KR20170123104A - Fiber reinforced polyolefin complex and preparation method of the same - Google Patents

Abstract

The present invention relates to a fiber-reinforced polyolefin composite capable of realizing excellent compatibility and mechanical properties through chemical bonding between a polyolefin resin and a fiber, and capable of being produced in a short period of time through high reactivity, and a method for producing the same.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a fiber reinforced polyolefin composite,

The present invention relates to a fiber-reinforced polyolefin composite and a method for producing the same. More particularly, the present invention relates to a fiber-reinforced polyolefin composite capable of realizing excellent compatibility and mechanical properties through chemical bonding between a polyolefin resin and a fiber, and capable of being produced in a short period of time through high reactivity, and a method for producing the same.

The polyolefin resin has various characteristics such as excellent moldability, mechanical properties and chemical resistance, and is widely used in the fields of automobile interior parts, home appliance parts, industrial materials, textile field, and film. However, since such a polyolefin resin has a relatively low tensile strength and bending strength, its use has been limited in areas requiring toughness and rigidity, such as automobile parts.

In order to improve the tensile strength, flexural strength and impact strength of the polyolefin resin, methods of adding a reinforcing material such as another polymer resin or a rubber component have been used. However, the general reinforcing material does not sufficiently improve the mechanical properties of the resin There was a limit.

In recent years, a fiber material such as glass fiber has been used as a rigid reinforcing material in order to apply polyolefin resin to automobile parts and electric / electronic parts. The glass fiber is applied to various fields because it can obtain a property improvement effect even though it is used in a small amount compared to talc or whisker which has been used before, but the polyolefin resin to which the glass fiber is added is molded There is a phenomenon that the glass fiber is broken and scattered, and the mechanical properties are deteriorated.

Accordingly, it is required to develop a polyolefin-fiber composite capable of reducing the scattering phenomenon of the glass fiber due to the strong bonding force between the polyolefin and the glass fiber, and maintaining or improving mechanical properties such as flexural modulus and impact strength to a certain level or higher have.

The present invention is to provide a fiber-reinforced polyolefin composite capable of realizing excellent compatibility and mechanical properties through chemical bonding between a polyolefin resin and a fiber, and capable of being produced quickly with high reactivity.

The present invention also provides a method for producing the fiber-reinforced polyolefin composites.

In this specification, a polymer substrate containing a polyolefin resin; And a fiber reinforcing material impregnated with the polymer substrate, wherein the polymer substrate and the fiber reinforcing material are bonded via an aromatic divalent functional group containing a urethane group.

The present invention also relates to a method for producing a fiber-reinforced polyolefin composite comprising a step of melt-extruding a polyolefin resin composition containing a modified polyolefin resin, a fiber reinforcement, and an aromatic diisocyanate compound in which a dicarboxylic acid component or an acid anhydride thereof is grafted / RTI >

A fiber-reinforced polyolefin composite according to a specific embodiment of the present invention and a method of manufacturing the same will be described in detail below.

According to one embodiment of the invention, a polymer substrate comprising a polyolefin resin; And a fiber reinforced polyolefin composite in which the polymer substrate and the fiber reinforcing material are bonded via an aromatic divalent functional group containing a urethane group can be provided.

Using the specific fiber reinforced polyolefin composites described above, the inventors have found that 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, And confirmed that the physical properties can be realized and completed the invention.

Particularly, the chemical covalent bond between the above-mentioned fiber reinforcement and the polyolefin is an inter-atomic bond formed between atoms, and it has a higher bonding force than the intermolecular bond formed by the compatibilizer added for improving the compatibility between the conventional fiber reinforcement and the polyolefin Can be implemented.

The chemical covalent bond between the above-mentioned fiber reinforcement and the polyolefin is mediated by an aromatic divalent functional group containing a urethane group, and the urethane group can be obtained from a reaction between an isocyanate group and a hydroxyl group. Such urethane group forming reaction is highly reactive and can induce the reaction within a short time, thereby improving not only the process efficiency but also the mechanical properties.

Specifically, the fiber-reinforced polyolefin composite of one embodiment comprises a polymer substrate comprising a polyolefin resin; And a fiber reinforcement impregnated with the polymeric substrate. By impregnating the fiber reinforcement into the polymer matrix, the fiber-reinforced polyolefin composites can achieve high impact strength as well as high rigidity. The fiber reinforcing material impregnated with the polymer base material may mean a fiber reinforcing material immersed in the polymer base material.

Specifically, the polymer base material means a composite material obtained by mixing a large amount of a polymer compound with a small amount of a ceramic material, a metal material, or another polymer compound, and as the polymer compound, a polyolefin resin can be used. The specific examples of the polyolefin resin are not limited, and various polyolefin resins widely known in the related art can be used without limitation.

The weight average molecular weight of the polyolefin resin may be 130,000 g / mol to 200,000 g / mol, and the weight average molecular weight refers to a weight average molecular weight in terms of polystyrene measured by a GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a detector such as a known analyzer and a refractive index detector, and an analyzing column can be used. Conditions, solvents, and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 30 DEG C, a chloroform solvent (Chloroform), and a flow rate of 1 mL / min.

The content of the polyolefin resin may be 0.1 wt% to 95 wt%, or 40 wt% to 75 wt%, based on the weight of the fiber-reinforced polyolefin composite. If the content of the polyolefin resin is less than 0.1% by weight based on the weight of the fiber-reinforced polyolefin composite, the molding processability may be reduced. In addition, if the content of the polyolefin resin exceeds 95% by weight based on the weight of the fiber-reinforced polyolefin composite, the mechanical properties such as impact strength may be decreased.

On the other hand, the polymer substrate may further include a modified polyolefin resin in which a dicarboxylic acid component or an acid anhydride thereof is grafted. As described later, most of the modified polyolefin resins contained in the polymer substrate react with the compatibilizing agent to form bonds, but some modified polyolefin resins may remain unreacted. That is, the modified polyolefin resin contained in the fiber-reinforced polyolefin composite means the resin remaining in a state that does not react with the compatibilizing agent.

Examples of the fiber reinforcement include glass fiber, carbon fiber, metal fiber, aramid fiber, ultrahigh molecular weight polyethylene fiber, polyacrylonitrile fiber, arylate fiber, polyetheretherketone fiber, Kevlar fiber, And preferably glass fibers or carbon fibers can be used.

The fiber reinforcement may have a length of from 5 mm to 20 mm, or from 5 mm to 15 mm. The fiber reinforcement may have a diameter of 100 탆 or less, or 1 탆 to 50 탆. In addition, the fiber reinforcement may further comprise a reactive functional group modified on the surface. Examples of the reactive functional groups are not particularly limited, and for example, an epoxy group, a urethane group, a silane group, a silanol group, an acrylic group, or two or more of them may be used. As the fiber reinforcement contains a reactive functional group, the fiber reinforcement can realize excellent compatibility in the process of mixing with the polyolefin resin.

The content of the fiber reinforcement may be 0.1 wt% to 70 wt%, or 1 wt% to 50 wt%, or 5 wt% to 50 wt%, based on the weight of the fiber-reinforced polyolefin composite. If the content of the fiber reinforcement is less than 0.1% by weight based on the weight of the fiber-reinforced polyolefin composite, the mechanical properties of the fiber-reinforced polyolefin composite may be deteriorated.

Also, in the fiber-reinforced polyolefin composite of one embodiment, the polymer substrate and the fiber reinforcement may be bonded through an aromatic divalent functional group including a urethane group. That is, in the above-mentioned fiber-reinforced polyolefin composite, an aromatic divalent functional group containing a urethane group is located between the polymer substrate and the fiber reinforcing material, one end of the aromatic divalent functional group containing the urethane group is bonded to the polymeric base, The other end of the bifunctional group may be bonded to the fiber reinforcement.

The bond may be a covalent bond between an atom and an atom, thereby achieving a higher bonding force than an intermolecular bond formed by a compatibilizer added to improve compatibility between a conventional fiber reinforcement and a polyolefin resin . Accordingly, the compatibility between the fiber reinforcement and the polyolefin resin and the interfacial adhesion strength can be increased, thereby realizing excellent surface properties and mechanical properties.

Specifically, the aromatic divalent functional group including the urethane group may include an arylene group functional group having 6 to 50 carbon atoms and a urethane group bonded at one end of the arylene group 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 an arylene group or an arylene group.

More specifically, the arylene group functional group having 6 to 50 carbon atoms may include a functional group represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ and R ₃ are each independently an arylene group having 6 to 20 carbon atoms and R ₂ is an alkylene group having 1 to 10 carbon atoms. In the above formula (1), "*" may mean a bonding point. R ₁ and R ₃ may be the same or different from each other.

The arylene group corresponding to R ₁ and R ₃ is a divalent functional group derived from arene such as a phenylene group, a biphenylene group, a terphenylene group, a stilbene group, a naphthylenyl group and the like But is not limited thereto. The at least one hydrogen atom contained in the arylene group may each be substituted with a substituent.

Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 12 carbon atoms, A halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amido group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carbamate group and an alkoxy group having 1 to 10 carbon atoms.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the substituted position is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.

The alkylene group corresponding to R ₂ is a bivalent group derived from an alkane such as a straight chain, branched or cyclic alkylene group, an ethylene group, a propylene group, an isobutylene group, sec-butylene group, tert-butylene group, pentylene group, hexylene group and the like. The at least one hydrogen atom contained in the alkylene group may be substituted with the same substituent as in the case of the arylene group.

Preferably, R ₁ and R ₃ in formula (1) are each independently an arylene group having 6 to 10 carbon atoms or a phenylene group, and R ₂ is an alkylene group having 1 to 5 carbon atoms or a methylene group. Specifically, specific examples of the arylene group having 6 to 50 carbon atoms include 4,4'-methylenebisphenyl and the like.

On the other hand, the urethane group bonded to one end of the arylene group having 6 to 50 carbon atoms is a functional group or a bond form formed by the reaction of the hydroxyl group of the alcohol with the isocyanate group, and the specific chemical structure of the urethane group can be represented by -OCONH- .

When the urethane group is bonded to one terminal of the arylene group having 6 to 50 carbon atoms, the arylene group having 6 to 50 carbon atoms may be bonded to the nitrogen atom contained in the urethane group.

On the other hand, the arylene-based functional group having 6 to 50 carbon atoms can be bonded to the fiber reinforcement through a urethane group bonded at one end. That is, a urethane group is positioned between the arylene group-containing functional group having 6 to 50 carbon atoms and the fiber reinforcing material, one end of the urethane group is bonded to an arylene group having 6 to 50 carbon atoms, and the other end of the urethane group is bonded can do.

As described above, the above-mentioned aryl-based functional group having 6 to 50 carbon atoms can be bonded to the nitrogen atom at one end included in the urethane group, and thus the fiber reinforcing material can be bonded to the oxygen atom at the other end included in the urethane group .

The aromatic divalent functional group containing the urethane group may further include an urethane functional group bonded to the other terminal of the arylene functional group having 6 to 50 carbon atoms or an amide functional group bonded to the other terminal of the arylene functional group having 6 to 50 carbon atoms have. The other terminal of the arylene group functional group having 6 to 50 carbon atoms means that the arylene group functional group having 6 to 50 carbon atoms is the other end excluding the one terminal group of the arylene group functional group having 6 to 50 carbon atoms in which a urethane group is bonded .

The arylene-based functional group having 6 to 50 carbon atoms may be bonded to the polymer substrate via an urethane-based functional group or an amide-based functional group. As described above, since the arylene group-containing functional group having 6 to 50 carbon atoms can be bonded to the fiber reinforcing material via the urethane group bonded at one end thereof, the other end of the arylene group-containing functional group having 6 to 50 carbon atoms is bonded to the urethane- The bond between the polymer substrate and the fiber reinforcing material can be formed.

The urethane functional group bonded to the other terminal of the arylene group having 6 to 50 carbon atoms is a functional group derived from a urethane group and may further include a functional group in which a specific functional group is substituted or added to the urethane group or the urethane group.

Specifically, the urethane-based functional group may include a functional group represented by the following general formula (2).

(2)

In the above formula (2), R ₄ is an alkylene group having 1 to 10 carbon atoms and a branched chain having 1 to 5 carbon atoms in which a carboxyl group is bonded to the terminal, and R ₅ is a carbonyl group. In the above formula (2), "*" may mean a bonding point. As a specific example of R ₄ , there can be mentioned a methylene group having a methylene group having a terminal carboxyl group bonded thereto as a branch chain. The specific chemical structure of the methylene group having a methylene group bonded to the carboxyl group at the terminal as a branch chain can be represented by the following formula (2-1).

[Formula 2-1]

In addition, the amide-based functional group bonded to the other terminal of the arylene group functional group having 6 to 50 carbon atoms may include a functional group represented by the following general formula (3). In the formula (3), "* " may mean a bonding point.

(3)

In the above formula (3), R ₆ is an alkylene group having 1 to 10 carbon atoms and having an alkylene group having 1 to 5 carbon atoms in which a carboxyl group is bonded at the terminal thereof as a branched chain. In the above formula (3), "*" may mean a bonding point. As a specific example of R ₆ , a methylene group having a methylene group having a carboxyl group at the terminal thereof as a branch chain can be mentioned. The specific chemical structure of the methylene group having a methylene group having a carboxyl group bonded to the terminal as a branch chain may be represented by the formula (2-1). That is, R ₆ is the same as R ₄ in the formula (2).

More specifically, the aromatic divalent functional group containing the urethane group may include a functional group represented by the following formula (4).

[Chemical Formula 4]

Wherein R ₁ 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, and R ₄ is an alkyl group having 1 to 5 carbon atoms to which a carboxyl group is bonded at the terminal An alkylene group having 1 to 10 carbon atoms and having 5 to 30 carbon atoms, and R < ₅ > In the formula (4), "*" may mean a bonding point.

In Formula 4, R ₁ and R ₃ are each independently an arylene group having 6 to 10 carbon atoms or a phenylene group, and R ₂ is an alkylene group having 1 to 5 carbon atoms or a methylene group.

Specific examples of R ₄ in the general formula (4) may be mentioned a methylene group having a carboxyl group is a methylene group bonded to the terminal as a branched chain. The specific chemical structure of the methylene group having a methylene group having a carboxyl group bonded to the terminal as a branch chain can be represented by the following Chemical Formula 4-1.

[Formula 4-1]

The aromatic divalent functional group containing the urethane group may include a functional group represented by the following general formula (5).

[Chemical Formula 5]

In Formula 5, R ₁ 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, R ₆ is an alkyl group having 1 to 5 carbon atoms, And an alkylene group having 1 to 10 carbon atoms having a phenylene group as a branching group. In the above formula (5), "*" may mean a bonding point.

In the formula (5), R ₁ and R ₃ are each independently an arylene group having 6 to 10 carbon atoms or a phenylene group, and R ₂ is an alkylene group having 1 to 5 carbon atoms or a methylene group.

Specific examples of R ₆ in the above formula (5) include a methylene group having a methylene group having a carboxyl group at the terminal thereof as a branch chain. The specific chemical structure of the methylene group having a methylene group bonded to the carboxyl group at the terminal as a branch chain can be represented by the following chemical formula 5-1.

[Formula 5-1]

Examples of specific methods for producing the fiber-reinforced polyolefin composites are not limited. For example, a modified polyolefin resin in which a dicarboxylic acid component or its acid anhydride is grafted, a fiber reinforcement, and a polyolefin including an aromatic diisocyanate compound Reinforced polyolefin composites of another embodiment of the invention comprising a step of melt-extruding the resin composition.

The use of the fiber-reinforced polyolefin composites is also not limited, and can be applied to various technical fields in which polyolefins can be used. For example, it can be applied not only to automobile fields including automobile interior and exterior parts such as door modules, crash pads, door trim, instrument panel, bumpers and fillers but also to various fields such as air, space, sports, industrial machinery, medical equipment, It can be used in various fields.

On the other hand, according to another embodiment of the present invention, there is provided a method for producing a fiber reinforced resin composition, which comprises melt-extruding a polyolefin resin composition containing a modified polyolefin resin having a dicarboxylic acid component or an acid anhydride thereof grafted, a fiber reinforcing material and an aromatic diisocyanate compound A process for producing a polyolefin complex can be provided.

The fiber-reinforced polyolefin composites of this embodiment can be obtained by the above-described method of producing a fiber-reinforced polyolefin composite.

Specifically, the method for producing a fiber-reinforced polyolefin composite of another embodiment includes a step of melt-extruding a polyolefin resin composition containing a modified polyolefin resin having a dicarboxylic acid component or an acid anhydride thereof grafted, a fiber reinforcement, and an aromatic diisocyanate compound .

The polyolefin resin composition may include a modified polyolefin resin in which a dicarboxylic acid component or an acid anhydride thereof is grafted, a fiber reinforcement, and an aromatic diisocyanate compound.

The modified polyolefin resin in which the dicarboxylic acid component or an acid anhydride thereof is grafted is a polymer in which a dicarboxylic acid component or an acid anhydride thereof is grafted to a polyolefin main chain to form a branched chain.

The content of the grafted dicarboxylic acid component or the acid anhydride thereof in the modified polyolefin resin may be 0.5 wt% to 6 wt%. If the dicarboxylic acid component or an acid anhydride thereof is grafted to less than 0.5% by weight in the polyolefin resin, the modified polyolefin resin may be difficult to have sufficient compatibility or bonding strength to the fiber reinforcement. If the dicarboxylic acid component or an acid anhydride thereof is grafted to the polyolefin resin in an amount exceeding 6% by weight, the mechanical properties or flexibility of the modified polyolefin resin or the fiber-reinforced polyolefin composite may be deteriorated.

The dicarboxylic acid component or an acid anhydride thereof means a compound containing two carboxyl groups or a derivative thereof and includes, for example, maleic acid, phthalic acid, itaconic acid, citraconic acid, alkenylsuccinic acid, , 6 tetrahydrophthalic acid and 4-methyl-1,2,3,6 tetrahydrophthalic acid, or a linear or branched alkyl ester of 1 to 10 carbon atoms have.

The grafting ratio of the dicarboxylic acid component or its acid anhydride can be determined from the results obtained by acid-base titration of the modified polyolefin resin. For example, about 1 g of the modified polypropylene resin is placed in 150 ml of xylene saturated with water and refluxed for about 2 hours. A small amount of a 1% by weight thymol blue-dimethylformamide solution is added, and a 0.05 N sodium hydroxide-ethyl alcohol solution To obtain a solution of a blue-brownish color. The solution was again back-adjusted with 0.05N hydrochloric acid-isopropyl alcohol solution until it showed yellow color, and the acid value was determined. From this, the acid value of the dicarboxylic acid grafted to the modified polypropylene resin The amount of acid can be calculated.

More specific examples of the modified polyolefin resin in which the dicarboxylic acid component or an acid anhydride thereof is grafted include modified polypropylene in which maleic acid or maleic anhydride is grafted.

The modified polyolefin resin in which the dicarboxylic acid component or an acid anhydride thereof is grafted may have a weight average molecular weight of 100,000 to 900,000, or 130,000 to 200,000. The weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a detector such as a known analyzer and a refractive index detector, and an analyzing column can be used. Conditions, solvents, and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 30 DEG C, a chloroform solvent (Chloroform), and a flow rate of 1 mL / min.

On the other hand, the polyolefin resin contained in the modified polyolefin resin is not particularly limited, and may include, for example, polypropylene and the like.

On the other hand, the aromatic diisocyanate compound can be used as a compatibilizing agent to form a crosslinked structure by conducting a chemical crosslinking reaction with the modified polyolefin resin and the fiber reinforcement. The aromatic diisocyanate compound has a very high reactivity and can improve the compatibility and bonding strength between the polyolefin resin and the fiber reinforcing agent in a short period of time.

Specifically, the aromatic diisocyanate compound may include an arylene group having 6 to 50 carbon atoms and an isocyanate group bonded at both ends of the arylene 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 an arylene group or an arylene group.

More specifically, the arylene group functional group having 6 to 50 carbon atoms may include a functional group represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ and R ₃ are each independently an arylene group having 6 to 20 carbon atoms and R ₂ is an alkylene group having 1 to 10 carbon atoms. In the above formula (1), "*" may mean a bonding point. R ₁ and R ₃ may be the same or different from each other.

The arylene group may be a bivalent group derived from arene and may be, for example, a phenylene group, a biphenylene group, a terphenylene group, a stilbene group, a naphthylenyl group, and the like, but is not limited thereto. The at least one hydrogen atom contained in the arylene group may each be substituted with a substituent.

Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 12 carbon atoms, A halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amido group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carbamate group and an alkoxy group having 1 to 10 carbon atoms.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the substituted position is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.

The alkylene group is a bivalent group derived from an alkane, for example, a straight chain, branched or cyclic group, and includes a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec- a tert-butylene group, a pentylene group, a hexylene group, and the like. The at least one hydrogen atom contained in the alkylene group may be substituted with the same substituent as in the case of the arylene group.

Preferably, R ₁ and R ₃ in formula (1) are each independently an arylene group having 6 to 10 carbon atoms or a phenylene group, and R ₂ is an alkylene group having 1 to 5 carbon atoms or a methylene group. Specifically, specific examples of the arylene group having 6 to 50 carbon atoms include 4,4'-methylenebisphenyl and the like.

The isocyanate functional group bonded to both ends of the arylene group functional group having 6 to 50 carbon atoms has a chemical structure represented by -NCO- and reacts with a hydroxyl group (-OH) contained in the modified polyolefin resin or fiber reinforcing agent surface to form urethane Group can be formed.

More specifically, the aromatic diisocyanate compound may be chemically cross-linked with the modified polyolefin resin and the fiber reinforcement to form a crosslinked structure. Examples thereof include a maleic anhydride-modified polypropylene homopolymer, a diphenylmethane diisocyanate compound , When a glass fiber surface-treated with a silanol coupling agent is mixed and reacted, a urethane group is formed through an isocyanate action reaction of the maleic anhydride functional group and the diphenylmethane diisocyanate compound of the maleic anhydride-modified polypropylene homopolymer .

Urethane groups can also be formed through the isocyanate-terminated reaction of the hydroxy group of the glass fiber surface-treated with the silanol-based coupling agent and the diphenylmethane diisocyanate compound. At this time, depending on the reaction conditions and the like, the de-carbon dioxide reaction may further proceed.

Further, the content of the fibrous reinforcement material is the same as that of the above embodiment.

Wherein the polyolefin resin composition comprises 0.1 to 95% by weight of a modified polyolefin resin grafted with a dicarboxylic acid component or an acid anhydride thereof, 0.1 to 70% by weight of a fiber reinforcement, and 0.1 to 50% by weight of an aromatic diisocyanate compound %. ≪ / RTI >

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 in which the dicarboxylic acid component or an acid anhydride thereof is grafted. In order to improve the compatibility between the polyolefin resin and the fiber reinforcing material, when an aromatic diisocyanate compound is used together with a dicarboxylic acid component or an acid anhydride thereof, only a dicarboxylic acid component or an acid anhydride thereof is used as a compatibilizer , Superior compatibility and mechanical properties can be realized.

The polyolefin resin composition may further include at least one additive selected from the group consisting of a reaction catalyst, a stabilizer, a colorant, an inorganic filler, an ultraviolet screening agent, an antioxidant, a lubricant, an antistatic agent, an impact modifier and fine particles.

The specific kinds of materials used as the additives may be various materials known in the art without limitation, and the amount of each added material is not limited. However, the functional properties of the additive are realized and the physical properties of the fiber-reinforced polyolefin composite To about 10% by weight based on the weight of the fiber-reinforced polyolefin composite.

However, in the case of the catalyst, 0.01 to 0.5 part by weight of the aromatic diisocyanate is added to 100 parts by weight of the aromatic diisocyanate, thereby preventing side reactions caused by excessive addition of the catalyst.

Examples of the method for producing the polyolefin resin composition are not limited, and a method of simultaneously mixing or sequentially mixing the modified polyolefin resin, the fiber reinforcement, the aromatic diisocyanate compound, and the additive may be applied without limitation. For example, the polyolefin resin composition may be prepared by simultaneously mixing the modified polyolefin resin, the fiber reinforcement, and the additive, and then adding an aromatic diisocyanate compound separately.

The step of melt-extruding the polyolefin resin composition may be performed at 150 to 300 占 폚, or 200 to 300 占 폚. If the melt-extruding step is performed at a too low temperature, the polyolefin resin and the glass fiber are not uniformly melted and the mechanical properties of the produced fiber-reinforced composite may be deteriorated. If the polyolefin resin is thermally decomposed at too high a temperature, And the mechanical properties of the resin itself may deteriorate.

Examples of the specific method of the melt extrusion step are not limited to a specific method. For example, a method of injecting the polyolefin resin composition into an extruder having a screw rotating speed of 50 rpm to 300 rpm can be used.

On the other hand, the step of impregnating the polyolefin resin solution with the fiber reinforcement before the step of melt-extruding the polyolefin resin composition containing the modified dicarboxylic acid component or its acid anhydride grafted modified polyolefin resin, fiber reinforcement, and aromatic diisocyanate compound As shown in FIG.

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 contain the above-mentioned other additives. When the polyolefin resin in a solution state is used, the polyolefin resin is uniformly coated around the fiber reinforcement, and the fiber reinforcement is not scattered at the stage of melt-extruding the composite with the polyolefin, and the dispersibility of the fiber reinforcement is improved, Can be improved.

As the solvent, water, an organic solvent or a mixture thereof may be used. Specific examples of the organic solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert- , 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol and cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone and cyclohexanone, , Aromatic hydrocarbons such as toluene, xylene, cumene and cymene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, methylcyclohexane and methylcyclopentane, ethers such as tetrahydrofuran and dioxane, , Esters such as n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, , Ethylene glycol monomethyl ether, ethylene glycol Methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methoxy-2-propanol, and the like; glycol derivatives such as ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, recolmonyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether and ethylene glycol ethyl ether acetate; Butanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetate, 1,2-dimethylglycerin, 1,3-dimethylglycerin, trimethylglycerin, etc. These organic solvents may be used in combination of two or more kinds.

The solid content of the polyolefin resin solution may be 1 to 50% by weight, and preferably 3 to 50% by weight. If the concentration of the solid content is too low, the polyolefin may not be sufficiently coated on the surface of the fiber reinforcement. If the concentration of the solid content exceeds 50 wt%, the viscosity of the solution becomes high, There is a limit that this is not uniform.

The step of impregnating the fiber reinforcement with the polyolefin resin solution may be carried out at 10 to 50 ° C, preferably at 10 to 40 ° C. If the impregnation step is carried out at a temperature exceeding 50 캜, the solvent may be volatilized to a large extent and the viscosity may be increased. At a temperature lower than 10 캜, the solution may harden.

The step of impregnating the fiber reinforcement into 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 suitably from 1 to 60 seconds. The time less than 1 second is not sufficient to homogeneously impregnate the polyolefin resin solution, and if it stays for too long, the improvement of the degree of impregnation compared to the residence time is insignificant, and the process speed is slowed, and the process efficiency and economical efficiency may be deteriorated.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a fiber-reinforced polyolefin composite capable of realizing excellent compatibility and mechanical properties through chemical bonding between a polyolefin resin and a fiber and capable of being produced in a short period of time through high reactivity and a method for producing the same.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

≪ Example: Production of fiber-reinforced polypropylene resin composite >

(1) Production of polypropylene resin composition

75% by weight of a polypropylene resin having a weight average molecular weight of 150,000 and 1% by weight of a maleic anhydride-modified polypropylene homopolymer (maleic anhydride content: 2% by weight) were mixed using a Henschel mixer to prepare a polypropylene resin composition.

(2) Preparation of fiber-reinforced polypropylene resin composition

The glass fiber reinforced polypropylene resin composition was prepared by impregnating the above-prepared polypropylene resin composition at room temperature with glass fibers surface-treated with a silanol-based coupling agent.

(3) Production of fiber reinforced polypropylene resin composite

The fiber-reinforced polypropylene resin composition was injected into a main hopper of an extruder (L / D 30 mm or more), and a diphenylmethane diisocyanate (isocyanate group content: 30% by weight) and dibutyl The tin dilaurate-based catalyst (0.5 g per 1 g of diphenylmethane diisocyanate) was injected into the fiber-reinforced polypropylene resin composition and extruded at 230 DEG C in a screw extruder at a screw rotation speed of 100 rpm and a stay of 60 seconds To prepare a fiber-reinforced polypropylene resin composite.

≪ Comparative Examples 1 to 3: Production of fiber-reinforced polypropylene resin composite >

Comparative Example 1

A fiber-reinforced polypropylene resin composite was prepared in the same manner as in the above example, except that the 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 diphenylmethane diisocyanate was not used.

Comparative Example 3

A fiber-reinforced polypropylene resin composite was prepared in the same manner as in the above example except that hexamethylene diisocyanate was used instead of diphenylmethane diisocyanate.

< Experimental Example  : Example  And In the comparative example  Measurement of physical properties of the obtained fiber-reinforced polypropylene resin composite>

The physical properties of the fiber-reinforced polypropylene resin composite obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1.

Experimental Example 1: Measurement of tensile strength

A specimen having a size of 165 mm * 13 mm * 3.2 mm (length * width * thickness) was prepared from the fiber-reinforced polypropylene resin composite obtained in the above Examples and Comparative Examples using a 180-ton electric injection molding machine, In accordance with ASTM D638, the tensile strength was measured at room temperature and a test speed of 50 mm / min in an INSTRON 4466 instrument. The measurement result was determined by averaging the three values except for the maximum value and the minimum value after 5 measurements.

Experimental Example 2 : Flexural strength ( flexural Strength ) And flexural modulus ( flexural Modulus ) Measure

A specimen having a size of 127 mm * 12.7 mm * 6.4 mm (length * width * thickness) was prepared from the fiber-reinforced polypropylene resin composite obtained in the above Examples and Comparative Examples using a 180-ton electric injection molding machine, Flexural strength and flexural modulus were measured using INSTRON 4466 instrument according to ASTM D790 at room temperature, test speed 28 mm / min, and 5% strain limit. The measurement result was determined by averaging the three values except for the maximum value and the minimum value after 5 measurements.

Experimental Example 3: Measurement of Impact Strength

Izod impact strength of the fiber-reinforced polypropylene resin composite obtained in the above Examples and Comparative Examples was measured using an Izod impact tester (TOYOSEIKI CAT NO.612) according to ASTM D-256 (63.5 x 12.7 x 3 mm) Respectively.

Experimental Example Results of Examples and Comparative Examples division Tensile Strength (MPa) Flexural Strength (MPa) Flexural modulus (MPa) Impact strength
IZOD 30 (6T)
(kg · cm / cm) Example 1 53.8 73.0 2638 4.9 Comparative Example 1 41.1 56.2 2236 2.7 Comparative Example 2 47.4 64.1 2422 4.0 Comparative Example 3 49.2 64.9 2480 3.8

As shown in Table 1, in the case of Example 1 in which diphenylmethane diisocyanate was added as a compatibilizing agent together with the maleic anhydride-modified polypropylene homopolymer, a tensile strength of 53.8 MPa, a flexural strength of 73 MPa, a tensile strength of 2638 MPa A flexural modulus, and an impact strength of 4.9 kg · cm / cm. Thus, it was confirmed that excellent mechanical properties can be realized.

On the other hand, Comparative Example 1, which did not contain the maleic anhydride-modified polypropylene homopolymer and the diphenylmethane diisocyanate compatibilizer at all, contained only the maleic anhydride-modified polypropylene homopolymer, and did not contain the diphenylmethane diisocyanate compatibilizer It was confirmed that tensile strength, flexural strength, flexural modulus and impact strength of Comparative Example 2, in which hexamethylene diisocyanate was substituted for diphenylmethane diisocyanate, were all lower than those of Example 1.

Thus, in the case of a fiber-reinforced polyolefin composite in which diphenylmethane diisocyanate is used as a compatibilizer together with a maleic anhydride-modified polypropylene homopolymer as in the examples, the chemical reaction between the maleic anhydride-modified polypropylene homopolymer and diphenylmethane diisocyanate , It was confirmed that not only the compatibility between the fibers and the polymer was increased but also the mechanical properties could be improved.

Claims (18)

A polymer substrate including a polyolefin resin; And a fiber reinforcement impregnated with the polymeric substrate,
Wherein the polymer substrate and the fiber reinforcing material are bonded via an aromatic divalent functional group containing a urethane group.
The method according to claim 1,
The aromatic divalent functional group containing the urethane group comprises an arylene group functional group having 6 to 50 carbon atoms and a urethane group bonded at one end of the arylene group functional group having 6 to 50 carbon atoms.
3. The method of claim 2,
Wherein the arylene group functional group having 6 to 50 carbon atoms is bonded to the fiber reinforcing material via a urethane group bonded at one end thereof.
3. The method of claim 2,
Wherein the arylene group functional group having 6 to 50 carbon atoms includes a functional group represented by the following formula (1):
[Chemical Formula 1]

Wherein R ₁ and R ₃ are each independently an arylene group having 6 to 20 carbon atoms and R ₂ is an alkylene group having 1 to 10 carbon atoms.
3. The method of claim 2,
The aromatic divalent functional group containing the urethane group further comprises a urethane-based functional group or an amide-based functional group bonded to the other end of the arylene-based functional group having 6 to 50 carbon atoms.
6. The method of claim 5,
Wherein the arylene group functional group having 6 to 50 carbon atoms is bonded to the polymer substrate via a urethane group functional group or an amide group functional group.
6. The method of claim 5,
Wherein the urethane-based functional group bonded to the other terminal of the arylene group-containing functional group having 6 to 50 carbon atoms includes a functional group represented by the following formula (2):
(2)

In the above formula (2), R ₄ is an alkylene group having 1 to 10 carbon atoms and a branched chain having 1 to 5 carbon atoms in which a carboxyl group is bonded to the terminal, and R ₅ is a carbonyl group.
6. The method of claim 5,
Wherein the amide-based functional group bonded to the other terminal of the arylene group functional group having 6 to 50 carbon atoms comprises a functional group represented by the following general formula (3):
(3)

In the above formula (3), R ₆ is an alkylene group having 1 to 10 carbon atoms and having an alkylene group having 1 to 5 carbon atoms in which a carboxyl group is bonded at the terminal thereof as a branched chain.
The method according to claim 1,
Wherein the aromatic divalent functional group containing a urethane group comprises a functional group represented by the following formula (4) or (5):
[Chemical Formula 4]

Wherein R ₁ 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, and R ₄ is an alkyl group having 1 to 5 carbon atoms to which a carboxyl group is bonded at the terminal An alkylene group having 1 to 10 carbon atoms and having 5 to 20 carbon atoms in the form of a branched chain, R ₅ is a carbonyl group,
[Chemical Formula 5]

In Formula 5, R ₁ 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, R ₆ is an alkyl group having 1 to 5 carbon atoms, And an alkylene group having 1 to 10 carbon atoms having a phenylene group as a branching group.
The method according to claim 1,
Wherein the fiber reinforcement has the surface modified with a reactive functional group.
The method according to claim 1,
Wherein the polymeric substrate further comprises a modified polyolefin resin having a dicarboxylic acid component or an acid anhydride thereof grafted.
Extruding a polyolefin resin composition comprising a modified polyolefin resin having a dicarboxylic acid component or an acid anhydride thereof grafted, a fiber reinforcement, and an aromatic diisocyanate compound.
13. The method of claim 12,
Wherein the aromatic diisocyanate compound comprises an isocyanate group bonded at both ends of an arylene group functional group having 6 to 50 carbon atoms and an arylene group functional group having 6 to 50 carbon atoms.
14. The method of claim 13,
Wherein the arylene group having 6 to 50 carbon atoms includes a functional group represented by the following formula (1): &lt; EMI ID =
[Chemical Formula 1]

Wherein R ₁ and R ₃ are each independently an arylene group having 6 to 20 carbon atoms and R ₂ is an alkylene group having 1 to 10 carbon atoms.
13. The method of claim 12,
Wherein the fiber reinforcement has the surface modified with a reactive functional group.
13. The method of claim 12,
Wherein the polyolefin resin composition further comprises at least one additive selected from the group consisting of a reaction catalyst, a stabilizer, a colorant, an inorganic filler, an ultraviolet screening agent, an antioxidant, a lubricant, an antistatic agent, Way.
13. The method of claim 12,
Wherein the content of the aromatic diisocyanate compound is 0.1 to 50 parts by weight based on 100 parts by weight of the modified polyolefin resin in which the dicarboxylic acid component or an acid anhydride thereof is grafted.
13. The method of claim 12,
Wherein the melt extrusion step is conducted at a temperature of from 150 캜 to 300 캜.