CN106543555A - A kind of bumper ageing-resistant Shape memory polypropylene composite material and preparation method thereof - Google Patents

A kind of bumper ageing-resistant Shape memory polypropylene composite material and preparation method thereof Download PDF

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Publication number
CN106543555A
CN106543555A CN201610879788.7A CN201610879788A CN106543555A CN 106543555 A CN106543555 A CN 106543555A CN 201610879788 A CN201610879788 A CN 201610879788A CN 106543555 A CN106543555 A CN 106543555A
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parts
shape memory
ageing
temperature
polypropylene
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胡宁
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/06—Hydrocarbons
    • C08F112/08—Styrene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/12—Shape memory
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention discloses a kind of ageing-resistant Shape memory polypropylene composite material of bumper, is made up of the raw material of following weight portion：Polypropylene 50 65,12 17,3 aminopropyl triethoxysilane 6 10 of methyl silicate, maleic anhydride grafted ethene octene copolymer 48, nucleator 13, acetonitrile 60 70, deionized water 10 18, Pulvis Talci 49, azodiisobutyronitrile 4 10, styrene 20 30, appropriate chlorobenzene solution, appropriate methanol, methane Hinered phenols antioxidant are 0.3 0.9, white carbon black 0.4 0.8, dilauryl thiodipropionate 0.8 1.5.The present invention is using polystyrene cross-linked silica aeroge and polypropylene extrusion blending, the characteristic of polypropylene shape memory is imparted, as automobile bumper material, once as external stress generates deformation, it is heated to more than polyacrylic fusing point, sample can be returned to original shape.

Description

A kind of bumper ageing-resistant Shape memory polypropylene composite material and its system Preparation Method
Technical field
The invention belongs to technical field of polymer composite materials, more particularly to a kind of bumper is with ageing-resistant shape Memory PP composite material and preparation method thereof.
Background technology
With the fast development of automobile industry, automotive light weight technology becomes a trend of China Automobile Industry, therefore more next More auto parts and components mitigate vehicle weight using plastics come alternative metals.Bumper is difficult in use in addition Exempt to undergo external impacts, produce non-response deformation sometimes, now bumper can recovery characteristic it is particularly important.
Shape memory high molecule material development in the last few years is advanced by leaps and bounds, and wherein thermo-stimulative shape memory polymer material is Emphasis therein.Macromolecular material will reach shape memory function, it is necessary to have fixing phase and can two kinds of phases of anti-phase, work as shape When memory macromolecule produces deformation, rise high-temperature, can the molecule segment of anti-phase start to thaw, the work of the deformation of generation in internal stress Initial state is returned to under, and fixing phase now plays a part of physical crosslinking point solid shape.
Dong Baojian, Japanese plum material et al.《The preparation and performance study of PP/PET/POE-g-MAH marmems》One is literary In, using POE-g-MAH as PP/PET co-mixing system reactive compatibilizers, prepared using melt-blending process a kind of with physics The PP/PET thermal shape memory blend alloys of cross-linked structure.The addition of bulking agent POE-g-MAH increase both PP and PET it Between interfacial adhesion, be favorably improved the shape-memory properties and mechanical property of blend alloy, and it be good to maintain blend alloy Good heat resistance.
Aeroge（aerogel）It is a kind of lightweight, porous, amorphous solid material, particle size is between 1-100 nm Between, it is typical nano material, up to 80%-99.8%, with very excellent performance, its density is minimum to be reached its porosity 1kg/m3.The aerosil of crosslinked polymer has excellent toughness and certain intensity, the microgranule inside aeroge Structure includes primary granules and offspring, and the effect of crosslinked polymer defines one layer " coating " equivalent in gel surface, The presence of " coating " causes have certain cushioning effect between offspring, when certain external force is applied, between offspring Sliding can occur, and primary granules keep constant, when external force is removed, sample can be returned to original shape.
Therefore, a kind of light weight for bumper of research and utilization aerosil of the present invention exploitation, high resiliency, PP composite material with shape memory.
The content of the invention
It is an object of the invention to provide a kind of bumper has with ageing-resistant Shape memory polypropylene composite material Excellent shape-memory properties, the lower deformation for producing of external force effect can be replied by heating, and meet automobile bumper material pair The requirement of shape memory.
A kind of bumper with ageing-resistant Shape memory polypropylene composite material, by the raw material group of following weight portion Into：Polypropylene 50-65 parts, methyl silicate 12-17 parts, 3- aminopropyl triethoxysilane 6-10 parts, maleic anhydride grafting second Alkene-octene copolymer 4-8 parts, nucleator 1-3 parts, acetonitrile 60-70 parts, deionized water 10-18 parts, Pulvis Talci 4-9 parts, azo two Isopropyl cyanide 4-10 parts, styrene 20-30 parts, appropriate chlorobenzene solution, appropriate methanol, methane Hinered phenols antioxidant are 0.3-0.9 Part, carbon black 0.4-0.8 parts, dilauryl thiodipropionate 0.8-1.5 parts.
Comprise the following steps that：
（1）The preparation of silica dioxide gel：
Methyl silicate, acetonitrile and 3- aminopropyl triethoxysilanes are mixed into into solution A, deionized water and acetonitrile are mixed into B Solution A is cooled to less than 0 DEG C, pours in B solution and be uniformly mixed rapidly by solution, and gel is formed in putting room temperature, aging to put Put 3-4 days, washed with methanol and obtain silica wet gel, it is standby；
（2）Prepare polystyrene cross-linked silica aeroge：
Silica wet gel is placed in and is dissolved in azodiisobutyronitrile and cinnamic chlorobenzene solution, impregnated 2-4 days, be transferred to chlorine In benzole soln, 22-25 hours are reacted at 70-75 DEG C, are washed twice with chlorobenzene solution, then solvent displacement is carried out with methanol, Supercritical drying is obtained the Monolithic aerogel of polystyrene crosslinking, and ball mill pulverizing to size sieves between 20-80 mesh sieves To polystyrene cross-linked silica aerogel powder；
（3）Mixing：
1., polypropylene, maleic anhydride grafted ethene-octene copolymer, Pulvis Talci, nucleator are added in blender and stir equal It is even, step is added afterwards（2）The polystyrene cross-linked silica aerogel powder for obtaining continues stirring 20-30 minutes；
2. methane Hinered phenols antioxidant, carbon black and dilauryl thiodipropionate mixing 10-16 minutes, are continuously added, obtains mixed Close material standby；
（4）Above-mentioned batch mixing is added in the hopper of parallel double-screw extruder, blended melting extruding pelletization obtains car insurance Thick stick is with ageing-resistant Shape memory polypropylene composite material.
Wherein, the processing conditionss of the double screw extruder are that area's temperature is 240-250 DEG C, and two area's temperature are 250- 260 DEG C, three area's temperature are 260-270 DEG C, and four area's temperature are 260-280 DEG C, and five area's temperature are 270-290 DEG C, and six area's temperature are 280-295℃。
The present invention compared with prior art, with advantages below：
（1）The present invention is prepared surface and is contained the wet solidifying of amino using 3- aminopropyl triethoxysilanes and methyl silicate copolymerization Glue, is then crosslinked with polystyrene, improves elasticity, the heat stability of aerosil, compatible with polypropylene material Property, and before and after aeroge density, change little, vehicle weight can be mitigated in being added to bumper PP composite material, produced Product have excellent thermostability, resilience.
（2）Polyacrylic melt temperature at 165 DEG C or so, the present invention using polystyrene cross-linked silica aeroge with Polypropylene extrusion blending, imparts the characteristic of polypropylene shape memory, and polystyrene cross-linked silica aeroge itself With excellent toughness, product of the present invention as automobile bumper material, once as external stress generates deformation, by itself plus To more than polyacrylic fusing point, sample can be returned to original shape to heat.
（3）Polypropylene is very sensitive to ultraviolet, and the present invention adds methane Hinered phenols antioxidant, thiodipropionic acid dilauryl osmanthus Ester, carbon black can improve its ageing-resistant performance, improve the service life of product.
Specific embodiment
A kind of bumper with ageing-resistant Shape memory polypropylene composite material, by following weight portion（Kilogram）Original Material composition：55 parts of polypropylene, methyl silicate 15,3- aminopropyl triethoxysilanes 8, maleic anhydride grafted ethene-octene are common Polymers 6, nucleator 2, acetonitrile 67, deionized water 18, Pulvis Talci 6, azodiisobutyronitrile 6, styrene 26, appropriate chlorobenzene solution, Appropriate methanol, methane Hinered phenols antioxidant are 0.6, carbon black 0.5, dilauryl thiodipropionate 1.
Comprise the following steps that：
（1）The preparation of silica dioxide gel：
Methyl silicate, acetonitrile and 3- aminopropyl triethoxysilanes are mixed into into solution A, deionized water and acetonitrile are mixed into B Solution A is cooled to less than 0 DEG C, pours in B solution and be uniformly mixed rapidly by solution, and gel is formed in putting room temperature, aging to put Put 3 days, washed with methanol and obtain silica wet gel, it is standby；
（2）Prepare polystyrene cross-linked silica aeroge：
Silica wet gel is placed in and is dissolved in azodiisobutyronitrile and cinnamic chlorobenzene solution, impregnated 3 days, be transferred to chlorobenzene In solution, react 24 hours at 72 DEG C, washed twice with chlorobenzene solution, then solvent displacement, supercritical drying are carried out with methanol The dry Monolithic aerogel that polystyrene crosslinking is obtained, ball mill pulverizing to size between 80 mesh sieves sieve and obtain polystyrene Cross-linked silica aerogel powder；
（3）Mixing：
1., polypropylene, maleic anhydride grafted ethene-octene copolymer, Pulvis Talci, nucleator are added in blender and stir equal It is even, step is added afterwards（2）The polystyrene cross-linked silica aerogel powder for obtaining continues stirring 25 minutes；
2. methane Hinered phenols antioxidant, carbon black and dilauryl thiodipropionate, are continuously added to stir 12 minutes, compound is obtained It is standby；
（4）Above-mentioned batch mixing material is added in the hopper of parallel double-screw extruder, blended melting extruding pelletization, obtains automobile guarantor Dangerous thick stick is with ageing-resistant Shape memory polypropylene composite material.
Wherein, the processing conditionss of the double screw extruder are, area's temperature is 240 DEG C, and two area's temperature are 255 DEG C, three Area's temperature is 265 DEG C, and four area's temperature are 270 DEG C, and five area's temperature are 280 DEG C, and six area's temperature are 295 DEG C.
Performance data is as follows after testing：Tensile strength 36MPa, elongation at break 295%, heat distortion temperature（0.45MPa） 107 DEG C, shape recovery rate 96%, 176 DEG C of recovery of shape temperature, recovery of shape response time≤100s.

Claims (3)

1. a kind of bumper is with ageing-resistant Shape memory polypropylene composite material, it is characterised in that by following weight portion Raw material composition：Polypropylene 50-65 parts, methyl silicate 12-17 parts, 3- aminopropyl triethoxysilane 6-10 parts, maleic acid Acid anhydride grafted ethene-octene copolymer 4-8 parts, nucleator 1-3 parts, acetonitrile 60-70 parts, deionized water 10-18 parts, Pulvis Talci 4-9 Part, azodiisobutyronitrile 4-10 parts, styrene 20-30 parts, appropriate chlorobenzene solution, appropriate methanol, methane Hinered phenols antioxidant For 0.3-0.9 parts, carbon black 0.4-0.8 parts, dilauryl thiodipropionate 0.8-1.5 parts.
2. system of a kind of bumper according to claims 1 with ageing-resistant Shape memory polypropylene composite material Preparation Method, it is characterised in that comprise the following steps that：
（1）The preparation of silica dioxide gel：
Methyl silicate, acetonitrile and 3- aminopropyl triethoxysilanes are mixed into into solution A, deionized water and acetonitrile are mixed into B Solution A is cooled to less than 0 DEG C, pours in B solution and be uniformly mixed rapidly by solution, and gel is formed in putting room temperature, aging to put Put 3-4 days, washed with methanol and obtain silica wet gel, it is standby；
（2）Prepare polystyrene cross-linked silica aeroge：
Silica wet gel is placed in and is dissolved in azodiisobutyronitrile and cinnamic chlorobenzene solution, impregnated 2-4 days, be transferred to chlorine In benzole soln, 22-25 hours are reacted at 70-75 DEG C, are washed twice with chlorobenzene solution, then solvent displacement is carried out with methanol, Supercritical drying is obtained the Monolithic aerogel of polystyrene crosslinking, and ball mill pulverizing to size sieves between 20-80 mesh sieves To polystyrene cross-linked silica aerogel powder；
（3）Mixing：
1., polypropylene, maleic anhydride grafted ethene-octene copolymer, Pulvis Talci, nucleator are added in blender and stir equal It is even, step is added afterwards（2）The polystyrene cross-linked silica aerogel powder for obtaining continues stirring 20-30 minutes；
2. methane Hinered phenols antioxidant, carbon black and dilauryl thiodipropionate mixing 10-16 minutes, are continuously added, obtains mixed Close material standby；
（4）Above-mentioned batch mixing is added in the hopper of parallel double-screw extruder, blended melting extruding pelletization obtains car insurance Thick stick is with ageing-resistant Shape memory polypropylene composite material.
3. system of a kind of bumper according to claims 2 with ageing-resistant Shape memory polypropylene composite material Preparation Method, it is characterised in that the processing conditionss of the double screw extruder are that area's temperature is 240-250 DEG C, and two area's temperature are 250-260 DEG C, three area's temperature are 260-270 DEG C, and four area's temperature are 260-280 DEG C, and five area's temperature are 270-290 DEG C, six area's temperature Spend for 280-295 DEG C.
CN201610879788.7A 2016-10-09 2016-10-09 A kind of bumper ageing-resistant Shape memory polypropylene composite material and preparation method thereof Pending CN106543555A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102898723A (en) * 2011-07-28 2013-01-30 合肥杰事杰新材料股份有限公司 Polypropylene composition and preparation method thereof
CN102911431A (en) * 2012-08-23 2013-02-06 上海金发科技发展有限公司 Special low-shrinkage polypropylene compound for automobile bumper and preparation method thereof
CN103739957A (en) * 2013-12-31 2014-04-23 上海金发科技发展有限公司 Shape memory polypropylene composite material for automobile bumpers and preparation method thereof
CN103865177A (en) * 2012-12-13 2014-06-18 上海金发科技发展有限公司 Special polypropylene composite material for automobile bumper and preparation method thereof
CN105348642A (en) * 2015-11-20 2016-02-24 南京聚隆科技股份有限公司 High fluidity, high modulus, high impact strength polypropylene material used for vehicle bumpers, and preparation method thereof
CN105602179A (en) * 2015-12-30 2016-05-25 上海普利特复合材料股份有限公司 High-rigidity, low-shrinkage and good-appearance polypropylene composite material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102898723A (en) * 2011-07-28 2013-01-30 合肥杰事杰新材料股份有限公司 Polypropylene composition and preparation method thereof
CN102911431A (en) * 2012-08-23 2013-02-06 上海金发科技发展有限公司 Special low-shrinkage polypropylene compound for automobile bumper and preparation method thereof
CN103865177A (en) * 2012-12-13 2014-06-18 上海金发科技发展有限公司 Special polypropylene composite material for automobile bumper and preparation method thereof
CN103739957A (en) * 2013-12-31 2014-04-23 上海金发科技发展有限公司 Shape memory polypropylene composite material for automobile bumpers and preparation method thereof
CN105348642A (en) * 2015-11-20 2016-02-24 南京聚隆科技股份有限公司 High fluidity, high modulus, high impact strength polypropylene material used for vehicle bumpers, and preparation method thereof
CN105602179A (en) * 2015-12-30 2016-05-25 上海普利特复合材料股份有限公司 High-rigidity, low-shrinkage and good-appearance polypropylene composite material and preparation method thereof

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Title
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