WO2002018136A2 - Composites polymeriques de chlorotrifluoroethylene utilises dans des structures porteuses architecturales - Google Patents

Composites polymeriques de chlorotrifluoroethylene utilises dans des structures porteuses architecturales Download PDF

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Publication number
WO2002018136A2
WO2002018136A2 PCT/US2001/027292 US0127292W WO0218136A2 WO 2002018136 A2 WO2002018136 A2 WO 2002018136A2 US 0127292 W US0127292 W US 0127292W WO 0218136 A2 WO0218136 A2 WO 0218136A2
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WO
WIPO (PCT)
Prior art keywords
exposure
polymer
termonomer
bearing structures
composite
Prior art date
Application number
PCT/US2001/027292
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English (en)
Other versions
WO2002018136A3 (fr
Inventor
Katherine M. Sahlin
Laura Socha
John Effenberger
Original Assignee
Chemfab Corporation
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 Chemfab Corporation filed Critical Chemfab Corporation
Priority to AU2001287018A priority Critical patent/AU2001287018A1/en
Publication of WO2002018136A2 publication Critical patent/WO2002018136A2/fr
Publication of WO2002018136A3 publication Critical patent/WO2002018136A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/047—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with fluoropolymers

Definitions

  • the present invention relates generally to polymeric composites that are used in the construction of architectural load-bearing structures.
  • the invention concerns the unique advantages of amorphous copolymers of chlorotrifluoroethylene (CTFE) and vinylidene fluoride (VF 2 ), which improve the translucency of the composite without compromising the integrity of the composite in its long-term structural end use.
  • CTFE chlorotrifluoroethylene
  • VF 2 vinylidene fluoride
  • the integrity of the composite can be judged by its ability to retain strength and elongation as well as its ability to resist dirt, cracking, chipping and flaking after exposure to UN light.
  • the invention is the description of the structure and properties of a class of CTFE- VF 2 polymers which make them suitable as a polymer matrix material in composites for architectural structural load bearing structures.
  • This polymer was incorporated in U.S. Patent o. 5,759,924 (incorporated herein by reference) and this description sets forth the particular polymer and its advantageous properties.
  • a load-bearing structure is a building component that accommodates the application of external mechanical forces (or loads) without losing its physical integrity.
  • a typical load-bearing structure is composed of a frame constructed of arches and/or beams.
  • Load-bearing structures incorporating coated fabrics were employed initially in the design of air-supported shelters for travelling exhibits, and as enclosures for microwave antennae.
  • coated-fabric, load-bearing structures have evolved into prestressed (tensioned) members with tensioning provided by stretching a coated fabric over the arches and beams of the structure. As a prestressed member, the internal tension in the stretched fabric provides additional resistance to deformation when another load is applied to the structure.
  • the fabric served as a reinforcement to control the shape of the structure and to facilitate load-bearing behavior in the structure.
  • the most common coating materials included rubbers such as neoprene, and plastics, such as polyvinyl chloride or polyurethane.
  • the most commonly used woven fabric reinforcements were simple, plain-woven fabrics of nylon or polyester yarns.
  • Prior art coated-fabrics for load-bearing structures typically incorporate additives to the coating material to protect the structure from the environment.
  • additives may be incorporated into the coated fabric to reduce the ultra-violet burden of sunlight on both the coating polymers and the fibrous reinforcement and thus enhance the outdoor durability of the coated fabric. While such additives protect the coated fabric from the environment, they also substantially reduce or eliminate the translucency of the coated fabric. Light is transmitted through the coated fabric by passing through the myriad of tiny gaps or openings in the coated fabric (so called windows in the woven fabrics).
  • the polymer of the invention is of the class of copolymers containing CTFE and
  • VF 2 VF 2 .
  • MW high molecular weight
  • VF 2 a level of VF 2 sufficient to render the polymer amorphous
  • presence of vinyl ester or acid with an alpha hydrogen which acts to retard the formation of crystalline domains are as follows: high molecular weight (MW); a level of VF 2 sufficient to render the polymer amorphous; presence of vinyl ester or acid with an alpha hydrogen which acts to retard the formation of crystalline domains.
  • the recrystallization of the polymers considered unsuitable for outdoor exposure reduce the tensile strength of the matrix as well as reduce the elongation of the matrix.
  • the increased crystallinity and larger sized crystallites that are formed upon exposure to UV light at hot environmental temperatures can produce stress risers in the polymeric matrix material.
  • the preferred composite has a high molecular weight for thermal stability that allows for increased end use temperatures and less degradation for a given set of processing conditions; and a VF 2 content (approximately 17% by weight or more) sufficient to produce an amorphous copolymer. This amorphous nature also allows for a more conformable material with a wider processing window.
  • the CTFE-VF 2 blends alone still recrystallize with UN exposure.
  • the preferred composite further comprises a termonomer (a vinyl ester or acid with an alpha hydrogen) which suppresses the tendency of the polymer to recrystallize upon exposure to elevated temperatures and UN.
  • a termonomer a vinyl ester or acid with an alpha hydrogen
  • Vinyl propionate in the amount of approximately 1.5% by weight was found to be an effective termonomer.
  • CTFE-VF 2 copolymers While many CTFE-VF 2 copolymers remain clear (no hazing) after exposure to
  • the inventive polymer showed significant improvements in retaining elongation and tensile strength after exposure to UV and heat compared to other CTFE-VF 2 copolymers.
  • Fig. 1 is a diagram comparing tensile elongation retention after QUV exposure at 45 °C between commercial extruded PCTFE-VF 2 films of intermediate MW and films cast of low and high MW PCTFE-VF 2 .
  • Fig. 2 is a diagram comparing crystallinity as a function of QUV exposure at 45°C and 70°C between commercial extruded PCTFE-VF 2 films of intermediate MW and films cast of low and high MW PCTFE-VF 2 .
  • Fig. 3 is a diagram comparing tensile elongation retention after QUV exposure at
  • Fig. 4 is a diagram comparing tensile strength retention after QUV exposure at 45°C between high MW coatings of the invention and non-amorphous, high MW coatings.
  • CTFE-VF 2 fluoropolymer resins to achieve water white coatings on architectural membranes is of interest in the market.
  • This resin material imparts higher light transmission, as compared to current materials, such as PTFE, in the interstitial areas of the coated fabric membrane. While many compositions exhibit some translucency, only the fully amorphous, high molecular weight CTFE-VF 2 polymers of the invention would be suitable to tolerate the outdoor environment of such an application.
  • the percent of original tensile strength after QUV exposure at 45 °C is compared between commercial extruded PCTFE-VF 2 films of intermediate MW (Aclar 22 A) and films cast of low and high MW PCTFE-VF 2 .
  • Low MW films degrade to 0% of their original elongation after 325 hours of exposure at 45 °C.
  • High MW films retain 80% of original elongation after 200 hours and 40% after 500 hours of exposure at 45°C. All of these films recrystallize to some degree after UV exposure (see Figure 2) although the high MW sample exhibits fair tensile strength retention.
  • the increase in crystallinity is accelerated under UV light when the temperature of exposure is increased to 70°C.
  • the slightly crystalline film cast from the ⁇ 17% VF 2 , 1.5% vinyl propionate termonomer retains 8% of its original elongation after exposure for 3600 hours at 45°C, while the >17% VF 2 , 1.5% vinyl propionate film retains 100% of its elongation at the same conditions.
  • An embodiment of the present invention comprises a substrate and an amorphous, high MW coating disposed on the substrate, the coating comprising a fluoropolymer comprising CTFE, VF 2 , and a termonomer, wherein the termonomer comprises either a vinyl ester or an acid with an alpha hydrogen.
  • the substrate in this embodiment is typically a woven fabric, preferably fiberglass or polyester.
  • the VF 2 in this embodiment is present in the amount of approximately 15% or more and preferably approximately 17% or more by weight of the polymer.
  • the termonomer in this embodiment is present in an amount of approximately between 1.0% and 3.0% and preferably approximately 1.5% by weight of the coating.
  • Such composite preferred for such an application also has a translucency of at least about 23% of normally incident visible light.
  • the present invention comprises coatings of high molecular weight.
  • the MW of the polymer of the present invention can be determined and/or measured in a number of ways known in the relevant art.
  • One common method involves determining the intrinsic viscosity (IV) of the material and comparing it to the intrinsic viscosity of material of known molecular weight.
  • the coating of the invention may be dissolved in a solvent, such as orthochlorobutyltrifluoride (OCBTF), at approximately 135°C, and the flow of the resultant viscous material measured and compared to the flow rates of material of a known molecular weight.
  • OCBTF orthochlorobutyltrifluoride
  • the high MW coatings of the present invention have an intrinsic viscosity of approximately 2 dl/g and a molecular weight of approximately 800,000 to 1,000,000.
  • Films of various copolymer constructions were placed in a QUV tester, which provided the UV exposure. Chamber temperature was set at either 45°C or 70°C. Water was present, but not cycled in a particular pattern. Samples were removed after various exposure times and tested for tensile strength, elongation at break, crystallinity and crystallite size.
  • the film made with the 6% VF 2 and 3% vinyl propionate showed comparable loss of elongation and strength while the film cast from the ⁇ 17% VF 2 , 1.5% vinyl propionate termonomer retained 94% of its elongation after exposure for 576 hours at 45°C.
  • the ⁇ 17% VF 2 termonomer is lower in crystallinity than the 6% VF 2 termonomer in this example.
  • the film cast from the >17% VF 2 , 1.5% vinyl propionate termonomer retained 94% of its elongation after 1130 hours.
  • a comparison of Figures 3 and 4 illustrates that retention of tensile elongation is a dramatic indicator of the different material responses to UV which can be obtained when varying the crystallinity of these compositions.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des nouveaux composites polymériques amorphes de poids moléculaire élevée de CTFE-VF2 utilisés dans des structures porteuses architecturales. Ces composites comprennent un termonomère renfermant un ester de vinyle ou un acide pourvu d'un hydrogène alpha. Les composites de l'invention présentent un vaste champ d'applications et permettent d'obtenir des structures durables résistant à l'exposition aux UV, à la formation de taches, à la désagrégation, aux craquelures et à l'écaillage.
PCT/US2001/027292 2000-09-01 2001-08-31 Composites polymeriques de chlorotrifluoroethylene utilises dans des structures porteuses architecturales WO2002018136A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001287018A AU2001287018A1 (en) 2000-09-01 2001-08-31 Polymeric composites of chlorotrifluoroethylene for use in architectural load-bearing structures

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US65377900A 2000-09-01 2000-09-01
US09/653,779 2000-09-01

Publications (2)

Publication Number Publication Date
WO2002018136A2 true WO2002018136A2 (fr) 2002-03-07
WO2002018136A3 WO2002018136A3 (fr) 2002-06-06

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AU (1) AU2001287018A1 (fr)
WO (1) WO2002018136A2 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4610918A (en) * 1984-04-13 1986-09-09 Chemical Fabrics Corporation Novel wear resistant fluoropolymer-containing flexible composites
EP0905302A1 (fr) * 1996-10-18 1999-03-31 Chemfab Corporation Matériau composite polymère utile dans une structure porteuse architecturale

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0749548B2 (ja) * 1988-01-18 1995-05-31 セントラル硝子株式会社 コーティング用フッ素樹脂並びにフッ素樹脂液

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4610918A (en) * 1984-04-13 1986-09-09 Chemical Fabrics Corporation Novel wear resistant fluoropolymer-containing flexible composites
EP0905302A1 (fr) * 1996-10-18 1999-03-31 Chemfab Corporation Matériau composite polymère utile dans une structure porteuse architecturale

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 198935 Derwent Publications Ltd., London, GB; Class A14, AN 1989-253439 XP002192618 & JP 01 185376 A (CENTRAL GLASS CO LTD), 24 July 1989 (1989-07-24) *

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Publication number Publication date
AU2001287018A1 (en) 2002-03-13
WO2002018136A3 (fr) 2002-06-06

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