WO2007064680A1 - Copolymeres de tulipaline - Google Patents

Copolymeres de tulipaline Download PDF

Info

Publication number
WO2007064680A1
WO2007064680A1 PCT/US2006/045644 US2006045644W WO2007064680A1 WO 2007064680 A1 WO2007064680 A1 WO 2007064680A1 US 2006045644 W US2006045644 W US 2006045644W WO 2007064680 A1 WO2007064680 A1 WO 2007064680A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
structural units
units derived
copolymer
styrene
Prior art date
Application number
PCT/US2006/045644
Other languages
English (en)
Inventor
Qing Ye
James Edward Pickett
Steven Thomas Rice
Daniel Steiger
Original Assignee
General Electric Company
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
Priority claimed from US11/289,928 external-priority patent/US7465498B2/en
Application filed by General Electric Company filed Critical General Electric Company
Priority to JP2008543408A priority Critical patent/JP2009517538A/ja
Priority to EP06838545A priority patent/EP1954733A1/fr
Publication of WO2007064680A1 publication Critical patent/WO2007064680A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F224/00—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 a heterocyclic ring containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile

Definitions

  • the invention relates generally to copolymers of ⁇ -methylene- ⁇ -butyrolactone with methyl methacrylate, styrene and, optionally, acrylonitrile, and articles made therefrom.
  • MBL is called tulipalin because it is present in relatively high concentration in white tulips.
  • the homopolymer is a brittle glassy material with a glass transition temperature (T g ) of 195°C (Macromolecules 12, 546 (1979)).
  • T g glass transition temperature
  • the monomer can be viewed as a cyclic analogue of methyl methacrylate, and its reactivity in free radical polymerizations is comparable or even higher than methyl methacrylate (Akkapeddi, et ah, Journal of Polymer Science: Polymer Chemistry Edition, v 20, 2819, (1982) and Polymer, vol 20, 1215, (1979)).
  • the increase in free radical reactivity presumably comes from the ring strain of the molecule.
  • JP 9033736 discloses clear, heat- resistant resins composed of copolymers of MBL with (meth)acrylate monomers.
  • US 5,880,235 discloses MBL copolymers for producing cast glass and thermal dimensionally stable molding materials.
  • US 6,642,346 discloses compositions that include MBL copolymers for automotive clear coats and clear coat finishes.
  • the present invention relates to copolymers that include structural units derived from ⁇ -methylene- ⁇ -butyrolactone, styrene, methyl methacrylate and, optionally, acrylonitrile.
  • the copolymers have glass transition temperatures ranging from about 110 0 C to about 175°C, preferably from about 120 0 C to about 15O 0 C.
  • the present invention relates to multilayer articles that include at least one protective layer disposed on a substrate.
  • the protective layer comprises' a UV absorbing material; an MBL copolymer including structural units derived from MBL, styrene, methyl methacrylate and, optionally, acrylonitrile, and the substrate comprises a UV sensitive material.
  • the present invention relates to multilayer articles that include a silicone hardcoat, at least one protective layer comprising an MBL copolymer and a substrate comprising a UV sensitive material
  • FIG. 1 is a graph showing weatherability of MBL copolymers in comparison with a styrene- acrylonitrile copolymer or a copolymer of styrene, acrylonitrile and methyl methacrylate.
  • the present invention relates to copolymers comprising structural units derived from ⁇ -methylene- ⁇ -butyrolactone, styrene and methyl methacrylate and to copolymers comprising structural units derived from ⁇ -methylene- ⁇ -butyrolactone, styrene, methyl methacrylate and acrylonitrile.
  • the copolymers typically have glass transition temperatures ranging from about 110 0 C to about 175 0 C, particularly from about 120 0 C to about 15O 0 C.
  • the amount of structural units derived from ⁇ -methylene- ⁇ -butyrolactone ranges from about 10% by weight to about 75% by weight, particularly from about 20% by weight to about 50% by weight, and more particularly from about 20% by weight to about 35% by weight.
  • the amount of structural units derived from styrene ranges from about 20% by weight to about 80% by weight, particularly about 20% by weight to about 50% by weight, and more particularly from about 25% by weight to about 40% by weight.
  • the amount of structural units derived from methyl methacrylate ranges from about 5% by weight to about 50% by weight, particularly from about 10% by weight to about 45% by weight, and more particularly from about 15% by weight to about 45% by weight.
  • the amount of such units ranges from 5% by weight to about 40% by weight, and particularly from about 5% by weight to about 35% by weight.
  • the amount is based on total copolymer weight. Incorporation of MBL in an MMA- SAN polymer typically improves weathering while simultaneously increasing Tg and improving chemical resistance, without imparting a yellow color upon melt processing.
  • any of the known methods for polymerizing styrene and/or (meth)acrylate monomers may be used to prepare the ⁇ -MBL copolymers.
  • bulk and solution polymerization processes using solvents such as ⁇ -butyrolactone, toluene, NMP, DMF and DMSO, are particularly suitable.
  • the present invention relates to multilayer articles comprising a protective layer disposed on a substrate.
  • the protective layer includes a copolymer of ⁇ -methylene- ⁇ -butyrolactone with methyl methacrylate, styrene and/or acrylonitrile, and particularly MBL copolymers as described above.
  • the protective layer is typically disposed directly on the substrate, "but in some cases, it may be desirable to laminate the protective layer to the substrate by use of an adhesive or primer layer.
  • the protective layer may include additives such as fillers (clay, talc, etc.), reinforcing agents (glass fibers), impact modifiers, plasticizers, flow promoters, lubricants and other processing aids, stabilizers, antioxidants, antistatic agents, colorants, mold release agents, flame retardants, antioxidants, hindered amine light stabilizers, and/or UV absorbing agents (UVA).
  • Suitable UVAs include hydroxybenzophenones, hydroxyphenyl benzotriazoles, hydroxyphenyl triazines, cyanoacrylates, oxanilides, benzoxazinones; and particulate inorganic materials such as titanium oxide, cerium oxide, and zinc oxide, having a particle size less than about 100 nanometers.
  • UVAs known in the art and disclosed in standard reference works such as "Plastics Additives Handbook", 5th edition, edited by H. Zweifel, Hanser Publishers, may also be used. Mixtures of UVAs may be particularly effective, especially mixtures of the abovementioned agents.
  • the UVA is 2-(4,6-diphenyl-l,3,5-triazin-2-yl)-5-hexyloxy-phenol, sold by CIB A® as TINUVIN® 1577.
  • the amount of UVA for use in the protective layer ranges from about 0.0005 wt.% to about 10 wt.%, particularly from about 0.001 wt. % to about 10 wt. %, and more particularly from about 0.1 wt. % to about 5 wt. %, based on the total weight of polymer in the protective layer.
  • the thickness of the protective layer in multilayer articles typically ranges from about 2 ⁇ to about 2,500 ⁇ , preferably from about lO ⁇ to about 500 ⁇ and most preferably from about 50 ⁇ to about 250 ⁇ .
  • Substrates for use in the multilayer articles in various embodiments of the present invention are materials that are sensitive to UV radiation, i.e., they undergo some undesirable change upon exposure to UV radiation.
  • the undesirable change is typically a change in color, but chemical and mechanical properties of the substrate may be affected as well.
  • the UV sensitive materials include thermoplastic and thermoset polymers and copolymers and blends thereof.
  • thermoplastic polymers include polycarbonates, particularly aromatic polycarbonates, polyacetals, polyarylates, polyarylene ethers, including polyphenylene ethers, polyarylene sulfides, including polyphenylene sulfides, polyimides, including polyamideimides, polyetherimides, polyetherketones, including polyaryletherketones, ⁇ polyetheretherketones, polyetherketoneketones, polyamides, polyesters, including liquid crystalline polyesters, polyetheresters, polyetheramides, polyesteramides, and polyestercarbonates, aliphatic olefin and functionalized olefin polymers, including polyethylene, polypropylene, thermoplastic polyolefm (TPO), ethylene-propylene copolymer, polyvinyl chloride, poly( vinyl chloride-co-vinylidene chloride), polyvinyl fluoride, polyvinylidene fluoride, polyvinyl acetate, polyvinyl alcohol, polyvinyl buty
  • the substrate may be one or more homo- or co-polycarbonate, or a polycarbonate blend, or a blend of polycarbonate with other polymers, for example, blends of polycarbonates with polyesters, ABS copolymers or ASA copolymers.
  • Other thermoplastic polymers may be present therein, but the above-described polymers or blends typically constitute the major proportion thereof.
  • Suitable polycarbonates include homo- and copolycarbonates comprising structural units of the formula
  • each A 1 and A 2 is a monocyclic divalent aryl radical and Z is a bridging radical in which one or two carbon atoms separate A 1 and A 2 , hi particular, A 1 and A 2 may be unsubstituted phenylene or substituted derivatives thereof and the bridging radical Z maybe methylene, cyclohexylidene or isopropylidene.
  • the polycarbonates may be bisphenol A polycarbonates.
  • the polycarbonate may also be a copolyestercarbonate.
  • Such polymers contain, in addition to the carbonate units, ester units containing -A l -Z-A 2 - moieties linked to aromatic dicarboxylate groups such as isophthalate and/or terephthalate.
  • Suitable polyesters include poly(alkylene dicarboxylates), especially poly(ethylene terephthalate) (PET), poly(l,4-butylene terephthalate) (PBT), poly(trimethylene terephthalate) (PTT), poly(ethylene naphthalate) (PEN), poly(butylene naphthalate) (PBN), poly(cyclohexane dimethanol terephthalate), poly(cyclohexanedimethanol-co-ethylene terephthalate) (PETG), and poly(l,4-cyclohexanedimethyl-l ,4-cyclohexanedicarboxylate) (PCCD).
  • PET poly(ethylene terephthalate)
  • PBT poly(l,4-but
  • Suitable polyarylates include structural units derived from aromatic dihydroxy compounds and aromatic dicarboxylic acid compounds, particularly from terephthalate and/or isophthalate structural units in combination with bisphenol A and/or resorcinol.
  • Suitable polyetherimides are described in U.S. Pat. Nos. 3,803,085 and 3,905,942.
  • Blends of any of the foregoing polymers may also be employed. These include blends of thermoset polymers with thermoplastic polymers such as polyphenylene ether, polyphenylene sulfide, polysulfone, polyetherimide or polyester. The thermoplastic polymer is typically combined with thermoset monomer mixture before curing. Also included are blends of cellulosic materials and thermoset and/or thermoplastic polymers.
  • the substrate composed of polymeric materials may also incorporate fillers such as silicates, zeolites, titanium dioxide, stone powder, glass fibers or spheres, carbon fibers, carbon black, graphite, calcium carbonate, talc, mica, lithopone, zinc oxide, zirconium silicate, iron oxides, diatomaceous earth, calcium carbonate, magnesium oxide, chromic oxide, zirconium oxide, aluminum oxide, crushed quartz, calcined clay, talc, kaolin, asbestos, cellulose, wood flour, cork, cotton and synthetic textile fibers, especially reinforcing fillers such as glass fibers and carbon fibers, as well as colorants such as metal flakes, glass flakes and beads, ceramic particles, other polymer particles, dyes and pigments which may be organic, inorganic or organometallic.
  • fillers such as silicates, zeolites, titanium dioxide, stone powder, glass fibers or spheres, carbon fibers, carbon black, graphite, calcium carbonate, talc, mica, lithopone, zinc
  • the multilayer articles may be prepared by a variety of known processes such as coating from a solvent, film lamination, profile extrusion, sheet extrusion, coextrusion, extrusion blow molding and thermoforming, and injection molding.
  • the protective layer and substrate may be coextruded to form a multilayer article.
  • the multilayer articles may additionally include a silicone hardcoat disposed on the protective layer.
  • MBL copolymers may be used as primers for a silicone hardcoat.
  • the MBL copolymers for use with silicone hardcoats include structural units derived from other vinyl monomers in addition to those from MBL.
  • Suitable vinyl monomers include (meth)acrylic acid and derivatives thereof, such as methyl methacrylate, ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate, acrylonitrile, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, -2-ethylhexyl acrylate, lauryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylamide or methacrylamide, dimethylaminoethylacrylate and dimethylaminoethyl methacrylate, glycidyl acrylate and glycidylmethacrylate, and aromatic vinyl
  • silicone hardcoats there is no limitation with respect to the type of silicone hardcoats that may be used, other than that they adhere to the protective layer/primer. Therefore, coatings prepared from basic, neutral or acidic colloidal silica may be used.
  • silicone hardcoats that may be employed when the MBL copolymers are employed as protective layers/primers include those prepared by hydrolyzing an aqueous dispersion of colloidal silica and a trialkoxysilane or mixtures of trialkoxysilanes having the formula RSi(OR) 37 wherein each R is independently an alkyl group having 1 to 3 carbon atoms or a substituted or uns ⁇ bstituted aromatic radical; preferably, a methyl group.
  • the hardcoat may include conventional additives such as compatible ultraviolet light absorbing agents, and polysiloxane polyether copolymers. Other additives including thickening agents, pigments, and dyes may also be included for their conventionally employed purposes. A description of the preparation of suitable silicone hardcoats maybe found in U.S. 4,373,061.
  • alkyl is intended to include linear, branched, or cyclic hydrocarbon structures and combinations thereof, including lower alkyl and higher alkyl.
  • Preferred alkyl groups are those of C 2 o or below.
  • Lower alkyl refers to alkyl groups of from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, and n-, s- and t- butyl.
  • Higher alkyl refers to alkyl groups having seven or more carbon atoms, preferably 7-20 carbon atoms, and includes n-, s- and t-heptyl, octyl, and dodecyl.
  • Cycloalkyl is a subset of alkyl and includes cyclic hydrocarbon groups of from 3 to 8 carbon atoms.
  • Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and norbornyl
  • Aryl and heteroaryl mean a 5- or 6-membered aromatic or heteroaromatic ring containing 0-3 heteroatoms selected from nitrogen, oxygen or sulfur; abicyclic 9- or 10-membered aromatic or heteroaromatic ring system containing 0-3 heteroatoms selected from nitrogen, oxygen or sulfur; or a tricyclic 13- or 14-membered aromatic or heteroaromatic ring system containing 0-3 heteroatoms selected from nitrogen, oxygen or sulfur.
  • the aromatic 6- to 14-membered carbocyclic rings include, for example, benzene, naphthalene, indane, tetralin, and fluorene; and the 5- to 10-membered aromatic heterocyclic rings include, e.g., imidazole, pyridine, indole, thiophene, benzopyranone, thiazole, furan, benzimidazole, quinoline, isoquinoline, quinoxaline, pyrimidine, pyrazine, tetrazole and pyrazole.
  • Arylalkyl means an alkyl residue attached to an aryl ring. Examples are benzyl and phenethyl. Heteroarylalkyl means an alkyl residue attached to a heteroaryl ring. Examples include pyridinylmethyl and pyrimidinylethyl. Alkylaryl means an aryl residue having one or more alkyl groups attached thereto. Examples are tolyl and mesityl.
  • Alkoxy or alkoxyl refers to groups of from 1 to 8 carbon atoms of a straight, branched, cyclic configuration and combinations thereof attached to the parent structure through an oxygen. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, and cyclohexyloxy. Lower alkoxy refers to groups containing one to four carbons.
  • Acyl refers to groups of from 1 to 8 carbon atoms of a straight, branched, cyclic configuration, saturated, unsaturated and aromatic and combinations thereof, attached to the parent structure through a carbonyl functionality.
  • One or more carbons in the acyl residue may be replaced by nitrogen, oxygen or sulfur as long as the point of attachment to the parent remains at the carbonyl. Examples include acetyl, benzoyl, propionyl, isobutyryl, /-butoxy- carbonyl, and benzyloxycarbonyl.
  • Lower-acyl refers to groups containing one to four carbons.
  • Heterocycle means a cycloalkyl or aryl residue in which one to three of the carbons is replaced by a heteroatom such as oxygen, nitrogen or sulfur.
  • heterocycles that fall within the scope of the invention include pyrrolidine, pyrazole, pyrrole, indole, quinoline, isoquinoline, tetrahydroisoquinoline, benzofuran, benzodioxan, benzodioxole (commonly referred to as methylenedioxyphenyl, when occurring as a substituent), tetrazole, morpholine, thiazole, pyridine, pyridazine, pyrimidine, thiophene, furan, oxazole, oxazoline, isoxazole, dioxane, and tetrahydrofuran, triazole, benzotriazole, and triazine.
  • Substituted refers to structural units, including, but not limited to, alkyl, alkylaryl, aryl, arylalkyl, and heteroaryl, wherein up to three H atoms of the residue are replaced with lower alkyl, substituted alkyl, aryl, substituted aryl, haloalkyl, alkoxy, carbonyl, carboxy, carboxalkoxy, carboxamido, acyloxy, amidino, nitro, halo, hydroxy, OCH(COOH) 2 , cyano, primary amino, secondary amino, acylamino, alkylthio, sulfoxide, sulfone, phenyl, benzyl, phenoxy, benzyloxy, heteroaryl, or heteroaryloxy; each of said phenyl, benzyl, phenoxy, benzyloxy, heteroaryl, and heteroaryloxy is optionally substituted with 1-3 substituents selected from lower alkyl, alkeny
  • Haloalkyl refers to an alkyl residue, wherein one or more H atoms are replaced by halogen atoms; the term haloalkyl includes perhaloalkyl. Examples of haloalkyl groups that fall within the scope of the invention include CH 2 F, CHF 2 , and CF 3 .
  • any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value.
  • the amount of a component or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly enumerated in this specification.
  • one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
  • ⁇ -Methylene- ⁇ -butyrolactone was obtained from TCI, and methyl methacrylate, styrene, acrylonitrile all from Aldrich. All were purified from inhibitors using a basic alumina column right before use.
  • Poly(styrene-co-acrylonitrile-co-methyl-methacrylate-co- ⁇ -methylene- ⁇ -butyrolactone) were made in different ratios, with Mw ranging from 30 to 220 kDaltons. Compositions and molecular weights are shown in Table 1.
  • Polymer powder samples were compression molded into films about 100 microns thick, using Teflon coated aluminum foil as shim, a temperature of about 160°C, and a pressure of 4000 psi in a Carver press.
  • the films were mounted on an aluminum frame and exposed in an Atlas Ci4000 xenon arc Weatherometer.
  • the xenon arc lamp had a CIRA (IR-reflecting quartz) inner filter and a soda lime glass outer filter to best match sunlight.
  • the samples were continuously irradiated (except for the spray period) at an irradiance of 0.75W/m 2 /nm at 340 run.
  • the black panel temperature was 55 0 C and the air temperature was 35° C at a relative humidity of 30%.
  • MBL copolymer films were prepared using the procedure shown in Example 2. The film was placed in a crystallization dish and a drop (25 ⁇ L) of testing chemical was delivered onto the film surface by dispensing pipette. The dish with sample was placed in a oven at 65 °C for 1 hour. Pass and fail observation was made regarding whether there was visible damage to the film. Results are shown in Table 2. The MBL copolymers demonstrated improved chemical resistance.
  • MMASAN and SAN are products of GE Advanced Materials
  • Elvacite 2041 is a product of Lucite International
  • the solution was poured onto a glass plate, drawn using a 10 mil doctor blade, and the solvent was allowed to evaporate.
  • the film was floated from the glass using water and further dried for 2 hours at 65°C in a forced air oven.
  • the final films were approximately 40 micons thick. Portions of the films were laminated onto 2 Vz" x 2 Vz" x 1/8" plaques of Lexan® 140 polycarbonate resin containing 2% titanium dioxide pigment. Lamination was done in a heated press at 165°C using contact pressure for 3Vi minutes followed by 4000 psi pressure for 1 minute, and 6000 psi pressure for Vi minute. The caplayers were firmly adhered to the polycarbonate surface. The sample with no caplayer was an unlaminated Lexan polycarbonate plaque.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des copolymères comprenant des unités structurelles dérivées de la a-méthylène-?-butyrolactone, du styrène, du méthyl méthacrylate et, facultativement, de l'acrylonitrile, lesquels copolymères peuvent être utilisés comme couches protectrices dans des articles multicouche comprenant des matériaux substrats sensibles aux UV. Les articles multicouche peuvent également comprendre une couche dure en silicone.
PCT/US2006/045644 2005-11-30 2006-11-29 Copolymeres de tulipaline WO2007064680A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2008543408A JP2009517538A (ja) 2005-11-30 2006-11-29 チューリパリンコポリマー
EP06838545A EP1954733A1 (fr) 2005-11-30 2006-11-29 Copolymeres de tulipaline

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US28992705A 2005-11-30 2005-11-30
US11/289,927 2005-11-30
US11/289,928 US7465498B2 (en) 2005-11-30 2005-11-30 Tulipalin copolymers
US11/289,928 2005-11-30

Publications (1)

Publication Number Publication Date
WO2007064680A1 true WO2007064680A1 (fr) 2007-06-07

Family

ID=37776464

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2006/045644 WO2007064680A1 (fr) 2005-11-30 2006-11-29 Copolymeres de tulipaline

Country Status (3)

Country Link
EP (1) EP1954733A1 (fr)
JP (1) JP2009517538A (fr)
WO (1) WO2007064680A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170108516A (ko) * 2016-03-18 2017-09-27 주식회사 엘지화학 열가소성 수지 조성물 및 이로부터 제조된 성형품

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101549724B1 (ko) * 2012-12-14 2015-09-02 제일모직주식회사 열가소성 수지 조성물 및 이로부터 형성된 성형품
KR102087151B1 (ko) * 2016-03-18 2020-04-14 주식회사 엘지화학 열가소성 수지 및 이의 제조방법
KR101797391B1 (ko) 2016-09-20 2017-11-14 롯데케미칼 주식회사 고흡수성 수지 및 그 제조방법
JP7474771B2 (ja) * 2019-08-22 2024-04-25 株式会社日本触媒 共重合体及びその製造方法、共重合体混合物、ドープ樹脂組成物、並びに樹脂成形体及びその製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020010312A1 (en) * 2000-02-28 2002-01-24 Brandenburg Charles J. Coating compositions containing substituted and unsubstituted exomethylene lactone or lactam monomers
WO2002044845A2 (fr) * 2000-11-29 2002-06-06 E.I. Du Pont De Nemours And Company Groupes protecteurs dans les polymeres, les photoresines et procedes de microlithographie

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020010312A1 (en) * 2000-02-28 2002-01-24 Brandenburg Charles J. Coating compositions containing substituted and unsubstituted exomethylene lactone or lactam monomers
WO2002044845A2 (fr) * 2000-11-29 2002-06-06 E.I. Du Pont De Nemours And Company Groupes protecteurs dans les polymeres, les photoresines et procedes de microlithographie

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
H. KOINUMA, K. SATO, H. HIRAI: "alternating copolymerization of alpha methylene gamma butyrolactone with styrene", MAKROMOL. CHEM. RAPID COMMUN., vol. 3, 1982, pages 311 - 315, XP002423190 *
H. KOINUMA, K. SATO, T. TANABE, H. HIRAI: "polymer conformation and NMR chemical shifts 6a alternating copolymer of alpha methylene gamma butyrolactone with styrene", MAKROMOL. CHEM., vol. 183, 1982, pages 1533 - 1544, XP002423189 *
M. VAN DEN BRINK, W. SMULDERS, A.M. VAN HERK, A. L. GERMAN: "Nonlinear regression by visualization of the sum of residual space applied to the integrated copolymerization equation with errors in all variables II Application to the system methyl methacrylate alpha methylene gamma butyrolactone using on-line raman spectroscopy", JOURNAL OF POLYMER SCIENCE PART A POLYMER CHEMISTRY, vol. 37, 1999, pages 3804 - 3816, XP002423188 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170108516A (ko) * 2016-03-18 2017-09-27 주식회사 엘지화학 열가소성 수지 조성물 및 이로부터 제조된 성형품
KR101931585B1 (ko) 2016-03-18 2019-02-26 주식회사 엘지화학 열가소성 수지 조성물 및 이로부터 제조된 성형품

Also Published As

Publication number Publication date
EP1954733A1 (fr) 2008-08-13
JP2009517538A (ja) 2009-04-30

Similar Documents

Publication Publication Date Title
US7932336B2 (en) Tulipalin copolymers
JP4703869B2 (ja) 熱可塑性樹脂積層体
JP5339775B2 (ja) 積層板、積層板の製造方法および、表示装置用前面板
US8715406B2 (en) UV absorbers soluble in polar media
WO2007064680A1 (fr) Copolymeres de tulipaline
JPH10291282A (ja) 積層シート又はフィルム及びその成形体
EP0942830B1 (fr) Pellicules de revetement en polystyrene syndiotactique a protection anti-u.v.
CN105612210A (zh) 含有偏氟乙烯系树脂的膜和层叠膜、以及层叠体
AU2010209838A1 (en) Transparent, weather-resistant barrier film, production by lamination, extrusion lamination or extrusion coating
TWI280258B (en) Process for preparing an impact-modified polymethyl methacrylate, and an impact-modified polymethyl methacrylate (PMMA)
FR2725204A1 (fr) 2-hydroxyphenyltriazines comme agents photostabilisants
JP7045994B2 (ja) メタクリル樹脂組成物とその製造方法、成形体、フィルム、積層フィルム、積層成形体
KR20080069984A (ko) 비정성 열가소성 수지 및 압출 필름 또는 시트
TW201219225A (en) Transparent, weathering-resistant barrier film with improved barrier effect and scratch resistance properties
WO2014046230A1 (fr) Stratifié de résine synthétique
KR20120014161A (ko) 투명한 내후성 배리어 필름, 및 적층, 압출 적층 또는 압출 코팅에 의한 이의 제조
JP6625859B2 (ja) 重合体とこれを含む樹脂組成物および樹脂成形体、重合体の製造方法、共重合体ならびに新規モノマー
JP2009286960A (ja) アクリル樹脂フィルムの組成物ならびそれを用いた成形品
JP2014034112A (ja) 透明多層シート
JP6694685B2 (ja) アクリル系重合体およびその製造方法
JP2010179640A (ja) 熱可塑性樹脂成形体とそれを備える画像表示装置
WO2008025703A1 (fr) Pièce composite constituée d'une feuille multicouche et d'un substrat à base d'un polycarbonate
WO2018147234A1 (fr) Film à orientation biaxiale de résine acrylique et son procédé de production
CN101360768A (zh) 郁金香灵共聚物
CN110832023B (zh) 热塑性树脂组合物和热塑性树脂成形体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2006838545

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2008543408

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 200680051582.X

Country of ref document: CN