CN106810764A - A kind of low-shrinkage bumper Shape memory polypropylene composite material and preparation method thereof - Google Patents
A kind of low-shrinkage bumper Shape memory polypropylene composite material and preparation method thereof Download PDFInfo
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- CN106810764A CN106810764A CN201710038062.5A CN201710038062A CN106810764A CN 106810764 A CN106810764 A CN 106810764A CN 201710038062 A CN201710038062 A CN 201710038062A CN 106810764 A CN106810764 A CN 106810764A
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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
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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
- B29C48/92—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
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/12—Shape memory
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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
- 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 low-shrinkage bumper Shape memory polypropylene composite material, is made up of the raw material of following weight portion：Polypropylene 45 65, the aminopropyl triethoxysilane 4 11 of methyl silicate 11 17,3, maleic anhydride grafted ethene octene copolymer 49, nucleator 12, irgasfos 168 0.6 2, acetonitrile 55 70, deionized water 13 20, talcum powder 39, azodiisobutyronitrile 38, styrene 22 30, appropriate chlorobenzene solution, appropriate methyl alcohol, four-leg crystal whisker of zinc oxide 25, calcium sulfate crystal whiskers 36.The present invention extrudes blending using polystyrene cross-linked silica aeroge with polypropylene, the characteristic of polypropylene shape memory is imparted, as automobile bumper material, once because external stress generates deformation, it is heated to more than polyacrylic fusing point, sample can be returned to original shape.
Description
Technical field
The invention belongs to technical field of polymer composite materials, more particularly to a kind of low-shrinkage bumper shape
Memory PP composite material and preparation method thereof.
Background technology
With the fast development of automobile industry, automotive light weight technology turns into a trend of China Automobile Industry, therefore more next
More auto parts and components, come alternative metals, mitigate vehicle weight using plastics.Other bumper is difficult in use
Exempt to undergo external impacts, non-response deformation produced 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 under, and fixing phase now plays a part of physical crosslinking point solid shape.
Dong Baojian, Japanese plum material et al.《The preparation of PP/PET/POE-g-MAH marmems and performance study》One text
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 is 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 particulate inside aeroge
Structure includes primary granules and offspring, and the effect of crosslinked polymer forms one layer " coating " equivalent in gel surface,
The presence of " coating " causes there is certain cushioning effect between offspring, when certain external force is applied, between offspring
Can slide, 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 low-shrinkage bumper Shape memory polypropylene composite material, have
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 low-shrinkage bumper Shape memory polypropylene composite material, by the raw material group of following weight portion
Into：Polypropylene 45-65 parts, methyl silicate 11-17 parts, 4-11 parts of 3- aminopropyl triethoxysilanes, maleic anhydride grafting second
Alkene-octene copolymer 4-9 parts, nucleator 1-2 parts, irgasfos 168 0.6-2 parts, acetonitrile 55-70 parts, deionized water 13-20 parts,
Talcum powder 3-9 parts, azodiisobutyronitrile 3-8 parts, styrene 22-30 parts, appropriate chlorobenzene solution, appropriate methyl alcohol, the oxidation of four feet
2-5 parts, calcium sulfate crystal whiskers 3-6 parts of zinc whisker.
Comprise the following steps that：
（1）The preparation of silica dioxide gel：
Methyl silicate, acetonitrile and 3- aminopropyl triethoxysilanes are mixed into solution A, deionized water and acetonitrile are mixed into B
Solution, less than 0 DEG C is cooled to by solution A, is poured into B solution and is uniformly mixed rapidly, to be put and form gel in room temperature, aging to put
Put 3-4 days, washed with methyl alcohol and obtain silica wet gel, it is standby；
（2）Prepare polystyrene cross-linked silica aeroge：
Silica wet gel is placed in the chlorobenzene solution for being dissolved in azodiisobutyronitrile and styrene, is impregnated 2-4 days, be transferred to chlorine
In benzole soln, reacted 22-25 hours at 70-75 DEG C, washed twice with chlorobenzene solution, then carry out solvent displacement with methyl alcohol,
Supercritical drying is the Monolithic aerogel that can obtain polystyrene crosslinking, and ball mill grinding to size is sieved between 20-80 mesh sieves
To polystyrene cross-linked silica aerogel powder；
（3）Polypropylene, maleic anhydride grafted ethene-octene copolymer, talcum powder, irgasfos 168, nucleator are added to stirring
Stirred in machine, step is added afterwards（2）The polystyrene cross-linked silica aerogel powder for obtaining continues to stir 20-30
Minute；
（4）The above-mentioned material for stirring is added in the hopper of parallel double-screw extruder, it is lateral from double screw extruder
Spout addition calcium sulfate crystal whiskers, four-leg crystal whisker of zinc oxide are mixed 8-13 minutes, and blended melting extruding pelletization obtains one
Plant low-shrinkage bumper Shape memory polypropylene composite material.
Wherein, the processing conditions of the double screw extruder is 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 endurance of aerosil, compatible with polypropylene material
Property, and change is little before and after aeroge density, and being added in bumper PP composite material can mitigate vehicle weight, produces
Product have excellent heat resistance, 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 is in itself
With excellent toughness, product of the present invention as automobile bumper material, once because external stress generates deformation, by itself plus
More than heat to polyacrylic fusing point, sample can be returned to original shape.
（3）Four-leg crystal whisker of zinc oxide has highly regular 3-D solid structure, it can be extended from center
Four spicules are inserted directly into inside polypropylene, and the present invention is using calcium sulfate crystal whiskers, four-leg crystal whisker of zinc oxide is compounded can be more
Polypropylene is strengthened well and toughness reinforcing, polyacrylic inprocess shrinkage is greatly reduced while the mechanical property for improving material
Rate.
Specific embodiment
A kind of low-shrinkage bumper Shape memory polypropylene composite material, by following weight portion（Kilogram）Original
Material composition：Polypropylene 55, methyl silicate 15,3- aminopropyl triethoxysilanes 8, maleic anhydride grafted ethene-octene copolymer
Thing 7, nucleator 2, irgasfos 168 1, acetonitrile 60, deionized water 18, talcum powder 5, azodiisobutyronitrile 5, styrene 28, chlorobenzene
Appropriate solution, appropriate methyl alcohol, four-leg crystal whisker of zinc oxide 4, calcium sulfate crystal whiskers 5.
Comprise the following steps that：
（1）The preparation of silica dioxide gel：
Methyl silicate, acetonitrile and 3- aminopropyl triethoxysilanes are mixed into solution A, deionized water and acetonitrile are mixed into B
Solution, less than 0 DEG C is cooled to by solution A, is poured into B solution and is uniformly mixed rapidly, to be put and form gel in room temperature, aging to put
Put 3 days, washed with methyl alcohol and obtain silica wet gel, it is standby；
（2）Prepare polystyrene cross-linked silica aeroge：
Silica wet gel is placed in the chlorobenzene solution for being dissolved in azodiisobutyronitrile and styrene, is impregnated 3 days, be transferred to chlorobenzene
In solution, reacted 24 hours at 72 DEG C, washed twice with chlorobenzene solution, then carry out solvent displacement, supercritical drying with methyl alcohol
The dry Monolithic aerogel that can obtain polystyrene crosslinking, between 80 mesh sieves, sieving obtains polystyrene for ball mill grinding to size
Cross-linked silica aerogel powder；
（3）Polypropylene, maleic anhydride grafted ethene-octene copolymer, talcum powder, irgasfos 168, nucleator are added to stirring
Stirred in machine, step is added afterwards（2）The polystyrene cross-linked silica aerogel powder for obtaining continues to stir 25 points
Clock；
（4）The above-mentioned material for stirring is added in the hopper of parallel double-screw extruder, it is lateral from double screw extruder
Spout addition calcium sulfate crystal whiskers, four-leg crystal whisker of zinc oxide are mixed 10 minutes, and blended melting extruding pelletization obtains one kind
Low-shrinkage bumper Shape memory polypropylene composite material.
Wherein, the processing conditions of the double screw extruder is that 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 38MPa, elongation at break 305%, heat distortion temperature（0.45MPa）
110 DEG C, shape recovery rate 96%, 179 DEG C of recovery of shape temperature, recovery of shape response time≤100s.
Claims (3)
1. a kind of low-shrinkage bumper Shape memory polypropylene composite material, it is characterised in that by following weight portion
Raw material composition：Polypropylene 45-65 parts, methyl silicate 11-17 parts, 4-11 parts of 3- aminopropyl triethoxysilanes, maleic acid
Acid anhydride grafted ethene-octene copolymer 4-9 parts, nucleator 1-2 parts, irgasfos 168 0.6-2 parts, acetonitrile 55-70 parts, deionized water
13-20 parts, talcum powder 3-9 parts, azodiisobutyronitrile 3-8 parts, styrene 22-30 parts, appropriate chlorobenzene solution, appropriate methyl alcohol, four
Leg crystal whisker of zinc oxide 2-5 parts, calcium sulfate crystal whiskers 3-6 parts.
2. the system of a kind of low-shrinkage bumper Shape memory polypropylene composite material according to claims 1
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 solution A, deionized water and acetonitrile are mixed into B
Solution, less than 0 DEG C is cooled to by solution A, is poured into B solution and is uniformly mixed rapidly, to be put and form gel in room temperature, aging to put
Put 3-4 days, washed with methyl alcohol and obtain silica wet gel, it is standby；
（2）Prepare polystyrene cross-linked silica aeroge：
Silica wet gel is placed in the chlorobenzene solution for being dissolved in azodiisobutyronitrile and styrene, is impregnated 2-4 days, be transferred to chlorine
In benzole soln, reacted 22-25 hours at 70-75 DEG C, washed twice with chlorobenzene solution, then carry out solvent displacement with methyl alcohol,
Supercritical drying is the Monolithic aerogel that can obtain polystyrene crosslinking, and ball mill grinding to size is sieved between 20-80 mesh sieves
To polystyrene cross-linked silica aerogel powder；
（3）Polypropylene, maleic anhydride grafted ethene-octene copolymer, talcum powder, irgasfos 168, nucleator are added to stirring
Stirred in machine, step is added afterwards（2）The polystyrene cross-linked silica aerogel powder for obtaining continues to stir 20-30
Minute；
（4）The above-mentioned material for stirring is added in the hopper of parallel double-screw extruder, it is lateral from double screw extruder
Spout addition calcium sulfate crystal whiskers, four-leg crystal whisker of zinc oxide are mixed 8-13 minutes, and blended melting extruding pelletization obtains one
Plant low-shrinkage bumper Shape memory polypropylene composite material.
3. the system of a kind of low-shrinkage bumper Shape memory polypropylene composite material according to claims 2
Preparation Method, it is characterised in that the processing conditions of the double screw extruder is 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 is 280-295 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710038062.5A CN106810764A (en) | 2017-01-19 | 2017-01-19 | A kind of low-shrinkage bumper Shape memory polypropylene composite material and preparation method thereof |
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| CN201710038062.5A CN106810764A (en) | 2017-01-19 | 2017-01-19 | A kind of low-shrinkage bumper Shape memory polypropylene composite material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540711A (en) * | 2018-05-29 | 2019-12-06 | 合肥杰事杰新材料股份有限公司 | low-after-shrinkage polypropylene material and preparation method thereof |
| CN112724511A (en) * | 2020-12-22 | 2021-04-30 | 上海日之升科技有限公司 | Easy-to-clean mildew-proof PP composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2017
- 2017-01-19 CN CN201710038062.5A patent/CN106810764A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| 朱和国 等: "《复合材料原理》", 31 July 2013 * |
| 熊刚 等: ""柔韧性二氧化硅气凝胶的研究进展"", 《硅酸盐通报》 * |
| 赵云龙 等: "《石膏应用技术问答》", 30 September 2016 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540711A (en) * | 2018-05-29 | 2019-12-06 | 合肥杰事杰新材料股份有限公司 | low-after-shrinkage polypropylene material and preparation method thereof |
| CN110540711B (en) * | 2018-05-29 | 2022-05-10 | 合肥杰事杰新材料股份有限公司 | Low-after-shrinkage polypropylene material and preparation method thereof |
| CN112724511A (en) * | 2020-12-22 | 2021-04-30 | 上海日之升科技有限公司 | Easy-to-clean mildew-proof PP composite material and preparation method thereof |
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Application publication date: 20170609 |
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