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WO2003033567A1 - Nanocomposite polymere - Google Patents

Nanocomposite polymere Download PDF

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Publication number
WO2003033567A1
WO2003033567A1 PCT/NL2002/000653 NL0200653W WO03033567A1 WO 2003033567 A1 WO2003033567 A1 WO 2003033567A1 NL 0200653 W NL0200653 W NL 0200653W WO 03033567 A1 WO03033567 A1 WO 03033567A1
Authority
WO
WIPO (PCT)
Prior art keywords
nylon
anyone
graphite
polymer
nanocomposite
Prior art date
Application number
PCT/NL2002/000653
Other languages
English (en)
Inventor
Jawk Meijer
Elmar Wiejack-Symann
Original Assignee
Rag Aktiengesellschaft
Quadrant Ip Ag
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 Rag Aktiengesellschaft, Quadrant Ip Ag filed Critical Rag Aktiengesellschaft
Priority to CA002463589A priority Critical patent/CA2463589A1/fr
Priority to EP02765707A priority patent/EP1453884A1/fr
Priority to US10/492,797 priority patent/US20050032966A1/en
Publication of WO2003033567A1 publication Critical patent/WO2003033567A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon

Definitions

  • the present invention relates to a process for the preparation of a polymeric nanocomposite, said nanocomposite comprising a polymer selected from the group comprising nylon, polyester and polyurethane, said nanocomposite also comprising graphite.
  • a process for the preparation of a polymeric nanocomposite comprising a polymer selected from the group comprising nylon, polyester and polyurethane, said nanocomposite also comprising graphite.
  • the present process overcomes these deficiencies in providing an inventive process for the preparation of a polymeric composite, which fulfils the above mentioned needs.
  • This goal is achieved in a process, comprising the following steps: a) mixing the liquid monomer(s) for the polymer, or a liquid oligomer thereof, with an intercalated graphite using a specific mixing energy of at most 1 kW/m 3 , b) degassing the resulting mixture for a period of at least 5 minutes under a pressure of at most 50 kPa, c) polymerizing said mixture in the presence of a suitable catalyst system, the process resulting in a polymeric nanocomposite, comprising 5-20 wt% of delaminated graphite.
  • the elements of the process steps of the present invention will be dealt with below.
  • a monomer for nylon can be mentioned caprolactam, for the preparation of nylon-6; the skilled man of art knows the monomer(s) to be used for in-situ polymerization to the mentioned polymeric nanocomposite.
  • the monomer(s) can be either suited for the preparation of homopolymers as well as for the preparation of copolymers, like an impactresistant nylon/polyether blockcopolymer.
  • the skilled man is aware of suitable monomers therefor.
  • An alternative is the use of mixed monomers for a nylon/nylon mixture, like a combination of caprolactam and laurinolactam, resulting in a nylon-6/nylon-12 mixture.
  • the monomer(s) need(s) to be in liquid form, as a result of which often the monomer(s) need(s) to be brought in said form by a melt-process.
  • the skilled artisan can select the temperature at which said mixing should take place.
  • a liquid oligomer of the intended polymer can be used, again depending on the nature of the polymer and the related oligomer. Addition of a separate impact modifier can also be done at this stage; an example of such a modifier is jeffamine, like KU2-8112 of Bayer.
  • the viscosity of the monomer(s) or oligomer should not exceed 50 mPa.s.
  • any graphite-like product is useful, where the distance between crystalline layers of the graphite have been extended with a gas or liquid, resulting in an intercalated graphite; in the above mentioned literature reference referred to as graphite intercalation compound (G.I.C.).
  • G.I.C. graphite intercalation compound
  • Timrex ® from Timcal.
  • an expanded graphite can be used; this product is obtainable by rapid heating (at temperatures well above 250°C) of a G.I.C., resulting in an expanded and exfoliated graphite. Preferably this heating results in an EG having an expansion ratio of at least 150, more preferably an expansion ratio of at least 200.
  • Examples of such an E.G. are Nord-min ® of Nordmann, Rassmann GmbH
  • the mixture, resulting in step a) is to be degassed, during and/or after the mixing process, in order to facilitate the intimate mixing of the polymer precursor(s) and the graphite.
  • degassing ratio (D.G.-ratio), herein defined as the ratio between the time of degassing (in minutes), and the vacuum-pressure during degassing (in kPa), is at least 1 ; in formula:
  • This degassing should be performed while the precursor/graphite mixture is in liquid form.
  • a process variant hereof is, that both the G.I.C. and the E.G. are mixed with the precursor(s) of the final polymer, followed by step b).
  • An alternative is the mixing of the G.I.C. with the precursor(s), performing step b), followed by an addition of the EG to the resulting mixture, followed by a second degassing step (b)-step).
  • the degassed mixture is then polymerized in suitable equipment, optionally in the presence of a suitable catalyst system, under conditions known in the art for the polymerization to either nylon, polyester of polyurethane.
  • the graphite is substantially present in delaminated form in the polymeric nanocomposite.
  • the polymeric nanocomposite resulting form the described process should have a graphite content of between 5 and 20 wt.%, relative to the weight of the polymer.
  • the amount of G.I.C. in the polymer can preferably be varied between 5 and 10 wt%; the amount of E.G. in the polymer can preferably be varied between 5-15 wt%. In such a combination, both the required ESD and FR properties can be obtained.
  • the intercalated graphite to be used in the process of the invention should have a particle size of at most 75 ⁇ m, preferred at most 25 ⁇ m, and more preferred at most 10 ⁇ m. In doing so, the effectiveness of the graphite in the obtainance of both ESD- and FR-properties is improved.
  • the expanded graphite has a particle size of at most 200 ⁇ m; preferably 80% of the particles are smaller than 150 ⁇ m.
  • the process of the present invention is preferably suitable for an anionic polymerization; more preferred even where this polymerization is a monocast in-mould polymerization, wherein the mixture comprising precursor and graphite is cast (poured) into a mould with a predesigned shape, where in said mould the polymerization is performed.
  • the process of the present invention results in a polymeric nanocomposite, based on a nylon, selected from the group comprising nylon 6, nylon 11 and nylon 12.
  • the properties of the polymeric nanocomposite can be further improved by heat-annealing the composite at elevated temperatures (but below the melting point of the composite); in order to reduce the amount of residual monomer(s).
  • the invention also relates to a polymeric nanocomposite having both desired FR- and ESD-properties.
  • the nanocomposite comprises as polymeric element a polymer selected from the group comprising nylon, polyester, and polyurethane; preferably the polymer is nylon, selected from the group comprising nylon 6, nylon 11 and nylon 12.
  • the melt viscosity of the nylon determined at 260°C, preferably is at least 8 kPa.s, as determined according to ISO 6721 -10.
  • the polymeric nanocomposite of the invention is comprising 5-20 wt.% delaminated graphite, and is having a surface resistivity of between 10 4 and 10 10 ⁇ /square, as well as a flame-retardancy of at least UL94V1.
  • the surface resistivity is to be measured according to ASTMD257; the flame- retardancy according to Underwriter Laboratory Test '94.
  • the surface resistivity is between 5 x 10 5 and 10 10 ⁇ /square.
  • the FR-properties can also be determined according to DIN 22100-7, in which the dripping behaviour of a specimen under fire is determined. In this test, the time for the specimen to start dripping is determined. This time should be preferably at least 15 minutes, more preferred at least 20 minutes, in order to designate the product as being flame-retardant. Also preferred is a flame-retardancy of at least UL94V0.
  • the polymeric nanocomposite of the present invention may also comprise conventional additives and other fillers, as they are known in the art to be used in polymeric compositions comprising nylon, polyester of polyurethane.
  • additional components can comprise coulorants, reinforcing agents, fibers of polymeric or natural nature, etc. The skilled man of art knows which to select.
  • the polymeric nanocomposite of the present invention is very well suited, due to its ESD-and FR-properties, to be used in equipment and materials to be used in areas where these properties play a significant role.
  • Public authorities have evermore demanding requirements on such equipment and materials, in order to prevent casualties and material damage in case of fire and/or electrostatic problems.
  • underground mining activities, and more dedicated in coalmining activities these requirements play a significant role.
  • the polymeric nanocomposite of the present invention is able to meet these requirements and can therefor be used in such equipment and materials, which are at least partially made of said nanocomposite.
  • the equipment and materials which are at least partially made of said composite preferably are in the form of a flight bar, and/or of a conveyer roller. These parts are extremely sensitive for ESD-and FR-conditions. To date heavier and/or much more expensive materials are used, which can now be replaced, at least partially, by equipment and materials of this invention.
  • the referenced equipment and materials can, in a form according to the present invention, be of an hybride nature, being a combination of either the polymer and fibers of metal or of polymeric nature (like steel, or polyethylene fibers), or in which part of the equipment is made of metal (like steel or alumina) and the rest is made of the above described polymeric nanocomposite. Reference can be given to a metal-in-polymer product, as well as a metal-on-polymer product.
  • the polymeric nanocomposite can also be used in other types of equipment and materials, preferably in transportation elements where the FR- and ESD-properties can be exploited, preferably in transportation elements underground or in tunnels. Without limiting to the following areas of use, mentioning can be made of:
  • C20 caprolactam hexane di- isocyanate prepolymer (CAS 5888-87-9)) was given to the mixture under stirring at 100 rpm.
  • anionic catalyst Ba ⁇ ggolen ® C10.
  • C10 sodium salt of aliphatic cyclic acid amide; specifically sodium salt of caprolactam (CAS 2123-24-2)
  • the catalyst solution was poured to the graphite containing caprolactam/activator mixture and the mixture was homogenized by shaking for 5 seconds.
  • the homogenized mixture was poured in a glass mould (diameter 40 mm), preheated in an oil bath at 140°C. In the mould at 140°C, polymerization of the caprolactam and crystallization of the resulting nylon-6 occurred within 10 minutes. After demoulding, the surface resistivity of the polymer, containing 5 wt% of graphite, was 10 9 ⁇ /square.
  • Nylon-6 samples were produced according the procedure described in Example I except for the amount and kind of intercalated graphite.
  • the resulting surface resistivity of the samples after demoulding was:
  • the catalyst solution was poured to the graphite containing activator solution and the mixture was homogenized by stirring at 100 rpm for 4 seconds.
  • the homogenized mixture was poured in a stainless steel mould (10 * 10*20 cm), preheated in an oven at 140°C. After 15 minutes at 140°C, the mould was opened to obtain the polymer produced.
  • the surface resistivity of the polymer was 10 6 ⁇ /square.
  • a flame with a tip temperature of 900°C was placed at 40 mm from the product (according to DIN 22100-7). After 18 minutes the polymer started to drip. Extinguishing the flame resulted also in a switch-off of the burning of the product.
  • Example V The same procedure and amounts as described in Example V was used to produce a sample. After demoulding, the sample was annealed at 155°C for 24 hrs.
  • the result of the annealing procedure was that in the drip test, dripping started after 25 minutes.
  • a Nylon-6 sample was produced according to the procedure described in Example I, except for the amount and type of graphite: a mixture of 5 wt% of Timrex ® KS6 and 10 wt% of Nord-min ® 35.
  • the surface resistivity of the resulting mould was 10 8 ⁇ /square.
  • the moulded product showed a clear decrease of flame intensity compared to products only filled with intercalated graphite.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de préparation d'un nanocomposite polymère renfermant un polymère choisi dans le groupe comprenant le nylon, des polyesters et du polyuréthanne et contenant du graphite. Le procédé permet d'obtenir un nanocomposite renfermant de 5 à 20 % en poids de graphite, ledit nanocomposite présentant des propriétés à la fois ESD et FR. L'invention concerne en outre un matériel fabriqué, au moins en partie, au moyen de ce nanocomposite.
PCT/NL2002/000653 2001-10-17 2002-10-11 Nanocomposite polymere WO2003033567A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002463589A CA2463589A1 (fr) 2001-10-17 2002-10-11 Nanocomposite polymere
EP02765707A EP1453884A1 (fr) 2001-10-17 2002-10-11 Nanocomposite polymere
US10/492,797 US20050032966A1 (en) 2001-10-17 2002-10-11 Polymeric nanocomposite

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP01203923.6 2001-10-17
EP01203923 2001-10-17
US33080001P 2001-10-31 2001-10-31
US60/330,800 2001-10-31
EP02076623 2002-04-24
EP02076623.4 2002-04-24

Publications (1)

Publication Number Publication Date
WO2003033567A1 true WO2003033567A1 (fr) 2003-04-24

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2002/000653 WO2003033567A1 (fr) 2001-10-17 2002-10-11 Nanocomposite polymere

Country Status (5)

Country Link
EP (1) EP1453884A1 (fr)
CN (1) CN1571804A (fr)
CA (1) CA2463589A1 (fr)
PL (1) PL368115A1 (fr)
WO (1) WO2003033567A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005029997A1 (de) * 2005-06-28 2007-01-04 Hilti Ag Polyurethan-Graphitoxid-Verbundmaterial, Verfahren zu seiner Herstellung und seine Verwendung als Flammschutz-Material und zur Brandschutzabdichtung
EP1770115A1 (fr) 2005-09-30 2007-04-04 Quadrant Plastic Composites AG Produit semi-fini de forme plane renforcé de fibres
RU2332352C1 (ru) * 2007-03-15 2008-08-27 Евгений Петрович Гребенников Нанокомпозиционный материал
WO2010093598A3 (fr) * 2009-02-16 2010-12-16 Cytec Technology Corp. Couches de surfaçage conductrices et co-durcissables pour foudroiement et protecteur d'interférences électromagnétiques de matériaux composites thermodurcissables

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100434459C (zh) * 2006-07-12 2008-11-19 扬州大学 聚酯/石墨纳米导电复合材料的制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1277218A (zh) * 1999-06-11 2000-12-20 中国科学院化学研究所 聚酰胺/石墨导电纳米复合材料及其制法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1277218A (zh) * 1999-06-11 2000-12-20 中国科学院化学研究所 聚酰胺/石墨导电纳米复合材料及其制法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 200123, Derwent World Patents Index; Class A23, AN 2001-219148, XP002224843 *
PAN, YU-XUN ET AL: "A new process of fabricating electrically conducting nylon 6/ graphite nanocomposites via intercalation polymerization", J. POLYM. SCI., PART B: POLYM. PHYS. (2000), 38(12), 1626-1633, XP001066244 *
UHL, FAWN M. ET AL: "Nylon / graphite nanocomposites", POLYMER PREPRINTS (AMERICAN CHEMICAL SOCIETY, DIVISION OF POLYMER CHEMISTRY) (2001), 42(2), 176-177, XP008001748 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005029997A1 (de) * 2005-06-28 2007-01-04 Hilti Ag Polyurethan-Graphitoxid-Verbundmaterial, Verfahren zu seiner Herstellung und seine Verwendung als Flammschutz-Material und zur Brandschutzabdichtung
DE102005029997B4 (de) * 2005-06-28 2009-08-13 Hilti Aktiengesellschaft Polyurethan-Graphitoxid-Verbundmaterial, Verfahren zu seiner Herstellung und seine Verwendung
EP1770115A1 (fr) 2005-09-30 2007-04-04 Quadrant Plastic Composites AG Produit semi-fini de forme plane renforcé de fibres
RU2332352C1 (ru) * 2007-03-15 2008-08-27 Евгений Петрович Гребенников Нанокомпозиционный материал
WO2010093598A3 (fr) * 2009-02-16 2010-12-16 Cytec Technology Corp. Couches de surfaçage conductrices et co-durcissables pour foudroiement et protecteur d'interférences électromagnétiques de matériaux composites thermodurcissables
US8178606B2 (en) 2009-02-16 2012-05-15 Cytec Technology Corp. Co-curable, conductive surfacing films for lightning strike and electromagnetic interference shielding of thermoset composite materials
US8357740B2 (en) 2009-02-16 2013-01-22 Cytec Technology Corp. Co-curable, conductive surfacing films for lightning strike and electromagnetic interference shielding of thermoset composite materials
US8772391B2 (en) 2009-02-16 2014-07-08 Cytec Technology Corp. Co-curable, conductive surfacing films for lightning strike and electromagnetic interference shielding of thermoset composite materials

Also Published As

Publication number Publication date
PL368115A1 (en) 2005-03-21
CN1571804A (zh) 2005-01-26
EP1453884A1 (fr) 2004-09-08
CA2463589A1 (fr) 2003-04-24

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