GB951549A - Improvements in or relating to vapourpermeable films and coatings - Google Patents

Improvements in or relating to vapourpermeable films and coatings

Info

Publication number
GB951549A
GB951549A GB1768161A GB1768161A GB951549A GB 951549 A GB951549 A GB 951549A GB 1768161 A GB1768161 A GB 1768161A GB 1768161 A GB1768161 A GB 1768161A GB 951549 A GB951549 A GB 951549A
Authority
GB
United Kingdom
Prior art keywords
diisocyanate
copolymer
solution
water
glycol
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.)
Expired
Application number
GB1768161A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of GB951549A publication Critical patent/GB951549A/en
Expired legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, 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
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04Artificial 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
    • D06N3/10Artificial 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 styrene-butadiene copolymerisation products or other synthetic rubbers or elastomers except polyurethanes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Vapour-permeable microporous films and coatings are produced by forming a film or coating of a water-insoluble copolymer containing carboxyl groups on the polymer chain, with or without a proportion of a vinyl chloride polymer or a polyurethane elastomer which may exceed the proportion of the co-polymer, from a solution of the copolymer (and other polymer if employed) in a water-miscible solvent therefor, the solution containing also an oxide of a polyvalent metal, bathing the film or coating with water or an equivalent inert liquid to coagulate the copolymer and remove the solvent, and curing and drying the film or coating produced. The solution of the copolymer may also contain sulphur. The copolymer may be derived from two or more monomers, at least one of which is a conjugated diene having 4-9 carbon atoms in the molecule, and at least one of which is a carboxylic acid containing ethylenic unsaturation at which polymerization can take place. The copolymer may be a rubber ter-polymer of a butadiene-1,2-hydrocarbon, acrylonitrile or a substituted acrylic nitrile, or acrylic acid or a homologue or a -substitution product thereof. The solution may contain a vinyl chloride polymer in a weight ratio to the copolymer of up to 50:50. The solution may be brought to the verge of gelling before mixing it with water or an equivalent inert liquid. The solution may be applied as a coating to a substrate of a flexible porous fibrous material or of a smooth surfaced impervious material. In the latter case to form a film which is subsequently stripped from the film support. The copolymer in the film or layer may be partially cured by heating with water or an equivalent inert liquid to a temperature above normal room temperature. The copolymer may contain residual unsaturation and the solution may contain sulphur and after partial curing the film or coating may be heated until the copolymer is fully cured. An "equivalent" inert liquid is defined as one which is (a) a non-solvent for the copolymer and any other polymer which may be present in the solution; (b) miscible with water and the organic solvent in which the copolymer is dissolved; (c) chemically inert to all the constituents of the film-forming solution at the bathing temperature. Examples of suitable liquids are ethylene glycol, glycerol, glycol monoethyl ether, hydroxyethyl acetate, and water-miscible alcohols such as t-butyl alcohol. The preferred polyvalent metal oxide is zinc oxide, but oxides of calcium, magnesium, tin, dibutyl tin, lead, barium, cobalt or strontium known to be suitable for cross-linking polymers having carboxyl groups can also be used. The preferred solvent is N,N-dimethylformamide. Others which may be used include dimethyl sulphoxide, tetrahydrofuran, tetramethyl urea, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and g -butyrolacetone. These solvents may be blended with water-miscible organic liquids such as ketones, e.g. methyl ethyl ketone. Polyurethane elastomers which may be used as components of the copolymer solution are prepared by chain-extending the reaction product of a polyalkylene-ether glycol and an organic diisocyanate with a compound having two active hydrogen atoms attached to amino nitrogen atoms. These elastomers can be made from a prepolymer (or "capped dimer") obtained by heating the glycol mixed with the diisocyanate until a prepolymer is formed having terminal -NCO group, or by reacting the diisocyanate with a molar excess of the glycol, and capping the product by reacting it with more diisocyanate. Polyalkyleneether glycols which may be used in making the prepolymers include polyethyleneether glycol to polydecamethyleneether glycol. Diisocyanates which may be used in forming the prepolymers include tolylene-2, 4-diisocyanate, tolylene-2, 6-diisocyanate, m-phenylene diisocyanate, bisphenylene-4, 41-diisocyanate, naphthalene-1, 5-diisocyanate, tetramethylene-1, 4-diisocyanate, hexamethylene-1, 6-diisocyanate, decamethylene-1, 10-diisocyanate, cyclohexylene-1, 4-diisocyanate, methylene bis(4-cyclohexylene) isocyanate and tetrahydronaphthalene diisocyanate. The chain extending compound may be hydrazine (which is preferred), a substituted hydrazine or a primary or secondary diamine. Examples are dimethyl piperazine, 4-methyl-m-phenylene diamine, m-phenylene diamine, and 4,41-diaminodiphenyl-methane. Specification 849,155, U.S.A. Specifications 2,395,017, 2,724,707, and 3,067,483 are referred to.ALSO:Vapour-permeable microporous coatings are produced by forming a coating of a water-insoluble copolymer containing carboxyl groups on the polymer chain, with or without a proportion of a vinyl chloride polymer or a polyurethane elastomer which may exceed the proportion of the copolymer, from a solution of the copolymer (and other polymer if employed) in a water-miscible solvent therefor, the solution containing also an oxide of a polyvalent metal, bathing the coating with water or an equivalent inert liquid to coagulate the copolymer and remove the solvent, and curing and drying the coating produced. The solution of the copolymer may also contain sulphur. The copolymer may be derived from two or more monomers, at least one of which is a conjugated diene having 4-9 carbon atoms in the molecule, and at least one of which is a carboxylic acid containing ethylenic unsaturation at which polymerization can take place. The copolymer may be a rubber ter-polymer of a butadiene-1,2 hydrocarbon, acrylonitrile or a substituted acrylic nitrile, or acrylic acid or a homologue or a -substitution product thereof. The solution may contain a vinyl chloride polymer in a weight ratio to the copolymer of up to 50 : 50. The solution may be brought to the verge of gelling before mixing it with water or an equivalent inert liquid. The solution may be applied as a coating to a substrate of a flexible porous fibrous material or of a smooth surfaced impervious material from which it may be subsequently stripped. The copolymer may be partially cured by heating with water or an equivalent inert liquid to a temperature above normal room temperature. The copolymer may contain residual unsaturation and the solution may contain sulphur and after partial curing the coating may be heated until the copolymer is fully cured. An "equivalent" inert liquid is defined as one which is (a) a non-solvent for the copolymer and any other polymer which may be present in the solution; (b) miscible with water and the organic solvent in which the copolymer is dissolved; (c) chemically inert to all the constituents of the film-forming solution at the bathing temperature. Examples of suitable liquids are ethylene glycol, glycerol, glycol monoethyl ether, hydroxyethyl acetate, and water-miscible alcohols such as t-butyl alcohol. The preferred polyvalent metal oxide is zinc oxide, but oxides of calcium, magnesium, tin, dibutyl tin, lead, barium, cobalt or strontium known to be suitable for cross-linking polymers having carboxyl groups can also be used. The preferred solvent is N,N-dimethylformamide. Others which may be used include dimethyl sulphoxide, tetrahydrofuran, tetramethyl urea, N,N-dimethylacetamide, N-methyl - 2 - pyrrolidone and g - butyrolacetone. These solvents may be blended with water-miscible organic liquids such as ketones, e.g. methyl ethyl ketone. Polyurethane elastomers which may be used as components of the copolymer solution are prepared by chain-extending the reaction product of a polyalkyleneether glycol and an organic diisocyanate with a compound having two active hydrogen atoms attached to amino nitrogen atoms. These elastomers can be made from a prepolymer (or "capped dimer") obtained by heating the glycol mixed with the diisocyanate until a prepolymer is formed having terminal -NCO group, or by reacting the diisocyanate with a molar excess of the glycol, and capping the product by reacting it with more diisocyanate. Polyalkyleneether glycols which may be used in making the prepolymers include polyethyleneether glycol to polydecamethyleneether glycol. Diisocyanates which may be used in forming the prepolymers include tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, m-phenylene diisocyanate, bisphenylene - 4,41 - diisocyanate, naphthalene-1,5-diisocyanate, tetramethylene-1, 4-diisocyanate, hexamethylene-1,6-diisocyanate, decamethylene-1,10-diisocyanate, cyclohexylene-1,4-diisocyanate, methylene bis(4-cyclohexylene isocyanate and tetrahydronaphthalene diisocyanate. The chain extending compound may be hydrazine (which is preferred), a substituted hydrazine or a primary or secondary diamine. Examples are dimethyl piperazine, 4-methyl-m-phenylene diamine, m-phenylene diamine, and 4,41-diamino-diphenyl-methane. Specification 849,155 and U.S.A. Specifications 2,395,017, 2,724,707 and 3,067,483 are referred to.
GB1768161A 1960-05-16 1961-05-15 Improvements in or relating to vapourpermeable films and coatings Expired GB951549A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US2912560A 1960-05-16 1960-05-16

Publications (1)

Publication Number Publication Date
GB951549A true GB951549A (en) 1964-03-04

Family

ID=21847369

Family Applications (1)

Application Number Title Priority Date Filing Date
GB1768161A Expired GB951549A (en) 1960-05-16 1961-05-15 Improvements in or relating to vapourpermeable films and coatings

Country Status (3)

Country Link
BE (1) BE603821A (en)
DE (1) DE1470918A1 (en)
GB (1) GB951549A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2174641A (en) * 1985-04-29 1986-11-12 Grace W R & Co Non-adsorptive, semipermeable filtration membrane
WO2003095419A1 (en) * 2002-05-09 2003-11-20 Bayer Materialscience Llc Tetralin isocyanates
US9701824B2 (en) 2014-12-23 2017-07-11 Dow Global Technologies Llc Polyolefin dispersion compositions for making high vapor transport hydrophobic coatings

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2174641A (en) * 1985-04-29 1986-11-12 Grace W R & Co Non-adsorptive, semipermeable filtration membrane
US4787976A (en) * 1985-04-29 1988-11-29 W. R. Grace & Co. Non-adsorptive, semipermeable filtration membrane
GB2174641B (en) * 1985-04-29 1989-07-12 Grace W R & Co Non-adsorptive, semipermeable filtration membrane
WO2003095419A1 (en) * 2002-05-09 2003-11-20 Bayer Materialscience Llc Tetralin isocyanates
US6750367B2 (en) 2002-05-09 2004-06-15 Bayer Polymers Llc Tetralin isocyanates
US6841585B2 (en) 2002-05-09 2005-01-11 Bayer Materialscience Llc Tetralin isocyanates
JP2005524716A (en) * 2002-05-09 2005-08-18 バイエル マテリアルサイエンス エルエルシー Tetralin isocyanate
US9701824B2 (en) 2014-12-23 2017-07-11 Dow Global Technologies Llc Polyolefin dispersion compositions for making high vapor transport hydrophobic coatings

Also Published As

Publication number Publication date
DE1470918A1 (en) 1969-08-07
BE603821A (en) 1961-11-16

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