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WO2017188789A1 - Composite de polyoléfine renforcé par des fibres et procédé de préparation associé - Google Patents

Composite de polyoléfine renforcé par des fibres et procédé de préparation associé Download PDF

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Publication number
WO2017188789A1
WO2017188789A1 PCT/KR2017/004593 KR2017004593W WO2017188789A1 WO 2017188789 A1 WO2017188789 A1 WO 2017188789A1 KR 2017004593 W KR2017004593 W KR 2017004593W WO 2017188789 A1 WO2017188789 A1 WO 2017188789A1
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Prior art keywords
group
fiber
carbon atoms
functional group
arylene
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PCT/KR2017/004593
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English (en)
Korean (ko)
Inventor
정호근
고영관
한혜진
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Lotte Chemical Corp
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Lotte Chemical Corp
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Publication of WO2017188789A1 publication Critical patent/WO2017188789A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

Definitions

  • the present invention relates to a fiber reinforced polyolefin composite and a method for producing the same. More specifically, the present invention relates to a fiber-reinforced polyolefin composite and a method for manufacturing the same, which can realize excellent compatibility and mechanical properties through chemical bonding between polyolefin resin and fiber, and can be manufactured quickly through high reaction properties.
  • Polyolefin resins have characteristics such as excellent properties, formability, mechanical properties and chemical resistance, and are used in various fields such as automobile interior parts, home appliance parts, industrial materials, textile fields or films.
  • the polyolefin resin has a relatively low tensile strength and flexural strength, its use is limited in fields requiring toughness and rigidity such as automobile parts.
  • fiber materials such as glass fiber have been frequently used as rigid reinforcement materials.
  • the glass fiber can be used in various fields, even though a small amount of the glass fiber is used, compared to the previously used talc or whisker, and thus can be obtained.
  • the strong bonding force between the polyolefin and the glass fiber can reduce the scattering of the glass fiber, the development of a polyolefin-fiber composite that can maintain or improve the mechanical properties such as flexural modulus and laminar strength above a certain level is required. have.
  • the present invention is to provide a fiber-reinforced polyolefin composites that can realize excellent compatibility and mechanical properties through chemical bonding between the polyolefin resin and the fiber, and can be produced in a fast time through high reactivity.
  • the present invention is to provide a method for producing the fiber-reinforced polyolefin composite.
  • a polymer substrate including a polyolefin resin; And a fiber reinforcing material impregnated with the polymer base, and a fiber-reinforced polyolefin composite in which the polymer base and the fiber reinforcing material are bonded through an aromatic divalent functional group including a urethane group.
  • the present disclosure also provides a fiber-reinforced polyolefin composite preparation comprising the step of melt extruding a polyolefin resin composition comprising a modified polyolefin resin, a fiber reinforcing material, and an aromatic diisocyanate compound grafted with a dicarboxylic acid component or an acid anhydride thereof.
  • a method is provided.
  • a fiber-reinforced polyolefin composite and a method of manufacturing the same according to specific embodiments of the present invention will be described in detail.
  • a polymer substrate including a polyolefin resin; And a fiber reinforcing material impregnated with the polymer substrate, wherein the polymer reinforcing material and the fiber reinforcing material may be provided with a fiber reinforced polyolefin composite in which an aromatic divalent functional group including a urethane group is bonded.
  • the inventors have identified certain fiber reinforced polyolefin composites described above. When used, by forming a chemical covalent bond between the fiber reinforcement and the polyolefin, the compatibility and interfacial adhesion between the fiber reinforcement and the polyolefin can be increased, thereby confirming that excellent surface properties and mechanical properties can be realized, and completed the invention. .
  • the chemical covalent bond between the fiber reinforcement and the polyolefin is an interatomic bond formed between atoms, and is higher than the intermolecular bonds such as hydrogen bonds formed by a compatibilizer added to improve the compatibility between the existing fiber reinforcement and polyolefin. Cohesion can be achieved.
  • the chemical covalent bond between the aforementioned fiber reinforcement and the polyolefin is made through an aromatic divalent functional group including a urethane group, and the urethane group may be obtained from reaction of an isocyanate group and a hydroxyl group.
  • the urethane group formation reaction is very high reactivity can induce a reaction in a short time to improve the process efficiency, it is possible to implement the effect of improving the mechanical properties more.
  • the fiber-reinforced polyolefin composite of one embodiment includes a polymer substrate including a polyolefin resin; And it may include a fiber reinforcing material impregnated with the polymer substrate.
  • the fiber reinforcing material is impregnated into the polymer substrate as described above, the fiber-reinforced polyolefin composite can realize high layer strength with high rigidity.
  • the fiber reinforcing material impregnated with the polymer base may mean a fiber reinforcing material dipped in the polymer base.
  • the polymer substrate means a composite material in which a small amount of a ceramic material, a metal material, or another polymer compound is mixed with a large amount of polymer compound, and a polyolefin resin may be used as the polymer compound.
  • a polyolefin resin may be used as the polymer compound.
  • Specific examples of the polyolefin resin are not particularly limited, and various polyolefin resins well known in the art may be used without limitation.
  • the weight average molecular weight of the polyolefin resin may be 130, 000 g / mol to 200, 000 g / irol, the weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by the GPC method.
  • the weight average molecular weight of polystyrene conversion measured by the GPC method Commonly known detectors and analysis columns such as differential index detectors (Refract ive Index Detector) can be used, and commonly used silver conditions, solvents, f low rate can be applied. Specific examples of the measurement conditions include a temperature of 30 ° C, a chloroform solvent (Chloroform) and f low rate of 1 raL / min.
  • the content of the polyolefin resin may be 0.1 to 95% by weight, or 40 to 75% by weight based on the weight of the fiber reinforced polyolefin composite. If the content of the polyolefin resin is less than 0.01% by weight based on the weight of the fiber-reinforced polyolefin composite, moldability may be reduced. In addition, when the content of the polyolefin resin is more than 95% by weight based on the weight of the fiber-reinforced polyolefin composite, the mechanical properties may be lowered such as the layer strength decreases.
  • the polymer substrate may further include a modified polyolefin resin in which a dicarboxylic acid component or an acid anhydride thereof is grafted.
  • a modified polyolefin resin in which a dicarboxylic acid component or an acid anhydride thereof is grafted.
  • the modified polyolefin resin included in the polymer substrate react with the compatibilizer to form a bond, but some of the modified polyolefin resins may remain unreacted. That is, the modified polyolefin resin included in the fiber-reinforced polyolefin composite refers to a resin remaining without reacting with a compatibilizer.
  • the fiber reinforcing material examples include glass fiber, carbon fiber, metal fiber, aramid fiber, ultra high molecular weight polyethylene fiber, polyacrylonitrile fiber, arylate fiber, polyetheretherketone fiber, kevlar fiber, basalt fiber, and the like. It may be used, preferably glass fiber or carbon fiber can be used.
  • the fiber reinforcement may have a length of 5 mm to 20 mm, or 5 mm to 15 mm. In addition, the fiber reinforcement may have a diameter of 100 or less, or I / an to 50 kPa.
  • the fiber reinforcing material may further include a semi-functional group modified on the surface.
  • the reactive functional group are not particularly limited, but for example, an epoxy group, a urethane group, a silane group, a silane group, an acryl group, or two or more thereof can be used.
  • the fiber reinforcement material contains reactive functional groups, the fiber reinforcement material is excellent in mixing with the polyolefin resin. Compatibility can be achieved.
  • the content of the fiber reinforcing material may be 0.1% to 70% by weight, or 1% to 50% by weight, or 5% to 50% by weight based on the weight of the fiber reinforced polyolefin composite.
  • the content of the fiber reinforcing material is less than 0.1 wt% based on the weight of the fiber reinforced polyolefin composite, mechanical properties of the fiber reinforced polyolefin composite may be lowered.
  • the fiber-reinforced polyolefin pin composite of the embodiment may be bonded through the aromatic divalent functional group, the polymer base and the fiber reinforcement material including a urethane group. That is, in the fiber-reinforced polyolefin composite, an aromatic divalent functional group including a urethane group is positioned between the polymer substrate and the fiber reinforcing material, and one end of the aromatic divalent functional group including the urethane group is bonded to the polymer substrate, and an aromatic including a urethane group. The other end of the divalent functional group can associate with the fiber reinforcement.
  • the bond can be known covalent bonds between atoms, and thus, it is possible to implement a high binding force compared to the intermolecular bonds such as hydrogen bonds formed by the compatibilizer added to improve the compatibility between the existing fiber reinforcement and polyolefin resin. .
  • compatibility and interfacial adhesion between the fiber reinforcement and the polyolefin resin can be increased, thereby achieving excellent surface properties and mechanical properties.
  • the aromatic divalent functional group including the urethane group may include an arylene functional group having 6 to 50 carbon atoms and a urethane group bonded to one end of the arylene functional group having 6 to 50 carbon atoms.
  • the arylene-based functional group may be a functional group derived from an arylene group which is a divalent functional group derived from arene, and may further include a functional group in which a specific functional group is substituted or added to the arylene group or the arylene group.
  • the arylene functional group having 6 to 50 carbon atoms may include a functional group represented by Formula 1 below.
  • the arylene group corresponding to 3 ⁇ 4 and R 3 is derived from arene.
  • the divalent functional group may be, for example, a phenylene group, a biphenylene group, a terphenylene group, a stilbenylene group, a naphthyleneyl group, and the like, but is not limited thereto.
  • One or more hydrogen atoms included in the arylene group may each be substituted with a substituent.
  • substituents examples include alkyl groups having 1 to 10 carbon atoms and carbon atoms 2 to 10
  • substituted means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is a position at which the hydrogen atom is replaced;
  • the substituent is not limited as long as it can be substituted, and when two or more are substituted, two or more substituents may be the same or different from each other.
  • the alkylene group corresponding to 3 ⁇ 4 is derived from alkane.
  • Divalent functional groups for example, linear, branched or cyclic, methylene group, ethylene group, propylene group, isobutylene group, sec-butylene group, tert-butylene group, pentylene group, ..
  • This can be At least one hydrogen atom included in the alkylene group may be substituted with the same substituent as in the case of the arylene group, respectively.
  • 3 ⁇ 4 and R 3 in Formula 1 may each independently represent an arylene group having 6 to 10 carbon atoms, or a phenylene group, and 3 ⁇ 4 is an alkylene group having 1 to 5 carbon atoms, or a methylene group. That is, specific examples of the carbon atoms of 6 to 50 aryl-series functional groups are 4, 4, and the like '- - (Methyl enebi sphenyl 4,4 ) methylene bis phenyl group.
  • the urethane group bonded to one end of the arylene-based functional group having 6 to 50 carbon atoms is a functional group or bond form formed by reaction of the hydroxyl group and the isocyanate group of alcohol
  • the specific chemical structure of the urethane group may be represented by -0C0NH-. .
  • the arylene functional group having 6 to 50 carbon atoms may be bonded to the nitrogen atom included in the urethane group.
  • the arylene-based functional group having 6 to 50 carbon atoms can be bonded to the fiber reinforcing material through a urethane group bonded to one end. That is, a urethane group is positioned between the arylene functional group having 6 to 50 carbon atoms and the fiber reinforcing material, and one end of the urethane group is bonded to the arylene functional group having 6 to 50 carbon atoms, and the other end of the urethane group is combined with the fiber reinforcing material. Can be.
  • the arylene functional group having 6 to 50 carbon atoms may be bonded to one terminal nitrogen atom included in the urethane group, and thus, the fiber reinforcement may be bonded to the oxygen atom of the other terminal included in the urethane group.
  • the aromatic divalent functional group including the urethane group may further include a urethane-based functional group bonded to the other terminal of the arylene-based functional group having 6 to 50 carbon atoms , or an amide functional group bonded to the other end of the arylene-based functional group having 6 to 50 carbon atoms. Can be.
  • the arylene functional group having 6 to 50 carbon atoms may be combined with the polymer substrate through a urethane functional group or an amide functional group. As described above, the arylene functional group having 6 to 50 carbon atoms may be bonded to the fiber reinforcing material through a urethane group bonded to one end thereof, and the other end of the arylene functional group having 6 to 50 carbon atoms may be a urethane based functional group or an amide based functional group. By forming a bond with the polymer substrate through the medium, a bond between the polymer substrate and the fiber reinforcement, can be formed.
  • R 4 is an alkylene group of 1 to 10 carbon atoms having a branched chain alkylene group having 1 to 5 carbon atoms bonded to a carboxyl group
  • 3 ⁇ 4 is a carbonyl group ⁇
  • Formula 2 Can mean.
  • Specific examples of 3 ⁇ 4 include a methylene group having a branched chain with a methylene group bonded to a carboxyl group at the terminal.
  • the specific chemical structure of the methylene group having a branched chain of the methylene group bonded to the carboxyl group may be represented by the following Chemical Formula 2-1.
  • the amide-based functional group bonded to the other end of the arylene-based functional group having 6 to 50 carbon atoms may include a functional group represented by the following formula (3).
  • Chemical Formula 3 it may mean a bonding point.
  • 3 ⁇ 4 is a carbon number having a carboxyl group bonded to the terminal 1 to It is a C1-C10 alkylene group which has a branched alkylene group of five. In addition, in Chemical Formula 3, it may mean a bonding point.
  • R 6 include a methylene group having a branched chain with a methylene group bonded to a carboxyl group at the terminal.
  • the specific chemical structure of the methylene group having a branched chain methylene group having a carboxyl group bonded to the terminal may be represented by Chemical Formula 2-1. That is, 3 ⁇ 4 is the same as R4 of Formula 2.
  • the aromatic divalent functional group including the urethane group may include a functional group represented by the following formula (4).
  • Ri may each independently represent an arylene group having 6 to 10 carbon atoms, or a phenylene group, and 3 ⁇ 4 is an alkylene group having 1 to 5 carbon atoms, or a methylene group.
  • R 4 in Formula 4 may include a methylene group having a branched chain with a methylene group bonded to a carboxyl group at a terminal thereof.
  • bonded with the terminal in the branched chain can be represented by following formula (4-1).
  • aromatic divalent functional group including the urethane group may include a functional group represented by the following formula (5).
  • 3 ⁇ 4 and R 3 are each independently an arylene group having 6 to 20 carbon atoms
  • R 2 is an alkylene group having 1 to 10 carbon atoms
  • 3 ⁇ 4 is an alkylene group having 1 to 5 carbon atoms bonded to a carboxyl group at a terminal thereof. It is a C1-C10 alkylene group which has a branched chain.
  • "*" may mean a bonding point.
  • Formula 5 and 3 ⁇ 4 are each independently an arylene group having 6 to 10 carbon atoms, or a phenylene group, 3 ⁇ 4 is an alkylene group having 1 to 5 carbon atoms, or methylene group.
  • Specific examples of the general formula (5) include a methylene group having a branched chain with a methylene group bonded to a carboxyl group at the terminal.
  • the specific chemical structure of the methylene group having a branched chain of the methylene group bonded to the carboxyl group may be represented by the following Chemical Formula 5-1.
  • Examples of the specific method for preparing the fiber-reinforced polyolefin composites are not limited to, but include, for example, a modified polyolefin resin, a fiber reinforcing material, and an aromatic diisocyanate compound grafted with a dicarboxylic acid component or an acid anhydride thereof. It can be prepared through the fiber reinforced polyolefin composite production method of another embodiment of the invention comprising the step of melt extrusion of the polyolefin resin composition.
  • the use of the fiber-reinforced polyolefin composite is not particularly limited, it is possible to apply to various technical fields in which the polyolefin can be used.
  • fiber reinforced comprising the step of melt-extruded polyolefin resin composition comprising a modified polyolefin resin, a fiber reinforcing material, and an aromatic diisocyanate compound grafted dicarboxylic acid component or acid anhydride thereof
  • a method for producing a polyolefin composite may be provided.
  • the fiber-reinforced polyolefin composite of the embodiment may be obtained by the method of preparing the fiber-reinforced polyolefin composite of another embodiment.
  • the method of manufacturing a fiber-reinforced polyolefin pin composite of another embodiment is a step of melt-extruded polyolefin resin composition comprising a modified polyolefin resin, a fiber reinforcing material, and an aromatic diisocyanate compound grafted with a dicarboxylic acid component or an acid anhydride thereof It may include.
  • the polyolefin resin composition may include a modified polyolefin resin, a fiber reinforcing material, and an aromatic diisocyanate compound grafted with a dicarboxylic acid component or an acid anhydride thereof.
  • the modified polyolefin resin in which the dicarboxylic acid component or an acid anhydride thereof is grafted refers to a polymer in which a dicarboxylic acid component or an acid anhydride thereof is grafted onto a polyolefin pin chain to form a branched chain.
  • the content of the grafted dicarboxylic acid component or an acid anhydride thereof in the modified polyolefin resin may be 0.5% by weight to 6% by weight>.
  • the modified polyolefin resin may be difficult to have a good compatibility or bonding strength with respect to the fiber reinforcement.
  • the dicarboxylic acid component or an acid anhydride thereof is grafted to more than 6% by weight of the polyolefin resin, mechanical properties or flexibility of the modified polyolefin resin or the fiber-reinforced polyolefin composite may be reduced.
  • the dicarboxylic acid component or acid anhydride thereof refers to a compound containing two carboxyl groups or derivatives thereof, for example, maleic acid, phthalic acid, itaconic acid, citraconic acid, alkenylsuccinic acid, cis-1,2,3 ,
  • One dicarboxylic acid component selected from the group consisting of 6 tetrahydrophthalic acid and 4-methyl-1, 2, 3, 6 tetrahydrophthalic acid, or a linear or branched alkyl esterified product having 1 to 10 carbon atoms thereof. have.
  • the graft ratio of the dicarboxylic acid component or acid anhydride thereof can be measured from the result obtained by acid-base titration of the modified polyolefin resin.
  • the modified polypropylene resin was added to 150 xylene saturated with water, and refluxed for about 2 hours. Then, a small amount of 1% by weight thymol blue-dimethylformamide solution was added, and 0.05N sodium hydroxide-ethyl alcohol solution was used.
  • dicarboxylic acid component or an acid anhydride thereof is grafted
  • polyolefin resin include maleic acid or modified polypropylene grafted with maleic anhydride.
  • the weight average molecular weight of the modified polyolefin resin grafted with the dicarboxylic acid component or an acid anhydride thereof may be 100, 000 to 900, 000, or 130, 000 to 200, 000.
  • the said weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by the GPC method.
  • a detector and an analytical column such as a commonly known analytical device and a differential refractive index detector (Refractive Index Detector) may be used, Temperature conditions, solvents, f low rate can be applied. Specific examples of the measurement conditions include a temperature of 30 ° C, a chloroform solvent (Chloroform) and f low rate of 1 mL / min.
  • the polyolefin resin included in the modified polyolefin resin is not particularly limited, and may include, for example, polypropylene.
  • the aromatic diisocyanate compound may be used as a compatibilizer for chemically crosslinking reaction with the modified polyolefin resin and the fiber reinforcing material to form a crosslinked structure.
  • the aromatic diisocyanate compound has very high reaction properties, and can improve the compatibility and bonding strength between the polyolefin resin and the fiber reinforcing agent in a short time. '
  • the aromatic diisocyanate compound may include an isocyanate group bonded to an end of the arylene functional group having 6 to 50 carbon atoms and the arylene functional group having 6 to 50 carbon atoms.
  • the arylene-based functional group may further include a functional group in which a specific functional group is substituted or added to the arylene group or the arylene group, and a functional group derived from an arylene group which is a divalent functional group derived from arene.
  • the arylene functional group having 6 to 50 carbon atoms may include a functional group represented by Formula 1 below.
  • Rf ⁇ f3 ⁇ 4 ⁇ Rg ⁇ *
  • Ri and 3 ⁇ 4 are each independently an arylene group having 6 to 20 carbon atoms
  • R 2 is an alkylene group having 1 to 10 carbon atoms.
  • Ri and 3 ⁇ 4 may be the same or different from each other.
  • the arylene group is a divalent functional group derived from arene, and may be, for example, a phenylene group, a biphenylene group, a terphenylene group, a stilbenylene group, a naphthyleneyl group, or the like, but is not limited thereto.
  • One or more hydrogen atoms included in the arylene group may each be substituted with a substituent.
  • substituents examples include an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an alkynyl group of 2 to 10 carbon atoms, an aryl group of 6 to 12 carbon atoms, a heteroaryl group of 2 to 12 carbon atoms, and a 6 to 12 carbon atoms.
  • Aryl alkyl group, a halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amide group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carbamate group, a C1-C10 alkoxy group, etc. are mentioned.
  • substituted means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.
  • the alkylene group is a divalent functional group derived from alkane, for example, linear, branched or cyclic, methylene group, ethylene group, propylene group, isobutylene group, sec-butylene group, tert-butylene group, pentylene group, nucleosilane group and the like. At least one hydrogen atom included in the alkylene group may be substituted with the same substituent as in the case of the arylene group, respectively.
  • 3 ⁇ 4 and R 3 in Formula 1 are each independently carbon number
  • It may be an arylene group of 6 to 10, or a phenylene group, 3 ⁇ 4 is an alkylene group having 1 to 5 carbon atoms, or methylene group. That is, specific examples of the carbon atoms of 6 to 50 aryl-series functional group is 4,4 '- methylene bis phenyl group (4,4' -
  • Isocyanate functional groups have a chemical structure represented by -NC0-, and can react with the hydroxyl group (-0H) contained on the surface of the modified polyolefin resin or the fiber reinforcement to form a urethane group.
  • the aromatic diisocyanate compound undergoes chemical crosslinking reaction with the modified polyolefin resin and the fiber reinforcing material to form a crosslinked structure
  • maleic anhydride modified polypropylene homopolymer and diphenylmethane diisocyanate compound When mixing and reacting glass fibers surface-treated with a silanol-based coupling agent, urethane groups may be formed through the isocyanate functional period reaction of the maleic anhydride and the diphenylmethane diisocyanate compound of the maleic anhydride-modified polypropylene homopolymer. Can be.
  • the urethane group may be formed through the reaction period of the isocyanate of the hydroxy group and the diphenylmethane diisocyanate compound of the glass fiber surface-treated with the silanol-based coupling agent. At this time, additional carbon dioxide reaction may be further progressed according to reaction conditions.
  • the content of the fiber reinforcing material includes the above-described content as described in the embodiment.
  • the polyolefin resin composition may dicarboxylic acid component or its anhydride is the graft modified polrieul repin resin 0.1 wt% to 95 wt% by weight of fiber reinforcement 0.1 to 70,% by weight, and an aromatic diisocyanate compound 0. 1% by weight to 50% by weight 3 ⁇ 4>.
  • the content of the aromatic diisocyanate compound may be 0.1 to 50 parts by weight based on 100 parts by weight of the modified polyolefin resin grafted with the dicarboxylic acid component or an acid anhydride thereof.
  • an aromatic diisocyanate compound when used together with a dicarboxylic acid component or an acid anhydride thereof to improve the compatibility between the polyolefin resin and the fiber reinforcing material, when only the dicarboxylic acid component or an acid anhydride thereof is used as a compatibilizer as in the past In comparison, it is possible to implement better compatibility and mechanical properties.
  • the polyolefin resin composition is a reaction catalyst, stabilizer, colorant, inorganic layering agent, sunscreen, antioxidant, lubricant, charging ⁇ ⁇ 1 " paper, lamination It may further comprise at least one additive selected from the group consisting of a reinforcing agent and ' microparticles.
  • each of the addition amount is not very limited, but at the same time to implement the functionality as an additive, reducing the physical properties of the final fiber-reinforced polyolefin composite
  • To prevent the addition may be added in about 0.01% to 10% by weight based on the weight of the fiber reinforced polyolefin composite.
  • the catalyst by injection in an amount of 0.01 to 0.5 parts by weight relative to 100 parts by weight of aromatic diisocyanate it can prevent side reactions due to excessive addition of the catalyst.
  • Examples of the method for producing the polyolefin resin composition are not particularly limited, and the method of simultaneously or sequentially mixing the modified polyolefin resin, fiber reinforcing material, aromatic diisocyanate compound and additives may be applied without limitation.
  • the polyolefin resin composition may be prepared by mixing the modified polyolefin resin, the fiber reinforcing material, and the additive at the same time, and then adding the aromatic diisocyanate compound separately.
  • Melt-extruding the polyolefin resin composition may be carried out at 150 to 300 ° C, or 200 ° C to 300 ° C. If the melt extrusion is performed at a temperature that is too low, the polyolefin resin and glass fibers may not be uniformly melted, and thus the mechanical properties of the fiber reinforced composite produced may be degraded. As a result, the mechanical properties of the resin itself can be reduced.
  • An example of the specific method of the melt extrusion step is not limited to a large amount, for example, a method of injecting the polyolefin resin composition into an extruder having a screw conversion speed of 50 rpm to 300 rpm can be used.
  • impregnating the fiber reinforcing material in the polyolefin resin solution before the step of melt extrusion of the modified polyolefin resin, fiber reinforcing material, and an aromatic diisocyanate compound grafted with the dicarboxylic acid component or acid anhydride thereof may further include.
  • the polyolefin resin solution may be in a solution state in which the polyolefin resin is dissolved in a solvent.
  • the polyolefin resin solution may further include the other additives described above.
  • the polyolefin resin in a solution state, is uniformly coated around the fiber reinforcement, and the fiber reinforcement is not scattered at the stage of melt extrusion with the polyolefin to produce a composite, and the dispersibility of the fiber reinforcement is also improved.
  • Mechanical properties of the composite can be improved.
  • the solvent water, an organic solvent or a mixture thereof can be used.
  • the organic solvent include methanol, ethanol, n-propane, isopropane, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol ⁇ isoamyl alcohol, sec-amyl alcohol, tert -Amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butane, n-nucleic acid, alcohols such as cyclonucleic acid, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclonucleanone, etc.
  • Aromatic hydrocarbons such as ketones, benzene, toluene, xylene, cumene, cymene, alicyclic hydrocarbons such as cyclopentane, cyclonucleic acid, cyclooctane, methylcyclonucleic acid and methylcyclopentane, tetrahydrofuran and dioxane Ethers, ethyl acetate, -n-propyl acetate, isopropyl acetate, -n-butyl acetate, isobutyl acetate, -sec-butyl acetate, -3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate , Dime Carbonate Esters such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, glycol derivative
  • the content of the solid content in the polyolefin resin solution may be 1 to 50% by weight, preferably 3 to 50% by weight.
  • the solid content may include polyolefin resin or other additives, and if the concentration of the solid content is too low, polyolefin may not be coated on the surface of the fiber reinforcement layer. If the concentration of the solid content exceeds 50% by weight, the viscosity of the solution is high, there is a limit that the coating is not uniform.
  • Impregnating the fiber reinforcing material in the polyolefin resin solution may be performed for about 1 to 60 seconds. That is, the residence time of the fiber reinforcement in the polyolefin resin solution is preferably 1 second or more and 60 seconds or less. A time of less than 1 second is not sufficient to uniformly impregnate the polyolefin resin solution, and if the residence time is too long, the improvement of the impregnation degree compared to the residence time is insignificant, and the process speed may be slowed, resulting in poor process efficiency and economic efficiency.
  • the fiber-reinforced polypropylene resin composition was prepared by impregnating the surface of the polypropylene resin composition prepared above at room temperature with a glass fiber surface-treated with a silane-based coupling agent.
  • a fiber-reinforced polypropylene resin composite was prepared in the same manner as in the above example, except that maleic anhydride-modified polypropylene homopolymer and diphenylmethane diisocyanate were not used. Comparative Example 2
  • a fiber-reinforced polypropylene resin composite was prepared in the same manner as in the above example, except that nuxamethylene diisocyanate (H e x ame thylene di i socyanate) was used instead of diphenylmethane diisocyanate.
  • Example 1 in which diphenylmethane diisocyanate was added as a compatibilizer together with maleic anhydride-modified polypropylene homopolymer, tensile strength of 53.8 MPa, flexural strength of 73 MPa, and 2638 MPa of Flexural modulus, 4.9 kg ⁇ cm / cm exhibited a striking strength was confirmed that excellent mechanical properties can be achieved.
  • Comparative Example 1 containing no maleic anhydride-modified polypropylene homopolymer and a diphenylmethane diisocyanate compatibilizer at all, containing only maleic anhydride-modified polypropylene homopolymer and no diphenylmethane diisocyanate compatibilizer
  • Comparative Example 2 in the case of Comparative Example 3 in which nucleated methylene diisocyanate was added instead of diphenylmethane diisocyanate, tensile strength, flexural strength, flexural modulus, and laminar strength were all measured to be lower than those in Example 1.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

La présente invention concerne : un composite de polyoléfine renforcé par des fibres capable de conférer une compatibilité et des propriétés mécaniques excellentes par liaison chimique entre une résine de polyoléfine et une fibre, et pouvant être préparé en un court laps de temps grâce à une réactivité élevée ; et un procédé de préparation associé.
PCT/KR2017/004593 2016-04-28 2017-04-28 Composite de polyoléfine renforcé par des fibres et procédé de préparation associé Ceased WO2017188789A1 (fr)

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KR1020160052330A KR20170123104A (ko) 2016-04-28 2016-04-28 섬유 강화 폴리올레핀 복합체 및 그 제조방법

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KR20240077229A (ko) * 2022-11-24 2024-05-31 롯데케미칼 주식회사 열가소성 수지 조성물 및 이로부터 제조된 성형품

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US12379190B2 (en) * 2020-02-06 2025-08-05 Barrday Corp. Ballistic-resistant composite with maleic anhydride-grafted polypropylene

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