WO2017043987A1 - Méthode d'obtention de joints en polyamide-élastomère sans adhésif - Google Patents

Méthode d'obtention de joints en polyamide-élastomère sans adhésif Download PDF

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Publication number
WO2017043987A1
WO2017043987A1 PCT/PL2015/050041 PL2015050041W WO2017043987A1 WO 2017043987 A1 WO2017043987 A1 WO 2017043987A1 PL 2015050041 W PL2015050041 W PL 2015050041W WO 2017043987 A1 WO2017043987 A1 WO 2017043987A1
Authority
WO
WIPO (PCT)
Prior art keywords
raw rubber
polyamide
butadiene
mixtures
elastomer
Prior art date
Application number
PCT/PL2015/050041
Other languages
English (en)
Inventor
Justyna CZECH-POLAK
Maciej Heneczkowski
Rafał OLIWA
Mariusz Oleksy
Monika STĄCEL
Original Assignee
Politechnika Rzeszowska
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 Politechnika Rzeszowska filed Critical Politechnika Rzeszowska
Publication of WO2017043987A1 publication Critical patent/WO2017043987A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/04—Oxidation
    • C08C19/06—Epoxidation
    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the subject of the invention includes the way of obtaining polyamide-rubber joints without adhesive .
  • the Japanese patent JP2010111794 includes description of a solution where during vulcanisation the raw rubber mixture is connected with polyamide without putting an adhesive layer and leads to obtainment of a product which can create a rubber composite strengthened with a layer of polyamide for example hoses with increased durability.
  • the rubber mixture for direct connection with polyamide includes for 10 to 100 part of mass of talc and 0.1 to 30 part of mass of resin as a cross-linking agents converted into 100 part of mass of raw rubber mixture including from 60 to 90 % of mass of acrylonitrile-butadiene raw rubber and 40 to 10 % of mass of chlorinated butyl raw rubber.
  • the elastomer mixture includes some of the following raw rubbers: EPDM (used in the quantity of 70-0 part of mass in relation to other raw rubbers), E-SBR, S-SBR, BR, R, IR, IIR, CIIR, BUR, BR, CR, block copolymers including styrene or mixtures of mentioned raw rubbers.
  • EPDM used in the quantity of 70-0 part of mass in relation to other raw rubbers
  • E-SBR used in the quantity of 70-0 part of mass in relation to other raw rubbers
  • S-SBR S-SBR
  • BR R
  • IR IIR
  • IIR IIR
  • CIIR CIIR
  • BUR CIIR
  • BR CIIR
  • CR block copolymers including styrene or mixtures of mentioned raw rubbers.
  • the way of obtaining without adhesive layer polyamide-elastomer joints includes introduction of a modifier both to polyamide and mixtures of raw materials.
  • the modifier has been selected from copolymers which include in their mers groups which may react with function groups of polyamide and co-vulcanise with butadiene raw rubbers in particular for making moldings there were chosen mixtures of polyamide 6 and/or 66 with additive 5-20 % of mass, epoxidized natural raw rubber, favourably 15 % and vulcanizates of sulphur elastomer mixtures: natural raw rubber, or butadiene-styrene, or isoprene-butadiene with additive of the modifier - epoxidized natural raw rubber from 15-50 %.
  • the modifier is favourably introduced both to polyamide and raw rubber mixture.
  • 10 % additive of epoxidized raw rubber to the elastomer mixture of natural raw rubber and/or isoprene-butadiene and/or isoprene-styrene raw rubber is optimal due to obtainment of adhesion strength in connection with polyamide.
  • Mixtures of polyamide 6 or 66 with epoxidized natural raw rubber are prepared by mixing polyamide granulate or more favourably powder of this material with average granulation of 20 ⁇ in a twin screw extruder with rolled band of raw rubber with gap of 1-2 mm in temperature 220-280 °C, favourably 240- 270 °C with speed of rotation of the screws 200-400 1/min with the use of a finger head.
  • An embossed rod is next cut into granules 3-4 mm long.
  • Obtained polyamide, modified with raw rubber is injected in typical conditions for processing of this material not using anti-adhesive agents for lubricating formation surfaces of sockets. Obtained moldings are intended for injection or pressing on them rubber mixtures.
  • the elastomer mixture by means of the mixing rolling method, is prepared by mixing 1000 mass parts of natural raw rubber or butadiene-styrene raw rubber or isoprene-butadiene, or another butadiene raw rubber with 50 to 200 mass parts, favourably 120 mass parts of epoxidized natural raw rubber and soot in the quantity of 700-1000 mass parts, sulphur in the quantity of 10-40 mass parts and accelerators of vulcanisation by means of two-shaft laboratory rolling stand with dimensions of rollers: length: 450 mm and diameter: 200 mm.
  • friction 1, 1 - 1,2, temperature of rollers 40-60 °C and time of rolling from 8 to 15 minutes.
  • Prepared raw rubber mixture in the form of a band with gauge 3-5 mm is subject to injection onto moulders made of modified, according to earlier description, polyamide in a machine adapted to processing of rubber mixtures or compression pressing, or rib pressing obtaining plastomer-elastomer moldings with good adhesion of one type of material to another without the necessity to apply adhesive interlayer put in additional operation.
  • Strength of polyamide-elastomer joints obtained from such modified mixtures by means of the injection method or compression pressing confirm good adhesion of both materials equalling to joints obtained with application of an additional adhesive layer.
  • Mixtures of natural raw rubber with additive of modifier - raw rubber ENR 25 are prepared according to the formulas shown in table 1 (mixtures M7 - M9) in accordance with the procedure described in example 1. Connections with the polyamide 6, modified according to example 1, are prepared by means of the injection technique and marked durability properties are collected in table 2.
  • K ' - means an adhesive layer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une méthode d'obtention de polyamide-élastomère sans connexions adhésives qui comprend l'introduction d'un modificateur à la fois dans du polyamide et des mélanges de matières premières. Le modificateur a été choisi parmi des copolymères qui comprennent dans leurs groupes mères qui peuvent réagir avec des groupes fonctionnels de polyamide et co-vulcaniser avec des caoutchoucs butadiène bruts, en particulier pour la fabrication de moulages, il a été choisi des mélanges de polyamide 6 et/ou 66 avec un 5 à 20 % en masse d'additif, un caoutchouc brut naturel époxydé, de préférence 15 % et des vulcanisats de mélanges d'élastomères soufrés : caoutchouc brut naturel, ou butadiène-styrène, ou isoprène-butadiène avec un additif du modificateur-caoutchouc brut naturel époxydé de 15 à 50 %.
PCT/PL2015/050041 2015-09-09 2015-09-23 Méthode d'obtention de joints en polyamide-élastomère sans adhésif WO2017043987A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PLP.413891 2015-09-09
PL413891A PL413891A1 (pl) 2015-09-09 2015-09-09 Sposób otrzymywania bezklejowych połączeń poliamidowo-elastomerowych

Publications (1)

Publication Number Publication Date
WO2017043987A1 true WO2017043987A1 (fr) 2017-03-16

Family

ID=58231098

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/PL2015/050041 WO2017043987A1 (fr) 2015-09-09 2015-09-23 Méthode d'obtention de joints en polyamide-élastomère sans adhésif

Country Status (2)

Country Link
PL (1) PL413891A1 (fr)
WO (1) WO2017043987A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3137387A1 (fr) 2022-07-04 2024-01-05 Arkema France Composite d’elastomère comprenant des particules de caoutchouc réticulé
WO2024134119A1 (fr) 2022-12-22 2024-06-27 Arkema France Composite comprenant un élastomère comprenant des particules de caoutchouc et une couche de mousse

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0629653A1 (fr) 1993-06-09 1994-12-21 Hüls Aktiengesellschaft Procédé pour la fabrication d'articles composites de polyamides et d'élastomères
US20100112257A1 (en) * 2008-11-05 2010-05-06 The Yokohama Rubber Co., Ltd. Thermoplastic resin composition and laminate and tire manufactured using the same
JP2010111794A (ja) 2008-11-07 2010-05-20 Yokohama Rubber Co Ltd:The ポリアミド樹脂との加硫接着が可能なゴム組成物
EP2746046A1 (fr) * 2012-12-21 2014-06-25 LANXESS Deutschland GmbH Pièce composite
EP2792479A1 (fr) * 2011-12-12 2014-10-22 The Yokohama Rubber Co., Ltd. Manche composite caoutchouc/résine

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0629653A1 (fr) 1993-06-09 1994-12-21 Hüls Aktiengesellschaft Procédé pour la fabrication d'articles composites de polyamides et d'élastomères
US20100112257A1 (en) * 2008-11-05 2010-05-06 The Yokohama Rubber Co., Ltd. Thermoplastic resin composition and laminate and tire manufactured using the same
JP2010111794A (ja) 2008-11-07 2010-05-20 Yokohama Rubber Co Ltd:The ポリアミド樹脂との加硫接着が可能なゴム組成物
EP2792479A1 (fr) * 2011-12-12 2014-10-22 The Yokohama Rubber Co., Ltd. Manche composite caoutchouc/résine
EP2746046A1 (fr) * 2012-12-21 2014-06-25 LANXESS Deutschland GmbH Pièce composite

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
R. STELLER: "Reactive Blending of Polyamides with Epoxidized Elastomers", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 104, 2007, pages 2992 - 3000
R. STELLER: "Structure and Properties of Polyamides-Epoxidized Elastomers Blends", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 99, 2006, pages 1872 - 1879

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3137387A1 (fr) 2022-07-04 2024-01-05 Arkema France Composite d’elastomère comprenant des particules de caoutchouc réticulé
WO2024009038A1 (fr) 2022-07-04 2024-01-11 Arkema France Composite d'elastomere comprenant des particules de caoutchouc reticule
WO2024134119A1 (fr) 2022-12-22 2024-06-27 Arkema France Composite comprenant un élastomère comprenant des particules de caoutchouc et une couche de mousse
FR3144144A1 (fr) 2022-12-22 2024-06-28 Arkema France Composite comprenant un élastomère comprenant des particules de caoutchouc et une couche de mousse

Also Published As

Publication number Publication date
PL413891A1 (pl) 2017-03-13

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