CN101386695B - Polypropylene-nano particle compound material and preparation method thereof - Google Patents

Polypropylene-nano particle compound material and preparation method thereof Download PDF

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Publication number
CN101386695B
CN101386695B CN2008101217689A CN200810121768A CN101386695B CN 101386695 B CN101386695 B CN 101386695B CN 2008101217689 A CN2008101217689 A CN 2008101217689A CN 200810121768 A CN200810121768 A CN 200810121768A CN 101386695 B CN101386695 B CN 101386695B
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polypropylene
maleic anhydride
ive
copolymer
poly
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Expired - Fee Related
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CN2008101217689A
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Chinese (zh)
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CN101386695A (en
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王剑峰
田军
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Ningbo University of Technology
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Ningbo University of Technology
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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
    • B29C48/25—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
    • B29C48/03—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
    • B29C48/92—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
    • B29C2948/92561—Time, e.g. start, termination, duration or interruption
    • 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
    • B29C2948/9259—Angular velocity
    • 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
    • B29C2948/92704—Temperature
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a composite material which consists of polypropylene, nanometer particles and polyisobutyl vinyl ether-maleic anhydride and a preparation method thereof. Through the synergic action of the polyisobutyl vinyl ether-maleic anhydride copolymer and the nanometer particles in the material, the acting force between the polypropylene and the nanometer particles is enhanced, and cluster effect caused by hydrogen bonds among the nanometer particles is weakened, thereby, the nanometer particles can be scattered in the polypropylene evenly in the nanometer scale, and the obtained polypropylene-nanoparticle composite material has the advantages of good flexibility, high shock resistant strength and excellent processing property. The invention has the advantages of simple processing technique, high production efficiency and low cost.

Description

Polypropylene-nano composition and preparation method thereof
Technical field
The present invention relates to the polymer composite preparation field, a kind of nano modification polypropylene composite material and preparation method thereof.
Background technology
Polypropylene (PP) is because cheap, be easy to machine-shaping and have density low, resistance to chemical attack and excellent advantage such as physical and mechanical property itself, its application is very extensive, becomes versatility plastics with fastest developing speed.But because the existence of methyl, the flexible reduction of its molecular chain and its crystal grain are thick, make polyacrylic flexibility relatively poor, have seriously limited it in the further widespread use of every field.Improve the important topic that polyacrylic toughness is polypropylene modification always, common method of modifying is to dose elastomerics in PP matrix inside, as add ethylene-propylene rubber(EPR) (ERP), ethylene-propylene-diene terpolymers (EPDM), styrene-ethylene-styrol copolymer elastomericss such as (SBS), but because the consistency between polypropylene and the elastomerics is relatively poor, elastomerics is difficult to be evenly distributed in the polypropylene matrix, and the modulus of material reduces, and rigidity descends.
High molecule nano material becomes at present unexpectedly the novel high-performance material of exploitation mutually because of having excellent mechanical property, thermal characteristics and enough performances, and that succeeds in developing in succession has nano composite materials such as polyester, polystyrene.Because polypropylene has nonpolar structure, and nanoparticle has characteristics such as particle diameter is little, surfactivity is big, have intensive reunion trend between inorganic nano-particle, therefore, the degree of scatter of nanoparticle in polypropylene matrix is decision nano polypropylene flexible key.Because the restriction of dispersion means at present, when inorganic nano-particle content was low, inorganic nano-particle had certain toughening effect to polypropylene; When inorganic nano-particle content is higher, the agglomeration aggravation between nanoparticle, the nanoparticle coacervate becomes the focal point of stress in the material, causes the resistance to impact shock of matrix material to reduce, and toughness of material descends.CN1156530C discloses a kind of preparation method of high-toughness polypropylene composite material, it carries out electron beam irradiation back with inorganic nano-particle and melts blend system masterbatch with maleic anhydride inoculated polypropylene again with aminated compounds graft modification formation filler, be dispersed in the polypropylene with the certain proportion dilution at last, obtain high-toughness nanometer composite polypropylene material, this method complex process, the manufacturing cost height, incompatible with polyacrylic cost performance.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency of the prior art, the technical problem that solves is the cluster effect that is caused by hydrogen bond between nanoparticle by weakening, nanoparticle is dispersed in the polypropylene polymer uniformly, provide that a kind of technology is simple, nano-particle toughening is effective, excellent in cushion effect, polypropylene-nano composition that the simple cost of manufacturing process is low and preparation method thereof.
The technical solution used in the present invention is as follows:
1, the composition of nano modification polypropylene-nano composition and composition are:
Polypropylene 60～77% weight;
Nanoparticle 20～35% weight;
Poly-IVE-copolymer-maleic anhydride 2～6% weight;
Antioxidant 0.15～0.5% weight.
2, the step of preparation polypropylene-nano composition is:
(1) the poly-IVE-copolymer-maleic anhydride with 100 weight parts is dissolved in the water, the Nanoparticles Hydrosol that adds the 400-1000 weight part, after 2 hours, the solvent evaporate to dryness is obtained nanoparticle and poly-IVE-copolymer-maleic anhydride compound at 60 ℃ of following ultra-sonic dispersion;
(2) with the antioxidant of the nanoparticle of the polypropylene of 100 weight parts, 25～66 weight parts and poly-IVE-copolymer-maleic anhydride compound, 0.2～0.6 weight part, join in the twin screw extruder, barrel zone temperature is 150～180 ℃, screw speed is 60～200rpm, the blend time is 2～15min, obtains polypropylene-nanoparticle and poly-IVE-copolymer-maleic anhydride matrix material behind the extruding pelletization.
Described nanoparticle is at least a in lime carbonate, silicon-dioxide and/or the zinc oxide; Described self-control gathers IVE-copolymer-maleic anhydride, and its weight-average molecular weight is between 5000～50000, and structure is the alternating copolymer of IVE and maleic anhydride; Described antioxidant is at least a in four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propylamine] tetramethylolmethanes (commercial disignation antioxidant 1010) and/or (3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid octadecyl ester (commercial disignation antioxidant 1076).
The present invention compares with background technology, and the useful effect that has is:
Polypropylene-the nano composition of the present invention's preparation, because the synergy in the material between poly-IVE-copolymer-maleic anhydride and nanoparticle, reactive force between polypropylene and nanoparticle is strengthened, weakened the cluster effect that causes by hydrogen bond between nanoparticle, thereby make nanoparticle be evenly dispersed in the polypropylene high comprehensive performance with nanoscale.Prepared polypropylene-nano composition has good toughness, excellent in cushion effect, advantage such as processing characteristics is good, production technique is simple.Process of the present invention is simple, and production efficiency height and cost are lower.
Embodiment
Embodiment 1
The preparation method of poly-IVE-copolymer-maleic anhydride is: solid-state maleic anhydride monomer and initiator (AIBN) are joined in the reactor, fill the nitrogen after the purification behind the vacuum pump drainage, the mixed solvent of the ethyl acetate of reinjecting and hexanaphthene, be warmed up to 40-80 ℃, the vinyl ether monomers and the initiator of liquid state are dissolved in a spot of ethyl acetate, joining in the reactor dropwise, isothermal reaction 2-10 hour, add sherwood oil again, after filtration, dry, pulverize and obtain the poly-IVE of white solid product/copolymer-maleic anhydride particle.
Embodiment 2
With 200 grammes per square metre average molecular weights is that poly-IVE-maleic anhydride alternate copolymer of 45000 is dissolved in 4000 ml waters, add the water-sol that contains 1100 gram nano silicons, after 2 hours, the water evaporate to dryness is obtained 1300 gram nanoparticle and poly-IVE-copolymer-maleic anhydride compounds at 60 ℃ of following ultra-sonic dispersion; This compound and 2500 gram polypropylene, 8 are restrained antioxidant 1010s, join in the twin screw extruder, barrel zone temperature is 160 ℃, screw speed is 100rpm, the blend time is 12min, obtains 3880 gram polypropylene-nanoparticle and poly-IVE-copolymer-maleic anhydride matrix materials behind the extruding pelletization.The tensile strength of gained matrix material is 33.48MP, and elongation at break is 372%, and the socle girder notched Izod impact strength is 37.68kJ/m 2
Embodiment 3
With 200 grammes per square metre average molecular weights is that poly-IVE-maleic anhydride alternate copolymer of 23000 is dissolved in 5000 ml waters, add the water-sol that contains 2100 gram nano-calcium carbonates, after 2 hours, the water evaporate to dryness is obtained 2300 gram nanoparticle and poly-IVE-copolymer-maleic anhydride compounds at 60 ℃ of following ultra-sonic dispersion; This compound and 7400 gram polypropylene, 32 are restrained antioxidant 1010s, join in the twin screw extruder, barrel zone temperature is 180 ℃, screw speed is 100rpm, the blend time is 5min, obtains 9732 gram polypropylene-nanoparticle and poly-IVE-copolymer-maleic anhydride matrix materials behind the extruding pelletization.The tensile strength of gained matrix material is 32.27MP, and elongation at break is 315%, and the socle girder notched Izod impact strength is 31.58kJ/m 2
Embodiment 4
With 200 grammes per square metre average molecular weights is that poly-IVE-maleic anhydride alternate copolymer of 23000 is dissolved in 4000 ml waters, add the water-sol that contains 1200 gram nano zine oxides, after 2 hours, the water evaporate to dryness is obtained 1400 gram nanoparticle and poly-IVE-copolymer-maleic anhydride compounds at 60 ℃ of following ultra-sonic dispersion; This compound and 3500 gram polypropylene, 20 are restrained antioxidant 1010s, join in the twin screw extruder, barrel zone temperature is 160 ℃, screw speed is 100rpm, the blend time is 10min, obtains 4920 gram polypropylene-nanoparticle and poly-IVE-copolymer-maleic anhydride matrix materials behind the extruding pelletization.The tensile strength of gained matrix material is 30.32MP, and elongation at break is 412%, and the socle girder notched Izod impact strength is 41.32kJ/m 2
Embodiment 5
With 200 grammes per square metre average molecular weights is that poly-IVE-maleic anhydride alternate copolymer of 8000 is dissolved in 4000 ml waters, add the water-sol that contains 1000 gram nano silicons, after 2 hours, the water evaporate to dryness is obtained 1200 gram nanoparticle and poly-IVE-copolymer-maleic anhydride compounds at 60 ℃ of following ultra-sonic dispersion; This compound and 3600 gram polypropylene, 26 are restrained antioxidant 1010s, join in the twin screw extruder, barrel zone temperature is 160 ℃, screw speed is 100rpm, the blend time is 7min, obtains 4800 gram polypropylene-nanoparticle and poly-IVE-copolymer-maleic anhydride matrix materials behind the extruding pelletization.The tensile strength of gained matrix material is 31.78MP, and elongation at break is 349%, and the socle girder notched Izod impact strength is 34.12kJ/m 2

Claims (6)

1. polypropylene-nano composition is characterized in that this matrix material comprises following component, by weight the percentage ratio meter:
Polypropylene 60～77% weight;
Nanoparticle 20～35% weight;
Poly-IVE-copolymer-maleic anhydride 2～6% weight;
Antioxidant 0.15～0.5% weight;
Described nanoparticle is at least a in lime carbonate, silicon-dioxide and/or the zinc oxide.
2. a kind of polypropylene-nano composition according to claim 1 is characterized in that described nanoparticle is at least a in 40-150nm nano-calcium carbonate, 40-150nm nano silicon and the 40-150nm zinc oxide.
3. a kind of polypropylene-nano composition according to claim 1, it is characterized in that described poly-IVE-copolymer-maleic anhydride is that solid-state maleic anhydride monomer and initiator Diisopropyl azodicarboxylate (AIBN) are joined in the reactor, fill the nitrogen after the purification behind the vacuum pump drainage, the mixed solvent of the ethyl acetate of reinjecting and hexanaphthene, be warmed up to 40-80 ℃, the vinyl ether monomers and the initiator of liquid state are dissolved in a spot of ethyl acetate, joining in the reactor dropwise, isothermal reaction 2-10 hour, add sherwood oil again, after filtration, dry, pulverizing obtains the poly-IVE of white solid product-copolymer-maleic anhydride particle.
4. a kind of polypropylene-nano composition according to claim 1 is characterized in that described poly-IVE-copolymer-maleic anhydride is the IVE of weight-average molecular weight between 5000～50000 and the alternating copolymer of maleic anhydride.
5. a kind of polypropylene-nano composition according to claim 1, it is characterized in that described antioxidant is four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propylamine] at least a in tetramethylolmethane and/or (3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid octadecyl ester.
6. a method for preparing the described polypropylene-nano composition of claim 1 is characterized in that this method comprises the steps:
(1) the poly-IVE-copolymer-maleic anhydride with 100 weight parts is dissolved in the water, the Nanoparticles Hydrosol that adds the 400-1000 weight part, after 2 hours, the solvent evaporate to dryness is obtained nanoparticle and poly-IVE-copolymer-maleic anhydride compound at 60 ℃ of following ultra-sonic dispersion;
(2) with the antioxidant of the nanoparticle of the polypropylene of 100 weight parts, 25～66 weight parts and poly-IVE-copolymer-maleic anhydride compound, 0.2～0.6 weight part, join in the twin screw extruder, barrel zone temperature is 150～180 ℃, screw speed is 60～200rpm, the blend time is 2～15min, obtains polypropylene-nanoparticle and poly-IVE-copolymer-maleic anhydride matrix material behind the extruding pelletization.
CN2008101217689A 2008-10-17 2008-10-17 Polypropylene-nano particle compound material and preparation method thereof Expired - Fee Related CN101386695B (en)

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Application Number Priority Date Filing Date Title
CN2008101217689A CN101386695B (en) 2008-10-17 2008-10-17 Polypropylene-nano particle compound material and preparation method thereof

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CN101386695B true CN101386695B (en) 2011-02-02

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Publication number Priority date Publication date Assignee Title
CN101876091B (en) * 2010-05-25 2012-04-25 合肥利阳环保科技有限公司 Ultraviolet-resistant environmental-protection ecological cloth and preparation method thereof
CN102226024A (en) * 2011-05-05 2011-10-26 江勇 Nano-pad
CN105330962A (en) * 2015-11-17 2016-02-17 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of super-tough antibacterial masterbatch with high concentration

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