CN112442250B - Composition for preparing glass fiber reinforced polypropylene material, and prepared material and application thereof - Google Patents

Composition for preparing glass fiber reinforced polypropylene material, and prepared material and application thereof Download PDF

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CN112442250B
CN112442250B CN201910825973.1A CN201910825973A CN112442250B CN 112442250 B CN112442250 B CN 112442250B CN 201910825973 A CN201910825973 A CN 201910825973A CN 112442250 B CN112442250 B CN 112442250B
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polypropylene
glass fiber
polar monomer
parts
foam
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CN112442250A (en
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郭鹏
张琦
吕明福
徐耀辉
张师军
邵静波
权慧
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/107—Nitroso compounds
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/20—Ternary blends of expanding agents
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes

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Abstract

The invention provides a composition for preparing a glass fiber reinforced polypropylene material, which comprises the following components: 100 parts by weight of polar monomer modified polypropylene; 1-30 parts of compatilizer; 0.3-5 parts by weight of a toughening agent; 25-100 parts of glass fiber. The foamed sheet prepared from the glass fiber reinforced polypropylene material prepared by the composition through foaming has the characteristics of flat surface, compact cells, uniform cell diameter, closed-cell hard structure, good impact property and the like.

Description

Composition for preparing glass fiber reinforced polypropylene material, and prepared material and application thereof
Technical Field
The invention relates to a composition for preparing a glass fiber reinforced polypropylene material, a material prepared from the composition and application of the material, in particular to a composition for preparing a glass fiber reinforced polypropylene material, glass fiber reinforced polypropylene prepared from the composition, a glass fiber reinforced polypropylene foaming profile and application of the material.
Background
In recent years, because polypropylene has good mechanical properties, chemical stability and low price, glass fiber reinforced modified products thereof are widely used in industries of automobiles, household appliances, furniture and the like. However, polypropylene is a nonpolar high-crystalline polymer, and has poor compatibility with glass fibers, so that poor toughness, large molding shrinkage and surface fiber appearance of products are caused. At present, silane coupling agent and the like are mainly used for carrying out surface modification on glass fiber or grafted polypropylene is added as a compatilizer to improve the cohesive force between polypropylene and the glass fiber, and the mechanical property of the material is improved by using the method, but the improvement degree of the impact property is still limited, and the phenomenon of surface fiber floating is easy to occur. Therefore, the glass fiber reinforced polypropylene product with better compatibility among the components and further improved mechanical properties of the material can meet higher practical use requirements.
In addition, for the glass fiber and glass fiber reinforced polypropylene foaming material, after the foaming weight reduction process is finished, the internal part of the glass fiber reinforced polypropylene composite material is increased from the original single reinforced phase-continuous phase interface to the reinforced phase-continuous phase interface, the reinforced phase-gas phase interface and the gas phase-continuous phase interface, and defects are easy to generate. When the fiber is used as the reinforcing phase, the fiber-reinforced polymer relies on plastic deformation of the resin and interfacial bonding of the resin to the fiber to transfer stress and utilizes the high strength of the fiber to withstand stress loads. When the fiber is positioned in the foam cells, the foam cells cannot play a role in transmitting stress, so that the fiber cannot bear the stress and cannot play a role in reinforcing. In contrast, since the larger size cells exist in the form of defects, when the material is subjected to an external force, the cells are broken first; the cracks can expand along with the direction of the fibers in the cells, so that the fibers in the reinforcement phase-gas phase cannot bear stress, and can play a negative role in expanding the cracks. Therefore, the reinforced phase-continuous phase interface is beneficial to improving the mechanical property of the composite foaming material, and the reinforced phase-gas phase and the gas phase-continuous phase interface cannot play a role in reinforcing and toughening. Therefore, how to provide a material which can still have excellent mechanical properties after the glass fiber reinforced polypropylene composite material is subjected to the foaming weight reduction process is a problem which needs to be solved at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a novel composition for preparing a glass fiber reinforced polypropylene material, the glass fiber reinforced polypropylene material obtained by the composition and application thereof. The composition for preparing the glass fiber reinforced polypropylene material provided by the invention uses polypropylene as a base resin, glass fiber as a main filler, an elastomer as a toughening agent, and an extrusion foaming method is used for preparing the glass fiber reinforced polypropylene foaming section, so that the prepared foaming section has good mechanical properties, light weight, good heat resistance and environment friendliness and is easy to recycle.
According to a first aspect of the present invention there is provided a composition for the preparation of a glass fibre reinforced polypropylene material comprising or consisting of:
according to a preferred embodiment of the present invention, in the composition for preparing a glass fiber reinforced polypropylene material, the polar monomer modified polypropylene is calculated as 100 parts; the amount of the compatibilizing agent is 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts and any value therebetween, preferably 10 to 25 parts; the amount of the toughening agent is 0.3 part, 1 part, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, 5.0 parts and any value therebetween, preferably 0.5 to 3.0 parts; the amount of the glass fiber used is 25 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts and any value therebetween, preferably 40 to 80 parts. The above-mentioned dosage is the quality dosage.
According to a preferred embodiment of the present invention, the melt index (melt flow rate) of the polar monomer modified polypropylene is 3 to 60g/10min, for example, may be 3g/10min, 5g/10min, 10g/10min, 15g/10min, 20g/10min, 25g/10min, 30g/10min, 35g/10min, 40g/10min, 45g/10min, 50g/10min, 55g/10min, 60g/10min and any value therebetween under the test condition of 2.16kg at 230 ℃, preferably 5 to 40g/10min, more preferably 8 to 30g/10min.
According to a preferred embodiment of the present invention, the polypropylene is a copolymer polypropylene, preferably the copolymer polypropylene is an impact copolymer polypropylene comprising a propylene homopolymer component and a propylene/ethylene copolymer component, preferably the propylene/ethylene copolymer component is present in the impact copolymer polypropylene in an amount of 3 to 10wt%, such as 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt% and any value therebetween.
According to a preferred embodiment of the present invention, the polar monomer-modified polypropylene is a polar monomer-grafted modified polypropylene, and the polar monomer is one or more selected from glycidyl methacrylate, methyl acrylate and maleic anhydride, preferably glycidyl methacrylate.
According to a preferred embodiment of the present invention, the grafting ratio of the polar monomer in the polar monomer-modified polypropylene is 3 to 4.5wt%, for example, 3wt%, 3.2wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.8wt%, 4.0wt%, 4.2wt%, 4.4wt%, 4.5wt% and any value therebetween, preferably 3.5 to 4.5wt%. In the polar monomer modified polypropylene, the grafting rate of the polar monomer has obvious influence on the performance of the glass fiber reinforced polypropylene material, the compatibility of the polypropylene and the glass fiber cannot be solved due to the too low grafting rate, the mechanical performance, particularly the impact strength, is reduced due to the too high grafting rate, and the self-polymerization of the grafting monomer is caused due to the too high grafting rate.
In some more preferred embodiments of the invention, the polar monomer modified polypropylene is a glycidyl methacrylate graft modified polypropylene, in which the glycidyl methacrylate graft modified polypropylene has a grafting ratio of glycidyl methacrylate of 3 to 4.5wt%.
According to a preferred embodiment of the invention, the glass fibers are alkali-free glass fibers, preferably having a diameter of 11-13 μm and a length of 3.5-5.5mm.
According to a preferred embodiment of the present invention, the compatibilizer is a polar monomer grafted polyethylene or a polar monomer grafted polypropylene, the polar monomer preferably being selected from one or more of maleic anhydride, derivatives of maleic anhydride, acrylic acid and derivatives of acrylic acid. The compatilizer and the polar monomer modified polypropylene act together to further improve the compatibility of the polypropylene and the wood powder.
According to a preferred embodiment of the present invention, the toughening agent is selected from one or more of an ethylene-octene copolymer, a styrene-ethylene-butadiene-styrene copolymer, a polar monomer grafted ethylene-octene copolymer, and a polar monomer grafted styrene-ethylene-butadiene-styrene copolymer, the polar monomer being selected from one or more of maleic anhydride, derivatives of maleic anhydride, acrylic acid, and derivatives of acrylic acid.
According to a preferred embodiment of the present invention, the polar monomer modified polypropylene is glycidyl methacrylate grafted polypropylene and the toughening agent is a maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer. Wherein the styrene-ethylene-butadiene-styrene represents a styrene-ethylene-butadiene-styrene block copolymer terminated with styrene. Benzene rings in the maleic anhydride grafted styrene-ethylene-butylene-styrene copolymer form conjugation with GMA; GMA itself has acrylate double bonds and epoxy groups, and a conjugation effect is generated between the GMA and a benzene ring.
According to a preferred embodiment of the present invention, the raw materials of the composite material further include one or more of an antioxidant, a nucleating agent, an antistatic agent and an antibacterial agent, and preferably, the polar monomer modified polypropylene is used in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the antioxidant; the amounts of nucleating agent, antistatic agent and antimicrobial agent are all conventional in the art and can be adjusted according to the actual circumstances by those skilled in the art.
According to a preferred embodiment of the present invention, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 2246, antioxidant CA, antioxidant 168, antioxidant 626 and antioxidant 636.
According to a second aspect of the present invention there is provided a glass fiber reinforced polypropylene material made from the composition for the preparation of glass fiber reinforced polypropylene material described above.
According to a preferred embodiment of the present invention, the preparation method of the glass fiber reinforced polypropylene material comprises: the glass fiber reinforced polypropylene material is prepared by mixing the components according to the required dosage, and then carrying out melt blending, extrusion and granulation at 190-210 ℃.
According to still another aspect of the present invention, there is provided a glass fiber reinforced polypropylene foam profile prepared by foaming the above glass fiber reinforced polypropylene material.
According to a preferred embodiment of the invention, the density of the glass fiber reinforced polypropylene foaming section bar provided by the invention is 0.2-0.9g/cm -3 For example, it may be 0.2g/cm -3 、0.3g/cm -3 、0.4g/cm -3 、0.5g/cm -3 、0.6g/cm -3 、0.7g/cm -3 、0.8g/cm -3 、0.9g/cm -3 And any value therebetween, preferably 0.35 to 0.8g/cm -3 More preferably 0.45-0.7g/cm -3 。
According to a preferred embodiment of the invention, the foamed profile provided by the invention has a thickness of 0.1-100mm, for example 0.1mm, 1mm, 10mm, 20mm, 30mm, 50mm, 70mm, 90mm, 100mm and any value in between.
The glass fiber reinforced polypropylene foaming section provided by the invention has compact and uniform foam holes and good mechanical and heat resistance.
According to still another aspect of the present invention, there is provided the preparation method of the glass fiber reinforced polypropylene foaming profile, comprising the steps of:
a. mixing the glass fiber reinforced polypropylene material with a foaming agent and optionally a processing aid to obtain a foaming premix;
b. adding the foaming premix into an extruder, stirring, and heating to melt the premix;
c. extruding the melted premix to an extruder die, flowing to a plate extruding machine, and rolling to form the foaming plate.
According to a preferred embodiment of the invention, the foaming agent is a chemical organic foaming agent or an inorganic foaming agent. Wherein the chemical organic foaming agent is preferably selected from one or more of azo foaming agent, nitroso foaming agent and hydrazide foaming agent. The azo foaming agent is preferably selected from one or more of Azodicarbonamide (AC), azodiisobutyronitrile (AIBN), barium azodicarbonate (BaAC) and azodicarbonate; the nitroso foaming agent is preferably selected from one or more of Dinitroso Pentamethylene Tetramine (DPT), N '-dinitroso pentamethylene tetramine, N' -dimethyl-N, N-dinitroso terephthalamide (NTA) and trinitroso trimethylene triamine; the hydrazide-based foaming agent is preferably one or more of 4,4' -oxo-bis-benzenesulfonyl hydrazide (OBSH), tosyl semicarbazide (TSSC), triphosphotriazine (CTHT) and 5-phenyltetrazole. The inorganic foaming agent is selected from one or more of air, nitrogen, carbon dioxide, oxygen and water.
According to a preferred embodiment of the invention, the foaming agent is azodicarbonamide. Compared with the fluorine-containing foaming agent used in the prior art, the foaming agent selected in the invention has the characteristic of environmental friendliness.
According to a preferred embodiment of the present invention, the blowing agent is added in an amount of 1 to 15 parts by weight, preferably 1 to 10 parts by weight, more preferably 5 to 7 parts by weight, based on 100 parts by weight of the base resin.
According to a preferred embodiment of the invention, the processing aid is selected from one or more of antioxidants, co-antioxidants, lubricants and pigments, which may be added according to the needs of the specific processing.
The glass fiber reinforced polypropylene foaming section bar prepared by the invention has the characteristics of flat surface, compact cells, uniform cell diameter, low and controllable foaming multiplying power, closed-cell hard structure, good impact and the like.
In a preferred embodiment of the present invention, the preparation method of the glass fiber reinforced polypropylene foaming profile comprises the following steps:
mixing the glass fiber reinforced polypropylene material, the foaming agent and optionally the processing aid by adopting a high-speed stirrer to obtain a premix of the polypropylene foaming profile;
feeding the premix into a hopper of an extruder, and heating the extruder to 140-280 ℃, preferably 160-180 ℃, so as to smelt the premix; the rotating speed of the screw is regulated to 15-180rpm; extruding the premix into a die at 150-280 ℃, preferably 160-180 ℃, flowing into a gap between two rollers of a plate extruding unit, and rolling into sheet materials; naturally cooling to room temperature, and cutting into plates with certain specification according to the requirement, thus obtaining the finished product of the foaming plate.
The extruder can be a single screw extruder, two single screw extruders in a serial connection mode, a same-direction double screw extruder serial connection single screw extruder, an opposite-direction double screw extruder, a conical double screw extruder or a three-screw extruder.
The die can be a flat die, a T-shaped die, a round orifice die, a circular ring die or the like according to actual needs. For example, the molten premix is discharged from a flat die and then expanded, and the die size is controlled by a three-roll calender for adjusting the roll pitch to obtain a polypropylene foamed sheet having a desired thickness. Or the melted premix is discharged from the annular die and then expanded, and is rolled after being blown up and cooled inside and outside and being cut along the axial direction, so that the polypropylene plastic wood composite foam board with the required thickness is obtained.
In the process of extrusion foaming of the materials of the present invention, the melt blending temperature of the materials is generally selected within a range that ensures complete melting of the premix and does not decompose it, and is generally 160℃to 280 ℃. However, this temperature may be appropriately adjusted depending on the specific case, for example, the decomposition temperature of the industrial Azodicarbonamide (AC) blowing agent is 195 to 210℃and therefore, in consideration of the processability and the decomposition temperature of the AC blowing agent in combination, the processing temperature is preferably lower such as 180 to 205 ℃. In view of energy saving and emission reduction, zinc oxide is generally added to the AC blowing agent to lower the decomposition temperature of AC to 170-180 ℃, and the zinc oxide is preferably added in an amount of 1 part by weight based on 100 parts by weight of the base resin.
According to a preferred embodiment of the invention, the temperature is increased to 140-280 ℃, preferably 160-180 ℃ in step b. In some preferred embodiments of the invention, the temperature of the extruder is set as follows: the first region temperature is 145-155 ℃, the second region temperature is 155-160 ℃, the third region temperature is 160-170 ℃, the fourth region temperature is 165-175 ℃, the fifth region temperature is 165-175 ℃, the sixth region temperature is 160-170 ℃, and the machine head temperature is 155-165 ℃.
According to a preferred embodiment of the invention, in step c the temperature of the extruder die is 150-280 ℃, preferably 160-180 ℃.
The glass fiber reinforced polypropylene foaming section bar provided by the invention can be applied to occasions with high requirements on mechanical properties and light weight of plastic products, such as vehicles, aircrafts, high-speed rail internal and external decorations, building decorations, leisure and entertainment.
According to the composition for preparing the glass fiber reinforced polypropylene material, the polar monomer modified polypropylene is used as a base material, the grafting rate of the polar monomer and the melt index of the polypropylene base material are controlled, the performance of the composite material is improved while the excellent performance of the polypropylene is maintained, and the glass fiber is used as a filler, so that the prepared glass fiber reinforced polypropylene material has excellent performance due to the mutual coordination between the polar monomer modified polypropylene, the compatilizer, the toughening agent and the components in the composition, and the foamed sheet prepared by foaming has the characteristics of flat surface, compact foam cells, uniform foam cell diameter, low and controllable foaming multiplying power, closed-cell hard structure, good impact and the like.
The preparation method of the polypropylene foaming section bar provided by the invention is simple and effective, is easy to operate and low in cost, and realizes stabilization of the polypropylene raw material, so that a foaming window is effectively enlarged, and the process is easy to adjust.
The polypropylene plastic-wood foamed plate provided by the invention has a non-crosslinked structure, can be recycled according to a common polypropylene modified material, does not cause secondary pollution, and meets the requirement of recycling economy.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
In the examples of the present invention, the sources of the raw materials used are as follows:
polypropylene powder: brand SP179, petaloid;
in the examples of the present invention, the polar monomer modified polypropylene was a homemade glycidyl methacrylate grafted polypropylene, wherein the polypropylene was a copolymerized polypropylene produced by chinese petrochemical industry under the designation SP179, as described without a feature. In the glycidyl methacrylate-grafted polypropylene, the grafting ratio of the glycidyl methacrylate was 4.2% by weight (measured by acid-base titration) and the melt flow rate was 6.8g/10min at 230℃X 2.16 kg.
The preparation method of the glycidyl methacrylate grafted polypropylene with the grafting rate of the glycidyl methacrylate of 4.2 weight percent comprises the following steps:
200 parts by weight of aqueous sodium chloride solution with the concentration of 10wt% is heated to 90 ℃, 100 parts by weight of SP179 polypropylene powder is added, after stirring for 2 hours, 6 parts by weight of monomer GMA and 0.06 part by weight of initiator benzoyl peroxide are continuously added, stirring and mixing are carried out, reaction is carried out for 6 hours, and the reaction product is dried after unreacted monomer and initiator are removed by washing with deionized water and acetone, thus obtaining modified polypropylene particles.
As illustrated without features, in embodiments of the present invention, glass fibers: alkali-free glass fiber with diameter of 13 μm and length of 4.5mm is produced by the large stone group;
and (3) a compatilizer: maleic anhydride grafted polypropylene, brand CA100, manufactured by Arkema, france; the methacrylic acid grafted polypropylene is self-made by a conventional method, and the grafting rate is 2.23wt% by titration.
Toughening agent: styrene-ethylene-butadiene-styrene copolymer, trade mark YH688, manufactured by chinese petrochemical, baling petrochemical division; maleic anhydride grafted styrene-ethylene-butadiene-styrene copolymer, manufactured by Kraton, usa under the trade designation FG1901; ethylene-octene copolymer, trade name 8400, manufactured by the dow chemical company, usa; maleic anhydride-grafted ethylene-octene copolymer, trademark CMG9805, manufactured by henna, inc.
If not specified, the antioxidant used in the examples is selected from pentaerythritol tetrakis [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010) and phenyl tris (2, 4-di-tert-butyl) phosphite (antioxidant 168) which are compounded and used in a mass ratio of 1:1.
Example 1
According to the addition amount of each material in table 1, dry polar monomer modified polypropylene (grafting ratio 4 wt%), glass fiber, compatilizer, toughening agent and antioxidant are weighed, the components are uniformly mixed and then added into a double screw extruder, and the glass fiber reinforced polypropylene material is prepared through melt blending, extrusion and granulation. The processing temperature of the double-screw extruder is as follows: the temperature of the first area is 150 ℃, the temperature of the second area is 160 ℃, the temperature of the third area is 165 ℃, the temperature of the fourth area is 170 ℃, the temperature of the fifth area is 170 ℃, the temperature of the sixth area is 170 ℃, and the temperature of the machine head is 165 ℃.
Foaming and rolling process:
the glass fiber reinforced polypropylene material, the foaming agent and the processing aid are added into a high-speed stirrer according to the formula shown in the table 1 to be mixed for 1 min at high speed, and the premix of the polypropylene foaming profile is obtained. Wherein MB50-002 (high molecular weight polysiloxane) was used as the lubricant in an amount of 1 part by weight per 100 parts by weight of polypropylene.
The extruder temperature was adjusted to the foaming temperature shown in table 1, and then the premix was fed into the middle layer twin screw of the extruder, the torque was controlled to about 65%, and the screw speed was adjusted to 15-170rpm, so that the premix was melted in the extruder.
Extruding the melted premix into a T-shaped head die at the foaming temperature, flowing into a gap between two rollers of a plate extruding unit, rolling into a plate-shaped polypropylene foaming material, and naturally cooling to room temperature.
The surface and cell morphology of the product of the prepared polypropylene foam material were visually observed, and the density thereof was measured using a densitometer. The results are shown in Table 1.
Examples 2 to 7 and comparative examples 1 to 3
Examples 2-7 and comparative examples 1-3 differ from example 1 only in the amounts of the components used to prepare the glass fiber reinforced polypropylene material, wherein the polypropylene used in comparative examples 2 and 3 is unmodified polypropylene, designated SP179; the amounts of the components used in examples 2-7 and comparative examples 1-3 are shown in Table 1.
Examples 8 to 11
Examples 8-11 differ from example 2 only in the grafting ratio of glycidyl methacrylate in the glycidyl methacrylate grafted polypropylene.
The grafting ratio of glycidyl methacrylate in example 8 was 3.0wt%.
The grafting ratio of glycidyl methacrylate in example 9 was 4.5% by weight.
The grafting ratio of glycidyl methacrylate in example 10 was 2.0wt%.
The grafting ratio of glycidyl methacrylate in example 11 was 6.0wt%.
Example 12
Example 12 differs from example 2 in that the toughening agent uses maleic anhydride to graft the ethylene-octene copolymer.
Examples 13 to 17
Examples 13-16 differ from example 1 in that the glycidyl methacrylate grafted polypropylene has melt flow rates of 5g/10min, 10g/10min, 15g/10min, 20g/10min, 40g/10min, respectively, at 230℃X 2.16kg test.
Examples 18 to 22
Examples 18 to 22 differ from example 1 in the amounts of toughening agent, compatibilizer and/or foaming agent, the specific amounts being shown in Table 1.
Comparative examples 4 to 5
Comparative examples 4 and 5 are different from example 2 in that comparative examples 4 and 5 use maleic anhydride-grafted modified polypropylene and methyl acrylate-grafted modified polypropylene, respectively.
By comparing the data of the examples with the data of the comparative examples, the impact strength of the materials is improved after the polar monomer modified polypropylene is used as the matrix of the glass fiber reinforced polypropylene material. On the basis, after the compatilizer and the toughening agent are added, the impact strength of the material is greatly improved, the impact performance is obviously more excellent, and the modified polypropylene base can form more bonding points with the surface of the glass fiber, so that the surface fiber floating phenomenon is improved. The glass fiber plays a role of a cell nucleating agent in the polypropylene matrix, the foam material obtained by using the glass fiber reinforced polypropylene modified by adding the compatilizer and the toughening agent has uniform cells and excellent weight reduction and light weight performance, and the surface fiber floating condition of the foam product is obviously improved. The blending effect of the unmodified common polypropylene and the glass fiber is poor, the influence on the foaming process is large, the weight reduction of the foaming product is not obvious, and the mechanical property is poor. The glass fiber composite material prepared by grafting the polypropylene with the GMA has the smell which is obviously smaller than that of the polypropylene composite material grafted with the maleic anhydride or the methyl acrylate, and can be used in the fields with high requirements on smell, such as automotive interior materials.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (13)

1. The glass fiber reinforced polypropylene foaming forming body is formed by foaming glass fiber reinforced polypropylene material, and the glass fiber reinforced polypropylene material is prepared from the following composition:
100 parts by weight of polar monomer modified polypropylene;
1-30 parts of compatilizer;
0.3-5 parts by weight of a toughening agent;
25-100 parts by weight of glass fiber;
wherein the density of the foam molded body is 0.35-0.8g/cm 3 ；
The polar monomer modified polypropylene is polar monomer grafted modified polypropylene, and the polar monomer is glycidyl methacrylate; in the polar monomer modified polypropylene, the grafting rate of the polar monomer is 3-4.5wt%;
the compatilizer is polyethylene grafted by polar monomers or polypropylene grafted by polar monomers, and the polar monomers are selected from one or more of maleic anhydride, derivatives of maleic anhydride, acrylic acid and derivatives of acrylic acid.
2. The foam-molded body according to claim 1, wherein the amount of the compatibilizing agent in the composition is 10 to 25 parts by weight; and/or the amount of the toughening agent is 0.5 to 3 parts by weight; and/or the amount of the glass fiber is 40 to 80 parts by weight.
3. The foam-molded article according to claim 1, wherein the melt index of the polar monomer-modified polypropylene is 3 to 60g/10min at 230 ℃ under 2.16kg test conditions.
4. The foam-molded article according to claim 1, wherein the melt index of the polar monomer-modified polypropylene is 5 to 40g/10min at 230 ℃ under 2.16kg test conditions.
5. The foam-molded article according to claim 1, wherein the melt index of the polar monomer-modified polypropylene is 8 to 30g/10min at 230 ℃ under 2.16kg test conditions.
6. The foam-molded article according to claim 1, wherein the polypropylene is a copolymerized polypropylene.
7. The foam-molded article according to claim 6, wherein the copolymerized polypropylene is an impact copolymerized polypropylene comprising a propylene homopolymer component and a propylene/ethylene copolymer component, wherein the propylene/ethylene copolymer component is contained in an amount of 3 to 10% by weight.
8. The foam molded body according to any one of claims 1 to 7, wherein the grafting ratio of the polar monomer in the polar monomer-modified polypropylene is 3.5 to 4.5wt%.
9. The foam molded body according to any one of claims 1 to 7, wherein the glass fiber is alkali-free glass fiber; and/or the number of the groups of groups,
the diameter of the glass fiber is 11-13 mu m, and the length is 3.5-5.5mm; and/or the number of the groups of groups,
the toughening agent is selected from one or more of ethylene-octene copolymer, styrene-ethylene-butadiene-styrene copolymer, polar monomer grafted ethylene-octene copolymer and polar monomer grafted styrene-ethylene-butadiene-styrene copolymer, and the polar monomer is selected from one or more of maleic anhydride, derivatives of acrylic acid and derivatives of acrylic acid.
10. The foam-molded body according to any one of claims 1 to 7, wherein the composition further comprises one or more of an antioxidant, a nucleating agent, an antistatic agent, and an antibacterial agent.
11. The foam-molded article according to claim 10, wherein the antioxidant is used in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the polar monomer-modified polypropylene.
12. The method for producing a foam molded body according to any one of claims 1 to 11, comprising the steps of:
step a, mixing the glass fiber reinforced polypropylene material with a foaming agent and optionally a processing aid to obtain a foaming premix;
b, adding the premix into an extruder, stirring and heating to melt the premix;
and c, extruding the molten premix to an extruder die, flowing to a plate extruding machine, and rolling to form the foaming sheet.
13. Use of the foam molded body according to any one of claims 1 to 11 in automotive, aircraft and high-speed rail interior and exterior trim.
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Family Cites Families (4)

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Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Effects of compatilizers on mechanical and dynamic mechanical properties of polypropylene–long glass fiber composites;Daohai Zhang et al.;Journal of Thermoplastic Composite Materials;1-13 *
The Influence of Compatibilizers on the Structure and Mechanical Properties of Lightweight Reinforced Thermoplastics;Xun Fang et al.;POLYMER COMPOSITES;1-12 *

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