EP4413186A1 - Tire grade high tenacity and modulus recycle nylon 6.6 yarn and production method of it - Google Patents

Tire grade high tenacity and modulus recycle nylon 6.6 yarn and production method of it

Info

Publication number
EP4413186A1
EP4413186A1 EP21960051.7A EP21960051A EP4413186A1 EP 4413186 A1 EP4413186 A1 EP 4413186A1 EP 21960051 A EP21960051 A EP 21960051A EP 4413186 A1 EP4413186 A1 EP 4413186A1
Authority
EP
European Patent Office
Prior art keywords
nylon
pellet
recycled
tire grade
yarn
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
Application number
EP21960051.7A
Other languages
German (de)
French (fr)
Inventor
Cansu AKBASAK
Selvin CILINGIR
Mehmet Sadettin Fidan
Erhan KOP
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kordsa Teknik Tekstil AS
Original Assignee
Kordsa Teknik Tekstil AS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kordsa Teknik Tekstil AS filed Critical Kordsa Teknik Tekstil AS
Priority claimed from PCT/TR2021/051018 external-priority patent/WO2023059275A1/en
Publication of EP4413186A1 publication Critical patent/EP4413186A1/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F13/00—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like
    • D01F13/04—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like of synthetic polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/48—Tyre cords
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/02—Reinforcing materials; Prepregs
    • D10B2505/022—Reinforcing materials; Prepregs for tyres

Definitions

  • the present invention related to recycled nylon 6.6 pellet production from tire grade nylon 6.6 yam scraps.
  • Said recycled nylon 6.6 pellet is used in tire grade nylon 6.6 yarn production in different ratio with virgin nylon 6.6 pellet.
  • Aim of this study is to get the comparable physical, thermal, mechanical properties and production process with recycled nylon 6.6. tire grade yam with respect to virgin one.
  • the study also serves the global sustainability issues that will deeply explain in below.
  • Nylon is a polymer, composed of repetitive units of diamines and dicarboxylic acids that contains different numbers of carbon atoms. Polymerization reaction takes place in a batch or continuous process in accompany with pressure, vacuum and heat. Nylon 6.6 thermoplastic polymer is made from petrochemical monomers, combined to form a long chain through a condensation polymerisation reaction.
  • Petroleum based polymers have been used since a long time due to its handiness, durability, flexibility, and less reactivity towards the water and other chemical.
  • Petroleum based polymers have been used since a long time due to its handiness, durability, flexibility, and less reactivity towards the water and other chemical.
  • civilization begin to realize that word have limited petrochemical sources. This will endanger the balance between nature of the environment and development of science. Therefore, how to respect both of the environment and human development is became a challenging issue for the recent studies.
  • Nylon is not biodegradable, and will persist in the environment indefinitely.
  • the two of the largest sources of microplastic pollution in the ocean are nylon fishing nets and synthetic textile fibers. This means that the impact of nylon on the aquatic environment is significant.
  • the persistent nature of nylon means that it is infinitely recyclable and we could cease new nylon production now and still meet our desire for nylon if we recycled all of the nylon material currently in existence. Thus, it is need to increase the accessibility of nylon recycling schemes to the average consumer.
  • the present invention consists of two main processes and products as indicated below. i. Recycled nylon 6.6. pellet production from tire grade oiled and non-oiled nylon 6.6 drawn and undrawn yam scraps that are occurred standard tire grade yam production. ii. Tire grade yarn production with the mixture of virgin and recycled nylon 6.6 pellets in a different recycled pellet ratio with a comparable process and product properties.
  • Pellet mixture that is consist of certain proportion of virgin and recycled nylon 6.6 pellets are go through the solid state polymerization process in a certain conditioning temperature to get the desired relative viscosity level for the spinning process.
  • Virgin to recycle pellet level 10:90 to 90:10, preferably production performed in range of 80:20 to 50:50 to get the comparable yield, process performance, productivity, sustainability of the production and product and also yarn properties.
  • Both of the flake type has maximum 0,5 % moisture level.
  • nylon 6.6 recycled pellet has between 0,01 to 0,05 % finish oil level.
  • Figure 1 Standard yam bobbins (1.8)( tire grade nylon 6.6 yarn bobbins ) production steps consist of virgin nylon 6.6 pellets (virgin nylon 6.6 pellets flake) (1.1) fed to silos, first nylon 6.6 pellets purged (1.2) and then they have solid state polymerization process (1.3), polymerized nylon 6.6 pellets converted to molten nylon 6.6 polymer (1.4), molten nylon 6.6 polymer go through a die to get the round filament shape (1.5), nylon 6.6 polymer filament cooled(1.6), nylon 6.6 filament have some process steps to get the desire end properties(1.7), at the end tire grade nylon 6.6 yarn bobbins (1.8) were produced.
  • the method for recycling nylon 6.6 pellets includes the steps of collecting oiled and non-oiled nylon 6.6 drawn and undrawn yarn scraps during yarn production (2.1); chopping nylon 6.6 yarn scraps into short strands (2.2) ; transporting the chopped nylon 6.6 yarn scraps to the compressing unit (2.3); feeding the compressed nylon 6.6 scraps into the extruder(2.4); melting of nylon 6.6 scraps(2.5); vacuuming of oil from molten polymer (2.6) ; to form nylon 6.6 strands (2.7); cooling the nylon 6.6 strands in the water bath (2.8); drying nylon 6.6 strands coming out of the water bath (2.9); pelletizing of nylon 6.6 strands (2.10); collecting recycled nylon 6.6 pellets (2.11) and packaging of recycled nylon 6.6 pellets (2.12) .
  • Figure 3 This figure is very similar to Figure 1. Only difference is; at the beginning of the process, virgin (3.1) and recycled (3.2) flakes are mixed homogeneous with a blending system in a certain proportion.
  • Tire grade yarn Nylon 6.6 yarn that have minimum 8,0 gpd (grams per denier) tenacity and 100 to 5000 dtex density level.
  • nylon 6.6 pellet nylon 6.6 pellet that is form from scrap material
  • Tire grade nylon 6.6 yarn nylon 6.6 yarn used in cord in tires
  • Oiled and non-oiled nylon 6.6 drawn and undrawn yarn scraps yarn scraps that are processed and unprocessed
  • Nylon 6.6 strands molten polymer after the extruder (like a spaghetti)
  • the invention relates to a tire grade nylon 6,6 mono- and/or multi filament yam comprising at least 10 % recycled nylon 6,6, preferably 20% recycled nylon 6,6 wherein the said nylon 6,6 mono or multi filament yam has at least 8,0 gpd tenacity according to ASTM-D 885.
  • ASTM-D 885 is a standard test methods for tire cords, tire cord fabrics, and industrial filament yams made from man-made organic-base fibers.
  • the tire grade nylon 6,6 mono- and/or multi filament yarn has at least 1,25 gpd 4 % SASE according to ASTM-D 885.
  • a manufacturing method of a tire grade nylon 6,6 mono- and/or multi filament yam comprises the steps of: a) Recycled nylon 6.6 pellet production,
  • tire grade oiled and/or non-oiled drawn and/or undrawn nylon 6.6 fiber scraps including filament yarn is cut ranges from 3 cm to 5 cm to get nylon 6.6 chopped fibers.
  • Chopped fibers feed to extruder to get the molten polymer from the scrap yarns.
  • Vaccum is active during the tire grade recycled pellet production to remove the finish oil in the polymer matrix coming from the scrap oiled yam production process. It is very critical process for the production since the high finish oil level caused in low production yields and high break levels in spinning. Main aim is to minimize the finish oil level in the recycled pellet.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Artificial Filaments (AREA)

Abstract

In this invention, tire grade oiled and non-oiled nylon 6.6 drawn and undrawn scrap yarns converted to recycled nylon 6.6 pellet. Then, recycled nylon 6.6 pellet is used with virgin nylon 6.6 pellet in a different ratio to produce tire grade reycled nylon 6.6 yarn.

Description

TIRE GRADE HIGH TENACITY AND MODULUS RECYCLE NYLON 6.6 YARN AND PRODUCTION METHOD OF IT
Technical Field of the Invention
The present invention related to recycled nylon 6.6 pellet production from tire grade nylon 6.6 yam scraps. Said recycled nylon 6.6 pellet is used in tire grade nylon 6.6 yarn production in different ratio with virgin nylon 6.6 pellet. Aim of this study is to get the comparable physical, thermal, mechanical properties and production process with recycled nylon 6.6. tire grade yam with respect to virgin one. The study also serves the global sustainability issues that will deeply explain in below.
Prior Art
Nylon is a polymer, composed of repetitive units of diamines and dicarboxylic acids that contains different numbers of carbon atoms. Polymerization reaction takes place in a batch or continuous process in accompany with pressure, vacuum and heat. Nylon 6.6 thermoplastic polymer is made from petrochemical monomers, combined to form a long chain through a condensation polymerisation reaction.
Petroleum based polymers have been used since a long time due to its handiness, durability, flexibility, and less reactivity towards the water and other chemical. In the recent year, with the rise of global environment and sustainability issues, mankind begin to realize that word have limited petrochemical sources. This will endanger the balance between nature of the environment and development of science. Therefore, how to respect both of the environment and human development is became a challenging issue for the recent studies.
Nylon is not biodegradable, and will persist in the environment indefinitely. The two of the largest sources of microplastic pollution in the ocean are nylon fishing nets and synthetic textile fibers. This means that the impact of nylon on the aquatic environment is significant. On the other hand, the persistent nature of nylon means that it is infinitely recyclable and we could cease new nylon production now and still meet our desire for nylon if we recycled all of the nylon material currently in existence. Thus, it is need to increase the accessibility of nylon recycling schemes to the average consumer.
Brief Description and Objectives of the Invention
The present invention consists of two main processes and products as indicated below. i. Recycled nylon 6.6. pellet production from tire grade oiled and non-oiled nylon 6.6 drawn and undrawn yam scraps that are occurred standard tire grade yam production. ii. Tire grade yarn production with the mixture of virgin and recycled nylon 6.6 pellets in a different recycled pellet ratio with a comparable process and product properties.
Pellet mixture that is consist of certain proportion of virgin and recycled nylon 6.6 pellets are go through the solid state polymerization process in a certain conditioning temperature to get the desired relative viscosity level for the spinning process. Virgin to recycle pellet level of 10:90 to 90:10, preferably production performed in range of 80:20 to 50:50 to get the comparable yield, process performance, productivity, sustainability of the production and product and also yarn properties. Both of the flake type has maximum 0,5 % moisture level.
Addition to that, chopped nylon 6.6 yam scraps finish oil level is between 0, 7-1,0 %. Before the recycled nylon 6.6 pellet production, there is no washing unit for scraps to get rid of the oil. Finish oil is removed from the scrap polymer in the vacuum zone of the extruder during the recycled nylon 6.6 pellet production steps that was detailed explained in Figure 2. At the end of the production, nylon 6.6 recycled pellet has between 0,01 to 0,05 % finish oil level.
Definitions of the Figures Describing the Invention The present disclosure can be more understood by reading the following detailed description of the drawings as follows;
Figure 1: Standard yam bobbins (1.8)( tire grade nylon 6.6 yarn bobbins ) production steps consist of virgin nylon 6.6 pellets (virgin nylon 6.6 pellets flake) (1.1) fed to silos, first nylon 6.6 pellets purged (1.2) and then they have solid state polymerization process (1.3), polymerized nylon 6.6 pellets converted to molten nylon 6.6 polymer (1.4), molten nylon 6.6 polymer go through a die to get the round filament shape (1.5), nylon 6.6 polymer filament cooled(1.6), nylon 6.6 filament have some process steps to get the desire end properties(1.7), at the end tire grade nylon 6.6 yarn bobbins (1.8) were produced.
Figure 2: The method for recycling nylon 6.6 pellets includes the steps of collecting oiled and non-oiled nylon 6.6 drawn and undrawn yarn scraps during yarn production (2.1); chopping nylon 6.6 yarn scraps into short strands (2.2) ; transporting the chopped nylon 6.6 yarn scraps to the compressing unit (2.3); feeding the compressed nylon 6.6 scraps into the extruder(2.4); melting of nylon 6.6 scraps(2.5); vacuuming of oil from molten polymer (2.6) ; to form nylon 6.6 strands (2.7); cooling the nylon 6.6 strands in the water bath (2.8); drying nylon 6.6 strands coming out of the water bath (2.9); pelletizing of nylon 6.6 strands (2.10); collecting recycled nylon 6.6 pellets (2.11) and packaging of recycled nylon 6.6 pellets (2.12) .
Figure 3: This figure is very similar to Figure 1. Only difference is; at the beginning of the process, virgin (3.1) and recycled (3.2) flakes are mixed homogeneous with a blending system in a certain proportion.
Tire grade yarn: Nylon 6.6 yarn that have minimum 8,0 gpd (grams per denier) tenacity and 100 to 5000 dtex density level.
4 % SASE: Stress at 4 % elongation (gpd)
Tenacity: strength of yarn (gram) / density of yarn (denier) (gpd)
Virgin nylon 6.6 pellet: Raw nylon 6.6 pellet
Recycled nylon 6.6 pellet: nylon 6.6 pellet that is form from scrap material Tire grade nylon 6.6 yarn: nylon 6.6 yarn used in cord in tires
Oiled and non-oiled nylon 6.6 drawn and undrawn yarn scraps: yarn scraps that are processed and unprocessed
Nylon 6.6 strands: molten polymer after the extruder (like a spaghetti)
Detailed Description of the Invention
The invention relates to a tire grade nylon 6,6 mono- and/or multi filament yam comprising at least 10 % recycled nylon 6,6, preferably 20% recycled nylon 6,6 wherein the said nylon 6,6 mono or multi filament yam has at least 8,0 gpd tenacity according to ASTM-D 885.
ASTM-D 885 is a standard test methods for tire cords, tire cord fabrics, and industrial filament yams made from man-made organic-base fibers.
The tire grade nylon 6,6 mono- and/or multi filament yarn has at least 1,25 gpd 4 % SASE according to ASTM-D 885.
A manufacturing method of a tire grade nylon 6,6 mono- and/or multi filament yam comprises the steps of: a) Recycled nylon 6.6 pellet production,
• Cutting of tire grade oiled and/or non-oiled drawn and/or undrawn nylon 6.6 fiber scraps including mono- and/or multi- filament yarn into 3 cm to 5 cm to get nylon 6.6 chopped fibers,
• Feeding to extruder that has minimum 250°C and maximum 290°C in 6 zones to get the molten nylon 6.6 polymer from the scrap yarns,
• Cooling of strands,
• Cutting in a size between 300 to 500 pellet in 10 gram which is shaped as a pellet form, wherein recycled nylon 6.6 pellet that has maximum 0,05 % finish oil in it, b) Virgin nylon 6.6 pellet production, c) Mixture of virgin and recycled nylon 6.6 pellets in minimum 20 % recycle pellet ratio to produce tire grade recycled nylon 6.6 yam.
At the beginning of the process, tire grade oiled and/or non-oiled drawn and/or undrawn nylon 6.6 fiber scraps including filament yarn is cut ranges from 3 cm to 5 cm to get nylon 6.6 chopped fibers. Chopped fibers feed to extruder to get the molten polymer from the scrap yarns. Molten polymer shaped to molten fiber in a certain diameter and cool in a water bath. After cooling of the fiber polymer, they cut in a certain size that called strand pelletizing system in the literature.
Vaccum is active during the tire grade recycled pellet production to remove the finish oil in the polymer matrix coming from the scrap oiled yam production process. It is very critical process for the production since the high finish oil level caused in low production yields and high break levels in spinning. Main aim is to minimize the finish oil level in the recycled pellet.
Since the tire grade recycled pellet and virgin pellet mixed during the production, homogenious mixing is another critical parameter in the preparation phase of the solid state polymerization. Pellet size of the two pellet grade need to be as much as close each other to prevent separation in the silos. So that, granulometry of the tire grade recycled pellet were improved for the tire grade recycled yam production. Tire grade recycled amount in the yarn depends on the customer expectations and minimum specification requirements. However according to “Global Recycling Certification” system, minimum requirement of the recycled amount is 20 % in the end product. So that according to this regulation, studies were focused to 20 % recycled material in the tire grade yam. Recycled pellet and virgin pellet was mixed and fed to silo for conditioning. Solid state polymerization was adjusted according to new mixtured raw material to get the same RV level at the end of the conditioner exit.

Claims

CLAIMS A tire grade nylon 6,6 mono- and/or multi filament yam comprising at least 10 % recycled nylon 6,6 pellet wherein the said nylon 6,6 filament yarn has at least 8,0 gpd tenacity according to ASTM-D 885. The tire grade filament yam according to Claim 1 comprising 20% recycled nylon 6,6 The tire grade filament yarn according to Claim 1, characterized in having at least 1,25 gpd 4 % SASE according to ASTM-D 885. A manufacturing method of a tire grade filament yarn according to the Claim 1 comprising the steps of: a) Preparing recycled nylon 6.6 pellet by
• Cutting of tire grade oiled and/or non-oiled drawn and/or undrawn nylon 6.6 fiber scraps including mono- and/or multi- filament yarn into 3 - 5 cm to get nylon 6.6 chopped fibers,
• Feeding to extmder that has minimum 250°C and maximum 290°C in 6 zones to get the molten nylon 6.6 polymer from the scrap yams,
• Cooling of strands,
• Cutting in a size between 300 to 500 pellet in 10 gram which is shaped as a pellet form, wherein recycled nylon 6.6 pellet having maximum 0,05 % finish oil in it, b) Preparing Virgin nylon 6.6 pellet
Mixing virgin and recycled nylon 6.6 pellets
6
EP21960051.7A 2021-10-05 2021-10-06 Tire grade high tenacity and modulus recycle nylon 6.6 yarn and production method of it Pending EP4413186A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR202115509 2021-10-05
PCT/TR2021/051018 WO2023059275A1 (en) 2021-10-05 2021-10-06 Tire grade high tenacity and modulus recycle nylon 6.6 yarn and production method of it

Publications (1)

Publication Number Publication Date
EP4413186A1 true EP4413186A1 (en) 2024-08-14

Family

ID=91934293

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21960051.7A Pending EP4413186A1 (en) 2021-10-05 2021-10-06 Tire grade high tenacity and modulus recycle nylon 6.6 yarn and production method of it

Country Status (1)

Country Link
EP (1) EP4413186A1 (en)

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