CN103044781A - High-modulus low-shrinkage low-filling polypropylene composite material - Google Patents

High-modulus low-shrinkage low-filling polypropylene composite material Download PDF

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Publication number
CN103044781A
CN103044781A CN2013100245907A CN201310024590A CN103044781A CN 103044781 A CN103044781 A CN 103044781A CN 2013100245907 A CN2013100245907 A CN 2013100245907A CN 201310024590 A CN201310024590 A CN 201310024590A CN 103044781 A CN103044781 A CN 103044781A
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China
Prior art keywords
polypropylene
filling
districts
low
shrinkage
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CN2013100245907A
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Chinese (zh)
Inventor
翁永华
汪理文
丁贤麟
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SUZHOU RUNJIA ENGINEER PLASTIC CO Ltd
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SUZHOU RUNJIA ENGINEER PLASTIC CO Ltd
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Priority to CN2013100245907A priority Critical patent/CN103044781A/en
Publication of CN103044781A publication Critical patent/CN103044781A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion 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
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/926—Flow or feed rate

Abstract

The invention discloses a high-modulus low-shrinkage low-filling polypropylene composite material. The composite material comprises the following materials in parts by weight: 68-97 parts of polypropylene, 2-10 parts of modified filler master batch, 0.1-1.0 part of heat stabilizer DSTP (Disteaxyl Thiodipropionate), 0.1-1.0 part of antioxidant 1010, and 0.1-0.5 part of antioxidant 168. The preparation method for the high-modulus low-shrinkage low-filling polypropylene composite material comprises the following steps of: (1), preparing modified nanometer filler master batch; (2), weighing the materials in parts by weight; (3), carrying out dry-mixing on the polypropylene, the modified nanometer filler master batch, a flexibilizer, the heat stabilizer DSTP, the antioxidant 1010 and the antioxidant 168 in a high-speed mixer for 3-5 minutes; and (4), putting the mixed materials to a double-screw compressor for fusing, extruding and pelleting. The composite material has the advantages of small usage amount of the filling material, high modulus and low shrinkage; and the process for preparing the polypropylene composite material is simple and low in cost.

Description

A kind of high-modulus low-shrinkage hangs down filling polypropylene composite material
Technical field
The present invention relates to a kind of macromolecular material, more specifically, relate to the low filling polypropylene composite material of a kind of high-modulus low-shrinkage.
Background technology
Plastics have been widely used in national economy all trades and professions and the people's lives as a kind of novel artificial material.Usually the raw material of producing plastics is to adopt virgin resin, such as the directly machine-shaping such as PE, PP, ABS.Quickening along with macromolecular material and matrix material industryization application process, each industrial sector constantly proposes higher requirement, reach lower thermal expansivity and cost etc. such as higher tensile strength, modulus, thermal conductivity, heat distortion temperature, it is unable to do what one wishes that virgin resin seems.In virgin resin, add all kinds of nonmetal and metal-powder fillers, can promote all kinds of performances of Plastic Resin, make it reach needed technical indicator and high performance-price ratio.The material that can be used as plastic filler has a lot, and material commonly used has CaCO 3, modified montmorillonoid, white carbon black, titanium dioxide, flyash, kaolin, mica powder, wollastonite powder, graphite, red mud, diatomite, glass microballon, brucite, barite, asbestos etc.
Filler is added on that role mainly comprises following 3 aspects in the plastics:
(1) reduces cost.Because petroleum resources is in short supply, causes resin and petrochemical material price increase, the mineral powder price is lower than 10～15 times of synthetic resins, and an amount of filling can make the plastics cost decrease.For example, in polyvinyl chloride and polypropylene, add a large amount of calcium carbonate.
(2) strengthening action.Some filler can improve the physical and mechanical propertiess such as hardness, Young's modulus, dimensional stability and thermostability of plastics as strengthening agent.For example, add the bending elastic modulus that modified montmorillonoid can improve low pressure polyethylene.
(3) function.Plastic prod has the specific function that originally never has after adding most of fillers, as: light degradation property, perviousness, water tolerance, weathering resistance, fire protection flame retarding, oil-proofness, function solenoid etc.For example, add electroconductibility, the wear resistance that graphite can increase plastics.
But the adding of filler also can be brought adverse influence, increases degradation under the impact property such as the density of material.
In recent years, utilize nanomaterial-filled polypropylene, develop the matrix material with specific function, become the new direction of Filling and modifying of polypropylene.Nanoparticle refers to that size is between the solid particulate of 1-100 nm.It is generally acknowledged that the granularity of particle filled composite is less, specific surface area is larger, and is stronger with the interface binding power of polymeric matrix, obtains more high performance matrix material.Compare with traditional PP blend, nanometer PP matrix material has better rigidity, and has kept good low-temperature impact.The Nano filling of filling 5% is worked as with the rigid phase of the modified montmorillonoid gained matrix material of filling 25%.And the PP nano composite material also has good dimensional stability, lower coefficient of thermal expansion.But nano material has fatal drawback a----dispersiveness, more compound reports about Nano filling and polypropylene material, (Macromolecules, 2002,35 (6): 2042-2049.Eur Polym J, 2003,39 (6): 945-950. polymer material science and engineering, 2007,23 (5): 242-245.) they pass through the polynite of diverse ways modified Nano filling master batch at too much consideration, such as, fusion intercalation, situ-formed graft intercalations etc. make well dispersion and compatible in the organic polymer material matrix of nano material, thereby improve the mechanical property function of material, but ignored the impact of modified Nano filling master batch with polyacrylic shape and flowability, do not have well to control the dispersiveness of Nano filling yet, so up to the present, all do not have well to solve the dispersion problem of Nano filling.
Summary of the invention
For defects of the prior art, the invention provides low filling polypropylene composite material of a kind of high-modulus low-shrinkage and preparation method thereof, the method is well disperseed nano material in polypropylene material and is contacted, the advantage of nano material is well brought into play, this polypropylene composite material not only has the advantages such as hardness that common fillers brings and modulus height and shrinking percentage is low, and overcome impact strength decreased, the shortcoming that density increases, obtain a kind of high-modulus, hang down the low filling polypropylene composite material that shrinks, greatly widened the range of application of polypropylene material.。
The invention provides the low filling polypropylene composite material of a kind of high-modulus low-shrinkage, it is characterized in that: mark meter by weight comprises 68-97 part polypropylene, 2-10 part modified Nano filling master batch, 0.1-1.0 part thermo-stabilizer DSTP, 0.1-1.0 part antioxidant 1010,0.1-0.5 part irgasfos 168.
Prepare described modified Nano filling master batch, may further comprise the steps:
(1) in solution, will carry out swelling with a small amount of auxiliary swelling agent with Nano filling and the maleic anhydride that the octadecyl ammonium salt organises;
(2) the organic nano filler after the swelling carries out frit reaction with the high-flowability polypropylene of powdery and an amount of initiator again in mixing roll, so that Nano filling fully disperses with graft polypropylene and contacts, obtain a kind of PP/Nano filler grafting intercalation blend, be the modified Nano filling master batch.
Preferably, mark meter by weight, it also comprises 0-25 part toughner.
Preferably, described polypropylene is different mobile homopolymerization and Co-polypropylene mixtures.
Preferably, the comonomer of described Co-polypropylene is ethene, and described ethylene content is in the scope of 4-10%/mol, and described polyacrylic melt flow rate (MFR) is 5-50g/10min.
Preferably, described toughner is POE or EPDM rubber elastomer.
Preferably, the polypropylene that described modified filler is used is the high-flowability polypropylene of powdery, and its melt flow rate (MFR) is 80g/10min.
Preferably, described modified Nano filling master batch comprises silicate, and described silicate has laminate structure.
Preferably, described silicate is any in polynite, hectorite, sepiolite, mica, talcum, terre verte, kaolin, graphite, metal oxide, the metal dithionite compound.
The preparation method of the low filling polypropylene composite material of a kind of high-modulus low-shrinkage is provided, it is characterized in that: may further comprise the steps,
(1) modified Nano filling master batch: in solution, will carry out swelling with a small amount of auxiliary swelling agent with Nano filling and the maleic anhydride that the long-chain organic amine organises; Organic nano filler after the swelling carries out frit reaction with the high-flowability polypropylene of powdery and an amount of initiator again in mixing roll, so that Nano filling fully disperses with graft polypropylene and contacts, obtain a kind of PP/Nano filler grafting intercalation blend;
(2) take by weighing by weight ratio raw material;
(3) polypropylene, modified Nano filling master batch, toughner, thermo-stabilizer DSTP, antioxidant 1010, irgasfos 168 are dry mixed 3-5 minute in super mixer;
(4) place dual-screw-stem machine through melt extruding the raw material that mixes, granulation, its technique is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, 210～215, six districts 210～215, five districts, seven districts 215～225,215～225, ten districts 215～225,215～225, nine districts, eight districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
The present invention is the low filling polypropylene composite material of a kind of high-modulus low-shrinkage, and this matrix material has the advantage that the packing material usage quantity is little, modulus is high and shrinking percentage is low, and prepares that the technique of this polypropylene composite material is simple, cost is low.
Embodiment
In order to make those skilled in the art person understand better the present invention, and above-mentioned advantage of the present invention can be become apparent more, the present invention is further detailed explanation below in conjunction with specific embodiment.
The present invention is on the basis by intercalation in position, changing the modified nano powder filler is shape and the mobile characteristics of utilizing high-flowability polypropylene, come the modified nano powder filler of system by both combination, so that nano material is well disperseed in the high-flowability polypropylene material and is contacted, the advantage of nano material is well brought into play, polypropylene material not only has the advantages such as hardness that common fillers brings and modulus height and shrinking percentage is low, and overcome impact strength decreased and the shortcoming of density increase, obtain a kind of high-modulus, low-shrinkage, low filling polypropylene composite material.
A kind of high-modulus low-shrinkage hangs down filling polypropylene composite material, and the mark meter comprises 68-97 part polypropylene by weight, the filler master batch of 2-10 part modification, 0.1-1.0 part thermo-stabilizer DSTP, 0.1-1.0 part antioxidant 1010,0.1-0.5 part irgasfos 168.
Prepare the method for modified Nano filling master batch, may further comprise the steps:
(1) in solution, will carry out swelling with a small amount of auxiliary swelling agent with Nano filling and the maleic anhydride that the octadecyl ammonium salt organises;
(2) the organic nano filler after the swelling carries out frit reaction with the high-flowability polypropylene of powdery and an amount of initiator again in mixing roll, so that Nano filling fully disperses with graft polypropylene and contacts, obtain a kind of PP/Nano filler grafting intercalation blend, be the modified Nano filling master batch.
Also comprise 0-25 part toughner.
Polypropylene is different mobile homopolymerization and Co-polypropylene mixtures.
The comonomer of co-polypropylene is ethene, and its content is in the scope of 4-10%/mol, and polyacrylic melt flow rate (MFR) is 5-50g/10min under the condition of 230 ℃ * 2.16kg.
The polypropylene that modified filler is used is the high-flowability polypropylene of powdery, and its melt flow rate (MFR) is 80g/10min under the condition of 230 ℃ * 2.16kg.
The filler master batch of modification comprises silicate, and described silicate is laminate structure.
Silicate is any in polynite, hectorite, sepiolite, mica, talcum, terre verte, kaolin, graphite, metal oxide, the metal dithionite compound.
Toughner is the rubber elastomers such as POE or EPDM.
The preparation method of the low filling polypropylene composite material of a kind of high-modulus low-shrinkage may further comprise the steps:
(1) modified Nano filling master batch: in solution, will carry out swelling with a small amount of auxiliary swelling agent with Nano filling and the maleic anhydride that the octadecyl ammonium salt organises; Organic nano filler after the swelling carries out frit reaction with the high-flowability polypropylene of powdery and an amount of initiator again in mixing roll, so that Nano filling fully disperses with graft polypropylene and contacts, obtain a kind of PP/Nano filler grafting intercalation blend, be the modified Nano filling master batch;
(2) take by weighing by weight ratio raw material;
(3) polypropylene, modified Nano filling master batch, toughner, thermo-stabilizer DSTP, antioxidant 1010, irgasfos 168 are dry mixed 3-5 minute in super mixer;
(4) place dual-screw-stem machine through melt extruding the raw material that mixes, granulation, its technique is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, 210～215, six districts 210～215, five districts, seven districts 215～225,215～225, ten districts 215～225,215～225, nine districts, eight districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
The present invention adopts and adds a kind of modified Nano filling master batch, utilize the advantage of itself to reach dispersiveness and consistency good in polypropylene material, in the situation of a small amount of filler, still has very high modulus on the one hand, on the one hand in the situation of a small amount of filler, the good stability of the dimension of material, shrinking percentage is low, thereby prepares a kind of high-modulus, low-shrinkage, low filling polypropylene composite material.
Embodiment 1:
At first, preparation modified montmorillonoid master batch, concrete steps are: will carry out swelling with maleic anhydride and a small amount of auxiliary swelling agent in solution with the polynite that the octadecyl ammonium salt organises; Organo montmorillonite after the swelling is that 85:15,0.5% initiator carry out frit reaction in mixing roll with the high-flowability polypropylene weight ratio of powdery again, so that polynite fully disperses with graft polypropylene and contacts, obtain a kind of level polypropylene/montmorillonoid grafting intercalation blend, i.e. the nano imvite master batch of modification.
Then the according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 68
The modified montmorillonoid master batch Level polypropylene/montmorillonoid grafting intercalation blend 6
Toughner POE8842 25
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Will more than get the raw materials ready and in super mixer, be dry mixed 3-5 minute, again in twin screw extruder through melt extruding granulation, its technique is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, five districts 210～215,215～225, eight districts 215～225,210～215, seven districts, six districts, 215～225, ten districts 215～225, nine districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
Embodiment 2:
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 74
The modified montmorillonoid master batch Level polypropylene/montmorillonoid grafting intercalation blend 6
Toughner POE8842 19
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Will more than get the raw materials ready and in super mixer, be dry mixed 3-5 minute, again in twin screw extruder through melt extruding granulation, its technique is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, five districts 210～215,215～225, eight districts 215～225,210～215, seven districts, six districts, 215～225, ten districts 215～225, nine districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
Embodiment 3:
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 80
The modified montmorillonoid master batch Level polypropylene/montmorillonoid grafting intercalation blend 6
Toughner POE8842 13
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Will more than get the raw materials ready and in super mixer, be dry mixed 3-5 minute, again in twin screw extruder through melt extruding granulation, its technique is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, five districts 210～215,215～225, eight districts 215～225,210～215, seven districts, six districts, 215～225, ten districts 215～225, nine districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
Embodiment 4:
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 86
The modified montmorillonoid master batch Level polypropylene/montmorillonoid grafting intercalation blend 6
Toughner POE8842 7
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Will more than get the raw materials ready and in super mixer, be dry mixed 3-5 minute, again in twin screw extruder through melt extruding granulation, its technique is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, five districts 210～215,215～225, eight districts 215～225,210～215, seven districts, six districts, 215～225, ten districts 215～225, nine districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
 
Embodiment 5:
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 96
The modified montmorillonoid master batch Level polypropylene/montmorillonoid grafting intercalation blend 6
Toughner POE8842 0
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Will more than get the raw materials ready and in super mixer, be dry mixed 3-5 minute, again in twin screw extruder through melt extruding granulation, its technique is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, five districts 210～215,215～225, eight districts 215～225,210～215, seven districts, six districts, 215～225, ten districts 215～225, nine districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
Embodiment 6:
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 74
The polynite master batch Polynite 25
Toughner POE8842 0
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Will more than get the raw materials ready and in super mixer, be dry mixed 3-5 minute, again in twin screw extruder through melt extruding granulation, its technique is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, five districts 210～215,215～225, eight districts 215～225,210～215, seven districts, six districts, 215～225, ten districts 215～225, nine districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
Embodiment 7:
Embodiment 7 is simultaneous tests of embodiment 1, and the content of all the other addings changes the modified montmorillonoid master batch into common polynite master batch than in the constant situation, and all the other steps are all identical with embodiment 1.
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 69
The polynite master batch Polynite 5
Toughner POE8842 25
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Embodiment 8:
Embodiment 8 is simultaneous tests of embodiment 2, and the content of all the other addings changes the modified montmorillonoid master batch into common polynite master batch than in the constant situation, and all the other steps are all identical with embodiment 2.
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 75
The polynite master batch Polynite 5
Toughner POE8842 19
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Embodiment 9:
Embodiment 9 is simultaneous tests of embodiment 3, and the content of all the other addings changes the modified montmorillonoid master batch into common polynite master batch than in the constant situation, and all the other steps are all identical with embodiment 3.
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 81
The polynite master batch Polynite 5
Toughner POE8842 13
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Embodiment 10:
Embodiment 10 is simultaneous tests of embodiment 4, and the content of all the other addings changes the modified montmorillonoid master batch into common polynite master batch than in the constant situation, and all the other steps are all identical with embodiment 4.
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 87
The polynite master batch Polynite 5
Toughner POE8842 7
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Embodiment 11:
Embodiment 11 is simultaneous tests of embodiment 5, and the content of all the other addings changes the modified montmorillonoid master batch into common polynite master batch than in the constant situation, and all the other steps are all identical with embodiment 5.
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 94
The polynite master batch Polynite 5
Toughner POE8842 ?
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Embodiment 12:
Embodiment 12 is simultaneous tests of embodiment 3, polypropylene and toughner POE constant rate get basic on, the content of modified montmorillonoid master batch is adjusted to 3% analyzes as a comparison, all the other steps are all identical with embodiment 3.
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 83
The modified montmorillonoid master batch Level polypropylene/montmorillonoid grafting intercalation blend 3
Toughner POE8842 13
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Embodiment 13:
Embodiment 13 is simultaneous tests of embodiment 3, polypropylene and toughner POE constant rate get basic on, the content of modified montmorillonoid master batch is adjusted to 4% analyzes as a comparison, all the other steps are all identical with embodiment 3.
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 82
The modified montmorillonoid master batch Level polypropylene/montmorillonoid grafting intercalation blend 4
Toughner POE8842 13
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Embodiment 14:
Embodiment 14 is simultaneous tests of embodiment 3, polypropylene and toughner POE constant rate get basic on, the content of modified montmorillonoid master batch is adjusted to 7% analyzes as a comparison, all the other steps are all identical with embodiment 3.
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 79
The modified montmorillonoid master batch Level polypropylene/montmorillonoid grafting intercalation blend 7
Toughner POE8842 13
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Embodiment 15:
Embodiment 15 is simultaneous tests of embodiment 3, polypropylene and toughner POE constant rate get basic on, the content of modified montmorillonoid master batch is adjusted to 10% analyzes as a comparison, all the other steps are all identical with embodiment 3.
The according to the form below component proportion is got the raw materials ready:
Type Title Content (part)
Polypropylene Different mobile homopolymerization and Co-polypropylene mixtures 76
The modified montmorillonoid master batch Level polypropylene/montmorillonoid grafting intercalation blend 10
Toughner POE8842 13
Thermal oxidation stabilizer DSTP The thio-2 acid octadecyl ester 0.5
Antioxidant 1010 Four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.3
Thermal oxidation stabilizer 168 Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 0.2
Performance evaluation and implementation standard:
With the particulate material of finishing as stated above granulation in 90～100 ℃ convection oven dry 2～3 hours in advance, and then the particulate material that drying is good carries out the injection molding sample preparation at injection moulding machine, according to following testing standard sample carried out performance test at last:
Simple beam impact strength is undertaken by ISO 179, and specimen size is 80*6*4mm, and notch depth is 1/3rd of sample thickness;
The tensile property test is undertaken by ISO 527-2, and specimen size is 150*10*4mm, and draw speed is 50mm/min;
The bending property test is undertaken by ISO 178, and specimen size is 80*10*4mm, and rate of bending is 2mm/min, and span is 64mm;
Heat-drawn wire is undertaken by ISO 75, and specimen size is 120*10*3mm, and load is 1.8MPa;
The thermal-oxidative aging property of material is undertaken by ISO4577, and specimen size is 50*10*10mm, and probe temperature is 150 ℃;
The shrinking percentage of material changes by size of sample passes judgment on specimen size 150*100*3.2mm;
Density is undertaken by ISO 1183, and specimen size is 10*10*4mm.Test sample guarantees totally without greasy dirt before test.
The comprehensive mechanical property of material passes through the tensile strength of test gained, elongation at break, and modulus in flexure, the numerical value of thermal denaturation temperature and shock strength is passed judgment on; The thermal-oxidative aging property of material is passed judgment on according to the heat oxygen aging resistance time length of measuring by standard: the time is longer, and the heatproof air aging performance of material is better; The dimensional stability of material is passed judgment on by shrinking percentage, and the shrinking percentage value is less, and dimensional stability is better.
Results of property is shown in table 1, table 2, table 3:
Table 1
Performance Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Unnotched impact strength kJ/m 2 Constantly Constantly Constantly Constantly Constantly Constantly
Notched Izod impact strength kJ/m 2 30 28 20 15 5 3
Tensile strength MPa 17 19 21 23 25 26
Elongation at break % 80 70 60 40 30 20
Flexural strength MPa 28 30 31 32 34 34
Modulus in flexure MPa 1450 1550 1650 1700 1850 1900
Thermal-oxidative aging property H 500 500 500 500 500 500
Shrinking percentage % 1.15 1.15 1.15 1.15 1.15 1.15
Density g/cm 3 0.935 0.935 0.935 0.935 0.935 1.08
Table 2
Performance Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 7
Unnotched impact strength kJ/m 2 Constantly Constantly Constantly Constantly Constantly Constantly
Notched Izod impact strength kJ/m 2 25 23 15 10 4 25
Tensile strength MPa 16 18 20 22 24 16
Elongation at break % 75 65 55 35 30 75
Flexural strength MPa 19 20 21 22 24 19
Modulus in flexure MPa 1000 1050 1100 1200 1250 1000
Thermal-oxidative aging property H 500 500 500 500 500 500
Shrinking percentage % 1.4 1.4 1.4 1.4 1.4 1.4
Density g/cm 3 0.935 0.935 0.935 0.935 0.935 0.935
Table 3
Performance Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 3
Unnotched impact strength kJ/m 2 Constantly Constantly Constantly Constantly Constantly
Notched Izod impact strength kJ/m 2 25 25 18 19 20
Tensile strength MPa 24 24 25.5 25 25
Elongation at break % 80 70 40 50 60
Flexural strength MPa 31.5 32 36.5 35.5 35
Modulus in flexure MPa 1400 1500 2000 1900 1850
Thermal-oxidative aging property H 500 500 500 500 500
Shrinking percentage % 1.25 1.22 1.07 1.1 1.12
Density g/cm 3 0.915 0.922 0.956 0.942 0.935
Can be found out by table 1 and table 2 result, when adding the Nano filling of same part by weight, use the polynite of modification to improve a lot than common polynite mechanical property, shock strength has improved more than 20%, flexural strength has improved more than 40%, and modulus in flexure has improved more than 40%, and shrinking percentage is 1.15, reduced nearly 20%, good stability of the dimension.When modified montmorillonoid master batch content was 6%, rigidity and shrinking percentage were suitable with 25% common imvite modified polypropylene, and impact property obviously is better than the latter in addition, and density also is significantly smaller than the latter.As can be seen from Table 3, along with the content increase of modified montmorillonoid master batch, the rigidity of polypropylene composite material constantly strengthens, and impact property also improves a lot, but content 6% impact property of modified montmorillonoid master batch is best.
This shows and use the modified nano powder filler, so that nano material is well disperseed in polypropylene material and is contacted, the advantage of nano material is well brought into play, polypropylene material not only has the advantages such as hardness that common fillers brings and modulus height and shrinking percentage is low, and overcome impact strength decreased, the shortcoming that density increases obtains a kind of desirable high-modulus, the low low filling polypropylene composite material that shrinks.
The above; be the specific embodiment of the present invention only, protection scope of the present invention is not limited to this, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claim was defined.

Claims (10)

1. the low filling polypropylene composite material of a high-modulus low-shrinkage is characterized in that: mark meter by weight comprises 68-97 part polypropylene, 2-10 part modified Nano filling master batch, 0.1-1.0 part thermo-stabilizer DSTP, 0.1-1.0 part antioxidant 1010,0.1-0.5 part irgasfos 168.
2. a kind of high-modulus low-shrinkage according to claim 1 hangs down filling polypropylene composite material, it is characterized in that: prepare the method for described modified Nano filling master batch, may further comprise the steps:
(1) in solution, will carry out swelling with a small amount of auxiliary swelling agent with Nano filling and the maleic anhydride that the octadecyl ammonium salt organises;
(2) the organic nano filler after the swelling carries out frit reaction with the high-flowability polypropylene of powdery and an amount of initiator again in mixing roll, so that Nano filling fully disperses with graft polypropylene and contacts, obtain a kind of PP/Nano filler grafting intercalation blend, be the modified Nano filling master batch.
3. the low filling polypropylene composite material of a kind of high-modulus low-shrinkage according to claim 1 is characterized in that: mark meter by weight, it also comprises 0-25 part toughner.
4. a kind of high-modulus low-shrinkage according to claim 1 hangs down filling polypropylene composite material, it is characterized in that: described polypropylene is different mobile homopolymerization and Co-polypropylene mixtures.
5. a kind of high-modulus low-shrinkage according to claim 4 hangs down filling polypropylene composite material, it is characterized in that: the comonomer of described Co-polypropylene is ethene, described ethylene content is in the scope of 4-10%/mol, and described polyacrylic melt flow rate (MFR) is 5-50g/10min.
6. a kind of high-modulus low-shrinkage according to claim 1 hangs down filling polypropylene composite material, and it is characterized in that: described toughner is POE or EPDM rubber elastomer.
7. a kind of high-modulus low-shrinkage according to claim 2 hangs down filling polypropylene composite material,, it is characterized in that: the polypropylene that described modified filler is used is the high-flowability polypropylene of powdery, its melt flow rate (MFR) is 80g/10min.
8. a kind of high-modulus low-shrinkage according to claim 2 hangs down filling polypropylene composite material, and it is characterized in that: described modified Nano filling master batch comprises silicate, and described silicate has laminate structure.
9. a kind of high-modulus low-shrinkage according to claim 8 hangs down filling polypropylene composite material,, it is characterized in that: described silicate is any in polynite, hectorite, sepiolite, mica, talcum, terre verte, kaolin, graphite, metal oxide, the metal dithionite compound.
10. the preparation method of the low filling polypropylene composite material of a high-modulus low-shrinkage is characterized in that: may further comprise the steps,
(1) modified Nano filling master batch: in solution, will carry out swelling with a small amount of auxiliary swelling agent with Nano filling and the maleic anhydride that the long-chain organic amine organises; Organic nano filler after the swelling carries out frit reaction with the high-flowability polypropylene of powdery and an amount of initiator again in mixing roll, so that Nano filling fully disperses with graft polypropylene and contacts, obtain a kind of PP/Nano filler grafting intercalation blend;
(2) take by weighing by weight ratio raw material;
(3) polypropylene, modified Nano filling master batch, toughner, thermo-stabilizer DSTP, antioxidant 1010, irgasfos 168 are dry mixed 3-5 minute in super mixer;
(4) place dual-screw-stem machine through melt extruding the raw material that mixes, granulation, its technique is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, 210～215, six districts 210～215, five districts, seven districts 215～225,215～225, ten districts 215～225,215～225, nine districts, eight districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
CN2013100245907A 2013-01-23 2013-01-23 High-modulus low-shrinkage low-filling polypropylene composite material Pending CN103044781A (en)

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CN103772826A (en) * 2014-01-10 2014-05-07 德阳正邦环保科技有限公司 Environmental-friendly and durable composite building formwork and preparation method thereof
CN103772816A (en) * 2014-01-10 2014-05-07 无锡市天聚科技有限公司 High-strength high-modulus high heat resistance polypropylene composite material and preparation method thereof
CN104194285A (en) * 2014-08-12 2014-12-10 苏州卓越工程塑料有限公司 Nano-material-filled polybutylene terephthalate composite material and preparation method thereof
CN104558808B (en) * 2013-10-22 2017-03-08 中国石油化工股份有限公司 Prolylene polymer composition and product prepared therefrom
CN107805350A (en) * 2017-10-19 2018-03-16 中广核俊尔（上海）新材料有限公司 High-dispersion nano OMMT/Polypropylene Composites and preparation method thereof
CN110079019A (en) * 2019-05-21 2019-08-02 合肥市丽红塑胶材料有限公司 A kind of PA-PP hybrid resin material of toughening modifying and preparation method thereof
CN110305341A (en) * 2019-06-26 2019-10-08 苏州润佳工程塑料股份有限公司 A kind of preparation method of the low filled polypropylene of lower shrinkage
CN112552604A (en) * 2020-12-09 2021-03-26 哈尔滨理工大学 Heat-conducting and insulating polypropylene composite material and preparation method and application thereof

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CN1435437A (en) * 2002-08-27 2003-08-13 珠海公牛高性能复合材料股份有限公司 Process for preparing graft polyolefin/lamellar silicate composite nanomaterial
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CN104558808B (en) * 2013-10-22 2017-03-08 中国石油化工股份有限公司 Prolylene polymer composition and product prepared therefrom
CN103772826A (en) * 2014-01-10 2014-05-07 德阳正邦环保科技有限公司 Environmental-friendly and durable composite building formwork and preparation method thereof
CN103772816A (en) * 2014-01-10 2014-05-07 无锡市天聚科技有限公司 High-strength high-modulus high heat resistance polypropylene composite material and preparation method thereof
CN104194285A (en) * 2014-08-12 2014-12-10 苏州卓越工程塑料有限公司 Nano-material-filled polybutylene terephthalate composite material and preparation method thereof
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CN110079019A (en) * 2019-05-21 2019-08-02 合肥市丽红塑胶材料有限公司 A kind of PA-PP hybrid resin material of toughening modifying and preparation method thereof
CN110305341A (en) * 2019-06-26 2019-10-08 苏州润佳工程塑料股份有限公司 A kind of preparation method of the low filled polypropylene of lower shrinkage
CN112552604A (en) * 2020-12-09 2021-03-26 哈尔滨理工大学 Heat-conducting and insulating polypropylene composite material and preparation method and application thereof

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