GB2443471A - Treatment of polyamides - Google Patents

Treatment of polyamides Download PDF

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Publication number
GB2443471A
GB2443471A GB0618060A GB0618060A GB2443471A GB 2443471 A GB2443471 A GB 2443471A GB 0618060 A GB0618060 A GB 0618060A GB 0618060 A GB0618060 A GB 0618060A GB 2443471 A GB2443471 A GB 2443471A
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GB
United Kingdom
Prior art keywords
silicone
process according
coated
polyamide material
hydroxide
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.)
Withdrawn
Application number
GB0618060A
Other versions
GB0618060D0 (en
Inventor
William Bond
Rachel Andrews
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.)
PETLON POLYMERS Ltd
Original Assignee
PETLON POLYMERS Ltd
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 PETLON POLYMERS Ltd filed Critical PETLON POLYMERS Ltd
Priority to GB0618060A priority Critical patent/GB2443471A/en
Publication of GB0618060D0 publication Critical patent/GB0618060D0/en
Priority to PCT/GB2007/003442 priority patent/WO2008032052A1/en
Publication of GB2443471A publication Critical patent/GB2443471A/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00Recovery or working-up of waste materials
    • C08J11/04Recovery or working-up of waste materials of polymers
    • C08J11/06Recovery or working-up of waste materials of polymers without chemical reactions
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00Recovery or working-up of waste materials
    • C08J11/04Recovery or working-up of waste materials of polymers
    • C08J11/06Recovery or working-up of waste materials of polymers without chemical reactions
    • C08J11/08Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02Separating plastics from other materials
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D9/00Chemical paint or ink removers
    • C09D9/04Chemical paint or ink removers with surface-active agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04Disintegrating plastics, e.g. by milling
    • B29B17/0412Disintegrating plastics, e.g. by milling to large particles, e.g. beads, granules, flakes, slices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02Separating plastics from other materials
    • B29B2017/0213Specific separating techniques
    • B29B2017/0293Dissolving the materials in gases or liquids
    • B29B2017/0296Dissolving the materials in aqueous alkaline solutions, e.g. NaOH or KOH
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2083/00Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2022/00Hollow articles
    • B29L2022/02Inflatable articles
    • B29L2022/027Air bags
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/62Plastics recycling; Rubber recycling

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Sustainable Development (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A process for removing silicone from polyamide material is provided which comprises treating silicone-coated polyamide material at an elevated temperature with an aqueous composition containing a surfactant, an alkaline hydroxide at a concentration of less than 2.1 percent hydroxide ion content by weight, and an alcohol miscible at that elevated temperature with the hydroxide solution, under such conditions of temperature and pressure and for such a duration of time as to dissolve the silicone coating but also to produce a lowering of the relative viscosity in formic acid of the polyamide of no more than 25. The process is particularly suitable for removal of silicones from airbags made from silicone-coated polyamide textiles.

Description

TR1ATMENT OF POLYAMIDES This invention relates to the treatment of
polyamides, and, in particular, to a process for removal of silicone coatings from polyamides. The invention has particular utility in the removal of silicones from airbags made from silicone-coated polyamide textiles.
It is becoming common to treat polyamide textile materials with silicone coatings to render those materials air-proof The use of silicone-coated air-proof polyamide textiles for vehicle airbags is now widespread, and it is desirable to be able to remove the silicone coatings from the polyamide material in order that the polyamide be rendered available for recycling.
A process for recycling polyamide material coated with silicone resin is disclosed in published European Patent Application No. 950684 A2 in the name of F.A. Rueb Holding GmbH. The method there proposed involves the treatment of the coated polyamide at elevated temperature, with an alkaline hydroxide at a concentration of 5 to 50% by weight, preferably 10 to 30% by weight, of the alkaline hydroxide. It is indicated that the thermal treatment of the polyamide material can take place in the presence of a tenside. A disadvantage of the method proposed in European Patent Publication No. 950684 A2 is that the concentration of the hydroxide is so great as to degrade the polyamide being treated.
Specifically, the strength of the alkaline hydroxide solution is such as to shorten the polymer chains to such an extent that the physical properties of the polyamide are degraded, thus producing a recycled product of reduced commercial value.
I
Adc nally, US Patent No. 4654041 to Hansa Textil Chemie GmbH discloses a process for removal from textile materials such as cotton fabric, wool/polyacryl knitted fabric, and cottonlpolyester corduroy fabrics silicones which have been applied to those materials for the purpose providing those fabrics with a soft and pliant feel. The disclosed process comprises treating the material with an aqueous preparation containing surface active equilibration catalysts for organosiloxanes selected from the group consisting of alkyl or aryl or alkylaryl suiphonic acids, aliphatic alcohols with 3 to 15 carbon atoms, and surface-active quatemary ammonium compounds, said catalysts being present in an amount of 0.2 to 5 weight percent.
The aqueous preparation may additionally contain an alkali carbonate and may also contain auxiliary solvents for the equilibration catalysts, which may be low molecular weight water-soluble alcohols such as isopropyl alcohol. That invention, however, is not at all concerned with polyamide textiles nor with airbags produced from polyamide textiles and can be thought of merely as a laundering process, taking place in conventional washing machines as commonly used in the textile industry.
According to the present invention there is provided a process for removing silicone from polyamide material which comprises treating silicone-coated polyamide material at an elevated temperature with an aqueous composition containing a surfactant, an alkaline hydroxide at a concentration of less than 2.1 percent hydroxide ion content by weight, and an alcohol miscible at that elevated temperature with the hydroxide solution, under such conditions of temperature and pressure and for such a duration of time as to dissolve the silicone coating but also to produce a lowering of the relative viscosity in formic acid of the polyamide of no more than 25. 1.
The* .sent invention also extends to polyamide which has been treated by the process of the present invention.
The combination of temperature, pressure and period of contact of the silicone-coated polyamide material with the treatment solution is chosen to achieve efficient dissolution of the silicone coating with minimum degradation of the quality of the polyamide material as defined by the lowering of its relative viscosity (a measure of the degree of polymer chain shortening to which the polyamide material has been subjected). Suitable temperatures may be selected from the range 900 to 180 Centigrade, e.g. 130 Centigrade.
Preferably the polyamide material is reduced to small pieces since it has been found that the process performs better in such circumstances.
Any suitable surfactant may be employed in the process of the present invention; surfactants which have been found to be suitable include cationic or amphoteric surfactants, either used alone or used in combination with non-ionic surfactants. Preferred surfactants include quaternary ammonium salts, preferably quatemary ammonium chlorides, such as ditallowdimethylammonium chloride, dimethyldidecyl ammonium chloride (DDAC) as well as alcohol ethoxylates. Specific examples of suitable surfactants are those commercially available under the trade marks BEROL 185, ARQUAD 2.10-80, ARQUAD 2T-70 and HANSA SR 142.
Any suitable alcohol may be used; examples of alcohols which have been found to be satisfactory in the process of the present invention include ethanediol, isopropanol, 2,3-butanediol and 2,5 -dimethyl-2,5-hexanediol.
The alkaline hydroxides which may be used include sodium hydroxide, potassium hydroxide and ammonium hydroxide.
Preferably the proportion of the polyamide material to the aqueous composition is approximately 20:100 by weight. Preferably the alkaline hydroxide is used at a concentration of 0.5 to 2.85 percent by weight of the treatment liquor.
Although the invention is applicable to polyamide materials in general, the remainder of the specification will concentrate particularly on nylon-6,6 and upon nylon-6, and, in particular, upon the process of treating airbags made from nylon textiles coated with silicone, in order to retrieve high-quality nylon.
Reference has been made hereinbefore to determining the degradation in quality of the nylon by determination of its relative viscosity after being subjected to the process of the present invention. Relative viscosity is determined according to standard test method ASTM D789- 04: Determination of Relative Viscosity of Polyamide', and is with respect to 90% formic acid.
We now set out by way of example only, embodiments of the process of the present invention. In each example the airbag pieces were present in the solution in an amount of approximately 2.25g per lOOg of solution.
Exa ile 1 An airbag made of woven nylon-6,6 coated with a silicone was cut up into small pieces and was then treated with an aqueous solution containing 5% by weight of isopropanol and 2% by weight of sodium hydroxide for a period of one hour and at a temperature of 130 C. The pieces were then neutraliseci and washed to remove the treatment solution, and the relative viscosity of the recovered nylon-6,6 measured by the ASTM method referred to above. The relative viscosity was found to be 54, whereas the relative viscosity measured by the same method of virgin' nylon-6,6 was approximately 60, a drop in relative viscosity ofjust 6.
Example 2
An airbag made of woven nylon-6,6 coated with a silicone was cut up into small pieces and was then treated with an aqueous solution containing 5% by weight of ethylene glycol and 2% by weight of sodium hydroxide for a period of two hours and at a temperature of 130 C. The pieces were then neutral ised and washed to remove the treatment solution, and the relative viscosity of the recovered nylon-6,6 measured by the ASTM method referred to above. The relative viscosity was found to be 51, whereas the relative viscosity measured by the same method of virgin' nylon-6,6 was approximately 60, a drop in relative viscosity ofjust 9.
Example 3
An airbag made of woven nylon-6,6 coated with a silicone was cut up into small pieces and was then treated with an aqueous solution containing 4% by weight of ditallowdimethyl ammonium chloride, 2% by weight of sodium hydroxide and 1% by weight of Berol 185' (Berol 185 is a non-ionic surfactant based on a synthetic primary alcohol) for a period of one hour and at a temperature of 130 C. The pieces were then neutralised and washed to remove the treatment solution, and the relative viscosity of the recovered nylon-6,6 measured by the AS. method referred to above. The relative viscosity was found to be 54, whereas the relative viscosity measured by the same method of virgin' nylon-6,6 was approximately 60, a drop in relative viscosity ofjust 6.
It will be appreciated that the invention may be performed otherwise than as particularly described hereinbefore and the present invention includes within its scope all modifications and variations which would be apparent to one skilled in the art. r

Claims (14)

CL MS
1. A process for removing silicone from polyamide material which comprises treating silicone-coated polyamide material at an elevated temperature with an aqueous composition containing a surfactant, an alkaline hydroxide at a concentration of less than 2.1 percent hydroxide ion content by weight, and an alcohol miscible at that elevated temperature with the hydroxide solution, under such conditions of temperature and pressure and for such a duration of time as to dissolve the silicone coating but also to produce a lowering of the relative viscosity in formic acid of the polyamide of no more than 25.
2. A process according to claim I wherein the polyamide material is nylon-6,6 or nylon-6.
3. A process according to claim I or claim 2 wherein the silicone-coated polyamide material is a nylon textile coated with silicone.
4. A process according to claim 3 wherein the silicone-coated polyamide material is an airbag made from silicone-coated nylon textile.
:.
5. A process according to any one of the preceding claims wherein the silicone-coated *::::* polyamide material is reduced to small pieces before the treatment. s. * S S *
6. A process according to any one of the preceding claims wherein the elevated : temperature is a temperature selected from the range 9 0 to 1800 Centigrade.
S.....
S
7. A process according to any one of the preceding claims wherein the surfactant is selected from cationic and amphoteric surfactants, either used alone or used in combination with non-ionic surfactants.
8. A process according to claim 7 wherein the surfactant is selected from quaternary ammonium salts and alcohol ethoxylates.
9. A process according to claim 8 wherein the surfactant is a quaternary ammonium salt selected from ditallowdimethylammonium chloride and dimethyldidecyl ammonium chloride (DDAC).
10. A process according to any one of the preceding claims wherein the alkaline hydroxide is selected from sodium hydroxide, potassium hydroxide and ammonium hydroxide.
11. A process according to any one of the preceding claims wherein the alcohol is selected from ethanediol, isopropanol, 2,3-butanediol and 2,5-dimethyl-2,5-hexanedjol
12. A process according to any one of the preceding claims wherein the proportion of the :*. silicone-coated polyamide material to the aqueous composition is approximately 20:100 by *,_ weight. *... * S S S. I
13. A process according to any one of the preceding claims wherein the alkaline hydroxide is used at a concentration of 0.5 to 2.85 percent by weight of the aqueous composition.
14. Polyamide material which has been treated by a process according to any one of the preceding claims. * S * S.. S... * * .. *554 * S * *5 S
S * * S S *
S
S
GB0618060A 2006-09-13 2006-09-13 Treatment of polyamides Withdrawn GB2443471A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
GB0618060A GB2443471A (en) 2006-09-13 2006-09-13 Treatment of polyamides
PCT/GB2007/003442 WO2008032052A1 (en) 2006-09-13 2007-09-12 Treatment of polyamides

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB0618060A GB2443471A (en) 2006-09-13 2006-09-13 Treatment of polyamides

Publications (2)

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GB0618060D0 GB0618060D0 (en) 2006-10-25
GB2443471A true GB2443471A (en) 2008-05-07

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WO (1) WO2008032052A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2973274B1 (en) * 2011-03-31 2016-05-06 Rhodia Operations METHOD OF PROCESSING TECHNICAL TEXTILES
JP7024037B1 (en) 2020-10-30 2022-02-22 豊田通商株式会社 Polyamide fiber recovery method, recycled polyamide product manufacturing method, and silicone solution
JP7383093B1 (en) 2022-08-02 2023-11-17 信越化学工業株式会社 How to recycle silicone coated resin base material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0950864A1 (en) * 1998-04-15 1999-10-20 Industri Ab Sigarth An apparatus for mounting a radiator on a substrate
WO2007009856A1 (en) * 2005-07-15 2007-01-25 Cht R. Beitlich Gmbh Removing the silicone coating from coated fabrics and airbags

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3388029A (en) * 1965-01-19 1968-06-11 Monsanto Co Dimensionally stabilized polyamide yarns and rubber products reinforced therewith
GB1093203A (en) * 1965-02-05 1967-11-29 Monsanto Co Process for producing high viscosity nylon polymer and polymer so produced
GB1221123A (en) * 1967-03-09 1971-02-03 Fiber Industries Inc Improvements in production of shaped articles, such as filaments, from polyamides by melt spinning
DE3515077C1 (en) * 1985-04-26 1986-06-19 Hansa Textilchemie GmbH, 2806 Oyten Process for removing silicones on fibers, yarns or flat textile materials
JPS62149380A (en) * 1985-12-23 1987-07-03 Toray Ind Inc Method for removing cured film
EP0589642A1 (en) * 1992-09-24 1994-03-30 General Electric Company Salvaging organic thermoplastics
US5817183A (en) * 1996-08-12 1998-10-06 General Electric Company Method for removing coatings from thermoplastic substrates
US6011134A (en) * 1998-01-30 2000-01-04 E. I. Du Pont De Nemours And Company Method for manufacturing poly(hexamethylene adipamide) from monomethyladipate and hexamethylenediamine
DE19817160C2 (en) * 1998-04-17 2001-05-17 Rueb F A Holding Gmbh Process for recycling polyamide material containing silicone resin
JP3879348B2 (en) * 1999-12-24 2007-02-14 タカタ株式会社 Method for removing silicon from airbag scrap fabric

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0950864A1 (en) * 1998-04-15 1999-10-20 Industri Ab Sigarth An apparatus for mounting a radiator on a substrate
WO2007009856A1 (en) * 2005-07-15 2007-01-25 Cht R. Beitlich Gmbh Removing the silicone coating from coated fabrics and airbags

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Publication number Publication date
WO2008032052A1 (en) 2008-03-20
GB0618060D0 (en) 2006-10-25

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