EP4623028A1 - Glass fiber reinforced polymer composition - Google Patents
Glass fiber reinforced polymer compositionInfo
- Publication number
- EP4623028A1 EP4623028A1 EP23806293.9A EP23806293A EP4623028A1 EP 4623028 A1 EP4623028 A1 EP 4623028A1 EP 23806293 A EP23806293 A EP 23806293A EP 4623028 A1 EP4623028 A1 EP 4623028A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer composition
- range
- polypropylene
- glass fibers
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Definitions
- the invention relates to a glass fiber reinforced polymer composition, to a process for obtaining such composition, and to an article comprising such composition.
- WO2011042364A1 discloses a fiber reinforced composition comprising a heterophasic propylene copolymer, a propylene homopolymer and/or a propylene copolymer, and fibers, wherein the propylene copolymer comprises not more than 2.0 wt.-% C2 to C10 a-olefins other than propylene, the propylene homopolymer and the propylene copolymer have a melt flow rate MFR2 (230 °C) of at least 500 g/10min, and the composition has a melt flow rate MFR2 (230 °C) of at least 10 g/10min.
- the fiber reinforced composition has increased flowability without sacrificing mechanical performance.
- polypropylene wherein the polypropylene has a melt enthalpy in the first heating circle in the range of 80 to 95 J/g, wherein the amount of the polypropylene is in the range from 60 to 90 wt% based on the total amount of the polymer composition;
- the amount of the glass fibers is in the range from 10 to 35 wt% based on the total amount of the polymer composition.
- the polypropylene according to the invention may be a propylene random copolymer, or a heterophasic propylene copolymer or a propylene homopolymer, preferably the polypropylene is a polypropylene homopolymer.
- the polypropylene preferably has a melt flow rate (MFR) in the range from 50 to 150 g/10min, preferably from 60 to 120 g/10min as measured according to ISO 1133-1:2011 (2.16Kg, 230°C)
- the polypropylene according to the invention has a melt enthalpy in the first heating circle in the range of 80 to 95 J/g, preferably in the range from 85 to 90 J/g.
- the melt enthalpy in the first heating circle, the melt enthalpy in the second heating circle and the crystallization temperature is determined in a differential scanning calorimetry (DSC) with the setting of:
- the polypropylene having a melt enthalpy in the first heating circle in the preferred range and/or a melt enthalpy in the second heating circle in the preferred range and/or a crystallization temperature in the preferred range leads to even further improvement of stiffness.
- the glass fiber comprises at most 2 wt%, preferably in the range from 0.10 to 1wt% of a sizing based on the weight of the glass fiber.
- the amount of sizing can be determined using ISO 1887:2014.
- sizing compositions include solvent-based compositions, such as an organic material dissolved in aqueous solutions or dispersed in water and melt- or radiation cure-based compositions.
- solvent-based compositions such as an organic material dissolved in aqueous solutions or dispersed in water and melt- or radiation cure-based compositions.
- the sizing composition is an aqueous sizing composition.
- the coupling agents are generally used to improve the adhesion between the matrix thermoplastic polymer and the fibre reinforcements.
- Suitable examples of coupling agents known in the art as being used for the glass fibres include organofunctional silanes.
- the coupling agent which has been added to the sizing composition is an aminosilane, such as aminomethyl- trimethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyl- trimethoxysilane, gamma-aminopropyl-trimethoxysilane gamma-methylaminopropyl- trimethoxysilane, delta-aminobutyl-triethoxysilane, 1 ,4-aminophenyl- trimethoxysilane.
- the sizing composition contains an aminosilane to enable a good adhesion to the thermoplastic matrix.
- the sizing composition may further comprise any other additional components known to the person skilled in the art to be suitable for sizing compositions. Suitable examples include but are not limited to lubricants (used to prevent damage to the strands by abrasion) antistatic agents, crosslinking agents, plasticizers, surfactants, nucleation agents, antioxidants, pigments as well as mixtures thereof.
- the glass fibers preferably have an average length in the range from 0.1 to 1.5 mm, preferably from 0.2 to 1.2 mm, more preferably in the range from 0.2 to 1.0 mm.
- the length of the dispersed fibers reduce during the preparation of the polymer composition according to the invention, in avoidance of any confusion, the length of the glass fibers in the present invention refers to the length of the glass fibers in the polymer composition.
- the average length of the glass fibers can for example be obtained by incinerating the polymer composition, then the glass fibers are manually dispersed on a scanner using brushes and tweezers and a digital image is generated.
- a fully automated image processing algorithm detects all glass fibers without manual input by the operator. 350,000 to 750,000 fiber length are detected to calculate the average fiber length.
- the polymer composition according to the invention comprises
- polypropylene wherein the polypropylene has a melt enthalpy in the first heating circle in the range of 80 to 95 J/g, wherein the amount of the polypropylene is in the range from 60 to 90 wt%, preferably in the range from 65 to 75 wt% based on the total amount of the polymer composition;
- the polymer composition according to the invention preferably has a density in the range from 1.10 to 1.20 g/cm3 as measured according to ISO 1183-1 :2019.
- the polymer composition further comprise conventional additives, e.g. anti-oxidant, nucleating agent, UV stabilizer, etc.
- additives e.g. anti-oxidant, nucleating agent, UV stabilizer, etc.
- the amount of the additives is at most 5 wt%, preferably at most 3 wt% based on the total amount of the polymer composition.
- the present invention further relates to a process for the preparation of the polymer composition according to the invention comprising the sequential steps of:
- the present invention further relates to an article comprising the polymer composition according to the invention, wherein the amount of the polymer composition is in the range from 95 to 100 wt% based on the total amount of the article.
- the article is an automotive part, preferably an automotive exterior part.
- PP1 is a homopolymer commercially available from SABIC with grade name PP 595A. PP1 has an MFR of 47 dg/min as measured according to ISO 1133-1:2011 (2.16Kg, 230°C).
- SGF 1 refers to glass fibers with grade name T-480 commercially available from NEG having an average diameter of 13 pm.
- SGF 2 1 refers to glass fibers with grade name T-480H commercially available from NEG having an average diameter of 10 pm
- Additive package consists of 50 wt% color masterbatch, 40 wt% anti-oxidant and 10 wt% antiscratch agent basing on the total weight of the additive package.
- Examples were prepared by compounding the compositions in Table 1 in a twin screw extruder then injection molded in to the samples for measurements.
- DSC was measured in accordance to the following protocol: Sample is sealed in Tzero hermetic aluminum pan (40pl);
- Heat program on the DSC machine is set as: At the speed of 10 °C/min, o First heating circle:
- the thermal properties of PP1 and PP2 are shown in Table 1.
- Tm refers to melting temperature
- dHm refers to melt enthalpy
- Tc refers to crystallization temperature
- dHc refers to crystallization enthalpy
- the footnotes 1 and 2 refer to the heat circle.
- the thermal properties of PP1 and PP2 are shown in Table 1
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a glass fiber reinforced polymer composition with superior stiffness. The invention further relates to a process for obtaining such composition, and to an article comprising such composition.
Description
Glass fiber reinforced polymer composition
The invention relates to a glass fiber reinforced polymer composition, to a process for obtaining such composition, and to an article comprising such composition.
Glass fiber reinforced polymer composition is widely used in automotive industry thanks to its processability and mechanical performance, for example, WO2011042364A1 discloses a fiber reinforced composition comprising a heterophasic propylene copolymer, a propylene homopolymer and/or a propylene copolymer, and fibers, wherein the propylene copolymer comprises not more than 2.0 wt.-% C2 to C10 a-olefins other than propylene, the propylene homopolymer and the propylene copolymer have a melt flow rate MFR2 (230 °C) of at least 500 g/10min, and the composition has a melt flow rate MFR2 (230 °C) of at least 10 g/10min. The fiber reinforced composition has increased flowability without sacrificing mechanical performance.
With the development of automotive industry, there is more desire on lightweight automotive part, hence there is a need to have a glass fiber reinforced polymer composition with superior stiffness without a too high density.
This need is satisfied by a polymer composition comprising
- a polypropylene wherein the polypropylene has a melt enthalpy in the first heating circle in the range of 80 to 95 J/g, wherein the amount of the polypropylene is in the range from 60 to 90 wt% based on the total amount of the polymer composition;
- glass fibers wherein the amount of the glass fibers is in the range from 10 to 35 wt% based on the total amount of the polymer composition.
Polypropylene
The polypropylene according to the invention may be a propylene random copolymer, or a heterophasic propylene copolymer or a propylene homopolymer, preferably the polypropylene is a polypropylene homopolymer.
The polypropylene preferably has a melt flow rate (MFR) in the range from 50 to 150 g/10min, preferably from 60 to 120 g/10min as measured according to ISO 1133-1:2011 (2.16Kg, 230°C)
The polypropylene according to the invention has a melt enthalpy in the first heating circle in the range of 80 to 95 J/g, preferably in the range from 85 to 90 J/g.
The polypropylene according to the invention preferably has a melt enthalpy in the second heating circle in the range from 90 to 110 J/g, preferably from 95 to 105 J/g.
The polypropylene according to the invention preferably has a crystallization temperature in the range from 125 to 130 °C.
The melt enthalpy in the first heating circle, the melt enthalpy in the second heating circle and the crystallization temperature is determined in a differential scanning calorimetry (DSC) with the setting of:
At the speed of 10 °C/min, o First heating circle:
■ Cooling to -50 °C, isotherm for 1min;
■ Heating to 230 °C, isotherm for 1min (During heating, the melt enthalpy in the first heating circle is determined); o Second heating circle
■ Cooling to -50 °C, isotherm for 1min (During cooling, the crystallization temperature is determined);;
■ Heating to 230 °C, isotherm for 1min (During heating, the melt enthalpy in the second heating circle is determined).
It was surprisingly found that the polypropylene having a melt enthalpy in the first heating circle in the preferred range and/or a melt enthalpy in the second heating circle in the preferred range and/or a crystallization temperature in the preferred range leads to even further improvement of stiffness.
The polypropylene according to the invention can be prepared in conventional polymerization technology, e.g. Unipol or Spheripol technology.
The catalyst to produce polypropylene is also know in the art, for example Ziegler-Natta catalyst, metallocene catalyst. Preferably the catalyst used to produce the polypropylene of the
present invention is a Ziegler-Natta catalyst which is free of phthalate, for example the catalyst comprises compounds of a transition metal of Group 4 to 6 of IIIPAC, a Group 2 metal compound and an internal donor wherein said internal donor is a compound selected from a list consisting of substituted malonates, maleates, succinates, glutarates, cyclohexene-1 ,2- dicarboxylates, benzoates and derivatives and/or mixtures thereof, preferably the internal donor is a citraconate.
Glass fibers
The glass fibers are widely used to improve the mechanical properties of polypropylene. Glass fibers typically are circular in cross section. Preferably the glass fibers have an average diameter in the range from 11 to 16 pm, more preferably from 12 to 14 pm. It was surprisingly found that the glass fibers having an average diameter in the preferred range leads to even further improvement of stiffness.
In a preferred embodiment, the glass fiber comprises at most 2 wt%, preferably in the range from 0.10 to 1wt% of a sizing based on the weight of the glass fiber. The amount of sizing can be determined using ISO 1887:2014.
Suitable examples of sizing compositions include solvent-based compositions, such as an organic material dissolved in aqueous solutions or dispersed in water and melt- or radiation cure-based compositions. Preferably, the sizing composition is an aqueous sizing composition.
As described in the art, e.g. in documents EP1460166A1, EP0206189A1 or US4338233, the aqueous sizing composition may include coupling agents and other additional components.
The coupling agents are generally used to improve the adhesion between the matrix thermoplastic polymer and the fibre reinforcements. Suitable examples of coupling agents known in the art as being used for the glass fibres include organofunctional silanes. More particularly, the coupling agent which has been added to the sizing composition is an aminosilane, such as aminomethyl- trimethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyl- trimethoxysilane, gamma-aminopropyl-trimethoxysilane gamma-methylaminopropyl- trimethoxysilane, delta-aminobutyl-triethoxysilane, 1 ,4-aminophenyl- trimethoxysilane. Preferably, the sizing composition contains an aminosilane to enable a good adhesion to the thermoplastic matrix. The sizing composition may further comprise any other additional
components known to the person skilled in the art to be suitable for sizing compositions. Suitable examples include but are not limited to lubricants (used to prevent damage to the strands by abrasion) antistatic agents, crosslinking agents, plasticizers, surfactants, nucleation agents, antioxidants, pigments as well as mixtures thereof.
The glass fibers preferably have an average length in the range from 0.1 to 1.5 mm, preferably from 0.2 to 1.2 mm, more preferably in the range from 0.2 to 1.0 mm. The length of the dispersed fibers reduce during the preparation of the polymer composition according to the invention, in avoidance of any confusion, the length of the glass fibers in the present invention refers to the length of the glass fibers in the polymer composition.
The average length of the glass fibers can for example be obtained by incinerating the polymer composition, then the glass fibers are manually dispersed on a scanner using brushes and tweezers and a digital image is generated. A fully automated image processing algorithm detects all glass fibers without manual input by the operator. 350,000 to 750,000 fiber length are detected to calculate the average fiber length.
Polymer composition
The polymer composition according to the invention comprises
- a polypropylene wherein the polypropylene has a melt enthalpy in the first heating circle in the range of 80 to 95 J/g, wherein the amount of the polypropylene is in the range from 60 to 90 wt%, preferably in the range from 65 to 75 wt% based on the total amount of the polymer composition;
- glass fibers wherein the amount of the glass fibers is in the range from 10 to 35 wt%, preferably in the range of 25 to 34 wt% based on the total amount of the polymer composition.
The polymer composition according to the invention preferably has a density in the range from 1.10 to 1.20 g/cm3 as measured according to ISO 1183-1 :2019.
Optionally, the polymer composition further comprise conventional additives, e.g. anti-oxidant, nucleating agent, UV stabilizer, etc. Preferably the amount of the additives is at most 5 wt%, preferably at most 3 wt% based on the total amount of the polymer composition.
The present invention further relates to a process for the preparation of the polymer composition according to the invention comprising the sequential steps of:
- Providing the polypropylene and glass fibers according to the invention;
- Mixing the polypropylene and the glass fibers in an extruder.
The present invention further relates to an article comprising the polymer composition according to the invention, wherein the amount of the polymer composition is in the range from 95 to 100 wt% based on the total amount of the article. Preferably the article is an automotive part, preferably an automotive exterior part.
Material and sample preparation
PP1 is a homopolymer commercially available from SABIC with grade name PP 595A. PP1 has an MFR of 47 dg/min as measured according to ISO 1133-1:2011 (2.16Kg, 230°C).
PP2 is a homopolymer commercially available from Braskem with grade name F1000HC. PP2 is a polypropylene according to the invention. PP2 has an MFR of 115 dg/min as measured according to ISO 1133-1:2011 (2.16Kg, 230°C).
SGF 1 refers to glass fibers with grade name T-480 commercially available from NEG having an average diameter of 13 pm.
SGF 2 1 refers to glass fibers with grade name T-480H commercially available from NEG having an average diameter of 10 pm
Additive package consists of 50 wt% color masterbatch, 40 wt% anti-oxidant and 10 wt% antiscratch agent basing on the total weight of the additive package.
Examples were prepared by compounding the compositions in Table 1 in a twin screw extruder then injection molded in to the samples for measurements.
Measurement
DSC was measured in accordance to the following protocol:
Sample is sealed in Tzero hermetic aluminum pan (40pl);
The aluminum pan with sample is placed in Q2000 DSC machine;
Heat program on the DSC machine is set as: At the speed of 10 °C/min, o First heating circle:
■ Cooling to -50 °C, isotherm for 1min;
■ Heating to 230 °C, isotherm for 1min (During heating, Tm1, dHm were determined); o Second heating circle
■ Cooling to -50 °C, isotherm for 1min (During cooling, Tc1, dHc were determined);
■ Heating to 230 °C, isotherm for 1min (During heating, Tm2, dHm2 were determined).
Density was measured according to ISO 1183-1:2019;
Flex modulus was measured according to ISO178:2019 (II);
HDT A was measured according to ISO 75-2:2013/A Flatwise (L=1.8MPa).
Result
The thermal properties of PP1 and PP2 are shown in Table 1. Tm refers to melting temperature, dHm refers to melt enthalpy, Tc refers to crystallization temperature, dHc refers to crystallization enthalpy, the footnotes 1 and 2 refer to the heat circle. The thermal properties of PP1 and PP2 are shown in Table 1
Table 1
The composition of the Examples and their properties are shown in Table 2
Table 2 By the comparison between CE1 vs IE1, it is clear that the use of PP2 led to improved Flex mod, HDT; At a higher amount of glass fiber, CE2, CE3 showed a too high density, there is also no surprising effect of using PP2 in the comparison of CE2 and CE3; By the comparison between IE1 and IE2 using glass fibers with different average diameters, IE1 showed improved Flex modulus where glass fibers with a high diameter is used.
Claims
1. A polymer composition comprising
- a polypropylene wherein the polypropylene has a melt enthalpy in the first heating circle in the range of 80 to 95 J/g, wherein the amount of the polypropylene is in the range from 60 to 90 wt% based on the total amount of the polymer composition;
- glass fibers wherein the amount of the glass fibers is in the range from 10 to 35 wt% based on the total amount of the polymer composition.
2. The polymer composition according to claim 1 , wherein the polypropylene is a propylene homopolymer.
3. The polymer composition according to claim 1 or 2, wherein the polypropylene has a melt flow rate (MFR) in the range from 50 to 150 g/10min, preferably from 60 to 120 g/10min as measured according to ISO 1133-1 :2011 (2.16Kg, 230°C).
4. The polymer composition according to any one of the previous claims wherein the glass fibers have an average diameter in the range from 11 to 16 pm, preferably from 12 to 14 pm.
5. The polymer composition according to any one of the previous claims wherein the amount of polypropylene is in the range from 65 to 75 wt% based on the total amount of the polymer composition.
6. The polymer composition according to any one of the previous claims wherein the amount of the glass fiber is in the range of 25 to 34 wt% based on the total amount of the polymer composition.
7. The polymer composition according to any one of the previous claims wherein the density of the polymer composition is in the range from 1.10 to 1.20 g/cm3 as measured according to ISO 1183-1 :2019.
8. The polymer composition according to any one of the previous claims wherein the polypropylene has a melt enthalpy in the second heating circle in the range from 90 to 110 J/g.
9. The polymer composition according to any one of the previous claims wherein the polypropylene has a crystallization temperature in the range from 125 to 130 °C.
RECTIFIED SHEET (RULE 91 ) ISA/EP
10. A process for the preparation of the polymer composition according to any one of the previous claims comprising the sequential steps of:
- Providing the polypropylene and glass fibers;
- Mixing the polypropylene and the glass fibers in an extruder.
11. An article comprising the polymer composition according to any one of the claims 1 to 9, wherein the amount of the polymer composition is in the range from 95 to 100 wt% based on the total amount of the article.
12. The article according to claim 11 , wherein the article is an automotive part, preferably an automotive exterior part.
9
RECTIFIED SHEET (RULE 91 ) ISA/EP
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP22208468 | 2022-11-21 | ||
| PCT/EP2023/082041 WO2024110301A1 (en) | 2022-11-21 | 2023-11-16 | Glass fiber reinforced polymer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4623028A1 true EP4623028A1 (en) | 2025-10-01 |
Family
ID=84360729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23806293.9A Pending EP4623028A1 (en) | 2022-11-21 | 2023-11-16 | Glass fiber reinforced polymer composition |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP4623028A1 (en) |
| CN (1) | CN120112592A (en) |
| WO (1) | WO2024110301A1 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4338233A (en) | 1981-06-15 | 1982-07-06 | Ppg Industries, Inc. | Aqueous sizing composition and sized glass fibers and method |
| DE3675081D1 (en) | 1985-06-25 | 1990-11-29 | Ppg Industries Inc | CHEMICAL TREATED FIBERS FOR REINFORCING POLYMER MATERIALS AND METHOD. |
| EP1460166B1 (en) | 2001-12-27 | 2015-10-21 | Fiber Glass Japan Kabushiki Kaisha | Binder for glass fiber, glass fiber for olefin resin reinforcement, and process for producing olefin resin composition for fiber-reinforced molding |
| PL2308923T3 (en) | 2009-10-09 | 2012-11-30 | Borealis Ag | Glass fibre composite of improved processability |
| US8618214B2 (en) * | 2010-12-17 | 2013-12-31 | Exxonmobil Research And Engineering Company | Fiber-reinforced polypropylene/elastomer composite |
| US9290646B2 (en) * | 2013-10-04 | 2016-03-22 | Equistar Chemicals, Lp | Molded articles (including automobile parts) and related filled thermoplastic polyolefin compositions |
-
2023
- 2023-11-16 CN CN202380074443.2A patent/CN120112592A/en active Pending
- 2023-11-16 EP EP23806293.9A patent/EP4623028A1/en active Pending
- 2023-11-16 WO PCT/EP2023/082041 patent/WO2024110301A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024110301A1 (en) | 2024-05-30 |
| CN120112592A (en) | 2025-06-06 |
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