CN103497425A - High-strength and high-tenacity polypropylene composite materials and preparation method thereof - Google Patents

High-strength and high-tenacity polypropylene composite materials and preparation method thereof Download PDF

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CN103497425A
CN103497425A CN201310498105.XA CN201310498105A CN103497425A CN 103497425 A CN103497425 A CN 103497425A CN 201310498105 A CN201310498105 A CN 201310498105A CN 103497425 A CN103497425 A CN 103497425A
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polypropylene
strength
calcium sulfate
polypropylene composite
ductility
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何波兵
孙文道
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SICHUAN WANRUN NON-METALLIC MINERALS MATERIALS CO LTD
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SICHUAN WANRUN NON-METALLIC MINERALS MATERIALS CO LTD
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10Homopolymers or copolymers of propene
    • C08J2323/12Polypropene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00Characterised 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
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/06Polyethene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/08Copolymers of ethene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10Homopolymers or copolymers of propene
    • C08J2423/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses high-strength and high-tenacity polypropylene composite materials. The high-strength and high-tenacity polypropylene composite materials solve the problems that existing polypropylene is poor in tenacity and poor in strength. The high-strength and high-tenacity polypropylene composite materials are formed by the following components, by weight, 35-75% of polypropylene, 10-40% of calcium carbonate, 8-25% of calcium sulfate whisker masterbatch, 0.1-2% of coupling agents, 2-8% of compatilizer, 0.3-4% of lubricating agents and 0.2-0.8% of antioxygen. The invention further provides a preparation method of the high-strength and high-tenacity polypropylene composite materials. According to the preparation method of the high-strength and high-tenacity polypropylene composite materials, through the mode that calcium sulfate whiskers are made into masterbatch, the calcium sulfate whisker masterbatch is added to plastics to carry out co-extrusion mixing with the plastics and the like, thus, compared with powdery whiskers, material preparation can be evener and controllable, the problem that material preparation of the calcium sulfate whiskers is difficult is solved, meanwhile, the calcium sulfate whiskers are made to have better dispersity in plastic substrate, and the surfaces of products are smoother.

Description

Polypropylene composite material of a kind of high-strength and high ductility and preparation method thereof
Technical field
The present invention relates to polypropylene composite material of a kind of high-strength and high ductility and preparation method thereof.
Background technology
Proportion is little, intensity is high, chemical proofing is good owing to having for polypropylene, easily processing and the advantage such as cheap be in a large number for fields such as chemical industry, building, light industry, automobile making, household electrical appliances, wrapping material.Polypropylene is divided into homo-polypropylene and co-polypropylene at present, the homo-polypropylene glossiness is good, thermotolerance is good, heat-drawn wire is high, erosion resistance is strong, electrical insulating property is good, nonpoisonous and tasteless, easy processing, and Young's modulus, tensile strength and yield strength are all higher, but shock strength is lower.In order to overcome this shortcoming, vinyl monomer and the copolymerization of propylene of introducing certain content when polymerization can make block copolymerization polypropylene (PPB) and atactic copolymerized polypropene (PPR), polyacrylic normal temperature and low temperature impact properties are greatly improved, but its intensity also slightly have decline simultaneously.In addition in order to reduce material cost, the normal mineral filler of adding certain content, as calcium carbonate, talcum powder, mica, glass microballon etc., these fillers are when reducing material cost, also give material some special performance, as improved the intensity of material, improve moulding processability, reduce the shrinking percentage of goods, improve heat-drawn wire of goods etc.Can obviously improve polyacrylic rigidity although patent 200610045753.X adds talcum powder, tensile strength and the impact strength decreased of material are serious, need to improve the impelling strength of material by adding elastomerics, and material cost rises thereupon.Patent 200710044228.0 adopts nano level talcum powder and micron order talcum powder modified synergic polypropylene, and system has rigid-tough balance preferably, but the nano level talcum powder is expensive, and the material prescription cost is higher.Also there is patent to pass through to add magnesium salt whisker (CN102516662A) or other whisker in the polypropylene of talc and further improve the intensity of system as (CN 102070842 B) such as alumina whisker, calcium sulfate crystal whiskers, ZnOws.From patent, find out, all there is the shortcoming of sacrificing polypropylene toughness in the talcous Pp System of nearly all interpolation, usually needs to add elastomerics in toughness reguirements in higher goods and carries out toughness reinforcing.
In fact calcium carbonate be polypropylene good increase firm toughness reinforcing filler, calcium carbonate is not only cheap and easy to get, also can improve polyacrylic moulding processability, reduces the molding shrinkage of goods, is the rare toughness reinforcing particle of inorganic rigid.With talcum powder, compare, the calcium carbonate outstanding feature is that it is obvious to polyacrylic toughening effect, but is weaker than talcum powder increasing aspect firm.As patent CN 102391572 A will activate calcium carbonate-filled in co-polypropylene, improved the shock strength of co-polypropylene, but that modulus in flexure increases is not obvious, add 30% calcium carbonate, the modulus in flexure of co-polypropylene has also only improved 80% left and right.Patent (CN 102336955 A) is also arranged by talcum powder and calcium carbonate composite modified polypropylene, in fact because two kinds of fillers have different mechanism of nucleation to polypropylene, phase mutual interference between them when the polypropylene crystallisation by cooling, destroy polyacrylic crystallization, cause the performance of material to improve not obvious.Therefore the rigidity (as modulus in flexure) that improves calcium carbonate-filled Pp System is problem demanding prompt solution.
Calcium sulfate crystal whiskers, be again crystal whisker of gypsum, is a kind of elongated fibers of single crystal form growth, and general length is that 10~200 μ m, diameter are that 1~4 μ m, length-to-diameter ratio are in 10 ~ 100 left and right.There is uniform cross section, complete profile, perfect internal structure, it is a kind of fine crystalline fiber that almost reaches perfect condition, its mechanical property is considerably beyond the general particulate fillers that use in a large number at present, calcium sulfate crystal whiskers has gathered the two advantage of fortifying fibre and ultra-fine inorganic filler and has been integrated, fill it in plastic substrate and there is a series of advantage: in (1) calcium sulfate crystal whiskers additive correlated product, when on microcosmic, changing goods, also make goods show isotropy, make the shrinking percentage difference of other vertical and horizontal in various environment less, thereby guarantee the precision of product size and shape, (2) improve the surface smoothness of goods, (3) improve the heat resisting temperature of goods, (4) reduce the wearing and tearing to equipment, while adopting the high glass fiber reinforced polymer of surface hardness and rigidity, can make equipment can be subject to quite serious wearing and tearing, while with calcium sulfate crystal whiskers, strengthening polymkeric substance, but can not cause the wearing and tearing of equipment, because calcium sulfate crystal whiskers not only surface hardness is lower, and there is trickle structure and good mobility.(5) improve the full level of mould, when product molding, adding calcium sulfate crystal whiskers than adding other fibers has better mobility, can be full of whole mould, makes product size more accurate, and improves lumber recovery; (6) toughness reinforcing good with reinforced effects.
The proportion of calcium sulfate crystal whiskers is 2.69, but its apparent density is 0.1~0.4, for puffy, be difficult for flowing, therefore when calcium sulfate crystal whiskers is filled in plastics, if the addition means that adopts conventional fillers as main feeding or side feeding, the as easy as rolling off a log appearance phenomenons such as being difficult for blanking of building bridge, cause calcium sulfate crystal whiskers to add difficulty, the adding proportion generation larger fluctuation of calcium sulfate in plastics.Can not meet people's demand.
Summary of the invention
The object of the present invention is to provide polypropylene composite material of a kind of high-strength and high ductility and preparation method thereof, solve existing polypropylene toughness poor, and the not good problem of intensity.
The present invention is achieved through the following technical solutions:
A kind of polypropylene composite material of high-strength and high ductility, described matrix material is comprised of the component of following weight percent:
Polypropylene 35~75%
Calcium carbonate 10~40%
Calcium sulfate crystal whiskers master batch 8~25%
Coupling agent 0.1~2%
Compatilizer 2~8%
Lubricant 0.3~4%
Oxidation inhibitor 0.2~0.8%.
As a kind of preferred, described master batch is comprised of the component of following weight percent: polypropylene 50%, calcium carbonate 25%, calcium sulfate crystal whiskers master batch 17%, coupling agent 1%, compatilizer 4.4%, lubricant 2%, oxidation inhibitor 0.6%.
Further, described polypropylene is selected from one or more in homo-polypropylene, block copolymerization polypropylene.
Again further, described coupling agent is selected from one or more in KH550, Aluminate, titanate coupling agent, stearic acid.
Further, the polypropylene that described compatilizer is vinylformic acid or modified by maleic acid anhydride graft.
In addition, described lubricant is selected from one or more in calcium stearate, Zinic stearas, N.N '-ethylene bis stearamide; The compound that described oxidation inhibitor is antioxidant 1010 and irgasfos 168.
In addition, the polyolefine that described calcium sulfate crystal whiskers master batch is 10~30% by weight percent, 50~80% calcium sulfate crystal whiskers, 5~20% wax and 0.2~1.5% tensio-active agent form.
A kind of preparation method of polypropylene composite material of high-strength and high ductility comprises the following steps:
(1) calcium carbonate is added in high mixer, under the stirring velocity of 1500 rev/mins, coupling agent is slowly added, then mix 5~10 minutes, discharging, obtain surface active calcium carbonate;
(2) polypropylene, activated calcium carbonate, compatilizer, lubricant, oxidation inhibitor are added in high mixer, mix under the stirring velocity of 800 rev/mins 2~4 minutes, obtain compound;
(3) compound is placed in to twin screw extruder, then the mode by the side direction feeding adds by the calcium sulfate crystal whiskers master batch, through the melting mixing of forcing machine extrude, the water cooling bracing pelletizing.
Further, the extrusion temperature of described forcing machine is 160~210 ℃, and screw speed is 260~400 rev/mins.
The present invention has the following advantages and beneficial effect:
(1) calcium carbonate of the present invention has good toughness reinforcing performance, calcium sulfate not only has toughening effect, also there is obvious enhancement, make filling-modified polypropylene there is good rigidity and toughness, the composite modified polypropylene of the present invention all improves more than 30% than polypropylene material flexural strength and the modulus in flexure of adding separately same amount calcium carbonate, and shock strength does not descend.
(2) the present invention is due to Calcium Sulfate Whiskers and the reason such as major diameter is smaller, with other macrofiber, with chopped strand, compare, the calcium sulfate crystal whiskers that the present invention uses is orientated not obvious in polypropylene matrix, thereby make Injection moulded part show isotropy, the difference of goods vertical and horizontal shrinking percentage dimensionally less (glass modified polypropene shrinking percentage vertically/laterally than being 2.65, of the present invention is only 0.56), the good stability of the dimension of goods, be difficult for warpage and distortion occur, can guarantee the precision of product size and outward appearance.
(3) matrix material of the present invention is compared with the calcium carbonate of independent interpolation same amount, and calcium sulfate crystal whiskers of the present invention and calcium carbonate composite modified polypropylene have higher mobility (melting index improves 20%), may be molded to the product of large thin-wall.
(4) the present invention adopts calcium sulfate crystal whiskers can make the thermotolerance of system obviously improve (heat-drawn wire improves 10 ~ 15 ℃).
(5) the present invention is owing to adopting cheap calcium carbonate and calcium sulfate crystal whiskers to fill, and material modified formulation cost is low, proportion is little, has the obvious market competitiveness, can be used for making inner and outer decorative parts of automobile, electric appliance casing and building product.
(6) the present invention adopts the mode of calcium sulfate crystal whiskers being made to master batch, add to again in plastics and mix with co-extrusions such as plastics, with the powdery whisker, compare like this, blanking is more evenly controlled, solved the problem of calcium sulfate crystal whiskers blanking difficulty, also make the dispersiveness of calcium sulfate crystal whiskers in plastic substrate better, product surface is Paint Gloss simultaneously.
(7) calcium sulfate crystal whiskers of the present invention adopts coupling agent to carry out surface active, is combined better in the interface of whisker between matrix resin, strengthens toughening effect more obvious.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of polypropylene composite material of high-strength and high ductility, component by following weight percent forms: homo-polypropylene 51%, calcium carbonate 25%, calcium sulfate crystal whiskers master batch 15%, coupling agent KH550 1.2%, the polypropylene 5% of modified by maleic acid anhydride graft, calcium stearate 2.3%, antioxidant 1010 and 168 compound 0.5%.Wherein, the calcium sulfate crystal whiskers master batch is comprised of the component of following weight percent: polyethylene 10%, and calcium sulfate crystal whiskers (being produced by Sichuan Wan Run nonmetallic mineral material company limited) 80%, Poly Propylene Wax 9.8%, KH550 0.2%.
The preparation method of described master batch is as follows:
At first, add height to stir in machine calcium sulfate crystal whiskers, add coupling agent KH550 under the rotating speed of 1500 rev/mins, stir 6 minutes under the rotating speed of 1500 rev/mins;
Then, by polyethylene, Poly Propylene Wax adds height to stir in machine, under the rotating speed of 800 rev/mins, mixes 2 minutes, obtains compound;
Finally, compound is placed in to single screw extrusion machine and melt extrudes also granulation, obtain the calcium sulfate crystal whiskers master batch.Wherein, the extrusion temperature of forcing machine is 160~210 ℃, and adopts air-cooled fervent mode.
The preparation method of matrix material is as follows:
(1) calcium carbonate is added in high mixer, under the stirring velocity of 1500 rev/mins, coupling agent KH550 is slowly added, then mix 5~10 minutes, discharging, obtain surface active calcium carbonate;
(2) compound of the polypropylene of homo-polypropylene, activated calcium carbonate, modified by maleic acid anhydride graft, calcium stearate, antioxidant 1010 and 168 is added in high mixer, mix under the stirring velocity of 800 rev/mins 2~4 minutes, obtain compound;
(3) compound is placed in to twin screw extruder, then the mode by the side direction feeding adds by the calcium sulfate crystal whiskers master batch, through the melting mixing of forcing machine extrude, the water cooling bracing pelletizing.Wherein, extruder temperature is 160~210 ℃, and screw speed is 260~400 rev/mins.
Embodiment 2
A kind of polypropylene composite material of high-strength and high ductility, component by following weight percent forms: homo-polypropylene 37.8%, calcium carbonate 40%, calcium sulfate crystal whiskers master batch 8%, coupling agent Aluminate 2%, the polypropylene 8% of modified by maleic acid anhydride graft, Zinic stearas 4%, antioxidant 1010 and 168 compound 0.2%.Wherein, the calcium sulfate crystal whiskers master batch is comprised of the component of following weight percent: ethene-hexene copolymer 20%, and calcium sulfate crystal whiskers (being produced by Sichuan Wan Run nonmetallic mineral material company limited) 58.5%, polyethylene wax 20%, KH570 0.2%.
The preparation method of described master batch is as follows:
At first, add height to stir in machine calcium sulfate crystal whiskers, add coupling agent KH570 under the rotating speed of 1500 rev/mins, stir 8 minutes under the rotating speed of 1500 rev/mins;
Then, by ethene-hexene copolymer, polyethylene wax adds height to stir in machine, under the rotating speed of 800 rev/mins, mixes 3 minutes, obtains compound;
Finally, compound is placed in to single screw extrusion machine and melt extrudes also granulation, obtain the calcium sulfate crystal whiskers master batch.Wherein, the extrusion temperature of forcing machine is 160~210 ℃, and adopts air-cooled fervent mode.
The preparation method of matrix material is as follows:
(1) calcium carbonate is added in high mixer, under the stirring velocity of 1500 rev/mins, the coupling agent Aluminate is slowly added, then mix 8 minutes, discharging, obtain surface active calcium carbonate;
(2) compound of the polypropylene of homo-polypropylene, activated calcium carbonate, modified by maleic acid anhydride graft, Zinic stearas, antioxidant 1010 and 168 is added in high mixer, mix 3 minutes under the stirring velocity of 800 rev/mins, obtain compound;
(3) compound is placed in to twin screw extruder, then the mode by the side direction feeding adds by the calcium sulfate crystal whiskers master batch, through the melting mixing of forcing machine extrude, the water cooling bracing pelletizing.Wherein, extruder temperature is 160~210 ℃, and screw speed is 260~400 rev/mins.
Embodiment 3
A kind of polypropylene composite material of high-strength and high ductility, component by following weight percent forms: block copolymerization polypropylene 61.8%, calcium carbonate 10%, calcium sulfate crystal whiskers master batch 25%, coupling agent titanic acid ester 0.1%, the polypropylene 2% of modified by maleic acid anhydride graft, lubricant N.N '-ethylene bis stearamide 0.3%, antioxidant 1010 and 168 compound 0.8%.Wherein, the calcium sulfate crystal whiskers master batch is comprised of the component of following weight percent: polypropylene 15%, ethylene-octene copolymer 15%, calcium sulfate crystal whiskers (being produced by Sichuan Wan Run nonmetallic mineral material company limited) 50%, Poly Propylene Wax 18.7%, silicon 69(pair-[γ-(triethoxysilicane) propyl group] tetrasulfide) 1.3%.
The preparation method of described master batch is as follows:
At first, add height to stir in machine calcium sulfate crystal whiskers, add silicon 69(pair-[γ-(triethoxysilicane) propyl group] tetrasulfide under the rotating speed of 1500 rev/mins), under the rotating speed of 1500 rev/mins, stir 7 minutes;
Then, by polypropylene, ethylene-octene copolymer, 374 gram Poly Propylene Waxes add height to stir in machine, under the rotating speed of 800 rev/mins, mix 2 minutes, obtain compound;
Finally, compound is placed in to single screw extrusion machine and melt extrudes also granulation, obtain the calcium sulfate crystal whiskers master batch.Wherein, the extrusion temperature of forcing machine is 160~210 ℃, and adopts air-cooled fervent mode.
The preparation method of matrix material is as follows:
(1) calcium carbonate is added in high mixer, under the stirring velocity of 1500 rev/mins, the coupling agent titanic acid ester is slowly added, then mix 7 minutes, discharging, obtain surface active calcium carbonate;
(2) compound of the polypropylene of block copolymerization polypropylene, activated calcium carbonate, modified by maleic acid anhydride graft, lubricant N.N '-ethylene bis stearamide, antioxidant 1010 and 168 is added in high mixer, mix 2 minutes under the stirring velocity of 800 rev/mins, obtain compound;
(3) compound is placed in to twin screw extruder, then the mode by the side direction feeding adds by the calcium sulfate crystal whiskers master batch, through the melting mixing of forcing machine extrude, the water cooling bracing pelletizing.Wherein, extruder temperature is 160~210 ℃, and screw speed is 260~400 rev/mins.
Embodiment 4
A kind of polypropylene composite material of high-strength and high ductility, component by following weight percent forms: block copolymerization polypropylene 75%, calcium carbonate 11%, calcium sulfate crystal whiskers master batch 9%, coupling agent stearic acid 0.6%, acrylic graft-modified polypropylene 3%, N.N '-ethylene bis stearamide 1%, antioxidant 1010 and 168 compound 0.4%.Wherein, the calcium sulfate crystal whiskers master batch is comprised of the component of following weight percent: polypropylene 15%, calcium sulfate crystal whiskers (being produced by Sichuan Wan Run nonmetallic mineral material company limited) 69.2%, polyethylene wax 15%, titanate coupling agent 0.8%.
The preparation method of described master batch is as follows:
At first, add height to stir in machine calcium sulfate crystal whiskers, under the rotating speed of 1500 rev/mins, add titanate coupling agent, stir 5 minutes under the rotating speed of 1500 rev/mins;
Then, by polypropylene, polyethylene wax adds height to stir in machine, under the rotating speed of 800 rev/mins, mixes 3 minutes, obtains compound;
Finally, compound is placed in to single screw extrusion machine and melt extrudes also granulation, obtain the calcium sulfate crystal whiskers master batch.Wherein, the extrusion temperature of forcing machine is 160~210 ℃, and adopts air-cooled fervent mode.
The preparation method of matrix material is as follows:
(1) calcium carbonate is added in high mixer, under the stirring velocity of 1500 rev/mins, the coupling agent stearic acid is slowly added, then mix 6 minutes, discharging, obtain surface active calcium carbonate;
(2) compound of block copolymerization polypropylene, activated calcium carbonate, acrylic graft-modified polypropylene, lubricant N.N '-ethylene bis stearamide, antioxidant 1010 and 168 is added in high mixer, mix 4 minutes under the stirring velocity of 800 rev/mins, obtain compound;
(3) compound is placed in to twin screw extruder, then the mode by the side direction feeding adds by the calcium sulfate crystal whiskers master batch, through the melting mixing of forcing machine extrude, the water cooling bracing pelletizing.Wherein, extruder temperature is 160~210 ℃, and screw speed is 260~400 rev/mins.
Embodiment 5
A kind of polypropylene composite material of high-strength and high ductility, component by following weight percent forms: homo-polypropylene 21%, block copolymerization polypropylene 21%, calcium carbonate 30%, calcium sulfate crystal whiskers master batch 19%, coupling agent stearic acid 1.6%, acrylic graft-modified polypropylene 4%, N.N '-ethylene bis stearamide 2.8%, antioxidant 1010 and 168 compound 0.6%.Wherein, the calcium sulfate crystal whiskers master batch is comprised of the component of following weight percent: ethylene-octene copolymer 25%, calcium sulfate crystal whiskers (being produced by Sichuan Wan Run nonmetallic mineral material company limited) 68%, Poly Propylene Wax 6%, stearic acid 1%.
The preparation method of described master batch is as follows:
At first, add height to stir in machine calcium sulfate crystal whiskers, under the rotating speed of 1500 rev/mins, add stearic acid, stir 6 minutes under the rotating speed of 1500 rev/mins;
Then, by ethylene-octene copolymer, Poly Propylene Wax adds height to stir in machine, under the rotating speed of 800 rev/mins, mixes 2 minutes, obtains compound;
Finally, compound is placed in to single screw extrusion machine and melt extrudes also granulation, obtain the calcium sulfate crystal whiskers master batch.Wherein, the extrusion temperature of forcing machine is 160~210 ℃, and adopts air-cooled fervent mode.
The preparation method of matrix material is as follows:
(1) calcium carbonate is added in high mixer, under the stirring velocity of 1500 rev/mins, the coupling agent stearic acid is slowly added, then mix 6 minutes, discharging, obtain surface active calcium carbonate;
(2) compound of homo-polypropylene, block copolymerization polypropylene, activated calcium carbonate, acrylic graft-modified polypropylene, N.N '-ethylene bis stearamide, antioxidant 1010 and 168 is added in high mixer, mix 4 minutes under the stirring velocity of 800 rev/mins, obtain compound;
(3) compound is placed in to twin screw extruder, then the mode by the side direction feeding adds by the calcium sulfate crystal whiskers master batch, through the melting mixing of forcing machine extrude, the water cooling bracing pelletizing.Wherein, extruder temperature is 160~210 ℃, and screw speed is 260~400 rev/mins.
Embodiment 6
A kind of polypropylene composite material of high-strength and high ductility, component by following weight percent forms: homo-polypropylene 25%, block copolymerization polypropylene 25%, calcium carbonate 25%, calcium sulfate crystal whiskers master batch 17%, Aluminate 0.5%, titanic acid ester 0.5%, acrylic graft-modified polypropylene 4.4%, calcium stearate 1%, Zinic stearas 1%, antioxidant 1010 and 168 compound 0.6%.Wherein, the calcium sulfate crystal whiskers master batch is comprised of the component of following weight percent: polyethylene 17%, calcium sulfate crystal whiskers (being produced by Sichuan Wan Run nonmetallic mineral material company limited) 75%, polyethylene wax 7%, coupling agent KH550 0.5%, coupling agent KH570 0.5%.
The preparation method of described master batch is as follows:
At first, add height to stir in machine calcium sulfate crystal whiskers, add coupling agent KH550 and coupling agent KH570 under the rotating speed of 1500 rev/mins, stir 5 minutes under the rotating speed of 1500 rev/mins;
Then, by polyethylene, polyethylene wax adds height to stir in machine, under the rotating speed of 800 rev/mins, mixes 2 minutes, obtains compound;
Finally, compound is placed in to single screw extrusion machine and melt extrudes also granulation, obtain the calcium sulfate crystal whiskers master batch.Wherein, the extrusion temperature of forcing machine is 160~210 ℃, and adopts air-cooled fervent mode.
The preparation method of matrix material is as follows:
(1) calcium carbonate is added in high mixer, under the stirring velocity of 1500 rev/mins, coupling agent Aluminate and titanic acid ester are slowly added, then mix 10 minutes, discharging, obtain surface active calcium carbonate;
(2) compound of homo-polypropylene, block copolymerization polypropylene, activated calcium carbonate, acrylic graft-modified polypropylene, calcium stearate, Zinic stearas, antioxidant 1010 and 168 is added in high mixer, mix 2 minutes under the stirring velocity of 800 rev/mins, obtain compound;
(3) compound is placed in to twin screw extruder, then the mode by the side direction feeding adds by the calcium sulfate crystal whiskers master batch, through the melting mixing of forcing machine extrude, the water cooling bracing pelletizing.Wherein, extruder temperature is 160~210 ℃, and screw speed is 260~400 rev/mins.
Detection data of the present invention are as following table 1:
Table 1
? Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Tensile strength/MPa 38 32 29 27 37 36
Flexural strength/MPa 50 40 35 33 48 48
Modulus in flexure/MPa 2200 1950 1820 1794 2414 2300
Notched Izod impact strength/(kJ/m2) 7.2 6.3 31 36 19 21
Heat-drawn wire/℃ 85 83 75 74 82 81
Melting index/(g/10min) 2.6 1.8 2.8 3.1 2.2 2.5
Data from table 1 can find out, the prepared polypropylene of the present invention meets material and has good performance.
Should be noted that, above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although with reference to above-described embodiment, the present invention is had been described in detail, those of ordinary skill in the art is to be understood that: still can modify or be equal to replacement the present invention, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in claim scope of the present invention.

Claims (10)

1. the polypropylene composite material of a high-strength and high ductility, is characterized in that, described polypropylene composite material is comprised of the component of following weight percent:
Polypropylene 35~75%
Calcium carbonate 10~40%
Calcium sulfate crystal whiskers master batch 8~25%
Coupling agent 0.1~2%
Compatilizer 2~8%
Lubricant 0.3~4%
Oxidation inhibitor 0.2~0.8%.
2. the polypropylene composite material of a kind of high-strength and high ductility according to claim 1, it is characterized in that, described polypropylene composite material is comprised of the component of following weight percent: polypropylene 50%, calcium carbonate 25%, calcium sulfate crystal whiskers master batch 17%, coupling agent 1%, compatilizer 4.4%, lubricant 2%, oxidation inhibitor 0.6%.
3. the polypropylene composite material of a kind of high-strength and high ductility according to claim 1 and 2, is characterized in that, described polypropylene is selected from one or more in homo-polypropylene, block copolymerization polypropylene.
4. the polypropylene composite material of a kind of high-strength and high ductility according to claim 1 and 2, is characterized in that, described coupling agent is selected from one or more in KH550, Aluminate, titanate coupling agent, stearic acid.
5. the polypropylene composite material of a kind of high-strength and high ductility according to claim 1 and 2, is characterized in that, the polypropylene that described compatilizer is vinylformic acid or modified by maleic acid anhydride graft.
6. the polypropylene composite material of a kind of high-strength and high ductility according to claim 1 and 2, is characterized in that, described lubricant is selected from one or more in calcium stearate, Zinic stearas, N.N '-ethylene bis stearamide.
7. the polypropylene composite material of a kind of high-strength and high ductility according to claim 1 and 2, is characterized in that, the compound that described oxidation inhibitor is antioxidant 1010 and irgasfos 168.
8. the polypropylene composite material of a kind of high-strength and high ductility according to claim 1 and 2, it is characterized in that, the polyolefine that described calcium sulfate crystal whiskers master batch is 10~30% by weight percent, 50~80% calcium sulfate crystal whiskers, 5~20% wax and 0.2~1.5% tensio-active agent form.
9. the preparation method of the polypropylene composite material of the described a kind of high-strength and high ductility of claim 1~8 any one, is characterized in that, comprises the following steps:
(1) calcium carbonate is added in high mixer, under the stirring velocity of 1500 rev/mins, coupling agent is slowly added, then mix 5~10 minutes, discharging, obtain surface active calcium carbonate;
(2) polypropylene, activated calcium carbonate, compatilizer, lubricant, oxidation inhibitor are added in high mixer, mix under the stirring velocity of 800 rev/mins 2~4 minutes, obtain compound;
(3) compound is placed in to twin screw extruder, then the mode by the side direction feeding adds by the calcium sulfate crystal whiskers master batch, through the melting mixing of forcing machine extrude, the water cooling bracing pelletizing.
10. the preparation method of the polypropylene composite material of a kind of high-strength and high ductility according to claim 9, is characterized in that, the extrusion temperature of described forcing machine is 160~210 ℃, and screw speed is 260~400 rev/mins.
CN201310498105.XA 2013-10-22 2013-10-22 High-strength and high-tenacity polypropylene composite materials and preparation method thereof Pending CN103497425A (en)

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Cited By (7)

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CN104610660A (en) * 2015-01-31 2015-05-13 合肥江淮毅昌汽车饰件有限公司 Thin-wall high-rigidity plastic material for automobile bumpers and preparation method of thin-wall high-rigidity plastic material
CN106750897A (en) * 2016-11-25 2017-05-31 武汉理工大学 For the preparation method of the crystals of calcium salts modified polypropene cortex of bimodal polyethylene pipe
CN109679206A (en) * 2018-12-13 2019-04-26 广州市聚赛龙工程塑料股份有限公司 A kind of low nano-filler modified polypropylene material and the preparation method and application thereof that volatilizees
CN110003572A (en) * 2019-04-29 2019-07-12 上海金发科技发展有限公司 A kind of polypropylene for thin-walled automobile product-alkali magnesium sulfate crystal whisker composite material
CN110628229A (en) * 2019-09-28 2019-12-31 浙江杰上杰新材料有限公司 Precipitation-free lubricant and preparation method thereof
CN111847981A (en) * 2020-07-15 2020-10-30 吴礼根 Novel degradable environment-friendly packaging material and preparation method thereof
CN109679206B (en) * 2018-12-13 2021-09-28 广州市聚赛龙工程塑料股份有限公司 Low-volatility nano filler modified polypropylene material and preparation method and application thereof

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CN101759914A (en) * 2008-11-21 2010-06-30 上海普利特复合材料股份有限公司 Mineral/whisker toughening-reinforcing polypropylene composition
CN101798415A (en) * 2009-12-18 2010-08-11 南京金杉汽车工程塑料有限责任公司 Toughened and strengthened master batch
CN103059411A (en) * 2012-12-30 2013-04-24 苏州旭光聚合物有限公司 Low-shrinkage modified polypropylene composite material and preparation method thereof

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CN101759914A (en) * 2008-11-21 2010-06-30 上海普利特复合材料股份有限公司 Mineral/whisker toughening-reinforcing polypropylene composition
CN101798415A (en) * 2009-12-18 2010-08-11 南京金杉汽车工程塑料有限责任公司 Toughened and strengthened master batch
CN103059411A (en) * 2012-12-30 2013-04-24 苏州旭光聚合物有限公司 Low-shrinkage modified polypropylene composite material and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104610660A (en) * 2015-01-31 2015-05-13 合肥江淮毅昌汽车饰件有限公司 Thin-wall high-rigidity plastic material for automobile bumpers and preparation method of thin-wall high-rigidity plastic material
CN106750897A (en) * 2016-11-25 2017-05-31 武汉理工大学 For the preparation method of the crystals of calcium salts modified polypropene cortex of bimodal polyethylene pipe
CN106750897B (en) * 2016-11-25 2019-06-28 武汉理工大学 The preparation method of crystals of calcium salts modified polypropene cortex for bimodal polyethylene pipe
CN109679206A (en) * 2018-12-13 2019-04-26 广州市聚赛龙工程塑料股份有限公司 A kind of low nano-filler modified polypropylene material and the preparation method and application thereof that volatilizees
CN109679206B (en) * 2018-12-13 2021-09-28 广州市聚赛龙工程塑料股份有限公司 Low-volatility nano filler modified polypropylene material and preparation method and application thereof
CN110003572A (en) * 2019-04-29 2019-07-12 上海金发科技发展有限公司 A kind of polypropylene for thin-walled automobile product-alkali magnesium sulfate crystal whisker composite material
CN110628229A (en) * 2019-09-28 2019-12-31 浙江杰上杰新材料有限公司 Precipitation-free lubricant and preparation method thereof
CN111847981A (en) * 2020-07-15 2020-10-30 吴礼根 Novel degradable environment-friendly packaging material and preparation method thereof

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