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
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
  • C09D123/28—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
  • C09D123/286—Chlorinated polyethylene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/18—Introducing halogen atoms or halogen-containing groups
  • C08F8/20—Halogenation
  • C08F8/22—Halogenation by reaction with free halogens
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
  • Y10T428/2495—Thickness [relative or absolute]
  • Y10T428/24967—Absolute thicknesses specified
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31909—Next to second addition polymer from unsaturated monomers
  • Y10T428/31913—Monoolefin polymer
  • Y10T428/3192—Next to vinyl or vinylidene chloride polymer

Definitions

• Flashings made of roofing paper are weak. As they age, they tend to develop leaks around nail holes. They also, particularly on aging, become brittle. They are, in addition, combustible.
• Another object is to provide such a flashing or membrane material which does not require the addition or presence of elasticizing ingredients and which retains substantially its original flexibility under a wide variation of climatic and environmental conditions over extended periods of time.
• a related object is the provision of improved composite structures comprising the new flashing and membrane material.
• the flashing or membrane comprising the present invention is a structure formed from an inherently resilient thermoplastic sheet of solid chlorinated olefin polymer, which polymer is prepared by the chlorination, in suspension in an inert diluent, of polyethylene or interpolymers containing at least about mole percent of ethylene in the polymer molecule with any remainder being one or more ethylenically unsaturated comonomers, wherein such polymers are preferably of an essentially linear structure and have a molecular weight less than about 1,000,000, and preferably a molecular weight of from about 20,000 to 300,000.
• Such chlorinated olefin polymers may contain from about 25 to 50, and preferably between about 35 and 45, Weight percent of chemically combined chlorine and are further characterized by having a relative crystallinity of between about 15 and 28 percent when containing about 25 weight percent chlorine and a relative crystallinity of less than about 10 percent when containing about 34 or more weight percent of chlorine, wherein said relative crystallinity is a measure of the ratio of the crystalline peak areas to the sum of the amorphous plus crystalline peak area as determined by conventional X-ray ditlraction techniques; said sheet having a thickness of from about 0.005 to 0.25 of an inch, a tensile strength of at least about 1100 pounds per square inch, an elongation of between about 350 and 900 percent and a 100 percent modulus of between about 150 and 1500 pounds per square inch.
• the chlorinated polyolefins employed in the flashing and membrane compositions of the present invention can be readily obtained by practice of a chlorination procedure which comprehends the suspension chlorination in an inert medium of polymers and interpolymers of ethylene, as hereinafter more fully defined, to a desired total of combined chlorine, wherein such polyolefin is first chlorinated at a temperature of up to about 95 C., and preferably between about 65 C. and 90 C.
• Exemplary of preferred polyolefinic materials to be chlorinated are those distince species and varieties of essentially linear and unbranched highly porous, finely divided polymers containing at least about 90 mole percent ethylene in the polymer molecule with the remainder being one or more ethylenically unsaturated comonomers such as the non-aromatic hydrocarbon olefins having 3 or more carbon atoms, including propylene, butene-l and butene-2, and 1,7-octadiene and the like; cycloaliphatic olefius such as 1,5-cyclopentene and cyclooctadiene and the like; substituted olefins such as acrylic acid and its esters; conjugated diolefins such as butadiene and the like; and the alkenyl aromatic compounds such as styrene and its derivatives, among many other polymerizable materials known to the art.
• ethylenically unsaturated comonomers
• the polymers and interpolymers, described herein are prepared under the influence of catalyst systems comprising admixtures of strong reducing agents such as triethyl aluminum and compounds of groups IV-B, V-B and VI-B metals of the Periodic System, such as titanium tetrachloride, and the like, and are characterized by having molecular weights ranging generally less than about 1,000,000 and preferably between about 20,000 and 300,000.
• catalyst systems comprising admixtures of strong reducing agents such as triethyl aluminum and compounds of groups IV-B, V-B and VI-B metals of the Periodic System, such as titanium tetrachloride, and the like, and are characterized by having molecular weights ranging generally less than about 1,000,000 and preferably between about 20,000 and 300,000.
• the liquid which is employed to suspend the finely divided polymer may be any liquid which is inert to the polymer and is not affected to an appreciable extent by chlorine, or which, while wetting the polymer will not have an appreciable solvent effect on it. While water may be employed with especial advantage as a suspending liquid for the polyolefins to be chlorinated, the polymers may also be suspended in other inert liquids.
• wetting agents including organic sulfonates, sulfates, polyphosphates and other types of ionic and anionic sulfactant materials may be suitably employed, if desired, to assist the inert suspending liquid (particularly when such liquid is water) to wet the polymer.
• Such materials as sodium lauryl sulfate, alkyl aryl polyether alcohols and pentasodium pentacapryl pyrophosphate are illustrative of specific Wetting agents that may be utilized.
• the employment of a wetting agent facilitates the mechanical handling of the suspended polymer during the suspension chlorination. In some cases, however, it may not be necessary to employ wetting agents, especially when a freshly prepared polymer is employed that is undried after its preparation or when eflicient agitation is available for producing and maintaining the polymer slurry.
• the reaction may be assisted by the employment of small quantities of catalysts, such as the free-radical types and/or ultra-violet light.
• catalysts such as the free-radical types and/or ultra-violet light.
• the rate of reaction which is accomplished through the assistance of the catalyst will depend on such factors as the catalyst concentration, the temperature of the suspending medium in which the catalyst is dissolved,
• azo type compounds and peroxides selected from the group of free-radical catalysts consisting of diacetyl peroxide; peracetic acid; hydrogen peroxide; tertiaryl butyl peroxide; tertiary butyl hydroperoxide; potassium persulfate; diazodiisobutyro-nitrile; methylethyl ketone peroxide and the like, may advantageously be employed.
• catalysts when catalysts are employed, such catalyst should be one which has an efiicient rate of decomposition in the suspending medium in which it is dissolved, in the required temperature range.
• the suspension chlorination procedure described herein as a preferred chlorination technique may be carried out at atmospheric pressure, however, best results are generally obtained wherein superatmospheric pressures are employed. Such chlorination pressure is not critical except as necessary to obtain an eflicient rate of reaction. In this regard, it is pointed out that for a given catalyst or admixture thereof, at a given concentration in the suspending medium, the reaction rate is conveniently controlled by the rate of feed of chlorine and/or its partial pressure in the reaction vessel.
• the polyolefinic material After the polyolefinic material has been suspension chlorinated to a desired degree, it may be easily separated from the inert suspending liquid by conventional means and washed and dried to prepare it for subsequent use.
• the entire chlorination procedure or any desired part of it may be carried out batchwise or by continuous processing arrangements.
• batch operations it is ordinarily suitable to employ conventional autoclaves and kettles or the like for conducting the reaction.
• it may also be conveniently conducted in a continuous process by any one of several suitable techniques. For example, it may be conducted by counter-current movement of the reactants through either horizontally or vertically disposed reactors which may be in the form of tubes and towers, or by using a cascading principle with a series of interconnected reaction chambers.
• Substantially quantitative yields may be frequently obtained by the chlorinating technique described herein.
• the attainment of such yields may often be facilitated by the practice of recycling techniques for unreacted portions of the chlorine and by conducting the involved reactions at more moderate rates.
• pigment fillers examples include the clays, calcium sulfate, and mica, among others including coarse fillers such as pulverized marble or limestone, if desired.
• Suitable fibrous fillers include asbestos, cork, wood, flour, etc.
• Stabilizers are included in the compositions to protect the chlorinated olefin polymer against decomposition by the heat of processing or by subsequent exposure of the fabricated sheet material to climatic and environmental conditions.
• Suitable stabilizers include those materials conventionally employed in the preparation of vinyl polymer and copolymer sheet compositions, e.g., organic complexes and/or salts of lead, tin, barium, cadmium, zinc, sodium, etc., and particularly the barium-cadmium soaps as well as dibutyl tin laurate and dibutyl tin maleate, among others.
• Stabilizers are preferably used in amounts between about 1 and 5 parts by weight per 100 parts of the chlorinated olefin polymer constituent.
• epoxidized and non-epoxidized oils may be used.
• Low molecular Weight polymers and waxes may also be employed, if desired, in amounts of up to about parts per 100 parts of chlorinated olefin polymer.
• chlorinated olefin polymers employed for the purposes of the present invention are inherently resistant to burning, it may in some instances be advantageous to incorporate minor amounts, i.e., from between about 1 to 10 parts per hundred parts of chlorinated olefin polymer, of one or more flame-retarding agents, e.g., oxides of antimony and/or various halogenated materials such as tetrabromophthalic anhydride, perchloropentacyclodecane, tris (2,3-dibromopropyl) phosphate, tetrabromobisphenol-A, among many others.
• one or more flame-retarding agents e.g., oxides of antimony and/or various halogenated materials such as tetrabromophthalic anhydride, perchloropentacyclodecane, tris (2,3-dibromopropyl) phosphate, tetrabromobisphenol-A, among many others.
• the flashing and membrane materials of the present invention may be prepared by conventional techniques wherein the chlorinated olefin polymer is prepared as described herein and blended with the desired fillers and stabiizers, etc., substantially in the manner conventionally employed in preparing vinyl chloride polymer and copolymer sheeting compositions.
• the necessary ingredients may be initially dry blended in a mixer such as a ribbon blender and subsequently milled as on a two-roll compounding mill at roll temperatures between about 240 F. and 400 F. until the mixture becomes homogeneous.
• the blend may then be extruded into sheet form or calendered to give the desired sheet thickness.
• sheet-like structures having a thickness of between about 0.005 and 0.25 of an inch and preferably between about 0.020 and 0.1 of an inch are utilized as flashings and/or membranes in construction assemblies.
• the present invention contemplates utilization of such sheet-like structures in both a substantially unvulcanized or vulcanized form.
• the present invention contemplates utilization of the sheet-like structure as defined herein, in lamination with one or more self-supporting reinforcing materials such as woven or non-woven fabrics prepared from naturally occurring materials including glass fibers, wool, cotton, hemp, jute, and the like, and synthetic materials such as polyamide, polyesters, and acrylics among other materials.
• one or more self-supporting reinforcing materials such as woven or non-woven fabrics prepared from naturally occurring materials including glass fibers, wool, cotton, hemp, jute, and the like, and synthetic materials such as polyamide, polyesters, and acrylics among other materials.
• the present invention contemplates utilization of the sheet-like structures of this invention as fiashings and as roof membranes in any manner peculiar to the industry and includes the coating or other contacting of such materials with various adhesives and paints which include natural and synthetic polymer solutions, including solutions of the chlorinated olefin polymers as defined herein.
• Example 1 To 4000 grams of deionized water was added, with stirring, 200 grams of a polyethylene having an essentially linear and unbranched structure (containing less than about 1 methyl group per 100 methylene units), and having a melt index of about 1 and a molecular weight of about 67,000. Such polyethylene had been previously prepared by a process using a catalyst composed of triisobutyl aluminum and titanium tetrachloride. The resulting admixture was then charged to a 1 /2 gallon autoclave with 8 grams of calcium chloride; about 0.5 cc. of a 70 percent solution of ditertiary butyl peroxide in butanol; and about 10 drops of a commercially available wetting agent.
• a polyethylene having an essentially linear and unbranched structure (containing less than about 1 methyl group per 100 methylene units), and having a melt index of about 1 and a molecular weight of about 67,000.
• Such polyethylene had been previously prepared by a process using a catalyst composed of triis
• the charge was then chlorinated, in a first chlorination step, under about 30 p.s.i. (gauge) of chlorine pressure at a temperature of about C. until a chlorine content of about 20 percent was obtained.
• the charge was then chlorinated in a second suspension chlorination step, at a temperature of about 126 C. until a total chlorine content of about 42 percent was obtained.
• the chlorination product was then isolated from the dispersion by filtration, washed free of residual hydrochloric acid and dried.
• the above dry blend was then conveyed into the feed hopper of a two-stage vacuum vented single screw extruder.
• the first stage was operated at about 375400 F. and the second stage at 325400 F.
• the vacuum was about 26 inches of mercury.
• the melt was then extruded through a sheet die to form a sheet having a thickness of about 0.06 of an inch.
• This material is hereinafter identified as Sample Number 1.
• flashing material of the present invention has greatly ena hybrid since it possesses the desirable qualities of hanced low temperature flexibility and significantly im- 20 products prepared in ordinary suspension and ordinary proved modulus and elongation as compared to the consolution chlorination methods, while eliminating some of ventionally employed materials based on plasticized vinylthe undesirable characteristics inherent in both such prior idene chloride polymer and polyvinyl chloride respectively. known procedures and products.
• the composite materials of the present invention are 95 What is claimed is: further characterized by being inherently flexible under 1.
• the improvement which consists in applying a are resistant to burning are capable of being easily welded protective covering of an inherently resilient thermoplastic to each other by application of conventional solvents such sheet comprising a chlorinated olefin polymer prepared as methylethyl ketone, toluene, xylene and the like, and by the suspension chlorination of an olefin polymer having are susceptible to adhesion with conventionally employed an essentially linear structure, said olefin polymer being adhesives.
• interpolymers composed of at least about 90 mole percent utilization of chlorinated olefin polymers having molecular ethylene with the remainder being at least one ethyleniweights exceeding 1 million are generally incapable of cally unsaturated comonomer; said chlorinated olefin polybeing fabricated into sheet-like structures without the addimer containing from about 25 to 50 Weight percent of tion of significant amounts of plasticizers or other processchemically combined chlorine and having a relative crysing aids.
• tallinity of between about 15 and 28 percent when conthe non-plasticized chlorinated polyolefins as described in taining about 25 weight percent chlorine and a relative Example 1 above can be extruded through a standard crystallinity of less than about 10 percent when containing Instron rheometer orifice, using a 190 C. barrel temperabout 34 or more weight percent chlorine; said sheet ature, at a 150- sec.
• shear rate with a resultant shear having a thickness of from about 0.005 to 0.25 of an inch, stress of from 25-35 p.s.i., whereas, under the same cona tensile strength of at least about 1100 pounds per square ditiOIlS Chlorinated Polyethylenes having a molecular inch, an elongation of between about 350 and 900 percent weight of from 1 million to 5 million are characterized d 100 Percent odulus of between about 150 and 1500 by a shear stress of greater than about 85 p.s.i. and often pounds e square in h.
• references Cited so,c ormate p0 yoe ns, as erein escri e u aving a chlorine content of less than about 25 weight per- UNITED STATES PATENTS cent are characterized by reduced solvent weldability prop- 1,813 039 7/ 1931 Shakespeare 161--165 X erties and are less resistant to burning.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Laminated Bodies (AREA)
• Building Environments (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

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Cited By (10)

Citations (7)

• 1965
  • 1965-08-02 US US47666765 patent/US3399091A/en not_active Expired - Lifetime
• 1966
  • 1966-07-29 GB GB3425066A patent/GB1133635A/en not_active Expired
  • 1966-08-01 NL NL6610796A patent/NL6610796A/xx unknown
  • 1966-08-02 BE BE684962D patent/BE684962A/xx unknown
  • 1966-08-02 DE DE19661669915 patent/DE1669915A1/de active Pending

Patent Citations (7)

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