WO1993013164A1 - Procede de traitement de polymeres reticules - Google Patents
Procede de traitement de polymeres reticules Download PDFInfo
- Publication number
- WO1993013164A1 WO1993013164A1 PCT/FR1992/001181 FR9201181W WO9313164A1 WO 1993013164 A1 WO1993013164 A1 WO 1993013164A1 FR 9201181 W FR9201181 W FR 9201181W WO 9313164 A1 WO9313164 A1 WO 9313164A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solvent
- ozone
- polymer
- process according
- fragments
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/50—Partial depolymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- 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 invention relates to a process for treating crosslinked polymer materials of the polyolefin families and / or natural or synthetic rubber and / or polystyrene in order to obtain polymeric fragments of lower molecular mass.
- the method of the invention applies in particular to the treatment of waste based on these polymers with a view to their recovery, in particular as a texturing agent, coating binder, or raw material for manufacture.
- Crosslinked polymers are very specific compounds, due to their non-linear three-dimensional structure and the strong covalent bonds which ensure the cohesion of the three-dimensional network.
- the crosslinked polymers of the abovementioned families are insoluble in an aqueous medium and in all organic solvents.
- US Patent 1,851,694 describes a process for devulcanizing a rubber by thermal means of the above type, but in the presence of ozone.
- the polymer is heated above above the melting point of sulfur (see page 1 - lines 12 to 15; page 2 - lines 96 and 97) in order to break the sulfur bond; as is known, the ozone then produces the oxidation of the sulfur to lead to the gases S0 2 and SO3 (which facilitates the extraction of the products).
- This US patent indicates that devulcanization is generally carried out in a gaseous medium, but notes that the rubber can be placed in a liquid or solvent in order to fill the interstices between the particles and to slow down the passage of the ozone bubbles (and therefore to limit consumption of this gas).
- This liquid or solvent is not characterized and the ozonation conditions at high temperature show that its only function is the function indicated above, namely filling the voids between particles.
- devulcanization process consists in using devulcanization agents such as derivatives of guanadine, hydrazine or phenylhydroxy lamine which are dissolved in solvents (such as benzine , toluene and xylene, mixed with paraffinic solvents), and this in the presence of metal oxide causing oxidation of sulfur after breaking of the bond by the devulcanization agents.
- devulcanization agents such as derivatives of guanadine, hydrazine or phenylhydroxy lamine which are dissolved in solvents (such as benzine , toluene and xylene, mixed with paraffinic solvents), and this in the presence of metal oxide causing oxidation of sulfur after breaking of the bond by the devulcanization agents.
- solvents such as benzine , toluene and xylene, mixed with paraffinic solvents
- the patent application FR n ° 90.08425 of 06/26/90 in the name of the applicant describes a process for the de-crosslinking of crosslinked polymers based on EVA. a priori not obviously, that the process used for EVA was applicable to other families of polymers or copolymers other than E.V.A. : polyolefins, synthetic or natural rubber, polystyrene.
- the present invention therefore proposes to provide a process for the treatment of crosslinked polymeric materials based on compounds of these families or on corresponding copolymers other than E.V.A. in order to transform the material into polymer fragments of lower molecular mass; the invention thus aims to produce from the crosslinked polymers starting from usable fragments, in particular to allow recovery of the huge volumes of waste that these products give.
- An essential objective of the invention is to carry out this transformation without total destruction of the polymer, that is to say by limiting itself to a controlled cleavage of the molecule by breaking certain bonds.
- the method of the invention is applicable whether the crosslinking is constituted by sulfur bonds or by other bonds (in particular covalent bonds ca r bo n e / c a on e created by a crosslinking with peroxide).
- the process according to the invention is characterized in that it makes it possible to treat crosslinked polymeric materials of defined families, polyolefins, natural or synthetic rubber and polystyrene; he consists of:
- polymer fragments are obtained which are soluble in conventional organic solvents: THF, toluene, benzene, chlorobenzene ..., (the solubility generally exceeds 70% by weight of polymer), these fragments retaining the functionalities of the polymers. of departure.
- the solvent used in the process of the invention is in particular a halogenated solvent of the following group: chlorobutane,, 1, 1-trichloroethane, dichloromethane, carbon tetrachloride, cyclohexane.
- the polymer particles are advantageously incorporated into this. solvent in a concentration range between 10 g / 1 and 200 g / 1. Below 10 g / 1, there is a beginning of destruction of the polymer.
- an aliphatic alcohol is added to the reaction medium in order to facilitate the extraction of the solid phase and the separation of said solid phase by filtration; the solvent is then separated from the alcohol by evaporation for recycling.
- the starting polymeric materials are reduced beforehand in the form of particles having an average sorted granuloma of between 100 and 1500 microns. This size seems to correspond to the better reactivity of ozone with respect to the polymer network in the case of the families concerned.
- the solvent impregnation can be done before the passage of ozone or simultaneously.
- the process is carried out at a temperature between 20 ° C and 70 ° C: in the first case, a low temperature can be chosen within this range; in the second case, a higher temperature is preferable (40 ° C- 70 ° C) in order to accelerate the swelling and to homogenize the attack of ozone from the start of the reaction.
- the time for impregnation with the solvent depends on the concentration of polymer in said solvent and is preferably between 10 and 60 minutes for the concentration range mentioned above, the medium being kept under stirring.
- the swelling obtained corresponds, under these conditions, to an increase in the volume of the reaction medium of at least twice the initial volume.
- the ozone current can be generated by bubbling the reaction medium with stirring of said medium, said bubbling being carried out so that the amount of ozone brought into contact with the medium is between 30 and 200 mg of ozone per liter of medium. ; especially the ozone flow may be between 10 mg and 80 mg per liter of medium and per minute, the ozonation time being between 5 and 500 minutes.
- the bubbling can be carried out by means of a gaseous mixture comprising oxygen and ozone, conventionally prepared in a cold plasma reactor using oxygen or in any other type of ozone generator using oxygen or air.
- Crosslinked polymeric materials of the abovementioned families generally have molecular weights greater than 300,000, these molecular weights being able to reach much higher values.
- the process of the invention implemented under the conditions defined above, makes it possible to obtain polymer fragments with a molecular mass of less than 100,000. This mass can be checked by analyzing samples as the reaction progresses and by stopping it when the desired molecular weight is reached. This molecular weight control is essential in practice to allow the product obtained to be adapted to the applications envisaged.
- the process of the invention can in particular be used to recover industrial waste containing by weight at least 50% of crosslinked or vulcanized polyolefins, rubber or polystyrene, this compound being able to be combined with mineral fillers and other polymers crosslinked or not.
- the invention extends to specific applications in which the polymer fragments obtained have particularly advantageous properties.
- the polymer fragments are used as texturing agent for hydrocarbon binders, in particular bituminous, in which they are incorporated hot. This incorporation improves the rheological and thermal properties of the binder (flexibility, elasticity, mechanical resistance, thermal insensitivity).
- the fragments obtained at the end of the process are used as a binder for coating granules (granules of mineral or synthetic nature) with a view to producing coated materials benefiting, where appropriate, from pigmentation. of the coating layer.
- This coating can be carried out cold, emulsion or hot.
- the polymeric fragments resulting from the process of the invention can also be used as a raw material for manufacturing new products, these fragments being, where appropriate, mixed with other types of polymers.
- the polymeric fragments will be ground to reduce them to an average particle size of between 300 and 1000 microns.
- the incorporation can be carried out directly from the fragments in the form of a powder, or else after solubilization of said powder or emulsification thereof.
- Figure 1 of the accompanying drawing shows a diagram of the installation for implementing said method.
- the process is carried out in a closed reactor 1, equipped with an inlet 2 of oxygen charged with ozone, with distribution in the form of small bubbles by a diffuser 10, and an outlet 3 of residual gas provided with a condenser 4.
- the oxygen source consists of a cylinder 5 and the ozone is generated by an ozone generator 6 of conventional type (cold plasma reactor).
- Output 3 is connected to a conventional type ozone analyzer 7 (potassium iodide solution analyzer).
- a bypass provided with a valve 8 allows, before the treatment, to send the inlet gas to the analyzer 7 for an analysis of its composition.
- Reactor 1 contains the chosen solvent, into which the polymeric materials to be treated are incorporated.
- the medium is constantly agitated by means of an agitator 9.
- the reactor is provided with sample and evacuation outlets.
- the material is a polyethylene crosslinked with 0.8% by weight of peroxide (1,3-ditert-butyl peroxy isopropyl benzene: "Peroximon F").
- the product is ground to a grain size of 300 to
- This crosslinked product (still qualified as vulcanized) has a three-dimensional network of very high molecular mass: one fraction has a molecular mass of the order of 300,000, the other fraction has a much higher molecular mass.
- This product is very slightly soluble in conventional organic solvents.
- the ozonation is stopped after 45 minutes when the maximum solubility is reached.
- the ozonation reactor 1 is then emptied into a container containing i liter of aliphatic alcohol (ethanol, propanol, isopropanol), in this example ethanol; the polyethylene material precipitates. It is recovered by filtration.
- the peroxides and hydroperoxides were assayed with 5-diphenyl picrylhydrazine (DPPH) (2).
- DPPH 5-diphenyl picrylhydrazine
- the peroxide concentration is equal to 8.3 ⁇ 10 ⁇ 4 ⁇ mole equivalent per gram of polymer.
- the molecular mass of the soluble fraction of the final product was determined by gel permeation chromatography with tetrahydrofuran as eluent and a refractometer as a detector. Its value is 82,000. calibration curve was carried out using standard polystyrene on a linear TSK column thermostatically controlled at 40 ° C.
- Example 2 The products used in this application are obtained under the conditions of Example 1 ,. with the exception of the ozonation time which is varied between 60 and 90 minutes (table below).
- This example targets the following four crosslinked starting materials:
- - material B made from 90% polyethylene and 10% SBR (styrene butadiene rubber),
- - material C made from 90% polyethylene and 10% polybutadiene
- - material D made from 90% polyethylene and 10% polyisoprene
- the crosslinked materials A, B, C, D obtained were ground to a particle size of 300 to 800 microns and subjected to the treatment of Example 1, the duration of ozonation being however fixed at double (90 minutes).
- the results of the analyzes of the polymer fragments obtained are as follows:
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Civil Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5511475A JPH07502552A (ja) | 1991-12-23 | 1992-12-11 | 架橋したポリマーの処理方法 |
EP93902328A EP0618939A1 (fr) | 1991-12-23 | 1992-12-11 | Procede de traitement de polymeres reticules |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR91/16330 | 1991-12-23 | ||
FR9116330A FR2685339B1 (fr) | 1991-12-23 | 1991-12-23 | Procede de traitement de polymeres reticules a base de polyolefines, caoutchoucs ou polystyrenes. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993013164A1 true WO1993013164A1 (fr) | 1993-07-08 |
Family
ID=9420651
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1992/001181 WO1993013164A1 (fr) | 1991-12-23 | 1992-12-11 | Procede de traitement de polymeres reticules |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0618939A1 (fr) |
JP (1) | JPH07502552A (fr) |
CA (1) | CA2125042A1 (fr) |
FR (1) | FR2685339B1 (fr) |
WO (1) | WO1993013164A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000009598A1 (fr) * | 1998-08-14 | 2000-02-24 | Otkrytoe Aktsionernoe Obschestvo 'troitskaya Tekhnologicheskaya Laboratoriya' | Materiau caoutchouc-ok et procede de production de materiaux composites |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2728275B1 (fr) * | 1994-12-16 | 1997-03-14 | Europ Propulsion | Procede de traitement de materiaux composites en vue de leur recyclage |
DE69531003T2 (de) * | 1995-03-16 | 2004-05-06 | Ok Tech Inc. | Verfahren zum wiederverwenden von industriellen gummigegenständen |
JP3738403B2 (ja) * | 1996-09-12 | 2006-01-25 | 株式会社豊田中央研究所 | ポリオレフィン架橋材またはポリオレフィン発泡材の再生処理方法 |
DE10012010A1 (de) * | 2000-03-11 | 2001-09-20 | Axiva Gmbh | Verfahren zur Erhöhung der Effektivität der Zerkleinerung von Schüttgütern durch Oxitation |
JP2001261883A (ja) * | 2000-03-23 | 2001-09-26 | Okayama Prefecture | 加硫ゴムの再生方法 |
JP4423750B2 (ja) * | 2000-05-19 | 2010-03-03 | ソニー株式会社 | スルホン化ポリスチレンの製造方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1851694A (en) * | 1928-11-08 | 1932-03-29 | Harry H Culmer | Process of desulphurizing rubber materials |
WO1986005192A1 (fr) * | 1985-03-05 | 1986-09-12 | Oliveira Da Cunha Lima Luiz Ca | Procede de regeneration de caoutchouc vulcanise |
WO1992000334A1 (fr) * | 1990-06-26 | 1992-01-09 | Entreprise 'malet' | Procede de traitement de polymeres a base d'e.v.a. reticule et applications |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU852900A1 (ru) * | 1978-10-30 | 1981-08-07 | Рубежанский Филиал Ворошиловградскогомашиностроительного Института | Способ регенерации отходов пенополи-уРЕТАНА |
-
1991
- 1991-12-23 FR FR9116330A patent/FR2685339B1/fr not_active Expired - Fee Related
-
1992
- 1992-12-11 WO PCT/FR1992/001181 patent/WO1993013164A1/fr not_active Application Discontinuation
- 1992-12-11 EP EP93902328A patent/EP0618939A1/fr not_active Withdrawn
- 1992-12-11 CA CA 2125042 patent/CA2125042A1/fr not_active Abandoned
- 1992-12-11 JP JP5511475A patent/JPH07502552A/ja active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1851694A (en) * | 1928-11-08 | 1932-03-29 | Harry H Culmer | Process of desulphurizing rubber materials |
WO1986005192A1 (fr) * | 1985-03-05 | 1986-09-12 | Oliveira Da Cunha Lima Luiz Ca | Procede de regeneration de caoutchouc vulcanise |
WO1992000334A1 (fr) * | 1990-06-26 | 1992-01-09 | Entreprise 'malet' | Procede de traitement de polymeres a base d'e.v.a. reticule et applications |
Non-Patent Citations (1)
Title |
---|
DATABASE WPIL Derwent Publications Ltd., London, GB; AN 82-65269E (31) * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000009598A1 (fr) * | 1998-08-14 | 2000-02-24 | Otkrytoe Aktsionernoe Obschestvo 'troitskaya Tekhnologicheskaya Laboratoriya' | Materiau caoutchouc-ok et procede de production de materiaux composites |
Also Published As
Publication number | Publication date |
---|---|
EP0618939A1 (fr) | 1994-10-12 |
CA2125042A1 (fr) | 1993-06-24 |
FR2685339A1 (fr) | 1993-06-25 |
FR2685339B1 (fr) | 1995-03-10 |
JPH07502552A (ja) | 1995-03-16 |
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