CN106147171A - A kind of shape memory automobile baffle and preparation method thereof - Google Patents

A kind of shape memory automobile baffle and preparation method thereof Download PDF

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Publication number
CN106147171A
CN106147171A CN201610583579.8A CN201610583579A CN106147171A CN 106147171 A CN106147171 A CN 106147171A CN 201610583579 A CN201610583579 A CN 201610583579A CN 106147171 A CN106147171 A CN 106147171A
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automobile baffle
weight portion
shape memory
calcium sulfate
districts
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CN201610583579.8A
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CN106147171B (en
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丁文
罗立立
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Ningbo Lianhua Automobile Part Co Ltd
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Ningbo Lianhua Automobile Part Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17Component parts, details or accessories; Auxiliary operations
    • B29C45/76Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2945/00Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76Measuring, controlling or regulating
    • B29C2945/76003Measured parameter
    • B29C2945/7604Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • B29C2948/9259Angular velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/004Additives being defined by their length
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/12Shape memory
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00Crosslinking

Abstract

The present invention provides a kind of shape memory automobile baffle and preparation method thereof, following component prepare: polyhydroxyalkanoate, calcium sulfate crystal whiskers, polylactic acid, coupling agent, cross-linking agent, light stabilizer.Wherein, polyhydroxyalkanoate forms network structure with polylactic acid by cross-linking agent, improves the mechanical property of automobile baffle.Polyhydroxyalkanoate interacts with polylactic acid, form hard segment soft chain segment structure, in injection moulding process, first cool down near the glass transition temperature of material, make material memory original-shape, when deforming upon, temperature at deformation being maintained under glass transition temperature, the automobile baffle of deformation will restore to the original state.Secondly, calcium sulfate crystal whiskers is orientated along melt flows direction in injection moulding process, and after molding, calcium sulfate crystal whiskers is parallel is distributed in inside automobile baffle, effectively raises shock resistance and the dimensional stability of automobile baffle.

Description

A kind of shape memory automobile baffle and preparation method thereof
Technical field
The present invention relates to a kind of automobile baffle, more particularly, to a kind of shape memory automobile baffle and preparation method thereof.
Background technology
Chinese automobile production and marketing in 2015 is respectively completed 2450.33 ten thousand and 2459.76 ten thousand, records high, continuous 7 years Continue to hold a post or title the first in the world.Through high speed development for many years, the developing direction of automobile industry turn to top grade, miniaturization, lighting and Diversification, the most active with mould that Dai Gang research in automotive vehicles applications also becomes.Auto parts and components have employed a large amount of plastics zero Parts, such as: bumper, wheel cover, license plate, instrumental panel, baffle plate, knob, even hood, gas handling system.Automobile baffle is Important composition in automobile component, is used for protecting auto parts and components without damage, has good stability of the dimension, mechanical property strong Feature, uses Ppo/pa Alloy or metal to prepare at present, but when Ppo/pa Alloy or metal are clashed into Shi Rongyi is deformed, it is difficult to recover, and can only cause the biggest waste by more bringing solution.
Along with environmental protection, low-carbon (LC) theory are gradually rooted in the hearts of the people, and the release of energy-saving and emission-reduction policy, use rich and influential family as plastics Automobile necessarily face impact.Biodegradable plastic is just presenting growing trend in the demand of automobile manufacture industry, such as, The range of application of the product with starch base, PLA, PCL and PBS as main component the most progressively expands.But, biodegradable plastic Whether price or combination property aspect, all has gap with automobile engineering plastics, brings to the popularization of biodegradable plastic Hinder.
PHA full name polyhydroxyalkanoate, is a kind of important biodegradable plastics, can be as a lot of Microbe synthesis Intracellular polyester, be a kind of natural polymeric biomaterial.Owing to PHA monomeric species is more, it is that one can structure design Biodegradable plastics, therefore people have carried out substantial amounts of research, are mainly used as medical material.Application No. The Chinese patent literature of 201210570631.8 discloses a kind of material based on poly-hydroxy fatty acid and preparation method thereof, uses The method preparation of polyhydroxyalkanoate and polyurethane comixing is for biomedical engineering, weaving, toy for children, articles for daily use Degradable shape-memory material, but do not suggest that this material can be used for this severe rugged environment of automobile engineering.Close in addition with a large amount of In the research of PHA, as modified in PHA/PLA blending and modifying, PHA/ Inorganic Fillers Filled etc., but, the mechanical property of these PHA material Can be poor, dimensional stability is not enough, and shape is difficult to recover, relatively costly, thus causes PHA material to be difficult to as automobile baffle.
Summary of the invention
Present invention is primarily targeted at a kind of shape memory automobile baffle of offer and preparation method thereof, the automobile gear of preparation Plate mechanical property is good, good dimension stability, can shape recover.
For reaching object above, the technical solution used in the present invention is:
The present invention provides a kind of shape memory automobile baffle, following component prepare:
Polyhydroxyalkanoate 55-70 weight portion;
Calcium sulfate crystal whiskers 20-25 weight portion;
Polylactic acid 9-18 weight portion;
Coupling agent 0.5-1 weight portion;
Cross-linking agent 0.2-0.5 weight portion;
Light stabilizer 0.3-0.5 weight portion.
Preferably, the structural formula of described polyhydroxyalkanoate is as shown in Equation 1:
[-O-CHR1-(CH2)x-CO-O-CHR2-(CH2)Y-COO-]n
Formula 1),
Wherein, R1For phenethyl, R2For the carbon atom number alkyl less than 6, X < 5,4 < Y < 7, number-average molecular weight is 40000-50000。
Preferably, a diameter of 2.5-3.5 micron of described calcium sulfate crystal whiskers, average aspect ratio is 20-30.
Preferably, the number-average molecular weight of described polylactic acid is 30000-40000.
Preferably, described cross-linking agent is dialkyl peroxide.
Accordingly, the present invention also provides for the preparation method of a kind of shape memory automobile baffle, comprises the following steps: by 55- 70 weight portion polyhydroxyalkanoates and the mixing of 9-18 weight portion polylactic acid, obtain mixture A;To 20-25 parts sulfuric acid calcium Whisker adds 0.5-1 weight portion coupling agent, stirring, obtains activating calcium sulfate crystal whiskers;By described mixture A, activation calcium sulfate Whisker, 0.2-0.5 parts by weight of crosslinking agent and 0.3-0.5 weight portion light stabilizer add in double screw extruder, extruding pelletization, To plastic grain, head temperature is 170-200 DEG C, screw speed 80-120r/min;Described plastic grain is dried, is molded into Shape memory automobile baffle is obtained after type.
Preferably, obtaining in the step of activation calcium sulfate crystal whiskers, mixing time is 5-10min, and mixing speed is 20-40 Turn/min.
Preferably, obtaining in the step of plastic grain, the prilling temperature of double screw extruder is 130-150 DEG C of a district, two 150-160 DEG C of district, three 160-170 DEG C of districts, four 170-180 DEG C of districts, five 180-190 DEG C of districts.
Preferably, obtaining in the step of shape memory automobile baffle, the baking temperature of plastic grain is 60-80 DEG C, is dried Time is 5-8 hour.
Preferably, injection mo(u)lding is particularly as follows: add dried plastic grain in injection machine, and injection machine temperature is a district 150-160 DEG C, two 160-180 DEG C of districts, three 180-200 DEG C of districts, it is subsequently cooled to 80-85 DEG C of insulation 5-7min, continues cool to 20-30 DEG C of insulation 5-8min.
The present invention provides a kind of shape memory automobile baffle and preparation method thereof, following component prepare: poly-hydroxy aliphatic Acid esters 5-70 weight portion;Calcium sulfate crystal whiskers 20-25 weight portion;Polylactic acid 9-18 weight portion;Coupling agent 0.5-1 weight portion;Crosslinking Agent 0.2-0.5 weight portion;Light stabilizer 0.3-0.5 weight portion.Compared with prior art, polyhydroxyalkanoate leads to polylactic acid Cross cross-linking agent and define network structure, improve the mechanical property of automobile baffle, reach automobile engineering and use requirement.Poly-hydroxy aliphatic Acid esters interacts with polylactic acid, forms hard segment-soft chain segment structure, and in injection moulding process, the first vitrification at material turns Near temperature, cooling, makes material memory original-shape, when occurring because colliding, extruding the deformation caused, by temperature at deformation Degree is maintained under glass transition temperature, and the automobile baffle of deformation will restore to the original state.Secondly, calcium sulfate crystal whiskers is in injection moulding process Being orientated along melt flows direction, after molding, calcium sulfate crystal whiskers is parallel is distributed in inside automobile baffle, effectively raises automobile The shock resistance of baffle plate and dimensional stability.Therefore, the mechanical property of automobile baffle prepared by the present invention is good, dimensional stability Good, can shape recover.
Detailed description of the invention
Hereinafter describe and be used for disclosing the present invention so that those skilled in the art are capable of the present invention.Below describe in excellent Select embodiment to be only used as citing, it may occur to persons skilled in the art that other obvious modification.
The present invention provides a kind of shape memory automobile baffle, following component prepare:
Polyhydroxyalkanoate 55-70 weight portion;
Calcium sulfate crystal whiskers 20-25 weight portion;
Polylactic acid 9-18 weight portion;
Coupling agent 0.5-1 weight portion;
Cross-linking agent 0.2-0.5 weight portion;
Light stabilizer 0.3-0.5 weight portion.
The structural formula of described polyhydroxyalkanoate is as shown in Equation 1:
[-O-CHR1-(CH2)X-CO-O-CHR2-(CH2)Y-COO-]n
Formula 1),
Wherein, R1For phenethyl, R2For the carbon atom number alkyl less than 6, X < 5,4 < Y < 7, number-average molecular weight is 40000-50000.In the network structure formed after carrying out cross-linking reaction, it is firm that the phenethyl in polyhydroxyalkanoate contains Property group, with polylactic acid collectively as hard segment, and in polyhydroxyalkanoate, other alkyl is as soft chain segment, forms hard chain Section-soft chain segment structure, makes automobile baffle have shape memory function.Described polyhydroxyalkanoate is preferably 55-68 weight portion, More preferably 61-65 weight portion.
Described calcium sulfate crystal whiskers is prepared by manual control with Gypsum Fibrosum for raw material, with single crystal form growth, tool There are uniform cross section, complete profile, the threadiness of perfect internal structure, there is high intensity, high-modulus, high tenacity, height Insulating properties, abrasion performance, high temperature resistant, acid and alkali-resistance, anticorrosive, infrared reflectivity good, is prone to surface processes, easily answer with polymer Close, many excellent physicochemical properties such as nontoxic.The diameter of the calcium sulfate crystal whiskers that the present invention uses is preferably 2.5-3.5 micron, more Being preferably 3 microns, average aspect ratio is preferably 20-30, and calcium sulphate content is more than 99%, primarily serves the chi improving automobile baffle Very little stability and mechanical property, reduce manufacturing cost simultaneously.
Described polylactic acid, also known as polylactide, is a kind of degradable high polymer material deriving from plant, has the most crisp Property, the number-average molecular weight of the polylactic acid used in the present invention is preferably 30000-40000, produces crosslinking with polyhydroxyalkanoate Reaction, forms network structure and automobile baffle can be made to have shape memory function.
The coupling agent that the present invention uses is preferably silane coupler, utilizes calcium sulfate crystal whiskers and tree that silane coupler processes Aliphatic radical body has preferable caking property.The present invention use coupling agent be more preferably KH-540, KH-550, KH-560, KH-570, One in KH-590, KH-592, A-151, A-171, A-172, Si-563, Si-602.
Described cross-linking agent is preferably dialkyl peroxide, has half-life little advantage during cross-linking reaction.This The cross-linking agent of bright employing be more preferably di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis-(t-butylperoxy)-3-second Alkynes, 2,5-dimethyl-2, the one in 5-bis-(t-butylperoxy)-ethane, cumyl peroxide.
Light stabilizer is a kind of yellow powder, has the action of ultraviolet light in opposing sunlight, it is to avoid the light of automobile baffle Aging.The one that the light stabilizer that the present invention uses is preferably in UV-123, UV-531 and UV-9.
Accordingly, the present invention also provides for the preparation method of a kind of shape memory automobile baffle, comprises the following steps: by 55- 70 weight portion polyhydroxyalkanoates and the mixing of 9-18 weight portion polylactic acid, obtain mixture A;To 20-25 parts sulfuric acid calcium Whisker adds 0.5-1 weight portion coupling agent, stirring, obtains activating calcium sulfate crystal whiskers;By described mixture A, activation calcium sulfate Whisker, 0.2-0.5 parts by weight of crosslinking agent and 0.3-0.5 weight portion light stabilizer add in double screw extruder, extruding pelletization, To plastic grain, head temperature is 170-200 DEG C, screw speed 80-120r/min;Described plastic grain is dried, is molded into Shape memory automobile baffle is obtained after type.
Obtaining in the step of activation calcium sulfate crystal whiskers, the present invention uses suitable mixing time and mixing speed, makes coupling Agent can be sufficiently mixed with calcium sulfate crystal whiskers, and as incorporation time, speed are not suitable for, calcium sulfate crystal whiskers surface coupling agent is uneven, Calcium sulfate is brilliant bad with the resin matrix compatibility, causes automobile baffle mechanical properties decrease.Wherein, mixing time is preferably 5- 10min, more preferably 6-10min;Mixing speed is preferably 20-40 and turns/min, more preferably 25-35 and turn/min.
Obtaining in the step of plastic grain, the present invention utilizes double screw extruder to carry out extruding pelletization, by extruder Temperature sets, and makes cross-linking agent fully react, noresidue.Stop for a long time due to biodegradation material and can cause heat in an extruder Degraded, has burnt material to produce, but screw speed is too fast, and shearing force can cause macromolecular chain to rupture, and therefore, the present invention sets screw rod and turns Speed, makes each component mix homogeneously, and shortens material in the extruder time of staying.Preferably, the pelletize of double screw extruder Temperature is 130-150 DEG C of a district, two 150-160 DEG C of districts, three 160-170 DEG C of districts, four 170-180 DEG C of districts, five 180-190 DEG C of districts.
Cross-linking reaction in the present invention is extrusion crosslinking, and the response time is short, therefore needs cross-linking agent to possess half-life little spy Point, the cross-linking agent half-life selected by the present invention is less than 1min so that material has been carried out full cross-linked during extruding pelletization, There is no residual cross-linker, injection moulding process will not be produced impact.
Obtain, in the step of shape memory automobile baffle, being dried by described plastic grain, remove the moisture in plastic grain, Avoid forming defect at product surface.The baking temperature of plastic grain is preferably 60-80 DEG C, more preferably 7-80 DEG C;When being dried Between be preferably 5-8 hour, more preferably 6-8 hour.
Described injection mo(u)lding is particularly as follows: add dried plastic grain in injection machine, and injection machine temperature is a district 150-160 DEG C, two 160-180 DEG C of districts, three 180-200 DEG C of districts, it is subsequently cooled to 80-85 DEG C of insulation 5-7min, continues cool to 20-30 DEG C of insulation 5-8min.The present invention, by setting injection temperature, makes plastic grain fully plastify, forms certain mobility. The cooling procedure that the present invention uses is preferably divided into two stages, and the first stage is 80 DEG C-85 DEG C insulation 5-7min, makes automobile baffle Shaping at such a temperature, second stage is that 20 DEG C-30 DEG C insulation 5-8min make automobile baffle cooling and demolding.Use first stage temperature After degree, time carry out cooling and shaping, automobile baffle can remember this original-shape, when in use deforming, and will deformation Place is heated to first stage temperature, will restore to the original state, as cool time, temperature are not suitable for causing automobile baffle to recover at deformation Less than original-shape.
From above scheme it can be seen that the present invention provides a kind of shape memory automobile baffle and preparation method thereof, preparation The mechanical property of automobile baffle is good, good dimension stability, can shape recover.
In order to be further appreciated by the present invention, the technical scheme provided the present invention below in conjunction with embodiment is carried out specifically Bright, protection scope of the present invention is not limited by the following examples.
Polyhydroxyalkanoate used in the following embodiment of the present invention is by Yi Keman bio tech ltd, Shenzhen There is provided.
Polylactic acid used in the following embodiment of the present invention makes innovations from Nantong nine Materials Co., Ltd.
Calcium sulfate crystal whiskers used in the following embodiment of the present invention comes from seapeak Zhu trade Co., Ltd.
Coupling agent used in the following embodiment of the present invention is from union carbide corporation of the U.S..
Cross-linking agent used in the following embodiment of the present invention, gloomy Dihua work from Shanghai.
Light stabilizer used in the following embodiment of the present invention, from Germany's BASF.
Embodiment 1
Various raw material is weighed according to hereinafter described mass fraction ratio
Polyhydroxyalkanoate 70 weight portion;
Calcium sulfate crystal whiskers 20 weight portion;
Polylactic acid 9 weight portion;
Coupling agent KH550 0.5 weight portion;
Cross-linking agent cumyl peroxide 0.2 weight portion;
Light stabilizer UV-123 0.3 weight portion.
Described a kind of shape memory automobile baffle preparation method is as follows:
1) polyhydroxyalkanoate is dried with particles of polylactic acid, and mixes in proportion, obtain mixture A.
2) coupling agent is added in calcium sulfate crystal whiskers, stir 5-10min, 20 turns/min of mixing speed with blender, obtain The calcium sulfate crystal whiskers processed.
3) mixture A is added exhaust parallel double-screw extruder major ingredient storehouse, the calcium sulfate crystal whiskers processed, crosslinking Agent, light stabilizer are separately added into the side feeding machine of correspondence, carry out pelletize.Wherein twin screw prilling temperature is 130 DEG C of a district, 2nd district 150 DEG C, three 160 DEG C of districts, four 170 DEG C of districts, five 180 DEG C of districts, head 170 DEG C;Screw speed 80r/min.
4) plastic grain 70 DEG C obtained is dried 5 hours, dried plastic grain is added in injection machine, notes Mould sample preparation.Wherein injection machine temperature is 150 DEG C of a district, two 160 DEG C of districts, three 180 DEG C of districts, and cooling procedure is 80 DEG C of DEG C of 5min, 30 DEG C 5min, opens mould and i.e. obtains automobile baffle.
Embodiment 2
Various raw material is weighed according to hereinafter described mass fraction ratio
Polyhydroxyalkanoate 55 weight portion;
Calcium sulfate crystal whiskers 25 weight portion;
Polylactic acid 18 weight portion;
Coupling agent KH550 1.0 weight portion;
Cross-linking agent cumyl peroxide 0.5 weight portion;
Light stabilizer UV-123 0.5 weight portion.
Described a kind of shape memory automobile baffle preparation method is as follows:
1) polyhydroxyalkanoate is dried with particles of polylactic acid, and mixes in proportion, obtain mixture A.
2) coupling agent is added in calcium sulfate crystal whiskers, stir 10min, 40 turns/min of mixing speed with blender, obtain everywhere The calcium sulfate crystal whiskers managed.
3) mixture A is added exhaust parallel double-screw extruder major ingredient storehouse, the calcium sulfate crystal whiskers processed, crosslinking Agent, light stabilizer are separately added into the side feeding machine of correspondence, carry out pelletize.Wherein twin screw prilling temperature is 150 DEG C of a district, 2nd district 160 DEG C, three 170 DEG C of districts, four 180 DEG C of districts, five 190 DEG C of districts, head 200 DEG C;Screw speed 120r/min.
4) plastic grain 70 DEG C obtained is dried 8 hours, dried plastic grain is added in injection machine, notes Mould sample preparation.Wherein injection machine temperature is 160 DEG C of a district, two 180 DEG C of districts, three 200 DEG C of districts, and cooling procedure is 85 DEG C of 7min, 20 DEG C 8min, opens mould and i.e. obtains automobile baffle.
Embodiment 3
Various raw material is weighed according to hereinafter described mass fraction ratio
Polyhydroxyalkanoate 60 weight portion;
Calcium sulfate crystal whiskers 22 weight portion;
Polylactic acid 16.5 weight portion;
Coupling agent KH550 0.8 weight portion;
Cross-linking agent cumyl peroxide 0.3 weight portion;
Light stabilizer UV531 0.4 weight portion.
Described a kind of shape memory automobile baffle preparation method is as follows:
1) polyhydroxyalkanoate is dried with particles of polylactic acid, and mixes in proportion, obtain mixture A.
2) coupling agent is added in calcium sulfate crystal whiskers, stir 7min, 30 turns/min of mixing speed with blender, processed The calcium sulfate crystal whiskers crossed.
3) mixture A is added exhaust parallel double-screw extruder major ingredient storehouse, the calcium sulfate crystal whiskers processed, crosslinking Agent, light stabilizer are separately added into the side feeding machine of correspondence, carry out pelletize.Wherein twin screw prilling temperature is 140 DEG C of a district, 2nd district 155 DEG C, three 165 DEG C of districts, four 175 DEG C of districts, five 185 DEG C of districts, head 185 DEG C;Screw speed 100r/min.
4) plastic grain 70 DEG C obtained is dried 7 hours, dried plastic grain is added in injection machine, notes Mould sample preparation.Wherein injection machine temperature is 155 DEG C of a district, two 160 DEG C of districts, three 185 DEG C of districts, and cooling procedure is 82 DEG C of 6min, 25 DEG C 7min, opens mould and i.e. obtains automobile baffle.
Comparative example 1
Various raw material is weighed according to hereinafter described mass fraction ratio
Polyhydroxyalkanoate 80 weight portion;
Calcium sulfate crystal whiskers 0 weight portion;
Polylactic acid 19 weight portion;
Coupling agent KH570 0 weight portion;
Cross-linking agent 0.5 weight portion;
Light stabilizer 0.5 weight portion.
Described a kind of shape memory automobile baffle preparation method is as follows:
1) polyhydroxyalkanoate is dried with particles of polylactic acid, and mixes in proportion, obtain mixture A.
2) mixture A being added exhaust parallel double-screw extruder major ingredient storehouse, it is right that cross-linking agent, light stabilizer are separately added into The side feeding machine answered, carries out pelletize.Wherein twin screw prilling temperature is 135 DEG C of a district, two 150 DEG C of districts, three 160 DEG C of districts, 4th district 175 DEG C, five 180 DEG C of districts, head 175 DEG C;Screw speed 80r/min.
3) plastic grain 70 DEG C obtained is dried 5 hours, dried plastic grain is added in injection machine, notes Mould sample preparation.Wherein injection machine temperature is 150 DEG C of a district, two 160 DEG C of districts, three 180 DEG C of districts, and cooling procedure is 80 DEG C of 7min, 30 DEG C 5min, opens mould and i.e. obtains automobile baffle.
Comparative example 2
Various raw material is weighed according to hereinafter described mass fraction ratio
Polyhydroxyalkanoate 75 weight portion;
Calcium sulfate crystal whiskers 23.5 weight portion;
Polylactic acid 0 weight portion;
Coupling agent 1.0 weight portion;
Cross-linking agent 0 weight portion;
Light stabilizer 0.5 weight portion.
Described a kind of shape memory automobile baffle preparation method is as follows:
1) coupling agent is added in calcium sulfate crystal whiskers, stir 10min, 40 turns/min of mixing speed with blender, obtain everywhere The calcium sulfate crystal whiskers managed.
2) dried polyhydroxyalkanoate is added exhaust parallel double-screw extruder major ingredient storehouse, the sulfur processed Acid calcium pyroborate, light stabilizer are separately added into the side feeding machine of correspondence, carry out pelletize.Wherein twin screw prilling temperature is a district 150 DEG C, two 160 DEG C of districts, three 170 DEG C of districts, four 180 DEG C of districts, five 190 DEG C of districts, head 180 DEG C;Screw speed 120r/min.
3) plastic grain 70 DEG C obtained is dried 6 hours, dried plastic grain is added in injection machine, notes Mould sample preparation.Wherein injection machine temperature is 160 DEG C of a district, two 180 DEG C of districts, three 200 DEG C of districts, and cooling procedure is 80 DEG C of 7min, 30 DEG C 5min, opens mould and i.e. obtains automobile baffle.
Comparative example 3
Various raw material is weighed according to hereinafter described mass fraction ratio
Polyhydroxyalkanoate 61 weight portion;
Calcium sulfate crystal whiskers 20 weight portion;
Polylactic acid 18 weight portion;
Coupling agent 0 weight portion;
Cross-linking agent 0.5 weight portion;
Light stabilizer 0.5 weight portion.
Described a kind of shape memory automobile baffle preparation method is as follows:
1) polyhydroxyalkanoate is dried with particles of polylactic acid, and mixes in proportion, obtain mixture A.
2) mixture A being added exhaust parallel double-screw major ingredient storehouse, calcium sulfate crystal whiskers, cross-linking agent, light stabilizer are respectively Add corresponding side feeding machine, carry out pelletize.Wherein twin screw prilling temperature is 150 DEG C of a district, two 160 DEG C of districts, three districts 165 DEG C, four 175 DEG C of districts, five 185 DEG C of districts, head 180 DEG C;Screw speed 90r/min.
3) plastic grain 70 DEG C obtained is dried 8 hours, dried plastic grain is added in injection machine, notes Mould sample preparation.Wherein injection machine temperature is 160 DEG C of a district, two 175 DEG C of districts, three 190 DEG C of districts, and cooling procedure is 85 DEG C of 7min, 30 DEG C 5min, opens mould and i.e. obtains automobile baffle.
Comparative example 4
Various raw material is weighed according to hereinafter described mass fraction ratio
Polyhydroxyalkanoate 60.5 weight portion;
Calcium sulfate crystal whiskers 20 weight portion;
Polylactic acid 18 weight portion;
Coupling agent 1.0 weight portion;
Cross-linking agent 0 weight portion;
Light stabilizer 0.5 weight portion.
Described a kind of shape memory automobile baffle preparation method is as follows:
1) polyhydroxyalkanoate is dried with particles of polylactic acid, and mixes in proportion, obtain mixture A.
2) coupling agent is added in calcium sulfate crystal whiskers, stir 10min, 30 turns/min of mixing speed with blender, obtain everywhere The calcium sulfate crystal whiskers managed.
3) mixture A being added exhaust parallel double-screw major ingredient storehouse, the calcium sulfate crystal whiskers processed, light stabilizer are respectively Add corresponding side feeding machine, carry out pelletize.Wherein twin screw prilling temperature is 145 DEG C of a district, two 160 DEG C of districts, three districts 165 DEG C, four 175 DEG C of districts, five 190 DEG C of districts, head 190 DEG C;Screw speed 100r/min.
4) plastic grain 70 DEG C obtained is dried 8 hours, dried plastic grain is added in injection machine, notes Mould sample preparation.Wherein injection machine temperature is 160 DEG C of a district, two 180 DEG C of districts, three 200 DEG C of districts, and cooling procedure is 80 DEG C of 6min, 30 DEG C 8min, opens mould and i.e. obtains automobile baffle.
The automobile baffle prepared embodiment of the present invention 1-3 and comparative example 1-4 respectively detects, and with polyphenylene oxide/poly- Amide alloy automobile baffle plate as a comparison case 5, detects it, and result is as shown in table 1.
The material properties test result of automobile baffle prepared by table 1 embodiment of the present invention
The material properties test result of automobile baffle prepared by continued 1 embodiment of the present invention
Shape recovery rate η=(I1-I2)/(I1-I0) × 100%, wherein I0For original length, I1For length, I after deformation2 For length after replying.In table 1, shape recovery rate, recovery of shape time are used for weighing the shape-memory properties of automobile baffle, test Temperature is 85 DEG C.Shrinkage factor is used for weighing automobile baffle dimensional stability quality.
The test result corresponding from embodiment 1-3 is it can be seen that automobile baffle prepared by the present invention has reached the stone of routine The mechanical property of the automobile baffle of oil base plastic production, and there is preferable shape recovery rate and dimensional stability.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.The technology of the industry The personnel simply present invention it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and description Principle, the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, these change and Improvement both falls within the range of claimed invention.The protection domain of application claims by appending claims and Equivalent defines.

Claims (10)

1. a shape memory automobile baffle, it is characterised in that prepared by following component:
Shape memory automobile baffle the most according to claim 1, it is characterised in that the structure of described polyhydroxyalkanoate Formula is as shown in Equation 1:
[-O-CHR1-(CH2)X-CO-O-CHR2-(CH2)Y-COO-]n
Formula 1),
Wherein, R1For phenethyl, R2For the carbon atom number alkyl less than 6, X < 5,4 < Y < 7, number-average molecular weight is 40000- 50000。
Shape memory automobile baffle the most according to claim 1, it is characterised in that described calcium sulfate crystal whiskers a diameter of 2.5-3.5 micron, average aspect ratio is 20-30.
Shape memory automobile baffle the most according to claim 1, it is characterised in that the number-average molecular weight of described polylactic acid is 30000-40000。
Shape memory automobile baffle the most according to claim 1, it is characterised in that described cross-linking agent is dialkyl group peroxidating Thing.
6. the preparation method of a shape memory automobile baffle, it is characterised in that comprise the following steps:
55-70 weight portion polyhydroxyalkanoate and 9-18 weight portion polylactic acid are mixed, obtains mixture A;
In 20-25 parts sulfuric acid calcium pyroborate, add 0.5-1 weight portion coupling agent, stirring, obtain activating calcium sulfate crystal whiskers;
Described mixture A, activation calcium sulfate crystal whiskers, 0.2-0.5 parts by weight of crosslinking agent and 0.3-0.5 weight portion light stabilizer are added Enter in double screw extruder, extruding pelletization, obtain plastic grain, head temperature is 170-200 DEG C, screw speed 80-120r/ min;
Described plastic grain is dried, after injection mo(u)lding, obtains shape memory automobile baffle.
Preparation method the most according to claim 6, it is characterised in that obtain in the step of activation calcium sulfate crystal whiskers, stirring Time is 5-10min, and mixing speed is that 20-40 turns/min.
Preparation method the most according to claim 6, it is characterised in that obtain in the step of plastic grain, twin-screw extrusion The prilling temperature of machine is 130-150 DEG C of a district, two 150-160 DEG C of districts, three 160-170 DEG C of districts, four 170-180 DEG C of districts, 5th district 180-190℃。
Preparation method the most according to claim 6, it is characterised in that obtain, in the step of shape memory automobile baffle, moulding The baking temperature of material granule is 60-80 DEG C, and drying time is 5-8 hour.
Preparation method the most according to claim 6, it is characterised in that described injection mo(u)lding particularly as follows:
Being added in injection machine by dried plastic grain, injection machine temperature is 150-160 DEG C of a district, two 160-180 DEG C of districts, three 180-200 DEG C of district, is subsequently cooled to 80-85 DEG C of insulation 5-7min, continues cool to 20-30 DEG C of insulation 5-8min.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107337877A (en) * 2017-07-31 2017-11-10 武汉理工大学 A kind of mono-oriented crystal whisker of gypsum/polyvinyl chloride composite materials and preparation method thereof
CN111469390A (en) * 2019-01-24 2020-07-31 现代自动车株式会社 Method for recovering vehicle panel using shape memory polymer

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CN103030957A (en) * 2012-12-25 2013-04-10 深圳大学 Material based on polyhydroxyalkanoate and preparation method and application of material
CN105462193A (en) * 2014-09-03 2016-04-06 东北林业大学 Whisker reinforced biodegradable polyester composite material and preparation method

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US20120303056A1 (en) * 2011-05-06 2012-11-29 Guoqiang Li Thermosetting Shape Memory Polymers with Ability to Perform Repeated Molecular Scale Healing
CN103030957A (en) * 2012-12-25 2013-04-10 深圳大学 Material based on polyhydroxyalkanoate and preparation method and application of material
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107337877A (en) * 2017-07-31 2017-11-10 武汉理工大学 A kind of mono-oriented crystal whisker of gypsum/polyvinyl chloride composite materials and preparation method thereof
CN107337877B (en) * 2017-07-31 2019-11-26 武汉理工大学 A kind of mono-oriented crystal whisker of gypsum/polyvinyl chloride composite materials and preparation method thereof
CN111469390A (en) * 2019-01-24 2020-07-31 现代自动车株式会社 Method for recovering vehicle panel using shape memory polymer

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