US20060178456A1 - Surface improver for reinforced composite compositions - Google Patents

Surface improver for reinforced composite compositions Download PDF

Info

Publication number
US20060178456A1
US20060178456A1 US10/512,802 US51280205A US2006178456A1 US 20060178456 A1 US20060178456 A1 US 20060178456A1 US 51280205 A US51280205 A US 51280205A US 2006178456 A1 US2006178456 A1 US 2006178456A1
Authority
US
United States
Prior art keywords
composition
weight
epoxide
parts
epoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/512,802
Other languages
English (en)
Inventor
Robert Seats
Carroll Reid
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ineos Composites IP LLC
Original Assignee
Ashland Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ashland Inc filed Critical Ashland Inc
Priority to US10/512,802 priority Critical patent/US20060178456A1/en
Assigned to ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC reassignment ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ASHLAND INC.
Publication of US20060178456A1 publication Critical patent/US20060178456A1/en
Priority to US12/288,656 priority patent/US7834101B2/en
Priority to US12/899,083 priority patent/US7989557B2/en
Assigned to ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC reassignment ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE PATENT NUMBER 6763859 PREVIOUSLY RECORDED ON REEL 016408 FRAME 0950. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Assignors: ASHLAND INC.
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22Di-epoxy compounds
    • C08G59/226Mixtures of di-epoxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32Epoxy compounds containing three or more epoxy groups
    • C08G59/38Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04Epoxynovolacs
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/06Triglycidylisocyanurates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06Unsaturated polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/15Heterocyclic compounds having oxygen in the ring
    • C08K5/151Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515Three-membered rings

Definitions

  • the present invention relates to surface improver compositions useful in thermosetting compositions, for instance, unsaturated polyester and vinylester based molding compounds. It also relates to the thermosetting compositions containing the surface improver compositions.
  • thermosetting compositions such as polyester and vinyl ester based reinforced composites
  • molded composites do not present as smooth a surface as metals.
  • the invention is a composition comprising a blend of two or more epoxide containing compositions selected from epoxidized vegetable oils, epoxidized alkyl esters or cycloaliphatic epoxides.
  • the invention is a blend of one or more epoxidized vegetable oils, epoxidized alkyl esters, or cycloaliphatic epoxides with one or more aromatic epoxides or epoxy functionalized polyoxyalkylene polyols.
  • compositions containing compositions selected from epoxidized vegetable oils, epoxidized alkyl esters and cycloaliphatic epoxides means that two compositions are selected from one, or more than one, of the listed categories.
  • composition in this context means that the selected material may be a mixture of compounds.
  • the epoxy composition comprises greater than 50 percent by weight of one or more epoxy compositions comprising epoxidized vegetable oils, epoxidized alkyl esters or cycloaliphatic epoxides and 50 percent by weight or less of aromatic epoxides or epoxy functionalized polyoxyalkylene polyols.
  • the invention is an epoxy resin composition
  • an epoxy resin composition comprising two or more epoxy resin compositions selected from the group of epoxidized vegetable oil compositions, epoxidized alkyl ester compositions, cycloaliphatic epoxide compositions, aromatic epoxide compositions and polyoxyalkylene oxide compositions wherein the composition has an average oxirane number of 8.8 or less and a viscosity of ⁇ 1000 (1.0 Pa ⁇ s) cps or less
  • the invention is a composition comprising a blend of two or more epoxide compositions wherein at least one is selected from epoxidized vegetable oils, epoxidized alkyl esters, or cycloaliphatic epoxides and at least one may be selected from an aromatic epoxide or an epoxidized polyoxyalkylene polyol wherein the average oxirane number is 8.8 or less and the viscosity is 1000 centipoise (1 Pa ⁇ s) or less.
  • a more preferred epoxy resin composition comprises in one part epoxidized linseed oil and/or octyl epoxytallate and a liquid epoxy resin.
  • the first part is present in an amount of 50 percent by weight or greater of the composition.
  • the epoxy composition comprises a blend of epoxidized linseed oil and octyl epoxytallate.
  • the two epoxy components are present in a weight ratio of 3:1 to 1:3, and most preferably 1:1.
  • the epoxy compositions of the invention are useful as additives in surface improvers used in unsaturated thermosetting resin compositions, such as polyester and vinyl ester resin based compositions.
  • the invention is a novel composition useful as a surface improver for unsaturated thermosetting resin compositions which composition comprises an epoxy resin composition of this invention, a thermoplastic additive comprising a thermoplastic polymer, preferably having a weight average molecular weight of from 10,000 to 400,000 g/g mole; and a compound capable of dissolving the thermoplastic additive and epoxy composition.
  • a crosslinking monomer capable of copolymerizing with unsaturated thermosetting resins.
  • the surface improver composition comprises 25 parts to 45 parts by weight and preferably 30 to 40 parts of 100 parts of components a), b) and c).
  • the invention comprises molded parts comprising components a), b) and c), wherein the surface of the molded object has improved surface smoothness as compared to molded parts which do not contain part c).
  • Blends of epoxy compounds of the invention such as a blend of epoxidized linseed oil and octyl epoxytallate, when used in a thermosetting composite, such as polyester or vinyl ester based reinforced composite, provide improved surface smoothness of a molded panel of said composition. Additionally a 50/50 blend of two epoxy compounds provide better surface smoothness than either epoxy compound alone or other blend ratios.
  • the surface improver composition comprises a thermoplastic additive present in an amount from 12 to 35 parts by weight, preferably from 16 to 30 parts by weight, and more preferably from 20 to 27 parts by weight; an epoxy composition present in an amount from 12 to 25 parts by weight, preferably from 32 to 23 parts by weight, and more preferably from 10 to 16 parts by weight; a crosslinking monomer present in an amount from 40 to 87 parts by weight, preferably from 47 to 81 parts by weight, and more preferably from 57 to 70 parts by weight wherein there are 100 total parts by weight. Weights are based on the weight of the thermoplastic additive, epoxy composition, and crossliking monomer. Preferably, the amount of each component is chosen so as to form a single phase system.
  • the unsaturated thermosetting resins suitable for use in accordance with the present invention include those unsaturated polymeric materials which can be crosslinked to form thermoset articles.
  • the unsaturated thermosetting resins have an average molecular weight of at least 500, preferably from 500 to 10,000 grams per gram mole (“g/gmole”).
  • average molecular weight means weight average molecular weight. Methods for determining weight average molecular weight are known to those skilled in the art. One preferred method for determining weight average molecular weight is gel permeation chromatography.
  • Typical unsaturated thermosetting resins include, for example, polyesters, vinyl esters, epoxy diacrylates, polyester diacrylates, polyurethane diacrylates, acrylate capped polyurethane polyacrylates, acrylated polyacrylates, acrylated polyethers and the like.
  • Especially preferred thermosetting resins include polyesters and vinyl esters.
  • the term “polyesters” includes vinyl esters.
  • Such unsaturated thermosetting resins are commercially available or alternatively can be readily prepared by those skilled in the art. Examples of suitable unsaturated thermosetting resins for use in accordance with the present invention are described for example in U.S. Pat. Nos. 4,172,059 and 4,942,001, incorporated herein by reference.
  • One or more unsaturated thermosetting resins may be employed in the molding compositions of the present invention.
  • the total amount of unsaturated thermosetting resins in the molding compositions of the present invention is typically from 15 to 80 parts by weight, preferably from 20 to 60 parts by weight, and more preferably from 25 to 50 parts by weight based on the weight of the unsaturated thermosetting resin, thermoplastic additive, epoxide composition and crosslinking monomer. Further details concerning the selection and amounts of unsaturated thermosetting resins are known to those skilled in the art.
  • the crosslinking monomers suitable for use in accordance with the present invention include materials which are copolymerizable with the unsaturated thermosetting resins.
  • the crosslinking monomer also serves the function of dissolving the thermosetting resin thereby facilitating its interaction with the other components of the molding composition.
  • the monomer contains olefinic unsaturation, more preferably ethylenic unsaturation.
  • Typical olefinically unsaturated monomers include, for example, styrene, vinyl toluene isomers, methyl methacrylate, acrylonitrile and substituted styrene such as, for example, chlorostyrene and alphamethylstyrene.
  • Multifunctional monomers such as, for example, divinylbenzene or multifunctional acrylates or methacrylates may also be employed.
  • Styrene is a preferred monomer for use in the compositions of the present invention.
  • One or more crosslinking monomers may be used in the molding compositions of the present invention.
  • the total amount of the crosslinking monomer is from 20 to 80 parts by weight, preferably from 30 to 65 parts by weight, and more preferably from 40 to 55 parts by weight based on the weight of the unsaturated thermosetting resin, thermoplastic additive, epoxy resin composition and crosslinking monomer.
  • Such monomers are readily commercially available. Further details concerning the selection and amounts of the crosslinking monomers are known to those skilled in the art.
  • thermoplastic additives may be employed in the molding compositions of the present invention.
  • the total amount of the thermoplastic additive is from 3 to 30 parts, preferably from 5 to 25 parts, and more preferably from 8 to 20 parts based on the weight of the unsaturated thermosetting resin, thermoplastic additive, epoxide composition and crosslinking monomer.
  • thermoplastic additives suitable for use in accordance with the present invention are described, for example, in U.S. Pat. No. 4,172,059, incorporated herein by reference. Such thermoplastic additives are commercially available or alternatively can be prepared by those skilled in the art. Further details concerning the selection and amounts of the thermoplastic additives are known to those skilled in the art.
  • the average molecular weights of the thermoplastic additives of the present invention are 10,000 g/gmole or greater, preferably 25,000 or greater, more preferably from 50,000 or greater and most preferably 80,000 or greater.
  • the average molecular weights are preferably 400,000 g/gmole or less, more preferably 300,000 or less, even more preferably 250,000 or less and most preferably 200,000 or less.
  • These thermoplastic additives can be used in conjunction with lower molecular weight materials which can enhance their shrinkage control ability such as epoxies, lower reactivity secondary monomers and others. Examples of such approaches are disclosed in U.S. Pat. Nos. 4,525,498, 4,755,557, and 4,374,215, incorporated herein by reference.
  • the epoxy compounds of this invention can be based on aliphatic, cycloaliphatic, or aromatic backbones.
  • Preferred epoxy resins are liquid at room temperature.
  • One class of preferred epoxy resins are epoxidized vegetable oils. Vegetable oils are naturally occurring triglycerides (triesters of glycerol and mixed unsaturated fatty acids). Among preferred vegetable oils are linseed oil, soybean oil, safflower oil, corn oil, cottonseed oil, rapeseed oil and peanut oil. These oils can be epoxidized at unsaturated sites to produce epoxidized vegetable oils using processes well known to those of average skill in the art. More preferred vegetable oils are soybean and linseed oil, with linseed oil most preferred. Synthetic versions or refined versions of these epoxidized vegetable oils may be used in the invention.
  • Epoxidized alkyl esters are epoxidized versions of natural esters of fatty acids.
  • Preferred epoxidized alkyl esters are derived from alkyl esters of oleic or tall oil fatty acids or from alkyl epoxy stearates.
  • a more preferred class are the epoxidized tall oil fatty acids, commonly referred to epoxy tallates. Synthetic or refined versions of epoxidized alkyl esters may be used in this invention.
  • Cycloaliphatic epoxides as used herein refer to epoxy compositions containing compounds having cycloaliphatic resins with an oxirane ring attached or fused to the cycloaliphatic ring.
  • the oxirane ring is fused to the cycloaliphatic ring.
  • a more preferred cycloaliphatic ring is an epoxy cyclohexane (epoxy cyclohexyl) which is represented by the formula
  • Preferred cycloaliphatic epoxide containing compositions contain compounds with an average of one or more, preferably on average of two or more cycloaliphatic moieties with epoxide groups fused or attached.
  • preferred cycloaliphatic epoxides are 3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexane-carboxylate, available from The Dow Chemical Company under the trade designation ERL-4221E; bis(3,4-epoxycyclohexyl methyl) adipate available from The Dow Chemical Company under the trade designation ERL-4299 and 1,2-Epoxy-4-vinylcyclohexane available from The Dow Chemical Company.
  • Aromatic epoxides as used herein refer to compositions containing compounds having aromatic moieties with epoxide moieties attached thereto.
  • aromatic epoxides are novolac and bisphenol based aromatic epoxides.
  • preferred bisphenol resins useful in this invention are those disclosed in U.S. Pat. No. 5,308,895 at column 8, line 6 and represented by Formula 6. Relevant portions of such patent are incorporated herein by reference.
  • the aromatic epoxide is a liquid epoxy resin.
  • the most preferred aromatic epoxy resins are bisphenol-A and bisphenol-F based epoxy resins.
  • the epoxide terminated polyoxyalkylene polyols comprise compositions containing compounds wherein a polyoxyalkylene chain is functionalized with one or more epoxide moieties.
  • the polyoxyalkylene chains are preferably prepared from one or more alkylene oxides.
  • Representative examples of polyalkylene based epoxy resins are those described in U.S. Pat. No. 5,308,895 at column 8, line 9 and formula 9 and the description thereof following. Relevant portions of such description are incorporated herein by reference.
  • the polyoxyalkylene epoxide is derived from an ethylene oxide, propylene oxide or a mixture thereof.
  • the compositions of the invention preferably comprise a mixture of two or more epoxide compositions where at least two are selected from different groups comprising epoxidized vegetable oils, epoxidized alkyl esters and cycloaliphatic epoxides.
  • a most preferred blend is a blend of an epoxidized vegetable oil and an epoxidized alkyl ester.
  • at least one of the epoxides in the composition is an epoxidized vegetable oil.
  • all of the epoxides contained in the compositions are selected from epoxidized vegetable oil, epoxidized alkyl esters and cycloaliphatic epoxides.
  • the blend of epoxides used contains an epoxidized vegetable oil and most preferably epoxidized linseed oil.
  • the blend of epoxide compositions comprises at least 25 percent by weight of at least 2 epoxide compositions, based on the weight of the epoxide compositions, and more preferably 33 percent by weight of at least two epoxide compositions and most preferably 45 percent by weight or greater least two epoxide compositions.
  • the epoxide composition blend contains no more than 75 percent of one of the epoxide compositions, based on the weight of the epoxide compositions, and more preferably no more than 67 percent by weight of one epoxide composition and even more preferably no more than 55 percent by weight or less.
  • the epoxide blend is a blend of 50 percent of one epoxide composition and 50 percent of a second epoxide composition.
  • the preferred concentration of total epoxy compounds is 1 to 25 parts per hundred parts of the epoxy composition thermosetting resin, crosslinking monomer and thermoplastic additive, more preferred 2 to 10 parts per hundred parts and even more preferred 3 parts to 8 parts per hundred parts.
  • Thickening agents may also be employed in the compositions of the invention. Such materials are known in the art and include the oxides and hydroxides of the metals of Group I, II and III of the Periodic Table. Examples of preferred thickening agents include magnesium oxide, calcium oxide, calcium hydroxide, zinc oxide, barium oxide, magnesium hydroxide and the like, including mixtures of the same. Thickening agents are normally employed in proportions of from bout 0.1 to 6 weight percent based on the weight of the thermosetting resin, crosslinking monomer, thermoplastic additive and epoxide composition.
  • a dual thickening system may be employed wherein, for example, a metallic oxide or hydroxide and polyisocyanate in amounts of polyisocyanate sufficient to react with at least thirty percent of the hydroxyl groups but not more than one hundred and five percent of the hydroxyl groups present and an amount of metallic oxide or hydroxide sufficient to react with at least thirty percent of the carboxyl groups but not more than seventy-five percent of the carboxyl groups present.
  • the fiber reinforcements which are often employed in the molding compositions of the invention can be, for example, any of those known to the art for use in molding compositions. Examples of such materials are glass fibers or fabrics, carbon fibers and fabrics, asbestos fibers or fabrics, various organic fibers and fabrics such as those made of polypropylene, acrylonitrile/vinyl chloride copolymer, and others known to the art. These reinforcing materials are typically employed in the molding compositions at a level of from 5 to 80 weight parts, based on the total weight of the composition and preferably 15 to 50 weight parts.
  • the molding compositions of the present invention also frequently contain pigment.
  • the amount of pigment may vary widely, depending on the particular molding composition and pigment used.
  • the pigment is typically employed in the range of 0.5 to 15 weight parts based on the total weight of the composition.
  • the molding compositions of the invention may also contain one or more other conventional additives, which are employed for their known purposes in the amounts known to those skilled in the art.
  • additives which are employed for their known purposes in the amounts known to those skilled in the art.
  • the following are illustrative of such additives:
  • Polymerization initiators such as t-butyl hydroperoxide, t-butyl perbenzoate, benzoyl peroxide, t-butyl peroctoate, cumene hydroperoxide, methyl ethyl ketone peroxide, peroxy ketals, and others known to the art, to catalyze the reaction between the olefinically unsaturated monomer and the thermosetting resin.
  • the polymerization initiator is employed in a catalytically effective amount, such as from 0.3 to 3 parts, based on the weight of the unsaturated thermosetting resin, thermoplastic additive, and crosslinking monomer.
  • Fillers such as clay, alumina trihydrate, silica, calcium carbonate, and others known to the art;
  • Mold release agents or lubricants such as zinc stearate, calcium stearate, and others known to the art, and
  • One especially preferred molding composition in accordance with the present invention comprises:
  • the molding compositions of the present invention can be prepared by methods known to those skilled in the art, such as for example, mixing the components in a suitable apparatus such as Hobart mixer at temperatures on the order of 20° C. to 50° C.
  • the components may be combined in any convenient order.
  • the thermosetting resin and thermoplastic additive are added in liquid form by preparing a solution thereof in the crosslinking monomer. All the liquid components are then typically mixed together before adding the fillers, thickening agents and optional ingredients.
  • the molding compositions can be molded into thermoset articles of the desired shape, for example, automotive fenders, hoods, bathtubs, doors, and the like.
  • the specific conditions used in the molding process depend on the composition being molded as well as upon the nature of the particular articles desired, the details of which are known to those skilled in the art.
  • the molding compositions are suitable for use, for example, as sheet molding compounds and bulk molding compounds, with sheet molding compounds being more typical.
  • sheet molding compound can be produced by laying down a first layer of the molding composition, that is, paste, on a first layer of polyethylene film or the equivalent thereof, laying on this first layer of the paste filler reinforcements such as chopped glass fibers, and laying thereover a second layer of the paste. The two layers of the paste with the filler reinforcements sandwiched therebetween are then topped with a second sheet of polyethylene film and the resulting composite (sheet molding compound) is stored. Further details concerning the manufacture, handling and use of sheet molding compounds and bulk molding compounds are known to those skilled in the art.
  • S342 is a highly reactive unsaturated polyester resin sold by Alpha Owens Corning and is used for automotive SMC applications.
  • BMC stands for bulk molding composition.
  • CM-2015 is a 35 percent carbon black pigment dispersion available from Plasticolors, Inc., Ashtabula, Ohio.
  • Modifier E is a 5 percent solution of parabenzoquinone in diallylphthalate.
  • Luperox P is a 98 percent solution of t-butylperoxy benzoate sold by Elf Atochem North America, Philadelphia Pa.
  • VR-3 is a viscosity reducer for SMC/BMC sold by The Dow Chemical Company, Midland Mich.
  • Maglite D is a technical grade magnesium oxide sold by Marine Magnesium Company LPA refers to low profile additive.
  • Neulon G is a proprietary carboxylated poly(vinyl acetate) manufactured and sold by The Dow Chemical Company, Midland, Mich.
  • LP-90 is a 40 percent solution of poly(vinyl acetate) homopolymer dissolved in styrene and sold by The Dow Chemical Company, Midland Mich.
  • Hubercarb W4 is a calcium carbonate of 5 micron particle size sold by J. M. Huber Company.
  • SMC stands for sheet molding compound.
  • SWI stands for surface waviness index as measured by a Diffracto D-sight audit station produced and sold by Diffracto Ltd.
  • UPE stands for unsaturated polyester.
  • A-Paste is the portion of the formulation containing either some or all of the thermosetting resin, the crosslinking monomer, the thermoplastic additive, the polymerization initiators, the mold release agents, the pigments, the filler, etc.
  • B-Paste is the portion of the formulation containing either some or all of the vehicle, the pigment, the crosslinking monomer, the thickeners, the filler, etc.
  • PPG 5509 is a fiber glass reinforcement sold by PPG Industries.
  • the paste was next added to doctor boxes on a sheet molding compound (SMC) machine where the paste is metered into a film on the carrier sheet where it is further combined with fiber glass (1 inch (2.54 cm) fibers).
  • SMC sheet molding compound
  • the sheet molding compound was then allowed to mature to molding viscosity.
  • the surface waviness index (SWI) provided by this instrument is the standard deviation of the panel's surface with regard to long term waviness, as compared to the surface of a perfectly flat panel, whose long term waviness is zero. The smaller the SWI number, the smoother the panel.
  • Table 1 showed SMC formulations utilizing epoxidized linseed oil, octyl epoxytallate, and blends of the same. In Table 1 all numbers were parts by weight. In preparing the SMC, 72 percent of the composition described was blended with 28 percent by weight of PPG 5509 glass fibers. The B side comprised LP-90, 29.90 percent; Styrene, 12.80 percent; Maglite D, 9.90 percent, CM-2015, 0.50 percent and Hubercarb W4, 46.90 percent. Table 2 showed the surface waviness index of the molded panels as determined on the Diffracto D-sight audit station.
  • Table 3 illustrated that compositions containing blends of epoxidized vegetable oils, epoxy alkyl esters and cycloaliphatic epoxides with one another and with aromatic epoxides demonstrated lower surface waviness indices than compositions containing an individual class of epoxides. Data from Table 3 was represented below to better illustrate this.
  • the data in Table 3 was statistically analyzed to examine two parameters, first epoxide oxirane number greater than 8.8 and less than 8.8 and second viscosity less than 1000 cps (1.0 Pa ⁇ s) and greater than 1000 cps (1.0 Pa ⁇ s).
  • the average surface waviness index of formulations containing epoxides and epoxide blends meeting these criteria were segregated into four groups based on these criteria and averaged. The results were shown below.

Landscapes

  • 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)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Reinforced Plastic Materials (AREA)
  • Lubricants (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
US10/512,802 2002-04-25 2003-04-24 Surface improver for reinforced composite compositions Abandoned US20060178456A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US10/512,802 US20060178456A1 (en) 2002-04-25 2003-04-24 Surface improver for reinforced composite compositions
US12/288,656 US7834101B2 (en) 2002-04-25 2008-10-22 Epoxidized vegetable oil, epoxidized alkyl esters and/or cycloaliphatic epoxides
US12/899,083 US7989557B2 (en) 2002-04-25 2010-10-06 Surface improver for reinforced composite compositions

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US37594402P 2002-04-25 2002-04-25
PCT/US2003/013009 WO2003091335A1 (en) 2002-04-25 2003-04-24 Surface improver for reinforced composite compositions
US10/512,802 US20060178456A1 (en) 2002-04-25 2003-04-24 Surface improver for reinforced composite compositions

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/288,656 Division US7834101B2 (en) 2002-04-25 2008-10-22 Epoxidized vegetable oil, epoxidized alkyl esters and/or cycloaliphatic epoxides

Publications (1)

Publication Number Publication Date
US20060178456A1 true US20060178456A1 (en) 2006-08-10

Family

ID=29270729

Family Applications (3)

Application Number Title Priority Date Filing Date
US10/512,802 Abandoned US20060178456A1 (en) 2002-04-25 2003-04-24 Surface improver for reinforced composite compositions
US12/288,656 Expired - Fee Related US7834101B2 (en) 2002-04-25 2008-10-22 Epoxidized vegetable oil, epoxidized alkyl esters and/or cycloaliphatic epoxides
US12/899,083 Expired - Fee Related US7989557B2 (en) 2002-04-25 2010-10-06 Surface improver for reinforced composite compositions

Family Applications After (2)

Application Number Title Priority Date Filing Date
US12/288,656 Expired - Fee Related US7834101B2 (en) 2002-04-25 2008-10-22 Epoxidized vegetable oil, epoxidized alkyl esters and/or cycloaliphatic epoxides
US12/899,083 Expired - Fee Related US7989557B2 (en) 2002-04-25 2010-10-06 Surface improver for reinforced composite compositions

Country Status (13)

Country Link
US (3) US20060178456A1 (ja)
EP (1) EP1497369B1 (ja)
JP (1) JP4002896B2 (ja)
KR (1) KR100991935B1 (ja)
CN (2) CN101392089B (ja)
AT (1) ATE346118T1 (ja)
AU (1) AU2003225176A1 (ja)
BR (1) BR0309532B1 (ja)
CA (1) CA2484452C (ja)
DE (1) DE60309853T2 (ja)
ES (1) ES2275088T3 (ja)
MX (1) MXPA04010574A (ja)
WO (1) WO2003091335A1 (ja)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070265459A1 (en) * 2006-05-09 2007-11-15 University Of Missouri - Columbia Soy based polyols
WO2008058097A2 (en) * 2006-11-07 2008-05-15 Curators Of The University Of Missouri Soy-based polyols
US20100190951A1 (en) * 2006-05-09 2010-07-29 The Curators Of The University Of Missouri Soy-based polyols
US20110245393A1 (en) * 2008-05-09 2011-10-06 Rasoul Husam A A Branched low profile additives and methods of production
DE202011110361U1 (de) 2011-04-21 2013-09-19 BG Handelskontor Ltd. Epoxid Solarmodul

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2987049B1 (fr) * 2012-02-20 2014-03-07 Univ Montpellier 2 Sciences Et Techniques Resines epoxydes biosourcees a reactivite amelioree.
CN111072995B (zh) * 2019-12-31 2023-01-06 海聚高分子材料科技(广州)有限公司 一种水性环氧乳液、水性环氧涂料及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4314917A (en) * 1980-02-12 1982-02-09 General Electric Company High-solids epoxy prepolymer coating composition
US4477512A (en) * 1983-04-29 1984-10-16 Westinghouse Electric Corp. Flexibilized flame retardant B-staged epoxy resin prepregs and composite laminates made therefrom
US4665111A (en) * 1984-10-12 1987-05-12 Siemens Aktiengesellschaft Casting compound for electrical and electronic components and modules
US5158989A (en) * 1989-11-18 1992-10-27 Somar Corporation Electroless plating-resisting ink composition
US6194490B1 (en) * 1998-02-27 2001-02-27 Vantico, Inc. Curable composition comprising epoxidized natural oils
US6268403B1 (en) * 1998-02-11 2001-07-31 Rensselaer Polytechnic Institute Photopolymerizible compositions containing cycloaliphatic epoxyalcohol monomers

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL102413C (ja) * 1955-02-24
US3516955A (en) * 1966-05-31 1970-06-23 Ashland Oil Inc Curable compositions containing an epoxy,an unsaturated polyester,and a polymerizable vinyl monomer
US4525498A (en) * 1980-10-16 1985-06-25 Union Carbide Corporation Polyester fiber reinforced molding compounds
US4486561A (en) * 1981-08-21 1984-12-04 Ethyl Corporation Injection-moldable thermoplastic polyester composition
US4585833A (en) * 1983-05-26 1986-04-29 Union Carbide Corporation Low shrinkling curable poly(acrylate) molding compositions
US4653352A (en) * 1984-02-20 1987-03-31 Aisin Seiki Kabushiki Kaisha Automatic transmission system for automobiles having hydraulic and electronic control systems
US4551485A (en) * 1984-09-04 1985-11-05 Ethyl Corporation Poly(ethylene terephthalate) blends
JPS61108639A (ja) 1984-11-02 1986-05-27 Mitsubishi Monsanto Chem Co 軟質塩化ビニル系樹脂成形品の表面処理剤
DE3729626A1 (de) * 1986-09-09 1988-03-17 Zahnradfabrik Friedrichshafen Elektro-hydraulische steuerung fuer ein automatisch zu schaltendes kraftfahrzeuggetriebe
JP2943148B2 (ja) * 1989-02-15 1999-08-30 大日本インキ化学工業株式会社 熱硬化性樹脂組成物
DE69125276T2 (de) * 1990-04-26 1997-09-25 Chesnut Eng Tiefdruckplattenmaterial und verfahren zur herstellung einer tiefdruckvorrichtung unter verwendung dieses materials
JPH04136020A (ja) * 1990-09-28 1992-05-11 Sumitomo Durez Co Ltd 光硬化性樹脂組成物
JP2748298B2 (ja) * 1992-12-28 1998-05-06 三菱自動車工業株式会社 自動変速機の油圧制御装置
JP2693360B2 (ja) * 1993-09-20 1997-12-24 筒中プラスチック工業株式会社 難燃性樹脂組成物
AU5804696A (en) 1995-05-26 1996-12-11 Polyset Company, Inc. Epoxidize oil and cycloaliphatic epoxy resin coating
US6136497A (en) * 1998-03-30 2000-10-24 Vantico, Inc. Liquid, radiation-curable composition, especially for producing flexible cured articles by stereolithography
US20030075253A1 (en) * 1999-08-26 2003-04-24 Antonio Serra Process for producing tyres, tyres thus obtained and elastomeric compositions used therein
SE515747C2 (sv) * 1999-12-13 2001-10-01 Volvo Lastvagnar Ab Hydrauliskt reglersystem för en fordonstransmission
JP3519339B2 (ja) * 2000-03-29 2004-04-12 アイシン・エィ・ダブリュ株式会社 自動変速機の油圧制御装置
GB2369656A (en) * 2000-11-21 2002-06-05 Luk Lamellen & Kupplungsbau Automatic transmission hydraulic actuation system having an isolating valve which prevent leaks
JP4717268B2 (ja) * 2001-01-12 2011-07-06 富士通株式会社 絶縁樹脂組成物及びそれから形成した絶縁層を含む多層回路基板
GB2372080B (en) * 2001-02-12 2004-09-29 Luk Lamellen & Kupplungsbau Hydraulic actuation systems
US6949297B2 (en) * 2001-11-02 2005-09-27 3M Innovative Properties Company Hybrid adhesives, articles, and methods
JP3839368B2 (ja) * 2002-06-28 2006-11-01 アイシン・エィ・ダブリュ株式会社 自動変速機の油圧制御装置
US6715597B1 (en) * 2002-10-25 2004-04-06 Borgwarner, Inc. Dual clutch transmission clutch cooling control method
DE10320524A1 (de) * 2003-04-30 2004-11-25 Getrag Getriebe- Und Zahnradfabrik Hermann Hagenmeyer Gmbh & Cie Kg Hydraulikkreis zur Steuerung eines Antriebsstranges
FR2871205B1 (fr) * 2004-06-03 2007-10-05 Peugeot Citroen Automobiles Sa Element de transmission a embrayages humides pour chaine de traction de vehicule automobile, et vehicule automobile equipe d'un tel element
DE102005029964B4 (de) * 2005-06-28 2018-10-11 Volkswagen Ag Hydraulikkreislauf für ein Getriebe eines Kraftfahrzeuges
DE102008005144A1 (de) * 2007-02-12 2008-08-14 Luk Lamellen Und Kupplungsbau Beteiligungs Kg Vorrichtung zum Ansteuern einer Vielzahl von hydraulischen Schaltzylindern
EP1965101B1 (en) * 2007-03-01 2013-09-25 C.R.F. Società Consortile per Azioni Electro-hydraulic control system for a motor-vehicle transmission
ATE458940T1 (de) * 2007-12-18 2010-03-15 Fiat Ricerche Elektrohydraulisches steuergerät für ein kraftfahrzeuggetriebe mit mindestens fünf vorwärtsgängen und einem rückwärtsgang
ATE462097T1 (de) * 2007-12-18 2010-04-15 Fiat Ricerche Elektrohydraulische steuervorrichtung für ein kraftfahrzeuggetriebe mit mindestens fünf vorwärtsgängen und einem rückwärtsgang

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4314917A (en) * 1980-02-12 1982-02-09 General Electric Company High-solids epoxy prepolymer coating composition
US4477512A (en) * 1983-04-29 1984-10-16 Westinghouse Electric Corp. Flexibilized flame retardant B-staged epoxy resin prepregs and composite laminates made therefrom
US4665111A (en) * 1984-10-12 1987-05-12 Siemens Aktiengesellschaft Casting compound for electrical and electronic components and modules
US5158989A (en) * 1989-11-18 1992-10-27 Somar Corporation Electroless plating-resisting ink composition
US6268403B1 (en) * 1998-02-11 2001-07-31 Rensselaer Polytechnic Institute Photopolymerizible compositions containing cycloaliphatic epoxyalcohol monomers
US6194490B1 (en) * 1998-02-27 2001-02-27 Vantico, Inc. Curable composition comprising epoxidized natural oils

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070265459A1 (en) * 2006-05-09 2007-11-15 University Of Missouri - Columbia Soy based polyols
US7696370B2 (en) 2006-05-09 2010-04-13 The Curators Of The University Of Missouri Soy based polyols
US20100190951A1 (en) * 2006-05-09 2010-07-29 The Curators Of The University Of Missouri Soy-based polyols
US20100197820A1 (en) * 2006-05-09 2010-08-05 The Curators Of The University Of Missouri Soy-based polyols
US8178593B2 (en) 2006-05-09 2012-05-15 The Curators Of The University Of Missouri Urethane formulation
US8471072B2 (en) 2006-05-09 2013-06-25 The Curators Of The University Of Missouri Soy-based polyols
WO2008058097A2 (en) * 2006-11-07 2008-05-15 Curators Of The University Of Missouri Soy-based polyols
WO2008058097A3 (en) * 2006-11-07 2008-07-31 Univ Missouri Soy-based polyols
US20110245393A1 (en) * 2008-05-09 2011-10-06 Rasoul Husam A A Branched low profile additives and methods of production
US9868814B2 (en) * 2008-05-09 2018-01-16 Ashland Licensing And Intellectual Property Llc Branched low profile additives and methods of production
DE202011110361U1 (de) 2011-04-21 2013-09-19 BG Handelskontor Ltd. Epoxid Solarmodul
DE102011002246B4 (de) * 2011-04-21 2013-09-19 BG Handelskontor Ltd. Herstellungsverfahren eines Epoxid-Solarmoduls

Also Published As

Publication number Publication date
EP1497369B1 (en) 2006-11-22
US7834101B2 (en) 2010-11-16
BR0309532B1 (pt) 2013-05-07
ES2275088T3 (es) 2007-06-01
DE60309853T2 (de) 2007-09-20
CN101392089B (zh) 2011-01-12
CA2484452A1 (en) 2003-11-06
JP2005523970A (ja) 2005-08-11
CN1656169A (zh) 2005-08-17
US20110034631A1 (en) 2011-02-10
DE60309853D1 (de) 2007-01-04
KR100991935B1 (ko) 2010-11-04
ATE346118T1 (de) 2006-12-15
AU2003225176A1 (en) 2003-11-10
MXPA04010574A (es) 2005-02-17
CA2484452C (en) 2009-11-10
CN100439446C (zh) 2008-12-03
US7989557B2 (en) 2011-08-02
JP4002896B2 (ja) 2007-11-07
CN101392089A (zh) 2009-03-25
WO2003091335A1 (en) 2003-11-06
US20090131600A1 (en) 2009-05-21
BR0309532A (pt) 2005-02-15
EP1497369A1 (en) 2005-01-19
KR20050007336A (ko) 2005-01-17

Similar Documents

Publication Publication Date Title
US7989557B2 (en) Surface improver for reinforced composite compositions
US4525498A (en) Polyester fiber reinforced molding compounds
US5202366A (en) Crosslinkable polyester compositions with improved properties
US4172059A (en) Low shrinking thermosetting molding compositions having reduced initial viscosity
SE431222B (sv) Herdbar komposition av ett vinylesterharts och en sampolymeriserbar monomer
US5756554A (en) Low profile additives for polyester resin systems based on asymmetric glycols and aromatic diacids
EP1023394B1 (en) Water resistant unsaturated polyester resin compositions
US4673706A (en) Polyester molding compositions
US5552478A (en) Low profile additives for polyester resin systems based on asymmetric glycols and aromatic diacids
CA1171585A (en) Composition containing an unsaturated polyester, a low profile thermoplastic polymer additive, a polymerizable monomer and an epoxy compound
US5637630A (en) Composition of unsaturated polyester, copolymerizable monomer and poly (vinyl ether) shrinkage control agent
WO1997028204A9 (en) Low profile additives for polyester resin systems based on asymmetric glycols and aromatic diacids
EP0335406B1 (en) Low profile molding system
US5004765A (en) Low profile molding system
EP0383609B1 (en) Resin composition and method of manufacturing the same
US4151219A (en) Vinyl ester resins containing polyoxyalkylene low profile additives
EP0553495B1 (en) Pigmented unsaturated polyester-based molding compositions
EP0058740B1 (en) Improved polyester molding compositions and molded articles produced therefrom
EP0129725B1 (en) Improved low shrinking curable poly(acrylate) molding compositions
USH1276H (en) Curable, styrene-containing resin compositions having reduced styrene emissions

Legal Events

Date Code Title Description
AS Assignment

Owner name: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC, O

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ASHLAND INC.;REEL/FRAME:016408/0950

Effective date: 20050629

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

AS Assignment

Owner name: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC, O

Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE PATENT NUMBER 6763859 PREVIOUSLY RECORDED ON REEL 016408 FRAME 0950. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT;ASSIGNOR:ASHLAND INC.;REEL/FRAME:032867/0391

Effective date: 20050629