CN112442250A - Composition for preparing glass fiber reinforced polypropylene material, material prepared from composition and application of material - Google Patents
Composition for preparing glass fiber reinforced polypropylene material, material prepared from composition and application of material Download PDFInfo
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- CN112442250A CN112442250A CN201910825973.1A CN201910825973A CN112442250A CN 112442250 A CN112442250 A CN 112442250A CN 201910825973 A CN201910825973 A CN 201910825973A CN 112442250 A CN112442250 A CN 112442250A
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- 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
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- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- 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
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- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
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- 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
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- C08J2203/20—Ternary blends of expanding agents
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- 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
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- 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
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- 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 in percentage by weight: 100 parts by weight of polar monomer modified polypropylene; 1-30 parts of a compatilizer; 0.3-5 parts of a toughening agent; 25-100 parts of glass fiber. The foamed sheet prepared by foaming the glass fiber reinforced polypropylene material prepared from the composition has the characteristics of smooth surface, compact foam holes, uniform foam hole diameter, closed-cell hard structure, good impact property and the like.
Description
Technical Field
The invention relates to a composition for preparing a glass fiber reinforced polypropylene material, a prepared material and application thereof, 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 foamed profile and application thereof.
Background
In recent years, polypropylene has good mechanical properties, chemical stability and low price, so glass fiber reinforced and modified products thereof are widely used in industries such as automobiles, household electrical appliances, furniture and the like. However, polypropylene is a non-polar high crystalline polymer, and has poor compatibility with glass fibers, which results in poor product toughness, large molding shrinkage, surface fiber floating and other adverse phenomena. At present, silane coupling agent and the like are mainly used for carrying out surface modification on glass fibers or grafted polypropylene is added as a compatilizer to improve the bonding force between the polypropylene and the glass fibers, and although the mechanical property of the material is improved by using the method, the improvement degree of the impact property is limited, and the phenomenon of surface fiber floating is easy to occur. Therefore, the glass fiber reinforced polypropylene product which has better compatibility among all components and further improved mechanical properties of the material can meet higher actual use requirements on the basis of the prior stage.
In addition, for the glass fiber and glass fiber reinforced polypropylene foam material, after the foaming and weight reduction process is completed, the interior of the glass fiber reinforced polypropylene composite material is increased to three interfaces of a reinforcing phase-continuous phase, a reinforcing phase-gas phase and a gas phase-continuous phase from the original single reinforcing phase-continuous phase interface, so that defects are easily generated. When the fibers are used as a reinforcing phase, the fiber reinforced polymer relies on plastic deformation of the resin and interfacial bonding of the resin and the fibers to transmit stress and utilizes the high strength of the fibers to withstand stress loads. When the fibers are positioned in the cells, the cells cannot transfer stress, so that the fibers cannot bear the stress and cannot play a role in reinforcement. In contrast, since cells of larger size exist in the form of defects, the cells break first when the material is subjected to an external force; and the cracks can expand along with the direction of the fibers in the cells, so that the fibers in the reinforcing phase and the gas phase cannot bear stress, and can play a negative role in expanding the cracks. Therefore, the reinforcing phase-continuous phase interface is beneficial to improving the mechanical property of the composite foaming material, and the reinforcing phase-gas phase and the gas phase-continuous phase interface can not play a role in reinforcing and toughening. Therefore, how to provide a material which still has excellent mechanical properties after the glass fiber reinforced polypropylene composite material is subjected to a foaming weight reduction process is a problem which needs to be solved urgently 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 prepared from the composition and application of the glass fiber reinforced polypropylene material. 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 and an elastomer as a toughening agent, and an extrusion foaming method is used for preparing the glass fiber reinforced polypropylene foamed profile.
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 by 100 parts; the amount of the compatibilizer is 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts and any value therebetween, and 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, and preferably 0.5-3.0 parts; the amount of the glass fiber is 25 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts and any value therebetween, and preferably 40 to 80 parts. The above dosage is mass dosage.
According to a preferred embodiment of the present invention, the polar monomer modified polypropylene has a melt index (melt flow rate) of 3-60g/10min, for example, 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 in between, preferably 5-40g/10min, more preferably 8-30g/10min, under the test conditions of 230 ℃ and 2.16 kg.
According to a preferred embodiment of the present invention, the polypropylene is a co-polypropylene, preferably the co-polypropylene is an impact co-polypropylene comprising a propylene homopolymer component and a propylene/ethylene copolymer component, preferably the propylene/ethylene copolymer component is present in the impact co-polypropylene in an amount of 3 to 10 wt%, for example 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt% and any value in between.
According to a preferred embodiment of the present invention, the polar monomer modified polypropylene is polar monomer graft modified polypropylene, and the polar monomer is selected from one or more of glycidyl methacrylate, methyl acrylate and maleic anhydride, and is preferably glycidyl methacrylate.
According to a preferred embodiment of the present invention, the polar monomer modified polypropylene has a grafting ratio of the polar monomer of 3 to 4.5 wt%, for example, 3 wt%, 3.2 wt%, 3.4 wt%, 3.5 wt%, 3.6 wt%, 3.8 wt%, 4.0 wt%, 4.2 wt%, 4.4 wt%, 4.5 wt% and any value therebetween, preferably 3.5 to 4.5 wt%. 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 too low grafting rate, the mechanical property, particularly the impact strength, is reduced due to too high grafting rate, and the self-polymerization of the grafting monomer is caused due to too high grafting rate.
In some more preferred embodiments of the invention, the polar monomer-modified polypropylene is glycidyl methacrylate graft-modified polypropylene, and the grafting ratio of glycidyl methacrylate in the glycidyl methacrylate graft-modified polypropylene is 3 to 4.5 wt%.
According to a preferred embodiment of the invention, the glass fibers are alkali-free glass fibers, preferably having a diameter of 11 to 13 μm and a length of 3.5 to 5.5 mm.
According to a preferred embodiment of the invention, the compatibilizer is a polar monomer grafted polyethylene or 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 polar monomer modified polypropylene act together to further improve the compatibility of polypropylene and wood powder.
According to a preferred embodiment of the present invention, the toughening agent is selected from one or more of ethylene-octene copolymers, styrene-ethylene-butadiene-styrene copolymers, polar monomer grafted ethylene-octene copolymers and polar monomer grafted styrene-ethylene-butadiene-styrene copolymers, 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. The benzene ring in the maleic anhydride grafted styrene-ethylene-butylene-styrene copolymer forms conjugation with GMA; GMA has acrylate double bonds and epoxy groups and generates a conjugation effect with a benzene ring.
According to a preferred embodiment of the present invention, the raw materials of the composite material further comprise one or more of an antioxidant, a nucleating agent, an antistatic agent and an antibacterial agent, 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; the amounts of nucleating agent, antistatic agent and antimicrobial agent are conventional in the art and can be adjusted by one skilled in the art according to the actual situation.
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, which is prepared from the above composition for preparing a glass fiber reinforced polypropylene material.
According to a preferred embodiment of the present invention, the preparation method of the glass fiber reinforced polypropylene material comprises: the components are mixed according to the required dosage, and then the glass fiber reinforced polypropylene material is prepared by melt blending, extrusion and granulation at the temperature of 190-210 ℃.
According to another aspect of the invention, a glass fiber reinforced polypropylene foaming profile is provided, which is prepared by foaming the glass fiber reinforced polypropylene material.
According to the preferred embodiment of the invention, the density of the glass fiber reinforced polypropylene foaming section provided by the invention is 0.2-0.9g/cm-3For example, it may be 0.2g/cm-3、0.3g/cm-3、0.4g/cm-3、0.5g/cm-3、0.6 g/cm-3、0.7g/cm-3、0.8g/cm-3、0.9g/cm-3And any value therebetween, preferably 0.35 to 0.8g/cm-3More preferably 0.45 to 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 foamed section provided by the invention has compact and uniform foam holes and good mechanical and heat-resistant properties.
According to another aspect of the present invention, there is provided a preparation method of the glass fiber reinforced polypropylene foamed profile, which comprises the following steps:
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 molten premixed material to an extruder mouth die, flowing to a plate extruding machine, and rolling into a foamed plate.
According to a preferred embodiment of the invention, the blowing agent is a chemical organic blowing agent or an inorganic blowing agent. Wherein the chemical organic foaming agent is preferably selected from one or more of azo foaming agents, nitroso foaming agents and hydrazide foaming agents. The azo-based foaming agent is preferably selected from one or more of Azodicarbonamide (AC), Azobisisobutyronitrile (AIBN), barium azodicarboxylate (BaAC), and azodicarboxylate; the nitroso-based blowing agent is preferably selected from one or more of Dinitrosopentamethylenetetramine (DPT), N '-dinitrosopentamethylenetetramine, N' -dimethyl-N, N-dinitrosoterephthalamide (NTA) and trinitrotrimethylenetriamine; the hydrazide-type foaming agent is preferably one or more of 4, 4' -oxybis-benzenesulfonyl hydrazide (OBSH), Tosylsemicarbazide (TSSC), triphosphonyltriazine (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 blowing 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, and 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 present invention, the processing aid is selected from one or more of antioxidants, secondary antioxidants, lubricants and pigments, which may be added as required for a particular process.
The glass fiber reinforced polypropylene foamed profile prepared by the method has the characteristics of smooth surface, compact foam holes, uniform diameter of the foam holes, 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 foamed profile comprises the following steps:
mixing the glass fiber reinforced polypropylene material, the foaming agent and optionally a processing aid by adopting a high-speed stirrer to obtain a premix of the polypropylene foaming profile;
adding the premix into a hopper of an extruder, and heating the temperature of the extruder to 140-; adjusting the rotating speed of the screw to 15-180 rpm; extruding the premix to a neck mold at the temperature of 150 ℃ and 280 ℃, preferably 160 ℃ and 180 ℃, flowing to a gap between two rollers of a plate extruding machine, and rolling into a sheet material; naturally cooling to room temperature, and cutting into a plate with a certain specification as required to obtain a finished foamed plate.
The extruder can be a single screw extruder, two single screw extruders in series connection, a co-rotating twin screw extruder in series connection with the single screw extruder, a counter-rotating twin screw extruder, a conical twin screw extruder or a three screw extruder.
The neck ring mold can be a flat neck ring mold, a T-shaped neck ring mold, a round hole neck ring mold or a circular ring neck ring mold and the like according to actual needs. For example, the molten premix is discharged from a flat die, expanded, and passed through a three-roll calender having a roll gap adjusted to control the size of the die, thereby obtaining a polypropylene foamed sheet having a desired thickness. Or the melted premix is discharged from a circular ring-shaped die, expanded, cooled inside and outside, cut along the axial direction and rolled to obtain the polypropylene plastic wood composite foamed board with the desired thickness.
In the material extrusion foaming process, the melting and blending temperature of the materials is usually selected within the range of ensuring complete melting of the premix and not decomposing the premix, and is usually 160-280 ℃. However, this temperature may be suitably adjusted depending on the case, for example, the decomposition temperature of the industrial Azodicarbonamide (AC) blowing agent is 195-210 ℃ and, therefore, the processing temperature is preferably a lower temperature such as 180-205 ℃ in consideration of the combination of the processability and the decomposition temperature of the AC blowing agent. In consideration of energy conservation and emission reduction, zinc oxide is generally added to the AC foaming agent to lower the decomposition temperature of AC to 170-180 ℃, and the addition amount of zinc oxide is preferably 1 part by weight based on 100 parts by weight of the base resin.
According to a preferred embodiment of the present invention, the temperature in step b is raised to 280 ℃ of 140-. In some preferred embodiments of the invention, the temperature of the extruder is set as follows: the temperature of the first zone is 145-155 ℃, the temperature of the second zone is 155-160 ℃, the temperature of the third zone is 160-170 ℃, the temperature of the fourth zone is 165-175 ℃, the temperature of the fifth zone is 165-175 ℃, the temperature of the sixth zone is 160-170 ℃, and the temperature of the head is 155-165 ℃.
According to a preferred embodiment of the present invention, in step c, the temperature of the extruder die is 150-.
The glass fiber reinforced polypropylene foamed section provided by the invention can be applied to transportation tools, such as automobiles, aircrafts and high-speed rail interior and exterior decorations, architectural decorations, leisure and entertainment and other occasions with higher requirements on mechanical properties and light weight of plastic products.
In the composition for preparing the glass fiber reinforced polypropylene material, the polar monomer modified polypropylene is used as a base material, the excellent performance of the polypropylene is maintained and the performance of the composite material is improved at the same time by controlling the grafting rate of the polar monomer and the melt index of the polypropylene base material, the glass fiber is used as a filler, and the polar monomer modified polypropylene is matched with a compatilizer, a flexibilizer and the components in the composition, so that the prepared glass fiber reinforced polypropylene material has excellent performance, and a foamed plate prepared by foaming has the characteristics of smooth surface, compact pores, uniform pore diameter, low foaming multiplying power, controllability, closed pore hard structure, good impact and the like.
The preparation method of the polypropylene foaming section provided by the invention is simple and effective, is easy to operate and low in cost, and can realize the stabilization of the polypropylene raw material, so that the foaming window is effectively enlarged, and the process is easy to adjust.
The polypropylene plastic-wood foamed board provided by the invention is of a non-crosslinked structure, can be recycled according to common polypropylene modified materials, does not cause secondary pollution, and meets the requirement of circular 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, yanshan petrochemical;
in the embodiment of the present invention, the polar monomer modified polypropylene is homemade glycidyl methacrylate grafted polypropylene, wherein the polypropylene is copolymerized polypropylene produced by petrochemical industry in China and has the brand number of SP 179. In the glycidyl methacrylate-grafted polypropylene, the grafting ratio of glycidyl methacrylate was 4.2 wt% (measured by acid-base titration), and the melt flow rate was 6.8g/10min under the test conditions of 230 ℃ X2.16 kg.
The preparation method of the glycidyl methacrylate grafted polypropylene with the grafting rate of the glycidyl methacrylate of 4.2 wt% comprises the following steps:
heating 200 parts by weight of 10 wt% sodium chloride aqueous solution to 90 ℃, adding 100 parts by weight of SP179 polypropylene powder, stirring for 2 hours, continuing to add 6 parts by weight of monomer GMA and 0.06 part by weight of initiator benzoyl peroxide, stirring, mixing, reacting for 6 hours, washing a reaction product by deionized water and acetone to remove unreacted monomer and initiator, and drying to obtain the modified polypropylene particles.
In the examples of the invention, the glass fibers: alkali-free glass fiber with diameter of 13 μm and length of 4.5mm, and produced by boulder group;
a compatilizer: maleic anhydride-grafted polypropylene, brand CA100, manufactured by Arkema, france; the methacrylic acid grafted polypropylene is self-prepared by a conventional method, and the grafting rate is 2.23 wt% by titration.
A toughening agent: styrene-ethylene-butadiene-styrene copolymer, manufactured by the petrochemical division of ba ling, china under the designation YH 688; maleic anhydride-grafted styrene-ethylene-butadiene-styrene copolymer, manufactured by Kraton corporation, usa under the designation FG 1901; ethylene-octene copolymer, available from Dow chemical company, USA, under the designation 8400; a maleic anhydride-grafted ethylene-octene copolymer, manufactured by Jiangsu Nantong Rieger, Inc., under the designation CMG 9805.
Unless otherwise specified, the antioxidant used in the examples is selected from tetrakis [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (antioxidant 1010) and tris (2, 4-di-tert-butyl) phenyl phosphite (antioxidant 168) in a mass ratio of 1: 1.
Example 1
Weighing dry polar monomer modified polypropylene (with a grafting rate of 4 wt%), glass fiber, a compatilizer, a flexibilizer and an antioxidant according to the addition amount of the materials in the table 1, uniformly mixing the components, adding the mixture into a double-screw extruder, and carrying out melt blending, extrusion and granulation to obtain the glass fiber reinforced polypropylene material. The processing temperature of the double-screw extruder is as follows: the temperature in the first zone is 150 ℃, the temperature in the second zone is 160 ℃, the temperature in the third zone is 165 ℃, the temperature in the fourth zone is 170 ℃, the temperature in the fifth zone is 170 ℃, the temperature in the sixth zone is 170 ℃ and the temperature in the head is 165 ℃.
Foaming and rolling processes:
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 Table 1 and mixed for 1 minute at high speed to obtain the premix of the polypropylene foaming profile. MB50-002 (high molecular weight polysiloxane) was used as a lubricant, and the amount was 1 part by weight per 100 parts by weight of polypropylene.
The temperature of the extruder was adjusted to the foaming temperature shown in table 1, and then the premix was fed to the middle twin screw of the extruder, with the torque controlled at about 65% and the screw rotation speed adjusted to 15-170rpm, so that the premix was melted in the extruder.
Extruding the molten premix to a T-shaped head die at a foaming temperature, flowing into a gap between two rollers of a plate extruding machine set, rolling to form a plate-shaped polypropylene foaming material, and naturally cooling to room temperature.
The surface and cell morphology of the article of the polypropylene foam obtained 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 to 7 and comparative examples 1 to 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 and has the designation SP 179; the amounts of the respective components used in examples 2 to 7 and comparative examples 1 to 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 3.0 wt%.
The grafting ratio of glycidyl methacrylate in example 9 was 4.5 wt%.
The grafting ratio of glycidyl methacrylate in example 10 was 2.0 wt%.
The grafting ratio of glycidyl methacrylate in example 11 was 6.0 wt%.
Example 12
Example 12 differs from example 2 in that the toughening agent uses maleic anhydride grafted 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 at 230 ℃ under 2.16kg test conditions, respectively.
Examples 18 to 22
Examples 18-22 differ from example 1 in the amounts of toughening, compatibilizing and/or blowing agents, as specified 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 graft-modified polypropylene and methyl acrylate graft-modified polypropylene, respectively.
Compared with the data of the comparative example, the impact strength of the material 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, the modified polypropylene can form more bonding points with the surface of the glass fiber, and the phenomenon of fiber floating on the surface is improved. The glass fiber plays a role of a foam 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 flexibilizer has uniform foam cells and excellent weight-reducing and lightening properties, and the fiber floating condition on the surface 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 great, the weight reduction of a foaming product is not obvious, and the mechanical property is poor. The glass fiber composite material prepared by GMA grafted polypropylene has smell obviously less than that of polypropylene composite material grafted by maleic anhydride or methyl acrylate, and can be used in fields of automobile interior materials and the like with high requirements on smell.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A composition for preparing a glass fiber reinforced polypropylene material, comprising or consisting of:
2. the composition according to claim 1, wherein the polar monomer modified polypropylene has a melt index of 3 to 60g/10min, preferably 5 to 40g/10min, more preferably 8 to 30g/10min, at 230 ℃ under 2.16kg test conditions.
3. Composition according to claim 1 or 2, wherein the polypropylene is a co-polypropylene, preferably a co-polypropylene with impact resistance, comprising a propylene homopolymer component and a propylene/ethylene copolymer component, wherein the content of propylene/ethylene copolymer component is 3-10 wt%.
4. The composition according to any one of claims 1 to 3, wherein the polar monomer-modified polypropylene is a polar monomer graft-modified polypropylene, the polar monomer being selected from one or more of glycidyl methacrylate, methyl acrylate and maleic anhydride, preferably glycidyl methacrylate; preferably, the polar monomer-modified polypropylene has a grafting ratio of the polar monomer of 3 to 4.5 wt%, preferably 3.5 to 4.5 wt%.
5. Composition according to any one of claims 1 to 4, characterized in that the glass fibers are alkali-free glass fibers, preferably glass fibers having a diameter of 11 to 13 μm and a length of 3.5 to 5.5 mm; and/or the presence of a gas in the gas,
the compatilizer is polar monomer grafted polyethylene or polar monomer grafted polypropylene, and the polar monomer is preferably selected from one or more of maleic anhydride, derivatives of maleic anhydride, acrylic acid and derivatives of acrylic acid; and/or the presence of a gas in the gas,
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 maleic anhydride, acrylic acid and derivatives of acrylic acid.
6. The composition according to any one of claims 1 to 5, wherein the raw material of the composite material further comprises one or more of an antioxidant, a nucleating agent, an antistatic agent and an antibacterial agent, preferably the antioxidant is used in an amount of 0.1 to 0.5 parts by weight in 100 parts by weight of the polar monomer-modified polypropylene.
7. A glass fiber reinforced polypropylene material made from the composition of any one of claims 1-6.
8. A glass fiber reinforced polypropylene foamed molded body prepared from the glass fiber reinforced polypropylene material as claimed in claim 7, preferably the foamed molded body has a density of 0.2 to 0.9g/cm-3。
9. The process for producing a foamed molding according to claim 8, 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 opening die, flowing to a plate extruder, and rolling to form the foamed plate.
10. Use of the foamed molded body according to claim 8 for interior and exterior trims of automobiles, aircrafts and high-speed rails.
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