US20130287980A1 - Curable elastomer compositions with low temperature sealing capability - Google Patents

Curable elastomer compositions with low temperature sealing capability Download PDF

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US20130287980A1
US20130287980A1 US13796588 US201313796588A US2013287980A1 US 20130287980 A1 US20130287980 A1 US 20130287980A1 US 13796588 US13796588 US 13796588 US 201313796588 A US201313796588 A US 201313796588A US 2013287980 A1 US2013287980 A1 US 2013287980A1
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acrylate
methacrylate
tg
cured
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Matthew P. Burdzy
Dingsong Feng
Kevin J. Welch
Yanbing Wang
Robert P. Cross
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Henkel IP and Holding GmbH
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Henkel Corp
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING 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
    • C09D133/00Coating 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08Homopolymers or copolymers of acrylic acid esters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284Application of adhesive
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING 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
    • C09D123/00Coating 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
    • C09D123/02Coating 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 not modified by chemical after-treatment
    • C09D123/18Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09D123/20Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C09D123/22Copolymers of isobutene; Butyl rubber Homo- or copolymers of other iso-olefines
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C09J123/22Copolymers of isobutene; Butyl rubber Homo- or copolymers of other iso-olefines
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/10Materials in mouldable or extrudable form for sealing or packing joints or covers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/10Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16JPISTONS; CYLINDERS; SEALINGS
    • F16J15/00Sealings
    • F16J15/02Sealings between relatively-stationary surfaces
    • F16J15/14Sealings between relatively-stationary surfaces by means of granular or plastic material, or fluid
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/10Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2003/1034Materials or components characterised by specific properties
    • C09K2003/1068Crosslinkable materials
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0617Polyalkenes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625Polyacrylic esters or derivatives thereof
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]

Abstract

Curable sealant compositions having low temperature sealing ability improved over convention curable sealing compositions. The composition is flowable and can be cured to a cross linked form to provide cured reaction products that exhibit elastomeric properties. The curable elastomeric sealant composition can include a cross linkable elastomeric oligomer; an initiator or cross-linking agent; a glassy monomer and/or a rubbery monomer; and optionally one or more additives. Cured reaction products of the composition have a single Tg and retain a higher sealing force at low temperatures (but above the cured product Tg) as compared to a curable composition made from the same cross linkable elastomeric oligomer but without the glassy and/or rubbery monomer.

Description

    FIELD
  • The present disclosure relates generally to curable sealant compositions having low temperature sealing ability improved over convention curable sealing compositions.
  • BRIEF DESCRIPTION OF RELATED TECHNOLOGY
  • Sealants are used in a broad range of applications from automobiles to aircraft engines to contain or prevent solids, liquids, and/or gases from moving across a mating surface, boundary or interfacial region into or on a surrounding or adjacent area, region or surface. Sealants are available in many forms from low viscosity liquids to highly thixotropic pastes and depending on the application can vary in properties from a rigid glassy material to a rubbery elastic network. Elastomers are an important class of polymeric materials useful as sealing compositions and the focus of the current invention.
  • Sealants formulated with monomers, oligomers, polymers and/or other ingredients that react to form new covalent bonds that increase the molecular weight of the chemical backbone leading to entanglements and/or chemical cross-links that exhibits elastic properties are generally referred to as “curing” compositions. Sealants containing ingredients that do not react but exhibit elastic properties based on the thermodynamic properties of the polymer, entanglement of network chains or other molecular interactions are generally referred to as “non-curing” formulations.
  • Definitions used in the literature to describe rubbery and elastomer materials are very similar and sometimes used interchangeably. Elastomer is more general and typically refers to the elastic-bearing properties of a material. Rubber was originally referred to as an elastomer derived from naturally occurring polyisoprene and has expanded over the years to include both natural and synthetic based materials. IUPAC Compendium of Chemical Terminology, 2nd ed. (the “Gold Book”); compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997) defines an elastomer as a polymer that displays rubber-like elasticity. Elastomers are defined in the Physical Polymer Science Handbook by L. H. Sperling John Wiley & Sons, Inc., Publications, New York (2001) as an amorphous, cross-linked polymer above its glass transition temperature (Tg).
  • The equation of state for rubber elasticity describes the relationship between macroscopic sample deformation of a polymer (chain extension) and the retractive stress of the elastomer. The theory of rubber elasticity, derived from the second law of thermodynamics, states that the retractive stress of an elastomer arises as a result of the reduction in entropy upon extension and not changes in enthalpy. As a polymer chain is extended the number of conformations decrease (entropy decreases) and the retractive stress increases. Sperling writes that a long-chain molecule, capable of reasonably free rotation about its backbone, joined together in a continuous network is required for rubber elasticity.
  • σ = nRT r i 2 r o 2 ( α - 1 α 2 ) Equation of State for Rubber Elasticity
  • Where σ is the stress, n is the number of active network chains per unit volume, R is the ideal gas constant, T is temperature, a is the chain extension, and ri 2/ro 2 is the front factor that is approximately equal to one. The equation of state predicts that as the extension of an elastomer increases the observed stress increases. The stress is the retractive force created when for example an elastomer is placed under tension, biaxial tension or compression.
  • The theory of rubber elasticity can be observed in practice when a cured seal operating at a temperature above its glass transition temperature is compressed and exhibits sealing forces that can be measured using instruments know in the art. The glass transition temperature of the elastomer in the cured seal defines an important boundary condition where free rotation of the main chain is restricted as the elastomer transitions from the rubbery to the glassy region resulting in a loss of molecular free rotation, molecular chain extension and the resulting retractive stress. As the temperature of the elastomer approaches the glass transition temperature, the resulting elastic retractive force approaches zero.
  • The utility of an elastomeric sealant is measured by the ability of the cured sealant composition to provide a positive sealing force when exposed to operating conditions over the lifetime of the product. Temperature is an important factor that affects the performance of a sealant and can have a significant impact on the operating lifetime. The temperature range in harsh ambient conditions can vary from +150° C. to −65° C. In less severe applications temperatures can vary from +100° C. to −40° C.
  • It was observed that some cured elastomeric sealants at temperatures well above the glass transition temperature of the overall polymer network have a sealing force that decreases to nearly zero. In one case a cured, elastomeric sealant with a −61° C. Tg, measured by DSC, had a very low sealing force at −40° C. that would be unacceptable for most sealing applications.
  • It is known from statistical thermodynamics of rubber elasticity that the force generated during the deformation of an elastomer is directly proportional to the end-to-end distance of the cross-linked network and the temperature of the matrix. When an elastomer is deformed the retractive force should remain positive, in the rubbery region, as long as the temperature is above the Tg. There is nothing in the above equation of state of rubbery elasticity that would predict that changing the glassy or hard segment in an elastomer having a single Tg, and which exhibits no other first or second order thermodynamic transitions, could increase the low temperature sealing force within the rubbery region.
  • SUMMARY
  • One aspect of the disclosure provides a curable elastomeric sealant composition. The composition is flowable and can be cured to a cross linked form to provide cured reaction products that exhibit elastomeric properties. The curable elastomeric sealant composition can include a cross linkable elastomeric oligomer; an initiator or cross-linking agent; a glassy monomer and/or a rubbery monomer; and optionally one or more of a catalyst; a filler; an antioxidant; and an optional reaction modifier. The cross linkable elastomeric sealant composition can be prepared by reacting a cross linkable elastomeric oligomer having a Tg with at least one of a glassy monomer and a rubbery monomer. Cured reaction products of the composition have a single Tg and retain a higher sealing force at low temperatures (but above the cured product Tg) as compared to a curable composition made from the same cross linkable elastomeric oligomer but without the glassy and/or rubbery monomer.
  • In one embodiment the cross linkable elastomeric oligomer is a telechelic polyisobutylene (PIB) based material terminated at each end with acrylate moieties.
  • Another aspect provides a component having a first predetermined sealing surface aligned with a second predetermined sealing surface. A cured reaction product of a polyisobutylene (PIB) based composition is disposed between the sealing surfaces to prevent movement of materials such as liquids, gasses or fuels between the aligned sealing surfaces. The composition may be cured in contact with one, both or none of the sealing surfaces. Advantageously, the seal formed by the cured reaction product provides low temperature sealing (about −40° C.) within the rubbery region along with excellent resistance to moisture, water, glycols, acids, bases and polar compounds.
  • The disclosed compounds include any and all isomers and stereoisomers. In general, unless otherwise explicitly stated the disclosed materials and processes may be alternately formulated to comprise, consist of, or consist essentially of, any appropriate components, moieties or steps herein disclosed. The disclosed materials and processes may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants, moieties, species and steps used in the prior art compositions or that are otherwise not necessary to the achievement of the function and/or objective of the present disclosure.
  • When the word “about” is used herein it is meant that the amount or condition it modifies can vary some beyond the stated amount so long as the function and/or objective of the disclosure are realized. The skilled artisan understands that there is seldom time to fully explore the extent of any area and expects that the disclosed result might extend, at least somewhat, beyond one or more of the disclosed limits. Later, having the benefit of this disclosure and understanding the concept and embodiments disclosed herein, a person of ordinary skill can, without inventive effort, explore beyond the disclosed limits and, when embodiments are found to be without any unexpected characteristics, those embodiments are within the meaning of the term about as used herein.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • Referring now to the drawings wherein like elements are numbered alike in the several Figures:
  • FIG. 1 is a relaxation recovery sequence for the cured material of example 3. The lower plot is temperature at the time shown and the upper plot is sealing force of that cured material at the time shown.
  • FIG. 2 is a scan from the Differential Scanning calorimeter analysis of the cured products of composition of Example 1.
  • FIG. 3 is a scan from the Differential Scanning calorimeter analysis of the cured products of composition of Example 2.
  • FIG. 4 is a scan from the Differential Scanning calorimeter analysis of the cured products of composition of Example 3.
  • FIG. 5 is a scan from the Differential Scanning calorimeter analysis of the cured products of composition of Example 24.
  • FIG. 6 is a scan from the Differential Scanning calorimeter analysis of the cured products of composition of Example 30.
  • FIG. 7 is a scan from the Differential Scanning calorimeter analysis of the cured products of composition of Example 34.
  • FIG. 8 is a graph showing sealing force at −40° C. for compositions of Examples 1, 2 and 3 having varying oligomer:monomer ratio.
  • DETAILED DESCRIPTION
  • A curable elastomeric sealant composition is a composition that is flowable and can be cured to a cross linked form to provide cured reaction products of the composition that exhibit elastomeric properties. The curable elastomeric sealant composition can include a cross linkable elastomeric oligomer; an initiator or cross-linking agent; a glassy monomer and/or a rubbery monomer; and optionally one or more of a catalyst; a filler; an antioxidant; and an optional reaction modifier. The cross linkable elastomeric sealant composition can be prepared by reacting a cross linkable elastomeric oligomer having a Tg with at least one of a glassy monomer and a rubbery monomer. The cross linkable elastomeric sealant composition can be cured by exposure to conditions and for a time sufficient to at least partially cross-link and cure that composition. Suitable cure conditions, depending on formulation of the cross linkable elastomeric sealant composition include exposure to heat and radiation such as actinic radiation.
  • Cured reaction products of the composition have a single Tg as measured by Differential Scanning calorimetry (DSC) and retain a higher sealing force at low temperatures (but above the cured product Tg) as compared to a curable composition made from the same cross linkable elastomeric oligomer but without the glassy and/or rubbery monomer.
  • Cross Linkable Elastomeric Oligomer
  • A number of sealant chemistries are believed to be suitable for use in the sealant composition. These chemistries include fluoroelastomer; EPDM and other hydrocarbons; styrenic block elastomer; C4 and C5 monomers such as isoprene and isobutylene; acrylates and methacrylates; acrylic emulsion; ethylene acrylate elastomer; functionalized polyacrylate; silylated acrylate; silicone; silylated polyether; silylated polyester; silylated polyamide; polyurethane; silylated polyurethane; plastisol and polyvinyl chloride; polysulfide and polythioether; flexible epoxy; vinyl acetate-ethylene latex; unsaturated polyester; polyolefins, amides and acetates for example EVA. Non-curable chemistries such as oleoresinous based (for example linseed oil) sealants and bituminous sealants may also be useful.
  • The curable elastomeric sealant composition advantageously includes a cross linkable elastomeric oligomer. In one desirable embodiment the cross linkable elastomeric oligomer is a telechelic, polyisobutylene polymer with acrylate moieties at each end (polyisobutylene diacrylate or PIB diacrylate).
  • Glassy Monomer
  • The curable elastomeric sealant composition can include a glassy monomer that is reacted with the cross linkable elastomeric oligomer. A glassy monomer has a glass transition temperature above the glass transition temperature of the cross linkable elastomeric oligomer. Typically the glassy monomer has a glass transition temperature above 20° C.
  • Some examples of glassy monomers include stearyl acrylate (Tg 35° C.); trimethylcyclohexyl methacrylate (Tg 145° C.); isobornyl methacrylate (Tg 110° C.); isobornyl acrylate (Tg 88° C.); and the FANCRYL methacryl esters marketed by Hitachi Chemical Corporation such as dicyclopentanylmethacrylate (FA-513M Tg 175° C.) and dicyclopentanyl Acrylate (FA-513AS, Tg 140° C.). Other examples of glassy and rubbery monomers are listed in the Tables at the end of the specification.
  • Rubbery Monomer
  • The curable elastomeric sealant composition can include a rubbery monomer that is reacted with the cross linkable elastomeric oligomer. A rubbery monomer has a glass transition temperature below the glass transition temperature of the glassy monomer. Typically the rubbery monomer has a glass transition temperature below 20° C. Some examples of rubbery monomers include isooctyl acrylate (Tg −54° C.); isodecyl acrylate (Tg −60° C.); isodecyl methacrylate (Tg −41° C.); n-lauryl methacrylate (Tg −65); and 1,12-dodecanediol dimethacrylate (Tg −37° C.). Other examples of glassy and rubbery monomers are listed in the Tables at the end of the specification.
  • Initiator or Cross-Linking Agent
  • The curable elastomeric sealant composition can include an initiator or cross-linking agent to at least partially cross-link and cure that composition.
  • The initiator or cross-linking agent can be a heat-cure initiator or initiator system comprising an ingredient or a combination of ingredients which at the desired elevated temperature conditions produce free radicals. Suitable initiators may include peroxy materials, e.g., peroxides, hydroperoxides, and peresters, which under appropriate elevated temperature conditions decompose to form peroxy free radicals which are initiatingly effective for the polymerization of the curable elastomeric sealant compositions. The peroxy materials may be employed in concentrations effective to initiate curing of the curable elastomeric sealant composition at a desired temperature and typically in concentrations of about 0.1% to about 10% by weight of composition.
  • Another useful class of heat-curing initiators comprises azonitrile compounds which yield free radicals when decomposed by heat. Heat is applied to the curable composition and the resulting free radicals initiate polymerization of the curable composition. Compounds of the above formula are more fully described in U.S. Pat. No. 4,416,921, the disclosure of which is incorporated herein by reference.
  • Azonitrile initiators of the above-described formula are readily commercially available, e.g., the initiators which are commercially available under the trademark VAZO from E.I. DuPont de Nemours and Company, Inc., Wilmington, Del.
  • The initiator or cross-linking agent can be a photoinitiator. Photoinitiators enhance the rapidity of the curing process when the photocurable elastomeric sealant composition is exposed to electromagnetic radiation, such as actinic radiation, for example ultraviolet (UV) radiation. Examples of some useful photoinitiators include, but are not limited to, photoinitiators available commercially from Ciba Specialty Chemicals, under the “IRGACURE” and “DAROCUR” trade names, specifically “IRGACURE” 184 (1-hydroxycyclohexyl phenyl ketone), 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholino propan-1-one), 369 (2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone), 500 (the combination of 1-hydroxy cyclohexyl phenyl ketone and benzophenone), 651 (2,2-dimethoxy-2-phenyl acetophenone), 1700 (the combination of bis(2,6-dimethoxybenzoyl-2,4,4-trimethyl pentyl)phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one), and 819 [bis(2,4,6-trimethyl benzoyl)phenyl phosphine oxide] and “DAROCUR” 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one) and 4265 (the combination of 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one); and the visible light [blue] photoinitiators, dl-camphorquinone and “IRGACURE” 784DC. Of course, combinations of these materials may also be employed herein.
  • Other photoinitiators useful herein include alkyl pyruvates, such as methyl, ethyl, propyl, and butyl pyruvates, and aryl pyruvates, such as phenyl, benzyl, and appropriately substituted derivatives thereof. Photoinitiators particularly well-suited for use herein include ultraviolet photoinitiators, such as 2,2-dimethoxy-2-phenyl acetophenone (e.g., “IRGACURE” 651), and 2-hydroxy-2-methyl-1-phenyl-1-propane (e.g., “DAROCUR” 1173), bis(2,4,6-trimethyl benzoyl)phenyl phosphine oxide (e.g., “IRGACURE” 819), and the ultraviolet/visible photoinitiator combination of bis(2,6-dimethoxybenzoyl-2,4,4-trimethylpentyl)phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (e.g., “IRGACURE” 1700), as well as the visible photoinitiator bis(η5-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium (e.g., “IRGACURE” 784DC). Useful actinic radiation includes ultraviolet light, visible light, and combinations thereof.
  • Desirably, the actinic radiation used to cure the photocurable elastomeric sealant composition has a wavelength from about 200 nm to about 1,000 nm. Useful UV includes, but is not limited to, UVA (about 320 nm to about 410 nm), UVB (about 290 nm to about 320 nm), UVC (about 220 nm to about 290 nm) and combinations thereof. Useful visible light includes, but is not limited to, blue light, green light, and combinations thereof. Such useful visible lights have a wavelength from about 450 nm to about 550 nm. Photoinitiators can be employed in concentrations effective to initiate curing of the curable elastomeric sealant composition at a desired exposure to actinic radiation and typically in concentrations of about 0.01% to about 10% by weight of composition.
  • Catalyst
  • The curable elastomeric sealant composition can include a catalyst to modify speed of the initiated reaction.
  • Filler
  • The curable elastomeric sealant composition can optionally include a filler. Some useful fillers include, for example, lithopone, zirconium silicate, hydroxides, such as hydroxides of calcium, aluminum, magnesium, iron and the like, diatomaceous earth, carbonates, such as sodium, potassium, calcium, and magnesium carbonates, oxides, such as zinc, magnesium, chromic, cerium, zirconium and aluminum oxides, calcium clay, fumed silicas, silicas that have been surface treated with a silane or silazane such as the AEROSIL products available from Evonik Industries, silicas that have been surface treated with an acrylate or methacrylate such as AEROSIL R7200 or R711 available from Evonik Industries, precipitated silicas, untreated silicas, graphite, synthetic fibers and mixtures thereof. When used filler can be employed in concentrations effective to provide desired physical properties in the uncured composition and cured reaction products and typically in concentrations of about 0.1% to about 70% by weight of composition.
  • Antioxidant
  • The curable elastomeric sealant composition can optionally include an anti-oxidant. Some useful antioxidants include those available commercially from Ciba Specialty Chemicals under the tradename IRGANOX. When used, the antioxidant should be used in the range of about 0.1 to about 15 weight percent of curable composition, such as about 0.3 to about 1 weight percent of curable composition.
  • Reaction Modifier
  • The curable elastomeric sealant composition can include a reaction modifier. A reaction modifier is a material that will increase or decrease reaction rate of the curable elastomeric sealant composition. For example, quinones, such as hydroquinone, monomethyl ether hydroquinone (MEHQ), napthoquinone and anthraquinone, may also be included to scavenge free radicals in the curable elastomeric sealant composition and thereby slow reaction of that composition and extend shelf life. When used, the reaction modifier can be used in the range of about 0.1 to about 15 weight percent of curable composition.
  • Adhesion Promoter
  • The curable elastomeric sealant composition can include one or more adhesion promoters that are compatible and known in the art. Examples of useful commercially available adhesion promoters include octyl trimethoxysilane (commercially available from Chemtura under the trade designation A-137), glycidyl trimethoxysilane (commercially available from Chemtura under the trade designation A-187), methacryloxypropyl trimethoxysilane (commercially available from Chemtura under the trade designation of A-174), vinyl trimethoxysilane, tetraethoxysilane and its partial condensation products, and combinations thereof. When used, the adhesion promoter can be used in the range of about 0.1 to about 15 weight percent of curable composition.
  • Rheology Modifiers
  • The curable elastomeric sealant composition can optionally include a thixotropic agent to modify rheological properties of the uncured composition. Some useful thixotropic agents include, for example, silicas, such as fused or fumed silicas, that may be untreated or treated so as to alter the chemical nature of their surface. Virtually any reinforcing fused, precipitated silica, fumed silica or surface treated silica may be used.
  • Examples of treated fumed silicas include polydimethylsiloxane-treated silicas, hexamethyldisilazane-treated silicas and other silazane or silane treated silicas. Such treated silicas are commercially available, such as from Cabot Corporation under the tradename CAB-O-SIL ND-TS and Evonik Industries under the tradename AEROSIL, such as AEROSIL R805. Also useful are the silicas that have been surface treated with an acrylate or methacrylate such as AEROSIL R7200 or R711 available from Evonik Industries.
  • Examples of untreated silicas include commercially available amorphous silicas such as AEROSIL 300, AEROSIL 200 and AEROSIL 130. Commercially available hydrous silicas include NIPSIL E150 and NIPSIL E200A manufactured by Japan Silica Kogya Inc.
  • When used rheology modifier can be employed in concentrations effective to provide desired physical properties in the uncured composition and cured reaction products and typically in concentrations of about 0.1% to about 70% by weight of composition.
  • Coloring Agent.
  • The curable elastomeric composition can be clear to translucent. For some applications a colored composition can be beneficial to allow for inspection of the applied composition. A coloring agent, for example a pigment or dye, can be used to provide a desired color beneficial to the intended application. Exemplary coloring agents include titanium dioxide, C.I. Pigment Blue 28, C.I. Pigment Yellow 53 and phthalocyanine blue BN. In some applications a fluorescent dye can be added to allow inspection of the applied composition under UV radiation. The coloring agent will be present in amounts sufficient to allow for detection. If present, the coloring agent is desirably incorporated in amounts of about 0.002% or more by weight. The maximum amount is governed by considerations of cost and absorption of radiation that interferes with cure of the composition. More desirably, the dye is present in amounts of about 0.002% to about 1.0% weight by weight of the total composition.
  • The curable elastomeric sealant composition can optionally include other additives at concentrations effective to provide desired properties so long as they do not inhibit the desirable properties such as curing mechanism, elongation, low temperature sealing force, tensile strength, chemical resistance. Example of such optional additives include, for example, reinforcing materials such as fibers, diluents, reactive diluents, coloring agents and pigments, moisture scavengers such as methyltrimethoxysilane and vinyltrimethyloxysilane, inhibitors and the like may be included.
  • Exemplary Composition Ranges:
  • A curable elastomeric sealant composition can typically comprise:
  • about 50 to 99 wt % of a cross linkable elastomeric oligomer;
    about 1 to 30 wt % of a glassy monomer;
    about 0 to 30 wt % of a rubbery monomer;
    about 0.01 to 10 wt % of an initiator or cross-linking agent;
    about 0 to 5 wt % of a catalyst;
    about 0 to 70 wt % of a filler;
    about 0 to 15 wt % of a antioxidant;
    about 0 to 15 wt % of a reaction modifier;
    about 0 to 15 wt % of adhesion promoter;
    about 0 to 70 wt % of rheology modifier;
    about 0 to 1.0 wt % of coloring agent.
  • The glassy monomer(s) and the rubbery monomer(s) can be chosen so that a desired average glass transition temperature for that combination of monomers is obtained. The average glass transition temperature for a combination of monomers is defined by the Fox equation (1/Tgcomb=M1/Tg1+M2/Tg2 see T. G. Fox, Bull. Am. Phys. Soc., 1, 123 (1956), the contents of which are incorporated by reference herein.
  • The ratio of cross linkable elastomeric oligomer to glassy monomer must be chosen to provide sufficient glassy monomer to increase low temperature sealing force of the cured sealant reaction products. However, the ratio must not add so much glassy monomer that the elastomeric properties of the cured sealant reaction products are undesirably affected. Thus, there is a need to balance the ratio of cross linkable elastomeric oligomer to glassy monomer depending on desired properties: too little glassy material and the cured sealant composition will not have a desirable low temperature sealing force but too much glassy material and sealing ability of the cured sealant at higher temperatures is lost.
  • The ratio of cross linkable elastomeric oligomer to glassy monomer will depend on the oligomer and monomer used; the final application for the sealant; and the cured sealant properties desired for that application. A ratio of cross linkable elastomeric oligomer to glassy monomer in the range of 75:25 to 95:5 respectively provides a general starting point. At present there is no way to predict cured sealant properties for a cross linkable sealant composition formulation. Testing of formulations for low temperature sealing force and higher temperature sealing properties is required to arrive at a formulation and ratio providing desired properties.
  • Specific physical properties required for the uncured, sealant composition will depend on application. For example, sealant composition viscosity can be formulated for application method and desired cycle time. Viscosity of the uncured sealant composition can be 10,000 Cps to 1,000,000 Cps at 25° C.
  • Specific physical properties required for cured reaction products of the sealant composition will depend on sealing application, minimum and maximum operating temperatures within the application, desired tensile strength at high temperatures and desired sealing force at low temperatures. Some useful physical properties for the cured reaction products include: Hardness, Shore A about 20 to about 90 and desirably about 40 to about 60. Tensile strength, about 100 psi to about 2,000 psi and desirably about 500 psi to about 1,000 psi. Elongation, about 10% to about 1,000% and desirably about 100% to about 500%. Low temperature (−40° C.) sealing force, about 0 Newtons to about 50 Newtons and desirably about 6 Newtons to about 30 Newtons. Desirably the cured reaction product has a compression set value that allows a seal made therefrom to maintain a predetermined minimum sealing force throughout the design life of the seal.
  • Components to be sealed by the disclosed curable compositions have a first predetermined sealing surface that is aligned with a second predetermined sealing surface. Typically, the aligned sealing surfaces are in a fixed relationship and move very little relative to each other. The aligned sealing surfaces are generally in fluid communication with a chamber. The seal formed between the aligned sealing surfaces prevents movement of materials between the surfaces and into, or out of, the chamber.
  • One or both of the sealing surfaces can be machined or formed. The predetermined sealing surfaces are designed to allow a curable composition to be disposed on one or both surfaces during initial assembly of the component to form a seal therebetween. Design of the predetermined sealing surfaces enhances parameters such as alignment of the surfaces, contact area of the surfaces, surface finish of the surfaces, “fit” of the surfaces and separation of the surfaces to achieve a predetermined sealing effect. A predetermined sealing surface does not encompass surfaces that were not identified or designed prior to initial assembly to accommodate a seal or gasket, for example the outside surface of a component over which a repair material is molded or applied to lessen leaking. Sealing surfaces on an engine block and oil pan or engine intake manifold are examples of sealing surfaces in fixed relationship.
  • The disclosed curable compositions can be in a flowable state for disposition onto at least a portion of one sealing surface to form a seal between the surfaces when they are aligned. The curable composition can be applied as a film over the sealing surface. The curable composition can also be applied as a bead in precise patterns by tracing, screen printing, robotic application and the like. In bead applications the disclosed compositions are typically dispensed as a liquid or semi-solid under pressure through a nozzle and onto the component sealing surface. The nozzle size is chosen to provide a line or bead of composition having a desired width, height, shape and volume. The curable composition can be contained in a small tube and dispensed by squeezing the tube; contained in a cartridge and dispensed by longitudinal movement of a cartridge sealing member; or contained in a larger container such as a 5 gallon pail or 55 gallon drum and dispensed at the point of use by conventional automated dispensing equipment. Container size can be chosen to suit the end use application.
  • The curable composition can be used to form a formed in place gasket (FIPG). In this application the composition is dispensed onto a first predetermined sealing surface. The first predetermined sealing surface and dispensed composition is aligned and sealingly engaged with a second predetermined sealing surface before the composition has fully cured. The composition will adhere to both sealing surfaces as it cures.
  • The curable composition can be used to form a cured in place gasket (CIPG). In this application the composition is dispensed onto a first predetermined sealing surface and allowed to substantially cure before contact with a second predetermined sealing surface. The first sealing surface and cured composition is sealingly engaged with the second sealing surface thereby compressing the cured composition to provide a seal between the sealing surfaces. The composition will adhere to only the first sealing surface.
  • The curable composition can be used to form a mold in place gasket (MIPG). In this application the part comprising the first predetermined sealing surface is placed in a mold. The composition is dispensed into the mold where it contacts the first sealing surface. The composition is typically allowed to cure before removal from the mold. After molding, the first sealing surface and molded composition is sealingly engaged with a second predetermined sealing surface thereby compressing the cured composition to provide a seal between the sealing surfaces. The composition will adhere to only the first sealing surface.
  • The curable composition can be used in liquid injection molding (LIM). In this application uncured composition is dispensed into a mold without any predetermined sealing surface under controlled pressure and temperature. The composition is typically allowed to cure before removal from the mold. After removal the molded part will retain its shape. In sealing applications the molded gasket is disposed between two predetermined sealing surfaces and compressed to provide a seal between the sealing surfaces.
  • The following examples are included for purposes of illustration so that the disclosure may be more readily understood and are in no way intended to limit the scope of the disclosure unless otherwise specifically indicated.
  • Unless otherwise specified the following test procedures were used on cured specimens in the Examples.
  • Shore A hardness ASTM D2240-05
    Tensile strength ASTM D412-98A
    modulus ASTM D412-98A
    elongation ASTM D412-98A
  • Compression
  • set “A” ASTM D395. Samples were allowed to cool to room temperature in the uncompressed stated before testing.
  • Compression
  • set “B” ASTM D395 modified. Samples were allowed to cool to room temperature in a compressed state before testing.
    glass transition Tg Differential Scanning calorimetry (DSC).
  • Curable, elastomeric gasketing compositions were made. Polyisobutylene diacrylate (PIB diacrylate) is a telechelic, polyisobutylene polymer with acrylate moieties at each end, with a molecular weight of about 1,000 to about 1,000,000 and a very low glass transition temperature (Tg) of −67° C. PIB diacrylate was chosen as the rubber matrix of the elastomeric gasketing compositions. PIB diacrylate can be prepared using a number of known reactions schemes, some of which are listed below and the contents of which are incorporated by reference herein in their entirety. The method of scheme 2 can be used to prepare the PIB diacrylate used in the following compositions.
  • Figure US20130287980A1-20131031-C00001
    Figure US20130287980A1-20131031-C00002
  • Various acrylates and methacrylates having a Tg greater than 20° C. were selected as the glassy monomer. Various acrylates and methacrylates having a Tg less than 0° C. were selected as the rubbery monomer and as a reactive diluent. The ratio of rubber phase over glass phase was adjusted by trial and error to provide the desired elasticity and sealing force at lower temperature.
  • Preparation of Curable Gasketing Compositions:
  • 1) Premix preparation: Charge all liquids including initiator, antioxidant, reaction modifier. Mix until no solids remain.
    2) Charge elastomeric oligomer into premix. Mix until uniform.
    3) Add fillers and mix until uniform.
    4) Apply vacuum to degas sample. Discharge bubble free material into storage container.
  • Examples - curable gasketing composition
    1 2 3 4 5
    mass mass mass mass mass
    Component (gm) (gm) (gm) (gm) (gm)
    PIB diacry- 59.1 66.9 71.1 75.3 79.5
    late
    FA-513M1 19.7 16.7 12.6 8.4 4.2
    Irgacure 2.1 0.8 0.8 0.8 0.8
    8192
    Irganox 0.8 0.8 0.8 0.8 0.8
    10103
    Aerosil 3.8 4.1 4.1 4.1 4.1
    R1064
    H30RY5 4.0 4.2 4.2 4.2 4.2
    diluent6 4.7 5.0 5.0 5.0 5.0
    viscosity 180000 289000 456000 664500 995000
    (cps, 25° C.,
    12/s)
    1Dicyclopentanylmethacrylate glassy monomer marketed by Hitachi Chemical Corporation.
    2available from Ciba.
    3available from Ciba.
    4Available from Evonik.
    5Available from Wacker.
    62 CsT polyalphaolefin diluent.
  • Typical properties for thermally cured
    reaction products of Examples
    1 2 3 4 5
    Shore A hardness (point) 64 55 45 42 32
    Tensile strength (psi) 1084 727 543 398 296
    Elongation (%) 225 195 174 156 148
    100% modulus (psi) 460 323 264 215 156
    Compression set A (%, 25%) 9 5 6 7 4
    Compression set B (%, 25%) 62 41 27 17 11

    Compression set B values of greater than 0 but less than 40 indicate a cured material may have an advantageous low temperature sealing force. The high compression set B value (62) of Example 1 indicates a cured material that will not maintain desirable sealing force at low temperatures.
  • Example (mass, gm)
    Tg 6 7 8 9 10 11 12
    PIB diacrylate −67 62.7 59.1 63.8 64.8 65.9 62.7 62.7
    FA-513M 175 19.7
    FA-513AS1 140 20.9
    isobornyl acrylate 88 19.9 18.8 17.8 16 16
    isobornyl methacrylate 110
    trimethylcyclohexyl methacrylate 145
    stearyl acrylate 35
    isooctyl acrylate −54
    Isodecyl acrylate −60 2.6 2.6 2.6 5.0
    Isodecyl methacrylate −41
    n-lauryl methacrylate −65
    1,12-dodecanediol −37
    dimethacrylate
    Irgacure 819 0.8 2.1 0.8 0.8 0.8 0.8 0.8
    Irganox 1010 0.8 0.8 0.8 0.8 0.8 0.8 0.8
    Aerosil R106 4.1 3.8 4.1 4.1 4.1 4.1 2.5
    H30Ry 4.2 3.9 4.2 4.2 4.2 4.2 4.2
    2 cSt polyalphaolefin diluent 4.7
    9 cSt polyalphaolefin diluent
    uncured viscosity (cps, 25° C., 340,000 180000 252000 284000 299000 548000 181000
    12/s)
    Shore A hardness 51 64 44 40 41 40
    tensile strength (psi) 623 912 501 469 426 436
    elongation (%) 192 226 218 215 202 212
    100% modulus (psi) 326 388 197 187 187 166
    compression set A (% 25%) 14 25 11 12 11 13
    compression set B (% 25%) 46 72 31 32 30 25
    Example (mass, gm)
    Tg 13 14 15 16 17 18 19
    PIB diacrylate −67 62.7 62.7 62.7 62.7 62.7 62.7 62.7
    FA-513M 175 10.5 10.5
    FA-513AS 140
    isobornyl acrylate 88 15.7 15.7 15.7
    isobornyl methacrylate 110
    trimethylcyclohexyl methacrylate 145 10.5
    stearyl acrylate 35 11.5
    isooctyl acrylate −54 5.2 10.5 5.2 10.5
    Isodecyl acrylate −60 4.2 10.5
    Isodecyl methacrylate −41
    n-lauryl methacrylate −65
    1,12-dodecanediol −37 1.0 0.5
    dimethacrylate
    Irgacure 819 .8 0.4 0.8 0.8 0.8 0.8 0.8
    Irganox 1010 .8 0.5 0.8 0.8 0.8 0.8 0.8
    Aerosil R106 4.1 4.1 3.5 4.1 4.1 3.0 4.1
    H30Ry 4.2 4.2 4.2 4.2 4.2 4.2 4.2
    2 cSt polyalphaolefin diluent
    9 cSt polyalphaolefin diluent
    uncured viscosity (cps, 25° C., 235000 175000 204000 194000 130000 177000 170000
    12/s)
    Shore A hardness 48 36 45 44 41 45 48
    tensile strength (psi) 451 168 484 437 421 534 534
    elongation (%) 158 110 222 208 213 212 231
    100% modulus (psi) 251 150 183 187 172 196 198
    compression set A (% 25%) 15 14 8 14 13 11 23
    compression set B (% 25%) 34 20 29 33 30 26 40
    Example (mass, gm)
    Tg 20 21 22 23 24 25 26
    PIB diacrylate −67 62.7 62.7 62.7 62.7 62.7 62.7 62.7
    FA-513M 175
    FA-513AS 140 6.2 6.2
    isobornyl acrylate 88 15.7 12.6 12.6 6.2 15.7 7.8 15.7
    isobornyl methacrylate 110
    trimethylcyclohexyl methacrylate 145
    stearyl acrylate 35
    isooctyl acrylate −54 5.2 8.4 5.2 5.2 5.2
    Isodecyl acrylate −60 6.4 8.4
    Isodecyl methacrylate −41
    n-lauryl methacrylate −65
    1,12-dodecanediol dimethacrylate −37 0.5 0.5 0.5 0.5 0.5 0.5 0.5
    Irgacure 819 0.8 0.8 0.8 0.8 0.8 0.8 0.8
    Irganox 1010 0.8 0.8 0.8 0.8 0.8 0.8 0.8
    Aerosil R106 3.0 3.0 3.0 3.0 3.0 3.0 3.0
    H30Ry 4.2 4.2 4.2 4.2 4.2 4.2 4.2
    2 cSt polyalphaolefin diluent
    9 cSt polyalphaolefin diluent
    uncured viscosity (cps, 25° C., 164000 166000 148000 162000 177000 210000 182000
    12/s)
    Shore A hardness 43 44 40 42 45 46 47
    tensile strength (psi) 435 336 409 423 572 515 515
    elongation (%) 188 167 191 186 197 197 187
    100% modulus (psi) 192 181 180 189 222 212 219
    compression set A (% 25%) 7 5 6 7 7 7 6
    compression set B (% 25%) 26 21 20 18 23 24 20
    Example (mass, gm)
    Tg 27 28 29 30 31 32 33
    PIB diacrylate −67 62.7 62.7 62.7 62.7 62.7 62.7 62.7
    FA-513M 175 10.5 10.5 12.6
    FA-513AS 140
    isobornyl acrylate 88 20.9 12.6
    isobornyl methacrylate 110 20.9
    trimethylcyclohexyl methacrylate 145
    stearyl acrylate 35
    isooctyl acrylate −54
    Isodecyl acrylate −60 8.4 8.4
    Isodecyl methacrylate −41 10.5
    n-lauryl methacrylate −65 20.9 10.5
    1,12-dodecanediol −37
    dimethacrylate
    Irgacure 819 0.8 0.8 0.8 0.8 0.8 0.8 0.8
    Irganox 1010 0.8 0.8 0.8 0.8 0.8 0.8 0.8
    Aerosil R106 4.1 4.1 4.1 4.1 4.1 4.1 4.1
    H30Ry 4.2 4.2 4.2 4.2 4.2 4.2 4.2
    2 cSt polyalphaolefin diluent 5.0
    9 cSt polyalphaolefin diluent
    uncured viscosity (cps, 25° C., 69000 185000 184000 292000 228000 211000 345000
    12/s)
    Shore A hardness 29 48 53 53 53 43 79
    tensile strength (psi) 217 544 612 812 590 465 1134
    elongation (%) 157 171 194 217 187 189 213
    100% modulus (psi) 118 279 278 293 280 209 526
    compression set A (% 25%) 7 5 11 4 7 3 11
    compression set B (% 25%) 11 24 38 26 31 17 61
    Example (mass, gm)
    Tg 34 35 36 37 38 39 40
    PIB diacrylate −67 62.7 62.7 62.7 62.7 62.7 62.7 62.7
    FA-513M 175
    FA-513AS 140
    isobornyl acrylate 88 15.7 15.7 15.7 20.9 20.9
    isobornyl methacrylate 110
    trimethylcyclohexyl methacrylate 145 20.9
    stearyl acrylate 35 20.9
    isooctyl acrylate −54 5.2
    Isodecyl acrylate −60 4.2
    Isodecyl methacrylate −41
    n-lauryl methacrylate −65
    1,12-dodecanediol −37 5.2 1.0
    dimethacrylate
    Irgacure 819 0.8 0.8 0.8 0.8 0.8 0.8 0.8
    Irganox 1010 0.8 0.8 0.8 0.8 0.8 0.8 0.8
    Aerosil R106 4.1 4.1 4.1 4.1 4.1 4.1 4.1
    H30Ry 4.2 4.2 4.2 4.2 4.2 4.2 4.2
    2 cSt polyalphaolefin diluent
    9 cSt polyalphaolefin diluent 4.0
    uncured viscosity (cps, 25° C., 200000 200000 122000 260000 226000 257000 178000
    12/s)
    Shore A hardness 45 69 42 68 50 50 45
    tensile strength (psi) 478 883 218 924 598 614 428
    elongation (%) 179 201 111 100 161 205 191
    100% modulus (psi) 235 409 194 824 309 241 189
    compression set A (% 25%) 5 8 3 6 3 12 14
    compression set B (% 25%) 21 51 7 41 19 35 30
    Example (mass, gm)
    Tg 41 42 43 44
    PIB diacrylate −67 62.7 62.7 67.5 67.4
    FA-513M 175
    FA-513AS 140
    isobornyl acrylate 88 20.9 20.9 16.9 16.8
    isobornyl methacrylate 110
    trimethylcyclohexyl methacrylate 145
    stearyl acrylate 35
    isooctyl acrylate −54 5.6 5.6
    Isodecyl acrylate −60 2.6
    Isodecyl methacrylate −41
    n-lauryl methacrylate −65
    1,12-dodecanediol −37 0.5 0.5
    dimethacrylate
    lauroyl peroxide 1.0
    Irgacure 819 0.8 0.8 0.9
    Irganox 1010 0.8 0.8 0.9 0.9
    Aerosil R106 4.1 4.1 3.2 3.2
    H30Ry 4.2 4.2 4.5 4.5
    2 cSt polyalphaolefin diluent
    9 cSt polyalphaolefin diluent
    uncured viscosity (cps, 25° C., 169000 348000 177000 100000
    12/s)
    Shore A hardness 43 48 45 44
    tensile strength (psi) 523 612 534 413
    elongation (%) 209 220 212 150
    100% modulus (psi) 203 243 196 235
    compression set A (% 25%) 11 11 11
    compression set B (% 25%) 34 31 26
    1Glassy monomer marketed by Hitachi Chemical Corporation.
  • Example 43 is a UV curable composition. Example 43 was formed into samples. The samples were exposed to an UV A radiation source having an intensity of about 1434 mw/cm2 for an energy of about 9872 mJ/cm2. Cured samples of composition 43 had a sealing force at −40° C. of 8N at 25% compression. Example 44 is a thermally curable composition.
  • The sealing force for example 24 is shown in the table below as a function of temperature and percent compression. The composition in example 24 exhibits typical elastomeric properties. The sealing force at a constant temperature increases as the percent compression is increased, which is expected based on the theory of rubber elasticity as the extension increases. The force, at a constant compression, increases as the temperature is increased. This is also expected based on the temperature dependency defined in the equation of state of rubber elasticity.
  • Sealing Force (Newtons) vs Compression
    UV Cured Polyisobutylene, Example 24
    Temperature
    Compression −40° C. 23° C. 95° C.
     5% 3 3 28
    10% 3 21 66
    15% 5 28 81
    20% 6 48 103
    25% 9 70 154
    40% 18 154 289
  • The sealing force at −40° C. for several cured films that were compressed twenty-five percent are shown in the table below, titled UV cured Isoprene & PIB Cured-In-Place Gasketing Compositions. It was observed as shown in examples 1, 2 and 3 that the sealing force at −40° C. and 25 percent compression varied significantly as a function of the monomer content as shown in the table and graph below. The step function in change from examples 1, 2, and 3 was surprising and not expected based on observing a single glass transition temperature in the DSC scan. If there was a distinct or separate glassy phase that occurred as a result of the higher glass transition monomer, it should appear as a first or second order thermodynamic transition as measured by DSC. No such first or second order thermodynamic transition is observed in the DSC scans for examples 1, 2 and 3 shown in the figures. High monomer content is desirable to lower the viscosity of the uncured sealant. This allows the sealant to be dispensed quickly while obtaining a cured elastomer with high tensile strength and high elongation. As the monomer content decreases the viscosity increases, tensile strength decreases and the elongation decreases. A high viscosity is undesirable as it is difficult to rapidly dispense the composition. A low elongation is undesirable which can lead to cracks in the seal. A high sealing force at low temperature is desirable as this defines the practical lower limit of ability of the elastomeric seal to perform its intended function over the operating temperature range. The low temperature sealing force, i.e. at −40° C., can be modulated dramatically with changes in the glassy and/or rubbery monomer ratio.
  • Each of these cured networks exhibited a single glass transition temperature when measured with a differential scanning calorimetry (DSC) as shown in FIGS. 2, 3 and 4 (Examples 1, 24 and 30).
  • While preferred embodiments have been set forth for purposes of illustration, the description should not be deemed a limitation of the disclosure herein. Accordingly, various modifications, adaptations and alternatives may occur to one skilled in the art without departing from the spirit and scope of the present disclosure.
  • UV cured Isoprene & PIB Cured-in-Place Gasketing Compositions 25% Compression Sealing Force
    Example
    45 1 2 3 30 34 24
    PIB-Diacrylate 100.0 100.0 100.0 100.0 100.0 100.0
    Kuraray UC-203 100.0
    FA-513M, Tg = 175° C. 33.3 33.3 25.0 17.7
    Isobornyl Acrylate Tg = 88° C. 33.3 25.0 25.0
    isooctyl acrylate Tg = −54° C. 8.3 8.3
    Sartomer Ricacryl 3850 6.7
    2 cst PAO 8.0 8.0 7.6 7.1
    BHT 1.3
    Tinuvin 765 1.3
    Darocur 1173 4.0
    1,12-dodecanediol dimethacrylate 0.8
    Irgacure 819 1.3 3.6 1.2 1.1 1.3 1.3 1.3
    I-1010 1.3 1.3 1.2 1.3 1.3 1.3
    Aerosil R106 6.5 6.5 6.2 5.7 6.5 6.5 4.8
    H30RY 6.7 6.7 6.3 5.9 6.7 6.7 6.7
    Total 169.2 159.4 147.6 138.6 149.1 149.1 148.2
    Viscosity (cps, 25° C., 12/s) 82,100 180,200 288,700 456,600 291,900 200,200 177,200
    Shore A, ASTM D2240 44 64 55 45 53 45 45
    Tensile (psi) ASTM D412 871 1084 727 543 812 478 572
    Elongation (%) ASTM D412 150 225 195 174 217 179 197
    100% modulus (psi), D412 483 460 323 264 293 235 222
    CS % (25%), ASTM D395 9 5 6 4 5 7
    CS % (25%), Cooled closed fixture 62 41 27 26 21 26
    Tg, Degree ° C. −61 −61 −63 −64 −58 −59 −59
    Other DSC Transitions none none none none none none none
    −40° C. force, 25% comp. (Newtons) 4 5 6 15 6 11 8
  • Examples of glassy or rubbery monomers.
    Tg VISCOSITY
    COMPANY PRODUCT DESCRIPTION CAS # (° C.) (mPa · s) MW (Da)
    AkzoNobel Nourycryl MC 110 4-tert-Butylcylcohexyl Methacryalte
    AkzoNobel Nourycryl MA 123- Ethylene Ureaethyl Methacrylate
    M50 50% in MMA
    AkzoNobel Nourycryl MA 128 2,2-Pentamethylene-1,3-
    oxazolidyl-3) Ethylmethacryate
    Arkema MA: Methyl Methyl Acrylate 96-33-3 10
    Acrylate
    Arkema Norsocryl ® Tetrahydrofurfuryl Methacrylate 2455-24-5 60
    Tetrahydrofurfuryl
    Methacrylate
    (THFMA)
    Arkema MATRIFE Trifluoroethyl methacrylate
    (Trifluoroethyl
    methacrylate)
    Arkema Norsocryl ® Methacrylic Anhydride
    Methacrylic
    Anhydride
    (Norsocryl ® 500)
    Arkema LMA: Norsocryl ® Lauryl Methacryalate 142-90-5 −65
    Lauryl 2549-53-3
    Methacrylate 2495-27-4
    Arkema SMA: Norsocryl ® Stearyl Methacrylate 2495-27-4 −100
    Stearyl 32360-05-7
    Methacrylate
    Arkema A18-22: Behenyl Acrylate 4813-57-4
    Norsocryl ® 48076-38-6
    Acrylate C18-22 18299-85-9
    Arkema Norsocryl ® 121: Alkyl Acrylate in aromatic
    Norsocryl ® hydrocarbon (40/60)
    Acrylate C18-44 in
    solution in
    aromatic
    hydrocarbon
    solvents (40/60)
    Arkema Norsocryl ® Heptyl Heptyl Methacrylate
    Methacrylate
    (HMA)
    Arkema EA: Ethyl Acrylate Ethyl Acrylate 140-88-5 −24
    Arkema BA: Butyl Acrylate Butyl Acrylate 141-32-2 −54
    Arkema 2EHA: 2- 2-Ethylhexyl Acrylate 103-11-7 −70
    Ethylhexyl Acrylate
    Arkema Norsocryl ® 102: 2-ethyl (2-oxoimidazolidin-1-yl)
    25% MEIO methacrylate (MEIO), an ureido
    monomer, as two solutions in
    methyl methacrylate:
    Arkema Norsocryl ® 104: 2-ethyl (2-oxoimidazolidin-1-yl)
    50% MEIO methacrylate (MEIO), an ureido
    monomer, as two solutions in
    methyl methacrylate:
    Arkema Norsocryl ® 402: Methoxy PEG 2000 Methacrylate
    Methoxy PEG
    2000 Methacrylate
    Arkema Norsocryl ® 405: Methoxy PEG 5000 Methacrylate
    Methoxy PEG
    5000 Methacrylate
    Arkema Norsocryl ® Allyl Allyl Methacrylate 96-05-9
    Methacrylate
    (AMA)
    BASF Dihydrocyclopentadienyl Dihydrocyclopentadienyl Acrylate 12542-30-2 110 204
    Acrylate
    (DCPA)
    BASF Tertiarybutyl Tertiarybutyl acrylate 1663-39-4 55 128
    acrylate (TBA)
    BASF Cyclohexyl Cyclohexyl Methacrylate 101-43-9 83 168
    Methacrylate
    (CHMA)
    BASF Tertiarybutyl Tertiarybutyl methacrylate 585-07-9 107 142
    methacrylate
    (TBMA)
    BASF tert-Butyl tert-Butyl Methacrylate low acid 585-07-9 114 142
    Methacrylate low
    acid (TBMA LA)
    BASF tert-Butyl tert-Butyl Methacrylate low 585-07-9 114 142
    Methacrylate low stabilizer
    stabilizer (TBMA
    LS)
    BASF Ureido Ureido Methacrylate 25% in MMA 86261-90-7 198
    Methacrylate 25%
    in MMA (UMA
    25%)
    BASF N,N- N,N-Dimethylaminoethyl 2867-47-2 157
    Dimethylaminoethyl Methacrylate
    Methacrylate
    (DMAEMA)
    BASF N,N- N,N-Diethylaminoethyl 105-16-8 144
    Diethylaminoethyl Methacrylate
    Methacrylate
    (DEAEMA)
    BASF tert- tert-Butylaminoethyl Methacrylate 3775-90-4 185
    Butylaminoethyl
    Methacrylate
    (TBAEMA)
    BASF Hydroxypropyl Hydroxypropyl acrylate 25584-83-2 24
    acrylate (HPA)
    BASF 2-Ethylhexyl 2-Ethylhexyl acrylate 103-11-7 50,-68 
    acrylate (2-EHA)
    BASF 4-Hydroxybutyl 4-Hydroxybutyl acrylate 2478-10-6 144
    acrylate (4HBA)
    BASF Ethyldiglycol Ethyldiglycol acrylate 7328-17-8 188
    acrylate (EDGA)
    BASF Allyl Methacrylate Allyl Methacrylate 96-05-9 52 126
    (AMA)
    BASF Behenyl Acrylate Behenyl Acrylate 4813-57-4 325
    (BEA) (C18)
    BASF Lauryl Lauryl Methacrylate 142-90-5
    Methacrylate (C12)
    (LMA) 2549-53-3
    (C14)
    2495-27-4
    (C16)
    BASF Stearyl Stearyl Methacrylate 2495-27-4
    Methacrylate (C16)
    (SMA) 32360-05-7
    (C18)
    BASF Behenyl Behenyl Methacrylate 32360-05-7
    Methacrylate (C18)
    (BEMA) 45294-18-6
    (C20)
    16669-27-5
    (C22)
    BASF Stearyl Acrylate Stearyl Acrylate 4813-57-4
    (SA) (C16)
    13402-02-3 296
    (C18)
    BASF Lauryl acrylate Lauryl acrylate 2156-97-0 −3 240
    (LA)
    Butyl acrylate (BA) Butyl acrylate 141-32-2 −43 128
    Isodecyl Acrylate Isodecyl Acrylate 1330-61-6 −60
    (IDA)
    BASF Isobutyl acrylate Isobutyl acrylate 106-63-8 128
    (IBA)
    Hydroxyethyl Hydroxyethyl acrylate 818-61-1 −15 116
    acrylate (HEA)
    2-Propylheptyl 2-Propylheptyl Acrylate high grade 149021-58-9 −7 130
    Acrylate high
    grade (2-PHA HG)
    BASF 2-Propylheptyl 2-Propylheptyl Acrylate techn. 149021-58-9 −7 130
    Acrylate techn. (2-
    PHA TG)
    Methacrylic Acid Methacrylic Acid 79-41-4 228 1.4  86
    (MAA)
    tert-Butyl tert-Butyl Methacrylate 585-07-9 107 0.93 142
    Methacrylate
    (TBMA)
    Bimax BETA-C 2-Carobxyethyl Acrylate 24615-84-7 <30 144
    Bimax BX-ADMA 1-Adamantyl Methacrylate 16887-36-8 viscous liq. 220
    Bimax BX-PTEA Phenylthioethyl Acrylate 95175-38-5 208
    Bimax BX-DMANPA Dimethylaminoneopentyl acrylate 20166-73-8 285
    Bimax BX-NASME N-Acryloyl sarcosine methyl ester 72065-23-7 157
    Bimax BX-BHPEA 2-(4-Benzoyl-3- 16432-81-8 312
    hydroxyphenoxy)ethyl acrylate
    Bimax BX-AHBP 4-Allyloxy-2-hydroxy 2549-87-3 254
    benzophenone
    Bimax BX-DCPA Dicyclopentenyl acrylate 33791-58-1 204
    Bimax BX-DCPMA Dicyclopentenyl methacrylate 51178-59-7 218
    Bimax BX-HEMA 2-Hydroxyethyl methacrylate 868-77-9 130
    Bimax BX-EOEMA 2-Ethoxyethyl methacrylate 2370-63-0 158
    Bimax BX-TFEMA Trifluoroethyl methacrylate 352-87-4 168
    Bimax BX-MAA Methacrylic acid 79-41-4  86
    Bimax HEMA-5 Polyethoxy (5) methacrylate 95%
    active
    Bimax HEMA-10 Polyethoxy (10) methacrylate 90%
    active
    Bimax BEM-25 Behenylpolyethoxy (25) waxy solid
    methacrylate 93% active
    Bimax LEM-23 Laurylpolyethoxy (23) methacrylate
    93% active
    Bimax MPEM-7 Methoxypolyethoxy (7)
    methacrylate 95% active
    Bimax MPEM-12 Methoxypolyethoxy (12)
    methacrylate 95% active
    Bimax MPEM-16 Methoxypolyethoxy (16)
    methacrylate 95% active
    Bimax Development 3-PHENOXY-2-HYDROXY
    product 2 PROPYL METHACRYLATE
    Bimax Development METHOXYETHOXYETHYL
    product 3 METHACRYLATE
    Cytec B-CEA β-carboxyethyl acrylate 24615-84-7 <30 75 144
    Cytec IBO-A Isobornyl Acrylate 5888-33-5 95 9 208
    Cytec EBECRYL 110 Oxyethylated Phenol Acrylate 56641-05-5 −8 13-27 236
    Cytec EBECRYL 113 Mono-functional aliphatic epoxy 6  90-150
    acrylate
    Cytec EBECRYL 114 2-Phenoxyethyl Acrylate 48145-04-6 5 20 max 192
    Cytec EBECRYL 1039 Urethane Mono Acrylate 20-50
    Cytec ODA-N Octyl/Decyl Acrylate 2499-59-4 −65 2-3 184
    2156-96-9 312
    Dow Glacial Acrylic Glacial Acrylic Acid 79-10-7 106 1.2  72
    Chemical Acid (GAA) 99.0%
    Dow Methyl Acrylate Methyl Acrylate 96-33-3 8 0.5  86
    Chemical (MA)
    Dow Glacial Acrylic Glacial Acrylic Acid 79-10-7 106 1.2  72
    Chemical Acid (GAA-FG)
    Floculant Grade
    99.6%
    Dow Ethyl Acrylate (EA) Ethyl Acrylate 140-88-5 −71 0.6 100
    Chemical
    Dow Butyl Acrylate (BA) Butyl Acrylate 141-32-2 −54 0.9 128
    Chemical
    Dow 2-Ethylhexyl 2-Ethylhexyl Acrylate 103-11-7 −85 1.7 184
    Chemical Acrylate (2-HEA)
    Hitachi FA-512M (500-600 ppm Dicyclopentenyloxyethyl 68586-19-6 40-50 15-20 262
    MEHQ) Methacrylate
    Hitachi FA-512MT Dicyclopentenyloxyethyl 68586-19-6 40-50 15-20 262
    (325-375 ppm Methacrylate
    PTZ + 22-28 ppm HQ)
    Hitachi FA-THFA Tetrahydrofurly Acrylate 2399-48-6 1-5 156
    Hitachi FA-BZA Benzyl Acrylate 2495-35-4 3-8 162
    Hitachi FA-THFM Tetrahydrofurfyl Methacrylate 2455-24-5  8-18 170
    Hitachi FA-BZM Benzyl Methacrylate 2495-37-6 2-3.5 (20° C.) 176
    Hitachi FA-310A Phenoxyethyl Acrylate 48145-04-6  3-13 192
    Hitachi FA-711MM Pentamethylpiperldinyl 68548-08-3 11-14 239
    Methacrylate
    Hitachi FA-314A Nonylphenoxypolyethylene Glycol 50974-47-5 120-180 452
    Acrylate
    Hitachi FA-318A Nonylphenoxypolyethylene Glycol 50974-47-5 120-180 626
    Acrylate
    Hitachi FA-511AS Dicyclopentenyl Acrylate 33791-58-1 10-15  8-18 204
    Hitachi FA-512AS Dicyclopentenyloxyethyl Acrylate 65983-31-5 10-15 15-25 248
    Hitachi FA-513M Dicyclopentanyl Methacrylate 34759-34-7 175  7-17 220
    Hitachi FA-513AS Dicyclopentanyl Acrylate 79637-74-4 120  7-17 206
    Hitachi FA-310M Phenoxyethyl Methacrylate 10595-06-9 36  3-13 206
    Hitachi FA-712HM Tetramethylpiperldinyl 31582-45-3 3-6 (60° C.) 225
    Methacrylate
    Hitachi FA-400M(100) Methoxy Polyethylene Glycol 26915-72-0 20-30 496
    Methacrylate
    Jarchem Jarchem ® LA Lauryl Acrylate 2156-97-0
    Jarchem Jarchem ® LMA Lauryl Methacrylate 142-90-5
    Jarchem Jarchem ® SA Stearyl Acrylate 4813-57-4
    Jarchem Jarchem ® SMA Stearyl Methacrylate 32360-05-7
    Kyyoeisha LIGHT ESTER BZ Benzyl methacrylate 2495-37-6 54 3
    Kyyoeisha LIGHT ESTER IB Isobutyl methacrylate 97-86-9 48 2
    Kyyoeisha LIGHT ESTER G Glycidyl methacrylate 106-91-2 46
    Kyyoeisha LIGHT ESTER S n-Stearyl methacrylate 32360-05-7 38 9
    Kyyoeisha LIGHT ESTER 2-Hydroxpropyl methacrylate 923-26-2 26 10
    HOP(N)
    Kyyoeisha LIGHT ESTER DE Diethylaminoethyl methacrylate 105-16-8 20
    Kyyoeisha LIGHT ESTER NB n-Butyl metacrylate 97-88-1 20
    Kyyoeisha LIGHT ESTER DM Dimethylaminoethyl methacrylate 2867-47-2 18 3
    Kyyoeisha EPOXY ESTER 2-hydroxy 3-phenoxy propyl 16969-10-1 17 175
    M-600A acrylate
    Kyyoeisha LIGHT Lauryl acrylate 2156-97-0 −3 4
    ACRYLATE L-A
    Kyyoeisha LIGHT ESTER 2-Hydroxypropyl acrylate 25584-83-2 −7 6
    HOP-A(N)
    Kyyoeisha LIGHT ESTER 2-Hydroxypropyl acrylate 25584-83-2 −7
    HOP-A(N)
    Kyyoeisha LIGHT ESTER EH 2-Ethyl hexyl methacrylate 688-84-6 −10 3
    Kyyoeisha LIGHT ESTER 2-Hydroxyethyl acrylate 818-61-1 −15 5
    HOA(N)
    Kyyoeisha LIGHT ESTER 2-Hydroxyethyl acrylate 818-61-1 −15
    HOA(N)
    Kyyoeisha LIGHT Phenoxy ethyl acrylate 48145-04-6 −22 13
    ACRYLATE PO-A
    Kyyoeisha LIGHT Phenoxy polyethyleneglycol 56641-05-5 −25 11
    ACRYLATE P- acrylate
    200A
    Kyyoeisha HOA-MS(N) 2-Acryloyloxy ethyl succunate 50940-49-3 −40 180
    Kyyoeisha LIGHT ESTER ID Isodecyl methacrylate 29964-84-9 −41
    Kyyoeisha LIGHT Isoamyl acrylate 4245-35-6 −45 2
    ACRYLATE IAA
    Kyyoeisha LIGHT Methoxy triethyleneglycol acrylate 32171-39-4 −50 6
    ACRYLATE MTG-A
    Kyyoeisha LIGHT ESTER L n-Lauryl methacrylate 142-90-5 −65 6
    Kyyoeisha LIGHT Ethoxy diethyleneglycol acrylate 7328-17-8 −70 5
    ACRYLATE EC-A
    Kyyoeisha HOA-MPE(N) 2-Acryloyloxy ethyl 2-hydroxy ethyl 38056-88-1 800
    phthalate
    Kyyoeisha LIGHT 2-Acryloyloxy ethyl phosphate 32120-16-4 23000
    ACRYLATE P-
    1A(N)
    Kyyoeisha HOA-MPL(N) 2-Acryloyloxy ethyl phthalate 30697-40-6 7500
    Kyyoeisha LIGHT 2-Acryloyloxyethyl hexahydro 57043-35-3 6000
    ACRYLATE HOA- phthalate
    HH(N)
    Kyyoeisha LIGHT 2-Ethyl hexyl diglycol acrylate 117646-83-0 7
    ACRYLATE
    EHDG-AT
    Kyyoeisha LIGHT 2-Hydroxy butyl acrylate 2421-27-4 9
    ACRYLATE HOB-A
    Kyyoeisha LIGHT ESTER 2-Hydroxybutyl methacrylate 13159-51-8
    HOB(N)
    Kyyoeisha LIGHT ESTER P- 2-Methacryloyloxyethyl acid 52628-03-2 5250
    1M phoshate
    Kyyoeisha LIGHT ESTER 2-Methacryloyloxyethyl 51252-88-1
    HO-HH(N) hexahydrophthalate
    Kyyoeisha LIGHT ESTER 2-Methacryloyloxyethyl succynic 20882-04-6
    HO-MS(N) acid
    Kyyoeisha LIGHT ESTER PO 2-Phenoxy ethyl methacrylate 10595-06-9 7
    Kyyoeisha LIGHT ESTER L-7 Alkyl(C12~C13) methacrylate 142-90-5/
    C12?45%, C12?55% 2495-25-2
    Kyyoeisha LIGHT Arcylate of ethyleneoxide modified 50974-47-5 100
    ACRYLATE NP- nonylphenol
    4EA
    Kyyoeisha LIGHT ESTER BC Butoxy diethyleneglycol 7328-22-5
    methacrylate
    Kyyoeisha LIGHT Methoxy dipropyleneglycol acrylate 83844-54-6 3
    ACRYLATE DPM-A
    Kyyoeisha LIGHT Methoxy polyethylenegrycol 32171-39-4 25
    ACRYLATE 130A acrylate
    Kyyoeisha LIGHT ESTER Methoxy polyethylenegrycol 26915-72-0 25
    130MA methacrylate
    Kyyoeisha LIGHT ESTER Methoxy polyethylenegrycol 26915-72-0
    041MA methacrylate
    Kyyoeisha LIGHT Neopenthylglycol benzoate 66671-22-5 70
    ACRYLATE BA- acrylate
    104
    Kyyoeisha LIGHT Phenoxy diethyleneglycol acrylate 61630-25-9 11
    ACRYLATE P2H-A
    Kyyoeisha LIGHT Stearyl acrylate 4813-57-4 9
    ACRYLATE S-A
    Kyyoeisha LIGHT Tetrahydrofurfuryl acrylate 2399-48-6 5
    ACRYLATE THF-A
    Kyyoeisha LIGHT ESTER M- Trifluoroethyl methacrylate 352-87-4 3
    3F
    Kyyoeisha LIGHT Dimethylol tricylco decane 352-87-4
    ACRYLATE DCP-A diacrylate
    Lucite Methyl Methyl Methacrylate 80-62-6 105 0.56 100
    Methacrylate
    (MMA)
    Mitsubishi Methyl Methyl Methacrylate 80-62-6 105 0.56 100
    Rayon Methacrylate
    (MMA)
    Mitsubishi Cyclohexyl Cyclohexyl Methacrylate 101-43-9 83 2.5 168
    Rayon Methacrylate
    (CHMA)
    Mitsubishi Ethyl Methacrylate Ethyl Methacrylate 97-63-2 65 0.62 114
    Rayon (EMA)
    Mitsubishi 2-Hydoxyethyl 2-Hydoxyethyl Methacrylate 868-77-9 55 6.8 130
    Rayon Methacrylate
    (HEMA)
    Mitsubishi Benzyl Benzyl Methacrylate 2495-37-6 54 2.7 176
    Rayon Methacrylate
    (BZMA)
    Mitsubishi Allyl Methacrylate Allyl Methacrylate 96-05-9 52 1.1 126
    Rayon (AMA)
    Mitsubishi iso-Butyl iso-Butyl Methacrylate 97-86-9 48 0.88 142
    Rayon Methacrylate
    (IBMA)
    Mitsubishi Glycidyl Glycidyl Methacrylate 106-91-2 46 2.5 142
    Rayon Methacrylate
    (GMA)
    Mitsubishi Hydroxypropyl Hydroxypropyl Methacrylate 27813-02-1 26 9.3 144
    Rayon Methacrylate
    (HPMA)
    Mitsubishi n-Butyl n-Butyl Methacrylate 97-88-1 20 0.92 142
    Rayon Methacrylate
    (BMA)
    Mitsubishi Diethylaminoethyl Diethylaminoethyl Methacrylate 105-16-8 16~24 1.8 185
    Rayon Methacrylate
    (DEMA)
    Mitsubishi Dimethylaminoethyl Dimethylaminoethyl Methacrylate 2867-47-2 18 1.3 157
    Rayon Methacrylate
    (DMMA)
    Mitsubishi 2-Ethylhexyl 2-Ethylhexyl Methacrylate 688-84-6 −10 1.85 198
    Rayon Methacrylate
    (EHMA)
    Mitsubishi 2-Ethoxyethyl 2-Ethoxyethyl Methacrylate 2370-63-0 −31 3.5 158
    Rayon Methacrylate
    (ETMA)
    Mitsubishi Tridecyl Tridecyl Methacrylate 2495-25-2 −46 5.8 268
    Rayon Methacrylate
    (TDMA)
    Mitsubishi Alkyl Methacrylate Alkyl Methacrylate 142-90-5 −62 5.1 263 (avg)
    Rayon (SLMA) 2495-25-2
    Mitsubishi Lauryl Lauryl Methacrylate 142-90-5 −65 4.6 255
    Rayon Methacrylate
    (LMA)
    Mitsubishi Stearyl Stearyl Methacrylate 32360-05-7 −100 8.2 339
    Rayon Methacrylate (@30° C.)
    (SMA)
    Mitsubishi 2-Methoxyethyl 2-Methoxyethyl Methacrylate 6976-93-8 144
    Rayon Methacrylate
    (MTMA)
    Mitsubishi Tertahydrofurfuryl Tertahydrofurfuryl Methacrylate 2455-24-5 170
    Rayon Methacrylate
    (THFMA)
    MRC Unitec TBCHMA 4-tbutylcyclohexyl methacrylate 46729-07-1 224
    MRC Unitec MBP 4-methacryloxyoxybenzophenone 56467-43-7 solid 266
    MRC Unitec MEU 2- 3089-23-4 solid 255
    (methacryloxyoxyaceamidoethylene)N,
    N′-ethyleneurea
    Nippon (CHDMMA) 1,4-Cyclohexanedimethanol 23117-36-4 18 88 198
    Kasei Monoacrylate
    Nippon (4HBAGE) 4-Hydroxybutyl Acrylate 119692-59-0 −64 7 200
    Kasei Glycidylether
    Nippon (4HBA) 4-Hydroxybutyl Acrylate 2478-10-6 −40 10.2 144
    Kasei
    Osaka IBXA Iso-Bornyl Acylate 5888-33-5 97 7.7 208
    Organic
    Chemicals
    Osaka Viscoat 3FM 2,2,2-Trifluoroethyl Methacrylate 352-87-4 81 1 168
    Organic
    Chemicals
    Osaka TBA (C4) Tert.-butyl Acrylate 1663-39-4 41 1.3 128
    Organic
    Chemicals
    Osaka Viscoat 8FM 1H,1H,5H-Octafluoropentyl 355-93-1 36 4.1 300
    Organic Methacrylate
    Chemicals
    Osaka STA (C18) Stearyl Acrylate 4813-57-4 30 8.6 325
    Organic (30° C.)
    Chemicals
    Osaka CHDOL-10 Cyclohexanesppiro-2-(1,3-dioxate- 97773-09-6 22 16.9 154
    Organic 4-yl) Methyl Acrylate
    Chemicals
    Osaka LA (C12) Lauryl Acrylate 2156-97-0 15 4 240
    Organic
    Chemicals
    Osaka Viscoat#155 Cyclohexyl Acrylate 3066-71-5 15 2.5 154
    Organic (CHA)
    Chemicals
    Osaka Viscoat#160 (BZA) Benzyl Acrylate 2495-35-4 6 8 162
    Organic
    Chemicals
    Osaka OXE-30 3-Ethyl-3-oxetanyl Methacrylate 37674-57-0 2 4.1 192
    Organic
    Chemicals
    Osaka OXE-10 3-Ethyl-3-oxanylmethyl Acrylate 41988-14-1 4.3 162
    Organic
    Chemicals
    Osaka GBLMA gamma-Butylolactone 195000-66-9 Mp = 22-24 170
    Organic Methacrylate
    Chemicals
    Osaka Viscoat 3F 2,2,2-Trifluoroethyl Acrylate 407-47-6 −5 1.1 154
    Organic
    Chemicals
    Osaka Viscoat#150 Tetrahydofurfuryl Acrylate 2399-48-6 −12 2.8 156
    Organic (THFA)
    Chemicals
    Osaka Viscoat 8F 1H,1H,5H-Octafluoropentyl 376-84-1 −35 3.1 286
    Organic Acrylate
    Chemicals
    Osaka Viscoat 4F 2,2,3,3-Tetrafluropropyl Acrylate 7283-71-3 1.9 186
    Organic
    Chemicals
    Osaka HPA 2-hydroxypropyl Acrylate 25584-83-2999- −7 4.1 130
    Organic 61-1
    Chemicals
    Osaka MEDOL-10 (2-Ethyl-2-methyl-1,3-dioxolate-4- 69701-99-1 −7 5.1 208
    Organic yl) Methyl Acrylate
    Chemicals
    Osaka HEA Hydroxyethyl Acrylate 818-61-1 −15 5.9 116
    Organic
    Chemicals
    Osaka ISTA (C18) Iso-Steryl Acrylate 93841-48-6 −18 17 325
    Organic
    Chemicals
    Osaka Viscoat#192 (PEA) Phenoxyethyl Acrylate 48145-04-6 −22 8.7 192
    Organic
    Chemicals
    Osaka 4-HBA 4-hydroxybutyl Acrylate 10/6/2478 −32 5.5 144
    Organic
    Chemicals
    Osaka 2-MTA 2-Methoxyethyl Acrylate 3121-61-7 −50 1.5 130
    Organic
    Chemicals
    Osaka IOAA (C8) Iso-Octyl Acylate 29590-42-9 −58 2-4 184
    Organic
    Chemicals
    Osaka INAA (C9) Iso-Nonyl Acrylate 51952-49-9 −58 198
    Organic
    Chemicals
    Osaka NOAA (C8) N-Ocyl Acrylate 2499-59-4 −65 184
    Organic
    Chemicals
    Osaka Viscoat 190 Ethoxyethoxyethyl Acrylate 7328-17-8 −67 2.9 188
    Organic (EOEOEA, CBA)
    Chemicals
    Osaka Viscoat MTG Methoxytriethyleneglycol Acrylate 48067-72-7 218
    Organic
    Chemicals
    Osaka MPE400A Methoxypolyethyleneglycol 32171-39-4 25-30 470
    Organic Acrylate
    Chemicals
    Osaka MPE550A Methoxypolyethyleneglycol 32171-39-4 50-60 620
    Organic Acrylate
    Chemicals
    Osaka GBLA gamma-Butylolactone Acrylate 328249-37-2 156
    Organic
    Chemicals
    Osaka V#2100 acid functional acrylate 121915-68-2  5,000-10,000 278
    Organic
    Chemicals
    Osaka V#2150 acid functional acrylate 61537-62-0 8,200 284
    Organic
    Chemicals
    Osaka Viscoat#315 Structure only (Bis-F, PEG 170 226 + 44n
    Organic acrylate)
    Chemicals
    Polysciences 24891-100 Beta-Carboxyethyl Acrylate, >98% 24615-84-7 144
    Active
    Polysciences 02092-5 Cinnamyl methacrylate 31736-34-2 202
    Polysciences 22493-100 iso-Decyl methacrylate, min. 90% 29964-84-9 226
    Polysciences 24897-250 Methacrylic Acid, 99.9% 79-41-4  86
    Polysciences 24360-10 o-Nitrobenzyl methacrylate, min.
    95%
    Polysciences 06344-10 Pentabromophenyl acrylate 52660-82-9 solid 542
    Polysciences 04253-10 Pentabromophenyl methacrylate 18967-31-2 solid 557
    Polysciences 06349-5 Pentafluorophenyl acrylate 71195-85-2 238
    Polysciences 06350-5 Pentafluorophenyl methacrylate, 13642-97-2 252
    95%
    Polysciences 16712-100 Poly(ethylene glycol) (n) 25736-86-1 MW of
    monomethacrylate PEG
    Block =
    200
    Polysciences 16713-100 Poly(ethylene glycol) (n) 25736-86-1 MW of
    monomethacrylate PEG
    Block =
    400
    Polysciences 16664-500 Poly(ethylene glycol) (n) 26915-72-0 MW of
    monomethyl ether PEG
    monomethacrylate Block =
    200
    Polysciences 15934-250 Poly(propylene glycol) (300) 39240-45-6 MW of
    monomethacrylate PEG
    Block
    ~370
    Polysciences 06127-10 tert-Amyl Methacrylate 2397-76-4 156
    Polysciences 03057-10 Tribromoneopentyl methacrylate CASRN03057 393
    Polysciences 18556-500 Triethylene glycol monoethyl ether 39670-09-2 246
    monomethacrylate
    Polysciences 02544-25 Undecyl methacrylate 16493-35-9 240
    San Esters ADMA 1-Adamantyl Methacrylate 16887-36-8 220
    San Esters MADMA 2-Methyl-2-Adamantyl 177080-67-0 234
    Methacrylate
    San Esters MADA 2-Methyl-2-Adamantyl Acrylate 249562-06-9 220
    San Esters EtADA 2-Ethyl-3-Adamantyl Acrylate 303186-14-3 234
    San Esters EtADMA 2-Methyl-2-Adamantyl Acrylate 209982-56-9 Solid 220
    San Esters ADA 1-Adamantyl Acrylate 121601-93-2 Solid 206
    Sartomer SR423A Isobornyl Methacrylate 7534-94-3 110 11
    Sartomer SR506A Isobornyl Acrylate 5888-33-5 95 8
    Sartomer SR340 2-Phenoxyethyl Methacrylate 10595-06-9 54 10 206
    Sartomer CD535 Dicyclopentandienyl Methacrylate 31621-69-9 45 8 218
    Sartomer CD590 Aromatic Acrylate Monomer proprietary 38 180
    Sartomer SR324 Stearyl Methacrylate 32360-05-7 38 14 338
    2495-27-4
    (33%)
    Sartomer SR257 Stearyl Acrylate 4813-57-4 35 MP = 24 324
    Sartomer CD420 Acrylic Monomer Proprietary 29 6
    Sartomer SR531 Cyclic Trimethylpropane Formal 66492-51-1 10 15 200
    Acrylate 15625-89-5
    (5% tri-
    acrylate)
    Sartomer CD588 Acrylate Ester proprietary 6 7
    Sartomer SR339 2-Phenoxyethyl Acrylate 48145-04-6 5 12 192
    Sartomer CD9087 Alkoxylated Phenol Acrylate proprietary −24 24
    Sartomer SR285 Tetrahydrofurfuryl Acrylate 2399-48-6 −28 6 156
    Sartomer SR335 Lauryl Acrylate −30
    Sartomer CD9088 Alkoxylated Phenol Acrylate proprietary −40 65
    Sartomer SR493D Tridecyl Methacrylate 2495-25-2 −40 6 268
    Sartomer SR242 Isodecyl Methacrylate 29964-84-9 −41 5 226
    Sartomer CD9075 Alkoxylated Lauryl Acrylate proprietary −45 24
    Sartomer CD553 Methoxy Polyethylene Glycol (550) 32171-39-4 −50 50 693
    Monoacrylate 9004-74-4
    Sartomer SR484 Octadecyl Acrylate 2499-99-4 −50 4 203
    2156-96-9
    Sartomer CD611 Alkoxylated Tetrahydrofurfuryl proprietary −51 11
    Acylate
    Sartomer SR495B Caprolactone Acrylate 110489- −53 80 344
    0509 818-
    61-1
    Sartomer SR256 2(2-Ethoxyethoxy)-Ethyl Acrylate 7328-17-8 −54 6 188
    Sartomer SR440 Iso-Octyl Acrylate 29590-42-9 −54 5 184
    Sartomer SR440A Iso-Octyl Acrylate (high purity) 29590-42-9 −54 5 184
    Sartomer SR489D Tridecyl Acrylate 3076-04-8 −55 7 255
    Sartomer CD551 Methoxy Polyethylene Glycol (350) 32171-39-4 −57 22 550
    Monoacrylate 9004-74-4
    (2% di
    funct.)
    Sartomer SR395 Isodecyl acrylate 1330 −60 5 212
    Sartomer SR550 Methoxy Polyethylene Glycol (350) 26915-72-0 −62 100 450
    Monomethacrylate 9004-74-4
    (2%)
    Sartomer CD552 Methoxy Polyethylene Glycol (550) 26915-72-0 −65 39 693
    Monomethacrylate 9004-74-
    4 (2% di
    funct.)
    Sartomer SR313A Lauryl Methacrylate 142-90-5 −65 6 254
    Sartomer SR313B C12 C14 Alkyl Methacrylate 142-90-5 −65 6 254
    2549-53-3
    2495-27-4
    Sartomer SR313D C12 C14 Alkyl Methacrylate 142-90-5 −65 6 254
    2549-53-3
    2495-27-4
    Sartomer CD278 Acrylate Ester proprietary −74 5
    Sartomer CD545 Diethylene Glycol Methyl Ether 45103-58-0 3
    Methacrylate 111-77-
    3 (1% di
    funct.)
    Sartomer CD585 Acrylic Ester proprietary 8
    Sartomer CD586 Acrylic Ester proprietary 6-9 (38° C.)
    Sartomer CD587 Acrylic Ester proprietary solid
    (MP = 55° C.)
    Sartomer CD591 Acrylic Ester proprietary 20
    Sartomer CD613 Ethoxylated Nonyl Phenol Acrylate 678991-31- 75
    6 68412-54-
    4 (5-10%)
    Sartomer CD730 Triethylene Glycol Ethyl Ether proprietary 6
    Methacrylate

Claims (15)

    What is claimed:
  1. 1. A cross linkable sealant composition, prepared from:
    a cross linkable elastomeric oligomer having a Tg;
    a monomer having a Tg higher than the elastomeric oligomer Tg or a combination of monomers having an average Tg for the combination higher than the elastomeric oligomer Tg;
    an initiator or cross-linking agent; and
    optionally at least one of catalyst; filler; antioxidant; reaction modifier; adhesion promoter; diluent and coloring agent;
    wherein a cured reaction product of the composition has a single Tg and retains a higher sealing force at temperatures above the cured product Tg as compared to a similar composition made as above without the monomer.
  2. 2. The composition of claim 1 wherein the cross linkable elastomeric oligomer comprises reactive moieties adjacent each end and the oligomer backbone comprises polyisobutylene.
  3. 3. The composition of claim 1 wherein the cross linkable elastomeric oligomer backbone comprises about 1% to about 100% polyisobutylene.
  4. 4. The composition of claim 1 wherein the cross linkable elastomeric oligomer has spacing between reactive moieties to provide the oligomer with elastomeric properties.
  5. 5. The composition of claim 1 wherein the cross linkable elastomeric oligomer is a telechelic, (meth)acrylate terminated polyisobutylene.
  6. 6. The composition of claim 1 wherein the monomer is reacted to the cross linkable elastomeric oligomer.
  7. 7. The composition of claim 1 wherein cured reaction products are free of first and second order thermodynamic transitions as shown by DSC.
  8. 8. A method of increasing the low temperature sealing force of a cured elastomeric sealant comprising:
    providing a cross linkable sealant composition, prepared from a cross linkable elastomeric oligomer, an initiator or cross-linking agent, and optionally at least one of catalyst, filler, antioxidant, reaction modifier, and coloring agent; wherein cured reaction products of the sealant composition have a Tg; and
    adding about 10 to about 30% by weight of sealant composition of a monomer having a Tg higher than the elastomeric oligomer Tg or a combination of monomers having an average Tg for the combination higher than the elastomeric oligomer Tg to form an improved sealant composition;
    wherein cured reaction products of the improved sealant composition have a single Tg and have a higher sealing force at temperatures between their Tg and 0° C. than cured reaction products of the sealant composition.
  9. 9. A component defining an internal chamber, comprising:
    a first predetermined sealing surface in fluid communication with the chamber;
    a second predetermined sealing surface aligned with the first sealing surface and in fluid communication with the chamber; and
    a cured reaction product of the composition of claim 1 disposed between the first and second predetermined sealing surfaces and sealing the chamber.
  10. 10. The component of claim 9 wherein the first sealing surface and the second sealing surface do not move in relationship to each other.
  11. 11. The component of claim 9 wherein the reaction product is adhesively bonded to only one of the first and second sealing surfaces.
  12. 12. The component of claim 9 wherein the reaction product is adhesively bonded to both the first and second sealing surfaces.
  13. 13. The component of claim 9 wherein the reaction product is liquid injection molded or molded on the sealing surface.
  14. 14. A method of using the curable composition of claim 1 as a liquid gasketing composition, comprising:
    providing the composition of claim 1;
    dispensing the composition onto a first predetermined sealing surface,
    aligning the first predetermined sealing surface and dispensed composition with a second predetermined sealing surface; and
    exposing the dispensed the composition to conditions appropriate to effect cure thereof, wherein cured reaction products of the composition have a single Tg and retain a positive sealing force at temperatures above the cured product Tg.
  15. 15. The method of claim 14 wherein the composition is cured while in contact with the first and second sealing surfaces.
US13796588 2011-04-27 2013-03-12 Curable elastomer compositions with low temperature sealing capability Abandoned US20130287980A1 (en)

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US201161479710 true 2011-04-27 2011-04-27
PCT/US2012/035094 WO2012149091A3 (en) 2011-04-27 2012-04-26 Curable elastomer compositions with low temperature sealing capability
US13796588 US20130287980A1 (en) 2011-04-27 2013-03-12 Curable elastomer compositions with low temperature sealing capability

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US13796588 US20130287980A1 (en) 2011-04-27 2013-03-12 Curable elastomer compositions with low temperature sealing capability
US14682251 US10005919B2 (en) 2011-04-27 2015-04-09 Curable elastomer compositions with low temperature sealing capability

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JP2014517857A (en) 2014-07-24 application
US20150210882A1 (en) 2015-07-30 application
CN103492504A (en) 2014-01-01 application
KR20140045929A (en) 2014-04-17 application
WO2012149091A3 (en) 2013-01-17 application
EP2702112A4 (en) 2015-01-21 application
EP2702112A2 (en) 2014-03-05 application
JP2017206675A (en) 2017-11-24 application
WO2012149091A2 (en) 2012-11-01 application
US10005919B2 (en) 2018-06-26 grant
CN103492504B (en) 2017-06-23 grant

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