PL201262B1 - Method for manufacturing polymer compounds - Google Patents

Abstract

1. A method for producing polymer compositions, characterized in that a primary or waste material, which is a polyolefin, especially low-density polyethylene or linear low-density polyethylene, with the addition of maleic anhydride used in an amount of 0.05 to 5% by weight in relation to the weight of the polyolefin and an organic peroxide used in an amount of 1 to 10% by weight in relation to the maleic anhydride, optionally with the addition of polyamide and/or thermoplastic polyester, is mixed and extruded with synthetic textile waste, especially polyester and/or polyamide, used in an amount of 10 - 60% by weight in relation to the weight of the composition, for 1 to 5 minutes, preferably in an inert gas atmosphere, in a twin-screw extruder, preferably co-rotating, at a temperature of 230 - 260°C.

Description

(12) PATENT DESCRIPTION (19) PL (11) 201262 (13) B1 ( ²¹ ) Application number: ³⁷¹⁶⁴¹ ( ⁵¹ ) ^lnt - ^cl ·

C08L 23/06 (2006.01) C08L 23/12 (2006.01) C08K 5/092 (2006.01) ⁽²²⁾ Filing ^{date :} 08 ^{12 2004} C08K 7/02 (2WM.01)

C08J 11/04 (2006.01) (54)

Method for producing polymer compositions

(73) Patent holder: Industrial Chemistry Research Institute named after Professor Ignacy Mościcki, Warsaw, Poland (43) The application was announced: 12/06/2006 BUP 12/06 (72) Inventor(s): (45) The patent was granted on: Regina Jeziórska, Warsaw, PL Teresa Jaczewska, Warsaw, PL Jacek Dzierżawski, Warsaw, PL Agnieszka Szadkowska, Warsaw, PL 31/03/2009 WUP 03/09 (74) Representative: Anna Królikowska, Industrial Chemistry Research Institute, named after Professor Ignacy Mościcki

(57) 1. A method for producing polymer compositions, characterized in that a primary or waste material, which is a polyolefin, especially low-density polyethylene or linear low-density polyethylene, with the addition of maleic anhydride used in an amount of 0.05 to 5% by weight in relation to the weight of the polyolefin and an organic peroxide used in an amount of 1 to 10% by weight in relation to the maleic anhydride, optionally with the addition of polyamide and/or thermoplastic polyester, is mixed and extruded with synthetic textile waste, especially polyester and/or polyamide, used in an amount of 10 - 60% by weight in relation to the weight of the composition, for 1 to 5 minutes, preferably in an inert gas atmosphere, in a twin-screw extruder, preferably co-rotating, at a temperature of 230 - 260°C.

PL 201 262 B1

Description of the invention

The subject of the invention is a method for producing polymer compositions.

The method according to the invention uses the recycling of synthetic textile waste, especially polyester and/or polyamide.

The synthetic fiber and fabric industry generates waste during production, and its disposal poses increasing challenges. Environmental and economic considerations compel the search for ways to dispose of plastic waste, both post-production and post-consumer.

US Patent No. 844491 describes a method for recovering polyester from contaminated polyester waste mixed with cotton or other fibers, in the form of fabric or fibers, by dissolving the polyester in molten dimethyl terephthalate, methyl p-toluate, or dimethyl isophthalate as a solvent and separating the polyester solution from non-polyester components. The polymer is recovered by crystallization, or the polyester solution can be used as a feedstock in a methanolysis process to produce dimethyl terephthalate and alkylene glycol.

Patent description DE 19629042 describes a method for obtaining terephthalic acid and ethylene glycol from poly(ethylene terephthalate) waste, which consists in subjecting the crushed poly(ethylene terephthalate) waste to an aqueous solution of alkali metal or ammonium carbonate at an elevated temperature.

The description of patent application PL 342144 describes a method for obtaining high-purity terephthalic acid from poly(ethylene terephthalate) waste, which consists in subjecting the poly(ethylene terephthalate) waste to glycolysis with ethylene glycol and then hydrolysis.

The aim of the invention was to find a method for reprocessing polyester, polyamide and polyester-polyamide fabrics and fibers, especially polyethylene terephthalate and polyamide, optionally with an admixture of cotton, viscose or other fibers.

However, the recycling of plastics poses numerous challenges. This is related to aging of the material during use (post-consumer waste), thermal degradation during reprocessing, and, in particular, the unfavorable chemical interaction of one polymer with another in the molten state. Most polymers are mutually incompatible, which means that once the shear forces in the plasticized state subside, they separate into separate phases. Such a material lacks good mechanical properties and does not meet operational requirements.

To produce polymer compositions using the method according to the invention, so-called reactive extrusion was used, which involves not only the physical mixing of the components, but also enabling the formation of chemical or physical bonds between them by adding reactive components.

The method for producing polymer compositions according to the invention consists in mixing and extruding a primary or waste material, which is a polyolefin, especially low-density polyethylene or linear low-density polyethylene, with the addition of maleic anhydride used in an amount of 0.05 to 5% by weight in relation to the weight of the polyolefin and an organic peroxide used in an amount of 1 to 10% by weight in relation to the maleic anhydride, optionally with the addition of polyamide and/or thermoplastic polyester, with synthetic textile waste, especially polyester and/or polyamide, used in an amount of 10 - 60% by weight in relation to the weight of the composition, for 1 to 5 minutes, preferably in an inert gas atmosphere, in a twin-screw extruder, preferably co-rotating, at a temperature of 230 - 260°C.

It is preferable to use maleic anhydride in an amount of 0.2 to 3% by weight relative to the weight of the polyolefin.

The organic peroxide is preferably used in an amount of 2 to 5% by weight relative to the weight of maleic anhydride.

In the process for producing the polymer compositions of the invention, a polyolefin can first be melted and mixed with maleic anhydride and an organic peroxide in an inert gas atmosphere. The modified polyolefin is then mixed and extruded with polyester and/or polyamide textile waste.

The method according to the invention, which uses the recycling of textile waste to obtain polymer compositions, allows for the production of a product with good mechanical properties and high impact strength without the need to sort the waste materials used, which significantly reduces the costs of waste recycling.

PL 201 262 B1

The method according to the invention does not limit the possibility of using typical auxiliary additives such as fillers, antioxidants and antipyrines, as well as dyes and pigments to produce the polymer composition.

Products obtained from textile waste using the method according to the invention can be processed using various techniques and have various applications, e.g. pipes, hoses, plates, seals, structural shapes.

The method of preparing the polymer compositions according to the invention is illustrated by examples.

Example I. 0.9 kilograms of linear low-density polyethylene agglomerate was melt-blended with 0.1 kilograms of maleic anhydride, 2 g of dicumyl peroxide, 6 kilograms of shredded, post-consumer polyamide 6 waste, and 3 kilograms of defibrated polyester/polyamide textile waste fed to an extruder in the form of a ribbon. The process was carried out in a co-rotating twin-screw extruder with screws of 25 mm diameter and 33D length, in an air atmosphere, at a temperature of 230-250°C for 4 minutes.

A polymer was obtained in the form of granules, for injection and extrusion, with the following properties:

- yield strength Rpl = 53.3 MPa

- elongation at yield point ε _ρ ι = 5.1%

- elongation at break ε _Γ = 6.2°%

- breaking strength _5r = 53 MPa

- ^{impact strength} in ^{g Charpy} an > ^{100 kJ/ m2 ( samples without cracks} )

- Charpy notched impact strength a« = 7 kJ/m2;

Products made from the modified mixture granulate, unlike those made from unmodified waste, were characterized by high impact strength and good processing properties.

The granulate can be used to produce structural shapes in the automotive and machinery industries.

For comparison: the mixture forced through the extruder without the addition of maleic anhydride was brittle and had the following properties:

5r = 37 MPa; a _n = 18 kJ/m ² ; aK = 2 kJ/m ² .

Example II. 2 kilograms of linear low-density polyethylene agglomerate were melt-mixed with 0.04 kilograms of maleic anhydride, 0.8 g of dicumyl peroxide, 4.96 kilograms of ground, used low-density polyethylene waste and 3 kilograms of defibrated polyester/polyamide textile waste as in Example 1, in a co-rotating twin-screw extruder with screws of 25 mm diameter, length 33D, in an air atmosphere at a temperature of 230 - 250°C for 3 minutes.

A polymer was obtained in the form of granules, for injection and extrusion, with the following properties:

- yield strength Rpl = 17.2 MPa

- elongation at yield point spl = 25.3%

- elongation at break e _r = 50.4%

- breaking strength 5r = 15.5 MPa

- Charpy impact strength an > 100 kJ/m2 (samples did not crack)

- notched impact strength according to Charpy aK = 23 kJ/m2;

The granulate can be used to produce: housings of various devices, structural shapes, and in electrical engineering.

Example III. 9.88 kilograms of shredded, used low-density polyethylene waste was melt-mixed with 4 kilograms of low-density polyethylene agglomerate, 0.12 kilograms of maleic anhydride, 3.6 g of dicumyl peroxide and 6 kilograms of defibrated polyester textile waste in the form of a tape in a co-rotating twin-screw extruder with screws of 25 mm diameter and length 33D, in a nitrogen atmosphere at a temperature of 230 - 250°C for 3 minutes.

A polymer was obtained in the form of granules, for injection and extrusion, with the following properties:

- yield strength Rpl = 31.1 MPa

- elongation at yield point spl = 14.3%

- elongation at break ε _Γ = 31.9%

- breaking strength 5r = 13.4 MPa

PL 201 262 B1

- Charpy impact strength a _n > 100 kJ/ ^m2 (samples did not crack)

- Charpy notched impact strength a« = 23 kJ/m2;

Thanks to its high impact strength, the granulate can be used for manufacturing housings for various devices, laboratory equipment, industrial packaging, and electrical engineering. For comparison, unmodified textile waste was characterized by:

5 _r = 12 MPa, a _n = 21kJ/m ² , a« = 2.5 kJ/m ² ;

Example IV. 11.76 kilograms of crushed, used low-density polyethylene waste was melt-mixed with the addition of 0.24 kilograms of maleic anhydride and 7.2 g of di-tert-butyl peroxide in a co-rotating twin-screw extruder with a screw diameter of 25 mm and length of 33D, in a carbon dioxide atmosphere at a temperature of 190°C for 4 minutes.

kilograms of previously grafted low-density polyethylene waste were melt-mixed with the addition of 6 kilograms of defibrated polyester textile waste as in Example III in a co-rotating twin-screw extruder with a screw diameter of 25 mm, length 33D, in an air atmosphere, at a temperature of 230 - 250°C for 3 minutes.

A polymer was obtained in the form of granules, for injection and extrusion, with the following properties:

- yield strength Rpl = 16.9 MPa

- elongation at yield point spl = 27.8%

- elongation at break e _r = 45.5%

- breaking strength 5r = 15.7 MPa

- Charpy impact strength an > 100 kJ/m2 (samples did not crack)

- Charpy notched impact strength a« = 24 kJ/m2;

Granulate can be used to produce: pipes, housings of various devices, laboratory equipment.

Example V. 2.8 kilograms of shredded, used low-density polyethylene waste, 2 kilograms of agglomerated linear low-density polyethylene waste were melt-mixed with the addition of 0.2 kilograms of maleic anhydride, 8 g of dicumyl peroxide and 5 kilograms of defibrated polyester textile waste containing a small admixture of cotton, in the form of a ribbon in a twin-screw co-rotating extruder with a screw diameter of 25 mm, length 33D, in a nitrogen atmosphere, at a temperature of 230 - 250°C for 3 minutes.

A polymer was obtained in the form of granules, for injection and extrusion, with the following properties:

- yield strength Rpl = 12 MPa

- elongation at yield point spl = 82%

- elongation at break er = 98%

- breaking strength 5r = 10 MPa

- both unnotched and notched samples did not crack

Thanks to its very high impact strength and flexibility, the granulate can be used to produce shock absorbers, vibration-eliminating supports, and cable sheathing. For comparison, the extruded mixture without maleic anhydride was brittle and characterized by the following properties:

_5r =14MPa; a _n =17kJ/ ^m2 , aK=1.5kJ/m2.

Example VI. 1.92 kg of crushed, used low-density polyethylene waste was melt-mixed with the addition of 0.08 kilogram of maleic anhydride, 2.4 g of dicumyl peroxide, 12 kilograms of crushed, cleaned and dried to a water content of less than 0.05% by mass used poly(ethylene terephthalate) bottles and 6 kilograms of defibrated polyester textile waste in the form of a ribbon in a twin-screw co-rotating extruder with a screw diameter of 25 mm, length 33D, in an air atmosphere, at a temperature of 240 - 260°C for 5 minutes.

A polymer was obtained in the form of granules, for injection and extrusion, with the following properties:

- yield strength Rpl = 12 MPa

- elongation at yield point spl = 82%

- elongation at break er = 99%

- breaking strength 5r = 10 MPa

- Charpy impact strength an > 100 kJ/m2 (samples did not crack)

- notched impact strength according to Charpy aK = 6 kJ/m2;

PL 201 262 B1

Thanks to its high impact strength and flexibility, the granulate can be used to produce: seals, extruded profiles, e.g. hydraulic hoses.

For comparison: the mixture forced through the extruder without the addition of maleic anhydride was brittle and had the following properties:

5 _r = 16 MPa; a _n = 16 kJ/m ² ; a. = 1.8 kJ:m ² .

Example VII. 3.8 kilograms of shredded, used low-density polyethylene waste, 4.5 kilograms of linear low-density polyethylene were melt-mixed with the addition of 2.2 kilograms of maleic anhydride, 88 g of dicumyl peroxide and 4.5 kilograms of defibrated polyester textile waste containing cotton in the form of a ribbon in a twin-screw co-rotating extruder with screws of 25 mm diameter, length 33D, in a nitrogen atmosphere, at a temperature of 230 - 250°C for 3 minutes.

A polymer was obtained in the form of granules, for injection and extrusion, with the following properties:

- yield strength Rpl = 17.2 MPa

- elongation at yield point spl = 25.3%

- elongation at break er = 51.4%

- breaking strength 5r = 15.5 MPa

- Charpy impact strength an > 100 kJ/m2 (samples did not crack)

- Charpy notched impact strength a« = 24 kJ/m2;

Products made from the granulate composition according to the invention did not delaminate and were characterized by very high impact strength.

Thanks to its very high impact strength, the granulate can be used in the machine industry, e.g. for the production of industrial automation components.

For comparison: the mixture passed through the extruder without the addition of maleic anhydride was brittle and had the following properties:

5r = 14 MPa; an = 17 kJ/m ; a. = 1.5 kJ:m ² .

Example VIII. 6.435 kilograms of polypropylene were melt-blended with the addition of 0.065 kilograms of maleic anhydride, 1.8 g of dicumyl peroxide, and 3.5 kilograms of defibrated polyester textile waste in the form of a ribbon in a co-rotating twin-screw extruder with screws of 25 mm diameter and 33D length, in an air atmosphere, at a temperature of 240 - 260°C for 4 minutes.

A polymer was obtained in the form of granules, for injection and extrusion, with the following properties:

- yield strength Rpl = 22.2 MPa

- elongation at yield point spl = 5.7%

- elongation at break er = 9.2%

- breaking strength 5r = 16.1 MPa

- Charpy impact strength an = 58 kJ/m

- notched impact strength according to Charpy a« = 9 kJ/m

Thanks to its high impact strength, the granulate can be used to produce housings for various devices, laboratory equipment, in the machine industry, and in electrical engineering.

For comparison: the mixture forced through the extruder without the addition of maleic anhydride was brittle and had the following properties:

5r = 13.7 MPa; an = 15 kJ/m; aK = 3.8 kJ/m ² .

Claims (4)

Patent claims 1. Sppsóó produces pplymer compositions, changing the primary or waste material, which is a polyolefin, especially low-density polyethylene or linear low-density polyethylene, with the addition of maleic anhydride in an amount of 0.05 to 5% by weight based on the weight polyolefins and organic peroxide, used in an amount of 1 to 10% by weight based on maleic anhydride, possibly with the addition of polyamide and / or thermoplastic polyester, are mixed and extruded with synthetic textile waste, especially polyester and / or polyamide, used in an amount of 10 - 60% by weight, based on the weight of the composition, in 1 to 5 minutes, ko6 Preferably, under an inert gas atmosphere, in a twin-screw extruder, preferably co-rotating, at a temperature of 230-260 ° C. 2. Quickly follow the steps. The process of claim 1, wherein the maleic bbewood is from 0.2 to 3% by weight, based on the weight of the polyolefin. 3. Sppoóó weeług zzss-z. 1, with a substitute for this. that ζοΙΙΙθποΚ zdzgniccno s ^^ os ^^ is in and lies 2 to 5% by weight in relation to the weight of maleic anhydride. 4.weeług zzssz. The process of claim 1, wherein the ppliolefin noje first melts and mixes with maleic anhydride and organic peroxide in an inert gas atmosphere, and the modified polyolefin is mixed and extruded with polyester and / or polyamide textile waste. Publishing Department of the Polish Patent Office