WO1996028292A1 - Procede pour recycler des produits a base de (meth)acrylates - Google Patents

Procede pour recycler des produits a base de (meth)acrylates Download PDF

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Publication number
WO1996028292A1
WO1996028292A1 PCT/GB1996/000409 GB9600409W WO9628292A1 WO 1996028292 A1 WO1996028292 A1 WO 1996028292A1 GB 9600409 W GB9600409 W GB 9600409W WO 9628292 A1 WO9628292 A1 WO 9628292A1
Authority
WO
WIPO (PCT)
Prior art keywords
grp
glass fibre
polyester
acrylic
residual
Prior art date
Application number
PCT/GB1996/000409
Other languages
English (en)
Inventor
Philip Norton-Berry
Original Assignee
Imperial Chemical Industries Plc
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 Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to EP19960903136 priority Critical patent/EP0873228A1/fr
Priority to AU47280/96A priority patent/AU4728096A/en
Publication of WO1996028292A1 publication Critical patent/WO1996028292A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0217—Mechanical separating techniques; devices therefor
    • B29B2017/0227—Vibratory or shaking tables
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING 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
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING 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
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING 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
    • B29K2709/00—Use of inorganic materials not provided for in groups B29K2703/00 - B29K2707/00, for preformed parts, e.g. for inserts
    • B29K2709/08—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/769—Sanitary equipment
    • B29L2031/7692—Baths
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a process for reclaiming (meth)acrylate based materials, in particular glass fibre reinforced acrylic articles such as acrylic baths backed by a glass reinforced polyester Glass fibre reinforcement is commonly used to provide additional stiffness and rigidity to articles moulded from poly( methyl methacrylate), PMMA
  • glass fibre reinforcement is commonly used to provide additional stiffness and rigidity to articles moulded from poly( methyl methacrylate), PMMA
  • the glass fibre is applied to the reverse side of the moulded article as a mat, either woven or random, or as chopped fibres
  • the glass fibre is held in position by a suitable resin, most commonly a polyester resin, which on curing provides a firm bond to the PMMA
  • GRP glass fibre and cured polyester resin
  • PMMA is able to be depolyme ⁇ sed back to the original monome ⁇ c methyl methacrylate at high efficiencies make it desirable to provide a facile process for the separation of the GRP reinforcement from PMMA articles
  • WO 93/05883 there is disclosed a process for the reclaiming of fibre reinforcement from sheet moulded compound, SMC, in which the fibre is intimately associated with a thermosetting resin
  • the disclosed process requires an initial shredding of the SMC with the subsequent sequential and repeated pulverisation and classification of the shredded material
  • the present invention provides a process for reclaiming a reinforced acrylic article comprising a GRP layer, containing glass fibre reinforcement and a polyester, which is directly bonded to an acrylic layer containing an acrylic polymer which process comprises subjecting a portion of the acrylic article to a shear cutting action of such force that the acrylic layer is substantially detached from the GRP layer so as to produce a crude product comprising a mixture of particulate acrylic polymer which is substantially free of GRP, glass fibre which is substantially free of polyester, polyester which is substantially free of glass fibre and residual GRP which is substantially free from acrylic polymer
  • the reinforced acrylic article may undergo an initial comminution stage in order to produce pieces of material of a suitable size for the equipment in which the shear cutting is performed Typically, an acrylic bath is reduced to pieces of approximately 30 cm by 30 cm prior to shear cutting
  • the shear cutting action may be differentiated from the pulverisation action of the prior art in that in shear cutting the blades or other suitable cutting surfaces pass each other in a scissor like action (or for instance the action used in a cylinder lawn mower) between which the material which is to be cut is trapped whereas in a pulverisation action an accelerating force is provided to the material which causes it to impact on some other surface with such a percussive force that the material loses its structural integrity
  • the material undergoing shear cutting may be thought of having a portion which is being cut off from the remainder of the material This portion may be referred to as the bite of the shear cutting device
  • For a given material and cutting device it is possible to determine by simple experimentation the particular combination of shear force and range of bite size which causes the acrylic layer to be detached from the GRP layer If insufficient shear force is applied for a given bite size then the acrylic layer will not be sufficiently detached from the GRP whereas if too much shear force is applied for a given bite size then the acrylic layer
  • the crude product may be classified using known techniques of air classification and sieving so as to separate a substantial proportion of the acrylic polymer flakes from the glass fibre, polyester and residual GRP
  • a preferred feature of the present invention which comprises a table separator which is longitudinally and transversally inclined and which table separator is oscillated in an approximately circular motion in the general plane of the table
  • Various outlets may be positioned around the perimeter of the table so as to receive appropriate fractions of the crude product which is fed to the table, preferably continuously, at a desired feed position
  • the denser material, principally acrylic polymer will tend to move further up the length of the table whereas the lighter glass fibre, polyester and residual GRP will tend to accumulate lower down the table and by suitable transversal tilting of the table can be removed along the lower side of the table Fortuitously the oscillatory motion of the table has a tendency to cause at least some of the glass fibre to ball together
  • the polyester and the residual GRP to a fluidising
  • the volumetric rate of the fluidising air, and hence the superficial air velocity, used to remove the balls of glass fibre from the table may also be chosen so as to remove at least some of the polyester and GRP from the table thereby leaving a relatively pure fraction of acrylic polymer to be collected which may be depolyme ⁇ sed without significant further treatment and providing an eluted stream containing the eluted glass fibre, polyester, GRP and preferably a relatively small amount of or no acrylic.
  • the present invention provides a reclaimed mixture obtainable from such an eluted stream which reclaimed mixture comprises glass fibre, polyester, and residual GRP having the following size distribution (as expressed by the % by weight of the reclaimed mixture retained on a sieve having a mesh of the appropriate size)
  • Fraction (A) may more typically represent from 8 to 16 % by weight of the reclaimed mixture Within fraction (A), from 0 1 to 5 %, more typically from 0 3 to 1 5 % (by weight of the reclaimed mixture) may be greater than 4 mm.
  • Fraction (B) may more typically represent from 38 to 42 % by weight of the reclaimed mixture. Within fraction (B), from 5 to 20 %, more typically from 8 to 14 % (by weight of the reclaimed mixture) may be greater than 1 mm to 2 mm
  • Fraction (C) may more typically represent from 40 to 45 % by weight of the reclaimed mixture Within fraction (C), from 10 to 20 %, more typically from 12 to 16% (by weight of the reclaimed mixture) is 0.1 mm and less
  • the individual fractions may be separated from each other using conventional separating techniques
  • the reclaimed mixture preferably one or more of fractions (B), (C) and that part of fraction (A) having a size of up to 4 mm, may be reused as a reinforcing agent, particularly in combination with polyester or acrylic resins, for strengthening moulded acrylic articles such as acrylic baths and the like
  • Fractions (B) and (C) have particular utility as reinforcement material, either alone, together or when supplemented by fresh glass fibre, in such moulded articles or other GRP strengthened systems
  • a handlable GRP system containing 65 % or less, preferably 60 % or less, and particularly from 15 to 45 % by weight of the respective fraction may be formed
  • As fraction (C) generally contains a significant amount of polyester powder, also known as dust, it is usual that a GRP system using fraction (C) can contain a higher proportion of it, e g from 30 to 45 % by weight, than a comparable system using fraction (B)
  • the fractions of the reclaimed material which contain the glass fibre balls are reused as reinforcement material once the balls are disentangled
  • the balls of glass fibre are relatively easily disentangled
  • the reclaimed material may be applied as reinforcement by the use of a conventional GRP spray gun
  • a spray gun typically comprises a glass fibre delivery system which feeds glass fibre tow to an air driven chopper
  • the chopper cuts the glass fibre tow into an appropriate size and directs the chopped tow using the exhaust gas from the chopper into the fan of resin issuing from the nozzle of the spray gun
  • the chopped tow is wetted by the resin and is carried by the resin towards the face of the article to be reinforced
  • the reinforced material may be conveniently conveyed to the fan of resin by pneumatic means which also serves to disentangle the balls of glass fibre
  • the reclaimed material is then applied to the face of the article in a manner similar to that used for the glass fibre tow and may also be supplemented by the application of fresh tow at the same time
  • a GRP reinforced acrylic bath comprises an acrylic layer of about 3 mm depth and a GRP layer of comparable thickness
  • the bath is further strengthened by the use of a wooden baseboard which is incorporated into the reverse side of the acrylic bath It is preferred that such a baseboard is removed prior to the reclaiming of the bath as some of the denser material may remain with the reclaimed acrylic polymer Nevertheless, it is possible to perform the comminution of the bath with the baseboard in place
  • the definition of the reclaimed mixture above is on the basis that the reclaimed mixture is free from contaminants such as comminuted baseboard
  • Figure 1 is a plan view of a table separator capable of separating the crude product into various fractions
  • Figure 2a is a photograph of a sample of fraction (A) having a size greater than 4 mm
  • Figure 2b is a photograph of a sample of fraction (A) having a size greater than 2 mm to 4 mm,
  • Figure 3a is a photograph of a sample of fraction (B) having a size greater than 1 mm to 2 mm,
  • Figure 3b is a photograph of a sample of fraction (B) having a size greater than 0 3 mm to 1 mm
  • Figure 4 is a photograph of a sample of fraction (C) having a size greater than 0 1 mm to 03 mm
  • Figure (1 ) shows a table separator (1 ) having a feed zone (2) into which is introduced a crude product comprising acrylic polymer flakes, glass fibre, polyester and residual GRP
  • the table separator (1) has off-takes (3, 4, 5, 6, 7, and 8) for various fractions of material
  • the table separator (1 ) is inclined along direction B such that the feed zone (2) is generally higher than off-takes (3, 4, 5, 6, 7 and 8) and along direction A such that off-take (3) is generally lower than off take (8)
  • a clockwise rotational motion may be applied to the table separator (1 ) in the general plane of the table so as to promote the separation of the material on the table into fractions according to their respective densities This rotational motion may also promote the formation of balls of glass fibre
  • acrylic polymer tends to be migrate towards off-takes (7 and 8) whereas the lighter glass fibre, polyester and GRP tend to migrate to off-takes (3, 4, 5 and 6) from where the material may be collected, returned to the separator or recycled to a previous commin
  • FIGS. 2a and 2b show that fraction (A) mainly contains relatively large bundles of glass fibre with few balls of glass fibre being evident
  • FIGS. 3a and 3b show that fraction (B) contains a significant number of relatively large balls of glass fibre
  • fraction (C) may still contain balls of glass fibre but that the predominant component is polyester dust
  • a proprietary cutter and separator system commonly used for the separation of metal wire from its sheathing of plastic material was employed
  • the system known under the trade name "Firefox” and obtainable from Retech Recycling Technology AB comprises a comminutor, also known as a granulator, which accepts material for shear cutting
  • the cutting is performed by the action of five cylindncally mounted rotating knives against two co-operating stationery knives
  • the cylindncally rotating knives are each 0 5 m in length, have a 5° cut angle and are driven by a 37 kW motor
  • the reinforced acrylic material used in the Examples was prepared by pre-cutting a standard GRP reinforced acrylic bath with baseboard removed into pieces of approximately 30 cm by 30 cm
  • the crude product obtained from the comminutor was then conveyed by vibratory feeder and belt conveyer to a table separator
  • the table separator had an overall length of 1 2 m and was perforated to allow the use of fluidising air up to a maximum rate of 3000 m 3 hr 1
  • the table was inclined to the horizontal by 6° along direction A (as defined in Figure 1 ) and by 3° along direction B (as defined in Figure 1 )
  • Six off-takes were positioned along the length of the table of which the two furthest from the inlet zone were usually used to collect acrylic polymer [Example 1
  • Example 1 was repeated except that the apertures were of 8 mm diameter and 261 kg of material was processed of which 126 kg was eluted from the table separator
  • the eluted material which represents the reclaimed mixture of the present invention had the following size distribution (expressed as % weight of the reclaimed mixture) (i) greater than 4 mm 0.4 %
  • fractions (iii) and (iv) contained a significant number of relatively large balls of glass fibre.
  • Example 3 Example 1 was again repeated except that a total of 1040 kg of material was processed over a period of approximately 50 minutes. 538 kg of the material was eluted from the table separator.

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  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne un procédé pour recycler des articles acryliques renforcés comprenant une couche de composite de fibres de verre et de résine polyester (GRP) fixée sur une couche acrylique. Dans ce procédé, une portion de l'article acrylique est coupée par cisaillement avec une force suffisante pour détacher sensiblement la couche acrylique de la couche de GRP, de manière à fournir un produit brut constitué d'un mélange de particules de polymère acrylique qui sont sensiblement exemptes de GRP, de fibres de verre sensiblement exemptes de polyester, de polyester sensiblement exempt de fibres de verre et de GRP résiduel sensiblement exempt de polymère acrylique. Le mélange de fibres de verre, de polyester et de GRP résiduel constitue une matière première qui peut être réutilisée comme matériau de renforcement pour d'autres articles.
PCT/GB1996/000409 1995-03-09 1996-02-22 Procede pour recycler des produits a base de (meth)acrylates WO1996028292A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP19960903136 EP0873228A1 (fr) 1995-03-09 1996-02-22 Procede pour recycler des produits a base de (meth)acrylates
AU47280/96A AU4728096A (en) 1995-03-09 1996-02-22 A process for reclaiming (meth)acrylate materials

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9504719A GB9504719D0 (en) 1995-03-09 1995-03-09 A process for reclaiming (meth) acrylate materials
GB9504719.7 1995-03-09

Publications (1)

Publication Number Publication Date
WO1996028292A1 true WO1996028292A1 (fr) 1996-09-19

Family

ID=10770886

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1996/000409 WO1996028292A1 (fr) 1995-03-09 1996-02-22 Procede pour recycler des produits a base de (meth)acrylates

Country Status (5)

Country Link
EP (1) EP0873228A1 (fr)
AU (1) AU4728096A (fr)
GB (1) GB9504719D0 (fr)
TW (1) TW325489B (fr)
WO (1) WO1996028292A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2499392A (en) * 2012-02-14 2013-08-21 Future Polymers Llp Recycling a multilayer structure comprising an acrylate polymer substrate
RU2722499C1 (ru) * 2020-02-11 2020-06-01 Роман Александрович Федоров Утилизация многослойной структуры отходов изделий из акрила

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4105285A1 (de) * 1991-02-20 1992-08-27 Peter Pelz Verfahren und vorrichtung zum aufbereiten und wiederverwenden von bereits benutzten rohstoffen aus gebrauchtteilen, die thermo- und duroplaste enthalten
WO1993005883A1 (fr) * 1991-09-18 1993-04-01 Phoenix Fibreglass Inc. Procede de separation des fibres de materiaux composites
US5312052A (en) * 1992-06-01 1994-05-17 Dellekamp Michael D Method for reclaiming fiber reinforcement from a composite
EP0633110A1 (fr) * 1993-07-02 1995-01-11 Phoenix Fibreglass Inc. Procédé pour la séparation des fibres des matériaux renforcés

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4105285A1 (de) * 1991-02-20 1992-08-27 Peter Pelz Verfahren und vorrichtung zum aufbereiten und wiederverwenden von bereits benutzten rohstoffen aus gebrauchtteilen, die thermo- und duroplaste enthalten
WO1993005883A1 (fr) * 1991-09-18 1993-04-01 Phoenix Fibreglass Inc. Procede de separation des fibres de materiaux composites
US5312052A (en) * 1992-06-01 1994-05-17 Dellekamp Michael D Method for reclaiming fiber reinforcement from a composite
EP0633110A1 (fr) * 1993-07-02 1995-01-11 Phoenix Fibreglass Inc. Procédé pour la séparation des fibres des matériaux renforcés

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2499392A (en) * 2012-02-14 2013-08-21 Future Polymers Llp Recycling a multilayer structure comprising an acrylate polymer substrate
GB2499392B (en) * 2012-02-14 2016-10-26 Future Polymers Llp A method of recycling a multilayer structure
RU2722499C1 (ru) * 2020-02-11 2020-06-01 Роман Александрович Федоров Утилизация многослойной структуры отходов изделий из акрила

Also Published As

Publication number Publication date
EP0873228A1 (fr) 1998-10-28
GB9504719D0 (en) 1995-04-26
AU4728096A (en) 1996-10-02
TW325489B (en) 1998-01-21

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