WO2005066251A1 - Polyamide syntetic foam - Google Patents

Polyamide syntetic foam Download PDF

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Publication number
WO2005066251A1
WO2005066251A1 PCT/US2004/043826 US2004043826W WO2005066251A1 WO 2005066251 A1 WO2005066251 A1 WO 2005066251A1 US 2004043826 W US2004043826 W US 2004043826W WO 2005066251 A1 WO2005066251 A1 WO 2005066251A1
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WIPO (PCT)
Prior art keywords
composite
polyamide
nylon
glass bubbles
coupling agent
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Ceased
Application number
PCT/US2004/043826
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French (fr)
Inventor
Ronald J. Israelson
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3M Innovative Properties Co
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3M Innovative Properties Co
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Filing date
Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Priority to JP2006547534A priority Critical patent/JP2007517127A/en
Priority to US10/585,023 priority patent/US20070155858A1/en
Priority to EP04815824A priority patent/EP1699856A1/en
Publication of WO2005066251A1 publication Critical patent/WO2005066251A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass
    • 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 present invention relates to a filled resin composite.
  • fillers into resin compositions to adjust the physical properties of the resultant compositions (often referred to as "composites” or “filled composites”) such as reduce the density thereof, or reduce cost by reducing the proportion of relatively expensive resin with cheaper materials.
  • fillers include solid particulates such as titanium dioxide, glass, etc.
  • hollow particles such as hollow glass bubbles.
  • glass bubbles have often been used to successfully reduce density of the final composite, in many cases the glass bubbles are crushed during manipulation of the composite, thereby impairing the desired reduction in density.
  • resin composites containing glass bubbles have often exhibited undesirable loss of desired physical properties such as tensile strength.
  • Non-reinforcing fillers can be defined as any particle with an aspect ratio (length over diameter) less than 2. It is assumed that the loss in mechanical strength is due primarily to the filler causing a disruption of the polymer chains and also due to the inefficient bonding between the polymer and the filler; where the bond strength is assumed to be less than the tensile strength of the polymer chains themselves.
  • Illustrative examples of filled resin composites are disclosed in U.S. Patent No.
  • a composite of the invention comprises apolyamide such as nylon, e.g., nylon-6,6 (e.g., (Zytel 101L from Dupont)) and blends of nylon (e.g., NORYL GTX a blend of nylon and polyphenylene ether available from GE), and glass bubbles .
  • apolyamide such as nylon, e.g., nylon-6,6 (e.g., (Zytel 101L from Dupont)) and blends of nylon (e.g., NORYL GTX a blend of nylon and polyphenylene ether available from GE), and glass bubbles .
  • the glass bubbles have been treated with aminopropyltriethoxysilane ("APS") prior to incorporation into the composite.
  • APS aminopropyltriethoxysilane
  • the glass bubbles should exhibit a crush strength of at least 10,000 PSI to withstand many extrusion operations. In some embodiments, they will preferably exhibit a crush strength of at least 18,000 PSI to withstand injection molding as well as extrusion operations.
  • the strength of the glass bubbles is typically measured using ASTM D3102- 72; "Hydrostatic Collapse Strength of Hollow Glass Microspheres".
  • the invention provides filled nylon-6,6 composites that can be used to create lightweight parts which require the tensile properties of standard, i.e., unfilled nylon-6,6. Furthermore, molded parts made from filled nylon-6,6 will also have reduced shrinkage after molding (due to displaced polymer) and other benefits over standard nylon-6,6.
  • lightweight parts with good tensile properties will include sporting goods for reduced user fatigue and/or increases in performance, transportation (automotive, aerospace, etc.) parts for fuel savings, improved acceleration or higher top speed, and reduced fuel emissions.
  • parts made for "structural" applications are not suitable candidates for nylon-6,6 with non-reinforcing fillers.
  • lightweight structural parts can now be made with filled nylon-6,6.
  • the present invention may be used with commercially available glass bubble fillers for use in resin composites.
  • the bubbles are of the high strength variety such as
  • ScotchliteTM Glass Bubbles S60HS which are soda-lime-borosilicate glass. These bubbles exhibit an isostatic crush strength of 18,000 psi, density of 0.60 g/cc, and average diameter of about 30 microns .
  • Tensile Modulus was determined following ASTM Test Method D-638 and is reported in
  • Elongation at Break was determined following ASTM Test Method D-638 and is reported as %.
  • Density A fully automated gas displacement pycnometer obtained under the trade designation "ACCUPYC 1330 PYCNOMETER” from Micromeritics, Norcross, Georgia, was used to determine the density of the injection molded composite material according to ASTM D-2840-69, "Average True Particle Density of Hollow Microspheres".

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

A filled thermoplastic resin composite comprising at least one polyamide and glass bubbles having a crush strength of at least 10,000 PSI treated with at least one of a silane coupling agent or titanate coupling agent.

Description

POLYAMIDE SYNTETIC FOAM
Cross Reference and Priority Claim This application claims priority to U.S. Provisional Application No. 60/533,320 which was filed December 30, 2003.
Field of Invention The present invention relates to a filled resin composite.
Background It is well known to incorporate fillers into resin compositions to adjust the physical properties of the resultant compositions (often referred to as "composites" or "filled composites") such as reduce the density thereof, or reduce cost by reducing the proportion of relatively expensive resin with cheaper materials. Examples of known fillers include solid particulates such as titanium dioxide, glass, etc. It has also been known to use hollow particles such as hollow glass bubbles. Although glass bubbles have often been used to successfully reduce density of the final composite, in many cases the glass bubbles are crushed during manipulation of the composite, thereby impairing the desired reduction in density. Also, resin composites containing glass bubbles have often exhibited undesirable loss of desired physical properties such as tensile strength. It is well known that adding non-reinforcing fillers to polymers will result in a decrease in the mechanical strength (tensile, impact, etc.) of that polymer composition. Non-reinforcing fillers can be defined as any particle with an aspect ratio (length over diameter) less than 2. It is assumed that the loss in mechanical strength is due primarily to the filler causing a disruption of the polymer chains and also due to the inefficient bonding between the polymer and the filler; where the bond strength is assumed to be less than the tensile strength of the polymer chains themselves. Illustrative examples of filled resin composites are disclosed in U.S. Patent No. 3,769,126 (Kolek), 4,243,575 (Myers et al.), 4,923,520 (Anzai et al.), and 5,695,851 (Watanabe et al.) and EP Application No. 1,142,685 (Akesson).
Summary of Invention The present invention provides a filled resin composite. Composites of the invention provide a surprising combination of tensile strength and reduced weight. The improved properties provided by composites of the invention enables use of filled resin composites in product applications not otherwise possible. In brief summary, in a typical embodiment a composite of the invention comprises apolyamide such as nylon, e.g., nylon-6,6 (e.g., (Zytel 101L from Dupont)) and blends of nylon (e.g., NORYL GTX a blend of nylon and polyphenylene ether available from GE), and glass bubbles . In accordance with the invention, the glass bubbles have been treated with aminopropyltriethoxysilane ("APS") prior to incorporation into the composite. The glass bubbles should exhibit a crush strength of at least 10,000 PSI to withstand many extrusion operations. In some embodiments, they will preferably exhibit a crush strength of at least 18,000 PSI to withstand injection molding as well as extrusion operations. The strength of the glass bubbles is typically measured using ASTM D3102- 72; "Hydrostatic Collapse Strength of Hollow Glass Microspheres". The invention provides filled nylon-6,6 composites that can be used to create lightweight parts which require the tensile properties of standard, i.e., unfilled nylon-6,6. Furthermore, molded parts made from filled nylon-6,6 will also have reduced shrinkage after molding (due to displaced polymer) and other benefits over standard nylon-6,6. Some examples for the utility of lightweight parts with good tensile properties will include sporting goods for reduced user fatigue and/or increases in performance, transportation (automotive, aerospace, etc.) parts for fuel savings, improved acceleration or higher top speed, and reduced fuel emissions. In general, parts made for "structural" applications (load-bearing) are not suitable candidates for nylon-6,6 with non-reinforcing fillers. As a result of this invention, lightweight structural parts can now be made with filled nylon-6,6. The present invention may be used with commercially available glass bubble fillers for use in resin composites. Preferably, the bubbles are of the high strength variety such as
Scotchlite™ Glass Bubbles S60HS which are soda-lime-borosilicate glass. These bubbles exhibit an isostatic crush strength of 18,000 psi, density of 0.60 g/cc, and average diameter of about 30 microns .
Test Methods
Tensile Modulus Tensile Modulus was determined following ASTM Test Method D-638 and is reported in
Mpa.
Ultimate Tensile Modulus
Ultimate Tensile Modulus was determined following ASTM Test Method D-638 and is reported in Mpa.
Flexural Modulus
Flexural Modulus was determined following ASTM Test Method D-790 and is reported in Mpa.
Ultimate Flexural Strength
Ultimate Flexural Strength was determined following ASTM Test Method D-790 and is reported in Mpa.
Elongation at Break
Elongation at Break was determined following ASTM Test Method D-638 and is reported as %. Density A fully automated gas displacement pycnometer obtained under the trade designation "ACCUPYC 1330 PYCNOMETER" from Micromeritics, Norcross, Georgia, was used to determine the density of the injection molded composite material according to ASTM D-2840-69, "Average True Particle Density of Hollow Microspheres".
Silane Treatment of Glass Bubbles A Ross Mixer (available from Charles Ross & Son Company Hauppauge, NY) was charged with a solution of N-2-(aminoethyl)-3-amino propyltrimethoxysilane (1500 g; 0.5% by wt; available from Osi Specialties, Albany, NY under the trade designation "Al 120"). Glass Bubbles (Available from 3M Company, St. Paul, MN under the trade designation "S60HS") were slowly added under medium mix speed, and the mixture was allowed to mix for 15 minutes. The ensuing paste was poured into aluminum pans and dried overnight in a forced air oven at 80°C. . The dried glass bubbles were screened through a 180 micron screen to remove any clumps.
Compounding and Molding of Nylon Composites A twin screw extruder (Berstorff Ultra Glide; screw diameter 25mm; length to diameter ratio was 36:1; screw speed ranged from 200-250 rpm; temperature set points ranged from 200°F-575°F (93°C-302°C), while the actual values range from 148°F-575°F
(64°C-302°C); throughput was 10 lbs/hr(4.5 Kg/hr)) equipped with side feeders for glass bubbles, and pelletizer accessories was charged with nylon 66 (available from DuPont, Wilmington, DE, under the trade designation "ZYTEL 101L"; a melt index of 60g/10m at 275°C, Tg of 50 °C, Tm of 260-262 °C, and a density of 1.14 g/cm3). Test samples were molded on an injection molding machine (150 ton Engel Injection Molding Machine; with an ASTM four cavity mold) with a screw diameter of 30 mm and injection pressure maintained below 18,000 psi (124 MPa). Table 1.
Figure imgf000006_0001

Claims

What is claimed is:
1. A filled thermoplastic resin composite comprising at least one polyamide and glass bubbles having a crush strength of at least 10,000 PSI treated with at least one of a
5 silane coupling agent or titanate coupling agent.
2. The composite of claim 1 wherein said polyamide is selected from the group consisting of nylon and blends of nylon.
/ 0 3. The composite of claim 2 wherein said silane coupling agent is an aminosilane.
4. The composite of claim 3 wherein said silane coupling agent is selected from aminopropyltriethoxysilane and N-2-(aminoethyl)-3-amino propyltrimethoxysilane.
5 5. The composite of claim 1 wherein said glass bubbles exhibit a crush strength of at least 18,000 PSI.
6. An article comprising the composite of claim 1. 0
PCT/US2004/043826 2003-12-30 2004-12-30 Polyamide syntetic foam Ceased WO2005066251A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2006547534A JP2007517127A (en) 2003-12-30 2004-12-30 Polyamide synthetic foam
US10/585,023 US20070155858A1 (en) 2003-12-30 2004-12-30 Polyamide syntetic foam
EP04815824A EP1699856A1 (en) 2003-12-30 2004-12-30 Polyamide syntactic foam

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US53332003P 2003-12-30 2003-12-30
US60/533,320 2003-12-30

Publications (1)

Publication Number Publication Date
WO2005066251A1 true WO2005066251A1 (en) 2005-07-21

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PCT/US2004/043826 Ceased WO2005066251A1 (en) 2003-12-30 2004-12-30 Polyamide syntetic foam

Country Status (5)

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US (1) US20070155858A1 (en)
EP (1) EP1699856A1 (en)
JP (1) JP2007517127A (en)
CN (1) CN1902270A (en)
WO (1) WO2005066251A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007297432A (en) * 2006-04-28 2007-11-15 Tokyo Printing Ink Mfg Co Ltd Insulating resin composition
KR100828654B1 (en) 2006-04-13 2008-05-09 주식회사 코오롱 Polyamide Hybrid Resin Composition for Engine Cover
WO2008090235A3 (en) * 2007-02-28 2008-09-25 Solvay Advanced Polymers Llc Thermoplastic compositions containing microspheres
JP2009516023A (en) * 2005-11-10 2009-04-16 スリーエム イノベイティブ プロパティズ カンパニー Filled polymer composite
EP2155809B1 (en) * 2007-04-05 2017-10-25 Teijin Aramid B.V. Aramid or rigid rod polymer foam
WO2019185509A1 (en) 2018-03-27 2019-10-03 Basf Se A polyamide composition, manufacturing method, an application and article thereof

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US8617702B2 (en) 2010-04-28 2013-12-31 Sabic Innovative Plastics Ip B.V. Thermally insulated structural members, and doors and windows incorporating them
ES2716557T3 (en) 2010-09-08 2019-06-13 3M Innovative Properties Co Glass bubbles, composite materials from them and glass bubble manufacturing method
JP2012233087A (en) 2011-05-02 2012-11-29 Three M Innovative Properties Co Thermoplastic resin composite containing hollow glass microsphere
US9187609B2 (en) * 2013-10-02 2015-11-17 Greatario Industrial Storage Systems Ltd. System for covering hydrocarbon liquids and method of forming same
WO2015103099A1 (en) 2013-12-30 2015-07-09 3M Innovative Properties Company Polyolefin composition including hollow glass microspheres and method of using the same
EP3090022B1 (en) 2013-12-30 2018-09-05 3M Innovative Properties Company Poly(methylpentene) composition including hollow glass microspheres and method of using the same
MX2017010964A (en) 2015-02-27 2017-10-20 3M Innovative Properties Co Polyamide composition including hollow glass microspheres and articles and methods relating to the same.
EP3135731B1 (en) * 2015-08-31 2017-11-01 Ems-Patent Ag Polyamide moulding material and molded bodies made therefrom
KR101875883B1 (en) * 2016-10-28 2018-07-06 (주)타이리젠 Foam composition of low density resins
CN113993701B (en) 2019-05-15 2024-04-12 3M创新有限公司 Film comprising polymer elements interconnecting particles
MX2021013289A (en) 2019-05-24 2021-12-10 Dow Global Technologies Llc Crosslinked polymeric composition and coated conductor.
CN114729158B (en) * 2019-09-09 2024-11-01 赢彩科技股份有限公司 Lightweight reinforced composite material formulation and method for making the same
US11643524B2 (en) 2020-09-09 2023-05-09 Chromaflo Technologies Corp. Lightweight reinforced composite formulation and method of making the same

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US20020149138A1 (en) * 1999-07-27 2002-10-17 Campbell Richard W. Syntactic foam plugs
US20030134920A1 (en) * 2001-12-05 2003-07-17 Poisl William Howard Reinforced polymeric foams

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WO1985005113A1 (en) * 1984-05-07 1985-11-21 Hughes Aircraft Company Fiber-reinforced syntactic foam composites and method of forming same
US20020149138A1 (en) * 1999-07-27 2002-10-17 Campbell Richard W. Syntactic foam plugs
US20030134920A1 (en) * 2001-12-05 2003-07-17 Poisl William Howard Reinforced polymeric foams

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009516023A (en) * 2005-11-10 2009-04-16 スリーエム イノベイティブ プロパティズ カンパニー Filled polymer composite
CN101305042B (en) * 2005-11-10 2012-05-02 3M创新有限公司 filled polymer composite
KR100828654B1 (en) 2006-04-13 2008-05-09 주식회사 코오롱 Polyamide Hybrid Resin Composition for Engine Cover
JP2007297432A (en) * 2006-04-28 2007-11-15 Tokyo Printing Ink Mfg Co Ltd Insulating resin composition
WO2008090235A3 (en) * 2007-02-28 2008-09-25 Solvay Advanced Polymers Llc Thermoplastic compositions containing microspheres
US8362114B2 (en) 2007-02-28 2013-01-29 Solvay Advanced Polymers, L.L.C. Thermoplastic compositions containing microspheres
EP2155809B1 (en) * 2007-04-05 2017-10-25 Teijin Aramid B.V. Aramid or rigid rod polymer foam
WO2019185509A1 (en) 2018-03-27 2019-10-03 Basf Se A polyamide composition, manufacturing method, an application and article thereof

Also Published As

Publication number Publication date
JP2007517127A (en) 2007-06-28
CN1902270A (en) 2007-01-24
US20070155858A1 (en) 2007-07-05
EP1699856A1 (en) 2006-09-13

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