GB2074181A - Aqueous Fluoropolymer Compositions - Google Patents
Aqueous Fluoropolymer Compositions Download PDFInfo
- Publication number
- GB2074181A GB2074181A GB8111396A GB8111396A GB2074181A GB 2074181 A GB2074181 A GB 2074181A GB 8111396 A GB8111396 A GB 8111396A GB 8111396 A GB8111396 A GB 8111396A GB 2074181 A GB2074181 A GB 2074181A
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- United Kingdom
- Prior art keywords
- weight
- silane
- polymer
- lower alkyl
- coating
- 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.)
- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 229920002313 fluoropolymer Polymers 0.000 title abstract 2
- 239000004811 fluoropolymer Substances 0.000 title abstract 2
- 239000004744 fabric Substances 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011521 glass Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000077 silane Inorganic materials 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 13
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 238000009472 formulation Methods 0.000 claims description 15
- -1 hydrocarbyl siloxane Chemical class 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 229920006222 acrylic ester polymer Polymers 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 12
- 239000008199 coating composition Substances 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000010306 acid treatment Methods 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004103 aminoalkyl group Chemical group 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- RFJVDJWCXSPUBY-UHFFFAOYSA-N 2-(difluoromethylidene)-4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane Chemical compound FC(F)=C1OC(F)(F)C(F)(C(F)(F)F)O1 RFJVDJWCXSPUBY-UHFFFAOYSA-N 0.000 description 1
- MHFDRMLNBIUARQ-UHFFFAOYSA-N 3-[dimethoxy-[3-(3-phenylprop-2-enylamino)propoxy]silyl]propan-1-amine hydrochloride Chemical compound Cl.C(=CC1=CC=CC=C1)CNCCCO[Si](OC)(OC)CCCN MHFDRMLNBIUARQ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000000692 Student's t-test Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- FYZFRYWTMMVDLR-UHFFFAOYSA-M trimethyl(3-trimethoxysilylpropyl)azanium;chloride Chemical compound [Cl-].CO[Si](OC)(OC)CCC[N+](C)(C)C FYZFRYWTMMVDLR-UHFFFAOYSA-M 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/30—Polyolefins
- C03C25/305—Polyfluoroolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Fluoropolymer compositions for coating glass fabric comprises (a) water, (b) a polyhydrolysable silane, (c) a siloxane, (d) a tetrafluoroethylene polymer, and (e) a fluoro-acrylic ester polymer. The coatings improve the acid resistance of the fabric. The fabric may be coated with a composition of (a)-(d) first, and then with (e) subsequently.
Description
SPECIFICATION
Products and Process
Field of the Invention
This invention relates to aqueous dispersions of tetrafluoroethylene polymers and to coatings of such dispersions on glass fabric.
Background of the Invention
Fabric made of glass fiber is useful in filter applications to separate particles from a gas stream.
Commonly the glass fabric is coated with a tetrafluoroethylene polymer coating, usually polytetrafluoroethylene (PTFE), to increase the flex life, i.e., resistance to breaking on repeated flexing, of the fabric. Such a coating is especially useful when the glass fabric is employed as a filter bag to filter out particulate solid impurities such as carbon black or fly ash which may be present in flue gases.
Due to the passage of hot flue gases through the glass fabric and due to back flushing or pulse flushing during cleaning, the fabric is subjected to flexural stresses which weaken the glass fibers of the fabric and ultimately cause breakage.
While the tetrafluoroethylene polymer coating increases the flex life of the glass fabric, resistance of the coated glass fabric to attack by acids present in hot flue gases could be improved. Many hot flue gases contain oxides of sulfur and water vapor which combine to form an acidic environment. Glass fabric coated with tetrafluoroethylene polymer coatings heretofore were subject to attack by acids in the flue gas which weakened the fabric and shortened the fabric's flex life.
It would be desirable to have a tetrafluoroethylene polymer coating composition which imparts greater resistance to attack by acids than tetrafluoroethylene polymer coating compositions heretofore available.
Summary of the Invention
It has now been discovered that tetrafluoroethylene polymer coating dispersions which impart resistance to attack by acids to glass fabric coated with the dispersion can be obtained by employing in the coating dispersion, a water-soluble, polyhydrolyzable silane, a fluorinated acrylate water-repellant additive, and a siloxane.
Specifically, the composition of this invention is an aqueous dispersion consisting essentially of
a) water,
b) 565% by weight tetrafluoroethylene polymer, said weight based on weight of water and
polymer, said polymer being of film-forming molecular weight,
c) 260% by weight of a polyhydrolyzable silane of the formula R,Si+OR)3 wherein R is lower alkyl, preferably alkyl of 1-3 carbon atoms, and R, is phenyl or substituted lower alkyl, preferably of 1-3 carbon atoms, in which the substituents are selected from halogen, quaternary ammonium, or-NR'R" in which R' and R" are each H, lower alkyl, lower alkoxyalkyl, amino lower alkyl, hydroxyl lower alkyl, or substituted (amino lower alkyl), said weight based on weight of tetrafluoroethylene polymer,
d) 120% by weight of a hydrocarbyl siloxane, said weight based on weight of
tetrafluoroethylene polymer,
e) 120% by weight of a polymer of a fluorinated ester of an acrylic acid, said weight based on
weight of tetrafluoroethylene polymer.
Description of the Invention
The tetrafluoroethylene polymer in the compositions of this invention can consist of the homopolymer, polytetrafluoroethylene, or can be a copolymer of tetrafluoroethylene with a minor proportion, e.g. up to 35% by weight based on weight of copolymer, of another copolymedzable ethylenically unsaturated monomer. For example, the homopolymer can include small amounts of comonomer modifier, wherein the homopolymer still retains its non-melt fabricable character, such as up to two percent by weight of polymer units derived by copolymerization with tetrafluoroethylene of perfluoroalkyl or oxyperfluoroalkyl trifluoroethylene of 3 to 10 carbon atoms, and preferably hexafluoropropylene, as disclosed in U.S. Patent No. 3,142,665 to Cardinal, Edens, and Van Dyk or perfluoro(alkyl vinyl ether).Larger amounts of these comonomers or other comonomers render the resultant copolymer melt fabricable. Examples of such copolymers include copolymers of tetrafluoroethylene with such monomers as hexafluoropropylene, as disaclosed in U.S. Patent No.
3,946,763 to Bro and Sandt, higher perfluoroalkenes such as those containing from 4 to 10 carbon atoms, perfluoro(alky vinyl ethers) such as perfluoroethyl or perfluoropropyl vinyl ether, disclosed in
U.S. Patent No. 3,132,123 to Harris and McCane, perfluoro-(2-methylene-4-methyl-1 ,3-dioxolane) disclosed in U.S. Patent No. 3,308,107 to Selman and Squire, and the highly fluorinated monomers in which a single hydrogen is present which does not change the fluorocarbon character of the copolymer, such monomers being for example 2-hydroperfluoroalkene containing 1 to 3 carbon atoms such as 2-hydropentafluoropropene, the omega hydroperfluoroalkenes containing from 3 to 10 carbon atoms, and the omega-hydroperfluoro(alkyl vinyl ethers) in which the alkyl group contains from 1 to 5 carbon atoms.The tetrafluoroethylene polymers can be of the non-melt-fabricable type, having an extremely high molecular weight, as evidenced by a specific melt viscosity of 1 x109 poise or more measured at 3800C at a shear stress of 6.5 psi or can be of the melt fabricable type having a melt viscosity of from 1 xl oa to 1 xl 1 Off poise under the same conditions. Preferably, the polymer is polytetrafluoroethylene.
The polymers are preferably prepared by the aqueous dispersion method for preparing tetrafluoroethylene polymers in which sufficient ionic dispersing agent is present in the polymerization mixture to maintain the polymer particles in dispersion. The tetrafluoroethylene polymer dispersion can be used as prepared or redispersed in water using a suitable dispersing agent. A suitable dispersing agent in an amount of up to about 6% based on polymer may be present.
The water-soluble, polyhydrolyzable silane is preferably one in which R, is aminoalkyl or substituted amino alkyl. Representative of these amino alkyl groups are -CH2-CH2CH2NH2, -CH2- (CH2)2NH(CH2)2NH2, -CH2-(CH2)3N(CH3)2, and the like. The term lower alkyl means alkyl of 1-6 carbon atoms, as used herein. Representative silanes include y-aminopropyl triethoxy silane; (N,Ndimethyl-3-amino propyl trimethoxy silane; N-trimethoxy silylpropyl-N,N,N-trimethyl ammonium chloride; 3 (N-styryl methyl-2-aminoethyl) aminopropyl trimethoxy-silane hydrochloride; and the like.
Preferably the silane will be present in an amount between 312%.
The siloxane is preferably one of the formula
wherein R' and R" are each independently a hydrocarbyl group of 1-20 carbon atoms and one of R' and RD can be hydrogen, n is an integer of between about 5 and 5000, preferably between 10 and 2000 and most preferably between 10 and 100 and R is lower (i.e., 1 4 carbon atoms) alkyl or phenyl, and wherein the polysiloxane can be a homopolymer of a copolymer with another polysiloxane having different hydrocarbyl R' and R" substituents. More preferably R' and R" are each independently alkyl of 1-10 carbon atoms, aryl of 6-10 carbon atoms, alkaryl of 7--1 1 carbon atoms, or aralkyl of 7-11 1 carbon atoms. Preferably the siloxane is present in an amount of between 312%.
The polymers of a fluorinated ester of acrylic acid used herein are water-repellant additives and are commonly referred to as fluorinated acrylate polymers (including methacrylate). Such polymers include "Zepel" fluorinated water-repellant polymers, and the like. The fluorination of the ester group is generally in the form of a perfluoroalkyl group containing from 3 to 12 carbon atoms. The polymers can be homopolymer or copolymers, including segmented copolymers, with other copolymerizable monomers, with the ester repeat unit which supplies the water repellancy to the polymer being generally represented by the formula
wherein J is H or CH3, s is an integer of 1 to 12, and Q is an organic group which contains a perfluoroalkyl group of 3 to 12 carbon atoms. Examples of monomers from which this repeat unit is dervied by polymerization (or copolymerization) are as follows:
CH2=CHCOOCH2CH2(CF2)2CF3,
CH2=CHCOOCH2CH2(CF2)4CF3,
CH2=CHCOOCH2CH2(CF2)8CF3, CH2=CHCO0(CH2)1 1(CF2)7CF3,
CH2=C(CH3)COOCH2CH2N (CH3)SO2(CF2),CF3, CH2=CHCOOCH2CH2N (CH2CH2CH3)SO2(CF2),CF3t and CH2=C(CH3)COOCH2CH2(CF2)sCF3.
These water-repellant additives are soluble in some organic solvents and are generally available as an aqueous dispersion which can conveniently be added to the PTFE aqueous dispersion to form a codispersion. Preferably the fluorinated acrylate polymer will be present in an amount of between 312%.
To prepare the coating dispersions of this invention, the silane, siloxane and fluorinated acrylate polymer are generally added to an aqueous dispersion of the tetrafluoroethylene polymer. Neither temperature nor pressure are critical during the preparation.
The glass fabric to which coating dispersions of the present invention are applied can be made of any glass such as soda-lime-silica, aluminosilicate or borosilicate, but will usually be the glass from which commercially available glass yarn is made. Typically, the glass fabric will have a sizing, such as starch, on the surface thereof. Preferably, however, the glass fabric can be cleaned of sizing such as by conventional heating procedures prior to coating, such as passing a web of glass fabric through an oven heated at about 7000C in order to burn off the sizing, or batch heating in an oven.
To coat the glass fabric, the coating dispersion is adjusted to a solids content of 530% by weight, if necessary, and the fabric is conveniently dipped into the dispersion and then excess liquid is removed by passing through rollers or blades. Alternatively the dispersion can be sprayed on one or both sides of the fabric. The coated fabric is then heated at between 100 and 3400C to cure and dry the coating. The amount of coating on the cured and dried fabric can be between 3 and 20% by total weight and preferably is between 6 and 15%.
If desired, the coated glass fabric can be topcoated with a dispersion of the water-repellant fluorinated acrylate polymer.
Examples
"PTFE dispersion" means an aqueous dispersion of polytetrafluoroethylene containing nominally 60% solids and stabilized with octaphenoxy polyethylene oxide dispersing agent having an average of 10 ethylene oxide units and neutralized with ammonium hydroxide.
"Silane" means an y-aminopropyl triethoxy-silane (H2NCH2CH2CH2Sl[OCH2CH3]3).
"Siloxane" means 35% methyl phenyl siloxane polymer emulsion.
"Water Repellant" means fluorinated acrylate copolymer dispersion.
dispersion A" means a copolymer of tetrafluoroethylene/hexafluoropropylene (89.5/1 0.5) containing 55% solids and stabilized with octaphenoxy polyethylene oxide dispersing agent having an average of 10 ethylene oxide units and neutralized with ammonium hydroxide.
dispersion B" means a copolymer of tetrafluoroethylene/perfluoro propyl vinyl ether (97/3) containing 55% solids and stabilized with octaphenoxy polyethylene oxide dispersing agent having an average of 10 ethylene oxide units and neutralized with ammonium hydroxide.
The coating dispersions were prepared by adding water to the PTFE dispersion, and then adding the other ingredients. Amounts of ingredients of the coating dispersion are listed in each Example, as are % pickup of dried coating on glass fabric.
Six inchxsix inch pieces of glass fabric were immersed in the coating dispersion and wrung partially dry through rollers. The fabric was then cured at 2500C for ten minutes, unless otherwise noted. The percent pick-up was determined by weighing the fabric after heat cleaning and again after curing and drying.
Samples were tested for flex life in the warp direction using an MIT flex tester Model 2 (Tinius
Olson Co). Strips 1/2-inch wide were used and fabric tension was supplied by a four or five pound weight. Samples were conditioned prior to testing as shown below. Five or six strips were tested at each condition listed as follows unless otherwise noted:
Condition
As made-samples were conditioned 24 hours at 720C and 50% RH for at least 24 hours prior to
testing.
Acid treated-samples were heated four hours at 4500F or 5000F in an air circulating oven
(unless they had been subjected to prior longer term heating.. The samples were then
immersed for five minutes in 1 .ON sulfuric acid maintained at 800C. The samples were
removed from the acid and dried five minutes at 4500 F. The acid immersion was repeated
for a total of 4 times. The fabric was then heated one hour at 4500F or 5000F and allowed to
remain at 720F, 50% RH prior to testing.
Example 1
Six inchxsix inch pieces of Burlington 484 fabric were heat cleaned by placing them in an air circulating oven at 3500C for 10 minutes. The samples were dipped in the coating dispersions shown below, wrung dry and cured and dried 10 minutes at 2500C. Six fabric samples were coated with each formulation. Three samples were tested as made and three after acid treatment. Six 1/2" strips were tested from each piece giving a total of 1 8 strips per comFòsition per conditioning method, using a five pound weight.
Coating Dispersion (gm) Warp Flex Life
Water Acid
Formula- PTFE Repel- %Pick- As Treated
tion Disp. H20 Silane Siloxane lant Up Made 6450 OCI 1 100 289 3.6 3.6 3.6 10.7 10,000 4616
A 100 293 3.6 3.6 - 10.5 6817 930
B 100 293 3.6 - 3.6 10.6 11,795 1678
The results of these tests were analyzed using the Student's t test to establish confidence leads on the relative ranking. The results showed that the composition containing Silane, Siloxane and Water
Repellant had significantly better warp flex life after acid treatment than the other two compositions.
The confidence level is greater than 99%.
Example 2
The same procedure and fabric of Example 1 were used. Coating composition formulations and
results are shown in the following tables.
Composition (gm)
Water ~
Formula PTFE Repel
tion Disp. H20 Silane lant Siloxane % Pick-up
A 90 210 - - - 11.0
B 90 207 3.2 - - 9.7
C 180 404 6.4 - 6.4 9.6
1 90 200 3.2 3.2 3.2 9.3
D 90 200 3.2 3.2 - 10.7
Warp Flex Life (5 pound weight)
Acid
Sample As Made Treated (450 C) A 7146 1
B 4014 534
C 2755 1801
1 3045 2405
D 4438 973
Comparison A, B, C and D did not exhibit as good flex life after acid treatmemt as Sample 1 which is a sample of this invention.
Example 3
The procedure of Example 1 was followed except that the fabric employed was Clark Schwebel
Style 6758 in which the sizing had been removed by heat cleaning. Coat composition formulations and results are shown in the following tables.
Composition (gm)
Formu- PTFE Disp. Disp. Water
lation Disp. A B H20 Silane Siloxane Repellant
1 - 60 - 135 1.8 1.8 1.8
2 40 12 12 143 1.8 1.8 1.8
3 - - 53 142 1.8 1.8 1.8
4 40 - 10.6 144 1.8 1.8 1.8
5 40 - 10.6 144 1.8 1.8 1.8
6 90.4 - - 261 3.2 3.2 3.2
Dispersions A and B are melt-processible polymers. The coated fabric was cured for 1 0 minutes at the temperatures shown below and tested for warp flex life using a four pound weight.
Warp Flex Life
Formu- Cure Acid Treated
lation Temp (0C) As Made (500 0C) 1 250 3800 3400
2 280 50000 13000
3 250 2600 2900
4 250 24000 14700
5 310 35000 15600
6 250 23000 15300
Formulations 1 and 3 were cured below the melt temperature of the polymers in Dispersions A and B and thus have low warp flex life to begin with. Formulations 1 and 3 show good acid resistance after acid treatment even though the initial values are low. Formulations 2, 4, 5 and 6 show the advantage in employing PTFE along with the melt-processible polymers, as the warp flex life as made is improved several fold.
Example 4
The procedure of Example 1 was followed except that the fabric employed was Clark Schwebel
Style 6758 in which the sizing had been removed by heat cleaning and except that after dipping the coating dispersion, wringing dry, and cure-drying 10 minutes at 2500C, the coated fabric was dipped into a second dispersion containing only water repellant and then wrung dry and cured for 10 minutes at 2500C.
Coating composition formulations and results are shown in the following tables.
1st Coating Composition (gm)
Formu- PTFE Water
lation Disp H20 Silane Siloxane Repellant
1 90.4 261 3.2 3.2 3.2
2 50 146 1.8 1.8
3 50 146 1.8 1.8
4 50 146 1.8 1.8
2nd Coating Formulation (gm)
Formu- Water % Pick-up
lation Repellant H20 1 sot 2nd 1 -None- 10
2 50 50 9.8 0.58
3 25 75 9.9 0.30
4 10 90 10.1 0.09
Warp Flex Life
As Made Acid Treated
Formulation {4 pound weight) (500 0F) 1 23000 15300
2 28000 45000
3 35000 31000
4 36000 26000
Formulation 1 did not undergo a second coating of the water-repellant and its as made warp flex life is seen to be the poorest of the four. Formulation 2 in which the second coating contained the most water-repellant of Formulations 2-4 is seen to have the best warp flex life after acid treatment.
Claims (10)
1. A coating dispersion consisting essentially of
a) water,
b) 565% by weight tetrafluoroethylene polymer, said weight based on weight of water and polymer, said polymer being of film-forming molecular weight.
c) 260% by weight of a polyhydrolyzable silane of the formula R,Si+OR)3 wherein R is lower alkyl and R, is phenyi or substituted lower alkyl in which the substituents are selected from halogen, quaternary ammonium, or-NR'R" in which R' and R" are each H, lower alkyl, lower alkoxyalkyl, amino lower alkyl, hydroxyl lower alkyl, or substituted amino lower alkyl, said weight based on weight of tetrafluoroethylene polymer,
d) 120% by weight of a hydrocarbyl siloxane, said weight based on weight of tetrafluoroethylene polymer, and
e) 120% by weight of a polymer of a fluorinated ester of an acrylic acid, said weight based on weight of tetrafluoroethylene polymer.
2. A coating dispersion according to claim 1 wherein the tetrafluoroethylene polymer is polytetrafluoroethylene.
3. A coating dispersion according to claim 1 or 2 wherein R is alkyl of 1 to 3 carbon atoms and R, is substituted alkyl of 1 to 3 carbon atoms.
4. A coating dispersion according to claim 1, 2 or 3, wherein the silane has the formula R1Si(OR)3 wherein R is -CH3 or -C2H5 and R, is substituted lower alkyl in which the substituent is in the y position and is an amino- or amino-substituted group.
5. A coating dispersion according to claim 4 wherein the silane is y-aminopropyl triethoxy silane.
6. A coating dispersion according to claim 4 wherein the silane is y-aminopropyl trimethoxy silane.
7. A coating dispersion according to any one of the preceding claims wherein the siloxane is an alkyl or alkyl/phenyl siloxane.
8. A coating dispersion according to claim 1 substantially as described with reference to
Formulation 1 of Example 1 or 2, Formulation 2, 4, 5 or 6 of Example 3 or Formulation 1 of Example 4.
9. Glass fabric coated with a dispersion as claimed in any one of claims 1 to 8.
10. A method of treating a glass fabric to improve its acid resistance, which method comprises coating the glass fabric with a dispersion containing ingredients a) to d) as defined in any one of claims 1 to 7 but not ingredient e), and then with a dispersion of ingredient e).
1 A method according to claim 10 substantially as described with reference to formulation 2, 3 or4ofExample 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/296,825 US4370376A (en) | 1980-04-18 | 1981-08-27 | Tetrafluoroethylene polymer dispersions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14168880A | 1980-04-18 | 1980-04-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2074181A true GB2074181A (en) | 1981-10-28 |
| GB2074181B GB2074181B (en) | 1983-11-16 |
Family
ID=22496771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8111396A Expired GB2074181B (en) | 1980-04-18 | 1981-04-10 | Aqueous fluoropolymer compositions |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS56166269A (en) |
| BE (1) | BE888486A (en) |
| CA (1) | CA1171572A (en) |
| DE (1) | DE3115542A1 (en) |
| FR (1) | FR2480772A1 (en) |
| GB (1) | GB2074181B (en) |
| IT (1) | IT1211025B (en) |
| NL (1) | NL8101917A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0152282A2 (en) * | 1984-02-09 | 1985-08-21 | E.I. Du Pont De Nemours And Company | Tetrafluoroethylene polymer dispersions |
| EP0320257A2 (en) * | 1987-12-09 | 1989-06-14 | Pall Corporation | Compositions for use with fabrics |
| US5348769A (en) * | 1993-03-31 | 1994-09-20 | Osi Specialties, Inc. | Fluorosilicone compositions as wash durable soil and stain repellent finishes |
| US6288160B1 (en) * | 1996-11-28 | 2001-09-11 | Daikin Industries, Ltd. | Aqueous dispersion and waterproofing material |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2537985A1 (en) * | 1982-12-17 | 1984-06-22 | Bourit Claude | ANTI-ADHESIVE COATING COMPOSITION AND PROCESS FOR PREPARING THE SAME |
| DE29701878U1 (en) * | 1997-02-04 | 1997-07-10 | Hartmuth, Werner, 66955 Pirmasens | Polytetrafluoroethylene (PTFE) glass fabric film |
| US6410626B1 (en) * | 1997-04-30 | 2002-06-25 | Daikin Industries, Ltd. | Aqueous dispersion composition and coated articles |
| CN102031693B (en) * | 2010-11-15 | 2012-07-25 | 山东新力环保材料有限公司 | Film forming agent used for after finishing of medium low temperature composite needled filter felt and preparation method thereof |
| CN117136261A (en) * | 2021-04-09 | 2023-11-28 | 旭化成株式会社 | Glass cloth, prepreg and printed wiring board |
| WO2022215287A1 (en) * | 2021-04-09 | 2022-10-13 | 旭化成株式会社 | Glass cloth, prepreg, and printed wiring board |
| JP7183344B1 (en) * | 2021-06-30 | 2022-12-05 | 旭化成株式会社 | Glass cloth, prepreg, and printed wiring board |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3838082A (en) * | 1971-05-25 | 1974-09-24 | Du Pont | Polytetrafluoromethylene coatings containing water soluble polyhydrolyzable compound for glass fabrics |
| US3915916A (en) * | 1974-05-24 | 1975-10-28 | Du Pont | Process for reducing filler loss |
-
1981
- 1981-04-10 GB GB8111396A patent/GB2074181B/en not_active Expired
- 1981-04-16 CA CA000375645A patent/CA1171572A/en not_active Expired
- 1981-04-16 DE DE19813115542 patent/DE3115542A1/en active Granted
- 1981-04-16 JP JP5640181A patent/JPS56166269A/en active Granted
- 1981-04-16 NL NL8101917A patent/NL8101917A/en not_active Application Discontinuation
- 1981-04-16 FR FR8107690A patent/FR2480772A1/en active Granted
- 1981-04-17 BE BE0/204543A patent/BE888486A/en not_active IP Right Cessation
- 1981-04-17 IT IT8121284A patent/IT1211025B/en active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0152282A2 (en) * | 1984-02-09 | 1985-08-21 | E.I. Du Pont De Nemours And Company | Tetrafluoroethylene polymer dispersions |
| EP0152282A3 (en) * | 1984-02-09 | 1986-02-12 | E.I. Du Pont De Nemours And Company | Tetrafluoroethylene polymer dispersions |
| EP0320257A2 (en) * | 1987-12-09 | 1989-06-14 | Pall Corporation | Compositions for use with fabrics |
| EP0320257A3 (en) * | 1987-12-09 | 1990-03-07 | Pall Corporation | Compositions for use with fabrics |
| US5348769A (en) * | 1993-03-31 | 1994-09-20 | Osi Specialties, Inc. | Fluorosilicone compositions as wash durable soil and stain repellent finishes |
| WO1994022595A1 (en) * | 1993-03-31 | 1994-10-13 | Osi Specialties, Inc. | Fluorosilicone compositions as wash durable soil and stain repellent finishes |
| US6288160B1 (en) * | 1996-11-28 | 2001-09-11 | Daikin Industries, Ltd. | Aqueous dispersion and waterproofing material |
Also Published As
| Publication number | Publication date |
|---|---|
| NL8101917A (en) | 1981-11-16 |
| FR2480772B1 (en) | 1984-04-06 |
| BE888486A (en) | 1981-10-19 |
| DE3115542A1 (en) | 1982-02-18 |
| JPS6142946B2 (en) | 1986-09-25 |
| IT8121284A0 (en) | 1981-04-17 |
| IT1211025B (en) | 1989-09-29 |
| DE3115542C2 (en) | 1992-02-27 |
| CA1171572A (en) | 1984-07-24 |
| JPS56166269A (en) | 1981-12-21 |
| FR2480772A1 (en) | 1981-10-23 |
| GB2074181B (en) | 1983-11-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19990410 |