US3641216A - Thermoplastic compositions for the preparation of inherently flexible dimensionally-stabl esolvent-weldable sheet materials - Google Patents

Thermoplastic compositions for the preparation of inherently flexible dimensionally-stabl esolvent-weldable sheet materials Download PDF

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Publication number
US3641216A
US3641216A US818810A US3641216DA US3641216A US 3641216 A US3641216 A US 3641216A US 818810 A US818810 A US 818810A US 3641216D A US3641216D A US 3641216DA US 3641216 A US3641216 A US 3641216A
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percent
chlorinated
preparation
flashing
materials
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US818810A
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David F Schnebelen
Robert B Cramer
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Dow Chemical Co
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Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • 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

Definitions

  • thermoplastic compositions based on intimate fusion blends of certain chlorinated olefin polymers with minor amounts of essentially linear, non-chlorinated olefin polymers. These compositions are particularly useful for the preparation of sheet material for use as flashing or membrane in various construction assemblies such material having unexpectedly enhanced dimensional stability while retaining a necessary level of inherent flexibility and the ability to be easily solvent welded into unitary structures.
  • 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.
  • thermoplastic sheeting suffers from a lack of dimensional stability resulting in excessive shrinkage when exposed to elevated temperatures, as encountered during exposure to the sun, for extended periods of time, as well as a loss in tensile properties when exposed to conditions of fabrication and/or use.
  • a related object is the provision of improved structures comprising the new flashing and membrane material.
  • compositions comprising essentially an intimate fusion blend of:
  • compositions From 2 to 15 percent by weight of an essentially linear polymer of ethylene, containing at least about 90 mole percent of ethylene in the polymer molecule; wherein said compositions have a 100 percent modulus of less than 500 p.s.i.
  • the chlorinated polyolefins used in the present invention are obtained by practice of a chlorination procedure which comprehends the suspension chlorination in an inert medium of finely divided essentially linear polyethylene and interpolymers containing at least about 90 mole percent ethylene with the remainder being one or more ethylenically unsaturated comonomers, to a desired total of combined chlorine content, wherein such polymer is first chlorinated at a temperature below its agglomeration temperature for a period suflicient to provide a chlorine content of from about 2 to 23 percent chlorine, based on the total weight of the polymer; followed by the sequential suspension chlorination of such polymer, in a particulate form, at a temperature above its agglomeration temperature but at least about 2 C. below its crystalline melting point for a period suflicient to provide a combined chlorine content of up to about 50 weight percent based on the total weight of the polymer and wherein at least about 2 percent chlorine is added during the sequential chlorination step.
  • the polyolefinic materials to be chlorinated are those distinct species and varieties of essentially linear and unbranched highly porous polymers containing at least about 90 mole percent ethylene in the polymer molecule with a remainder being one or more ethylenically unsaturated comonomers, such polymers being 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 having a molecular weight 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 having a molecular weight less than about 1,000,000 and preferably between about 20,000 and 300,000.
  • Exemplary of useful ethylenically unsaturated comonomers are the non-aromatic hydrocarbon olefins having 3 or more carbon atoms such as propylene, butene-l and 1,7-octadiene and the like; cycloaliphatic olefins such as cyclopentene and 1,5-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.
  • inert substances of inorganic or organic chemical nature which are such that they have an affinity for adsorption onto the surfaces of the polyolefin during chlorination so that they may function as barriers to inhibit particle agglomeration.
  • inert materials are: carbon black and titanium dioxide and the like. Such materials may be employed for the desired purpose without significantly detracting from the highly desirable elastomeric properties of the polymer.
  • Stabilizers may also be included in the compositions to protect the chlorinated olefin polymer against possible decomposition by the heat of processing or by subsequent exposure of fabricated sheet material to climatic and environmental conditions of use.
  • 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, cadium, zinc, sodium, etc., and particularly the sulfur containing organo tin compounds including the alkyl tin mercaptides as well as dibutyl tin laurate and dibutyl tin maleate and various epoxide compounds such as the epoxidized fatty acids and oils, among others.
  • Stabilizers are preferably used in amounts sufficient to provide between about 1 and parts by weight per 100 parts of the chlorinated olefin polymer constituent.
  • Other conventional additives such as non-epoxidized fatty acids and oils, and low molecular weight polymers and waxes may also be employed, if desired.
  • 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 and 10 parts per 100 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, tetrabromo bisphenol-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, tetrabromo bisphenol-A, among many others.
  • the polymers of vinyl chloride which may optionally be used in the designated amounts include homopolymers of vinyl chloride and interpolymers of vinyl chloride wherin there is present at least about 95 mole percent of vinyl chloride in the polymer molecule.
  • copolymerization components there can be used vinyl esters such as vinyl acetate, vinyl propionate or vinyl butyrate, vinyl stearate, vinylidene chloride, esters of aliphatic, unsaturated alcohols containing from about 1 to 10 carbon atoms with acrylic acid, methacrylic acid, maleic acid or fu-maric acid.
  • Such polymers may be used as a filler if desired, without adversely affecting the inherent flexibility, dimensional stability and solvent-weldability of the described com positions and articles formed therefrom.
  • the essentially linear polymers of ethylene which are utilized for the purpose of the present invention are those polymers containing at least about 90 mole percent of ethylene in the polymer molecule. Distinct species and varieties of polyethylene and its interpolymers with one or more ethylenically unsautrated comonomers such as propylene, butene-l and the like are known which have essentially linear and unbranched molecular structures that are relatively free from extensive side-chain .networks and which have molecular weights in excess of 5,000 and, more advantageously,.from at least 20,000 to as much as 5,000,000 and greater.
  • Sheet materials may be prepared from the intimate fusion blend of the present invention by conventional techniques such as by extrusion through a single sheet die to form a sheet of desired thickness.
  • 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 dried material was then used to prepare the following formulations by dry-blending of the designated mate rials in a ribbon blender.
  • Table II summarizes the physical properties of each of the described sheet materials.
  • the column headings of Table II have the following meanings:
  • compositions as essentially described in Run No. l but having linear polyethylene present in amounts exceeding 15 percent by weight, are characterized by a 100 percent modulus of greater than 500 p.s.i. and form individual sheets which are incapable of being easily solvent weldable as required for use as flashing materials.
  • individual sheets prepared from any composition as essentially contemplated by the present invention but having a 100 percent modulus of 500 p.s.i. and above are insufficiently solvent-weldable for industrial use as flashing material.
  • chlorinated polyethylene having a molecular weight of from 1 million to 5 million are characterized by a shear stress of greater than about p.s.i. and often cannot be made to pass through the orifice of the rheometer.
  • chlorinated polyolefins as herein described, but having a chlorine content of greater than about 50 weight percent provides sheet material having reduced resistance to heat. Also, chlorinated polyolefins, as herein described, but having a chlorine content of less than about 25 weight percent are less resistant to burning, and utilization of chlorinated olefin polymers having in excess of about 10 percent relative crystallinity, results in sheet materials characterized by reduced ability to be solvent welded.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
US818810A 1967-07-24 1969-04-23 Thermoplastic compositions for the preparation of inherently flexible dimensionally-stabl esolvent-weldable sheet materials Expired - Lifetime US3641216A (en)

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US65955567A 1967-07-24 1967-07-24

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US3641216A true US3641216A (en) 1972-02-08

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US (1) US3641216A (pm)
BE (1) BE718448A (pm)
BR (1) BR6800553D0 (pm)
DE (1) DE1769826B2 (pm)
FR (1) FR1571136A (pm)
GB (1) GB1194494A (pm)
NL (1) NL6810382A (pm)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3891725A (en) * 1974-10-04 1975-06-24 Du Pont Vulcanizable chlorinated elastomer composition
US3934056A (en) * 1974-11-26 1976-01-20 Showa Denko Kabushiki Kaisha Resin compositions of high adhesivity comprising E/VA copolymer, chlorinated or chlorosulfonated polyethylene, an unsaturated acid and a peroxy compound
US4122230A (en) * 1977-04-22 1978-10-24 Lowell Ben T Flashing article comprising a chlorinated polyethylene layer adhered to an asphalt-saturated felt layer produced by joining the two layers under pressure at elevated temperature
US4503192A (en) * 1984-01-06 1985-03-05 E. I. Du Pont De Nemours And Company Cured elastomers with improved high temperature tear strength
US5481838A (en) * 1992-11-02 1996-01-09 Gencorp Inc. Anti-fracture, water-resistant, masonry-bondable membrane
US5860255A (en) * 1996-05-09 1999-01-19 Gencorp Inc. Masonry-bondable, water-resistant flexible membrane
US20060255501A1 (en) * 2005-05-11 2006-11-16 Shawcor Ltd. Crosslinked chlorinated polyolefin compositions
CN102906183A (zh) * 2010-05-21 2013-01-30 陶氏环球技术有限责任公司 热塑性组合物以及由该组合物形成的制品
JP2013526638A (ja) * 2010-05-21 2013-06-24 ダウ グローバル テクノロジーズ エルエルシー 熱可塑性組成物およびそれにより形成した物品

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1522776A (en) * 1976-06-09 1978-08-31 Stauffer Chemical Co Film-forming composition and film
US5525679A (en) * 1994-07-25 1996-06-11 The Dow Chemical Company Chlorinated and chlorosulfonated elastic substantially linear olefin polymers
US6706820B2 (en) 2000-08-21 2004-03-16 Showa Denko K.K. Vinyl chloride resin composition

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3891725A (en) * 1974-10-04 1975-06-24 Du Pont Vulcanizable chlorinated elastomer composition
US3934056A (en) * 1974-11-26 1976-01-20 Showa Denko Kabushiki Kaisha Resin compositions of high adhesivity comprising E/VA copolymer, chlorinated or chlorosulfonated polyethylene, an unsaturated acid and a peroxy compound
US4122230A (en) * 1977-04-22 1978-10-24 Lowell Ben T Flashing article comprising a chlorinated polyethylene layer adhered to an asphalt-saturated felt layer produced by joining the two layers under pressure at elevated temperature
US4503192A (en) * 1984-01-06 1985-03-05 E. I. Du Pont De Nemours And Company Cured elastomers with improved high temperature tear strength
US5481838A (en) * 1992-11-02 1996-01-09 Gencorp Inc. Anti-fracture, water-resistant, masonry-bondable membrane
US5595625A (en) * 1992-11-02 1997-01-21 Gencorp Inc. Method of manufacturing an anti-fracture, water-resistant, masonry-bondable membrane
US5860255A (en) * 1996-05-09 1999-01-19 Gencorp Inc. Masonry-bondable, water-resistant flexible membrane
US20060255501A1 (en) * 2005-05-11 2006-11-16 Shawcor Ltd. Crosslinked chlorinated polyolefin compositions
CN102906183A (zh) * 2010-05-21 2013-01-30 陶氏环球技术有限责任公司 热塑性组合物以及由该组合物形成的制品
JP2013526638A (ja) * 2010-05-21 2013-06-24 ダウ グローバル テクノロジーズ エルエルシー 熱可塑性組成物およびそれにより形成した物品
EP2571935A4 (en) * 2010-05-21 2013-12-11 Dow Global Technologies Llc THERMOPLASTIC COMPOSITIONS AND ARTICLES FORMED THEREFROM

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Publication number Publication date
DE1769826B2 (de) 1974-09-26
DE1769826A1 (de) 1971-03-04
FR1571136A (pm) 1969-06-13
BR6800553D0 (pt) 1973-02-01
NL6810382A (pm) 1969-01-28
BE718448A (pm) 1969-01-23
GB1194494A (en) 1970-06-10

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