WO2004035630A1 - Procede sans solvant de preparation de polymeres carboxyliques - Google Patents

Procede sans solvant de preparation de polymeres carboxyliques Download PDF

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Publication number
WO2004035630A1
WO2004035630A1 PCT/US2003/033031 US0333031W WO2004035630A1 WO 2004035630 A1 WO2004035630 A1 WO 2004035630A1 US 0333031 W US0333031 W US 0333031W WO 2004035630 A1 WO2004035630 A1 WO 2004035630A1
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Prior art keywords
polymer
carboxylic
anhydride
polymers
unsaturated
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PCT/US2003/033031
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English (en)
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Tanya Estrin
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Orbseal Llc A Missouri Limited Liability Company
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Priority to AU2003286466A priority Critical patent/AU2003286466A1/en
Publication of WO2004035630A1 publication Critical patent/WO2004035630A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring

Definitions

  • the invention relates to a solventless method for preparing elastomers with multiple pendant carboxyl groups and application of such elastomers for the cured compositions.
  • Carboxyl grafted elastomers are used as such or as co-reactants in a wide range of applications. Grafted carboxyl groups improve adhesion to various polar and non-polar substrates, compatibility with polar polymers, such as polyamides, polyurethanes, polyesters, acrylic, phenolic and epoxy resins, provide dyeing property, increase filler acceptance, etc. Reactions with carboxyl groups are employed in many crosslinkrng reactions, e.g., with epoxy, isocyanate, amine, hydroxyl, ester, ether, and polyvalent metal groups.
  • Carboxyl containing polymers are used in hot melt, pressure sensitive and biomedical adhesives; spray, powder and electrodepositional coatings; paints; inks; seals, packings and gaskets; for filler surface treatment; as polymeric binders and compatibilizing agents; for thermoforming and thermosetting articles; in water based systems, for detergents and surfactants preparation; as thickening agents, rheology modifiers, etc.
  • binders for solid propellant and binders for various fibers and fillers, chip resistant coatings, electrodepositional primers, laminates and adhesives for bonding identical or different materials, such as metals, plastics, rubbers, molding compounds, textile, cement, glass, and wood in various combination and form, e.g., as sheet, fiber, wire, foam, etc.
  • Carboxyl containing elastomers increase green strength and adhesiveness of rubber compositions and are used in joint sealants, tire formulations, and noise and vibration damping compositions, for example in automotive applications such as an adhesive or a sealant. For such applications it is especially important that the carboxyl containing elastomers are hydrophobic to repel the water and protect the metals from corrosion.
  • a random copolymer formed from ethylene, alkyl acrylate and a mono alkyl half-acid ester of 1,4-butenedioic acid can be formed by continuously feeding monomers and initiator to a stirred reaction zone and continuously withdrawing a reaction mixture containing the copolymer. This is reacted for 30 minutes at 180°C and 40,000-lb pressure.
  • a polymer is Vamac sold by E. I. DuPont. The method of making such a polymer is disclosed in U.S. Pat. No. 3,904,588.
  • This process also requires isolation of the carboxylic polymer from the reaction mixture.
  • the polymers obtained by this method are solids of high molecular weight and the process requires special high-pressure equipment.
  • Another disadvantage of this process is the use of a mono alkyl half-acid ester of 1,4-butenedioic acid as a carboxylic component. It is known that the carboxyl group of such half-acid esters has lower acid strength and therefore limited reactivity as compared to the non-esterified 1,4-butenedioic acid.
  • unsaturated carboxylic acids and their derivatives can be adducted onto polymers via different techniques.
  • maleic anhydride can be added through the reaction of maleic anhydride with a diene polymer.
  • Such a process is thoroughly described in literature, e.g., Trivedi, B.C. and Culbertson, R.M. "Maleic Anhydride” Plenum Press, NY, 1982.
  • maleinized polymers are prepared by reacting polymeric resins, such as, for example, polybutadiene homopolymers or copolymers of styrene and butadiene, with a dicarboxylic acid anhydride, such as maleic anhydride.
  • the maleinized polybutadienes are claimed to improve adhesion of elastomers to various substrates, as described in US Patent No. 5,300,569 assigned to Ricon Resins, Inc.
  • a solventless method for the synthesis of carboxylic polymers is described in US Patent No. 4,412,031 assigned to Nippon Zeon Co., Ltd., where a carboxyl modified rubber is obtained by the reaction of a rubber having an unsaturated carbon linkage with an organic compound having a carboxyl group and an aldehyde group in the presence of an acid catalyst, carried out in a rubber-kneading machine in the absence of a solvent.
  • Such process requires a prolong use of sophisticated mixing equipment, like a kneading machine, and can lead to side-reactions such as gellation of the unsaturated rubber caused by the high processing temperature of about 200°C or a chain scission caused by shear forces.
  • the organic compounds used for this process contain an aldehyde group, hence are potentially toxic.
  • anhydrides of maleic acid group are most widely used to graft or adduct unsaturated elastomers with carboxylic acid derivatives.
  • the anhydrides are less prone to hydrogen bonding, therefore such maleinized elastomers have significantly lower viscosity than their truly carboxylic analogues.
  • These elastomers found application as a replacement for the more difficult to prepare unsaturated carboxylic polymers.
  • maleic anhydride grafted polymers are highly moisture sensitive due to the hydrolysis of the anhydride moiety. Upon the hydrolysis of the anhydride, acid groups are produced changing physical properties of the polymer, e.g., the viscosity increases in the moisture-contact area resulting in "skinning" of the polymer surface.
  • maleic anhydride adducted to an unsaturated polymer such as a liquid polybutadiene accelerates its oxidative crosslinking to the extent that maleinized polybutadiene resins have been used in air-drying coatings (e.g., see US Patent No.
  • Carboxylic and carboxyl-grafted polymers can be used in a wide range of applications.
  • applications comprise hot-melt adhesives (e.g., US patent 5,883,172); PSA (e.g., US patent 5,435,879); biomedical adhesives (e.g., US patent 6,139,867), pumpable adhesives (e.g., US patent 5,521,248); adhesives for bonding identical or different materials (e.g., US patent 5,300,569 - rubber to metal adhesion, US patent 5,985,392 - thermoplastics to rubber adhesion, and Patent Application JP 09,299,261- polyolefin foam adhesion to steel); laminates of various substrates (e.g., US patents 0,369,808 - plastics, and 0,296,042 - glass); compositions of detergents (e.g., US patent 5,977,047); powder coatings (e.g., US patent 5,248,400) and electrocoating (e.g
  • an elastomer can be used in crosslinkable compositions to improve the compatibility of the components of the composition, increase the green strength, adhesion and tack.
  • the instant invention solves problems associated with conventional practices by providing a method for preparing an unsaturated elastomer containing multiple pendant carboxyl groups.
  • One aspect of the instant invention comprises a method for converting liquid elastomers containing organic acid anhydrides into substantially pure acidic form (e.g. to improve storage stability and adhesiveness).
  • the subject invention relates to a solventless process for making a polymeric composition having at least two pendant carboxyl groups, which comprises reacting at least one molecule of water with at least one dicarboxylic acid anhydride group of at least one suitable polymer.
  • solventless it is meant that the reaction medium comprises less than 5 weight percent, and typically less than 2 weight percent, and in some cases about zero weight percent, among other volatile organic compounds (V.O.C.).
  • liquid elastomer comprises elastomers having a flowable viscosity at a temperature between about 4°C and about 95°C at normal pressure.
  • suitable polymers comprise at least one unsaturated liquid polymer capable of forming an adduct with organic acid anhydride, including but not limited to polymers of various dienes, e.g., butadiene and its homologues such as isoprene and chloroprene, or copolymers of dienes with vinyl monomers such as styrene and its homologues, vinyl acetate and other vinyl esters or ethers, acrylonitrile and other (meth)acrylic monomers, and ethylene and its homologues.
  • dienes e.g., butadiene and its homologues such as isoprene and chloroprene
  • vinyl monomers such as styrene and its homologues, vinyl acetate and other vinyl esters or ethers, acrylonitrile and other (meth)acrylic monomers, and ethylene and its homologues.
  • Such unsaturated polymers can be grafted or copolymerized with unsaturated organic acid anhydrides, such as maleic anhydride, itaconic anhydride, acrylic anhydride, aconitic anhydride, among others.
  • unsaturated organic acid anhydrides such as maleic anhydride, itaconic anhydride, acrylic anhydride, aconitic anhydride, among others.
  • Polymer molecular weights may be in the range of 500 to 100,000, typically between about 1,000 and about 80,000 g/mol.
  • the quantity of anhydride groups may vary within broad limits depending on the type of the polymer and the intended applications. The quantity is generally between 1 and 80 moles of anhydride per polymer, and usually between about 2 and about 50 moles.
  • a polymeric adduct which can be employed in one aspect of this invention can comprise at least one unsaturated polymer such as polybutadiene or polyisoprene adducted with an organic acid anhydride such as maleic acid anhydride under conditions described in literature and known to the art, e.g., Trivedi, B.C. and Culbertson, R.M. "Maleic Anhydride” Plenum Press, NY, 1982; hereby incorporated by reference.
  • Homopolymers of 1,3-butadiene and its homologues, or copolymers with up to about 95% of a comonomer can also be employed.
  • Suitable comonomers comprise at least one vinyl- aromatic compounds, olefins having 2 to 12 carbon atoms and/or dienes having 4 to 12 carbon atoms, for example cycloalkadienes having 5 to 12 carbon atoms, such as dicyclopentadiene.
  • Desirable comonomers comprise at least one of styrene, cyclopentadiene, norbornylene and ethylene.
  • the amount of maleic anhydride should be sufficient to provide a polymer that contains at least 1 anhydride group, and typically greater than about 2 anhydride groups per molecule.
  • One aspect of the invention comprises a solventless method for preparing unsaturated carboxylic polymers.
  • This method comprises reacting polymers adducted with carboxylic anhydride, e.g., maleic acid anhydride, with the equivalent amounts of water in the presence of at least one catalyst, e.g., a tertiary amine, toluenesulfonic acid, among others, to hydrolyze the anhydride moiety to form a substantially pure acid form.
  • carboxylic anhydride e.g., maleic acid anhydride
  • at least one catalyst e.g., a tertiary amine, toluenesulfonic acid, among others
  • reaction temperature is in the range of between about 60°C and about 110°C, typically between 70°C and 100°C, and usually between 80°C and 90°C.
  • a suitable organic solvent such as xylene or a ketone, e.g. methylethyl ketone, or an appropriate mixture of solvents.
  • This invention also provides uncured adhesive compositions comprising the aforementioned unsaturated carboxylic polymer adduct that can be formulated with cure initiators such as at least one of peroxides or sulfur and accelerators, and optionally other elastomers and additives, wherein said adduct comprises between about 1 and about 99 weight percent of said adhesive composition.
  • cure initiators such as at least one of peroxides or sulfur and accelerators, and optionally other elastomers and additives
  • the composition can be vulcanized.
  • Another aspect of this invention relates to improved formulations of polymeric materials that are obtained by adding the aforementioned carboxylic polymer adducts, e.g., to achieve improved adhesive and physical properties of the compounded elastomers.
  • adhesive properties are improved with the relatively small addition of the carboxylic polymer to the composition during a compounding or formulating step and, typically, prior to vulcanization or cure.
  • E-coat to Nylon 66 examples include E-coat to Nylon 66, Nylon 66 to itself, E-coat to itself, coatings on plastics (e.g., PETG, E-coat, and Nylon 66), metals (e.g., cold-rolled steel, galvanized steel and aluminum), adhesion through oil to cold-rolled steel, among other substrates and coating systems.
  • plastics e.g., PETG, E-coat, and Nylon 66
  • metals e.g., cold-rolled steel, galvanized steel and aluminum
  • adhesion through oil to cold-rolled steel among other substrates and coating systems.
  • Adhesion is measured by means known to the art, such as lap shear test, e.g., ASTM D- 816-70, and through subjective observations of the substrate after removing the adhered material by peeling, scraping, etc.
  • the adhesive elastomers of this invention can exhibit lap shear adhesion to Nylon 66 between about 80 and about 500 lbf, and to E-coat between about 160 and about 600 lbf.
  • Such adhesive strengths are far superior to the formulation that does not contain a carboxylic polymer of this invention.
  • Polymers useful in practicing the instant invention comprise at least one member selected from the group of styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), hydrogenated acrylonitrile butadiene rubber (HNBR), polychloroprene rubber (CR), natural rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (BR), isoprene isobutylene rubber (IIR), halogenated isoprene isobutylene rubber (CUR, BUR), fluorocarbon rubber (FKM), polyethylene and various ethylene copolymers, e.g.
  • SBR styrene butadiene rubber
  • NBR acrylonitrile butadiene rubber
  • HNBR hydrogenated acrylonitrile butadiene rubber
  • CR polychloroprene rubber
  • NR natural rubber
  • IR polyisoprene rubber
  • BR polybutadiene rubber
  • IIR halogenated
  • ethylene propylene diene rubber EPDM
  • EVA ethylene-vinyl acetate copolymer
  • EPR ethylene-alkyl acrylate copolymers
  • blends of two or more of such elastomers among others.
  • the amount of inventive carboxylic polymer to be added to a formulation is sufficient to achieve a desired tack and/or adhesive bond of the elastomer to the substrate, and still provide an elastomer with satisfactory physical and chemical properties without adversely affecting the vulcanization rate and the ultimate cure of the elastomeric compound.
  • the adhesive adduct comprises between about 1 and about 25 weight percent of the mixture prior to curing, but may comprise more than 90 weight percent of the cured mixture.
  • An example of a method for making a curable adhesive elastomeric compositions of this invention comprises:
  • the catalysts comprises acid or base catalysts effective at anhydride ring opening reaction.
  • examples of such catalysts comprise at least one of bis(2-dimethylaminoethyl)ether (e.g. DABCO BL16 Catalyst of Air Products and Chemicals, Inc.), an amine salt of p-toluenesulfonic acid (e.g. BYK-451 of BYK Chemie or Nacure 2500 of King Industries, Inc.), among others. Desirable results are obtained by using the DABCO BL16 Catalyst,
  • step (b) pouring the cloudy blend from step (a) in a suitable leak-protected container, e.g., a plastic or rubber bag, or a plastic-lined fiber box;
  • a suitable leak-protected container e.g., a plastic or rubber bag, or a plastic-lined fiber box;
  • the carboxylic adduct is normally mixed with the uncured formulation prior to vulcanization. The best results are obtained when about 5-20 weight percent of the carboxylic adduct is used in the formulation.
  • the unvulcanized formulation can be extruded, injection molded, or otherwise pre-formed, then placed on a substrate and heated to bring about cure.
  • the instant invention relates to combining unsaturated polymeric materials adducted with carboxylic acid anhydride with water and at least one catalyst to yield polymeric organic acid, which can be used to promote adhesion to a variety of substrates.
  • These materials comprise at least one polymeric backbone bearing organic acid moieties attached as pendant groups to a polymeric chain.
  • substrates that can be adhered comprise at least one member selected from the group of plastics, such as nylon, polyethylene terephthalate, polyethylene vinyl acetate, polyester, polyether, polyacrylate, and polycarbonate, or metals, such as cold rolled and galvanized steel and aluminum, among others.
  • the polymeric backbone comprises a polybutadiene or polyisoprene polymer with a molecular weight of between about 500 g/mol and about 100,000 g/mol, typically between about 800 g mol and about 50,000 g/mol, e.g., sufficient to provide elastomeric properties to a final adducted product.
  • Said polymeric backbone is adducted with pendant acid groups originated from the hydrolysis reaction of suitable carboxylic anhydride containing polymers.
  • suitable carboxylic anhydride containing polymers are commercially available and produced by many manufacturers worldwide, e.g., Kuraray, Inc. (trademark LIR), Ricon Resins, a division of Sartomer (trademarks Ricon and Ricobond), Degussa Corporation (trademark Polyvest), and Rivertex Co., Ltd. of UK (trademark Lithene).
  • the polymers useful in this invention may bear additional functionality or groups, such as styrene moieties, which contribute to the physical properties of the polymer; but generally will not interfere with the polymer's ability to form organic acid adducts, or with the ability of the final product to form strong adhesive bonds to a substrate, or with the vulcanization reaction of the formulated compound.
  • non-interfering groups comprise at least one of methyl, ethyl, benzyl, tolyl, cyclohexyl, norbornyl, cyclopentadienyl, non-highly-reactive substituents such as cyano or halides, mixtures thereof, among others.
  • the adducted unsaturated resins of this invention may comprise up to about 95 weight percent of such substituents, e.g., styrene, without interfering with the adhesiveness of the adduct.
  • the organic acid anhydride adducted to the polymers described above may be any suitable unsaturated anhydride.
  • the polymeric backbone can be reacted with the organic acid anhydride by methods known to the art.
  • Alpha, beta-ethylenically unsaturated dicarboxylic anhydrides, such as maleic anhydrides, are especially suitable for this invention as they can be easily adducted to unsaturated polymeric units and produce two carboxyl groups upon hydrolysis according the following general reaction:
  • P is a polymeric unit
  • X and Y are hydrogen atoms or alkyl groups, and may be the same or different.
  • the carboxylic polymers of this invention can be compounded with other elastomers and additives by one of several methods known in this industry. These methods comprise at least one of roll mill, extruder and intensive internal mixers of the Banbury type, among others. After compounding, the materials may either be used immediately or stored for use at a later time. Most elastomers can be compounded during the formulating and mixing operations with cure packages. Methods for curing elastomers are similar to those used for the particular elastomer when no adhesion promoters corresponding to the materials of this invention are used.
  • the uncured but compounded elastomer mixtures have adequate storage stability when adhesion promoters of this invention are used.
  • Storage stability is defined as resistance of the compounded elastomer to change with time in storage. Depending upon the concentration, storage environment, and additives used, the uncured but compounded elastomer can be stored for about 12 months.
  • the cured elastomers of this invention containing the adhesion promoter compositions described herein have superior properties of adhesion to a variety of elastomers, plastics, metals, mineral fillers, fibers, fabrics, ceramics, glass, paints and electrocoats among other substrates.
  • the vulcanized elastomer has adequate to superior properties of adhesive strength and heat, cold, and moisture resistance depending upon the composition and the purpose for which the elastomeric compound was designed and formulated.
  • the uncured compounded mixture in addition to the adhesion promoters of this invention and the elastomer to be cured, may contain other components and additives comprises at least one of carbon black, mineral fillers such as silica, talc, and calcium carbonate; metal oxides, such as zinc oxide and calcium oxide; curatives such as peroxides, sulfur, TMTD, MBTS, resin and quinone cures; co-accelerators, antioxidants, plasticizers, resins, various fibers, such as nylon, cotton, and cellulose fiber, fiberglass, and mixtures thereof among others.
  • the temperature is typically similar to that at which the formulation would normally be cured without the introduction of the adhesion promoter, e.g., between about 90°C and about 300°C, depending on the type and amount of curing agent and intended application.
  • Examples 1 - 5 illustrate the method that prepared carboxylic polymers from maleic anhydride adducts listed in Table 1 below.
  • carboxylic polymers were prepared in accordance with the method described in Example 1.
  • Examples 6 - 7 illustrate individual adhesiveness of Carboxylic Polymers that were formed in accordance with the invention.
  • Example 1 60g of the solid carboxylic polymer (Example 1) and 30g of xylene were placed in a plastic beaker. After the polymer dissolved, added 0.6g of a curing agent TBP-XL (tert- butylperoxybenzoate) and mixed it with the polymeric solution. Coated the mixture onto substrates of pre-cleaned cold-rolled steel (CRS), PETG, and CRS covered with a thin layer of the protective oil Ferrocote-61 MALHCLl. Allowed xylene to evaporate, placed coated substrates in the preheated oven and cured for 15 minutes at 135°C, then 15 minutes at 145°C. Removed the substrates from the oven and tested the adhesion according to Tape Adhesion Test ASTM D-5359. The cured formulation produces a clear, glossy coating with 100% adhesion to all substrates.
  • TBP-XL tert- butylperoxybenzoate
  • carboxylic polymer Example 4
  • Example 4 50g of carboxylic polymer (Example 4) were placed in a tin and warmed at 70°C to reduce the viscosity and then mixed with 0.6g of DiCup-40C (dicumyl peroxide, 40% on calcium carbonate).
  • DiCup-40C dicumyl peroxide, 40% on calcium carbonate.
  • Warmed the substrates aluminum, Nylon 66, and galvanized steel
  • the cured formulation produces a clear, glossy coating with 100% adhesion to all substrates.
  • Examples 8 - 9 illustrate effect of the carboxylic polymers of this invention in a sulfur- cured adhesive formulations.
  • Examples 10 - 13 illustrate application of carboxylic polymers of this invention in peroxide-cured adhesive formulations.
  • Formulation 11 was also tested for adhesion between Nylon 66 and E-coat. Test samples were prepared and lap-shear test was performed in accordance with ASTM D-816-70. Samples were cured at 165°C for 30 minutes. Some cured samples were then treated for 500 hrs in salt-fog bath at 50°C and some were heat-aged for 90 minutes at 199°C to test the stability of the adhesive bond. The adhesion was measured as ultimate load resulting in separation of the substrates. Results are as follows.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un procédé sans solvant permettant de fabriquer une composition polymère possédant au moins deux groupes carboxyliques pendants, qui consiste à faire réagir au moins une molécule d'eau avec au moins un groupe anhydride d'acide dicarboxylique d'au moins un polymère approprié.
PCT/US2003/033031 2002-10-17 2003-10-16 Procede sans solvant de preparation de polymeres carboxyliques WO2004035630A1 (fr)

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AU2003286466A AU2003286466A1 (en) 2002-10-17 2003-10-16 A solventless method for preparation of carboxylic polymers

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US41926302P 2002-10-17 2002-10-17
US60/419,263 2002-10-17

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WO2009080554A1 (fr) * 2007-12-21 2009-07-02 Basf Se Compositions ignifugeantes comprenant des amines à empêchement stérique
CN101845153B (zh) * 2010-06-04 2011-12-28 深圳市联合鑫科技有限公司 一种无机粉体添加型阻燃剂及其制备方法
TW201930570A (zh) * 2017-11-13 2019-08-01 瑞士商科萊恩塑料和塗料公司 用於聚烯烴之新穎阻燃劑組成物
CN115831462A (zh) * 2022-12-02 2023-03-21 特变电工山东鲁能泰山电缆有限公司 无卤低烟耐温电缆及其制备方法

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GB1404291A (en) * 1972-06-16 1975-08-28 Kuraray Co Rubber compositions
GB1495457A (en) * 1975-03-06 1977-12-21 Int Paint Co Electropaints
US5407784A (en) * 1990-04-26 1995-04-18 W. R. Grace & Co.-Conn. Photocurable composition comprising maleic anhydride adduct of polybutadiene or butadiene copolymers

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IT1273607B (it) * 1995-04-26 1997-07-08 Ciba Geigy Spa Combinazione di stabilizzanti per polimeri sintetici organici
KR100540156B1 (ko) * 1997-06-30 2005-12-29 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 방염제 조성물
MY124060A (en) * 1999-01-11 2006-06-30 Ciba Holding Inc Synthetic polymers comprising additive blends with enhanced effect
TWI273115B (en) * 2000-12-12 2007-02-11 Ciba Sc Holding Ag Improved weatherability of flame retardant polyolefin

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Publication number Priority date Publication date Assignee Title
GB1404291A (en) * 1972-06-16 1975-08-28 Kuraray Co Rubber compositions
GB1495457A (en) * 1975-03-06 1977-12-21 Int Paint Co Electropaints
US5407784A (en) * 1990-04-26 1995-04-18 W. R. Grace & Co.-Conn. Photocurable composition comprising maleic anhydride adduct of polybutadiene or butadiene copolymers

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