99/24479 and particularly WO 00/68315, incorporated herein by reference with respect to the reaction conditions concerning the modification of the catalyst as well as with respect to the polymerization reaction.

Accordingly it is appreciated that the heterophasic propylene copolymer (HECO) is α-nucleated. In case the α-nucleation is not effected by a vinylcycloalkane polymer or a vinylalkane polymer as indicated above, the following α-nucleating agents may be present.

(iv) mixtures thereof.

The propylene homopolymer (H-PP3)

As mentioned above the heterophasic propylene copolymer (HECO) must contain a matrix (M) with rather high melt flow rate. To further improve the processability it might be advantageous to add a further polymer with high melt flow rate. Thus it is preferred that the additional propylene homopolymer (H-PP3) has a melt flow rate MFR₂ (230 ℃, 2.16 kg) measured according to ISO 1133 of at least 40 g/10min, more preferably in the range of 45 to 150 g/10min, more preferably in the range of 50 to 100 g/10min, like in the range of 55 to 80 g/10min.

Accordingly it is preferred that the propylene homopolymer (H-PP3) and the propylene homopolymer (HPP-2) fulfil together the inequation (IIa) , preferably inequation (IIb) , even more preferably inequation (IIc) , yet more preferably inequation (IId)

wherein

MFR (HPP-3) is the melt flow rate MFR₂ (230 ℃) [g/10 min] of the polypropylene (H-PP3) and

The the propylene homopolymer (H-PP3) and the propylene homopolymer (H-PP1) can have the same melt flow rate or can have a different melt flow rate. Accordingly it is preferred that the propylene homopolymer (H-PP3) and the propylene homopolymer (HPP-1) fulfil together the inequation (IIIa) , preferably inequation (IIIb) , even more preferably inequation (IIIc) , yet more preferably inequation (IIId)

wherein

MFR (HPP-1) is the melt flow rate MFR₂ (230 ℃) [g/10 min] of the propylene homopolymer (H-PP1) .

Preferably the weight ratio between the propylene homopolymer (H-PP3) and the propylene homopolymer (H-PP1) [ (H-PP3) / (H-PP1) ] is 2.0 to 8.0, more preferably in the range of 3.0 to 7.0, like in the range of 4.0 to 6.0.

Still more preferably the weight ratio between the propylene homopolymer (H-PP2) and the sum of the propylene homopolymer (H-PP3) and the propylene homopolymer (H-PP1) [ (H-PP2) / ( (H-PP3) + (H-PP1) ) ] is 0.1 to 1.0, more preferably in the range of 0.2 to 0.7, like in the range of 0.3 to 0.6.

More preferably the propylene homopolymer (H-PP3) has a melting temperature T_m in the range of 155 to 170 ℃, like in the range of 158 to 170 ℃.

The propylene homopolymer (H-PP3) is state of the art and commercial available. A suitable propylene homopolymer is for instance Borpure HJ311MO of Borouge Pte Ltd.

The adhesion promoter (AP)

The adhesion promotor (AP) according to this invention is a polar modified polypropylene (PMP) . An adhesion promoter (AP) is applied in order to achieve a chemical reaction between the fibers (F) and the adhesion promoter. As a result, the fibers (F) can be easier and more uniformly dispersed in the polymer components which act in the fiber reinforced composition as a matrix.

The polar modified polypropylene (PMP) preferably is a polypropylene containing polar groups. The polypropylene is preferably a propylene homopolymer or copolymer, like a copolymer of propylene with other α-olefins, like ethylene.

In terms of structure, the polar modified polypropylene (PMP) is preferably selected from graft or block copolymers. In this context, preference is given to a polar modified polypropylene (PMP) containing polar groups selected from the group consisting of acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazoline and epoxides.

Specific examples of the said polar groups are unsaturated cyclic anhydrides and their aliphatic diesters, and the diacid derivatives. In particular, one can use maleic anhydride and compounds selected from C₁ to C₁₀ linear and branched dialkyl maleates, C₁ to C₁₀ linear and branched dialkyl fumarates, itaconic anhydride, C₁ to C₁₀ linear and branched itaconic acid dialkyl esters, maleic acid, fumaric acid, itaconic acid and mixtures thereof.

Particular preference is given to using a propylene polymer grafted with maleic anhydride as the polar modified polypropylene (PMP) , i.e. the adhesion promotor (AP) .

The polar modified polypropylene (PMP) can be produced in a simple manner by reactive extrusion of the polymer, for example with maleic anhydride in the presence of free radical generators (like organic peroxides) , as disclosed for instance in EP 0 572 028.

Preferred amounts of groups deriving from polar groups in the polar modified polypropylene (PMP) are from 0.5 to 3.0 wt. -％.

Preferred values of the melt flow rate MFR₂ (190 ℃) for the polar modified polypropylene (PMP) are from 1.0 to 500 g/10 min, like in the range of 20 to 150 g/10min.

The polar modified polypropylene (PMP) is known in the art and commercially available. A suitable example is SCONA TPPP 8112 GA of BYK.

The fiber (F)

Essential component of the fiber reinforced composition is the fiber (F) . Preferably the fiber (F) is selected from the group consisting of glass fiber, metal fiber, mineral fiber, ceramic fiber and graphite fiber. The glass fiber is preferred. In particular, the glass fiber is a cut glass fiber, also known as short fiber or chopped strand.

The cut or short glass fiber used in the fiber reinforced composition preferably has an average length of from 1 to 10 mm, more preferably from 1 to 7 mm, for example 3 to 5 mm, or 4 mm. The cut or short glass fiber used in the fiber reinforced composition preferably has an average diameter of from 8 to 20 μm, more preferably from 9 to 16 μm, for example 10 to 15 μm.

Preferably, the fibers (F) have an aspect ratio of 125 to 650, preferably of 150 to 450, more preferably 200 to 450. The aspect ratio is the relation between average length and average diameter of the fibers.

The phenolic antioxidant (AO)

As a further component the fiber reinforced composite comprises a phenolic antioxidant (AO) . Preferably the phenolic antioxidant (AO) is a sterically hindered phenol (SHP) . Such antioxidant is an excellent H-donor. The stability of the radical form is governed by the sterical hindrance of the substituent in the 2, 6 position of the phenol.

In the following the sterically hindered phenol (SHP) is defined more precisely. The term “sterically hindered” according to this invention means that the hydroxyl group (HO-) of the sterically hindered phenol (SHP) is surrounded by sterical alkyl residues.

Accordingly the sterically hindered phenol (SHP) preferably comprise the residue of formula (I)

wherein

R₁ being located at the ortho-or meta-position to the hydroxyl-group and R₁ is (CH₃) ₃C-, CH₃-or H, preferably (CH₃) ₃C-, and

A₁ constitutes the remaining part of the sterically hindered phenol (SHP) and is preferably located at the para-position to the hydroxyl-group.

Preferably the sterically hindered phenol (SHP) preferably comprise the residue of formula (Ia)

wherein

R₁ is (CH₃) ₃C-, CH₃-or H, preferably (CH₃) ₃C-, and

A₁ constitutes the remaining part of the sterically hindered phenol (SHP) .

Preferably A₁ is in para-position to the hydroxyl-group.

Additionally the sterically hindered phenol (SHP) shall preferably exceed a specific molecular weight. Accordingly the sterically hindered phenol (SHP) has preferably a molecular weight of more than 500 g/mol. On the other hand the molecular weight should be not too high, i.e. not higher than 1300 g/mol. A preferred range is from 500 to 1300 g/mol, more preferably from 700 to 1300 g/mol.

Further the sterically hindered phenol (SHP) can be additionally defined by the amount of phenolic residues, in particular by the amount of phenolic residues of formula (I) or (Ia) . Accordingly the sterically hindered phenol (SHP) may comprise (s) 1, 2, 3, 4 or more phenolic residues, preferably 3, 4 or more phenolic residues of formula (I) or (Ia) .

Moreover the sterically hindered phenol (SHP) comprises mainly only carbon atoms, hydrogen atoms and minor amounts of O-atoms, mainly caused due to the hydroxyl group (HO-) of the phenolic residues. However the sterically hindered phenol (SHP) may comprise additionally minor amounts of N, S and P atoms. Preferably the sterically hindered phenol (SHP) is constituted by C, H, O, N and S atoms only, more preferably the sterically hindered phenol (SHP) is constituted by C, H, O and optionally N only.

As stated above the sterically hindered phenol (SHP) shall have a rather high molecular weight. A high molecular weight is an indicator for several phenolic residues. Thus it is in particular appreciated that the sterically hindered phenol (SHP) has 3 or more, especially 3, phenolic residues, like the phenolic residue of formula (I) or (Ia) .

Considering the above requirements the sterically hindered phenol (SHP) is preferably selected from the group consisting of

2,6-di-tert-butyl-4-methylphenol (CAS no. 128-37-0； M 220 g/mol) , pentaerythrityl-tetrakis (3- (3’ , 5’ -di-tert-butyl-4-hydroxyphenyl) propionate (CAS no. 6683-19-8； M 1178 g/mol) ,

octadecyl 3- (3’ , 5’ -di-tert-butyl-4-hydroxyphenyl) propionate (CAS no. 2082-79-3； M 531 g/mol)

1,3, 5-trimethyl-2, 4, 6-tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (CAS no. 1709-70-2； M 775 g/mol) ,

2,2'-thiodiethylenebis (3, 5-di-tert. -butyl-4-hydroxyphenyl) propionate (CAS no. 41484-35-9； M 643 g/mol) ,

calcium bis (ethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate) (CAS no. 65140-91-2； M 695 g/mol) ,

1,3, 5-tris (3’ , 5’ -di-tert. butyl-4’ -hydroxybenzyl) -isocyanurate (CAS no. 27676-62-6, M 784 g/mol) ,

1,3, 5-tris (4-tert. butyl-3-hydroxy-2, 6-dimethylbenzyl) -1, 3, 5-triazine-2, 4, 6- (1H, 3H, 5H) -trione (CAS no. 40601-76-1, M 813 g/mol) ,

bis (3, 3-bis (3’ -tert-butyl-4’ -hydroxyphenyl) butanic acid) glycolester (CAS no. 32509-66-3； M 794 g/mol) ,

4,4'-Thiobis (2-tert-butyl-5-methylphenol) (CAS no. 96-69-5； M 358 g/mol) ,

2,2'-methylene-bis- (6- (l-methyl-cyclohexyl) -para-cresol) (CAS no. 77-62-3； M 637 g/mol) ,

3,3'-Bis (3, 5-di-tert-butyl-4-hydroxyphenyl) -N, N'-hexamethylenedipropionamide (CAS no. 23128-74-7； M 637 g/mol) ,

2,5, 7, 8-tetramethyl-2- (4’ , 8’ , 12’ -trimethyltridecyl) -chroman-6-ol (CAS no. 10191-41-0； M 431 g/mol) ,

2,2-ethylidenebis (4, 6-di-tert-butylphenol) (CAS no. 35958-30-6； M 439 g/mol) ,

1,1, 3-tris (2-methyl-4-hydroxy-5'-tert-butylphenyl) butane (CAS no. 1843-03-4； M 545 g/mol) ,

3,9-bis (1, 1-dimethyl-2- (beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl) -2,4, 8, 10-tetraoxaspiro [5.5] undecane (CAS no. 90498-90-1； M 741 g/mol) ,

1,6-hexanediyl-bis (3, 5-bis (1, 1dimethylethyl) -4-hydroxybenzene) propanoate) (CAS no. 35074-77-2； M 639 g/mol) ,

2,6-di-tert-butyl-4-nonylphenol (CAS no. 4306-88-1； M 280 g/mol) ,

4,4'-butylidenebis (6-tert-butyl-3-methylphenol (CAS no. 85-60-9； M 383 g/mol) ；

2,2'-methylene bis (6-tert-butyl-4-methylphenol) (CAS no. 119-47-1； M 341 g/mol) ,

triethylenglycol-bis- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (CAS no. 36443-68-2； M 587 g/mol) ,

6,6’ -di-tert-butyl-2, 2'-thiodip-cresol (CAS no. 90-66-4； M 359 g/mol) ,

diethyl- (3, 5-di-tert-butyl-4-hydroxybenzyl) phosphate (CAS no. 976-56-7； M 356 g/mol) , 4,6-bis (octylthiomethyl) -o-cresol (CAS no. 110553-27-0； M 425 g/mol) , and

1,1, 3-tris [2-methyl-4- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane (CAS no. 180002-86-2； M 1326 g/mol) ,

More preferably the sterically hindered phenols (SHP) is selected from the group consisting of

pentaerythrityl-tetrakis (3- (3’ , 5’ -di-tert-butyl-4-hydroxyphenyl) propionate (CAS no. 6683-19-8； M 1178 g/mol) ,

triethylenglycol-bis- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (CAS no. 36443-68-2； M 587 g/mol) , and

benzenepropanoic acid, 3, 5-bis (1, 1-dimehtyl-ethyl) -4-hydroxy-, C7-C9-branched and linear alkyl esters (CAS no. 125643-61-0； M_w 399 g/mol) ,

The most preferred sterically hindered phenols (SHP) is 1, 3, 5-tris (3’ , 5’ -di-tert. butyl-4’ -hydroxybenzyl) -isocyanurate (CAS no. 27676-62-6, M 784 g/mol) .

As mentioned above the fiber reinforced composite is preferably free sulphur containing antioxidants. Accordingly it is preferred that the fiber reinforced composite does not contain di-stearyl-thio-di-propionate, di-lauryl-thio-di-propionate, di-tridecyl-thio-di-propionate, di-myristyl-thio-di-propionate, di-myristyl-thio-di-propionate, di-octadecyl-disulphide, bis [2-methyl-4- (3-n-dodecylthiopropionyloxy) -5-tert-butylphenyl] sulfide and pentaerythritol-tetrakis- (3-laurylthiopropionate) .

The hindered amine light stabilizer (HALS)

Essential finding is that the inventive fiber reinforced composite must contain a hindered amine light stabilizer. It has been found out in the present invention that the hindered amine light stabilizer (HALS) can be used as a heat stabilizer, especially at a temperature above 120℃, and thus reduces the amount of malodour in the final product.

Hindered amine light stabilizers (HALS) are known in the art. Preferably such hindered amine light stabilizers (HALS) are 2, 6-alkyl-piperidine derivatives, like 2, 6-methyl-piperidine derivatives, in particular 2, 2, 6, 6-alkyl-piperidine derivatives, like 2, 2, 6, 6-tetramethyl-piperidine derivatives. Especially suitable are hindered amine light stabilizers (HALS) of the formula (II)

wherein U constitutes the remaining part of the hindered amine light stabilizer (HALS) .

Especially suitable hindered amine light stabilizers (HALS) are those with rather high molecular weight. Accordingly the hindered amine light stabilizers (HALS) has preferably a molecular weight of more than 800, more preferably in the range of 800 to 4000, yet more preferably in the range of 1000 to 3500, like in the range of 1500 to 3000.

Accordingly it is preferred that the fiber reinforced composite comprises a hindered amine light stabilizer (HALS) selected from the group consisting of dimethyl succinate polymer with 4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidine ethanol (e.g. CAS-no. 65447-77-0) , poly ( (6-((1, 1, 3, 3-tetramethylbutyl) amino) -1, 3, 5-triazine-2, 4-diyl) (2, 2, 6, 6-tetramethyl-4-piperidyl) imino) -1, 6-hexanediyl ( (2, 2, 6, 6-tetramethyl-4-piperidyl) imino) ) (e.g. CAS-no. 71878-19-8) , 1, 3, 5-triazine-2, 4, 6-triamine, N, N” ’ - (1, 2-ethane-diylbis ( ( (4, 6-bis(butyl (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) amino) -1, 3, 5-triazine-2-yl) imino) -3, 1-propanediyl) ) -bis- (N’ , N” -dibutyl-N’ , N” -bis- (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) (e.g. CAS-no. 106990-43-6) , 1, 6-hexanediamine, N, N’ -bis (2, 2, 6, 6-tetramethyl-4-piperidinyl) -, polymer with 2, 4, 6-trichloro-1, 3, 5-triazine, reaction product with, N-butyl-1-butanamine and N-butyl-2, 2, 6, 6-tetramethyl-4-piperidinamine (e.g. CAS-no. 192268-64-7) , poly ( (6-morpholino-s-triazine-2, 4-diyl) (2, 2, 6, 6-tetramethyl-4-piperidyl) imino) hexamethylene (2,2, 6, 6-tetramethyl-4-piperidyl) imino) ) (e.g. CAS-no. 82451-48-7) , poly ( (6-morpholino-s-triazine-2, 4-diyl) (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) hexamethylene (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) ) (CAS-NO. 193098-40-7) , 1, 3-propanediamine, N, N” -1,2-ethanediylbis -, polymer with 2, 4, 6-trichloro-1, 3, 5-tri-azine, reaction products with N-butyl -2, 2, 6, 6 -tetramethyl -4 –piperidinamine (e.g. CAS-no. 136504-96-6) , N- (2, 2, 6, 6-tetramethyl-4-piperidyl) -maleinimid, C20 : C24 -olefin-copolymer (e.g. CAS-no. 152261-33-1).

Especially suitable are the hindered amine light stabilizers (HALS) selected from the group consisting of dimethyl succinate polymer with 4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidine ethanol of formula (III) , poly ( (6- ( (1, 1, 3, 3-tetramethylbutyl) amino) -1, 3, 5-triazine-2, 4-diyl) (2, 2, 6, 6-tetramethyl-4-piperidyl) imino) -1, 6-hexanediyl ( (2, 2, 6, 6-tetramethyl-4-piperidyl) imino) ) of formula (IV) , 1, 3, 5-triazine-2, 4, 6-triamine, N, N” ’ - (1, 2-ethane-diylbis ( ( (4, 6-bis (butyl (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) amino) -1, 3, 5-triazine-2-yl) imino) -3, 1-propanediyl) ) -bis- (N’ , N” -dibutyl-N’ , N” -bis- (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) of formula (V) and poly ( (6-morpholino-s-triazine-2, 4-diyl) (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) hexamethylene (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino)) of formula (VI) .

Formula (III) is

preferably with n in the range of 8 to 25, more preferably with n in the range of 9 to 17.

Preferably the dimethyl succinate polymer with 4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidine ethanol is the commercial product Tinuvin 622 of BASF or Sabostab UV 62 of Sabo.

Formula (IV) is

preferably with n in the range of 2 to 15, more preferably with n in the range of 2 to 10.

Preferably the poly ( (6- ( (1, 1, 3, 3-tetramethylbutyl) amino) -1, 3, 5-triazine-2, 4-diyl) (2, 2, 6, 6-tetramethyl-4-piperidyl) imino) -1, 6-hexanediyl ( (2, 2, 6, 6-tetramethyl-4-piperidyl) imino)) is the commercial product Chimassorb 944 of BASF or Sabostab UV 94 of Sabo.

Formula (V) is

Preferably the 1, 3, 5-triazine-2, 4, 6-triamine, N, N” ’ - (1, 2-ethane-diylbis ( ( (4, 6-bis(butyl (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) amino) -1, 3, 5-triazine-2-yl) imino) -3, 1-propanediyl) ) -bis- (N’ , N” -dibutyl-N’ , N” -bis- (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) is the commercial product Sabostab UV 119 of Sabo.

Formula (VI) is

preferably with n in the range of 2 to 10, more preferably with n in the range of 2 to 8.

Preferably the poly ( (6-morpholino-s-triazine-2, 4-diyl) (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) hexamethylene (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino)) is the commercial product Cyasorb UV 3529 of Cytec.

As mentioned above the hindered amine light stabilizers (HALS) of the formula (II) are especially preferred. Accordingly the 1, 3, 5-triazine-2, 4, 6-triamine, N, N” ’ - (1, 2-ethane-diylbis ( ( (4, 6-bis (butyl (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) amino) -1, 3, 5-triazine-2-yl) imino) -3, 1-propanediyl) ) -bis- (N’ , N” -dibutyl-N’ , N” -bis- (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) and poly ( (6-morpholino-s-triazine-2, 4-diyl) (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) hexamethylene (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) ) are especially preferred.

The lubricant (L)

The inventive fiber reinforced composite may further comprise a lubricant (L) . The lubricant (L) enhances processability and thus the formation of undesired side products like aldheyde and ketone is reduced.

Preferably the lubricant (L) is a fatty acid amide. The amount of carbons of the fatty acids is preferably in the range of C10 to C25 carbon atoms.

Accordingly the lubricant (s) (L) is (are) preferably selected from the group consisting of

cis-13-docosenoic amide (erucamide) (CAS no. 112-84-5； M_w 337.6) ,

cis-9, 10 octadecenoamide (oleamide) (CAS no. 301-02-0； M_w 281.5)

octadecanoylamide (CAS no. 124-26-5； M_w 283.5) ,

behenamide (CAS no. 3061-75-4； M_w 339.5) ,

N,N’ -ethylene-bis-stearamide (CAS no. 110-30-5； M_w 588) ,

N-octadecyl-13-docosenamide (CAS no. 10094-45-8； M_w 590) , and

oleylpalmitamide (CAS no. 16260-09-6； M_w 503)

Especially suitable is (are) cis-13-docosenoic amide (CAS no. 112-84-5； M_w 337.6) and/or cis-9, 10 octadecenoamide (CAS no. 301-02-0； M_w 281.5) .

The automotive article

The invention is also directed to an automotive article comprising the fiber reinforced composite according to this invention. Preferably the automotive article comprises at least 80 wt.-％, like 80 to 99.9 wt. -％, more preferably at least 90 wt. -％, like 90 to 99.9 wt. -％, yet more preferably at least 95 wt. -％, like 95 to 99.9 wt. -％, of the fiber reinforced composite according to this invention. In one embodiment the automotive article consists of the fiber reinforced composite according to this invention.

Preferably the automotive article is an automotive interior article. Preferred automotive articles are selected from the group consisting of parts under the hood (including front end mould) , dashboards, step assists, interior trims, ash trays, interior body panels and gear shift levers.

Automotive articles are typically molded articles, preferably injection molded articles as well as foamed articles. Preferably the automotive articles, especially those defined in the previous paragraph are injection molded articles.

The Use of the hindered amine light stabilizer (HALS)

The invention is also directed to the use of a hindered amine light stabilizer (HALS) in a fiber reinforced composite as a heat stabilizer, wherein the fiber reinforced composite comprises, in addition to the hindered amine light stabilizer (HALS) , polypropylene (PP) and fibers (F) .

Preferably the hindered amine light stabilizer (HALS) increases the heat resistance in the fiber reinforced composite, wherein the heat resistance is increased in case the odor measured according to PV3900, preferably measured according to PV3900 over 120 ℃, like at 150 ℃, of the fiber reinforced composite comprising the hindered amine light stabilizer (HALS) is lower compared to the odor measured according to PV3900, preferably measured according to PV3900 over 120°, like at 150 ℃, of the same fiber reinforced composite without said hindered amine light stabilizer (HALS) .

Preferably the hindered amine light stabilizer (HALS) used in a fiber reinforced composite is defined above under the section “the hindered amine light stabilizer (HALS) ” .

The fibers are preferably those as defined in the section “the fiber (F) ” .

The polypropylene (PP) is preferably a mixture of different polypropylenes. More preferably the polypropylene (PP) is at least a combination of the propylene homopolymer (H-PP2) and the heterophasic propylene copolymer (HECO) . Still more preferably the polypropylene (PP) is a combination of the propylene homopolymer (H-PP2) , the propylene homopolymer (H-PP3) , the polar modified polypropylene (PMP) and the heterophasic propylene copolymer (HECO) . With regard to these components reference is made to the sections “the propylene homopolymer (H-PP2) ” , “the propylene homopolymer (H-PP3) ” , “the heterophasic propylene copolymer (HECO) ” and “the polar modified polypropylene (PMP) ” .

It is especially preferred that the hindered amine light stabilizer (HALS) is used in a fiber reinforced composite as defined in detail above.

In the following the invention is described in more detail.

EXAMPLES

1.Definitions/Measuring Methods

The following definitions of terms and determination methods apply for the above general description of the invention as well as to the below examples unless otherwise defined.

Quantification of microstructure by NMR spectroscopy

Quantitative nuclear-magnetic resonance (NMR) spectroscopy is used to quantify the isotacticity and regio-regularity of the polypropylene homopolymers.

Quantitative ¹³C {¹H} NMR spectra were recorded in the solution-state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for ¹H and ¹³C respectively. All spectra were recorded using a ¹³C optimised 10 mm extended temperature probehead at 125℃ using nitrogen gas for all pneumatics.

For polypropylene homopolymers approximately 200 mg of material was dissolved in 1, 2-tetrachloroethane-d₂ (TCE-d₂) . To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatary oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz. This setup was chosen primarily for the high resolution needed for tacticity distribution quantification (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443； Busico, V. ； Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromolecules 30 (1997) 6251) . Standard single-pulse excitation was employed utilising the NOE and bi-level WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225； Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289) . A total of 8192 (8k) transients were acquired per spectra.

Quantitative ¹³C {¹H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs.

For polypropylene homopolymers all chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm.

Characteristic signals corresponding to regio defects (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253；； Wang, W-J., Zhu, S., Macromolecules 33 (2000) , 1157； Cheng, H. N., Macromolecules 17 (1984) , 1950) or comonomer were observed.

The tacticity distribution was quantified through integration of the methyl region between 23.6-19.7 ppm correcting for any sites not related to the stereo sequences of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443； Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromolecules 30 (1997) 6251) .

Specifically the influence of regio-defects and comonomer on the quantification of the tacticity distribution was corrected for by subtraction of representative regio-defect and comonomer integrals from the specific integral regions of the stereo sequences.

The isotacticity was determined at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences with respect to all pentad sequences:

[mmmm] ％＝ 100 * (mmmm /sum of all pentads)

The presence of 2, 1 erythro regio-defects was indicated by the presence of the two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites. Characteristic signals corresponding to other types of regio-defects were not observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253) .

The amount of 2, 1 erythro regio-defects was quantified using the average integral of the two characteristic methyl sites at 17.7 and 17.2 ppm:

P_21e ＝ (I_e6 + I_e8) /2

The amount of 1, 2 primary inserted propene was quantified based on the methyl region with correction undertaken for sites included in this region not related to primary insertion and for primary insertion sites excluded from this region:

P₁₂ ＝ I_CH3 + P_12e

The total amount of propene was quantified as the sum of primary inserted propene and all other present regio-defects:

P_total ＝ P₁₂ + P_21e

The mole percent of 2, 1-erythro regio-defects was quantified with respect to all propene: [21e] mol. -％＝ 100 * (P_21e /P_total)

Characteristic signals corresponding to the incorporation of ethylene were observed (as described in Cheng, H. N., Macromolecules 1984, 17, 1950) and the comonomer fraction calculated as the fraction of ethylene in the polymer with respect to all monomer in the polymer.

The comonomer fraction was quantified using the method of W-J. Wang and S. Zhu, Macromolecules 2000, 33 1157, through integration of multiple signals across the whole spectral region in the ¹³C {¹H} spectra. This method was chosen for its robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.

The mole percent comonomer incorporation was calculated from the mole fraction.

The weight percent comonomer incorporation was calculated from the mole fraction.

MFR₂ (230℃) is measured according to ISO 1133 (230℃, 2.16 kg load) .

MFR₂ (190℃) is measured according to ISO 1133 (190℃, 2.16 kg load) .

Melting temperature (T_m) : measured with a TA Instrument Q2000 differential scanning calorimetry (DSC) on 5 to 7 mg samples. DSC is run according to ISO 11357 /part 3 /method C2 in a heat /cool /heat cycle with a scan rate of 10 ℃/min in the temperature range of -30 to +225℃. Melting temperature is determined from the second heating step.

The xylene cold solubles (XCS, wt. -％) : Content of xylene cold solubles (XCS) is determined at 25 ℃ according to ISO 16152； first edition； 2005-07-01

Intrinsic viscosity is measured according to DIN ISO 1628/1, October 1999 (in Decalin at 135 ℃) .

Flexural Modulus was determined in 3-point-bending according to ISO 178 on injection molded specimens of 80 x 10 x 4 mm prepared in accordance with ISO 294-1: 1996.

Charpy impact test: The Charpy (notched) impact strength (Charpy NIS /IS) is measured according to ISO 179 2C /DIN 53453 at 23 ℃, using injection molded bar test specimens of 80x10x4 mm³ prepared in accordance with ISO 294-1: 1996.

Aging test

In an oven (Heraeus) , continuous aging the specimen material in mechanically circulated air at 150±1℃ (as required by VW company) . Brittling time is reached when the specimen exhibits signs of disintegration typical for decomposed PP at any point (cracks appear on surface of the specimen by naked eyes, and then material starts to crumble) .

PV3900 (of Volkswagen Germanx)

Testing sets

a) heat chamber with air circulation according to DIN 50 011-12； accuracy class 2

b) 1 or 3 litre glass testing cup with unscented sealing and lid； the cup, the sealing and the lid have to be cleaned before use.

50 +/-5 g sample is put in 1 litre glass cup and then heated for 2 hours at 80+/-2 ℃ in the heat chamber. The sample is taken away from the heat chamber, and conditioned at room temperature till it is cooled to 65℃, and then the test is conducted.

Analysis

The rating of smell for all samples is accomplished by the scale as given in table below. Grades are given from 1 to 6, whereby half grades are possible.

Rating of smell

Grade	Rating
Grade	Rating	1	not noticeable
2	noticeable； undisturbing	1	not noticeable
2	noticeable； undisturbing	3	clearly noticeable； but not yet disturbing
4	Disturbing	3	clearly noticeable； but not yet disturbing
4	Disturbing	5	severely disturbing
6	Intolerable	5	severely disturbing

The result is given as an average value, rounded by half grades.

2.Examples

The present invention is illustrated by the following examples. The heterophasic propylene copolymer (HECO) was used for the inventive examples, which was prepared with one slurry loop reactor and three gas phase reactors by the known

technology, as disclosed in EP 0 887 379 A1.

The catalyst used in the polymerization processes has been produced as follows: First, 0.1 mol of MgCl₂ x 3 EtOH was suspended under inert conditions in 250 ml of decane in a reactor at atmospheric pressure. The solution was cooled to the temperature of –15℃ and 300 ml of cold TiCl₄ was added while maintaining the temperature at said level. Then, the temperature of the slurry was increased slowly to 20 ℃. At this temperature, 0.02 mol of dioctylphthalate (DOP) was added to the slurry. After the addition of the phthalate, the temperature was raised to 135 ℃ during 90 minutes and the slurry was allowed to stand for 60 minutes. Then, another 300 ml of TiCl₄ was added and the temperature was kept at 135 ℃ for 120 minutes. After this, the catalyst was filtered from the liquid and washed six times with 300 ml heptane at 80 ℃. Then, the solid catalyst component was filtered and dried. Catalyst and its preparation concept is described in general e.g. in patent publications EP491566, EP591224 and EP586390. The catalyst was prepolymerized with vinyl cyclohexane in an amount to achieve a concentration of 200 ppm poly (vinyl cyclohexane) (PVCH) in the final polymer (see EP 1183307 A1) . As co-catalyst triethyl-aluminium (TEAL) and as donor dicyclo pentyl dimethoxy silane (D-donor) were used. The aluminium to donor ratio is indicated in table 1.

Table 1a: Preparation and Properties of HECO

Loop		HECO
Loop		HECO	TEAL/Ti	[mol/mol]	220
TEAL/D donor	[mol/mol]	8.1	TEAL/Ti	[mol/mol]	220
TEAL/D donor	[mol/mol]	8.1	Temperature	[℃]	72
Pressure	[kPa]	55	Temperature	[℃]	72
Pressure	[kPa]	55	H₂/C₃ ratio	[mol/kmol]	14.5
MFR₂	[g/10 min]	55	H₂/C₃ ratio	[mol/kmol]	14.5
MFR₂	[g/10 min]	55	XCS	[wt. -％]	1.5
C2	[mol-％]	0	XCS	[wt. -％]	1.5
C2	[mol-％]	0	Split	[wt. -％]	35
GPR 1			Split	[wt. -％]	35
GPR 1			Temperature	[℃]	80
Pressure	[kPa]	21	Temperature	[℃]	80
Pressure	[kPa]	21	H₂/C₃ ratio	[mol/kmol]	155
MFR₂	[g/10 min]	55	H₂/C₃ ratio	[mol/kmol]	155
MFR₂	[g/10 min]	55	C2	[mol-％]	0
XCS	[wt. -％]	1.5	C2	[mol-％]	0
XCS	[wt. -％]	1.5	Split	[wt. -％]	30
GPR 2			Split	[wt. -％]	30
GPR 2			Temperature	[℃]	70
Pressure	[kPa]	21	Temperature	[℃]	70
Pressure	[kPa]	21	H₂/C₂ ratio	[mol/kmol]	108
C₂/C₃ ratio	[mol/kmol]	564	H₂/C₂ ratio	[mol/kmol]	108
C₂/C₃ ratio	[mol/kmol]	564	MFR₂	[g/10 min]	20
XCS	[wt. -％]	20	MFR₂	[g/10 min]	20
XCS	[wt. -％]	20	C2 of XCS	[mol-％]	47.9
IV of XCS	[dl/g]	2.5	C2 of XCS	[mol-％]	47.9
IV of XCS	[dl/g]	2.5	C2 total	[mol-％]	12.2
Split	[wt. -％]	19	C2 total	[mol-％]	12.2

Table 1b: Preparation and Properties of HECO

GPR 3 (Final)		HECO
GPR 3 (Final)		HECO	Temperature	[℃]	84
Pressure	[kPa]	15	Temperature	[℃]	84
Pressure	[kPa]	15	H₂/C₂ ratio	[mol/kmol]	87
C₂/C₃ ratio	[mol/kmol]	600	H₂/C₂ ratio	[mol/kmol]	87
C₂/C₃ ratio	[mol/kmol]	600	MFR₂	[g/10 min]	11
MFR of Matrix	[g/10min]	55	MFR₂	[g/10 min]	11
MFR of Matrix	[g/10min]	55	C2 total	[mol-％]	18.3
XCS	[wt. -％]	32	C2 total	[mol-％]	18.3
XCS	[wt. -％]	32	C2 of XCS	[mol-％]	47.9
IV of XCS	[dl/g]	2.5	C2 of XCS	[mol-％]	47.9
IV of XCS	[dl/g]	2.5	Split	[wt. -％]	16

Fiber reinforced composites were produced by melt blending. The inventive polypropylene compounding compositions based on the recipe as summarized in Tables 2a and 2b are prepared by using a Coperion STS-35 twin-screw extruder (available from Coperion (Nanjing) Corporation, China) with a diameter of 35 mm. The twin-screw extruder runs at an average screw speed of 400 rpm with a temperature profile of zones from 170-240 ℃. It has a L/D of 44. The temperature of each zone, throughput and the screw speed of the extruder for preparing the compositions of inventive examples are listed in Tables 3a and 3b. The temperature of each zone, throughput and screw speed of the extruder are initiative parameters, and are set on control panel of the extruder. Melt temperature (temperature of the melt in the die) and torque of the extruder are passive parameters shown on control panel of the extruder. A vacuum bump is located in zone 9 and generates a vacuum of -0.01 MPa inside the extruder.

Table 2a: Recipe and properties of the inventive examples (IE1 to IE4) and comparative example (CE1)

Example		IE 1	IE 2	IE 3	IE 4	CE 1
Example		IE 1	IE 2	IE 3	IE 4	CE 1	HECO	[wt％] *	11.0	11.0	11.0	11.0	11.0
H-PP2	[wt％] *	20.0	20.0	20.0	20.0	20.0	HECO	[wt％] *	11.0	11.0	11.0	11.0	11.0
H-PP2	[wt％] *	20.0	20.0	20.0	20.0	20.0	H-PP3	[wt％] *	34.5	34.5	34.5	34.5	34.5
PMP	[wt％] *	1.0	1.0	1.0	1.0	1.0	H-PP3	[wt％] *	34.5	34.5	34.5	34.5	34.5
PMP	[wt％] *	1.0	1.0	1.0	1.0	1.0	Fiber	[wt％] *	31.0	31.0	31.0	31.0	31.0
AO	[wt％] *	0.3	0.3	0.3	0.3	0.3	Fiber	[wt％] *	31.0	31.0	31.0	31.0	31.0
AO	[wt％] *	0.3	0.3	0.3	0.3	0.3	HALS1	[wt％] *	0.3	-	-	-	-
HALS2	[wt％] *	-	0.3	-	-	-	HALS1	[wt％] *	0.3	-	-	-	-
HALS2	[wt％] *	-	0.3	-	-	-	HALS3	[wt％] *	-	-	0.3	-	-
HALS4	[wt％] *	-	-	-	0.3	-	HALS3	[wt％] *	-	-	0.3	-	-
HALS4	[wt％] *	-	-	-	0.3	-	L	[wt％] *	0.4	0.4	0.4	0.4	0.4
MFR	[g/10min]	8.0	8.0	8.0	8.0	8.0	L	[wt％] *	0.4	0.4	0.4	0.4	0.4
MFR	[g/10min]	8.0	8.0	8.0	8.0	8.0	Flexural Modulus	[MPa]	7200	7200	7200	7200	7200
Brittling time	[h]	480	500	1100	1200	450	Flexural Modulus	[MPa]	7200	7200	7200	7200	7200
Brittling time	[h]	480	500	1100	1200	450	NIS	[kJ/m²]	12	12	12	12	12
Odour	[-]	4.0	4.0	3.5	3.5	4.5	NIS	[kJ/m²]	12	12	12	12	12

Table 2b: Recipe and roperties of the inventive examples (IE 5 to IE 8)

Example		IE 5	IE 6	IE 7	IE 8
Example		IE 5	IE 6	IE 7	IE 8	HECO	[wt％] *	11.0	11.0	5.0	5.0
H-PP2	[wt％] *	10.0	40.0	20.0	40.0	HECO	[wt％] *	11.0	11.0	5.0	5.0
H-PP2	[wt％] *	10.0	40.0	20.0	40.0	H-PP3	[wt％] *	44.5	14.5	39.5	16.3
PMP	[wt％] *	1.0	1.0	1.0	1.2	H-PP3	[wt％] *	44.5	14.5	39.5	16.3
PMP	[wt％] *	1.0	1.0	1.0	1.2	Fiber	[wt％] *	31.0	31.0	31.0	35.0
AO	[wt％] *	0.3	0.3	0.3	0.3	Fiber	[wt％] *	31.0	31.0	31.0	35.0
AO	[wt％] *	0.3	0.3	0.3	0.3	HALS1	[wt％] *	-	-	-	-
HALS2	[wt％] *	-	-	-	-	HALS1	[wt％] *	-	-	-	-
HALS2	[wt％] *	-	-	-	-	HALS3	[wt％] *	-	-	-	-
HALS4	[wt％] *	0.3	0.3	0.3	0.3	HALS3	[wt％] *	-	-	-	-
HALS4	[wt％] *	0.3	0.3	0.3	0.3	L	[wt％] *	0.4	0.4	0.4	0.4
MFR	[g/10min]	10.0	5.0	10.0	4.0	L	[wt％] *	0.4	0.4	0.4	0.4
MFR	[g/10min]	10.0	5.0	10.0	4.0	Flexural Modulus	[MPa]	7100	7300	7200	8800
Brittling time	[h]	1100	1300	1200	1100	Flexural Modulus	[MPa]	7100	7300	7200	8800
Brittling time	[h]	1100	1300	1200	1100	NIS	[kJ/m²]	13	11	11	13
Odour	[-]	3.5	3.4	3.5	3.6	NIS	[kJ/m²]	13	11	11	13

*rest to 100 wt. -％are Irgafos 168 and black pigments

NIS is notched impact strength at 23 ℃

“Fiber” is the short glas fiber “T438” of from Taishan GF Co. Ltd, Shandong, China, having an average diameter of 13 μm and an average length of 4.5 mm；

“H-PP2 “is the commercial propylene homopolymer HD915CF of Borealis AG having a melt flow rate MFR2 (230 ℃) of 8 g/10min and a melting temperature of 168 ℃；

“H-PP3” is the commercial propylene homopolymer HJ311MO of Borouge Pte Ltd having a melt flow rate MFR₂ (230 ℃) of 60 g/10min；

“PMP” is the polypropylene (functionalized with maleic anhydride) “TPPP8112” of BYK Co.Ltd, Germany, having a MFR₂ (190 ℃) of more than 80 g/10min and a maleic anhydride content of 1.4 ％；

“AO” is the sterically hindered phenol 1, 3, 5-tris (3’ , 5’ -di-tert. butyl-4’ -hydroxybenzyl) -isocyanurate (CAS-no. 27676-62-6) “Irganox 3114 “of BASF；

“HALS1” is the hindered amin light stabilizer poly ( (6- ( (1, 1, 3, 3-tetramethylbutyl) amino) -1,3, 5-triazine-2, 4-diyl) (2, 2, 6, 6-tetramethyl-4-piperidyl) imino) -1, 6-hexanediyl ( (2, 2, 6, 6-tetramethyl-4-piperidyl) imino) ) (CAS-no. 71878-19-8 ) , “Chimassorb 944 “of BASF；

“HALS2” is the hindered amin light stabilizer dimethyl succinate polymer with 4-hydroxy-2,2, 6, 6-tetramethyl-1-piperidine ethanol (CAS-no. 65447-77-0) , “Tinuvin 622” of BASF；

“HALS3” is the hindered amin light stabilizer 1, 3, 5-triazine-2, 4, 6-triamine, N, N” ’ - (1, 2-ethane-diylbis ( ( (4, 6-bis (butyl (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) amino) -1, 3, 5-triazine-2-yl) imino) -3, 1-propanediyl) ) -bis- (N’ , N” -dibutyl-N’ , N” -bis- (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) (CAS-no. 106990-43-6) , “Sabostab UV 119” of Sabo；

“HALS4” is the hindered amin light stabilizer poly ( (6-morpholino-s-triazine-2, 4-diyl) (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) hexamethylene (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) ) (CAS-NO. 193098-40-7) `Cyasorb UV-3529 “of Cytec；

“L” is the lubricant erucamide (CAS-no. 112-84-5) of Croda, UK.

Table 3a: Extruder conditions of the composites of IE1 to IE6

Process condition		IE 1	IE 2	IE 3	IE 4	IE 5	IE 6
Process condition		IE 1	IE 2	IE 3	IE 4	IE 5	IE 6	Zone 1	[℃]	170	170	170	170	170	170
zone2	[℃]	180	180	180	180	180	180	Zone 1	[℃]	170	170	170	170	170	170
zone2	[℃]	180	180	180	180	180	180	zone 3	[℃]	210	210	210	210	210	210
zone 4	[℃]	210	210	210	210	210	208	zone 3	[℃]	210	210	210	210	210	210
zone 4	[℃]	210	210	210	210	210	208	zone 5	[℃]	200	200	200	200	205	200
zone 6	[℃]	200	200	200	200	210	200	zone 5	[℃]	200	200	200	200	205	200
zone 6	[℃]	200	200	200	200	210	200	zone 7	[℃]	200	200	200	200	200	205
zone 8	[℃]	200	200	200	200	200	205	zone 7	[℃]	200	200	200	200	200	205
zone 8	[℃]	200	200	200	200	200	205	zone 9	[℃]	200	200	200	200	220	200
zone 10	[℃]	200	200	200	200	200	200	zone 9	[℃]	200	200	200	200	220	200
zone 10	[℃]	200	200	200	200	200	200	zone 11	[℃]	200	200	200	200	200	200
die	[℃]	215	215	215	215	210	210	zone 11	[℃]	200	200	200	200	200	200
die	[℃]	215	215	215	215	210	210	melt temp.	[℃]	230	230	230	230	225	235
throughput	[kg/hour]	50	50	50	50	50	50	melt temp.	[℃]	230	230	230	230	225	235
throughput	[kg/hour]	50	50	50	50	50	50	screw speed	[rpm]	350	350	350	350	350	350
vacuum	[MPa]	-0.01	-0.01	-0.01	-0.01	-0.01	-0.01	screw speed	[rpm]	350	350	350	350	350	350

Table 3b: Extruder conditions of the composites of IE7 to IE8

Process condition		IE 7	IE 8
Process condition		IE 7	IE 8	Zone 1	[℃]	170	170
zone2	[℃]	180	180	Zone 1	[℃]	170	170
zone2	[℃]	180	180	zone 3	[℃]	210	210
zone 4	[℃]	210	210	zone 3	[℃]	210	210
zone 4	[℃]	210	210	zone 5	[℃]	210	200
zone 6	[℃]	200	200	zone 5	[℃]	210	200
zone 6	[℃]	200	200	zone 7	[℃]	200	200
zone 8	[℃]	210	220	zone 7	[℃]	200	200
zone 8	[℃]	210	220	zone 9	[℃]	200	200
zone 10	[℃]	210	200	zone 9	[℃]	200	200
zone 10	[℃]	210	200	zone 11	[℃]	200	210
die	[℃]	215	215	zone 11	[℃]	200	210
die	[℃]	215	215	melt temp.	[℃]	230	240
throughput	[kg/hour]	50	50	melt temp.	[℃]	230	240
throughput	[kg/hour]	50	50	screw speed	[rpm]	350	350
vacuum	[MPa]	-0.01	-0.01	screw speed	[rpm]	350	350

It can be seen that the inventive composites with UV-119, UV-3529, UV-944 and UV-622, especially the composites with UV-119 and UV-3529, have an extended longer brittling time than the composites with no HALS at 150℃. It results in a reduced odor of the composites. In the prior art, it is believed that HALS can be used as a heat stabilizer at a temperature below 120℃, but lose activity as a heat stabilizer at a temperature above 120℃. The inventors of the invention surprising found that the some HALS, especially UV-119 and UV-3529, still have an activity as a heat stabilizer over 120℃, and can impart the composites with a much better heat-resistance at 150℃.

Claims

Fiber reinforced composite comprising

(a) at least 10 wt. -％, based on the total weight of the fiber reinforced composite, of a propylene homopolymer (H-PP2) having melt flow rate MFR₂ (230℃, 2.16 kg) measured according to ISO 1133 of not more than 30 g/10 min；

(b) at least 5 wt. -％, based on the total weight of the fiber reinforced composite, of a heterophasic propylene copolymer (HECO) comprising

(b1) a matrix (M) being a propylene homopolymer (H-PP1) having melt flow rate MFR₂ (230℃, 2.16 kg) measured according to ISO 1133 of at least40 g/10 min, and

(b2) an elastomeric propylene copolymer (EC) ；

(c) at least 15 wt. -％, based on the total weight of the fiber reinforced composite, of fibers (F) ；

(d) at least 0.1 wt. -％, based on the total weight of the fiber reinforced composite, of a phenolic antioxidant (AO) ； and

(e) at least 0.1 wt. -％, based on the total weight of the fiber reinforced composite, of a hindered amine light stabilizer (HALS) .
Fiber reinforced composite according to claim 1, wherein the fiber reinforced composite comprising additionally

(a) at least 20 wt. -％, based on the total weight of the fiber reinforced composite, of a propylene homopolymer (H-PP3) having melt flow rate MFR₂ (230℃, 2.16 kg) measured according to ISO 1133 of at least 40 g/10 min；

and/or

(b) at least 0.1 wt. -％, based on the total weight of the fiber reinforced composite, of a lubricant (L) ；

and/or

(c) at least 0.6 wt. -％, based on the total weight of the fiber reinforced composite, of a polar modified polypropylene (PMP) as adhesion promoter (AP) .
Fiber reinforced composite according to claim 1 or 2, wherein the fiber reinforced composite has a melt flow rate MFR₂ (230℃, 2.16 kg) measured according to ISO 1133 in the range of 3 to 20 g/10min.
Fiber reinforced composite according to any one of the preceeding claims, wherein the fibers (F) are selected from the group consisting of glass fibers, metal fibers, ceramic fibers and graphite fibers.
Fiber reinforced composite according to any one of the preceeding claims, wherein the propylene homopolymer (H-PP2) has

(a) a melt flow rate MFR₂ (230℃, 2.16 kg) measured according to ISO 1133 in the range of 2 to 20 g/10 min；

and/or

(b) a melting temperature T_m in the range of 160 to 170℃.
Fiber reinforced composite according to any one of the preceeding claims, wherein the propylene homopolymer (H-PP3) has

(a) a melt flow rate MFR₂ (230℃, 2.16 kg) measured according to ISO 1133 in the range of 50 to 150 g/10 min；

and/or

(b) a melting temperature T_m in the range of 155 to 170℃.
Fiber reinforced composite according to any one of the preceeding claims, wherein the propylene homopolymer (H-PP1) of the heterophasic propylene copolymer (HECO) has a melt flow rate MFR₂ (230℃, 2.16 kg) measured according to ISO 1133 in the range of 45 to 150 g/10 min.
Fiber reinforced composite according to any one of the preceeding claims, wherein the heterophasic propylene copolymer (HECO) has

(a) a comonomer content, preferably ethylene content, in the range of 7 to 25 mol-％；

and/or

(b) a xylene soluble fraction (XCS) in the range of 20 to 40 wt. -％.
Fiber reinforced composite according to any one of the preceeding claims, wherein the xylene soluble fraction (XCS) of the heterophasic propylene copolymer (HECO) has

(a) a comonomer content, preferably ethylene content, in the range of 40 to 55 mol-％；

and/or

(b) an intrinsic viscosity (IV) in the range of 2.0 to 4.0 dl/g.
Fiber reinforced composite according to any one of the preceeding claims, wherein phenolic antioxidant (AO) is a sterically hindered phenol (SHP) , like 1, 3, 5-tris (3’, 5’-di-tert. butyl-4’-hydroxybenzyl) -isocyanurate, or pentaerythrityl-tetrakis (3- (3’, 5’-di-tert. butyl-4-hydroxyphenyl) -propionate.
Fiber reinforced composite according to any one of the preceeding claims, wherein the hindered amine light stabilizer (HALS) is selelected from the group consisting of poly ( (6-morpholino-s-triazine-2, 4-diyl) (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) hexamethylene (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) ) (CAS-NO. 193098-40-7) , 1, 3, 5-triazine-2, 4, 6-triamine, N, N”’- (1, 2-ethane-diylbis ( ( (4, 6-bis (butyl (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) amino) -1, 3, 5-triazine-2-yl) imino) -3, 1-propanediyl) ) -bis- (N’, N”-dibutyl-N’, N”-bis- (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) (CAS-no. 106990-43-6) , dimethyl succinate polymer with 4-hydroxy-2， 2, 6, 6-tetramethyl-1-piperidine ethanol (CAS-no. 65447-77-0) , and poly ( (6-( (1, 1, 3, 3-tetramethylbutyl) amino) -1, 3, 5-triazine-2, 4-diyl) (2, 2, 6, 6-tetramethyl-4-piperidyl) imino) -1, 6-hexanediyl ( (2, 2, 6, 6-tetramethyl-4-piperidyl) imino) ) (CAS-no. 71878-19-8) , more preferably the hindered amine light stabilizer (HALS) is poly ( (6-morpholino-s-triazine-2, 4-diyl) (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) hexamethylene (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) imino) ) (CAS-NO. 193098-40-7) and/or 1, 3, 5-triazine-2, 4, 6-triamine, N, N”’- (1, 2-ethane-diylbis ( ( (4, 6-bis (butyl (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) amino) -1, 3, 5-triazine-2- yl) imino) -3, 1-propanediyl) ) -bis- (N’, N”-dibutyl-N’, N”-bis- (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) (CAS-no. 106990-43-6) .
Fiber reinforced composite according to any one of the preceeding claims, wherein the lubricant (L) is erucamide (CAS-no. 112-84-5) and/or oleamide (CAS-no. 301-02-0) .
Automotive article comprising the fiber reinforced composite according to any one of the preceeding claims.
Automotive article according to claim 14, wherein the article is an automotive interior article.
Use of a hindered amine light stabilizer (HALS) in a fiber reinforced composite as a heat stabilizer, wherein the fiber reinforced composite comprises, in addition to the hindered amine light stabilizer (HALS) , polypropylene (PP) and fibers (F) .
Use according to claim 15, wherein the hindered amine light stabilizer (HALS) increases the heat resistance of the fiber reinforced composite, wherein the heat resistance is increased, in case the odor measured according to PV3900, of the fiber reinforced composite comprising the hindered amine light stabilizer (HALS) is lower compared to the odor measured according to PV3900 of the same fiber reinforced composite without said hindered amine light stabilizer (HALS) .
Use according to claim 15 or 16, wherein the hindered amine light stabilizer (HALS) is used together with a phenolic antioxidant (AO) .
Use according to claim any one of the preceeding vlaims 15 to 17, wherein the fiber reinforced composite is defined according to any one of the preceeding claims 1 to 12.
Use according to claim 16, wherein the heat resistance of the fiber reinforced composite is increased at a temperature above 120℃.