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WO2008066399A2 - Procédé de fabrication de nanocomposites polymères - Google Patents

Procédé de fabrication de nanocomposites polymères Download PDF

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Publication number
WO2008066399A2
WO2008066399A2 PCT/PL2007/000079 PL2007000079W WO2008066399A2 WO 2008066399 A2 WO2008066399 A2 WO 2008066399A2 PL 2007000079 W PL2007000079 W PL 2007000079W WO 2008066399 A2 WO2008066399 A2 WO 2008066399A2
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WO
WIPO (PCT)
Prior art keywords
silicate
polar substance
manner according
polymer
mixing
Prior art date
Application number
PCT/PL2007/000079
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English (en)
Other versions
WO2008066399A3 (fr
Inventor
Jerzy Morawiec
Andrzej Galeski
Jan Golebiewski
Janusz Dzwonkowski
Original Assignee
Centrum Badan Molekularnych I Makromolekularnych Pan
Instytut Przetworstwa Tworzym Sztucznych, Metalchem
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.)
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Publication date
Application filed by Centrum Badan Molekularnych I Makromolekularnych Pan, Instytut Przetworstwa Tworzym Sztucznych, Metalchem filed Critical Centrum Badan Molekularnych I Makromolekularnych Pan
Publication of WO2008066399A2 publication Critical patent/WO2008066399A2/fr
Publication of WO2008066399A3 publication Critical patent/WO2008066399A3/fr

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    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the subject of the invention is the manner of making polymer nanocomposites, which are used as materials for products in the wrapping and textile industry as well as construction materials, especially in the aviation and motor industry, and in health care.
  • Polymer nanocomposites are the result of research aimed to combine organic polymer materials and inorganic materials such as calcium carbonate, mineral clay, mica, and the like.
  • polymer nanocomposites with plate-like nanofillers (nanoclay) in its composition.
  • plate-like nanofillers montmoriyllonite (MMT), hectorite, bentonite and saponite; montmoriyllonite being used most frequently.
  • MMT montmoriyllonite
  • the plate structure of MMT is composed of three interlinked layers: two outer layers made up of tertrahedric crystals of silicon dioxide and an inner layer made up of octoahedric crystals of magnesium oxide or aluminium oxide.
  • the thickness of the MMT plate is 0.96 nm, while the magnitude of its other dimensions is in the range of 200-1000 nm.
  • Particular plates are mutually linked by van der Waals forces and the distance between the two successive plates referred to as a "gallery" is approximately 0.3 nm.
  • the plates have a negative charge whose superficial density established theoretically is 1 ion/1.36 nm 2 of the plate surface. In the space between the plates there are ions of alkali metals, which neutralise the negative charge of the plates.
  • the sum of the plate thickness and the distance between two successive plates is in the range of 1.24-1.45 nm.
  • MMT Five to ten mutually parallel plates attracted by van der Waals forces form a primary MMT particle of a total thickness of 7-12 nm. Of these particles agglomerates of dimensions of 200-1000 nm are formed.
  • Commercially available MMT is intended for filling polymer materials and generally has the form of white or yellow powder of moisture smaller than 2% and a grain size of 2-13 ⁇ m.
  • the key aspect of nanocomposites of this type is the intercalation and exfoliation (delamination) of the montmorylonite layers; however best properties of the nanocomposite, is exfoliation.
  • the specific surface of the dispersed MMT amounting to 750-800 m 2 /g and the cation exchange capacity coefficient (CEC) ranging from 80 to 150 meg/lOOg are the main reasons why MMT is used as a component of polymer nanocomposites. It has hydrophilic properties and is thermodynamically miscible only with such polymers as poly(ethylene oxide) and polyvinyl alcohol). On the other hand, the use of MMT for filling the remaining polymers, especially nonpolar polymers, makes it necessary to modify its surface properties.
  • modifier of this type has two fundamental restrictions: for health reasons the permissible concentration of alkylamine compounds should not exceed 5ppm. Additionally, these compounds have low thermal stability and most of them undergo thermal decomposition at a temperature lower than 220-250 0 C, which limits their use to selected polymer materials only.
  • the properties of a nanocomposite are affected by the degree of dispersion of the filler plates in the polymer matrix. It is impossible to obtain the uniform structure of a nanocomposite, especially in the case of nonpolar polymers, due to the thermodynamical nonmiscibility of the MMT and the polymer. This problem is aggravated by the fact that the average radius of the rotational motion of a polymer chain is greater than the average distance between the MMT plates. In such a situation, apart from modifying MMT, it is necessary to use an additional component which has polar groups built-in and performs the function of a compatibiliser between the polymer and the nanofiller undergoing modification.
  • the compatibiliser miscible with the polymer matrix, performs the following functions: it facilitates the dispersion of nanofiller particles in the polymer warp and leads to the formation of chemical bonds between the plates of the MMT being modified and i strong hydrogen bonds that are formed here, which not only strengthen interphase interaction, but are also the basic cause of migration of particular chains of the compatibiliser and the polymer into the spaces between the MMT plates.
  • polymers functionalized with compounds containing unsaturated functional monomers, i.e. containing acrylic acid or maleine anhydride are used as compatibilisers. Most of well-known solutions and methods are described in the extensive monograph: L.A. Utracki, Clay-Containing Polymeric Nanocomposites, ed. RAPRA Technology, Shawbury U.K., 2004, vol. 2, pp. 435-630.
  • compatibilisers are that they remain between the nanoclay plates and thereby hinder its dispersion in the nanocomposite matrix. Furthermore, this process requires using a compatibiliser in quantities that are the multiple of the amount of nanoclay introduced into the nanocomposite, which has a considerable effect on the nanocompossite properties, not necessarily as intended. Moreover, such a large addition of a compatibiliser impedes the technological process of nanocomposite production and increases the costs of the process.
  • the saturation of layer silicate is conducted favourably in the presence of a solvent of a polar substance from the group of glycidyl derivatives, which is later removed from the silicate by evaporation or drying.
  • the layered silicate thus saturated is then mixed with the plasticized polymer or any mixture of polymers.
  • vapours of a polar substance from the group of glycidyl derivatives are removed and dyes, pigments, UV stabilisers and additives facilitating its further processing are added.
  • Montmorillonite, hectorite, bentonite or saponite modified with organic ammonium salts are used as a layered silicate.
  • the method according to the invention consists in the introduction - into spaces between the layers of nanoday or organically modified nanoclay - of a low molecular mas substance from the group of glycidyl derivatives, which, in the process of mixing with the polymer, is gradually removed by evaporation, but remains chemically or physically bonded to the nanoclay or bonded to the polymer in the same way.
  • the research has demonstrated that the high degree of exfoliation can already be obtained with a multiple lower content of a substance from the group of glycidyl derivatives in relation to the nanoclay content.
  • the polymer matrix is not modified or modified only to a slight degree.
  • Another advantage of using the manner according to the invention lowers the cost of use of small quantities of a substance from the group of glycidyl derivatives compared with the cost of 5- to 10-fold larger amount of a compatibiliser (maleine polypropylene, in this case). Moreover, in the majority of cases in which the manner according to the invention is used, a higher degree of exfoliation of nanokaolin is obtained than in the case of use of polymer compatibilisers.
  • the polymer nanocomposites with layered silicates obtained using the manner presented are characterised by much improved barrier properties, an increased impact resistance, an increased modulus of rigidity, increased nonflammability and/or an increased heat temperature deflection (HDT).
  • barrier properties an increased impact resistance, an increased modulus of rigidity, increased nonflammability and/or an increased heat temperature deflection (HDT).
  • Examples 1 to 3 show the introduction of glycidyl deri a direct method by the preliminary mixing of nanoday with a glycidyl derivative.
  • Nanocomposite designated as LDPE/NF8/GMA NF8 :GMA - 1:1 (w/w); fraction of NF8 - 6% (w/w)
  • Low-density polyethylene LDPE FGAN 18-D003, MFR 0.2 - 0.4 g/10 min, designated as LDPE (supplier: PKN Orlen)
  • Glycidyl methacrylate molecular weight -142.15, boiling temperature - 189 0 C, designated as GMA (supplier: Sigma-Aldrich)
  • the nanocomposite was made in two stages; during the first stage GMA compatibiliser was mixed with NF8 at a ratio of 1:1; next the NF8/GMA mixture was crushed and then an NF8/GMA mixture with LDPE was prepared with the final fraction of 6 % (w/w) NF8.
  • TSE twin-screw extruder
  • Low-density polyethylene LDPE FGAN 18-D003, MFR 0.2 - 0.4 g/10 min., designated as LDPE (supplier: PKN Orlen),
  • the material obtained with participation of GMA does not reveal the characteristic peak caused by the planes of (001) montmorillonite.
  • a diffractogram of a composite without participation of a glycidyl derivative has been presented.
  • LDPE the following were used: FGAN 18-D003, and FABS.
  • the nanocomposite composition LDPE - 91 % (w/w) + NF8 - 6 (w/w) + GMA - 3 % (w/w)
  • the nanocomposites were made as in Example 2.
  • the free-blowing method was used to extrude film from the granulate.
  • the process of film extrusion was carried out on a PlastiCorder PLV 151 Brabender test stand equipped with a screw of a compression ratio of 3:1 and an extrusion head of a diameter of the nozzle outlet of ⁇ 14 mm.
  • the nanocomposite was made with participation of low-density polyethylene (LDPE) and isotactic polypropylene (iPP) as basic materials, montmorillonite Cloisite 15A and Nanomer I30P, and with a reduced participation of glycidyl derivatves: Glycidyl Methacrylate (GMA ) - molecular weight - 142.15, boiling temperature - 189 0 C and Glycidyl 4-nonylphenyl ether (GD) - molecular weight - 276.41, boiling temperature - 312 0 C. Glycidyl was introduced into the montmorillonite in the presence of a solvent.
  • LDPE low-density polyethylene
  • iPP isotactic polypropylene
  • GMA Glycidyl methacrylate - as compatibiliser
  • GMA was diluted with acetone, while C15A was dispersed with water, GMA - 2Og
  • the material obtained with participation of GMA does not reveal the charcateristic peak caused by the planes of (001) montmorylonite.
  • iPP F 401 polypropylene designated as iPP (supplier: PKN Orlen)
  • Montmorylonite I30P nanomer designated as I30P, (supplier: Nanocor INC) Glycidyl 4-nonylphenyl ether - as a compatibiliser, desi
  • the mixtures were made in two stages; the first stage - mixing GD with I30P, at the ratio of GD:I30P 1:4.
  • XRD Fig.5 According to the diffractogram of X-ray radiation, XRD Fig.5, the material obtained with participation of GD does not reveal the characteristic peak cused by the planes (001) of montmorillonite.
  • iPP polypropylene Malen P F401, designated as iPP, (supplier: PKN Orlen)
  • Glycidyl Methacrylate - as a compatibiliser designated as GMA
  • the XRD diffractogram in Fig. 6 shows that the use of a GMA glycidyl derivative leads to the intercalation of Cloisite I30P nanoday and partial exfoliation.
  • PET - ELPET intrinsic viscosity 0.81 g/dl Elana Toru ⁇
  • the mixtures were made in two stages; the first stage - mixing the compatibiliser (GD) with Cloisite30B nanoclay, at the ratio of GD:CL30B 1:4.
  • the manner of preparation of the mixture was analogous as in Example 4.
  • the XRD rentgenogram in fig. 7 shows that the use of a GD glycidyl derivative leads to the intercalation of Closite 3OB nanoclay, and stronger partial exfoliation than in the case of the material without GD.

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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)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne un procédé de fabrication de nanocomposites polymères. Selon ce procédé, avant son mélange avec un polymère à l'état fondu, un phyllosilicate est saturé au moyen d'une substance polaire présentant une température d'ébullition supérieure à la température de mélange ou proche de celle-ci, en quantité égale ou inférieure à la quantité de phyllosilicate utilisée. Une substance polaire appropriée est alors sélectionnée dans un groupe de dérivés glycidyliques, les conditions étant favorables si la substance polaire sélectionnée forme une liaison chimique ou physique avec un silicate et/ou des sels d'ammonium organiques utilisés pour la modification du silicate.
PCT/PL2007/000079 2006-11-28 2007-11-26 Procédé de fabrication de nanocomposites polymères WO2008066399A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PL381173A PL214040B1 (pl) 2006-11-28 2006-11-28 Sposób wytwarzania nanokompozytów polimerowych
PLP-381173 2006-11-28

Publications (2)

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WO2008066399A2 true WO2008066399A2 (fr) 2008-06-05
WO2008066399A3 WO2008066399A3 (fr) 2008-08-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210035633A (ko) 2019-09-24 2021-04-01 한국과학기술연구원 고분자 수지 및 동일반응계 분산제를 포함하는 질화붕소 복합체 및 그 제조방법
KR20210065582A (ko) 2019-11-27 2021-06-04 한국과학기술연구원 열전도도를 통한 질화붕소 나노물질의 고분자 수지 내 분산 균일도 평가 방법

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001005880A1 (fr) * 1999-07-19 2001-01-25 Dsm N.V. Moulage de polyolefine extrude

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001005880A1 (fr) * 1999-07-19 2001-01-25 Dsm N.V. Moulage de polyolefine extrude

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210035633A (ko) 2019-09-24 2021-04-01 한국과학기술연구원 고분자 수지 및 동일반응계 분산제를 포함하는 질화붕소 복합체 및 그 제조방법
KR20210065582A (ko) 2019-11-27 2021-06-04 한국과학기술연구원 열전도도를 통한 질화붕소 나노물질의 고분자 수지 내 분산 균일도 평가 방법

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Publication number Publication date
PL214040B1 (pl) 2013-06-28
WO2008066399A3 (fr) 2008-08-28
PL381173A1 (pl) 2008-06-09

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