EP1511804A1 - Nanocomposites a base de polyolefine, leur procede de production et leur utilisation - Google Patents
Nanocomposites a base de polyolefine, leur procede de production et leur utilisationInfo
- Publication number
- EP1511804A1 EP1511804A1 EP03732205A EP03732205A EP1511804A1 EP 1511804 A1 EP1511804 A1 EP 1511804A1 EP 03732205 A EP03732205 A EP 03732205A EP 03732205 A EP03732205 A EP 03732205A EP 1511804 A1 EP1511804 A1 EP 1511804A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyamide
- polyolefin
- nanocomposites
- hdpe
- matrix
- 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- Withdrawn
Links
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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Definitions
- the invention relates to nanocomposites based on polyolefins, in particular based on high density polyethylene (HDPE)
- HDPE high density polyethylene
- the nanocomposites contain an HDPE of 70 to 99% by weight, a polyamide, preferably polyamide 6, of 1 to 30% by weight and a layered silicate of 1 to 10% by weight.
- the layered silicate can for example
- 15 can be a natural sodium montmorillonite, hectorite, bentonite or synthetic mica modified with onium ions.
- organophilic phyllosilicates into polymers by in-situ polymerization or via melt compounding is described in the literature and known to the person skilled in the art. It is usually associated with an improvement in the mechanical and barrier properties, dimensional stability under heat and 5 flame resistance. The prerequisite for the improvement of the properties is due to the ability of the individual layers of the layered silicates to expand (intercalate) or to separate completely from one another (exfoliation). This creates an enlarged surface of the filler and also an enlarged interface with the matrix polymer. Intercalation or exfoliation in the manufacture of polymer In order to achieve nanocomposites, the layered silicates are first modified with organic compounds by cation exchange, ie they are made organophilic.
- organic compounds are usually tetraalkylammonium ions, which contain one or two C12 to C18 long chains. Since the affinity for the matrix polymer is also a prerequisite for the improvement of the corresponding properties, this takes place predominantly when using polar polymers, such as polyamide, polyester, polyethylene oxide, polyvinyl alcohol, polyethyleneimine and others, which belong to the organophi - contain structural units compatible with layered silicates. In order to improve the compatibility with the non-polar polyolefins, additional modifications of the layered silicates with monomers, oligomers, silanes or block copolymers are applied [WO 0105879 AI, US 5910523,
- WO 9907790 AI The preparation of the additional modification is usually carried out in solution and is associated with high costs and effort.
- An alternative to binding layered silicates in non-polar polymer matrices is to use adhesion promoters and intercalants directly in the melt compounding. This is done in one or two stages using highly concentrated compositions with subsequent dilution.
- oligomers or polymers which are functionalized with carboxyl or anhydride groups are suitable as adhesion promoters. These include maleic anhydride (MA) grafted polyolefins or olefin-based copolymers as appropriate.
- MA maleic anhydride
- the aim of the invention is therefore to improve the mechanical properties, in particular the modulus of elasticity and the impact strength, of polyolefin nanocomposites, preferably of high density polyethylene (HDPE nanocomposites).
- polyolefin nanocomposites preferably of high density polyethylene (HDPE nanocomposites).
- This aim is achieved according to the invention by compounding the HDPE or optionally polypropylene with a highly concentrated polyamide / layered silicate masterbatch and optionally with a maleic anhydride grafted polyolefin in an extrusion process.
- the layered silicate is first incorporated into polyamide to form a highly concentrated masterbatch (20-40% by weight) via melt compounding and mixed in a second step with the HDPE in the melt.
- a maleic anhydride-grafted polyolefin is added in the second stage.
- the process according to the invention for the production of the HDPE nanocomposites with improved mechanical properties thus comprises the following stages: a) melt intercalation of the organophilic phyllosilicates in a polyamide matrix and production of a highly concentrated polyamide / phyllosilicate masterbach with a proportion of 20 to 40% by weight organophilic layered silicate and 80-60 wt .-% polyamide 6 and b) compounding the masterbatch into the HDPE matrix and the optional addition of a carboxylated polyolefin.
- polyamides are fundamentally immiscible with polyolefins because of different polarities, but also structural differences.
- Mixing for example in a single-screw extruder and without a conventional adhesion promoter, with limited shear intensities, occurs strong phase separation in the HDPE / PA 6 blends.
- Adhesion promoters are used to improve compatibility.
- Carboxyl acid or anhydride modified polyolefins or copolymers are suitable as adhesion promoters.
- Despite a compatibility of this type even with intensified shear forces in the twin-screw extruder, no improvement in the mechanical properties of HDPE in the blend with PA 6 has been described in the literature to date.
- highly concentrated polyamide 6 / layered silicate compositions were first mixed in a ratio of 13: 7 at temperatures in the range from 210 to 250 ° C. by means of a ZSK25 twin-screw extruder: Tetraalkylammonium ion-modified montmorillonite was used as the organophilic layered silicate.
- HDPE was compounded with the corresponding concentrate at temperatures in the range of 200 to 230 ° C and a speed of 400 min "1.
- the HDPE-PA 6 nanocomposites became test specimens for mechanical and HDT tests and 1 mm thick plates for WAKS analysis using an Arburg Allrounder 320M 850-210 injection molding machine Based on the WAXS analyzes, a complete exfoliation of the layered silicates was found for all HDPE-PA 6 nanocomposites according to the invention and confirmed by means of transmission electron microscopy (TEM).
- TEM transmission electron microscopy
- the polyamide 6 / layered silicate concentrate was compounded into the HDPE matrix polymer with a melt index of 11 ccm / 10 min (HDPE-1) using a twin-screw extruder in accordance with the aforementioned conditions to give nanocomposites with 4.2% by weight of organophilic layered silicate.
- HDPE with a melt index of 11 ccm / 10 min (HDPE-1) was compounded with 8.2% by weight of polyamide 6 to form blends under the same conditions as the HDPE nanocomposites.
- the polyamide 6 / layered silicate concentrate was compounded into the HDPE matrix polymer with a melt index of 0.2 ccm / 10 min (HDPE-2) using a twin-screw extruder in accordance with the aforementioned conditions to give nanocomposites with 3.2% by weight of layered silicate.
- HDPE-2 melt index of 0.2 ccm / 10 min
- the polyamide 6 / layered silicate concentrate and a maleic anhydride-grafted HDPE were converted into nanocomposites using a twin-screw extruder in accordance with the aforementioned conditions compounded with 3.2% by weight of layered silicate.
Landscapes
- 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 des nanocomposites à base de polyoléfine HDPE aux propriétés mécaniques améliorées, notamment un module d'élasticité supérieur et un meilleur indice de résilience. Les nanocomposites contiennent au moins deux matières plastiques thermoplastiques: (A) un polyoléfine, de préférence, un polyéthylène de 70 à 99 % en poids, (B) un polyamide, de préférence, un polyamide 6, de 1 à 30 % en poids, et un silicate en couche réglé organophile de 1 à 10 % en poids. Eventuellement, un polyoléfine greffé par un anhydride d'acide maléique de 1 à 10 % en poids de la quantité totale. L'invention concerne également un procédé de production de ces nanocomposites et leur utilisation comme pièces moulées par injection, notamment comme contenants ou tuyaux.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10222169 | 2002-05-18 | ||
DE10222169A DE10222169A1 (de) | 2002-05-18 | 2002-05-18 | Nanocomposites auf Polyolefin-Basis und Verfahren zu deren Herstellung sowie Verwendung |
PCT/DE2003/001158 WO2003097738A1 (fr) | 2002-05-18 | 2003-04-09 | Nanocomposites a base de polyolefine, leur procede de production et leur utilisation |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1511804A1 true EP1511804A1 (fr) | 2005-03-09 |
Family
ID=29413942
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03732205A Withdrawn EP1511804A1 (fr) | 2002-05-18 | 2003-04-09 | Nanocomposites a base de polyolefine, leur procede de production et leur utilisation |
Country Status (5)
Country | Link |
---|---|
US (1) | US20050228102A1 (fr) |
EP (1) | EP1511804A1 (fr) |
AU (1) | AU2003238342A1 (fr) |
DE (1) | DE10222169A1 (fr) |
WO (1) | WO2003097738A1 (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100419017C (zh) * | 2004-08-13 | 2008-09-17 | 于志文 | 一种全塑微观层状复合材料及其制备方法 |
US8674010B2 (en) * | 2004-12-28 | 2014-03-18 | Polyone Corporation | Blends of nanocomposites and their use |
US20100028583A1 (en) * | 2006-10-27 | 2010-02-04 | E.I. Du Pont De Nemours And Company | Pipes containing nanoclays and method for their manufacture |
US20180177254A1 (en) * | 2016-12-22 | 2018-06-28 | Russell Neuman | Method of extruding a thermoplastic polymer to produce random coloration and a product using same |
CN109593249A (zh) * | 2018-11-12 | 2019-04-09 | 张桂芬 | 一种耐摩擦pe合金 |
CN113789012A (zh) * | 2021-09-29 | 2021-12-14 | 重庆会通科技有限公司 | 一种高油漆附着力聚丙烯复合材料及其制备方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5910523A (en) * | 1997-12-01 | 1999-06-08 | Hudson; Steven David | Polyolefin nanocomposites |
KR20010040964A (ko) * | 1998-02-13 | 2001-05-15 | 마크 에프. 웍터 | 폴리머 나노복합체 조성물 |
NL1013520C2 (nl) * | 1999-07-19 | 2001-01-22 | Dsm Nv | GeÙxtrudeerd polyolefine vormdeel. |
US6906127B2 (en) * | 2002-08-08 | 2005-06-14 | Amcol International Corporation | Intercalates, exfoliates and concentrates thereof formed with low molecular weight; nylon intercalants polymerized in-situ via ring-opening polymerization |
KR100733922B1 (ko) * | 2004-12-03 | 2007-07-02 | 주식회사 엘지화학 | 차단성 물품 |
-
2002
- 2002-05-18 DE DE10222169A patent/DE10222169A1/de not_active Ceased
-
2003
- 2003-04-09 AU AU2003238342A patent/AU2003238342A1/en not_active Abandoned
- 2003-04-09 WO PCT/DE2003/001158 patent/WO2003097738A1/fr not_active Application Discontinuation
- 2003-04-09 EP EP03732205A patent/EP1511804A1/fr not_active Withdrawn
- 2003-04-09 US US10/514,752 patent/US20050228102A1/en not_active Abandoned
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO03097738A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2003097738A1 (fr) | 2003-11-27 |
AU2003238342A1 (en) | 2003-12-02 |
DE10222169A1 (de) | 2003-12-04 |
US20050228102A1 (en) | 2005-10-13 |
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Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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Effective date: 20070612 |