CN106750977A - A kind of bumper cold-resistant anti-freezing type shape memory polypropylene material and preparation method thereof - Google Patents
A kind of bumper cold-resistant anti-freezing type shape memory polypropylene material and preparation method thereof Download PDFInfo
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- CN106750977A CN106750977A CN201710038053.6A CN201710038053A CN106750977A CN 106750977 A CN106750977 A CN 106750977A CN 201710038053 A CN201710038053 A CN 201710038053A CN 106750977 A CN106750977 A CN 106750977A
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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
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- 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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- 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
- C08L2205/24—Crystallisation aids
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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
- C08L2312/00—Crosslinking
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- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a kind of bumper with cold-resistant anti-freezing type shape memory polypropylene material, is made up of the raw material of following weight portion：Polypropylene 45 65, the aminopropyl triethoxysilane 6 10 of methyl silicate 12 18,3, maleic anhydride grafted ethene octene copolymer 49, nucleator 12, irgasfos 168 0.8 2, acetonitrile 50 70, deionized water 13 22, talcum powder 59, azodiisobutyronitrile 39, styrene 22 30, appropriate chlorobenzene solution, appropriate methyl alcohol, acicular wollastonite 13, titanate coupling agent 0.4 1, two sub- benzylidene sorbitols 0.5 1.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 bumper anti-freezing type shape that resists cold
Shape memory polypropylene 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 bumper with cold-resistant anti-freezing type shape memory polypropylene material, with excellent
Different shape-memory properties, the lower deformation for producing of external force effect can be replied by heating, and meet automobile bumper material to shape
The requirement of shape memory.
A kind of bumper is made up of with cold-resistant anti-freezing type shape memory polypropylene material the raw material of following weight portion：
Polypropylene 40-60 parts, methyl silicate 10-15 parts, 5-10 parts of 3- aminopropyl triethoxysilanes, maleic anhydride grafted ethene-
It is octene copolymer 3-8 parts, nucleator 1-3 parts, irgasfos 168 0.5-2 parts, acetonitrile 50-70 parts, deionized water 10-18 parts, sliding
Stone flour 4-9 parts, azodiisobutyronitrile 4-10 parts, styrene 20-30 parts, appropriate chlorobenzene solution, appropriate methyl alcohol.
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）The preparation of modified acicular wollastonite：
By in acicular wollastonite addition high-speed mixer, titanate esters coupling is slowly added to from the upper end aperture of high-speed mixer afterwards
Agent carries out being mixed to get modified acicular wollastonite；
（4）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 30-50
Minute；
（5）Well mixed above-mentioned material is added in the hopper of parallel double-screw extruder, then in the way of the feeding of side
Add step（3）The modified acicular wollastonite of preparation and two sub- benzylidene sorbitols continue to knead, and blended melting extruding pelletization is obtained
A kind of bumper anti-freezing type shape memory polypropylene material that resists cold.
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）The present invention uses titanate coupling agent modified acicular wollastonite as the cold-resistant agent of polypropylene material, sub- with two
Benzylidene sorbitol compounding use improves polyacrylic low-temperature flexibility and keeps effect, anti-freezing property, also can in the area of some colds
Meet the use requirement of bumper.
Specific embodiment
A kind of bumper anti-freezing type shape memory polypropylene material that resists cold, by following weight portion（Kilogram）Raw material
Composition：Polypropylene 55, methyl silicate 16,3- aminopropyl triethoxysilanes 8, maleic anhydride grafted ethene-octene copolymer
6, nucleator 1, irgasfos 168 1, acetonitrile 65, deionized water 22, talcum powder 8, azodiisobutyronitrile 6, styrene 25, chlorobenzene is molten
Appropriate liquid, appropriate methyl alcohol, acicular wollastonite 2, titanate coupling agent 0.8, two sub- 0.7 part of benzylidene sorbitols.
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）The preparation of modified acicular wollastonite：
By in acicular wollastonite addition high-speed mixer, titanate esters coupling is slowly added to from the upper end aperture of high-speed mixer afterwards
Agent carries out being mixed to get modified acicular wollastonite；
（4）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 40 points
Clock；
（5）Well mixed above-mentioned material is added in the hopper of parallel double-screw extruder, then in the way of the feeding of side
Add step（3）The modified acicular wollastonite of preparation and two sub- benzylidene sorbitols continue to knead, and blended melting extruding pelletization is obtained
A kind of bumper anti-freezing type shape memory polypropylene material that resists cold.
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 39MPa, elongation at break 310%, heat distortion temperature（0.45MPa）
113 DEG C, shape recovery rate 98%, 176 DEG C of recovery of shape temperature, recovery of shape response time≤100s.
Claims (3)
1. a kind of bumper is with cold-resistant anti-freezing type shape memory polypropylene material, it is characterised in that by following weight portion
Raw material is constituted：Polypropylene 45-65 parts, methyl silicate 12-18 parts, 6-10 parts of 3- aminopropyl triethoxysilanes, maleic anhydride
Grafted ethene-octene copolymer 4-9 parts, nucleator 1-2 parts, irgasfos 168 0.8-2 parts, acetonitrile 50-70 parts, deionized water
13-22 parts, talcum powder 5-9 parts, azodiisobutyronitrile 3-9 parts, styrene 22-30 parts, appropriate chlorobenzene solution, appropriate methyl alcohol, pin
1-3 parts of shape wollastonite, titanate coupling agent 0.4-1 parts, two sub- 0.5-1 parts of benzylidene sorbitols.
2. the preparation of cold-resistant anti-freezing type shape memory polypropylene material of a kind of bumper according to claims 1
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）The preparation of modified acicular wollastonite：
By in acicular wollastonite addition high-speed mixer, titanate esters coupling is slowly added to from the upper end aperture of high-speed mixer afterwards
Agent carries out being mixed to get modified acicular wollastonite；
（4）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 30-50
Minute；
（5）Well mixed above-mentioned material is added in the hopper of parallel double-screw extruder, then in the way of the feeding of side
Add step（3）The modified acicular wollastonite of preparation and two sub- benzylidene sorbitols continue to knead, and blended melting extruding pelletization is obtained
A kind of bumper anti-freezing type shape memory polypropylene material that resists cold.
3. the preparation of cold-resistant anti-freezing type shape memory polypropylene material of a kind of bumper according to claims 2
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 |
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| CN201710038053.6A CN106750977A (en) | 2017-01-19 | 2017-01-19 | A kind of bumper cold-resistant anti-freezing type shape memory polypropylene material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710038053.6A CN106750977A (en) | 2017-01-19 | 2017-01-19 | A kind of bumper cold-resistant anti-freezing type shape memory polypropylene material and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086882A (en) * | 2014-07-03 | 2014-10-08 | 合肥杰事杰新材料股份有限公司 | Application of needle-like wollastonite served as polypropylene cold-resistant agent and cold-resistant polypropylene material containing needle-like wollastonite |
| CN104629581A (en) * | 2015-02-03 | 2015-05-20 | 芜湖市宝艺游乐科技设备有限公司 | High-toughness silicon oxide aerogel super-adiabatic thermal-insulation coating and preparation method thereof |
| CN105820443A (en) * | 2016-05-22 | 2016-08-03 | 王刚 | Cold-resistant toughened polypropylene material |
| CN105924775A (en) * | 2016-05-22 | 2016-09-07 | 金婷婷 | Low-temperature-resistant polypropylene material |
| CN106009251A (en) * | 2016-05-22 | 2016-10-12 | 金婷婷 | Cold-resistant high-toughness polypropylene material |
-
2017
- 2017-01-19 CN CN201710038053.6A patent/CN106750977A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086882A (en) * | 2014-07-03 | 2014-10-08 | 合肥杰事杰新材料股份有限公司 | Application of needle-like wollastonite served as polypropylene cold-resistant agent and cold-resistant polypropylene material containing needle-like wollastonite |
| CN104629581A (en) * | 2015-02-03 | 2015-05-20 | 芜湖市宝艺游乐科技设备有限公司 | High-toughness silicon oxide aerogel super-adiabatic thermal-insulation coating and preparation method thereof |
| CN105820443A (en) * | 2016-05-22 | 2016-08-03 | 王刚 | Cold-resistant toughened polypropylene material |
| CN105924775A (en) * | 2016-05-22 | 2016-09-07 | 金婷婷 | Low-temperature-resistant polypropylene material |
| CN106009251A (en) * | 2016-05-22 | 2016-10-12 | 金婷婷 | Cold-resistant high-toughness polypropylene material |
Non-Patent Citations (2)
| Title |
|---|
| 熊刚: ""柔韧性二氧化硅气凝胶的研究进展"", 《硅酸盐通报》 * |
| 辛忠: "《小分子调控大分子结晶——理论与实践》", 31 August 2016, 华东理工大学出版社 * |
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