CN117999313A - Glass fiber reinforced composition with flame retardancy and low warpage - Google Patents
Glass fiber reinforced composition with flame retardancy and low warpage Download PDFInfo
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- CN117999313A CN117999313A CN202080107131.3A CN202080107131A CN117999313A CN 117999313 A CN117999313 A CN 117999313A CN 202080107131 A CN202080107131 A CN 202080107131A CN 117999313 A CN117999313 A CN 117999313A
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- polypropylene
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- 238000009827 uniform distribution Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
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Abstract
A fiber reinforced Polypropylene Composition (PC), the fiber reinforced Polypropylene Composition (PC) comprising: a) 60 to 80 wt.% of a polypropylene Base Composition (BC) comprising: a) 50.0 to 75.0 wt% of a heterophasic propylene-ethylene copolymer (HECO) consisting of: i) A crystalline propylene homopolymer matrix (M); ii) an elastomeric ethylene-propylene copolymer (EC); wherein the heterophasic propylene-ethylene copolymer (HECO) has an MFR 2 in the range of 70.0 to 150.0g/10 min; b) 20.0 to 45.0 weight percent of a Flame Retardant (FR); and c) 0.1 to 5.0% by weight of at least one additive (A) other than Flame Retardants (FR).
Description
Technical Field
The present invention relates to a fiber reinforced polypropylene composition comprising glass fibers and a polypropylene base composition comprising a heterophasic propylene-ethylene copolymer, a flame retardant and an additive, and to an article comprising said composition.
Background
The field of electric and hybrid vehicles has evolved at an increasing rate over the last decade, driven mainly by the following factors: reduction of emissions is desirable for reasons of increasingly stringent regulations on particulate emissions in the construction field and for reasons of desiring to limit contributions to greenhouse gas-promoted climate change. One of the key developments in this area is the battery required to achieve longer mileage between charges and improved charge time.
In addition, common gasoline-powered vehicles and diesel-powered vehicles will contain batteries for starting the motor and powering the various electrical components in the vehicle.
These cells can be large and heavy, with a large amount of electrolyte. Furthermore, as with any electrical component, the risk of fire is always present. Therefore, the casing material of such a battery is required to have highly optimized mechanical properties and minimized warpage, as well as flame retardant properties.
Vehicle battery covers are traditionally made of metal, which is non-flammable and provides a good balance of mechanical properties. The polymer-based battery cover is much lighter than a battery cover made of metal, and is therefore advantageous as a light-weight alternative. However, it is desirable to develop specific polymer compositions to avoid battery covers having poor mechanical and flame retardant properties. In addition, the polymer composition is required to have low warpage to avoid any leakage or overflow of the battery liquid.
Flame retardants are chemicals used in polymers to inhibit or stop the spread of fire. In order to improve the flame retardancy of polymer compositions used in wires or cables, halide-containing compounds have historically been added to the polymer. These compounds act by releasing relatively stable halogen radicals that quench the radical chain reactions involved in the combustion process. Another approach to achieving high flame retardant properties in halogen-free polymer compositions is to add large amounts (typically in excess of 60 wt%) of inorganic flame retardant fillers such as hydrated compounds and hydroxyl compounds. This filler comprising Al (OH) 3 and Mg (OH) 2 decomposes endothermically at temperatures between 200 and 300 ℃ releasing an inert gas. The disadvantage of using large amounts of filler is that the processability and mechanical properties of the polymer composition are deteriorated. Another group of non-halogenated flame retardants are organic phosphorus species. These compounds generally act by forming a thermal barrier (typically a layer of burnt phosphoric acid) between the burning portion and the unburned plastic.
As previously mentioned, the addition of large amounts of flame retardant is known to reduce the mechanical and processing properties of the flame retardant composition.
Accordingly, new compositions that combine flame retardant properties with improved mechanical properties (flexural strength, impact strength) and warp resistance are needed for use in vehicle battery covers.
Disclosure of Invention
Accordingly, the present invention relates to a fiber reinforced Polypropylene Composition (PC) comprising:
A) 60 to 80 wt% of a polypropylene Base Composition (BC) based on the weight of the polypropylene composition, the polypropylene Base Composition (BC) comprising:
a) 50.0 to 75.0 wt% based on the total weight of the base composition of a heterophasic propylene-ethylene copolymer (HECO) consisting of:
i) A crystalline propylene homopolymer matrix (M);
ii) an elastomeric ethylene-propylene copolymer (EC);
Wherein the heterophasic propylene-ethylene copolymer (HECO) has a melt flow rate (MFR 2) in the range of 70.0 to 150.0g/10min measured according to ISO 1133 at 230 ℃ and 2.16 kg;
b) 20.0 to 45.0 weight percent of a Flame Retardant (FR), based on the total weight of the base composition; and
C) 0.1 to 5.0% by weight, based on the total weight of the base composition, of at least one additive (A) other than Flame Retardants (FR),
B) 20 to 40 weight percent glass fiber based on the weight of the polypropylene composition.
In a preferred embodiment, the heterophasic propylene-ethylene copolymer (HECO) has one or more, preferably all, of the following properties:
i) A Xylene Cold Soluble (XCS) content in the range of 5.0 to 20.0 wt%, preferably in the range of 10.0 to 18.0 wt%, most preferably in the range of 13.0 to 16.0 wt%;
ii) a total ethylene (C2) content in the range of 3.0 to 10.0 wt%, preferably in the range of 4.5 to 8.5 wt%, most preferably in the range of 5.5 to 7.5 wt%;
iii) An ethylene content (C2 (XCS)) of the xylene cold soluble fraction in the range of 30.0 to 50.0 wt. -%, preferably in the range of 35.0 to 45.0 wt. -%, most preferably in the range of 37.0 to 41.0 wt. -%; and
IV) intrinsic viscosity (IV (XCS)) of the xylene cold soluble fraction in the range of 1.5 to 3.0dl/g, preferably in the range of 1.8 to 2.7dl/g, most preferably in the range of 2.1 to 2.5 dl/g.
In another preferred embodiment, the heterophasic propylene-ethylene copolymer (HECO) has one or more, preferably all, of the following properties:
i) A melting temperature measured by DSC analysis in the range 160 to 169 ℃, more preferably in the range 161 to 168 ℃, most preferably in the range 162 to 168 ℃;
ii) a flexural modulus according to ISO 178 measured on an 80 x 10x 4mm 3 test bar injection molded according to EN ISO 1873-2 in the range of 1000 to 2500MPa, more preferably in the range of 1200 to 2000MPa, most preferably in the range of 1400 to 1700 MPa;
iii) The notched impact strength of a simply supported beam measured at 23℃in accordance with ISO 179-1 eA in the range of 1.0 to 10.0kJ/m 2, more preferably in the range of 3.0 to 8.0kJ/m 2, most preferably in the range of 4.0 to 6.0kJ/m 2, using an injection molded bar test specimen of 80X 10X 4mm 3 prepared in accordance with ISO 1873-2:2007.
In another preferred embodiment, the heterophasic propylene-ethylene copolymer (HECO) contains a polymeric nucleating agent, preferably a vinylcycloalkane polymer, more preferably a vinylcyclohexane polymer, most preferably a vinylcyclohexane homopolymer.
In another preferred embodiment, the crystalline propylene homopolymer matrix (M) of the heterophasic propylene-ethylene copolymer (HECO) has a melt flow rate (MFR 2) measured according to ISO 1133 at 230℃and 2.16kg in the range of 100.0 to 300.0g/10min, more preferably in the range of 130 to 260g/10min, most preferably in the range of 160 to 220g/10 min.
In another preferred embodiment, the Flame Retardant (FR) is a non-halogenated flame retardant, more preferably a non-halogenated organophosphorus flame retardant, most preferably selected from piperazine pyrophosphate, melamine polyphosphate, calcium bis (dihydrogen orthophosphate), calcium hydrogen phosphate, and mixtures thereof.
In another preferred embodiment, the Glass Fiber (GF) is a continuous glass fiber introduced into the composition using an LFT-D extruder, preferably wherein the continuous glass fiber has a nominal diameter in the range of 5 to 30 μm, preferably in the range of 10 to 20 μm, most preferably in the range of 13 to 17 μm.
In another preferred embodiment, the polypropylene Base Composition (BC) further comprises:
d) From 0.1 to 5.0% by weight, based on the total weight of the base composition, of a Polar Modified Polypropylene (PMP), preferably a maleic anhydride modified polypropylene.
In another preferred embodiment, the Polar Modified Polypropylene (PMP) has a polar group content in the range of 0.5 to 3.0 wt%.
In another preferred embodiment, the fiber reinforced Polypropylene Composition (PC) has a flame retardant rating of V-0 as measured according to test standard UL 94-2013.
In another aspect, the present invention relates to an article, preferably a molded article, most preferably a compression molded article, comprising more than 75% by weight of the fiber reinforced Polypropylene Composition (PC) according to any one of claims 1 to 10.
In a preferred embodiment, the article is a vehicle article, preferably the article is a vehicle battery cover.
In another aspect, the present invention relates to the use of a polypropylene Base Composition (BC) with continuous glass fibers in an LFT-D process to form a compression molded article, preferably a vehicle battery cover, wherein the article contains 60 to 80 wt% of a polypropylene Base Composition (BC) and 20 to 40 wt% of continuous glass fibers, the polypropylene Base Composition (BC) comprising:
a) 50.0 to 75.0 wt% based on the total weight of the base composition of a heterophasic propylene-ethylene copolymer (HECO) consisting of:
i) A crystalline propylene homopolymer matrix (M);
ii) an elastomeric ethylene-propylene copolymer (EC);
Wherein the heterophasic propylene-ethylene copolymer (HECO) has a melt flow rate (MFR 2) in the range of 70.0 to 150.0g/10min measured according to ISO 1133 at 230 ℃ and 2.16 kg;
b) 20.0 to 45.0 weight percent of a Flame Retardant (FR), based on the total weight of the base composition;
c) 0.1 to 5.0% by weight, based on the total weight of the base composition, of at least one additive (a) other than Flame Retardant (FR); and
D) Optionally 0.1 to 3 wt% of a Polar Modified Polypropylene (PMP), preferably a maleic anhydride modified polypropylene, based on the total weight of the base composition.
Detailed Description
The present invention will now be described in more detail.
Heterophasic propylene-ethylene copolymer (HECO)
The main component of the polyolefin Base Composition (BC) is a heterophasic propylene-ethylene copolymer (HECO).
The heterophasic propylene-ethylene copolymer (HECO) comprises at least two different phases, namely a propylene homopolymer crystalline matrix phase (M) and an elastomeric ethylene-propylene copolymer (EC). The combination of these two very different phases results in a composition with a beneficial balance of mechanical properties (as given by stiffness and impact strength).
It is particularly preferred that the crystalline matrix (M) of the heterophasic propylene-ethylene copolymer (HECO) of the present invention is bimodal or unimodal, most preferably bimodal, whereas the elastomeric ethylene-propylene copolymer (EC) is unimodal.
The heterophasic propylene-ethylene copolymer (HECO) of the invention has a melt flow rate (MFR 2) measured according to ISO 1133 at 230 ℃ and 2.16kg in the range of 70.0 to 150.0g/10min, preferably in the range of 80.0 to 130.0g/10min, more preferably in the range of 85.0 to 120.0g/10min, most preferably in the range of 90.0 to 110.0g/10 min.
The heterophasic propylene-ethylene copolymer (HECO) of the invention preferably has a Xylene Cold Soluble (XCS) content in the range of 5.0 to 20.0 wt. -%, preferably in the range of 10.0 to 18.0 wt. -%, most preferably in the range of 13.0 to 16.0 wt. -%.
Preferably, the heterophasic propylene-ethylene copolymer (HECO) of the invention has an ethylene content (C2 (XCS)) of the xylene cold soluble fraction in the range of 30.0 to 50.0 wt. -%, preferably in the range of 35.0 to 45.0 wt. -%, most preferably in the range of 37.0 to 41.0 wt. -%.
Preferably, the heterophasic propylene-ethylene copolymer (HECO) of the invention has a total ethylene (C2) content in the range of 3.0 to 10.0 wt%, preferably in the range of 4.5 to 8.5 wt%, most preferably in the range of 5.5 to 7.5 wt%.
Preferably, the heterophasic propylene-ethylene copolymer (HECO) of the invention has an intrinsic viscosity (IV (XCS)) of the xylene cold soluble fraction in the range of 1.5 to 3.0dl/g, preferably in the range of 1.8 to 2.7dl/g, most preferably in the range of 2.1 to 2.5 dl/g.
Preferably, the crystalline propylene homopolymer matrix (M) has a melt flow rate (MFR 2) measured according to ISO 1133 at 230℃and 2.16kg in the range of 100.0 to 300.0g/10min, more preferably in the range of 130 to 260g/10min, most preferably in the range of 160 to 220g/10 min.
Preferably, the heterophasic propylene-ethylene copolymer (HECO) of the invention has a flexural modulus measured according to ISO 178 in the range of 1000 to 2500MPa, more preferably in the range of 1200 to 2000MPa, most preferably in the range of 1400 to 1700 MPa.
Preferably, the heterophasic propylene-ethylene copolymer (HECO) of the invention has a notched impact strength of the simple beam measured at +23 ℃ according to ISO 179/1eA in the range of 1.0 to 10.0kJ/m 2, more preferably in the range of 3.0 to 8.0kJ/m 2, most preferably in the range of 4.0 to 6.0kJ/m 2.
The heterophasic propylene-ethylene copolymer (HECO) of the invention may be synthetic or selected from commercially available polypropylene.
The heterophasic propylene-ethylene copolymer (HECO) preferably comprises a polymeric nucleating agent.
Preferred examples of such polymeric nucleating agents are vinyl polymers, such as vinyl polymers derived from monomers having the formula
CH2＝CH-CHR1R2
Wherein R 1 and R 2 together with the carbon atoms to which they are attached form an optionally substituted saturated or unsaturated or aromatic or fused ring system wherein the ring or fused ring moiety contains from 4 to 20 carbon atoms, preferably from 5 to 12 membered saturated or unsaturated or aromatic or fused ring system, or independently represent a straight or branched C4-C30 alkane, C4-C20 cycloalkane, or C4-C20 aromatic ring. Preferably, R 1 and R 2 together with the C-atom to which they are attached form a five-or six-membered saturated or unsaturated or aromatic ring, or independently represent a lower alkyl group containing 1 to 4 carbon atoms. Preferred vinyl compounds for the preparation of the polymeric nucleating agents used according to the present invention are in particular vinylcycloalkanes, in particular Vinylcyclohexane (VCH), vinylcyclopentane and vinyl-2-methylcyclohexane, 3-methyl-1-butene, 3-ethyl-1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene or mixtures thereof. It is particularly preferred that the vinyl polymer is a vinylcycloalkane polymer, preferably selected from Vinylcyclohexane (VCH), vinylcyclopentane and vinyl-2-methylcyclohexane, wherein a vinylcyclohexane polymer is a particularly preferred embodiment.
It is further preferred that the vinyl polymer of the polymeric nucleating agent is a homopolymer, most preferably a vinylcyclohexane homopolymer.
The heterophasic propylene-ethylene copolymer (HECO) of the invention may be synthetic or selected from commercially available polypropylene.
Process for the preparation of heterophasic propylene-ethylene copolymers (HECO)
The heterophasic propylene-ethylene copolymer (HECO) comprised in the composition according to the invention is preferably produced in a sequential polymerization process in the presence of a ziegler-natta catalyst, more preferably in the presence of a catalyst (system) as defined below.
Preferably, the heterophasic propylene-ethylene copolymer (HECO) is reactor manufactured, preferably has been produced in a sequential polymerization process, wherein the crystalline matrix (M) has been produced in at least one reactor, preferably in two reactors, and subsequently the elastomeric ethylene-propylene copolymer (EC) has been produced in at least one further reactor, preferably in one further reactor.
The term "polymerization reactor" shall indicate that the main polymerization takes place. Thus, in case the process consists of three polymerization reactors, this definition does not exclude the option that the whole process comprises a prepolymerization step, e.g. in a prepolymerization reactor. The term "consisting of" is only a closed description in terms of the main polymerization reactor, i.e. a prepolymerization reactor preceding the three reactors is not excluded.
Preferably, the method comprises the steps of:
(a1) Polymerizing propylene in a first reactor (R1) to obtain a first propylene homopolymer fraction (h-PP 1),
(B1) The first propylene homopolymer fraction (h-PP 1) is transferred to a second reactor (R2),
(C1) Polymerizing propylene in a second reactor (R2) and in the presence of said first propylene homopolymer fraction (h-PP 1), thereby obtaining a second propylene homopolymer fraction (h-PP 2), the first propylene homopolymer fraction (h-PP 1) forming a crystalline propylene homopolymer matrix (M) together with the second propylene homopolymer fraction (h-PP 2),
(D1) Transferring the crystalline propylene homopolymer matrix (M) of step (c 1) to a third reactor (R3),
(E1) Polymerizing propylene and ethylene in a third reactor (R3) and in the presence of a crystalline propylene homopolymer matrix (M) obtained in step (c 1), thereby obtaining an elastomeric ethylene-propylene copolymer (EC), said crystalline propylene homopolymer matrix (M) and said elastomeric ethylene-propylene copolymer (EC) forming a heterophasic propylene-ethylene copolymer (HECO).
For preferred embodiments of the heterophasic propylene copolymer (HECO), the crystalline matrix (M), the first propylene homopolymer (h-PP 1), the second propylene homopolymer (h-PP 2) and the elastomeric ethylene-propylene copolymer (EC), reference is made to the definitions given above.
The first reactor (R1) is preferably a Slurry Reactor (SR) and may be any continuous or simple stirred batch tank reactor or loop reactor operating in bulk or slurry. Bulk refers to polymerization in a reaction medium comprising at least 60% (w/w) monomer. According to the invention, the Slurry Reactor (SR) is preferably a (bulk) Loop Reactor (LR).
The second reactor (R2) and the third reactor (R3) are preferably Gas Phase Reactors (GPR). Such a Gas Phase Reactor (GPR) may be any mechanically mixed or fluidized bed reactor. Preferably, the Gas Phase Reactor (GPR) comprises a mechanically stirred fluidized bed reactor having a gas velocity of at least 0.2 m/s. It will thus be 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), such as a Loop Reactor (LR), while the second reactor (R2) and the third reactor (R3) are Gas Phase Reactors (GPR). Thus, for the process of the present invention, at least three polymerization reactors, preferably three polymerization reactors, i.e.slurry reactors (SR), such as Loop Reactor (LR), first gas phase reactor (GPR-1) and second gas phase reactor (GPR-2), are used, which are connected in series. If desired, a prepolymerization reactor is arranged before the Slurry Reactor (SR).
A preferred multi-stage process is a "loop-gas phase" process such as that developed by Borealis A/S of Denmark (known asTechnology) and are described, for example, in patent documents such as EP 0 887 379, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or WO 00/68315.
Another suitable slurry-gas phase process is BasellMethods are described, for example, in FIG. 20 of the paper prog.Polym.Sci.26 (2001) 1287-1336 by Galli and Vecello.
Preferably, in the process of the invention for producing a crystalline matrix (M) as defined above, the conditions for the first reactor (R1) of step (a 1), i.e. the Slurry Reactor (SR), such as the Loop Reactor (LR), may be the following conditions:
The temperature is in the range 40 ℃ to 110 ℃, preferably between 60 ℃ and 100 ℃, such as 68 to 95 ℃,
The pressure is in 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 1), preferably comprising the first propylene homopolymer fraction (h-PP 1), is transferred to a second reactor (R2), i.e. a first gas phase reactor (GPR-1), wherein the conditions are preferably the following conditions:
The temperature is in the range 50 ℃ to 130 ℃, preferably between 60 ℃ and 100 ℃,
The pressure is in the range of 5 bar to 50 bar, preferably between 15 bar and 35 bar,
Hydrogen can be added for controlling the molar mass in a manner known per se.
If desired, the polymerization can be carried out in a known manner under supercritical conditions in the first reactor (R1), i.e.in the Slurry Reactor (SR), as in the Loop Reactor (LR), and/or in condensed mode in the gas-phase reactor (GPR-1).
The second gas phase reactor (GPR-2) of step (e 1) is preferably also operated under the abovementioned conditions, preferably, except for the following conditions, in the second gas phase reactor (GPR-2),
The pressure is in the range 5 bar to 50 bar, preferably between 10 bar and 30 bar.
The residence time may be different in the different reactors described above.
In one embodiment of the process for producing propylene copolymer, the residence time in the first reactor (R1), i.e. the Slurry Reactor (SR), such as the Loop Reactor (LR) is in the range of 0.2 to 4 hours, for example in the range of 0.3 to 1.5 hours, whereas the residence time in the gas phase reactor (GPR 1 to GPR 2) is typically in the range of 0.2 to 6.0 hours, such as 0.5 to 4.0 hours.
In the process of the present invention, a well-known prepolymerization step may be carried out prior to the actual polymerization in the reactors (R1) to (R3). The pre-polymerization step is typically carried out at a temperature of from 0 to 50 ℃, preferably from 10 to 45 ℃, and more preferably from 15 to 40 ℃.
More preferably, the heterophasic propylene-ethylene copolymer (HECO) is obtained in the presence of and in the sequential polymerization process defined in the present invention:
(I) A solid catalyst component comprising a magnesium halide, a titanium halide and an internal electron donor; and
(II) a cocatalyst comprising an aluminum alkyl and optionally an external electron donor, and
(III) optionally a nucleating agent, preferably in the presence of a nucleating agent as defined above or below.
It is particularly preferred that the method according to the invention comprises the following method steps:
Polymerizing a vinyl compound, preferably Vinylcyclohexane (VCH), as defined above in the presence of a catalyst system comprising a solid catalyst component to obtain a modified catalyst system, which is a reaction mixture comprising the solid catalyst system and a polymer of the vinyl compound produced, preferably, and wherein the weight (g) ratio of polymer of the vinyl compound to solid catalyst system is at most 5 (5:1), preferably at most 3 (3:1), most preferably 0.5 (1:2) to 2 (2:1), and feeding the obtained modified catalyst system to the polymerization step (a 1) of the process for producing heterophasic propylene copolymer (HECO).
The catalyst used is preferably a ziegler-natta catalyst system, even more preferably a modified ziegler-natta catalyst system as defined in more detail below.
Such Ziegler-Natta catalyst systems typically comprise a solid catalyst component, preferably a solid transition metal component, and a co-catalyst, and optionally an external donor. The solid catalyst component most preferably comprises magnesium halide, titanium halide and an internal electron donor. Such catalysts are well known in the art. Examples of such solid catalyst components are disclosed in particular in WO 87/07620, WO 92/21305, WO 93/11165, WO 93/11166, WO 93/19100, WO 97/36939, WO 98/12234, WO 99/33842.
Suitable electron donors are, in particular, carboxylic esters, such as phthalates, citraconates and succinates. Oxygen-containing or nitrogen-containing silicon compounds may also be used. Examples of suitable compounds are shown in WO 92/19659、WO 92/19653、WO 92/19658、US 4,347,160、US 4,382,019、US 4,435,550、US 4,465,782、US 4,473,660、US 4,530,912 and US 4,560,671.
Further, the solid catalyst component is preferably used in combination with well known external electron donors including, but not limited to, ethers, ketones, amines, alcohols, phenols, phosphines, and silanes, such as organosilane compounds containing a Si-OCOR, si-OR, OR Si-NR 2 bond, with silicon as the central atom, and R being an alkyl, alkenyl, aryl, aralkyl, OR cycloalkyl group having 1 to 20 carbon atoms, and well known cocatalysts to polymerize propylene copolymers; the cocatalyst preferably comprises an alkyl aluminum compound known in the art.
When the nucleating agent is introduced into the heterophasic propylene-ethylene copolymer (HECO) during the polymerization process of the propylene copolymer, the amount of nucleating agent present in the heterophasic propylene-ethylene copolymer (HECO) is preferably not more than 500ppm, more preferably from 0.025 to 200ppm, still more preferably from 1 to 100ppm, and most preferably from 5 to 100ppm, based on the total weight of the heterophasic propylene-ethylene copolymer (HECO) and the nucleating agent, preferably based on the heterophasic propylene-ethylene copolymer (HECO) including all additives.
Flame Retardant (FR)
As another essential component, the polypropylene Base Composition (BC) contains a Flame Retardant (FR).
The skilled artisan will appreciate that the term flame retardant refers to any compound commonly used in the art to improve the flame retardant properties of polypropylene compositions.
The Flame Retardant (FR) may be a halogenated flame retardant or a non-halogenated flame retardant. Preferably, the Flame Retardant (FR) is a non-halogenated flame retardant.
Typical halogenated flame retardants include organohalogen compounds selected from the group consisting of organochlorides such as chlorfenac derivatives and chlorinated paraffins; organic bromine, such as decabromodiphenyl ether (decaBDE), decabromodiphenyl ethane (a substitute for decaBDE), polymeric brominated compounds, such as brominated polystyrene, brominated Carbonate Oligomers (BCO), brominated Epoxy Oligomers (BEO), tetrabromophthalic anhydride, tetrabromobisphenol a (TBBPA), and Hexabromocyclododecane (HBCD);
and inorganic synergists such as antimony pentoxide, sodium antimonite and antimony trioxide.
If the flame retardant of the present invention is a halogenated flame retardant, it is preferably selected from the list above or a mixture of flame retardants in the list above. In one embodiment, the halogenated flame retardant is a mixture of decabromodiphenylethane and antimony trioxide.
Typical non-halogenated flame retardants include minerals such as aluminum hydroxide (ATH), magnesium hydroxide (MDH), huntite and hydromagnesite, red phosphorus and borates, and organophosphorus compounds including ammonium polyphosphate, melamine polyphosphate, triphenyl phosphate (TPP), bis (diphenyl phosphate) Resorcinol (RDP), bisphenol A Diphenyl Phosphate (BADP), tricresyl phosphate (TCP), dimethyl methylphosphonate (DMMP), aluminum diethylphosphinate, piperazine pyrophosphate, melamine polyphosphate, calcium bis (dihydrogen orthophosphate) and calcium hydrogen phosphate. These flame retardants may be used alone or in the form of a mixture.
The flame retardant of the present invention is preferably a non-halogenated flame retardant, more preferably a non-halogenated organophosphorus flame retardant, most preferably selected from piperazine pyrophosphate, melamine polyphosphate, calcium bis (dihydrogen orthophosphate), calcium hydrogen phosphate, and mixtures thereof.
One suitable commercially available non-halogenated flame retardant is ambard PP1, commercially available from Solvay s a. (china).
Additive (A)
The polypropylene Base Composition (BC) of the present invention may contain the additive (a) in an amount of 0.1 to 5.0% by weight. The skilled practitioner is able to select suitable additives well known in the art.
The additive (a) is preferably selected from antioxidants, uv stabilizers, scratch inhibitors, mold release agents, acid scavengers, lubricants, antistatic agents, colorants or pigments and mixtures thereof.
It should be understood that the content of additive (a) given with respect to the total weight of the polypropylene Base Composition (BC) includes any carrier polymer used for introducing the additive into the polypropylene Base Composition (BC), i.e. a masterbatch carrier polymer. An example of such a carrier polymer is a polypropylene homopolymer in powder form.
Polar Modified Polypropylene (PMP)
In certain preferred embodiments, the polypropylene Base Composition (BC) of the present invention may further comprise a Polar Modified Polypropylene (PMP).
While not wishing to be bound by any theory, it is believed that the Polar Modified Polypropylene (PMP) acts as a compatibilizer in the composition, which further aids in dispersing the glass fibers within the fiber reinforced Polypropylene Composition (PC).
Preferably, the Polar Modified Polypropylene (PMP) has a polar group content in the range of 0.5 to 3.0 wt%, more preferably in the range of 0.7 to 2.0 wt%, most preferably in the range of 0.8 to 1.5 wt%.
It is also preferred that the Polar Modified Polypropylene (PMP) has a melt flow rate (MFR 2) measured according to ISO 1133 at 230 ℃ and 2.16kg in the range of 30.0 to 150.0g/10min, more preferably in the range of 40.0 to 120.0g/10min, most preferably in the range of 50.0 to 100.0g/10 min.
It is particularly preferred that the Polar Modified Polypropylene (PMP) is maleic anhydride modified polypropylene.
Suitable commercially available polar modified polypropylene includes CMG5701 available from Jiangsu limited (Fine-Blend Compatibilizer Jiangsu co., ltd.) which is a good Yi Rong compatibilizer.
Polypropylene Base Composition (BC)
The polypropylene base composition of the present invention comprises several essential components including a heterophasic propylene-ethylene copolymer (HECO), a Flame Retardant (FR) and at least one additive (a) other than the Flame Retardant (FR). Accordingly, the polypropylene Base Composition (BC) comprises:
a) 50.0 to 75.0 wt% based on the total weight of the base composition of a heterophasic propylene-ethylene copolymer (HECO) consisting of:
i) A crystalline propylene homopolymer matrix (M);
ii) an elastomeric ethylene-propylene copolymer (EC);
Wherein the heterophasic propylene-ethylene copolymer (HECO) has a melt flow rate (MFR 2) in the range of 70.0 to 150.0g/10min measured according to ISO 1133 at 230 ℃ and 2.16 kg;
b) 20.0 to 45.0 weight percent of a Flame Retardant (FR), based on the total weight of the base composition; and
C) 0.1 to 5.0% by weight, based on the total weight of the base composition, of at least one additive (A) other than Flame Retardants (FR),
The polypropylene Base Composition (BC) may further comprise:
d) 0.1 to 5.0 wt% of a Polar Modified Polypropylene (PMP) based on the total weight of the base composition.
The polypropylene Base Composition (BC) of the present invention may contain other components in addition to the essential components as defined above. However, it is preferred that the respective content of heterophasic propylene-ethylene copolymer (HECO), flame Retardant (FR), at least one additive (a) and optionally Polar Modified Polypropylene (PMP) amounts to at least 90wt%, more preferably at least 95 wt%, based on the total weight (BC) of the polypropylene base composition. Most preferably, the polypropylene Base Composition (BC) consists only of heterophasic propylene-ethylene copolymer (HECO), flame Retardant (FR), at least one additive (a) and optionally a Polar Modified Polypropylene (PMP).
The heterophasic propylene-ethylene copolymer (HECO) is present in the polypropylene Base Composition (BC) in an amount of from 50.0 to 75.0 wt. -%, more preferably in an amount of from 55.0 to 72.0 wt. -%, most preferably in an amount of from 60.0 to 70.0 wt. -%, based on the total weight of the base composition.
The Flame Retardant (FR) is present in the polypropylene Base Composition (BC) in an amount of 20.0 to 45.0 wt. -%, more preferably in an amount of 23 to 40.0 wt. -%, most preferably in an amount of 26.0 to 35.0 wt. -%, based on the total weight of the base composition.
If present, it is preferred that the Polar Modified Polypropylene (PMP) is present in the polypropylene composition in an amount of from 0.1 to 5.0 wt%, more preferably in an amount of from 1.0 to 4.0 wt%, most preferably in an amount of from 2.0 to 3.0 wt%, based on the total weight of the base composition.
Thus, in a preferred embodiment, the polypropylene Base Composition (BC) comprises, preferably consists of:
a) 50.0 to 75.0 wt% based on the total weight of the base composition of a heterophasic propylene-ethylene copolymer (HECO) consisting of:
i) A crystalline propylene homopolymer matrix (M);
ii) an elastomeric ethylene-propylene copolymer (EC);
Wherein the heterophasic propylene-ethylene copolymer (HECO) has a melt flow rate (MFR 2) in the range of 70.0 to 150.0g/10min measured according to ISO 1133 at 230 ℃ and 2.16 kg;
b) 20.0 to 45.0 weight percent of a Flame Retardant (FR), based on the total weight of the base composition;
c) 0.1 to 5.0% by weight, based on the total weight of the base composition, of at least one additive (a) other than Flame Retardant (FR); and
D) Optionally 0.1 to 5.0 wt% of a Polar Modified Polypropylene (PMP), based on the total weight of the base composition.
Thus, in a further preferred embodiment, the polypropylene Base Composition (BC) comprises, preferably consists of:
a) 55.0 to 72.0 wt% based on the total weight of the base composition of a heterophasic propylene-ethylene copolymer (HECO) consisting of:
i) A crystalline propylene homopolymer matrix (M);
ii) an elastomeric ethylene-propylene copolymer (EC);
Wherein the heterophasic propylene-ethylene copolymer (HECO) has a melt flow rate (MFR 2) in the range of 70.0 to 150.0g/10min measured according to ISO 1133 at 230 ℃ and 2.16 kg;
b) 23.0 to 40.0 weight percent of a Flame Retardant (FR), based on the total weight of the base composition;
c) 0.1 to 5.0% by weight, based on the total weight of the base composition, of at least one additive (a) other than Flame Retardant (FR); and
D) Optionally from 1.0 to 4.0 wt% of a Polar Modified Polypropylene (PMP), based on the total weight of the base composition.
Thus, in yet another preferred embodiment, the polypropylene Base Composition (BC) comprises, preferably consists of:
a) 60.0 to 70.0 wt% based on the total weight of the base composition of a heterophasic propylene-ethylene copolymer (HECO) consisting of:
i) A crystalline propylene homopolymer matrix (M);
ii) an elastomeric ethylene-propylene copolymer (EC);
Wherein the heterophasic propylene-ethylene copolymer (HECO) has a melt flow rate (MFR 2) in the range of 70.0 to 150.0g/10min measured according to ISO 1133 at 230 ℃ and 2.16 kg;
b) 25.0 to 35.0 weight percent of a Flame Retardant (FR), based on the total weight of the base composition;
c) 0.1 to 5.0% by weight, based on the total weight of the base composition, of at least one additive (a) other than Flame Retardant (FR); and
D) Optionally from 2.0 to 3.0 wt% of a Polar Modified Polypropylene (PMP), based on the total weight of the base composition.
Glass fiber
Another essential component of the fiber reinforced Polypropylene Composition (PC) is Glass Fiber (GF).
The glass fibers are preferably provided in the form of continuous glass fibers.
Preferably, the continuous glass fibers have a nominal diameter in the range of 5 to 30 μm, preferably in the range of 10 to 20 μm, most preferably in the range of 13 to 17 μm.
It is also preferred that the glass fibers are incorporated into the composition using an LFT-D (long fiber reinforced thermoplastic-direct) extruder. As a result of the introduction of the LFT-D extruder, the glass fibers are mixed with the pre-compounded base composition that has been subjected to the compounding process, rather than all of the components of the fiber reinforced composition being mixed in the same extruder. Furthermore, the glass fibers were introduced into the middle section of the LFT-D extruder, rather than at the beginning of the barrel with the pre-compounded base composition. This ensures that the base composition is already in a molten state when the fibers are added, thereby reducing the stress on the fibers. Finally, the compounded fiber reinforced composition is extruded directly into a blank sheet, which is delivered directly into a compression molding machine and compression molded to form a fiber reinforced article. Thus, the process does not involve granulation of the fiber reinforced composition at any stage. LFT-D process is understood to reduce excessive breakage of continuous fibers, ensuring that the fibers in the final fiber-reinforced composition (and fiber-reinforced article) are longer than if other extrusion techniques were used or indeed if chopped fibers were used.
Fiber reinforced Polypropylene Composition (PC)
The fiber reinforced polypropylene composition according to the invention comprises, preferably consists of, 60 to 80 wt. -% of the polypropylene Base Composition (BC) and 20 to 40 wt. -% of the Glass Fibers (GF) based on the weight of the fiber reinforced polypropylene composition.
Preferably, the fiber reinforced Polypropylene Composition (PC) comprises, preferably consists of, 63 to 75 wt.% of the polypropylene Base Composition (BC) and 25 to 37 wt.% of the Glass Fibers (GF) based on the weight of the fiber reinforced polypropylene composition.
It is further preferred that the fiber reinforced Polypropylene Composition (PC) comprises, preferably consists of, 65 to 70 wt. -% of the polypropylene Base Composition (BC) and 30 to 35 wt. -% of the Glass Fibers (GF) based on the weight of the fiber reinforced polypropylene composition.
In order to be suitable for use in vehicle battery covers, the fiber reinforced Polypropylene Composition (PC) according to the present invention requires advantageous mechanical properties such as bending and impact strength, low warpage, and good flame retardant properties.
Accordingly, it is preferred that the fiber reinforced Polypropylene Composition (PC) has a flexural strength measured according to ISO 178 of at least 80MPa, more preferably at least 83MPa, most preferably at least 86 MPa.
The bending strength is generally not more than 100MPa.
It is also preferred that the fiber reinforced Polypropylene Composition (PC) has a notched impact strength of at least 20kJ/m 2, more preferably at least 22kJ/m 2, as measured according to ISO 179-1 eA at +23℃.
The notched impact strength of a simply supported beam is typically no more than 40kJ/m 2.
Furthermore, it is preferred that the fiber reinforced Polypropylene Composition (PC) has a flame retardant rating of V-0 as measured according to test standard UL 94-2013.
Further, it is preferable that the Polypropylene Composition (PC) has low warpage.
Method for preparing a fiber reinforced Polypropylene Composition (PC)
The invention also relates to a process for preparing the fiber reinforced Polypropylene Composition (PC) of the invention, comprising the steps of:
a) Providing at least one additive (a), preferably in the form of a masterbatch;
b) Providing a heterophasic propylene-ethylene copolymer (HECO) and optionally a Polar Modified Polypropylene (PMP);
c) Providing a Flame Retardant (FR);
d) Blending and extruding a heterophasic propylene-ethylene copolymer (HECO) with at least one additive (a) and a Flame Retardant (FR) in a "compounding" extruder, preferably a twin screw extruder, at a temperature in the range of 120 ℃ to 220 ℃, thereby forming a polypropylene Base Composition (BC) in pellet form;
e) The pellets of the obtained polypropylene Base Composition (BC) are fed into an LFT-D extruder, preferably a twin screw extruder,
F) Providing continuous Glass Fibers (GF) and feeding the fibers into the LFT-D extruder through a side feeder located in the middle of the extruder barrel;
g) Blending and extruding the polypropylene Base Composition (BC) with Glass Fibers (GF) in an LFT-D extruder at a temperature in the range of 120 ℃ to 220 ℃, thereby forming a fiber reinforced Polypropylene Composition (PC) in the form of a blank sheet;
h) The blank sheet obtained is directly delivered to a compression molding machine and the sheet is compression molded to form a fiber reinforced article, i.e., LFT-D article.
In particular, it is preferred that the first blending and extrusion be performed using conventional compounding or blending equipment to form the polypropylene Base Composition (BC) in pellet form, such as a banbury mixer, a twin roll rubber mill, a Buss-co-kneader, or a twin screw extruder. More preferably, the mixing is accomplished in a co-rotating twin screw extruder. The polymeric material recovered from the extruder (in this case, the polypropylene Base Composition (BC)) is typically in pellet form.
In addition, a twin screw extruder is also preferably used as the LFT-D extruder for compounding and blending the polypropylene Base Composition (BC) and continuous glass fibers to form a fiber reinforced Polypropylene Composition (PC). LFT-D extruders are similar in structure to extruders of compounding processes, but have weaker shear stresses. The LFT-D extruder has a plate die.
Article and use
The invention also relates to articles comprising the fiber reinforced Polypropylene Composition (PC) of the invention.
Preferably, the article of the present invention comprises more than 75 wt.% of the fiber reinforced Polypropylene Composition (PC), more preferably more than 85 wt.% of the fiber reinforced Polypropylene Composition (PC), still more preferably more than 90 wt.% of the fiber reinforced Polypropylene Composition (PC), most preferably more than 95 wt.% of the fiber reinforced Polypropylene Composition (PC).
The article is preferably a molded article, most preferably a compression molded article.
Preferably, the article is a vehicle article, more preferably the article is a housing for a battery of an electric vehicle.
The invention also relates to the use of a polypropylene Base Composition (BC) with continuous glass fibers in an LFT-D process to form a compression molded article, preferably a vehicle battery cover, wherein the article contains 60 to 80 wt% of a polypropylene Base Composition (BC) and 20 to 40 wt% of continuous glass fibers, the polypropylene Base Composition (BC) comprising:
a) 50.0 to 75.0 wt% based on the total weight of the base composition of a heterophasic propylene-ethylene copolymer (HECO) consisting of:
i) A crystalline propylene homopolymer matrix (M);
ii) an elastomeric ethylene-propylene copolymer (EC);
Wherein the heterophasic propylene-ethylene copolymer (HECO) has a melt flow rate (MFR 2) in the range of 70.0 to 150.0g/10min measured according to ISO 1133 at 230 ℃ and 2.16 kg;
b) 20.0 to 45.0 weight percent of a Flame Retardant (FR), based on the total weight of the base composition;
c) 0.1 to 5.0% by weight, based on the total weight of the base composition, of at least one additive (a) other than Flame Retardant (FR); and
D) Optionally 0.1 to 3 wt% of a Polar Modified Polypropylene (PMP), preferably a maleic anhydride modified polypropylene, based on the total weight of the base composition.
All the preferred embodiments and features discussed in the previous section can equally be applied to articles and uses according to the invention.
Examples
1. Definition/measurement method
Unless otherwise defined, the following definitions of terms and assay methods apply to the above general description of the invention as well as to the following examples.
The melting temperature T m is measured according to ISO 11357-3.
MFR 2: melt Flow Rate (MFR) is determined according to ISO 1133 and is expressed in g/10 min. MFR characterizes the flowability of the polymer and thus the processability of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR 2 of the polypropylene was determined at a temperature of 230℃and a load of 2.16 kg.
Quantification of copolymer microstructure by NMR spectroscopy
The comonomer content of the polymer was quantified using quantitative Nuclear Magnetic Resonance (NMR) spectroscopy.
Quantitative 13C{1 H } NMR spectra were recorded in solution using a Bruker ADVANCE III NMR spectrometer operating at 400.15 and 100.62MHz for 1 H and 13 C, respectively. All spectra were recorded at 125 ℃ using a 13 C optimized 10mm extended temperature probe, with nitrogen for all pneumatic devices. About 200mg of the material was dissolved in 3ml of 1, 2-tetrachloroethane-d 2(TCE-d2 together with chromium (III) acetylacetonate (Cr (acac) 3) to give a 65mM solution of the relaxation agent in a solvent, as described in G.Singh, A.Kothari, V.Gupta, polymer Testing 2009,28 (5), 475.
To ensure homogeneity of the solution, the NMR tube was further heated in a rotating oven for at least 1 hour after initial sample preparation in the heating block. After insertion into the magnet, the tube was rotated at 10 Hz. This setting is chosen primarily for high resolution and accurate quantification of ethylene content. With a standard single pulse excitation without NOE, an optimized tip angle (tip angle), a 1s cyclic delay, and a dual stage WALTZ16 decoupling scheme were used, as described in Z.Zhou, R.Kuemmerle, X.Qiu, D.Redwine, R.Cong, A.Taha, D.Baugh, B.Winniford, J.Mag.Reson.187 (2007) 225 and V.Busico,P.Carbonniere,R.Cipullo,C.Pellecchia,J.Severn,G.Talarico,Macromol.Rapid Commun.2007,28,1128. A total of 6144 (6 k) transients were acquired per spectrum. Quantitative 13C{1 H } NMR spectra were processed, integrated and the relevant quantitative properties were determined from the integration. Using chemical shifts of the solvent, all chemical shifts are indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm. This method allows for a comparable reference even if the building block is not present.
Characteristic signals corresponding to 2,1 erythro region defects (as described in L.Resconi, L.Cavallo, A.Fait, F.Piemontesi, chem.Rev.2000,100 (4), 1253, cheng, h.n., macromolecules 1984,17,1950 and W-j. Wang and s.zhu, macromolecules 2000,33 1157) were observed, and the effect of the region defects on the determined performance required to be corrected. No characteristic signal corresponding to other types of region defects is observed.
Characteristic signals corresponding to ethylene incorporation were observed (as described in Cheng, h.n., macromolecules 1984,17,1950) and comonomer fractions were calculated as the fraction of ethylene in the polymer relative to all monomers in the polymer.
Comonomer fractions were quantified by integration of multiple signals over the entire spectral region of the 13C{1 H } spectrum using the method of W-J.Wang and S.Zhu, macromolecules 2000,33 1157. This method is chosen for its robustness and ability to account for the presence of region defects when needed. The integration zone is slightly adjusted to improve applicability across the entire range of comonomer content encountered.
The mole percent of comonomer incorporation was calculated from the mole fraction.
The weight percent of comonomer incorporation was calculated from the weight fractions.
The comonomer content of the elastomeric propylene-ethylene copolymer fraction (EC), i.e. of the xylene soluble fraction of the final heterophasic propylene copolymer (HECO), was tested and calculated in the same way as mentioned above.
Maleic anhydride content: FT-IR standards were prepared by blending PP homopolymer with varying amounts of MAH to create a calibration curve (absorption/thickness (cm) versus MAH content (% by weight). The MAH content was determined in the solid state by IR spectroscopy using a Bruker Vertex 70FTIR spectrometer on a 25X 25mm square film of thickness 100 μm (precision.+ -. 1 μm) prepared by compression moulding at 190℃with a clamping force of 4 to 6 mPa. Using standard transmission FTIR spectroscopy, a spectral range of 4000 to 400cm -1, an aperture of 6mm, a spectral resolution of 2cm -1, 16 background scans, 16 spectral scans, an interferogram zero fill factor of 32 and using Norton Beer strong apodization was used.
MAH was measured at the peak of the absorption spectrum of 1787cm -1. For the calculation of MAH content, the range between 1830 and 1727cm -1 (after baseline correction) was evaluated according to a calibration standard curve.
Xylene solubles fraction (XCS) at room temperature (XCS, wt%): the amount of xylene-soluble polymer is according to ISO 16152; a first plate; 2005-07-01 was measured at 25 ℃. The remainder is the xylene cold insoluble (XCU) fraction.
Intrinsic Viscosity (IV) is measured according to ISO 1628-1 (in decalin at 135 ℃).
Impact test of simple beam: the Notched Impact Strength (NIS) of the simply supported beams and the notched impact strength (UIS) of the simply supported beams were measured according to ISO 179-1eA at +23℃usinginjection molded bar-shaped test specimens of 80X 10X 4mm 3 prepared according to ISO 1873-2:2007.
Flexural strength: flexural strength was determined according to ISO 178 at 23℃in 3-point bending on 80X 10X 4mm 3 test bars injection molded according to EN ISO 1873-2.
Flame retardancy test: the flame retardant properties of the compositions were tested according to standard UL 94-2013.
Prior to testing, the sample must be conditioned. This conditioning requires that the sample be maintained at 23 ℃ and 50% relative humidity for at least 48 hours prior to testing.
Samples with dimensions 125mm (length) by 13mm (width) by 1.5mm (thickness) were used in the test. One end of the sample is clamped with a clamp and the other end is free and the sample is suspended vertically downward.
The burner flame was applied to the free end of the coupon for the first 10 seconds and then removed. After the flame of the coupon extinguished (if any), the burner flame was reapplied to the free end of the coupon for a second 10 seconds and then removed. A set of 5 samples was tested. In addition, a small piece of cotton wool was placed under the burning coupon during the test. For each sample, test results were recorded as follows:
█ apply the duration of the flaming combustion time after the first 10 seconds of the burner flame.
█ Apply the second 10 seconds after the burner flame the duration of the flaming combustion time.
█ Apply the second 10 seconds of the burner flame.
█ Burns whether the drop ignites cotton placed under the specimen.
█ Whether the sample burned into the mounting clip.
The rating criteria for the test results are shown in table 1 below:
table 1: rating criteria for flame retardant rating V-0 to V-2
The main difference between the V-1 and V-2 grades is whether the combustion pendant ignites cotton placed under the test specimen. For polypropylene based materials, it is easy to change from V-0 grade to V-2 grade (no transition state of V-1 grade) because the burning drool of polypropylene is easy to ignite cotton.
Warpage test: to measure warpage, the cell cover produced by LFT-D process was placed on a horizontal surface (x-y surface-see fig. 1). The heights of 6 points on the surface of the compression molded battery cover, i.e., 3 points (A, B, C) near the center on the surface of the cover, 1 point at the center on the left side on the surface of the cover, 1 point at the center on the right side on the surface of the cover, and 1 point at the center on the rear side on the surface of the cover were then measured in the z-direction. In the z-direction, the difference between the measured height at a given point and the corresponding height in the originally designed compression molding die is recorded as Δh at that point. The data Δh is used to quantify the warp at this point: the larger Δh, the more severe the warpage at a given point.
2. Examples
2.1. Synthesis of heterophasic propylene-ethylene copolymer (HECO)
The catalyst used in the polymerization was a Ziegler-Natta catalyst from Borealis having a titanium content of 1.9% by weight (as described in EP 591 224). The catalyst was prepolymerized with vinyl-cyclohexane (VCH) prior to polymerization, as described in EP 1 028 984 and EP 1 183 307. The ratio of VCH to catalyst used in the preparation is 1:1, so the final poly-VCH content is below 100ppm.
In the first stage, the above catalyst was fed into the prepolymerization reactor together with propylene and small amounts of hydrogen (2.5 g/h) and ethylene (330 g/h). Triethylaluminum was used as cocatalyst and dicyclopentyl dimethoxy silane was used as donor. The ratio of aluminum to donor was 7.5 moles/mole and the ratio of aluminum to titanium was 300 moles/mole. The reactor was operated at a temperature of 30℃and a pressure of 55 bar (gauge).
The subsequent polymerization was carried out under the following conditions.
Table 2: polymerization conditions for heterophasic propylene-ethylene copolymer (HECO)
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2.2. Compounding of examples
The polypropylene base compositions of inventive examples IE1 to IE4 and comparative example CE1 were prepared by compounding in a "compounding" co-rotating twin screw extruder under the conditions described in table 4, based on the formulations shown in table 3. The extruder had 12 heating zones. CE1 represents a market benchmark for compositions like LFT-D processes.
Table 3: formulation of polypropylene base composition for comparative example and invention
A propylene homopolymer having a h-PP melt flow rate of 80g/10 min.
PMP maleic anhydride grafted polypropylene, commercially available under the trade name CMG5701 from Jiangsu Co., ltd (China), which is a good Yi Rong compatibilizer, has a grafted maleic anhydride content of 1.0% by weight.
FR1 flame retardant comprising 20% piperazine pyrophosphate, 20% melamine polyphosphate, 30% calcium bis (dihydrogen orthophosphate) and 30% calcium hydrogen phosphate.
FR2 was a mixture of 70% decabromodiphenylethane (CAS-No. 84852-53-9) and 30% antimony trioxide (CAS-No. 1309-64-4).
An additive masterbatch commercially available from Hong Gai petrochemicals (china) under the trade name PP-H225, MFR 2 (230 c,
2.16 Kg) of a carrier propylene homopolymer having a concentration of 27g/10min, 1.3% by weight of Irganox PS 802FL (CAS No. 693-36-7),
A heat stabilizer commercially available from BASF SE (Germany) 0.8% by weight of a catalyst having the trade name Irganox 3114 (CAS-number 27676-62-6),
An antioxidant commercially available from BASF SE (Germany), 0.7% by weight of a compound having the trade name Irgafos 168 (CAS-number 31570-04-4),
An antioxidant commercially available from BASF SE (Germany), and 0.1
The composition of weight percent calcium stearate (CAS-number 1592-23-0) commercially available from FACI CHEMICALS (Zhangjihong Kong) Inc. (China).
CMB color concentrate, commercially available from privet (Shanghai) limited company (China), under the trade name TP90002452 BG.
Table 4: compounding conditions of the Polypropylene base composition for use in the present invention in a twin screw extruder
After compounding the polypropylene base composition, these polypropylene base compositions are further compounded with long glass fibers in an LFT-D (long fiber thermoplastic-direct) process.
In the process, the polypropylene base composition previously obtained in pellet form was fed into the main feeder of an LFT-D twin screw extruder having 7 heating zones, commercially available under the trade name "CTE PLUS" from Coperion machinery co.ltd (nanjing, china). Continuous glass fibers in the form of coils (commercially available from eulerian composite (Owens Corning Composites) (china), nominal diameter 15 μm) were fed into a side feeder located in a heating zone 4, the temperature of which heating zone 4 was about 190 ℃. At the die of the extruder, the temperature was about 200 ℃, the mixture was extruded in the form of a blank sheet having a thickness of 20mm and cut into pieces having a width of 200mm, a length of 200mm and a thickness of 20 mm. A blank sheet was delivered directly to a compressor (model "TM-500", available from the company of samara (Tianma co.ltd.,) (china); the forming pressure was 3000 tons and the temperature was 170 to 180 c) and the compressor compressed the sheet into the desired part (in this case the battery cover as shown in fig. 1).
The LFT-D twin screw extruder was operated under the conditions set forth in table 5, with the productivity adjusted appropriately so that the final LFT-D product contained 33 wt% glass fibers and 67 wt% polypropylene base composition, the properties of the final fiber reinforced composition are shown in table 6.
Table 5: conditions in a twin screw extruder in LFT-D process
Table 6: comparative examples of LFT-D products and Performance of examples of the invention
As can be seen from the examples in table 6, the inventive examples exhibited significantly improved warp characteristics both at the edges and in the center of the molded article. From a comparison of IE1 to IE4, it can be seen that the addition of the flame retardant surprisingly improves the warpage resistance, since the flame retardant in the form of an inorganic powder can suppress warpage in addition to increasing the flame retardancy. Further effects can be seen in the increase in flexural strength. The amount of flame retardant can be adjusted within the desired range to optimize warpage/flame retardancy/flexural strength or impact strength (which appears to decrease with the addition of more flame retardant) depending on the exact requirements of the final product.
IE3 has in particular the same amounts of the components as CE1, the only difference being the choice of base polypropylene and the choice of flame retardant. Due to the presence of the heterophasic propylene-ethylene copolymer (HECO), all mechanical/warpage properties (flexural strength, impact strength and warpage) of IE3 with respect to CE1 are improved and the flame retardancy is maintained at V-0.
It is believed that the heterophasic propylene-ethylene copolymer (HECO) has a lower crystallinity than the propylene homopolymer used in CE1, which is believed to help reduce shrinkage and inhibit warpage of the final article. Furthermore, while not wishing to be bound by theory, it is also believed that the use of polyvinylcyclohexane as a nucleating agent results in smaller crystal sizes and a more uniform distribution of small crystals in the nucleating composition, thereby improving warp resistance.
As discussed in the measurement methods, no composition with V1 flame retardancy was observed, as molten polypropylene readily ignites the cotton of the flame retardancy test.
The high flame retardancy of IE2 to IE4, combined with its reduced warpage and beneficial mechanical properties (flexural and impact strength), makes it an excellent candidate for vehicle battery covers.
Claims (13)
1. A fiber reinforced Polypropylene Composition (PC) comprising:
a) From 60 to 80 wt% of a polypropylene Base Composition (BC) based on the weight of the polypropylene composition, the polypropylene Base Composition (BC) comprising:
a) 50.0 to 75.0 wt% of a heterophasic propylene-ethylene copolymer (HECO) based on the total weight of the base composition, the heterophasic propylene-ethylene copolymer (HECO) consisting of:
i) A crystalline propylene homopolymer matrix (M);
ii) an elastomeric ethylene-propylene copolymer (EC);
Wherein the heterophasic propylene-ethylene copolymer (HECO) has a melt flow rate (MFR 2) in the range of 70.0 to 150.0g/10min measured according to ISO 1133 at 230 ℃ and 2.16 kg;
b) 20.0 to 45.0 weight percent of a Flame Retardant (FR) based on the total weight of the base composition; and
C) 0.1 to 5.0% by weight, based on the total weight of the base composition, of at least one additive (A) other than the Flame Retardant (FR),
B) 20 to 40 wt% glass fiber based on the weight of the polypropylene composition.
2. The fiber reinforced Polypropylene Composition (PC) according to claim 1, wherein the heterophasic propylene-ethylene copolymer (HECO) has one or more, preferably all of the following properties:
i) A Xylene Cold Soluble (XCS) content in the range of 5.0 to 20.0 wt%, preferably in the range of 10.0 to 18.0 wt%, most preferably in the range of 13.0 to 16.0 wt%;
ii) a total ethylene (C2) content in the range of 3.0 to 10.0 wt%, preferably in the range of 4.5 to 8.5 wt%, most preferably in the range of 5.5 to 7.5 wt%;
iii) An ethylene content (C2 (XCS)) of the xylene cold soluble fraction in the range of 30.0 to 50.0 wt. -%, preferably in the range of 35.0 to 45.0 wt. -%, most preferably in the range of 37.0 to 41.0 wt. -%; and
IV) intrinsic viscosity (IV (XCS)) of the xylene cold soluble fraction in the range of 1.5 to 3.0dl/g, preferably in the range of 1.8 to 2.7dl/g, most preferably in the range of 2.1 to 2.5 dl/g.
3. The fiber reinforced Polypropylene Composition (PC) according to claim 1 or 2, wherein the heterophasic propylene-ethylene copolymer (HECO) has one or more, preferably all of the following properties:
i) A melting temperature measured by DSC analysis in the range 160 to 169 ℃, more preferably in the range 161 to 168 ℃, most preferably in the range 162 to 168 ℃;
ii) a flexural modulus according to ISO 178 measured on an 80 x 10 x 4mm 3 test bar injection molded according to ENISO 1873-2 in the range of 1000 to 2500MPa, more preferably in the range of 1200 to 2000MPa, most preferably in the range of 1400 to 1700 MPa;
iii) The notched impact strength of a simply supported beam measured at 23℃in accordance with ISO 179-1 eA in the range of 1.0 to 10.0kJ/m 2, more preferably in the range of 3.0 to 8.0kJ/m 2, most preferably in the range of 4.0 to 6.0kJ/m 2, using an injection molded bar test specimen of 80X 10X 4mm 3 prepared in accordance with ISO 1873-2:2007.
4. The fiber reinforced Polypropylene Composition (PC) according to any of the preceding claims, wherein the heterophasic propylene-ethylene copolymer (HECO) contains a polymeric nucleating agent, preferably a vinylcycloalkane polymer, more preferably a vinylcyclohexane polymer, most preferably a vinylcyclohexane homopolymer.
5. The fiber reinforced Polyolefin Composition (PC) according to any of the preceding claims, wherein the crystalline propylene homopolymer matrix (M) of the heterophasic propylene-ethylene copolymer (HECO) has a melt flow rate (MFR 2) measured according to ISO 1133 at 230 ℃ and 2.16kg in the range of 100.0 to 300.0g/10min, more preferably in the range of 130 to 260g/10min, most preferably in the range of 160 to 220g/10 min.
6. The fiber reinforced Polypropylene Composition (PC) according to any of the preceding claims, wherein the Flame Retardant (FR) is a non-halogenated flame retardant, more preferably a non-halogenated organophosphorus flame retardant, most preferably selected from piperazine pyrophosphate, melamine polyphosphate, calcium bis (dihydrogen orthophosphate), calcium hydrogen phosphate and mixtures thereof.
7. The fiber reinforced Polypropylene Composition (PC) according to any one of the preceding claims, wherein the Glass Fiber (GF) is a continuous glass fiber introduced into the composition using an LFT-D extruder, preferably wherein the continuous glass fiber has a nominal diameter in the range of 5 to 30 μιη, preferably in the range of 10 to 20 μιη, most preferably in the range of 13 to 17 μιη.
8. The fiber reinforced Polypropylene Composition (PC) according to any one of the preceding claims, wherein the polypropylene Base Composition (BC) further comprises:
d) 0.1 to 5.0 wt% of a Polar Modified Polypropylene (PMP) based on the total weight of the base composition,
Preferably maleic anhydride modified polypropylene.
9. The fiber reinforced Polypropylene Composition (PC) according to claim 8, wherein the Polar Modified Polypropylene (PMP) has a polar group content in the range of 0.5 to 3.0 wt%.
10. The fiber reinforced Polypropylene Composition (PC) according to any of the preceding claims, wherein the fiber reinforced Polypropylene Composition (PC) has a flame retardant rating of V-0 measured according to test standard UL 94-2013.
11. An article, preferably a molded article, most preferably a compression molded article, comprising more than 75% by weight of the fiber reinforced Polypropylene Composition (PC) according to any one of claims 1 to 10.
12. The article of claim 11, wherein the article is a vehicle article, preferably the article is a vehicle battery cover.
13. Use of a polypropylene Base Composition (BC) with continuous glass fibers in an LFT-D process to form a compression molded article, preferably a vehicle battery cover, wherein the article contains 60 to 80 wt% of the polypropylene Base Composition (BC) and 20 to 40 wt% of the continuous glass fibers, the polypropylene Base Composition (BC) comprising:
a) 50.0 to 75.0 wt% of a heterophasic propylene-ethylene copolymer (HECO) based on the total weight of the base composition, the heterophasic propylene-ethylene copolymer (HECO) consisting of:
i) A crystalline propylene homopolymer matrix (M);
ii) an elastomeric ethylene-propylene copolymer (EC);
Wherein the heterophasic propylene-ethylene copolymer (HECO) has a melt flow rate (MFR 2) in the range of 70.0 to 150.0g/10min measured according to ISO 1133 at 230 ℃ and 2.16 kg;
b) 20.0 to 45.0 weight percent of a Flame Retardant (FR) based on the total weight of the base composition;
c) 0.1 to 5.0 wt% of at least one additive (a) other than the Flame Retardant (FR), based on the total weight of the base composition; and
D) Optionally 0.1 to 3 wt% of a Polar Modified Polypropylene (PMP), preferably a maleic anhydride modified polypropylene, based on the total weight of the base composition.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2020/132320 WO2022110037A1 (en) | 2020-11-27 | 2020-11-27 | Glass fiber-reinforced composition with flame-retardancy and low warpage |
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| Publication Number | Publication Date |
|---|---|
| CN117999313A true CN117999313A (en) | 2024-05-07 |
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| CN202080107131.3A Pending CN117999313A (en) | 2020-11-27 | 2020-11-27 | Glass fiber reinforced composition with flame retardancy and low warpage |
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| CN (1) | CN117999313A (en) |
| WO (1) | WO2022110037A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2964654C (en) * | 2014-10-27 | 2019-03-12 | Borealis Ag | Heterophasic polypropylene with improved impact strength/stiffness balance, improved powder flowability, reduced emissions and low shrinkage |
| WO2019010672A1 (en) * | 2017-07-13 | 2019-01-17 | Borouge Compounding Shanghai Co., Ltd. | Glass fiber reinforced composition with low odor |
| EP3856829A1 (en) * | 2018-09-25 | 2021-08-04 | SABIC Global Technologies B.V. | Glass fiber filled flame retardant propylene composition |
| CN109486021A (en) * | 2018-12-28 | 2019-03-19 | 广东圆融新材料有限公司 | Fire-retardant PP material of fiberglass reinforced and preparation method thereof |
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