EP1068267A1 - Procede de preparation d'une composition polymere - Google Patents

Procede de preparation d'une composition polymere

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Publication number
EP1068267A1
EP1068267A1 EP99908782A EP99908782A EP1068267A1 EP 1068267 A1 EP1068267 A1 EP 1068267A1 EP 99908782 A EP99908782 A EP 99908782A EP 99908782 A EP99908782 A EP 99908782A EP 1068267 A1 EP1068267 A1 EP 1068267A1
Authority
EP
European Patent Office
Prior art keywords
polymer
preparing
polymer composition
radical generator
filler
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.)
Withdrawn
Application number
EP99908782A
Other languages
German (de)
English (en)
Inventor
Bjorn Winther-Jensen
Chaabane Armand
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.)
NKT Research Center AS
Original Assignee
NKT Research Center AS
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 NKT Research Center AS filed Critical NKT Research Center AS
Publication of EP1068267A1 publication Critical patent/EP1068267A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the present invention relates to a method of preparing a highly filled polymer composition such as a flame retardant or reinforced polymer composition.
  • inorganic fillers are frequently used to reduce cost, improve stiffness and tensile properties, or enhance the flame retardant properties of the polymers.
  • the presence of a high level of inorganic fillers reduces the cohesiveness and thereby the mechanical properties of the polymer composition.
  • the presence of high levels of fi] lers may reduce the processibility of the composition, and this is undesirable, particularly if the composition is to be used in an injection moulding or extrusion process.
  • methods of improving the processibility e.g. by using higher processing temperatures or by using processing aids.
  • processing aid adversely affect the mechanical properties of the composition, for example the mechanical strength, elongation, flexibility, low temperature performance, the flexural and impact properties.
  • processing aid is generally more flammable than the inorganic solid and hence higher levels of the processing aid are particularly undesirable in compositions intended to possess fire retardant characteristics.
  • Another method of improving processibility is to incorporate a coupling agent into the polymer compositions.
  • EP-A2-0 467 549 relates to such a polymer composition.
  • This polymer composition is prepared by blending together a particulate inorganic filler, a dicarboxylic acid or an anhydride and a polymer.
  • the filler is a hydrated alumina as it is preferred in the EP application, the dicarboxylic acid or the anhydride is bonded to the filler by an ester bonding.
  • This known polymer composition is very much improved with respect to processibility, however. The mechanical properties still need to be improved when the polymer comprises high proportions of filler.
  • US patent No. 3,694,403 describes a polyolefin composition prepared from a polyolefin, a particulate magnesium carbonate, a dicarboxylic acid or an anhydride and a conventional radical generator such as a peroxide.
  • a conventional radical generator such as a peroxide.
  • the polyolefin, magnesium carbonate and dicarboxylic acid or anhydride is mixed together m a melt at a temperature above the softening temperature of the polyolefin.
  • the radical generator may be incorporated.
  • This known polymer composition obtained is transparent and has acceptable mechanical properties, which, however, still need to be improved when the polymer composition comprises high proportions of filler.
  • polymeric Coupling Agents as Property Enhancers in Highly Filled Polymer Systems
  • Polymers & Polymer compositions Vol. 5, No. 2, 1997, R. Hausmann and V. Flans, a polymer composition composed of a polyolefinic polymer, a polymeric coupling agent and a filler is described.
  • the polymeric coupling agent consists essentially of two parts: a polyolefinic backbone, chosen from polyethylene (PE) , polypropylene
  • PP polypropylene
  • EVA ethylene-vmyl acetate copolymer
  • the filler is bonded to the polymer component, and thereby the mechanical properties are highly improved.
  • Similar polymer compositions are known from EP 0 370 517 and US 4,839,412. However all these known polymer compositions, are prepared by mixing a filler with a polymer which has been grafted with an unsaturated carboxylic acid or an unsaturated anhydride.
  • carboxylic acid or anhydride grafted polymer grades are very expensive, and the number of different carboxylic acid or anhydride grafted polymer grades on the market are very limited.
  • the object of the present invention is therefore to provide a new method of preparing a highly filled polymer composition which have good mechanical strength and which can be produced using a simple and economical acceptable method.
  • a further object of the invention is to provide a new method of preparing a highly filled polymer composition wherein the polymer and the filler are bonded to each other .
  • Another object of the invention is to provide a new method of preparing a highly filled polymer composition wherein the polymer and the filler are bonded to each other and which method does not require the use of a pregrafted polymer.
  • the filler used in the composition may be any inorganic mineral or reinforcing material, preferably in the form of sphere, flake, powder or fibre.
  • a wide range of particulate inorganic solids may be used as fillers depending on the intended use of the polymer composition and, if desired, a mixture of particulate inorganic solids may be used as a filler.
  • the filler or fillers may preferably be selected from the group comprising aluminium hydroxide, magnesium hydroxide, potassium hydroxide, zirconium hydroxide, calcium hydroxide, potassium titanate, antimony trioxide, barium metaborate, zinc metaborate, kaolinite, montmorillonite, talc, clay, mica, red phosphorus, barium borate, silica, white carbon, diatomaceous earth, barium sulphate, cellite, alumina, titanium oxide, zinc oxide, molybdenum disulphide, calcium phosphate, ammonium phosphate, ammonium bromide, ammonium borate, ammonium sulfamate, asbestos and lithopone.
  • the filler may preferably be a reinforcing fibre material in the form of organic or inorganic fibres.
  • Inorganic fibres are more preferred particularly in the form of glass fibres or carbon fibres.
  • the most preferred reinforcing filler material is glass fibres.
  • Another type of preferred fillers are the flame retardants.
  • the most preferred flame retardant fillers are carbonates and particularly hydroxides.
  • the filler or fillers are selected with respect to their compatibility with the polymer in the polymer composition.
  • the filler is one or more halogen-free compounds which provide fire retardant and/or smoke suppressant characteristics to a polymer composition.
  • the particulate inorganic solid is both a fire retardant component and a smoke suppressant component.
  • the preferred fire retardant filler is a compound which liberates water under heating, for example the material referred to as hydrated alumina which may also be regarded as a form of aluminium hydroxide or a compound which liberates water at a temperature of at least 260 'C, for example magnesium hydroxide (alternatively referred to as hydrated magnesia) .
  • the flame retardant filler may be used in an admixture with other filler materials, for example precipitated calcium carbonate.
  • the proportion of the fire retardant filler is preferably in the range from 30 up to 100 c . by weight of the total amount of filler in the polymer composition .
  • the preferred amount of filler material in the poJ ymer composition depends largely on the desired degree of flame retardancy, the desired strength or the desired degree of other properties affected by the filler, of the resulting polymer composition.
  • the amount of said at least one filler may be between 10 and 350 % by weight relative to the amount of polymers, and preferably between 60 and 200 % by weight relative to the amount of polymers. If the polymer composition is to be used in the production of cables, it is preferred that the amount of fillers is between 75 and 180 c by weight relative to the amount of polymers, and preferably between 80 and 150 ° by weight relative to the amount of polymers.
  • the mono- or di-carboxylic acid or anhydride thereof which may be used in the method of the invention is mono- or di-carboxylic acid or anhydride thereof or a mixture thereof having up to 100 carbon atoms preferable up to 50 carbon atoms and more preferably op to ]0 carbon atoms, and having at least one double bond.
  • the unsaturated mono-/d ⁇ ac ⁇ d may e.g. be one of the following : a) a mono-acid having up to 100 carbon atoms, and having at least one aliphatic substituent R,
  • R is an unsaturated aliphatic group containing up to 20 carbon atoms, preferably up to 10 carbon atoms
  • Ri is a saturated or unsaturated aliphatic group containing up to 20 carbon atoms, preferably up to 10 carbon atoms
  • n is either zero, one or two.
  • Dicarboxylic acids and anhydrides thereof aie most preferred, and are in the following designated "diacids".
  • the mono-/diacid contains at least 4 carbon atoms.
  • Group R and group R can be a linear or branched aliphatic groups and typically are branched chain groups.
  • the polymer composition may comprise a plurality of different mono-/diacids .
  • the polymer composition may comprise a plurality of mono-/diacids of either one or more of (a) , (b) , (c) and (d) which differ in the identity of the group R.
  • the different R groups may be different isomers, for example, different branched chain isomers and/or may contain different number of carbon atoms, for example, alkyl or alkenyl groups having 12 to 16 or 12 to 14 carbon atoms.
  • Mono-/diacids which may be used in the composition of the present invention include oleic acid, palmitoleic acid, ricinoleic acid, linoleic acid, arachidonic acid, fumaric acid, itaconic acid and maleic acid and their anhydrides. Most preferred are itaconic acid and maleic acid and their anhydrides and most preferred is maleic anhydride.
  • the amount of mono-/diacid depends naturally on the type of mono-/diacid used, on the type and amount of fillers, and on the type and molecular weight of the polymers.
  • the amount of mono-/diacid is preferably between 0.05 and 10 % by weight relative to the amount of polymers, and more preferably between 0.1 and 3 % by weight relative to the amount of polymers.
  • the radical generator may preferably be a ultrasound activable, a microwave activable, a UV activable or most preferably a heat activable radical generator.
  • the temperature in step i) is below T-, and the temperature in step ii) is above T a , where T ? , is the activating temperature of said at least one peroxide or if more than one radical generator, the activating temperature of the radical generator having the lowest activating temperature.
  • the temperature T a is defined as the temperature at which the T ⁇ 5 of the radical generator is less than 1 min.
  • the heat activable radical generator is preferably a Azo compound (e . g. ⁇ , ⁇ -azobis (isobutyronitrile) ) or a peroxide such as organic peroxides.
  • the radical generator is selected with a view to the polymer in the polymer composition and the necessary activating conditions for activation of the radical generator.
  • Preferred radical generators are alkyl peroxides, peroxyesters, diacyl peroxides, hydroperoxides and/or peroxyketals . More preferred radical generators are alkyl peroxides such as dicumyl peroxide.
  • Preferred ultrasound activable radical generators are the above listed heat activable radical generators, however, the most preferred ultrasound activable radical generators are bis- (2, -dichlorobenzoyl) peroxide and dibenzoyl peroxide .
  • Preferred UV activable radical generators are the above listed heat activable radical generators, however, the most preferred UV activable radical generators are dibebzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide and dicumyl peroxide
  • Preferred microwave activable radical generators are very polar peroxides, such as bis- (2,4- dichlorobenzoyl) peroxide and dibenzoyl peroxide. 10
  • the amount of radical generator used in the method of the invention may be adjusted in relation to the amount and type of filler and thermoplastic polymer.
  • the amount of the radical generator is between 0.001 and 2 % by weight relative to the amount of polymer, and more preferably between 0.01 and 0,1 % by weight relative to the amount of polymer.
  • the amount of radical generator for use in the initiation of the reaction between the thermoplastic polymer and the mono-/d ⁇ ac ⁇ d, should preferably be sufficiently low as to avoid any substantially crosslmkmg of the thermoplastic polymer under the step of reaction between the thermoplastic polymer and the mono-/d ⁇ ac ⁇ ds .
  • the thermoplastic polymer may be any type of heat processable polymer preferably comprising an olefinic component.
  • the polymeric material is very conveniently an olefin polymer.
  • the olefin polymer which term is used herein to include both homopolymers and copolymers containing at least 50% by weight of one, or more, olefin monomers, is a polymer of an olefin monomer which typically contains not more than ten carbon atoms, and preferably of the monomers ethylene or propylene.
  • the olefin polymer may be any ethylene homopolymer, copolymer or terpolymer, particularly high density polyethylene or linear low density polyethylene which is a copolymer of ethylene with a higher alfaolefin monomer such as butene, hexene octeneor 4-methylpentene .
  • Other ethylene polymers are the copolymers of ethylene and a monomer, for example an ethylene-vmyl acetate copolymer typically one containing 10 to 40i by weight of vinyl acetate.
  • the olefin polymer may be a propylene homopolymer or copolymer, for example a random copolymer of propylene with up to 8', by weight, relative to the polymer, of ethylene, or a sequential polymer obtained by polymerising propylene in the essential 1 1
  • Preferred polymers are homo- and copolymers of Linear low density polyethylene (LLDPE) , Low density polyethylene (LDPE) , High density polyethylene (HDPE) , Ethylene/vinyl acetate (EVA) , Ethylene-methyl-acrylate (EMA) , Ethylene- acrylic-acid (EAA) , Ethylene-butyl-acr ylate (EBA) , Ethylene-ethyl-aciylate (EEA) , Polypropylene (PP) , Ethylene-propylene copolymer (EPM) , and Ethylene- propylene-diene terpolymer (EPDM) .
  • LLDPE Linear low density polyethylene
  • LDPE Low density polyethylene
  • HDPE High density polyethylene
  • EVA Ethylene/vinyl acetate
  • EEMA Ethylene-methyl-acrylate
  • EAA Ethylene- acrylic-acid
  • a particularly preferred polymer is one having a molecular weight which is appropriate for a material which can be used for the production of shaped articles by an injection moulding or extrusion process.
  • suitable olefin polymers such as LLDPE, LDPE, HDPE, EVA, EEA, EMA, EAA, EBA and PP are those having a melt flow index, measured according to ASTM Test Method 1238-79 using a 2.16 kg weight at a temperature of 230 °C, which is in the range from 0.5 g/10 minutes up to 50 g/10 minutes, preferably from 1.0 g/10 minutes up to 30 g/10 minutes .
  • the incorporation of a high proportion of fillers into the polymeric material may reduce the melt flow index, and the polymer composition containing the filler typically has a melt flow index, measured at 190 °C with a weight of 2.16 kg, but otherwise under the conditions specified previously herein, of not more than 10 g/10 minutes and typically at least 0.05 g/10 minutes.
  • the polymer composition preferably has a melt flow index of not more than 8 g/10 minutes. 12
  • a such solvent may e.g. be water or preferably dichloromethane .
  • step i) all ingredients mixed in step i) including the filler, the mono- or di-carboxylic acid or anhydride thereof, the radical generator, and the polymer is mixed together in one single mixing step, and the mixing step i) is preferably continued until a substantially homogeneous mixture is obtained.
  • the mixing step i) comprises the substep
  • the radical generator and the mono-/diacid is dissolved in a solvent e.g. a volatile solvent, and thereafter mixed with the filler or preferably coated onto the filler.
  • a solvent e.g. a volatile solvent
  • the steps ib) and ii) may preferably be carried out simultaneously and under condition where the radical generator is activated at an temperature above T,.
  • step ia) comprises mixing together the filler and the i ⁇ ono- /diacid until a homogeneous premixture is obtained
  • step ib) comprises mixing this premixture with the radical generator and the polymer at a temperature below T a until a homogeneous mixture is obtained.
  • the mixing step i) or ia) /ib) respectively is carried out at a temperature below T - 30 °C. Furthermore, it is preferred that said mixture in step ii) is heated to a temperature of at least Collector + 30 °C for a period sufficiently to form a chemically bonding between the mono-/diacid and the polymer, preferably this period is about 5 x T> ; of the heat activable radical generator or more.
  • the mixing step i) and the heating step ii) are carried out simultaneously in one single step i-ii) .
  • a step similar to step ia) as defined above of mixing together the filler, the radical generator and the mono-/diacid until a homogeneous premixture is obtained is carried out before the step ib-ii) of mixing this premixture with the polymer and heating.
  • the radical generator is a heat activable radical generator
  • the single step i-ii) or ib-ii) is initiated at a temperature below T.-.-30 "C and said step i-ii) comprises heating the filler, the peroxide, the 1 4
  • the temperature should preferably be sufficient to soften the polymer. This means that the temperature should be selected to be T,, of the polymer or higher.
  • the mixing time depends largely on the equipment used. However, 10 minutes are usually sufficient.
  • the chemical bondings between the mono-/diacid and the polymer are preferably covalent bondings, and these will usually be established within about 10 seconds - 10 minutes. In most situations, a reaction temperature of about 160 °C should be sufficient.
  • a particular preferred second method of preparing a polymer composition ia claimed in claim 25 comprises the step of
  • the preferred mono-/d ⁇ ac ⁇ d, the preferred filler, the preferred heat activable radical generator and the preferred polymer is as described above, further the premixture preferably is in the form of coated filler as described above.
  • the polymer composition is preferably made in a continuous process e.g. in a compounding extruder.
  • the temperature in the compounding extrudei varies from about r lg of the initial thermoplastic polymer to above 'I of the radical generator.
  • the starting materials are feed into the extruder in the low- temperature end and passes through the extruder.
  • polymeric compositions in accordance with the present invention may be formed ⁇ nto shaped articles by any suitable technique, particularly by injection moulding or extrusion.
  • the polymer compositions may be obtained using any suitable blending technique, particularly a melt mixing technique using, for example, a two roll mill or, preferably, an internal mixer such as a Banbui y or Brabender mixer.
  • the mixing may be effected using a compounding extruder which may be a single screw extruder or, preferably, a twin screw extruder.
  • the polymer composition may be formed directly into a shaped article but more conveniently is first formed into granules which are subsequently injection moulded or extruded to form the desired shaped article.
  • the polymer composition can for example be used for coating electrical conductors, as fire retardant panels, as a floor covering or for preparing cables. 16
  • Evatane 2083 (EVA) delivered from elf Atochem. Maleic anhydride delivered from Ald ⁇ ch.
  • ATH Apyral 60 (alumina trihydrate) delivered from WAW aluminium AG.
  • the mixer used was a HAAKE record 9000
  • the mixer was started and tne temperature was set at 90 "C .
  • the speed was set at 20 rotations per minute (r/min) .
  • 152 g Evetane, 3.1 g maleic anhydride, 216 g ATH and 0.062 g of peroxide were added simultaneously to the mixer.
  • the temperature was adjusted to 170 °C and the speed was raised to 50 r/mm.
  • the mixing was terminated and the polymer melt was removed from the mixer and granulated (us mg a granulator: Meltic) .
  • the granulate was extruded to a thickness of about 1,5 mm and cut into "Dump-bell" test pieces (CE1-IEC 1 166/93).
  • test pieces of the resulting polymer composition were tested (using an Instron 4301) with respect to elongation at rupture and tensile strength, and the results are listed in table 1.
  • Dicumyl peroxide 400 (ppm EVA) (0.062 g) 60 200 300 0 600
  • ATH was coated with maleic anhydride and peroxide: 10 g maleic anhydride and 0.2 g peroxide was dissolved in 300 ml dichloromethane . 1 kg ATH was added to a high speedmixer at a speed of 1000 r/min. After 5 minutes the dichloromethane solution was injected into the mixer. The mixing was carried out for about 15 minutes in order to evaporate the dichloromethane.
  • This polymer composition was prepared and tested as the polymer composition in example 11. The amount of starting 19
  • example 13 (according to the invention) and example 14 (a comparative example), the following starting materials were used:
  • LLDPE polymer Clearflex 508 cl, delivered from Polyme ⁇ . Glass fibres: length about 4 cm, thickness about 10 ⁇ m. Maleic anhydride delivered from Ald ⁇ ch. Dicumyl peroxide delivered from Ciba.
  • the mixer used was a HAAKE record 9000
  • the mixer was started and the temperature was set at 135 U C. The speed was set at 50 rotations per minute (r/min) . LLDPE, glass fibres, maleic anhydride and dicumyl were added simultaneously to the mixer. After 10 minutes the temperature was adjusted from 135 °C to 185°C over a period of about 5 minutes. After 10 minutes the mixing was terminated and the polymer melt was removed from the mixer and formed into "Dump-bell" test pieces and tested as in example 1. The test results are listed in table 3.

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de préparation d'une composition polymère à forte quantité de charge telle qu'une composition polymère ignifuge ou renforcée dans laquelle le polymère et la charge sont liés chimiquement. Le procédé consiste à i) mélanger la charge, un acide mono- ou dicarboxylique ou son anhydre, un générateur de radicaux et un polymère thermoplastique, dans des conditions où au moins un générateur de radical n'est pas activé, ii) à activer le générateur de radicaux pour former une liaison chimique entre l'acide dicarboxylique ou son anhydre et le polymère. Ce procédé est simple et économiquement viable, de plus il permet d'obtenir une composition polymère à forte charge qui est douée d'une bonne résistance mécanique.
EP99908782A 1998-03-23 1999-03-23 Procede de preparation d'une composition polymere Withdrawn EP1068267A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DK40498 1998-03-23
DK40498 1998-03-23
PCT/DK1999/000156 WO1999048975A1 (fr) 1998-03-23 1999-03-23 Procede de preparation d'une composition polymere

Publications (1)

Publication Number Publication Date
EP1068267A1 true EP1068267A1 (fr) 2001-01-17

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Country Status (3)

Country Link
EP (1) EP1068267A1 (fr)
AU (1) AU2827099A (fr)
WO (1) WO1999048975A1 (fr)

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Publication number Priority date Publication date Assignee Title
CA2771827C (fr) 2009-08-24 2017-11-28 Albemarle Europe Sprl Solutions et catalyseurs comprenant un metal du groupe vi, un metal du groupe viii et du phosphore
US11633727B2 (en) 2012-10-10 2023-04-25 Albemarle Catalysts Company B.V. Supported hydrotreating catalysts having enhanced activity
US11731118B2 (en) 2012-10-10 2023-08-22 Albemarle Catalysts Company B.V. Supported hydrotreating catalysts having enhanced activity
CN102936376B (zh) * 2012-12-04 2015-07-15 上海日之升新技术发展有限公司 一种高cti值、高gwit值环保阻燃玻纤增强pp/pa610合金材料及其制备方法
CN104829926B (zh) * 2015-04-29 2018-08-14 德阳中达铁路加固材料有限公司 一种三角挡
CN114269830A (zh) * 2019-08-29 2022-04-01 陶氏环球技术有限责任公司 制备聚烯烃固体和有机过氧化物的均匀混合物的方法
CN113355148B (zh) * 2021-05-28 2022-12-20 中国石油化工股份有限公司 一种用于汽车驱动轴轮毂轴承结合面的润滑剂及其制法

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GB1326238A (en) * 1969-12-13 1973-08-08 Asahi Chemical Ind Polyolefin compositions
DE3689096T2 (de) * 1985-07-09 1994-01-27 Nippon Petrochemicals Co Ltd Feuerhemmende Polyolefinzusammensetzung.
US4952428A (en) * 1988-12-07 1990-08-28 Union Carbide Chemicals And Plastics Company Inc. Flame retardant compositions
GB9016028D0 (en) * 1990-07-20 1990-09-05 Ici Plc Inorganic solid and polymer composition

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Title
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WO1999048975A1 (fr) 1999-09-30

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