CN110914360B

CN110914360B - Low odor glass fiber reinforced composition

Info

Publication number: CN110914360B
Application number: CN201780092722.6A
Authority: CN
Inventors: 朱江磊; 潘甚颐; 陈世平
Original assignee: Bolu Plastic Shanghai Co ltd
Current assignee: Bolu Plastic Shanghai Co ltd
Priority date: 2017-07-13
Filing date: 2017-07-13
Publication date: 2021-10-29
Anticipated expiration: 2037-07-13
Also published as: CN110914360A; WO2019010672A1

Abstract

A glass fiber reinforced composition, an automotive article comprising the glass fiber reinforced composition, and a method of making the glass fiber reinforced composition, the composition comprising (based on the total weight of the composition): 50 to 80 wt% of a propylene homopolymer (H-PP) having a melt flow rate MFR determined according to ISO1133₂(230 ℃, 2.16kg) is 5 to 70g/10 min; 15 to 35 wt% of Glass Fiber (GF); optionally 3 to 10 wt% of an elastomeric Ethylene Copolymer (EC) comprising more than one monomer derived from C₄To C₈Comonomer units of alpha-olefins; 0.8 to 1.5 wt% of Polar Modified Polypropylene (PMP) as compatibilizer; 0.5 to 1.5 wt% of one or more antioxidants free of sulfur atoms; 0.2 to 0.5 wt% of a mold release agent; and 0.5 to 2 wt% of one or more additives.

Description

Low odor glass fiber reinforced composition

Technical Field

The present invention relates to glass fiber reinforced materials. In particular to a low-odor glass fiber reinforced composition, and application and a manufacturing method thereof.

Background

Polypropylene is a material used in various technical fields, in particular reinforced polypropylene has been linked in various fields that previously relied entirely on non-polymeric materials, in particular metals. One particular example of reinforced polypropylene is glass fiber reinforced polypropylene. Such materials enable tailoring of the properties of the composition by selection of the type of polypropylene, the amount of glass fibers, and sometimes the type of coupling agent used. Thus, nowadays glass fiber reinforced polypropylene is a well known material for applications requiring good mechanical properties (e.g. high stiffness and thermal stability). However, one disadvantage of commercially available glass fiber reinforcements is that they often release volatile organic small molecules (such as aldehydes and ketones as well as sulfur-containing compounds or maleic anhydride) resulting from the degradation of the base resin and/or several additives (such as antioxidants, mold release agents and compatibilizers) added to the composition. Thus, these glass fiber reinforcements generally do not meet the odor requirements set by the automotive industry for automotive interior parts.

Accordingly, there remains a need in the art to provide a glass fiber reinforced composition having low emissions of small volatile organic molecules and, therefore, low odor.

Disclosure of Invention

The finding of the present invention is that with a combination of specific propylene homopolymers and defined components, it is possible to obtain glass fiber reinforced compositions with low odor and acceptable mechanical properties of stiffness and impact strength.

Accordingly, the present invention relates to a glass fiber reinforced composition comprising:

(a) 50 to 80 wt%, based on the total weight of the composition, of a propylene homopolymer (H-PP) having a melt flow rate MFR determined according to ISO1133₂(230 ℃, 2.16kg) is 5 to 70g/10 min;

(b) 15 to 35 wt%, based on the total weight of the composition, of Glass Fibers (GF);

(c) optionally 3 to 10 wt%, based on the total weight of the composition, of an elastomeric Ethylene Copolymer (EC) comprising one or more monomers derived from C₄To C₈Comonomer units of alpha-olefins;

(d) 0.8 to 1.5 wt% of Polar Modified Polypropylene (PMP) based on the total weight of the composition as a compatibilizer;

(e) 0.5 to 1.5 wt% of one or more antioxidants containing no sulfur atom, based on the total weight of the composition;

(f) 0.2 to 0.5 weight percent of a mold release agent, based on the total weight of the composition; and

(g) from 0.5 to 2 weight percent, based on the total weight of the composition, of one or more additives.

According to one embodiment of the invention, the propylene homopolymer (H-PP) has a comonomer content of ≦ 2.0 wt% (based on the total weight of the propylene homopolymer) and/or the propylene homopolymer (H-PP) has a Xylene Cold Soluble (XCS) content of less than 2.5 wt% (based on the total weight of the propylene homopolymer).

According to another embodiment of the present invention, the propylene homopolymer (H-PP) is a mixture of at least two propylene homopolymers, preferably a mixture of two propylene homopolymers, more preferably the mixture comprises two propylene homopolymers and one propylene homopolymer (H-PP1) has a melt flow rate MFR measured according to ISO1133₂(230 ℃, 2.16kg) is from 5 to 30g/10min and the melt flow rate MFR, measured according to ISO1133, of another propylene homopolymer (H-PP2)₂(230 ℃, 2.16kg) is>30 to 70g/10 min.

According to yet another embodiment of the present invention, the mixture of two propylene homopolymers comprises the two propylene homopolymers in a weight ratio of from 5:1 to 1.2:1 (preferably from 3:1 to 1.5: 1).

According to one embodiment of the invention, the mixture of at least two propylene homopolymers comprises an alpha-nucleated propylene homopolymer, preferably the melt flow rate MFR measured according to ISO1133₂A propylene homopolymer (H-PP1) of 5 to 30g/10min (230 ℃, 2.16kg) was alpha-nucleated.

According to another embodiment of the present invention, the Glass Fibers (GF) have a fiber average diameter of 5 to 30 μm and/or an average fiber length of 0.1 to 20 mm.

According to yet another embodiment of the present invention, an elastomeric Ethylene Copolymer (EC) comprising one or more comonomer units in an amount of from 20 to 40 wt. -%, based on the total weight of the elastomeric Ethylene Copolymer (EC); and/or has a melt flow rate MFR of 1 to 40g/10min₂(190℃，2.16kg)。

According to yet another embodiment of the present invention, the Polar Modified Polypropylene (PMP) comprises groups derived from polar groups selected from: anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazolines (oxazolines) and epoxides, and also ionic compounds.

According to one embodiment of the present invention, the Polar Modified Polypropylene (PMP) is a propylene polymer grafted with maleic anhydride; preferably, the Polar Modified Polypropylene (PMP) is a propylene polymer grafted with maleic anhydride, and the propylene polymer grafted with maleic anhydride contains 100ppm or less of free maleic anhydride, based on the total weight of the Polar Modified Polypropylene (PMP).

According to another embodiment of the invention, the one or more antioxidants are selected from: phenolic Antioxidants (AO), phosphorus Antioxidants (AO) and mixtures thereof; preferably, the phenolic antioxidant is a Sterically Hindered Phenol (SHP), such as 1,3, 5-tris (3',5' -di-tert-butyl-4 ' -hydroxybenzyl) -isocyanurate or pentaerythritol tetrakis (3- (3',5' -di-tert-butyl-4-hydroxyphenyl) -propionate), and/or the phosphorus based antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.

According to yet another embodiment of the invention, the release agent is free of glycerol monostearate, more preferably free of alkane glycerol esters (alkone glycerol ester).

According to one embodiment of the invention, the release agent is silicone rubber.

According to yet another embodiment of the invention, the composition of the invention is completely free of glyceryl monostearate, more preferably completely free of alkylglyceride.

According to another aspect, the present invention relates to an automotive article comprising a glass fiber reinforced composition as described herein. Preferably, the automotive article is an automotive interior article.

According to another aspect, the present invention relates to a method of making a glass fiber reinforced composition as described herein, the method comprising the steps of:

the following ingredients were added to an extruder,

(g) 0.5 to 2 wt% of one or more additives, based on the total weight of the composition; and

and extruding the components to obtain the glass fiber reinforced composition.

The present invention will be defined in more detail below.

Detailed Description

Glass fiber reinforced composition

The glass fiber reinforced composition according to the invention comprises: propylene homopolymer (H-PP); glass Fibers (GF); optionally an elastomeric Ethylene Copolymer (EC) comprising more than one monomer derived from C₄To C₈Comonomer units of alpha-olefins; polar Modified Polypropylene (PMP) as a compatibilizer; one or more antioxidants free of sulfur atoms; a release agent; and one or more additives.

Thus, it is preferred that the glass fiber reinforced composition comprises:

(a) from 50 to 80% by weight, preferably from 60 to 75% by weight, based on the total weight of the composition, of a propylene homopolymer (H-PP) having a melt flow rate MFR determined according to ISO1133₂(230 ℃, 2.16kg) is 5 to 70g/10 min;

(b) 15 to 35 wt%, preferably 20 to 35 wt%, based on the total weight of the composition, of Glass Fibers (GF);

(c) optionally 3 to 10 wt%, preferably 5 to 10 wt%, of elastomeric ethylene, based on the total weight of the compositionA copolymer (EC) comprising more than one monomer derived from C₄To C₈Comonomer units of alpha-olefins;

(d) 0.8 to 1.5 wt%, preferably 0.8 to 1.2 wt%, based on the total weight of the composition, of a Polar Modified Polypropylene (PMP) as a compatibilizer;

(e) from 0.5 to 1.5% by weight, preferably from 1 to 1.5% by weight, based on the total weight of the composition, of one or more antioxidants which do not contain a sulfur atom;

(f) 0.2 to 0.5 wt%, preferably 0.2 to 0.4 wt%, based on the total weight of the composition, of a mold release agent;

(g) from 0.5 to 2% by weight, preferably from 0.8 to 1.2% by weight, based on the total weight of the composition, of one or more additives.

In a preferred embodiment, the glass fiber reinforced composition according to the invention comprises not more than 2 wt.% in total, preferably not more than 1 wt.%, of one or more other polymers, which are different from the polymers present in the fiber reinforced composition, i.e. different from propylene homopolymer (H-PP), optionally elastomeric Ethylene Copolymer (EC), Polar Modified Polypropylene (PMP) and mould release agent, based on the total weight of the glass fiber reinforced composition. Typically, such polymers, if present, are carrier polymers for the additives and therefore do not contribute to improving the properties of the claimed glass fiber reinforced composition.

Thus, in one embodiment, the glass fiber reinforced composition consists of propylene homopolymer (H-PP), glass fibers, Polar Modified Polypropylene (PMP), one or more antioxidants and mold release agents that do not contain sulfur atoms, and further other additives, which may contain a small amount of a polymeric carrier material. In an alternative embodiment, the glass fiber reinforced composition consists of propylene homopolymer (H-PP), glass fibers, elastomeric Ethylene Copolymer (EC), Polar Modified Polypropylene (PMP), one or more antioxidants and mold release agents that do not contain sulfur atoms, and additional other additives, which may contain a small amount of a polymeric carrier material. However, such polymeric carrier material is present in the glass fiber reinforced composition in an amount of no more than 2 wt.%, preferably no more than 1 wt.%, based on the total weight of the glass fiber reinforced composition.

The term "additive" also covers additives provided as a masterbatch containing a polymeric carrier material as described above. However, the term "additive" does not encompass nucleating agents, such as alpha-nucleating agents. Typical additives (a) are acid scavengers, colorants, pigments (e.g. carbon black), anti-scratch agents (anti-scratch agents), dispersants and carriers.

Furthermore, the glass fiber reinforced composition preferably contains an alpha-nucleating agent. Even more preferably, the present invention is free of beta-nucleating agents.

Thus, preferably the nucleating agent is selected from:

(i) mono-and poly-carboxylic acid salts, for example, sodium benzoate or aluminum tert-butylbenzoate; and

(ii) dibenzylidene sorbitol (e.g., 1,3:2,4 dibenzylidene sorbitol) and C₁-C₈Alkyl-substituted dibenzylidene sorbitol derivatives, such as methyl dibenzylidene sorbitol, ethyl dibenzylidene sorbitol or dimethyl dibenzylidene sorbitol (e.g. 1,3:2,4 di (methylbenzylidene) sorbitol); or substituted nonitol (nonitol) derivatives, e.g. 1,2, 3-trideoxy-4, 6:5, 7-bis-O- [ (4-propylphenyl) methylene]-nonitol; and

(iii) salts of diesters of phosphoric acid, for example sodium 2,2 '-methylenebis (4, 6-di-tert-butylphenyl) phosphate or aluminum hydroxy-bis [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) phosphate ]; and

(iv) polymers of vinyl cycloalkanes and polymers of vinyl alkanes; and

(v) mixtures thereof.

Preferably, the glass fiber reinforced composition comprises a vinylcycloalkane polymer and/or a vinylalkane polymer as alpha-nucleating agent. From the viewpoint of production of the propylene homopolymer (H-PP), it is preferable to include such a nucleating agent.

Such Additives and nucleating agents are generally commercially available and are described, for example, in "plastics Additives Handbook" by Hans Zweifel (2001, 5 th edition).

Preferably, the glass fiber reinforced composition has a melt flow rate MFR determined according to ISO1133₂(230 ℃, 2.16kg) is from 5 to 70g/10min, more preferably from 8 to 50g/10min, for example from 8 to 30g/10 min.

In a preferred embodiment, the glass fiber reinforced composition:

(a) a flexural modulus (flexural modulus) measured according to ISO 178 of at least 6,000MPa, more preferably at least 6,200MPa, even more preferably from 6,200 to 7,600MPa, for example from 6,500 to 7,400 MPa;

and/or

(b) A notched Charpy (Charpy) strength of at least 10kJ/m measured according to ISO 179(23 ℃)²More preferably 10.0 to 25.0kJ/m²And even more preferably from 12.0 to 20.0kJ/m²。

Furthermore, the present invention also relates to a process for preparing a glass fiber reinforced composition as described above and as detailed below, comprising the steps of:

the following ingredients were added to an extruder,

and extruding the components to obtain the glass fiber reinforced composition.

The glass fiber reinforced compositions according to the present invention may be compounded and pelletized using any of a 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 composition of the present invention, conventional compounding or blending equipment may be used, for example, a Banbury (Banbury) internal mixer, a two-roll rubber mill, a Buss (co-kneader), or a twin-screw extruder. The polymeric material recovered from the extruder/mixer is typically in the form of pellets. Preferably, these particles are then further processed, for example by injection moulding, to produce articles and products of the composition of the invention.

The individual components of the glass fiber reinforced composition are described in more detail below.

Propylene homopolymer

The fiber-reinforced composition must comprise a propylene homopolymer (H-PP). Preferably, the propylene homopolymer (H-PP) has a melt flow rate MFR determined according to ISO1133₂(230 ℃, 2.16kg) is 5 to 70g/10 min.

In one embodiment, it is particularly preferred that the fiber reinforced composition comprises several polymer components. In order to achieve a better balance of properties and processability, the propylene homopolymer preferably comprises a mixture of at least two different propylene homopolymers. One propylene homopolymer contributes particularly to the properties of the final product, while the other propylene homopolymer contributes to the processability of the composition.

In a preferred embodiment, the propylene homopolymer (H-PP) is thus a mixture of at least two propylene homopolymers.

It is understood that the expression "mixture of at least two propylene homopolymers" means that two or more of said propylene homopolymers are present in the composition according to the invention.

It is therefore noted that the mixture of at least two propylene homopolymers (H-PP) may be a mixture of two of said propylene homopolymers (H-PP). Alternatively, the mixture of at least two propylene homopolymers (H-PP) may be a mixture of three or more of said propylene homopolymers (H-PP), for example a mixture of three of said propylene homopolymers (H-PP).

In one embodiment of the present invention, the mixture of at least two propylene homopolymers (H-PP) comprises two propylene homopolymers.

If the mixture of at least two propylene homopolymers (H-PP) comprises two propylene homopolymers (H-PP), preferably the mixture comprises two propylene homopolymers in a weight ratio of 5:1 to 1.2: 1. For example, the mixture comprises two propylene homopolymers in a weight ratio of 3:1 to 1.5:1 or 2.5:1 to 1.8: 1. Most preferably, the mixture comprises two propylene homopolymers in a weight ratio of 2.5:1 to 2: 1.

The term "propylene homopolymer" as used in the present invention refers to a polypropylene consisting essentially of propylene units, i.e. comprising more than 98.0 wt%, preferably more than 99.0 wt%, even more preferably more than 99.7 wt%, even more preferably at least 99.8 wt% propylene units. In a preferred embodiment, only propylene units are detectable in the propylene homopolymer.

In one embodiment, the propylene homopolymer (H-PP), preferably a mixture of at least two propylene homopolymers, has a comonomer content of 2.0 wt.% or less per propylene homopolymer (H-PP), based on the total weight of the propylene homopolymers (H-PP). Preferably, the comonomer content of each propylene homopolymer in the propylene homopolymer (H-PP), preferably the mixture of at least two propylene homopolymers (H-PP), is less than 1.0 wt%, more preferably less than 0.3 wt%, most preferably less than 0.2 wt%, based on the total weight of the propylene homopolymers. In a preferred embodiment no comonomer units are detected for the propylene homopolymer (H-PP), preferably for each propylene homopolymer (H-PP) in the mixture of at least two propylene homopolymers.

Additionally or alternatively, each propylene homopolymer (H-PP), preferably a mixture of at least two propylene homopolymers (H-PP), has a Xylene Cold Soluble (XCS) content of less than 2.5 wt. -%, based on the total weight of the propylene homopolymers. For example, the propylene homopolymer (H-PP), preferably the mixture of at least two propylene homopolymers (H-PP), has a Xylene Cold Soluble (XCS) content of each propylene homopolymer of less than 2.2 wt. -%, e.g. in the range of 0.5 to 2.2 wt. -%, based on the total weight of the propylene homopolymers (H-PP).

Preferably, the propylene homopolymer (H-PP), preferably the mixture of at least two propylene homopolymers (H-PP), is free of glycerol monostearate, more preferably free of alkane glycerides.

Another requirement of the present invention is that each of the propylene homopolymers (H-PP), preferably of the at least two propylene homopolymers in a mixture of at least two propylene homopolymers (H-PP), has a melt flow rate MFR determined in accordance with ISO1133₂(230 ℃, 2.16kg) is 5 to 70g/10 min.

If the propylene homopolymer (H-PP) is a mixture of at least two propylene homopolymers (H-PP), preferably the melt flow rate of one of the propylene homopolymers (H-PP1) in the mixture of at least two propylene homopolymers is relatively low and the melt flow rate of the other propylene homopolymer (H-PP2) in the mixture of at least two propylene homopolymers is relatively high.

Good stiffness can be achieved due to the presence of a propylene homopolymer (H-PP1) with a relatively low melt flow rate.

Thus, if the mixture of at least two propylene homopolymers (H-PP) comprises two propylene homopolymers, preferably one propylene homopolymer (H-PP1) has a melt flow rate MFR determined according to ISO1133₂(230 ℃, 2.16kg) is from 5 to 30g/10min and the melt flow rate MFR, measured according to ISO1133, of another propylene homopolymer (H-PP2)₂(230 ℃, 2.16kg) is>30 to 70g/10 min.

Thus, preferably, the propylene homopolymer (H-PP1) having a relatively low melt flow rate has a melt flow rate MFR determined according to ISO1133₂(230 ℃, 2.16kg) is ≦ 30g/10min, such as 5 to 30g/10min, more preferably 5 to 20g/10min, even more preferably 5 to 15g/10min, such as 7 to 12g/10 min.

Preferably, the mixture of at least two propylene homopolymers comprises one alpha-nucleated propylene homopolymer. In one embodiment, a propylene homopolymer (H-PP1) having a relatively low melt flow rate is alpha-nucleated. It will therefore be appreciated that it is preferred to include a nucleating agent which may be present in the glass fibre reinforced composition in the preparation of a propylene homopolymer (H-PP1) having a relatively low melt flow rate.

Preferably, the nucleating agent which may be present in the propylene homopolymer having a relatively low melt flow rate is selected from:

(ii) dibenzylidene sorbitol (e.g. 1,3:2,4 dibenzylidene sorbitol) and C₁-C₈Alkyl-substituted dibenzylidene sorbitol derivatives, such as methyl dibenzylidene sorbitol, ethyl dibenzylidene sorbitol or dimethyl dibenzylidene sorbitol (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

(iv) polymers of vinyl cycloalkanes and polymers of vinyl alkanes; and

(v) mixtures thereof.

Preferably, the propylene homopolymer (H-PP1) having a relatively low melt flow rate contains a vinylcycloalkane polymer and/or a vinylalkane polymer as the α -nucleating agent.

More preferably, the vinylcycloalkane polymer and/or the vinylalkane polymer used as the alpha-nucleating agent is formed during polymerization of the propylene homopolymer. As a result, the propylene homopolymer produced has a better crystalline structure (including smaller crystal size and more uniform crystal dispersion) resulting in better mechanical properties of stiffness, strength and impact.

In particular, a ziegler-natta catalyst for the preparation of propylene homopolymers (H-PP1) is modified by polymerizing a vinyl compound in the presence of the catalyst system, wherein the vinyl compound has the following formula:

CH₂＝CH-CHR³R⁴

wherein R is³And R⁴Together form a five-or six-membered saturated, unsaturated or aromatic ring, or independently represent an alkyl group containing from 1 to 4 carbon atoms. The catalyst thus modified was used to prepare a propylene homopolymer (H-PP1) to achieve alpha-nucleation of the polymer (BNT technology), of the composition (Co) and thus of the whole moulded article.

As mentioned above, one embodiment of a process for propylene homopolymers (H-PP) is the loop phase process or loop-gas phase process, which is for example the process developed by Borealis and referred to as the Loop-gas phase process

Methods of the art, which are described, for example, in EP0887379A1 and WO 92/12182.

As mentioned above, preferably the melt flow rate of one propylene homopolymer (H-PP1) in the mixture of at least two propylene homopolymers (H-PP) is relatively low and the melt flow rate of the other propylene homopolymer (H-PP2) in the mixture of at least two propylene homopolymers (H-PP) is relatively high.

It will be appreciated that processability can be advantageously improved by the addition of a propylene homopolymer (H-PP2) having a relatively high melt flow rate.

Thus, if the mixture of at least two propylene homopolymers (H-PP) comprises two propylene homopolymers (H-PP), preferably the propylene homopolymer (H-PP2) has a melt flow rate MFR determined according to ISO1133₂(230 ℃, 2.16kg) is>30g/10min, e.g.>From 30 to 70g/10min, more preferably from 45 to 70g/10min, even more preferably from 50 to 70g/10min, for example from 55 to 70g/10 min.

Thus, it is preferred that the propylene homopolymer (H-PP2) and the propylene homopolymer (H-PP1) together satisfy the inequality (Ia), preferably the inequality (Ib), even more preferably the inequality (Ic), even more preferably the inequality (Id):

wherein the content of the first and second substances,

MFR (H-PP2) is the melt flow Rate MFR of Polypropylene (H-PP2)₂(230℃)[g/10min](ii) a And

MFR (H-PP1) is the melt flow Rate MFR of the propylene homopolymer (H-PP1)₂(230℃)[g/10min]。

Preferably, the weight ratio [ (H-PP2)/(H-PP1) ] of the propylene homopolymer (H-PP2) and the propylene homopolymer (H-PP1) is from 5:1 to 1.2: 1. For example, the weight ratio of propylene homopolymer (H-PP2) to propylene homopolymer (H-PP1) [ (H-PP2)/(H-PP1) ] is from 3:1 to 1.5:1 or from 2.5:1 to 1.8: 1. Most preferably, the weight ratio [ (H-PP2)/(H-PP1) ] of the propylene homopolymer (H-PP2) and the propylene homopolymer (H-PP1) is from 2.5:1 to 2: 1.

Preferably, the melt temperature T of the propylene homopolymer (H-PP2) is relatively high in melt flow rate_mFrom 150 to 165 ℃ for example from 155 to 160 ℃.

Glass Fiber (GF)

The composition of the present invention must contain Glass Fibers (GF). It is understood that Glass Fibers (GF) impart improved stiffness and strength to the compositions of the present invention.

In particular, the glass fibers are cut Glass Fibers (GF), also known as short fibers or chopped strands.

Preferably, the Glass Fibers (GF) have a fiber average diameter of 5 to 30 μm. More preferably, the Glass Fibers (GF) have a fiber average diameter of 5 to 25 μm, most preferably 7 to 20 μm.

For example, the Glass Fiber (GF) has a fiber average diameter of 9 to 17 μm. More preferably, the Glass Fibers (GF) have a fiber average diameter of 9 to 15 μm, most preferably 10 to 14 μm.

In one embodiment, the Glass Fibers (GF) have an average fiber length of 0.1 to 20mm, most preferably 0.5 to 10 mm.

The Glass Fibers (GF) suitable for use in the present invention may be surface treated with a so-called sizing agent (sizing agent).

Examples of sizing agents suitable for Glass Fibers (GF) include: the silane-based sizing agent, titanate-based sizing agent (titanium sizing agent), aluminum-based sizing agent, chromium-based sizing agent, zirconium-based sizing agent, and borane-based sizing agent are preferably the silane-based sizing agent or the titanate-based sizing agent, and more preferably the silane-based sizing agent. The amount of the sizing agent with respect to the Glass Fiber (GF) is within the common knowledge of those skilled in the art, and for example, the amount of the sizing agent may be 0.1 to 10 parts by weight with respect to 100 parts by weight of the Glass Fiber (GF).

In one embodiment, the Glass Fibers (GF) comprise a sizing agent. Preferably, the sizing agent is a silane-based sizing agent.

The surface treatment of the Glass Fibers (GF) with the sizing agent can be carried out by a known method, for example, dipping the fibers in a tank filled with the sizing agent, holding the fibers, and then drying the fibers in a hot air oven or with a hot roll or a hot plate.

Optional elastomeric Ethylene Copolymer (EC)

A further optional component of the glass fiber reinforced composition of the present invention is an elastomeric Ethylene Copolymer (EC).

Elastomeric Ethylene Copolymers (EC) may be added to the glass fiber reinforced composition according to the invention for improving impact strength.

It is to be understood that the elastomeric Ethylene Copolymer (EC) may be more than one elastomeric Ethylene Copolymer (EC), preferably the elastomeric Ethylene Copolymer (EC) is added in combination with a propylene homopolymer (H-PP) to the glass fiber reinforced composition.

Thus, the elastomeric Ethylene Copolymer (EC) may be an elastomeric Ethylene Copolymer (EC). Alternatively, the elastomeric Ethylene Copolymer (EC) is a mixture of two or more elastomeric Ethylene Copolymers (EC). For example, the elastomeric Ethylene Copolymer (EC) is a mixture of two or three elastomeric Ethylene Copolymers (ECs). Preferably, the elastomeric Ethylene Copolymer (EC) is an elastomeric Ethylene Copolymer (EC).

Elastomeric Ethylene Copolymers (EC) are ethylene copolymers comprising ethylene monomer units and one or more comonomer units selected from: c₄-C₈Alpha-olefins, preferably 1-butene, 1-hexene and 1-octene. In a more preferred embodiment, the one or more comonomers are selected from: 1-butene, 1-hexene and 1-octene, with 1-butene or 1-octene being most preferred as comonomer. Preferably, the elastomeric Ethylene Copolymer (EC) preferably comprises ethylene monomer units and one comonomer unit selected from: c₄-C₈Alpha-olefins, preferably 1-butene, 1-hexene and 1-octene, most preferably 1-butene.

The elastomeric Ethylene Copolymer (EC) preferably contains from 55.0 to 90.0 wt% of ethylene, preferably from 60.0 to 85.0 wt% of ethylene, more preferably from 60.0 to 80.0 wt% of ethylene, based on the total amount of the elastomeric polyolefin copolymer. The remainder was made up to 100.0% by weight of the constituent comonomer units.

Thus, the elastomeric Ethylene Copolymer (EC) comprises one or more comonomer units in an amount of from 10 to 45 wt% (preferably from 15 to 40 wt%, most preferably from 20 to 40 wt%) based on the total weight of the elastomeric Ethylene Copolymer (EC). The remainder was made up to 100.0 wt% constituting an ethylene unit.

In a preferred embodiment, the elastomeric Ethylene Copolymer (EC) has a total melt flow rate MFR determined according to ISO1133₂(190 ℃, 2.16kg) is 1 to 40g/10 min. More preferably, the total melt flow rate MFR of the elastomeric Ethylene Copolymer (EC)₂(190 ℃, 2.16kg) is 1 to 30g/10min, more preferably 1 to 20g/10min, most preferably 1 to 15g/10 min. For example, elastomers BThe total melt flow rate MFR of the olefin copolymer (EC) determined according to ISO1133₂(190 ℃, 2.16kg) is 1 to 10g/10 min.

Additionally or alternatively, the elastomeric Ethylene Copolymer (EC) has a glass transition temperature of from-70 ℃ to-30 ℃, more preferably from-70 ℃ to-45 ℃.

Elastomeric Ethylene Copolymers (EC) are known in the art, and in a preferred embodiment, the elastomeric Ethylene Copolymers (EC) are Tafmers belonging to the Mitsui well (Mitsui) respectively^TMAnd Engage of Dow^TMAnd (4) series.

Preferably, the amount of elastomeric Ethylene Copolymer (EC) in the glass fiber reinforced composition is relatively low compared to propylene homopolymer (H-PP).

For example, the weight ratio of propylene homopolymer (H-PP) to elastomeric Ethylene Copolymer (EC) [ H-PP/EC ] is from 30:1 to 2: 1. Preferably, the weight ratio [ H-PP/EC ] of propylene homopolymer (H-PP) to elastomeric Ethylene Copolymer (EC) is from 25:1 to 5: 1.

Polar Modified Polypropylene (PMP) as compatibilizer

In order to achieve an easier and more uniform dispersion of Glass Fibers (GF) in the polymer component, which functions as a matrix in the glass fiber reinforced polymer composition, the glass fiber reinforced polymer composition comprises a specific compatibilizer.

The compatibilizer according to the present invention is a specific Polar Modified Polypropylene (PMP).

Most preferred are modified alpha-olefin polymers, especially propylene homopolymers and propylene copolymers, for example copolymers of ethylene and propylene, or copolymers of ethylene and propylene with other alpha-olefins, because they are highly compatible with the polymers of the compositions of the present invention.

In terms of structure, it is preferred that the polar modified polypropylene is selected from: graft copolymers or block copolymers.

In this case, it is preferable that the polar modified polypropylene contains a group derived from a polar compound, particularly, the polar compound is selected from: anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazolines and epoxides, and also ionic compounds.

Specific examples of the polar compound are: unsaturated cyclic anhydrides and their aliphatic diesters and diacid derivatives. In particular, it may use maleic anhydride and a compound selected from: c₁-C₁₀Linear and branched dialkyl maleates, C₁-C₁₀Linear and branched dialkyl fumarates, itaconic anhydride, C₁-C₁₀Linear and branched dialkyl itaconates, maleic acid, fumaric acid, itaconic acid, and mixtures thereof.

Maleic anhydride grafted polypropylene is particularly preferred as compatibilizer.

The amount of groups derived from polar groups (e.g., maleic anhydride) in the modified polymer (e.g., modified polypropylene) is preferably from 0.1 to 5.0 wt%, more preferably from 0.2 to 5.0 wt%, most preferably from 0.3 to 4.0 wt%, for example from 0.4 to 3.0 wt%, based on the total weight of the polar modified polypropylene.

In one embodiment, the free amount of maleic anhydride of the compatibilizer (e.g., polar modified polypropylene) is less than 100ppm, preferably less than 80ppm, and most preferably less than 60ppm based on the total weight of the polar modified polypropylene.

Particularly preferably, the compatibilizer is a polar modified propylene copolymer or a polar modified propylene homopolymer, the former being particularly preferred.

In one embodiment, the compatibilizer is a polar modified (block) propylene copolymer containing polar groups as described above. In one embodiment, the compatibilizer is a (block) propylene copolymer grafted with maleic anhydride. Thus, in a particularly preferred embodiment, the compatibilizer is a (block) propylene ethylene copolymer grafted with maleic anhydride, more preferably wherein the ethylene content is from 1.0 to 20.0 wt%, more preferably from 3.0 to 18.0 wt%, and even more preferably from 5.0 to 15.0 wt%, based on the total amount of the block propylene ethylene copolymer.

The amount of groups derived from polar groups required in the polar modified (block) propylene copolymer or modified propylene homopolymer is preferably from 0.1 to 5.0 wt%, more preferably from 0.2 to 5.0 wt%, most preferably from 0.3 to 4.0 wt%, for example from 0.4 to 3.0 wt%, based on the total weight of the polar modified (block) propylene copolymer.

Melt flow Rate MFR of the compatibilizer measured according to ISO1133₂Preferred values (190 ℃, 2.1kg) are from 1.0 to 500.0g/10min, for example from 50.0 to 150.0g/10 min. For example, the melt flow rate MFR of the compatibilizer measured according to ISO1133₂(190 ℃, 2.1kg) is 70.0 to 130.0g/10min, for example 95.0 to 120.0g/10 min.

Polar modified polypropylene (i.e. compatibilizer) can be produced in a simple manner by reactive extrusion of the polymer, for example with maleic anhydride, in the presence of a free-radical generator (e.g. an organic peroxide), as disclosed for example in EP 0572028.

Thus, it is preferred that the Polar Modified Polypropylene (PMP) is a propylene block copolymer grafted with maleic anhydride.

To further reduce the amount of volatile organic small molecules and thus further reduce the amount of odorous molecules released from the final article, it is preferred that the Polar Modified Polypropylene (PMP) contains a small amount of a small polar compound that generates polar groups of the Polar Modified Polypropylene (PMP) when the Polar Modified Polypropylene (PMP) is prepared.

Therefore, it is preferable that the Polar Modified Polypropylene (PMP) contains 100ppm or less of free polar compounds based on the total weight of the Polar Modified Polypropylene (PMP).

In a particularly preferred embodiment, the Polar Modified Polypropylene (PMP) is a propylene polymer grafted with maleic anhydride and the propylene polymer grafted with maleic anhydride contains 100ppm or less of free maleic anhydride or free maleic acid, particularly preferably 80ppm or less of free maleic anhydride or free maleic acid, based on the total weight of the Polar Modified Polypropylene (PMP).

Polar Modified Polypropylene (PMP) is known in the art and is commercially available. One suitable example is FH118 from Ningbo energy, Inc. of New materials science and technology, Inc. of China.

In one embodiment, the fiber reinforced polymer composition comprises the Polar Modified Polypropylene (PMP) as described above as the only Polar Modified Polypropylene (PMP).

More than one antioxidant

As an additional essential component, the glass fiber reinforced composition comprises one or more antioxidants free of sulfur atoms. It will be appreciated that more than one antioxidant containing no sulphur atoms is particularly helpful in reducing the odour released from the article, since the amount of volatile gases (e.g. hydrogen sulphide) is significantly reduced.

Thus, it is understood that more than one antioxidant may be an antioxidant. Alternatively, the one or more antioxidants may be a mixture of two or more antioxidants. For example, the one or more antioxidants are a mixture of two or three or four antioxidants. Preferably, the one or more antioxidants are a mixture of three antioxidants.

For completeness, preferably, the one or more antioxidants do not contain more than one sulfur atom.

In one embodiment, the one or more antioxidants are selected from: phenolic Antioxidants (AO), phosphorus Antioxidants (AO), alkyl radical scavengers, aromatic amines, hindered amine stabilizers and mixtures thereof.

Preferably, the one or more antioxidants are selected from: phenolic Antioxidants (AO), phosphorus Antioxidants (AO) and mixtures thereof, which do not contain a sulfur atom.

Preferably, the one or more antioxidants are selected from the group consisting of phenolic Antioxidants (AO) which are Sterically Hindered Phenols (SHP). Such antioxidants are excellent H donors. The stability of the free radical form is determined by the steric hindrance of the substituents at the 2,6 positions of the phenol.

In the following, Sterically Hindered Phenols (SHP) are defined more precisely. The term "sterically hindered" according to the invention means that the hydroxyl group (HO-) of the Sterically Hindered Phenol (SHP) is surrounded by a sterically hindered alkyl residue.

Thus, the Sterically Hindered Phenol (SHP) preferably comprises a residue of formula (II):

wherein the content of the first and second substances,

R₁is in ortho-or meta-position to the hydroxy group, and R₁Is (CH)₃)₃C-、CH₃-or H, preferably (CH)₃)₃C-; and

A₁constituting the remainder of the Sterically Hindered Phenol (SHP) and preferably located para to the hydroxyl group.

Preferably, the Sterically Hindered Phenol (SHP) preferably comprises a residue of formula (IIa):

wherein the content of the first and second substances,

R₁is (CH)₃)₃C-、CH₃-or H, preferably (CH)₃)₃C-; and

A₁constituting the remainder of the Sterically Hindered Phenol (SHP).

Preferably A₁Para to the hydroxyl group.

Furthermore, the Sterically Hindered Phenol (SHP) should preferably exceed a specific molecular weight. Thus, the molecular weight of the Sterically Hindered Phenol (SHP) is preferably greater than 500 g/mol. On the other hand, the molecular weight should not be too high, i.e.should not be higher than 1300 g/mol. Preferably, the molecular weight is from 500 to 1300g/mol, more preferably from 700 to 1300 g/mol.

Furthermore, the Sterically Hindered Phenol (SHP) can also be defined by the amount of phenol residues, in particular by the amount of phenol residues represented by the formula (II) or (IIa). Thus, the Sterically Hindered Phenol (SHP) may comprise 1,2,3, 4 or more phenol residues, preferably 3, 4 or more phenol residues of formula (II) or (IIa).

Furthermore, Sterically Hindered Phenols (SHP) contain mainly only carbon atoms, hydrogen atoms and a small number of O atoms, which are mainly generated by the hydroxyl groups (HO-) of the phenol residues. However, the Sterically Hindered Phenol (SHP) may additionally contain small amounts of N atoms and/or P atoms. Preferably, the Sterically Hindered Phenol (SHP) consists only of C, H, O and N atoms, more preferably, the Sterically Hindered Phenol (SHP) consists only of C, H, O and optionally N.

Sterically Hindered Phenols (SHP) may have a relatively high molecular weight. High molecular weight is an indication of several phenolic residues. Thus, it is particularly preferred that the Sterically Hindered Phenol (SHP) has more than 3, in particular 3, phenol residues, for example as shown in formula (II) or (IIa).

In view of the above requirements, it is preferred that the Sterically Hindered Phenol (SHP) is selected from:

2, 6-di-tert-butyl-4-methylphenol (CAS number 128-37-0; molecular weight (M)220g/mol),

Pentaerythritol tetrakis (3- (3',5' -di-tert-butyl-4-hydroxyphenyl) propionate (CAS number 6683-19-8; M1178 g/mol),

Octadecyl 3- (3',5' -di-tert-butyl-4-hydroxyphenyl) propionate (CAS number 2082-79-3; M531 g/mol),

1,3, 5-trimethyl-2, 4, 6-tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (CAS number 1709-70-2; M775 g/mol),

Calcium bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonate) (CAS number 65140-91-2; M695 g/mol),

1,3, 5-tris (3',5' -di-tert-butyl-4 ' -hydroxybenzyl) -isocyanurate (CAS number 27676-62-6; M784 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 number 40601-76-1; M813 g/mol),

Ethylene glycol bis (3, 3-bis (3 '-tert-butyl-4' -hydroxyphenyl) butyrate) (CAS number 32509-66-3; M794 g/mol),

2,2' -methylene-bis- (6- (1-methyl-cyclohexyl) -p-cresol) (CAS No. 77-62-3; M637 g/mol),

3,3 '-bis (3, 5-di-tert-butyl-4-hydroxyphenyl) -N, N' -hexamethylenedipropionamide (CAS No. 23128-74-7; M637 g/mol),

2,5,7, 8-tetramethyl-2- (4',8',12' -trimethyltridecyl) -chroman-6-ol (CAS number 10191-41-0; M431 g/mol),

2, 2-ethylidenebis (4, 6-di-tert-butylphenol) (CAS number 35958-30-6; M439 g/mol),

1,1, 3-tris (2-methyl-4-hydroxy-5' -tert-butylphenyl) butane (CAS number 1843-03-4; M545 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 number 90498-90-1; M741 g/mol),

1, 6-hexanediyl-bis (3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl) propionate) (CAS number 35074-77-2; m639 g/mol),

2, 6-di-tert-butyl-4-nonylphenol (CAS number 4306-88-1; M280 g/mol),

4,4' -butylidenebis (6-tert-butyl-3-methylphenol) (CAS number 85-60-9; M383 g/mol),

2,2' -methylenebis (6-tert-butyl-4-methylphenol) (CAS number 119-47-1; M341 g/mol),

Triethylene glycol-bis- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (CAS number 36443-68-2; M587 g/mol),

Diethyl (3, 5-di-tert-butyl-4-hydroxybenzyl) phosphate (CAS number 976-56-7; M356 g/mol) and

4, 6-bis (octylthiomethyl) -o-cresol (CAS number 110553-27-0; M425 g/mol),

1,1, 3-Tris [ 2-methyl-4- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] -5-tert-butylphenyl ] butane (CAS number 180002-86-2; M1326 g/mol).

More preferably, the Sterically Hindered Phenol (SHP) is selected from:

Triethylene glycol bis- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (CAS number 36443-68-2; M587 g/mol) and

3, 5-bis (1, 1-dimethyl-ethyl) -4-hydroxy-phenylpropionic acid-C7-C9-branched and straight chain alkyl esters (CAS number 125643-61-0; Mw (399 g/mol).

Most preferably, the Sterically Hindered Phenol (SHP) is 1,3, 5-tris (3',5' -di-tert-butyl-4 ' -hydroxybenzyl) -isocyanurate (CAS number 27676-62-6; M784 g/mol) and/or pentaerythritol tetrakis (3- (3',5' -di-tert-butyl-4-hydroxyphenyl) propionate (CAS number 6683-19-8; M1178 g/mol).

In one embodiment, the Sterically Hindered Phenol (SHP) is 1,3, 5-tris (3',5' -di-tert-butyl-4 ' -hydroxybenzyl) -isocyanurate (CAS number 27676-62-6; m784 g/mol) or pentaerythrityl tetrakis (3- (3',5' -di-tert-butyl-4-hydroxyphenyl) propionate (CAS number 6683-19-8; m1178 g/mol) or, the Sterically Hindered Phenol (SHP) is 1,3, 5-tris (3',5' -di-tert-butyl-4 ' -hydroxybenzyl) -isocyanurate (CAS number 27676-62-6; m784 g/mol) and pentaerythrityl tetrakis (3- (3',5' -di-tert-butyl-4-hydroxyphenyl) propionate (CAS number 6683-19-8; m1178 g/mol).

Preferably, the Sterically Hindered Phenols (SHP) are 1,3, 5-tris (3',5' -di-tert-butyl-4 ' -hydroxybenzyl) -isocyanurate (CAS number 27676-62-6; M784 g/mol) and pentaerythritol tetrakis (3- (3',5' -di-tert-butyl-4-hydroxyphenyl) propionate (CAS number 6683-19-8; M1178 g/mol).

Additionally or alternatively, preferably the one or more antioxidants are selected from: a phosphorus Antioxidant (AO).

Preferably, the phosphorus-based Antioxidant (AO) exceeds a specific molecular weight. Therefore, the molecular weight of the phosphorus-based Antioxidant (AO) is preferably more than 400 g/mol. On the other hand, the molecular weight should not be too high, i.e.not higher than 1200 g/mol. The molecular weight is preferably from 500 to 1000g/mol, more preferably from 600 to 800 g/mol.

Suitable phosphorus-based Antioxidants (AO) are selected from:

tris (2, 4-di-tert-butylphenyl) phosphite (CAS number 31570-04-4; M647 g/mol),

Tetrakis (2, 4-di-tert-butylphenyl) -4,4' -biphenylene-diphosphonite (CAS number 119345-01-6; M991 g/mol),

Bis (2, 4-di-tert-butylphenyl) pentaerythrityl-diphosphite (CAS number 26741-53-7; M604 g/mol),

Bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythrityl-diphosphite (CAS number 80693-00-1; M633 g/mol),

Bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (CAS number 154862-43-8; M852 g/mol),

Bis (2-methyl-4, 6-bis (1, 1-dimethylethyl) phenyl) ethyl phosphite (CAS number 145650-60-8; M514 g/mol),

2,2',2 "-nitrilotriethyl-tris (3,3',5,5' -tetra-tert-butyl-1, 1' -biphenyl-2, 2' -diyl) phosphite) (CAS number 80410-33-9; m1465 g/mol),

6-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy) -2,4,8, 10-tetra-tert-butyldibenzo (d, t) (1.3.2) dioxaphosphepin (dioxaphosphepin) (CAS number 203255-81-6; m660 g/mol) and

tetrakis- (2, 4-di-tert-butyl-5-methyl-phenyl) -4,4' -biphenylene-bis-phosphonite (CAS number 47192-62-9; M1092 g/mol).

Most preferably, the phosphorus based Antioxidant (AO) is tris (2, 4-di-tert-butylphenyl) phosphite (CAS number 31570-04-4; M647 g/mol).

As noted above, the one or more antioxidants can be a mixture of two or more antioxidants.

For example, the one or more antioxidants, which is a mixture of two or more antioxidants, may be a mixture of one or more phenolic Antioxidants (AO) and one or more phosphorus-based Antioxidants (AO). This embodiment is particularly advantageous in order to achieve low odour.

Preferably, the mixture of two or more antioxidants is a mixture of two or more (e.g., two or three) phenolic Antioxidants (AO) and one or more (e.g., one or two) phosphorus-based Antioxidants (AO). More preferably, the mixture of two or more antioxidants is a mixture of two or more (e.g., two) phenolic Antioxidants (AO) and one phosphorus-based Antioxidant (AO).

If the mixture of two or more antioxidants is a mixture of two or more (e.g., two or three) phenolic antioxidants and one or more (e.g., one or two) phosphorus-based antioxidants, the weight ratio of phenolic antioxidants to phosphorus-based antioxidants is preferably from 10:1 to 1:1, more preferably from 7:1 to 2:1, and most preferably from 6:1 to 3: 1.

In one embodiment, the one or more antioxidants is a mixture of 1,3, 5-tris (3',5' -di-tert-butyl-4 ' -hydroxybenzyl) -isocyanurate, pentaerythritol tetrakis (3- (3',5' -di-tert-butyl-4-hydroxyphenyl) propionate, and tris (2, 4-di-tert-butylphenyl) phosphite.

For example, 1,3, 5-tris (3',5' -di-tert-butyl-4 ' -hydroxybenzyl) -isocyanurate, pentaerythritol tetrakis (3- (3',5' -di-tert-butyl-4-hydroxyphenyl) propionate, and tris (2, 4-di-tert-butylphenyl) phosphite are present in the composition in a weight ratio of about 3:2: 1.

As mentioned above, one or more antioxidants do not contain a sulfur atom, i.e., do not contain an antioxidant containing a sulfur atom. Therefore, it is preferred that the glass fiber reinforced composition also does not contain an antioxidant containing a sulfur atom. Thus, it is preferred that the one or more antioxidants and the glass fiber reinforced composition do not contain distearyl thiodipropionate, dilauryl thiodipropionate, bis (tridecyl) thiodipropionate, dimyristyl thiodipropionate, dioctadecyl disulfide, bis [ 2-methyl-4- (3-n-dodecylthiopropionyloxy) -5-tert-butylphenyl ] sulfide, and pentaerythritol-tetrakis- (3-laurylthiopropionate).

Release agent

Advantageously, the release agent is used to improve the processability of the glass fiber reinforced composition. It should be noted that the release agent may also be referred to as a slip agent.

Preferably, the release agent is preferably free of glycerol monostearate, more preferably free of alkane glycerides. This is advantageous for achieving low odor. In the process, alkane glycerides (e.g., glycerol monostearate) can be decomposed to aldehydes at elevated temperatures.

In view of this, the release agent is preferably silicone rubber. More preferably, the release agent is in the form of a particulate concentrate containing the reaction product of the ultrahigh molecular weight siloxane polymer reactively dispersed in the thermoplastic carrier. For example, the mold release agent is in the form of a particulate concentrate containing the reaction product of the ultrahigh molecular weight siloxane polymer reactively dispersed in the polypropylene homopolymer.

In one embodiment, the mold release agent consists of 50% propylene homopolymer having an MFR measured according to ISO1133 and 50% ultra-high molecular weight vinyl terminated (poly) dimethylsiloxane (PDMS)₂(230 ℃, 2.16kg) was 12g/10 min.

One example of a release agent that may be used is MB50-001 from Dow Corning, Inc., which is commercially available as a granular concentrate containing the reaction product of an ultra-high molecular weight siloxane polymer reactively dispersed in a polypropylene homopolymer.

Additive agent

The glass fiber reinforced compositions of the present invention also contain typical other additives used in, for example, the automotive industry, such as carbon black, other pigments, UV stabilizers, nucleating agents and antistatic agents, in amounts conventional in the art. Preferably, the glass fiber reinforced composition comprises carbon black.

The additives may be incorporated into the glass fiber reinforced composition by using a carrier polymer to ensure a more uniform distribution of the additives in the composition. Such carrier polymers for the additives do not contribute to improving the properties of the claimed glass fiber reinforced composition.

The carrier polymer may be present in the composition in an amount of no more than 2.0 wt%, preferably in an amount of no more than 1.5 wt%, more preferably in an amount of no more than 1.0 wt%, based on the total weight of the composition.

The carrier polymer is not limited to a specific polymer. The carrier polymer may be an ethylene homopolymer, and/or a copolymer of ethylene and an alpha-olefin comonomer (e.g. C)₃-C₈Alpha-olefin comonomer), and/or a propylene homopolymer, and/orFrom propylene and alpha-olefin comonomers (e.g. ethylene and/or C)₄-C₈Alpha-olefin comonomer). Preferably, the carrier polymer is a propylene homopolymer and/or a propylene copolymer, for example a propylene homopolymer.

Method and article

Furthermore, the present invention relates to a process for preparing a glass fiber reinforced composition, comprising the steps of:

the following ingredients were added to an extruder,

(c) optionally 3 to 10 wt%, based on the total weight of the composition, of an elastomeric Ethylene Copolymer (EC); the elastomeric Ethylene Copolymer (EC) comprises more than one monomer derived from C₄To C₈Comonomer units of alpha-olefins;

and extruding the components to obtain the glass fiber reinforced composition.

With regard to the components (a), (b), (c), (d), (e), (f) and (g) and the preferred embodiments provided in step (a), when defining the glass fiber reinforced composition of the present invention and its individual components, reference is made to the above definitions.

In view of the above, preferably, the glass fiber reinforced composition is preferably obtained by a process as described herein (i.e. a process for preparing a glass fiber reinforced composition) comprising the steps of:

the following ingredients were added to an extruder,

and extruding the components to obtain the glass fiber reinforced composition.

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

The composition of the glass fiber reinforced composition of the present invention can be used for producing molded articles, preferably injection molded articles, and foamed articles. Still more preferably for the production of automotive articles, in particular automotive interior and exterior articles, such as instrument carriers (instrument carriers), front end modules, hoods (shrouds), structural carriers (structural carriers), bumpers, side trims, step aids, body panels, spoilers, dashboards (dashboards), interiors and the like.

Accordingly, another aspect of the present invention relates to an automotive article comprising a glass fiber reinforced composition as defined herein.

The present invention will now be described in more detail by the examples provided below.

Examples

1. Defining/measuring method

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

The density was measured according to ISO 1183-. Sample preparation was carried out by compression molding according to ISO 1872-2: 2007.

Melting temperature T_mThe measurements were carried out according to ISO 11357-3.

Glass transition temperature T_gMeasured by dynamic mechanical analysis according to ISO 6721-7. Measurements were made in torsional mode while under compression.

MFR₂(230 ℃) according to ISO1133 (230 ℃, 2.16kg load) were measured.

MFR₂(190 ℃) according to ISO1133 (190 ℃, 2.16kg load) were measured.

Xylene cold soluble (XCS, wt.%) was determined according to ISO 16152 (first edition; 2005-07-01) at 25 ℃;

comonomer content quantification by FTIR spectroscopy

By quantification in a manner well known in the art¹³Comonomer content was determined by quantitative fourier transform infrared spectroscopy (FTIR) after basic partitioning for C Nuclear Magnetic Resonance (NMR) spectral calibration. The film was pressed to a thickness of 100 to 500 μm and the spectrum was recorded in transmission mode.

Specifically, the probe is used at 720-722cm^-1And 730 and 733cm^-1The ethylene content of the polypropylene-co-ethylene copolymer was determined from the baseline corrected peak area of the quantitative band found. Quantitative results were obtained based on the reference film thickness.

Tensile strength was measured according to ISO 527-2 (crosshead speed 50 mm/min; 23 ℃) using injection moulded specimens (dog bone shape, 4mm thickness) as described in EN ISO 1873-2.

Elongation at break was measured according to ISO 527-2 (crosshead speed 50 mm/min; 23 ℃) using injection moulded specimens (dog bone shape, 4mm thickness) as described in EN ISO 1873-2.

Flexural modulus was measured according to ISO 178.

Charpy (Charpy) notched impact strength was determined according to ISO 179/1eA at 23 ℃. The impact strength was determined by using 80X 10X 4mm prepared according to EN ISO19069-2³The injection molded specimens of (1) were subjected to the measurement.

Charpy (Charpy) unnotched impact strength according to ISO 179/1eU at 23 ℃ by using 80X 10X 4mm prepared according to EN ISO19069-2³Was used to perform the measurement.

The average fiber diameter was determined according to ISO 1888:2006(E), method B, 1000 times microscope magnification.

The ash content is measured according to ISO 3451-1 (1997).

The aging characteristics were measured by heating in an oven at a temperature of 150 ℃ for 1000 hours.

And (3) odor test: PV3900 according to the public automobile (Volkswagen) (Germany)

Test setup

a) Heating chamber with air circulation according to DIN 50011-12, accuracy class 2;

b) 1 or 3 liter glass test cups with an odorless seal and a lid; the cup, seal and lid must be cleaned prior to use.

50+/-5g of the sample was placed in a1 liter glass and then heated in a heating chamber at 80+/-2 ℃ for 2 hours. The sample was removed from the heating chamber, conditioned at room temperature until it cooled to 65 ℃, and then tested.

Analysis of

The odor rating of all samples was done by the scale given in the table below. The ratings are given from 1 to 6, with half the rating possible.

Table 1: odor rating

Grade	Rating
		1	Is imperceptible
2	Is perceptible; is not disturbed by sleeping
		3	Can be clearly perceived; but not yet trapped
4	Suffer from troubles
		5	Is seriously troubled
6	Cannot tolerate

The results are given as mean values, rounded off on a half scale.

2. Examples of the embodiments

The following inventive examples IE1 and IE2 were prepared by compounding with a co-rotating twin screw extruder having an L/D ratio of 44:1 and a D of 35 mm. The temperature profiles used for inventive examples IE1 and IE2 and further process characteristics are listed in tables 3a and 3 b.

Table 2: summary of the compositions of examples IE1 and IE2 of the present invention

		IE1	IE2
				H-PP1	[wt％]	46.5	49.5
H-PP2	[wt％]	20.0	10.0
				EC	[wt％]	--	7.0
Compatibilizer	[wt％]	1.0	1.0
				Glass fiber	[wt％]	30.0	30.0
AO 1	[wt％]	0.6	0.6
				AO 2	[wt％]	0.2	0.2
AO 3	[wt％]	0.4	0.4
				Release agent	[wt％]	0.3	0.3
Additive agent^*	[wt％]	1.0	1.0

Carbon black included in a propylene homopolymer carrier.

H-PP1 is a commercially available propylene homopolymer HJ311A1 from Boroughe Pte Ltd, melt flow Rate MFR₂60g/10min (230 ℃) without Glycerol Monostearate (GMS);

H-PP2 is a commercially available propylene homopolymer HD915CF from Nordic chemical (Borealis AG), melt flow Rate MFR₂(230 ℃) 8g/10min, a melting temperature of 168 ℃, prepared by the BNT technique of Borealis, free of Glycerol Monostearate (GMS);

the compatibilizer is a copolymer of propylene and ethylene grafted by maleic anhydride, which is FH118 of New optical Material science and technology Co., Ltd, Ningbo, China; free maleic anhydride level 50 ppm;

the glass fiber is a glass fiber T438H sold in Taishan mountain in Shandong, China, and the average diameter is 10-14 μm;

AO 1 is the commercially available antioxidant from BASF "Irganox 3114", a sterically hindered phenolic antioxidant, 1,3, 5-tris (3',5' -di-tert-butyl-4 ' -hydroxybenzyl) -isocyanurate;

AO 2 is BASF commercially available antioxidant "Irgafos 168", a phosphorus antioxidant, tris (2, 4-di-tert-butylphenyl) phosphite;

AO 3 is the commercially available antioxidant from BASF "Irganox 1010", a sterically hindered phenolic antioxidant, pentaerythritol tetrakis (3- (3',5' -di-tert-butyl-4-hydroxyphenyl) -propionate;

the mold release agent was a commercially available blend of 50 wt% of an ultra-high molecular weight siloxane polymer with 50 wt% of a polypropylene homopolymer carrier, "MB 50-001," by Dow Corning, and was free of Glycerol Monostearate (GMS);

EC is a commercially available elastomeric ethylene/butene copolymer "TafmerDF 640", MFR, from Mitsui chemical Co., Ltd₂(190 ℃, 2.16kg) was 4g/10min, and the glass transition temperature was>-70 ℃ and a density of 0.864g/cm³。

Table 3 a: temperature (. degree. C.) and other processing conditions in various zones of the twin screw extruder of inventive example IE1

Table 3 b: temperature (. degree. C.) and other processing conditions in various zones of the twin screw extruder of inventive example IE2

The mechanical and odor properties of inventive examples IE1 and IE2 and of comparative example CE are shown in table 4 below. Comparative example CE includes: polypropylene homopolymer (said polypropylene homopolymer containing 0.3% by weight of Glycerol Monostearate (GMS)), 30% by weight of glass fibres, the sulphur-based antioxidant "distearyl thiodipropionate (DSTDP)", and, as compatibilizer, a propylene polymer grafted with maleic anhydride (which contains 150ppm of free maleic anhydride).

Table 4: mechanical and odor Properties

The glass fiber reinforced composition of the present invention has a significantly improved odor, high stiffness and improved toughness. It meets the usual odor requirements for automotive interior articles and has a high melt flow rate suitable for use in the improved process. It can therefore also be used to produce thin-walled motor vehicle parts of low odour and high strength.

Claims

1. A glass fiber reinforced composition comprising:

(a) 50 to 80 wt.%, based on the total weight of the composition, of a mixture of two propylene homopolymers (H-PP) having a melt flow rate MFR, measured according to ISO1133 at 230 ℃, 2.16kg₂5 to 70g/10 min;

(g) 0.5 to 2 wt% of one or more additives, based on the total weight of the composition;

wherein the composition and the release agent do not contain an alkane glyceride.

2. The glass fiber reinforced composition according to claim 1, wherein the mixture of two propylene homopolymers (H-PP) has:

a) a comonomer content equal to or lower than 2.0 wt%, based on the total weight of the propylene homopolymer (H-PP); and/or

b) The Xylene Cold Soluble (XCS) content is below 2.5 wt. -%, based on the total weight of the propylene homopolymer (H-PP).

3. The glass fiber reinforced composition according to claim 1, wherein a propylene homopolymer (H-PP1) has a melt flow rate MFR measured according to ISO1133 at 230 ℃, 2.16kg₂5 to 30g/10min, another propylene homopolymer (H-PP2) having a melt flow rate MFR, measured according to ISO1133 at 230 ℃, 2.16kg₂Is higher than 30 to 70g/10 min.

4. The glass fiber reinforced composition of claim 1, wherein the mixture of two propylene homopolymers comprises the two propylene homopolymers in a weight ratio of 5:1 to 1.2: 1.

5. The glass fiber reinforced composition of claim 4, wherein the mixture of two propylene homopolymers comprises the two propylene homopolymers in a weight ratio of 3:1 to 1.5: 1.

6. The glass fiber reinforced composition of claim 1, wherein the blend of two propylene homopolymers comprises an alpha-nucleated propylene homopolymer.

7. The glass fiber reinforced composition of claim 3, wherein the rootMelt flow Rate MFR determined according to ISO1133 at 230 ℃ and 2.16kg₂Propylene homopolymers (H-PP1) of 5 to 30g/10min were alpha-nucleated.

8. The glass fiber reinforced composition according to claim 1 or 2, wherein the Glass Fibers (GF) have a fiber average diameter of 5 to 30 μm and/or an average fiber length of 0.1 to 20 mm.

9. The glass fiber reinforced composition according to claim 1 or 2, wherein the elastomeric Ethylene Copolymer (EC):

a) comprising one or more comonomer units in an amount of from 20 to 40 wt. -%, based on the total weight of the elastomeric Ethylene Copolymer (EC); and/or

b) Having a melt flow rate MFR at 190 ℃ of 2.16kg of 1 to 40g/10min₂。

10. The glass fiber reinforced composition according to claim 1 or 2, wherein the Polar Modified Polypropylene (PMP) comprises groups derived from polar groups selected from: carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazolines and epoxides, and ionic compounds.

11. The glass fiber reinforced composition of claim 10, wherein the carboxylic acid derivative is an anhydride.

12. The glass fiber reinforced composition according to claim 1 or 2, wherein the Polar Modified Polypropylene (PMP) is a propylene polymer grafted with maleic anhydride.

13. The glass fiber reinforced composition of claim 12, wherein the Polar Modified Polypropylene (PMP) is a propylene polymer grafted with maleic anhydride, and the propylene polymer grafted with maleic anhydride contains 100ppm or less of free maleic anhydride, based on the total weight of the Polar Modified Polypropylene (PMP).

14. The glass fiber reinforced composition of claim 1 or 2, wherein the one or more antioxidants are selected from the group consisting of: phenolic Antioxidants (AO), phosphorus Antioxidants (AO) and mixtures thereof.

15. The glass fiber reinforced composition of claim 14, wherein the phenolic antioxidant is a Sterically Hindered Phenol (SHP), and/or the phosphorous antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.

16. The glass fiber reinforced composition of claim 15, wherein the sterically hindered phenol is 1,3, 5-tris (3',5' -di-tert-butyl-4 ' -hydroxybenzyl) -isocyanurate or pentaerythritol tetrakis (3- (3',5' -di-tert-butyl-4-hydroxyphenyl) -propionate).

17. The glass fiber reinforced composition of claim 1 or 2, wherein the release agent is a silicone rubber.

18. An automotive article comprising the glass fiber reinforced composition of claim 1 or 2.

19. The automotive article of claim 18, wherein the automotive article is an automotive interior article.

20. A method of making the glass fiber reinforced composition of claim 1 or 2, comprising the steps of:

the following ingredients were added to an extruder,

and extruding the components to obtain the glass fiber reinforced composition.