Polymer composition made of recycled material for improved grade plastics
阅读说明：本技术 由回收材料制成的用于改进级塑料的聚合物组合物 (Polymer composition made of recycled material for improved grade plastics ) 是由 F·E·J·埃塞斯 M·H·M·恩克沃特范 M·P·A·霍特曼 J·维尼里乌斯 于 2020-04-28 设计创作，主要内容包括：一种聚合物组合物,包括：a.60-80wt％的回收聚丙烯；b.10-35wt％的回收聚乙烯；c.5-20wt％的聚烯烃弹性体(POE)；d.0.1-10wt％苯乙烯乙烯丁烯苯乙烯嵌段共聚物(SEBS)；其中,wt％是相对于聚合物组合物的总重量；其中,所述聚合物组合物包含至少11wt％的聚烯烃弹性体和苯乙烯乙烯丁烯苯乙烯嵌段共聚物。(A polymer composition comprising: 60-80 wt% recycled polypropylene; b.10 to 35 wt% of recycled polyethylene; c.5 to 20 wt% of a polyolefin elastomer (POE); 0.1-10 wt% styrene ethylene butylene styrene block copolymer (SEBS); wherein wt% is relative to the total weight of the polymer composition; wherein the polymer composition comprises at least 11 wt% of a polyolefin elastomer and a styrene ethylene butylene styrene block copolymer.)
1. A polymer composition comprising:
60-80 wt% recycled polypropylene;
b.10 to 35 wt% of recycled polyethylene;
c.5 to 20 wt% of a polyolefin elastomer (POE);
0.1-10 wt% styrene ethylene butylene styrene block copolymer (SEBS);
wherein wt% is relative to the total weight of the polymer composition;
wherein the polymer composition comprises at least 11 wt% of a polyolefin elastomer and a styrene ethylene butylene styrene block copolymer.
2. The polymer composition of claim 1, comprising:
a 60 to 77.5 wt% recycled polypropylene;
12-35 wt% of recycled polyethylene;
c.6-20 wt% of a polyolefin elastomer (POE);
0.1-8 wt% of styrene ethylene butylene styrene block copolymer (SEBS).
3. The polymer composition according to claim 1 or 2, wherein the reclaimed PP content of the polymer composition consists of 25-75 wt% BOPP and 25-75 wt% rubber-containing injection molded material, wherein wt% is relative to the total weight of reclaimed PP.
4. The polymer composition according to any of the preceding claims, wherein the recycled PP is present in the polymer composition between 60 and 80 wt%, preferably between 60 and 77.5 wt%, most preferably between 62 and 75 wt%; wherein wt% is relative to the total weight of the polymer composition.
5. Polymer composition according to any of the preceding claims, wherein the recycled PP is a material collected according to DSD324 or DSD324-1 standard.
6. The polymer composition according to any of the preceding claims, wherein the recycled PE preferably comprises at least 90 wt% recycled High Density Polyethylene (HDPE), more preferably at least 92 wt%, most preferably at least 95 wt%, and wherein the density of the recycled PE is from 0.94 to 0.97g/cm3。
7. The polymer composition according to any of the preceding claims, wherein the recycled PE is a material collected according to DSD 329 standards.
8. The polymer composition according to any of the preceding claims, wherein the recycled PE has an MFR 2.16kg, 230 ℃ (g/10min) between 0.4 and 0.9 and an MVR 2.16kg, 230 ℃ (ml/10min) between 0.3 and 1.3, and wherein the recycled PE is present in the polymer composition in 10-35 wt%, wherein wt% is relative to the total weight of the polymer composition.
9. The polymer composition according to any of the preceding claims, wherein the recycled PE and the POE are present in the polymer composition in a weight ratio of 3:1 to 1: 1.
10. The polymer composition according to any of the preceding claims, wherein the total rubber content of the polymer composition is preferably between 5 and 24 wt%, more preferably between 8 and 20 wt%, most preferably between 11 and 18 wt%, measured with Cold Xylene Solubles (CXS).
11. The polymer composition according to any of the preceding claims, wherein the POE used in the invention comprises an ethylene (C2) octene (C8) metallocene rubber having a block structure.
12. Polymer composition according to any of the preceding claims, wherein the POE preferably has a density between 0.85 and 0.89, an MFR between 0.3 and 1, and wherein the POE is present in the polymer composition between 5 and 20 wt%.
13. The polymer composition according to any of the preceding claims, wherein the composition has a charpy notched impact strength, determined using ISO 179-1: eA2010, in the range of from 20 to 60kJ/m2Preferably in the range of 22-55kJ/m2More preferably between 26 and 51kJ/m2In the meantime.
14. A process for the preparation of a composition as claimed in any one of claims 1 to 11, wherein the process comprises the steps of:
a. treating the mixed polyolefin with water without increasing heat energy to recover a fraction;
b. treating the solution of the recovered fraction from the mixed polyolefin obtained in a) with an alkaline medium in a washing step at a temperature of at least 60 ℃;
c. sorting the mixed polyolefin recovery fraction solution obtained in b) to obtain PE reclaimed materials and/or mixed PP recovery fractions, wherein the steps a) and b) can also be carried out in reverse order;
d. treating the PE reclaimed material and/or the mixed PP reclaimed fraction solution obtained in the step above at the temperature of 50-155 ℃, preferably for at least 60 minutes;
e. adding the fraction of the dry recovered PE and/or mixed recovered PP fraction obtained in step d) to an extruder, while adding POE and SEBS; optionally, additives; wherein the mixture is treated to obtain recycled PP and recycled PE material;
wherein step e) is carried out for 1-10 minutes between 200-250 ℃, preferably between 210-240 ℃, more preferably between 220-230 ℃.
15. An article comprising the polymer composition of any of claims 1-11.
Technical Field
The present invention relates to an improved polymer composition comprising a high amount of recycled polypropylene (PP) and Polyethylene (PE), as well as the use of the polymer composition in the manufacture of articles, articles manufactured from the polymer composition and a process for preparing the polymer composition.
Background
The ubiquity of plastic packaging and the importance of environmental policies have led to an increasing importance of recyclable plastic materials.
The recycling of paper, textiles, glass or metal has been carried out on a large scale, whether by individual collection or sorting of the recyclates. The recycling of plastic waste and the reuse of plastic are also increasing.
The replacement of the original polymer component is considered as the only way to solve the global plastic waste problem, prevent the exhaustion of natural resources, and promote the recycling economy.
To date, recycled polymer compositions obtained in flake or granular form can be obtained from a collection of commercially available polyolefin packages, containers or films, wherein the polyolefin is present in the recycled polymer composition in a low percentage between 5 and 8 wt%, the remaining 92 to 95 wt% of the polyolefin consisting of the original polyolefin.
The object of the present invention is to produce polymer compositions containing a high amount of recyclable polyolefin, which polymer compositions are competitive with the starting materials in terms of product properties and price. To date, the polymer compositions of the recycled polyolefin blends have not been comparable to the impact strength and stiffness of the original polyolefin blends.
Currently available polyolefin polymer compositions suffer from variability and poor consistency of polystyrene contaminants, rubber contaminants, and recycled plastic feed.
Subsequently, the polyolefin polymer compositions currently available have low impact strength and stiffness compared to the original material.
It is another object of the present invention to produce a recycled polyolefin polymer composition that can be used to make blow molded and injection molded packaging and durable products without further blending with the original polyolefin material.
No polymer compositions are known that contain a high percentage of recyclable polyolefin (at least 75 wt%, preferably 80 wt%, more preferably 85 wt% of the polymer composition from the recycled polyolefin), have properties suitable for consumer products, are manufactured by processes such as blow molding and injection molding, and have high impact strength and stiffness. Wt% is relative to the total weight of the polymer composition, if not otherwise specified.
The material source for the polymer composition for recycling polymer materials may be food and household packaging, for example polyolefin plastics (such as PP and PE) which may be contaminated by other polymer families, such as styrene polymers.
Styrene polymers are used in the form of Polystyrene (PS) for the production of packaging and containers for perishable foods; in the production of industrial packaging, in the form of Acrylonitrile Butadiene Styrene (ABS); in the production of packaging, containers, and as a filler for packaging and containers, it is present in the form of Expanded Polystyrene (EPS). Therefore, the styrene polymer needs to be removed during the processing of the material to be recycled. Complete removal is technically and economically impossible. But any residual polystyrene has a significant negative impact on the mechanical properties of the recycled polyolefin composition. For example, EPS can accelerate the generation of free radicals leading to material degradation and making the manufactured article more brittle. Furthermore, polyethylene terephthalate (PET) has a negative impact on the mechanical properties of the polymer composition.
Polyvinyl chloride (PVC), polyvinylidene chloride (PVDC) and styrene polymers are considered to be only partially compatible with PP and PE, especially when producing new recycled polyolefin blends by extrusion recycling.
In order to recycle polymer flakes or pellets at a competitive cost relative to the original polyolefin material, it must be accepted that a significant amount of other polymer contaminants coexist with the recycled polyolefin from the recycle package.
Another problem with using recycled polyolefin polymer compositions, particularly from recycle packaging, is variability and poor consistency of the polymer in the feed. Thus, such variability and poor consistency are also found in recycled granules or flakes and manufactured articles. This variability and poor consistency of the polymer results in surface aesthetics and unstable mechanical properties of the final product. At the same time, the use of the particles in an injection molding process is limited or prevented by at least one of the following drawbacks: extreme brittleness, low impact strength and low stiffness of granules or flakes and products obtained from recycling.
Disclosure of Invention
It is an object of the present invention to address at least one of the above problems. It is a further object of the present invention to obtain a polymer composition which is effective for use in moulding processes, in particular injection moulding, wherein the percentage of recovered polyolefin in the polymer composition is high, i.e. at least 70 wt%, preferably 75 wt%, more preferably 80 wt%, most preferably 85 wt%. The polymer composition can be used to produce sheets or pellets and products with high impact strength and stiffness at competitive costs compared to the original polyolefin product. The polymer composition can produce a product having high impact strength (charpy) and optionally increased stability upon exposure to the environment, e.g., temperature, humidity or sun exposure.
A polymer composition comprising:
60-80 wt% recycled polypropylene;
b.10 to 35 wt% of recycled polyethylene;
c.5 to 20 wt% of a polyolefin elastomer (POE);
0.1-10 wt% styrene ethylene butylene styrene block copolymer (SEBS);
wherein wt% is relative to the total weight of the polymer composition;
wherein the polymer composition comprises at least 11 wt% of a polyolefin elastomer and a styrene ethylene butylene styrene block copolymer.
The recycled PP and recycled PE polymer compositions according to the present invention have increased impact strength compared to standard recycled PP and recycled PE polymer compositions despite contamination with other polymers. Tensile modulus remains at a high level while impact strength is improved. The polymer compositions of the present invention can have a melt flow rate sufficient for effective injection molding. Furthermore, the present invention may allow for controlled shrinkage during and/or after processing.
The invention has at least one of the following advantages: polymer compositions useful for molding, particularly injection molding, have reduced peroxide requirements and improved impact strength relative to other recycled PP and recycled PE polymer compositions.
Detailed Description
The polymer composition preferably comprises a major amount of recycled polypropylene and recycled polyethylene, with the addition of a styrene ethylene butylene styrene block copolymer and a polyolefin elastomer; and optionally additives.
Recycled polypropylene
PP raw materials include plastic waste, mainly Post Consumer Waste (PCW) PP packaging waste, such as detergents and shampoo bottles, milk cans and meat trays, etc. PP raw material waste may be pre-classified by waste management companies. For example, a suitable PP source may be waste material collected according to DSD324 (05-2012) and DSD324-1 standards (03-2018).
The PP DSD324 (05-2012) raw material may comprise at least one of used, slagged, rigid, system compatible items made of polypropylene, such as: bottles, cups and trays, including secondary components such as lids, labels, etc. The PP DSD324 (05-2012) raw material may contain a total amount of impurities of at most 6% by mass. Impurities in the PP DSD324 (05-2012) raw material may include mass fraction < 0.5% of other metal articles, mass fraction < 1% of rigid PE articles, mass fraction < 0.5% of expanded plastics (including EPS articles), mass fraction < 2% of plastic films and mass fraction < 3% of other residues. Other examples of impurities in the PP DSD324 (05-2012) raw material may include glass, paper, cardboard, paperboard, composite paper/paperboard material (e.g., liquid packaging board), aluminized plastic, other materials (e.g., rubber, stone, wood, textiles, diapers), and compostable waste (e.g., food, garden waste).
The second standard for PP recovery is the PP DSD324-1 standard (03-2018). This standard is very similar to the previously discussed PP DSD324 standard, but the recycled PP can contain more film material, up to around 10 wt%. The film material comprises recycled PP film, such as bi-directional (BOPP) PE film. The impurities in the PP DSD324-1 standard (03-2018) raw material may comprise a maximum total of 4%, the impurities in the PP DSD324-1 standard (03-2018) raw material may comprise a mass fraction < 0.5% of other metal articles, a mass fraction < 1% of rigid PE articles, a mass fraction < 0.5% of expanded plastics (including EPS articles), a mass fraction < 1% of paper, paperboard, cardboard, composite paper/cardboard materials (e.g. liquid packaging board) and a mass fraction < 3% of other residues. Other examples of impurities in the PP DSD324-1 standard (03-2018) raw materials may include glass, aluminized plastic, other materials (e.g., rubber, stone, wood, textiles, diapers), and compostable waste (e.g., food, garden waste)
Examples of recycled PP are EXPP152A (MFR 15)/300P and EXPP163A (MFR 50)/300T.
Optical sorting can also be used to remove unwanted polymers, but polystyrene or polyethylene contamination in the feed is still present and has a significant negative impact on the mechanical properties of the recovered polymer composition.
There are three different varieties of PP, namely PP homopolymer (PPh), PP random copolymer (PPr) and PP impact copolymer (or heterophasic PP copolymer, PPc).
For example, scrap can be characterized as originating from (a) extruded sheet and film materials, primarily PP homopolymer (PPh) and PP random copolymer (PPr), with little rubber (e.g., biaxially stretched polypropylene (BOPP)); (b) injection moulding material, which is a mixture of PP homopolymer (PPh), PP random copolymer (PPr) and impact copolymer (PPc), contains about 15 wt.% of rubber.
Recycled PP may comprise about half of the packaging material (BOPP) and half of the rubber-containing injection molding material. The injection molding material may comprise a rubber, such as C2-C3 rubber, thermoplastic elastomer (TPE), Ethylene Propylene Diene Monomer (EPDM), or Ethylene Propylene Rubber (EPR).
The resulting mixture of recycled PP itself used in the polymer composition has a rubber content of between 1.5 and 12 wt% (rubber made from rubber-containing injection moulding material; wherein wt% is relative to the total amount of the mixture of recycled PP). Additional rubber is added to the polymer composition on top of the rubber from the rubber-containing injection molding material. The additional rubber at least comprises POE and SEBS.
The reclaimed PP content of the polymer composition preferably consists of 25 to 75 wt.% BOPP and 25 to 75 wt.% rubber-containing injection molding material; wherein wt% is relative to the total weight of the recycled PP.
In the polymer composition, the recycled PP is present between 60 and 80 wt%, preferably between 60 and 77.5 wt%, more preferably between 62 and 75 wt%; wherein wt% is relative to the total weight of the polymer composition.
Recovery of polyethylene
The recycled PE comprises PE waste collected according to DSD 329 standard (04/2009), PE waste based on british milk bottles, PE waste based on french milk bottles, PE containers having a volume of 5 litres or more and cleaned according to environmental regulations or PE squeeze tubes. Other PE sources are not excluded.
Recycled PE DSD 329 standard (04/2009) raw materials may comprise at least one of used, slagged, rigid, system compatible articles made of polyethylene, such as bottles and trays, including packaging parts such as bottle caps, lids, labels, and the like. The recovered PE DSD 329 standard (04/2009) raw material may contain a maximum total of 6% impurities. Recycled PE DSD 329 standard (04/2009) raw materials may include mass fraction < 0.5% other metal articles, mass fraction < 1% dimensionally stable PP articles, mass fraction < 0.5% expanded plastics (including EPS articles), mass fraction < 5% plastic films and mass fraction < 3% other residues. Other examples of impurities in recycled PE DSD 329 standard (04/2009) raw materials may include glass, paper, cardboard, paperboard, composite paper/paperboard materials (e.g., beverage cartons), aluminized plastic, other materials (e.g., rubber, stone, wood, textiles, diapers), and compostable waste (e.g., food, garden waste).
An example of recovered PE from DSD 329 standard (04/2009) raw materials is HDPE 54040216.
Preferably, recovering the PE comprises recovering at least 90 wt%, more preferably at least 92 wt%, most preferably at least 95 wt% of High Density Polyethylene (HDPE).
Recycled PE collected according to DSD 329 standards contains a variety of contaminants that may have negative effects when used in blow molding. These are removed by a number of steps, including cleaning, washing and sorting steps. For example, the recovered PE may be separated into, for example, different streams, such as a membrane fraction (PE + EPS), a light fraction, and a dark fraction. The PE recyclate may preferably comprise from 0 to 6 wt%, more preferably from 1 to 5 wt%, most preferably from 3 to 4.5 wt% of polypropylene and up to 1 wt% of polystyrene contaminants, wherein wt% is relative to the total weight of the recycled PE.
The recovered PE preferably has a density of about 0.94-0.97g/cm3Density within the range and may have different molecular weight distributions. The standard gaussian distribution of molecular weight is referred to as "single peak". The specific and broad distribution is referred to as "bimodal". PE may have an intermediate mode of "1.5 x singlet".
The MFR (2.16kg, 190 ℃) of the PE may preferably be in the range of 0.1 to 0.5, which is suitable for blow molding materials. PE may be a light recyclate. The recovered PE may preferably have a value of between 71 and 80L, a between-6 and 0 a, b between 0 and 12 b; determined according to CIELAB.
The recovered PE may preferably have an MFR 2.16kg, 230 ℃ (g/10min) of between 0.4 and 0.9, more preferably between 0.45 and 0.85.
The recovered PE may preferably have an MVR of 2.16kg, 230 deg.C (ml/10min), between 0.3 and 1.3, more preferably between 0.6 and 1.0. The recycled PE may preferably have a Charpy (23 ℃, kJ/m) of between 10 and 20, more preferably between 12 and 172). The recovered PE may have a density (kg/m) preferably between 850-3). The recovered PE may preferably have a tensile modulus (MPa) of between 1030-1230, more preferably between 1080-1180.
The tensile rigidity of the standard pure PP and pure PE blended polymer composition is between 600-1300MPa, and the Charpy notched impact strength is between 23 and 50kJ/m2In the meantime. The mechanical properties of the polymer composition according to the invention are very close to the mechanical property values of the starting material.
The recovered PE is present in the polymer composition in an amount of from 10 to 35 wt%, preferably from 12 to 35 wt%, more preferably from 15 to 25 wt%, wherein wt% is relative to the total weight of the polymer composition.
In the polymer composition, the recycled PE is preferably present in the polymer composition in a weight ratio of from 3:1 to 1:1 with respect to POE.
Additional rubber
It has been surprisingly found that both types of rubber can increase the impact strength of the final product produced using the polymer composition of the present invention while maintaining a high tensile modulus. The first was POE and the second rubber used was SEBS rubber.
The polymer composition preferably has a total rubber content, determined as Cold Xylene Solubles (CXS), of between 5 and 24 wt.%, more preferably between 8 and 20 wt.%, most preferably between 11 and 18 wt.%.
The polymer composition comprises at least 11 wt%, preferably at least 12 wt% of a polyolefin elastomer and a styrene ethylene butylene styrene block copolymer.
Polyolefin elastomer
The polymer composition comprises a polyolefin elastomer (POE), which is an ethylene alpha olefin copolymer. Examples of POEs are C2-C4 copolymers, C2-C6 copolymers and C2-C8 copolymers.
POE may preferably be a C2-C6 copolymer or a C2-C8 copolymer, the ethylene content being between 70 and 80 wt.%, more preferably between 73 and 78 wt.%, most preferably between 74 and 77 wt.%; wherein wt% is relative to the total weight of the POE.
The POE used in the present invention preferably comprises an ethylene (C2) octene (C8) metallocene rubber having a block structure.
The density of POE is preferably between 0.85 and 0.89, more preferably between 0.855 and 0.885, and most preferably between 0.86 and 0.875.
POE has an MFR (190 ℃, 2.16kg) preferably between 0.3 and 1, more preferably between 0.4 and 0.8, most preferably between 0.45 and 0.7.
The added C2-C8 rubber can be matched with the C2-C3 rubber in the injection molding material. This has a surprisingly positive effect on the impact strength of the polymer composition.
It was further found that the addition also surprisingly increases the stiffness. The C2-C8 rubber may also increase flowability or reduce the use of peroxides in the process.
POE is preferably selected from Infuse or Engage polymers, such as Infuse 9107, Infuse 9077 and Engage XLT 8677.
POE is present in the polymer composition at between 5 and 20 wt%, preferably between 6 and 20 wt%, more preferably between 6 and 15 wt%.
Styrene ethylene butylene styrene block copolymer
The second rubber of the polymer composition is SEBS rubber.
SEBS rubber is a (partially) hydrogenated styrene-butadiene-styrene block copolymer. They belong to the family of Styrene Block Copolymers (SBC). These polymers are triblock copolymers with styrene at both ends of the polymer chain and polybutadiene, polyisoprene or hydrogenated polybutadiene or polyisoprene blocks inside.
SEBS copolymers are commercially available, for example under the trade names Kraton and Tuftec, for example Kraton SEBS G1657 MS.
The SEBS copolymer surprisingly reduces the negative impact of e.g. EPS or PET on the mechanical properties of the polymer composition, such as impact strength.
SEBS is present in the polymer composition at 0.1 to 10 wt%, preferably 0.1 to 8 wt%, more preferably 1 to 4 wt%, more preferably 0.2 to 3 wt%, more preferably 0.3 to 2 wt%, most preferably 0.4 to 1.5 wt%.
Additive agent
The polymer composition may also comprise from 0.05 to 10% by weight, preferably from 0.1 to 8% by weight, of additives in the polymer composition.
The additives include stabilizers, peroxides, calcium oxide (CaO), EBA wax, pigment binders, talc or colorants.
A stabilizer may be added, for example a masterbatch like TosafME 833848, which is a blend of about 70 wt% Low Density Polyethylene (LDPE) with a phenolic stabilizer and Irgafos. The stabilizer may be added to the polymer composition in an amount preferably between 0 and 4 wt.%, more preferably between 0.1 and 1.5 wt.%. Other examples of stabilizers are exxelor pe1040 and Irganox B225.
The peroxide may be added in the form of an organic compound or a masterbatch. Peroxides improve the flowability of the material. The peroxide may for example be selected from the group of Zebraflow T028, Zebraflow T0214 or Zebraflow T0318. For example, peroxides can be used to shorten the polymer chains, thereby reducing the viscosity and improving the flow of the polymer composition. For example, 0 to 2 wt% of a masterbatch may be added, which may contain, for example, 2 to 10 wt% of a suitable peroxide. The peroxide may preferably be added to the polymer composition in an amount of between 0 and 4 wt%, more preferably between 0.05 and 1.5 wt%.
Calcium oxide (CaO) may be added to suppress the release of HCl. For example CaO may be added as a masterbatch with LDPE. An example of CaO suitable for use in the present invention is W & R Master Desiccant 60003. CaO may be added preferably in the range of between 0 and 4 wt%, more preferably between 0.05 and 2 wt%, most preferably between 0.1 and 1.5 wt%.
The pigment binder may be added preferably in the range of between 0-4 wt%, more preferably between 0.1-1.5 wt%. For example, PE maleic anhydride may be added to the polymer composition as a pigment binder in an amount of between 0.1 and 2 wt.%, preferably between 0.2 and 1 wt.%, more preferably between 0.5 and 1 wt.%.
Talc may be added, an example of a suitable talc being stemic OOSd.
The black colorant may be added to the polymer composition in an amount of between 0.1 and 5 wt%, more preferably between 1 and 2 wt%, preferably in the form of a masterbatch blend.
Ash content
For example, the ash content of the polymer composition may be between 4 and 8 wt%.
Composition comprising a metal oxide and a metal oxide
The compositions according to the invention have surprisingly good mechanical properties.
The polymer composition preferably has a melt flow rate MFR (230 ℃, 2.16kg) of between 5 and 25g/10min, more preferably between 12 and 18g/10 min.
The modulus of the polymer composition is preferably between 600-1300MPa, more preferably between 700-1200 MPa.
Polymer compositions were determined using ISO 179-1eA:2010The Charpy notched impact strength of (A) is preferably from 20 to 60kJ/m2Preferably 23 to 50kJ/m2More preferably 25 to 35kJ/m2More preferably 22 to 55kJ/m2Most preferably 26-51kJ/m2。
The composition according to the invention can meet the ISO 14021:2016 standard and be labelled as a class II environment using ISO 14021: 2016.
Method
The invention further relates to a process for preparing the polymer composition of the invention.
The method comprises the following steps:
a. treating the mixed polyolefin with water without increasing heat energy to recover a fraction;
b. treating the solution of the recovered fraction from the mixed polyolefin obtained in a) with an alkaline medium in a washing step at a temperature of at least 60 ℃;
c. sorting the mixed polyolefin recovery fraction solution obtained in b) to obtain PE reclaimed materials and/or mixed PP recovery fractions, wherein the steps a) and b) can also be carried out in reverse order;
d. treating the PE reclaimed material and/or the mixed PP reclaimed fraction solution obtained in the step above at the temperature of 50-155 ℃, preferably for at least 60 minutes;
e. adding the fraction of the dry recovered PE and/or mixed recovered PP fraction obtained in step d) to an extruder, while adding POE and SEBS; optionally, additives; wherein the mixture is treated to obtain recycled PP and recycled PE material;
wherein step e) is carried out for 1-10 minutes between 200-250 ℃, preferably between 210-240 ℃, more preferably between 220-230 ℃.
The process of preparing the polymer composition may include mixing and extrusion.
The process for preparing the polymer composition may use a co-rotating twin screw tandem extruder to which recycled polypropylene, recycled polyethylene, styrene ethylene butylene styrene block copolymer and polyolefin elastomer and optional additives are added.
The additives may be added in the recycling extruder (first extruder) and the compounding extruder (second extruder) of the tandem extruder.
Article with a cover
The polymer composition may be present in the form of granules or flakes for use in the manufacture of articles.
The polymer compositions of recycled PP and recycled PE are suitable for use in the manufacture of long-term use products such as boxes, trays, paint pails or consumer products.
Articles made from the polymer composition are preferably formed by injection molding.
Detailed description of the preferred embodiments
In a preferred embodiment, the polymer composition comprises 60 to 80 wt% recycled polypropylene, 10 to 35 wt% recycled polyethylene, 5 to 20 wt% polyolefin elastomer (POE) and 0.1 to 4 wt% styrene ethylene butylene styrene block copolymer (SEBS), wherein the polymer composition comprises at least 11 wt% polyolefin elastomer and styrene ethylene butylene styrene block copolymer.
In another embodiment, a polymer composition comprises 62 to 75 wt% recycled polypropylene, 10 to 35 wt% recycled polyethylene, 5 to 20 wt% polyolefin elastomer (POE), and 0.1 to 4 wt% styrene ethylene butylene styrene block copolymer (SEBS), wherein the polymer composition comprises at least 11 wt% polyolefin elastomer and styrene ethylene butylene styrene block copolymer.
In another embodiment, a polymer composition comprises 62 to 75 wt% recycled polypropylene, 15 to 25 wt% recycled polyethylene, 5 to 20 wt% polyolefin elastomer (POE), and 0.1 to 4 wt% styrene ethylene butylene styrene block copolymer (SEBS), wherein the polymer composition comprises at least 11 wt% polyolefin elastomer and styrene ethylene butylene styrene block copolymer.
In another embodiment, a polymer composition comprises 62 to 75 wt% recycled polypropylene, 15 to 25 wt% recycled polyethylene, 6 to 15 wt% polyolefin elastomer (POE), and 0.5 to 1.5 wt% styrene ethylene butylene styrene block copolymer (SEBS), wherein the polymer composition comprises at least 11 wt% polyolefin elastomer and styrene ethylene butylene styrene block copolymer.
In another embodiment, a polymer composition comprises 60 to 80 wt% recycled polypropylene, 10 to 35 wt% recycled polyethylene, 6 to 15 wt% polyolefin elastomer (POE), and 0.5 to 1.5 wt% styrene ethylene butylene styrene block copolymer (SEBS), wherein the polymer composition comprises at least 11 wt% polyolefin elastomer and styrene ethylene butylene styrene block copolymer.
In another embodiment, the polymer composition is preferably used for injection molding of articles.
The polymer composition according to the invention may further comprise optional components, e.g. additives, different from the aforementioned components of the polymer composition, wherein the sum of the aforementioned components and optional components amounts to 100 wt% of the total polymer composition.
Accordingly, the present invention relates to a polymer composition consisting of the aforementioned components and optional components.
It is to be noted that the invention relates to all possible combinations of features described herein, particularly preferred combinations of features present in the claims. Thus, it is to be understood that all feature combinations related to the polymer composition according to the present invention; all combinations of features associated with the process according to the invention, all combinations of features associated with the polymer composition according to the invention and all combinations of features associated with the process according to the invention are described herein.
It is further noted that the term "comprising" does not exclude the presence of other elements. However, it is also understood that the description of a product/polymer composition comprising certain components also discloses product/polymer compositions consisting of these components. An advantage of a product/polymer composition consisting of these components is that it provides a simpler, more economical process for preparing the product/polymer composition. Similarly, it should also be understood that the description of a process that includes certain steps also discloses a process that consists of those steps. A process consisting of these steps may be advantageous because it provides a simpler, more economical method.
When referring to lower and upper values of a parameter, it is also understood to disclose the range formed by the combination of the lower and upper values.
The invention will now be illustrated by, but is not limited to, the following examples.
Examples
Quality detection and calibration
For quality testing, samples were taken during processing and from the final product. Melt Mass Flow Rate (MFR) was measured on days 3 and 10 of aging. MFR and melt volume flow rate (MVR) were evaluated using ISO 1133-1:2011, 2.16kg, T230 ℃. For POE and PE, MFR and MVR were evaluated using ISO 1133-1:2011 at 190 ℃ and 2.16 kg.
CIELAB (L, a, b) was used to identify the color of the product during and at the end of the process. L marks the light and shade contrast quantity; a represents red and green, b represents blue and yellow. These are parameters standardized by the international commission on illumination (CIE) in 1976, called CIELAB.
Cold Xylene Solubles (CXS) were measured using ISO 16152:2005, T25 ℃.
The ash content of the polymer composition or product was measured using ISO 3451-12008.
The density of the polymer composition or product is measured using ISO 1183-1:2019, T ═ 23 ℃, tensile bars.
Tensile strength/test of the polymer composition or product was measured using ISO 527-1A:2012, T ═ 23 ℃, II.
The tortuosity of a polymer composition or product is measured using ISO 178:2010, T23 ℃, II.
Tensile bar testing of molded articles made from the polymer compositions or products was measured using ISO 527-1A: 2012.
ISO 179-1eA:2010(T ═ 20 ℃ and T ═ 23 ℃, II, molded bar 527/1 a-notched) and ISO 179-1eA:2010(T ═ 20 ℃ molded bar 527/1 a-unnotched) were used.
The production and evaluation of extruded and injection-molded articles follow ISO 19069-2:2016, ISO 294-1:2017 and ISO 294-3: 2002.
Product example
A polymer composition of recycled PP and HDPE is prepared.
The POE used was Infuse 9077.
0.75 wt% TOSAF was used as a stabilizer.
Master batches containing 70 wt% CaO were used as CaO (particle size <10 μm).
EXPP152A and EXPP163A are recycled polypropylene that meets the DSD324 standard.
HDPE54040216 is recycled HDPE which meets DSD 329 criteria (04/2009).
DOW Infuse 9077 is a POE.
Kraton G1657MS is a SEBS rubber.
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