CN109776961A - A kind of non-polar polymer negative poisson's ratio foamed material and preparation method thereof - Google Patents
A kind of non-polar polymer negative poisson's ratio foamed material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of non-polar polymer negative poisson's ratio foamed materials and preparation method thereof, belong to functional polymer foam technology field.That this method solve the preparation method preparation process of negative poisson's ratio polymer foams in the prior art is cumbersome, preparation efficiency is low, it is restricted to polymer, be unfavorable for the technical issues of large-scale production.Preparation method of the invention, non-polar polymer and hydrophile composite molding are first prepared into composite material, then composite material is placed in foaming machine, introduce physical blowing agent and water, under 80~180 DEG C of saturation temperature and the saturation pressure of 3~25MPa, saturation time 0.5h or more, then quick pressure releasing obtain non-polar polymer negative poisson's ratio foamed material.This method can one-step method composite material is prepared into negative poisson's ratio foamed material, preparation process is simple, and preparation efficiency is high, highly-safe, environmentally protective, can prepare large scale negative poisson's ratio foamed material, be suitble to large-scale production.
Description
Technical field
The invention belongs to functional polymer foam technology fields, and in particular to a kind of negative Poisson of non-polar polymer
Than foamed material and preparation method thereof.
Background technique
Poisson's ratio (ν) is a kind of mechanical property of material.French mathematician simon Poisson by it is defined as: stretching experiment
Middle material cross-direction shrinkage strains (εx) and longitudinal elongation strain (εy) ratio, it is the important parameter of a reaction material property.
It is formulated as follows:
ν=- εx/εy
The Poisson's ratio of most of materials is positive value, such as rubber material, and cross-direction shrinkage occurs when being stretched for they, and
Lateral expansion occurs when being compressed.However, there is also have a small number of negative poisson's ratio materials, also referred to as auxetic materials (auxetic
materials).Natural negative poisson's ratio material has pyrite, skin of cat etc..Made negative poisson's ratio material has poly- ammonia
Ester (PU) foam, polyethylene (PE) foam etc..Negative poisson's ratio material has typical Negative poisson's ratio, the hair when being stretched
Raw lateral expansion, cross-direction shrinkage occurs when being compressed.Due to this unique property, make this kind of material that there is resistance to indentation
Greatly, the excellent performances such as modulus of shearing is high, yield strength is high, rebound good toughness, anti-notch performance is good, fracture toughness is big, so
In baffle, insulation, buffer, back cushion, especially artificial intervertebral disc, artificial blood vessel, sandwich sheet, fastener, safety belt, with
And the fields such as carrier material of catalyst converter have broad application prospects in internal combustion engine.
Negative poisson's ratio polymer foams are using polymer as matrix, and being become by different preparation methods has
The foamed material of Negative poisson's ratio.In the prior art, preparing the most common method of negative poisson's ratio polymer foams is three
Axis compression method, if patent WO2010049511 discloses a kind of preparation method of negative poisson's ratio foamed material, this method uses three
Using acetone as processing solvent while axis compresses, it is prepared for the negative poisson's ratio foamed material with more regular foam structure；
But the use of a large amount of volatile organic solvents brings environmental pollution and product safety hidden danger, solvent removal and drying in this method
Process considerably increases manufacturing complexity and process time, and the foamed material of acquisition has typical strain dependent form Poisson's ratio.
In addition, prepare in the prior art the methods of negative poisson's ratio polymer foams there are also vacuum-heating, high pressure-heating with
And Steam soak condensation method etc..Such as Martz under high pressure or vacuum condition, realize from conventional ethylene closed cell foam to
The transformation of negative poisson's ratio foam, although this method technique is relatively easy, preparation foamed material can only (32% answers in small deformation
Become) under obtain negative poisson's ratio.Fan etc. is prepared for closed-cell polyethylene negative poisson's ratio bubble using Steam soak condensation method under normal pressure
Foam, this method whole process carries out under normal pressure, low for equipment requirements, and preparation process is simple, and due to being completed using water vapour auxiliary
Preparation, thus it is highly-safe, it is environmentally protective, larger-size negative poisson's ratio polymer foams can be prepared, are suitble to extensive
Production；But this method is limited by type of polymer, fusing point and softening point etc..
Summary of the invention
In view of this, the present invention provides a kind of non-polar polymer negative poisson's ratio foamed material and preparation method thereof, solve
The preparation method preparation process of negative poisson's ratio polymer foams is cumbersome in the prior art, preparation efficiency is low, has to polymer
It limits, be unfavorable for the technical issues of large-scale production.
It is as follows that the present invention solves the technical solution that above-mentioned technical problem is taken.
The preparation method of non-polar polymer negative poisson's ratio foamed material, comprising the following steps:
Step 1: non-polar polymer is compound with hydrophile, molding obtains hydrophile and accounts for 0.2wt%~40wt%'s
Composite material；
Step 2: the composite material that step 1 is obtained is placed in foaming machine, physical blowing agent and water are introduced, 80~
Under 180 DEG C of saturation temperature and the saturation pressure of 3~25MPa, saturation time 0.5h or more, quick pressure releasing obtains nonpolarity
Polymer negative poisson's ratio foamed material.
Preferably, while the non-polar polymer and hydrophile are compound, composite assistant is gone back.
Preferably, the auxiliary agent be calcium carbonate powder, talcum powder, wollastonite powder, SiO 2 powder, aluminium oxide,
Aluminium hydroxide, magnesia, aluminium hydroxide, zinc oxide, titanium dioxide, zirconium oxide, barium monoxide, barium sulfate, active carbon, carbon black, carbon
Nanotube, carbon fiber, graphene, graphene oxide, manganese dioxide, the oxide of iron, the oxide of nickel, iron powder, iron fiber, copper
Powder, copper fiber, stainless steel powder, stainless steel fibre, nickel powder, nickel fiber, silver powder, silver fiber, bronze, golden fiber, wood powder, bamboo powder,
The mixture of one or more of powdered rice hulls, straw powder.
Preferably, the compound method is that addition mixer is compound or addition extruder is compound, the molding side
Method is extruding pelletization, extrusion molding, calendering formation, compression molding or injection molding.
Preferably, the non-polar polymer is polyethylene, ethylene copolymer, polypropylene, propylene copolymer, poly- fourth
Alkene, butylene copolymer, polystyrene, polybutadiene, polyisoprene, olefin hydrocarbons thermoplasticity elastic body, styrene analog thermoplastic
One of polymer or a variety of mixtures；
It is further preferred that the olefin hydrocarbons thermoplasticity elastic body be ethylene propylene diene rubber-polypropylene thermoplastic vulcanized rubber,
Ethylene propylene diene rubber-polythene thermoplastic vulcanized rubber, natural rubber-polypropylene thermoplastic vulcanized rubber, the poly- second of natural rubber-
Olefinic thermoplastic vulcanized rubber, isoprene-polypropylene thermoplastic vulcanized rubber, isoprene-polythene thermoplastic vulcanized rubber,
One of butadiene rubber-polypropylene thermoplastic vulcanized rubber, butadiene rubber-polythene thermoplastic vulcanized rubber is a variety of mixed
Close object；
The styrene analog thermoplastic polymer is styrene-butadiene block copolymer, styrene-butadiene-benzene second
Alkene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene/butylene-styrene block copolymerization
One of object or a variety of mixtures.
Preferably, the hydrophile be hydrophilic macromolecule, hydrophilic organics hydrophilicity, water absorbing inorganic object powder, can
One of molten inorganic salts or a variety of mixtures；
It is further preferred that the hydrophilic macromolecule be polyethylene glycol, ethylene-vinyl acetate copolymer, polypropylene glycol,
Polyvinyl acetate, polyacrylamide, poly- (methyl) acrylic acid, poly- (methyl) acrylate, poly- (methyl) acrylates, starch,
Cellulose, polypropylene-polyethyleneglycol-graft copolymer, polypropylene-polyethyleneglycol block copolymer, polyethylene-polyethylene alcohol connect
Graft copolymer, polyethylene-polyethylene alcohol block copolymer, polystyrene-poly ethylene glycol graft copolymer, polystyrene-poly second
One of diol block copolymer or a variety of mixtures；
The hydrophilic organics hydrophilicity is ethylene glycol, propylene glycol, glycerol, pentaerythrite, stearic acid, stearic acid sodium salt, tristearin
Acid potassium salt, stearic acid calcium salt, stearic acid zinc salt, palmitic acid, palmitic acid sodium salt, palmitin acid potassium salt, palmitin acid calcium salt, zinc palmitate
Salt, adipic acid, adipic acid sodium salt, adipic acid sylvite, adipic acid calcium salt, adipic acid zinc salt, suberic acid, suberic acid sodium salt, pungent two
Acid potassium salt, suberic acid calcium salt, suberic acid zinc salt, decanedioic acid, decanedioic acid sodium salt, decanedioic acid calcium salt, decanedioic acid zinc salt, hexamethylene diamine,
Octamethylenediamine, melamine, oleamide, erucyl amide, cetyl trimethylammonium bromide, dodecyl polyoxyethylene ether, ten
Tetraalkyl polyoxyethylene ether, cetyl polyoxyethylene ether, Steareth, alkyl phenol polyoxyethylene ether, palmitin
Acid glyceride, tristerin, department Pan's series of surfactants, TWEEN Series surfactant, bromide sixteen alkyls pyridine,
Bromododecane yl pyridines, lauryl sodium sulfate, neopelex, hexadecanyl phosphate, octadecyl phosphoric acid
One of ester or a variety of mixtures；
The water absorbing inorganic object powder is expanded perlite, expanded vermiculite, sepiolite, montmorillonite, diatomite, concave convex rod
One of stone, bentonite, sepiolite, zeolite, molecular sieve or a variety of mixtures；
The solvable inorganic salts are the sulfuric acid of the borate of sodium, the carbonate of sodium, the nitrate of sodium, the phosphate of sodium, sodium
Salt, the chloride salt of sodium, the bromide salt of sodium, the borate of potassium, the carbonate of potassium, the nitrate of potassium, the phosphate of potassium, potassium
Sulfate, the chloride salt of potassium, the bromide salt of potassium, the borate of magnesium, the carbonate of magnesium, the nitrate of magnesium, magnesium phosphate,
The sulfate of magnesium, the chloride salt of magnesium, the bromide salt of magnesium, the borate of calcium, the carbonate of calcium, the nitrate of calcium, calcium phosphorus
Hydrochlorate, the sulfate of calcium, the chloride salt of calcium, the bromide salt of calcium, the borate of aluminium, the carbonate of aluminium, the nitrate of aluminium, aluminium
Phosphate, the sulfate of aluminium, the chloride salt of aluminium, the bromide salt of aluminium, the borate of iron, the carbonate of iron, iron nitric acid
Salt, the phosphate of iron, the sulfate of iron, the chloride salt of iron, the bromide salt of iron, ferrous borate, ferrous carbonate,
Ferrous nitrate, ferrous phosphate, ferrous sulfate, ferrous chloride salt, ferrous bromide salt, copper boric acid
Salt, the carbonate of copper, the nitrate of copper, the phosphate of copper, the sulfate of copper, the chloride salt of copper, the bromide salt of copper, zinc
The bromide salt of borate, the carbonate of zinc, the nitrate of zinc, the phosphate of zinc, the sulfate of zinc, the chloride salt of zinc, zinc
One of or a variety of mixtures.
Preferably, in the composite material, hydrophile accounts for 2wt%~20wt%.
Preferably, the physical blowing agent is carbon dioxide (CO2), nitrogen (N2), butane, one of pentane or more
The mixture of kind；It is further preferred that the physical blowing agent is CO2Or/and N2。
Preferably, the saturation temperature is 90~170 DEG C；It is further preferred that the saturation temperature is 100~170 DEG C.
Preferably, the saturation pressure is 5~16MPa.
Preferably, the saturation time is 0.5~10h；It is further preferred that the saturation time is 0.5~8h.
Preferably, the pressure release speed of the quick pressure releasing is 2~50MPa/s.
The present invention also provides the nonpolarity of the preparation method preparation by above-mentioned non-polar polymer negative poisson's ratio foamed material
Polymer negative poisson's ratio foamed material.
Compared with prior art, the invention has the benefit that
The preparation method of non-polar polymer negative poisson's ratio foamed material of the invention proposes one kind in foaming process
Non-polar polymer is directly prepared into the new method of negative poisson's ratio foamed material, improves preparation efficiency.
The preparation method of non-polar polymer negative poisson's ratio foamed material of the invention, do not need in the process using acetone,
The volatile organic solvents such as ether, it is highly-safe, it is environmentally protective.
The preparation method simple process of non-polar polymer negative poisson's ratio foamed material of the invention, production cost is low, can
Larger-size negative poisson's ratio polymer foams are prepared, large-scale production is suitble to.
Non-polar polymer negative poisson's ratio foamed material of the invention is low to the degree of restriction of type of polymer and physical property,
Has universality.
Non-polar polymer negative poisson's ratio foamed material of the invention is with resistance to indentation is big, modulus of shearing is high, surrender is strong
The excellent performances such as degree is high, rebound good toughness, anti-notch performance is good, fracture toughness is big, baffle, insulation, buffer, back cushion,
Footwear material, especially catalyst turns in artificial intervertebral disc, artificial blood vessel, sandwich sheet, manufacture fastener or safety belt, internal combustion engine
Change the fields such as the carrier material of device to have broad application prospects.
Detailed description of the invention
Fig. 1 is the process flow chart of the preparation method of non-polar polymer negative poisson's ratio foamed material of the invention；
Fig. 2 is the SEM photograph of polypropylene negative poisson's ratio foamed material prepared by the embodiment of the present invention 1；
Fig. 3 is the SEM photograph of polyethylene negative poisson's ratio foamed material prepared by the embodiment of the present invention 2.
Specific embodiment
In order to further appreciate that the present invention, embodiment of the present invention is described in detail below, but it is to be understood that
The limitation that these descriptions only require for further explanation the features and advantages of the present invention rather than to the invention patent.
As shown in Figure 1, the preparation method of non-polar polymer negative poisson's ratio foamed material of the invention, steps are as follows:
Step 1: first that non-polar polymer is compound with hydrophile, molding obtains composite material；
Step 2: the composite material that step 1 is obtained is placed in foaming machine, physical blowing agent and water are introduced, 80~
Under 180 DEG C of saturation temperature and the saturation pressure of 3~25MPa, saturation time 0.5h or more, quick pressure releasing obtains nonpolarity
Polymer negative poisson's ratio foamed material.
In above-mentioned technical proposal, non-polar polymer and hydrophile it is compound during, field technical staff can be with root
According to experience and demand in system composite assistant, specifically can be with composite calcium carbonate powder, talcum powder, wollastonite powder, titanium dioxide
Si powder, aluminium oxide, aluminium hydroxide, magnesia, aluminium hydroxide, zinc oxide, titanium dioxide, zirconium oxide, barium monoxide, barium sulfate,
Active carbon, carbon black, carbon nanotube, carbon fiber, graphene, graphene oxide, manganese dioxide, the oxide of iron, nickel oxide,
Iron powder, iron fiber, copper powder, copper fiber, stainless steel powder, stainless steel fibre, nickel powder, nickel fiber, silver powder, silver fiber, bronze, gold are fine
One or more of dimension, wood powder, bamboo powder, powdered rice hulls, straw powder reach reduction on the basis of not destroying system foam performance
The purpose of increased costs performance, the additive amount of usual auxiliary agent are 0.1%VOL~10%VOL.
In above-mentioned technical proposal, non-polar polymer is that hetero atom (chlorine, fluorine, silicon, ether are not contained on polymer molecular chain
Deng) or polar group (amide, carboxylic acid (ester, salt), hydroxyl, amino, ester group, cyano etc.) thermoplastic polymer, as polyethylene,
Ethylene copolymer, polypropylene, propylene copolymer, polybutene, butylene copolymer, polystyrene, polybutadiene, polyisoprene,
One of olefin hydrocarbons thermoplasticity elastic body, styrene analog thermoplastic polymer or a variety of mixtures.Wherein, olefin type thermoplastic
Property elastomer be that ethylene propylene diene rubber-polypropylene thermoplastic vulcanized rubber, ethylene propylene diene rubber-polythene thermoplastic vulcanize rubber
Glue, natural rubber-polypropylene thermoplastic vulcanized rubber, natural rubber-polythene thermoplastic vulcanized rubber, isoprene-poly- third
Olefinic thermoplastic vulcanized rubber, isoprene-polythene thermoplastic vulcanized rubber, butadiene rubber-polypropylene thermoplastic vulcanized rubber
Or one of butadiene rubber-polythene thermoplastic vulcanized rubber or a variety of mixtures；Styrene analog thermoplastic polymer can
Think styrene-butadiene block copolymer, Styrene-Butadiene-Styrene Block Copolymer, styrene-isoprene-benzene
One of ethylene block copolymer, styrene-ethylene/butylene-styrene block copolymer or a variety of mixtures.But not
It is limited to polymer kind listed above.
In above-mentioned technical proposal, hydrophile be hydrophilic macromolecule, hydrophilic organics hydrophilicity, water absorbing inorganic object powder, can
One of molten inorganic salts or a variety of mixing.Wherein, hydrophilic macromolecule can be total for polyethylene glycol, ethene-vinyl acetate
Polymers, polypropylene glycol, polyvinyl acetate, polyacrylamide, poly- (methyl) acrylic acid, poly- (methyl) acrylate, poly- (methyl)
Acrylates, starch, cellulose, polypropylene-polyethyleneglycol-graft copolymer, polypropylene-polyethyleneglycol block copolymer, poly- second
The polyvinyl alcohol graft copolymerized copolymer of alkene-, polyethylene-polyethylene alcohol block copolymer, polystyrene-poly ethylene glycol graft copolymer,
One of polystyrene-poly ethylene glycol block copolymer or a variety of mixtures；Hydrophilic organics hydrophilicity can be ethylene glycol, third
Glycol, glycerol, pentaerythrite, stearic acid, stearic acid sodium salt, stearic acid sylvite, stearic acid calcium salt, stearic acid zinc salt, palmitic acid,
Palmitic acid sodium salt, palmitin acid potassium salt, palmitin acid calcium salt, palmitic acid zinc salt, adipic acid, adipic acid sodium salt, adipic acid sylvite, oneself two
Acid calcium salt, adipic acid zinc salt, suberic acid, suberic acid sodium salt, suberic acid sylvite, suberic acid calcium salt, suberic acid zinc salt, decanedioic acid,
Decanedioic acid sodium salt, decanedioic acid calcium salt, decanedioic acid zinc salt, hexamethylene diamine, octamethylenediamine, melamine, oleamide, erucyl amide, ten
Six alkyl trimethyl ammonium bromides, dodecyl polyoxyethylene ether, myristyl polyoxyethylene ether, cetyl polyoxyethylene ether,
Steareth, alkyl phenol polyoxyethylene ether, tripalmitin, tristerin, department Pan's series surface are living
Property agent, TWEEN Series surfactant, bromide sixteen alkyls pyridine, bromododecane yl pyridines, lauryl sodium sulfate, 12
One of sodium alkyl benzene sulfonate, hexadecanyl phosphate, octadecyl phosphate or a variety of mixtures；Water absorbing inorganic object
Powder can be expanded perlite, expanded vermiculite, sepiolite, montmorillonite, diatomite, attapulgite, bentonite, sepiolite, boiling
One of stone, molecular sieve or a variety of mixtures；Solvable inorganic salts can be the nitre of the borate of sodium, the carbonate of sodium, sodium
Hydrochlorate, the phosphate of sodium, the sulfate of sodium, the chloride salt of sodium, the bromide salt of sodium, the borate of potassium, the carbonate of potassium, potassium
Nitrate, the phosphate of potassium, the sulfate of potassium, the chloride salt of potassium, the bromide salt of potassium, the borate of magnesium, magnesium carbonic acid
Salt, the nitrate of magnesium, the phosphate of magnesium, the sulfate of magnesium, the chloride salt of magnesium, the bromide salt of magnesium, the borate of calcium, calcium
Carbonate, the nitrate of calcium, the phosphate of calcium, the sulfate of calcium, the chloride salt of calcium, the bromide salt of calcium, aluminium borate,
The carbonate of aluminium, the nitrate of aluminium, the phosphate of aluminium, the sulfate of aluminium, the chloride salt of aluminium, the bromide salt of aluminium, iron boron
Hydrochlorate, the carbonate of iron, the nitrate of iron, the phosphate of iron, the sulfate of iron, the chloride salt of iron, the bromide salt of iron, Asia
The borate of iron, ferrous carbonate, ferrous nitrate, ferrous phosphate, ferrous sulfate, ferrous chloride
Salt, ferrous bromide salt, the borate of copper, the carbonate of copper, the nitrate of copper, the phosphate of copper, the sulfate of copper, copper
Chloride salt, the bromide salt of copper, the borate of zinc, the carbonate of zinc, the nitrate of zinc, the phosphate of zinc, zinc sulfate,
One of bromide salt of the chloride salt of zinc, zinc or a variety of mixtures.
In above-mentioned technical proposal, it is excellent to account for 0.2wt%~40wt% for hydrophile in non-polar polymer/hydrophile composite material
Select 2wt%~20%.
In above-mentioned technical proposal, compound and molding is the common knowledge of those skilled in the art, is not particularly limited, multiple
The method of conjunction can be compound for addition mixer or addition extruder is compound, and molding method can be extruding pelletization, be extruded into
Type, calendering formation, compression molding or injection molding.Composite material can be graininess, and the size of any needs can also be made
And shape.
In above-mentioned technical proposal, foaming machine is polymer foaming commonly used equipment, such as autoclave, molding, box foaming machine,
But not limited to this, polymer foaming is realized in the operation such as all achievable pressure maintainings, the injection and infiltration of foaming agent and water, quick pressure releasing
Equipment can be used as foaming machine of the invention and use.
In above-mentioned technical proposal, physical blowing agent CO2、N2, butane, one of pentane or a variety of mixtures.Consider
To the production safety of gas, environmental protection and production cost, preferably physical blowing agent is CO2Or/and N2。
The process conditions of preparation method of the invention:
Temperature is selected at 80~180 DEG C, because if temperature is lower than 80 DEG C, foamed polymer matrices are ineffective, if
Temperature is higher than 180 DEG C, and the melt strength of polymeric matrix is lower, and abscess, which is easy to happen, to be collapsed and rupture, and is unfavorable for negative poisson's ratio
Transformation.Preferable temperature is 90~170 DEG C, more preferably 100~170 DEG C.
Pressure selection is in 3~25MPa, because pressure is lower than 3MPa, the abscess of non-polar polymer foam is larger, and mechanics is strong
Spend lower, and when pressure is higher than 25MPa, the melt strength of non-polar polymer resin matrix bears incessantly so big pressure,
The phenomenon that prepared foam will appear holes, is unfavorable for negative poisson's ratio transformation.Saturation pressure is preferably 5~16MPa.
The infiltration of physical blowing agent needs the regular hour, too low lower than the physical blowing dosage that 0.5h then penetrates into, foaming
Not exclusively.Consider preparation efficiency, standing time is preferably 0.5~10h, more preferably 0.5~8h.
The process of quick pressure releasing is to make non-polar polymer/hydrophile composite material foaming.It specifically may is that opening
After the pressure relief valve of foaming machine, pressure in foaming machine is quickly reduced to normal pressure from blow pressure, or first set foaming
Standby interior pressure quickly drops to normal pressure after quickly dropping to some intermediate pressure again, or divides the pressure in foaming machine to several stages
It is quickly reduced to normal pressure.It is preferred that the pressure release speed of quick pressure releasing is 2~50MPa/s.Non-polar polymer/hydrophile of the invention
Completion foaming outside foaming machine can be discharged with pressure release gas and obtain negative poisson's ratio foam material in pressure release foaming process for composite material
Material can also be retained in after completing foaming in foaming machine and further take out to obtain negative poisson's ratio foamed material.
The present invention also provides the apolar polymerics of above-mentioned non-polar polymer negative poisson's ratio foamed material preparation method preparation
Object negative poisson's ratio foamed material.Negative poisson's ratio can be -0.3~-0.8.
The present invention is further illustrated with reference to embodiments.
Embodiment 1
First 98:2 in mass ratio adds twin-screw extrude polypropylene (Daqing petrochemical, T30S) with sodium chloride, is kneaded
200 DEG C of Duan Wendu, 200 turns/min of revolving speed, extruding pelletization, then 10 × 10 × 10mm is made with injection molding machine3Cube composite wood
Material；Then composite material is placed in the CO of 180 DEG C, 3MPa2After 10h in the foaming machine of water, pressure release to normal pressure, pressure release speed
For 2MPa/s, composite material, with completing to foam outside pressure release gas discharge foaming machine, obtains polypropylene in pressure release foaming process
Negative poisson's ratio foamed material.
Through detecting, which has the foam structure with " re-entrant angle ", and SEM photograph is as shown in Figure 2；The material Poisson
Than being detected according to GB/T1040.1-2006 standard, Poisson ratio is -0.8.
Embodiment 2
First high density polyethylene (HDPE) (Fushun petrochemical industry, FHC7260) and odium stearate are added twin-screw and squeezed by 96:4 in mass ratio
Machine out, 200 DEG C of mixing section temperature, extruding pelletization, then 50 × 50 × 20mm is made with injection molding machine3Flaky composite material, injection molding
195 DEG C of machine temperature；Then composite material is placed in the CO of 130 DEG C, 25MPa2After 0.5h in the foaming machine of water, pressure release is to normal
Pressure, pressure release speed are 50MPa/s, and composite material is retained in foaming machine in pressure release foaming process and completes foaming, then opens
Foaming machine takes out, and obtains polyethylene negative poisson's ratio foamed material.
Through detecting, which has the foam structure with " re-entrant angle ", and SEM photograph is as shown in Figure 3；The material Poisson
Than being detected according to GB/T1040.1-2006 standard, Poisson's ratio is -0.7.
Embodiment 3
First ethylene-octene copolymer (Dow, 7256), polyethylene vinyl acetate are copolymerized by 60:35:5 in mass ratio
Object (South Korea LG, EA19150) and talcum powder (1250 mesh), the melting mixing 10min in mixer, turn by 160 DEG C of mixer temperature
100 turns/min of speed, is put into spherical die while hot, is pressed into the spherical composite material that diameter is 20mm；Then compound by what is obtained
Material is placed in the N of 140 DEG C, 15MPa2After 4h in the foaming machine of water, pressure release to normal pressure, pressure release speed is 30MPa/s, compound
Material is retained in foaming machine in pressure release foaming process and completes foaming, then opens foaming machine taking-up, obtains negative poisson's ratio
Foamed material.
The material Poisson's ratio is detected according to GB/T1040.1-2006 standard, and Poisson's ratio is -0.5.
Embodiment 4
First 92:5:3 in mass ratio is de- by Styrene-Butadiene-Styrene Block Copolymer (Maoming Petrochemical, F675), illiteracy
Native (Sigma-Aldrich, K10) and oleamide are added in mixer and are kneaded 8min, and 150 DEG C of melting temperature, 100 turns of revolving speed/
Min obtains 3 × 3 × 2mm subsequently into extruding pelletization in single screw extrusion machine3Granular composite material；Then it will obtain
Composite material, be placed in the CO of 80 DEG C, 25MPa2, pentane and water foaming machine in after 5h, pressure release to normal pressure, pressure release speed is
25MPa/s, composite material, with completing to foam outside pressure release gas discharge foaming machine, obtain negative Poisson in pressure release foaming process
Compare foamed material.
Through detecting, which has reentrant features by Electronic Speculum observation, using the method for heat bonding by multiple bubbles
Foam is bonded into longer sample, is stretched to it, while measuring the change width in its stretched vertically direction, and Poisson is roughly calculated
Than being -0.3.
Embodiment 5
First 95:5 in mass ratio is by polyisoprene (Qingdao send the, TPT-II) and potassium octanoate addition single screw extrusion machine,
150 DEG C of mixing section temperature, extruding pelletization, and 60 × 60 × 20mm is made with injection molding machine3Flaky composite material, injection molding machine temperature
150 DEG C, obtain composite material；Then the composite material that will be obtained is placed in 110 DEG C, in the foaming machine of the butane of 3MPa and water
After 2h, pressure release to normal pressure, pressure release speed is 6MPa/s, and composite material is retained in complete in foaming machine in pressure release foaming process
At foaming, then foaming machine taking-up is opened, obtains negative poisson's ratio foamed material.
The material Poisson's ratio is detected according to GB/T1040.1-2006 standard, and Poisson's ratio is -0.7.
Embodiment 6
60:35:15 in mass ratio by polyisoprene (Qingdao sends, TPT-II), ethylene propylene diene rubber (three wells,
3092M) with ethylene-vinyl acetate copolymer (South Korea LG, EA19150), be added double screw extruder, 160 DEG C of mixing section temperature,
200 turns/min of revolving speed, extruding pelletization, and 60 × 60 × 20mm is made with injection molding machine3Flaky composite material, injection molding machine temperature
150℃；Then the composite material that will be obtained is placed in the CO of 130 DEG C, 10MPa2With 4h in the foaming machine of water, pressure release to normal pressure,
Pressure release speed is 4MPa/s, and composite material is retained in foaming machine in pressure release foaming process and completes foaming, then opens equipment
It takes out, obtains negative poisson's ratio foamed material.
The material Poisson's ratio is detected according to GB/T1040.1-2006 standard, and Poisson's ratio is -0.7.
It is above that certain exemplary embodiments of the invention are only described by way of explanation, undoubtedly, for ability
The those of ordinary skill in domain without departing from the spirit and scope of the present invention can be with a variety of different modes to institute
The embodiment of description is modified.Therefore, foregoing description is regarded as illustrative in nature, and should not be construed as wanting right of the present invention
Ask the limitation of protection scope.
Claims (10)
1. the preparation method of non-polar polymer negative poisson's ratio foamed material, which comprises the following steps:
Step 1: non-polar polymer is compound with hydrophile, molding obtains hydrophile and accounts for the compound of 0.2wt%~40wt%
Material；
Step 2: the composite material that step 1 is obtained is placed in foaming machine, physical blowing agent and water are introduced, 80~180
DEG C saturation temperature and 3~25MPa saturation pressure under, saturation time 0.5h or more, quick pressure releasing obtains apolar polymeric
Object negative poisson's ratio foamed material.
2. the preparation method of non-polar polymer negative poisson's ratio foamed material according to claim 1, which is characterized in that institute
While stating non-polar polymer and compound hydrophile, composite assistant is gone back.
3. the preparation method of non-polar polymer negative poisson's ratio foamed material according to claim 2, which is characterized in that institute
Stating auxiliary agent is calcium carbonate powder, talcum powder, wollastonite powder, SiO 2 powder, aluminium oxide, aluminium hydroxide, magnesia, hydrogen-oxygen
Change aluminium, zinc oxide, titanium dioxide, zirconium oxide, barium monoxide, barium sulfate, active carbon, carbon black, carbon nanotube, carbon fiber, graphene,
Graphene oxide, manganese dioxide, the oxide of iron, the oxide of nickel, iron powder, iron fiber, copper powder, copper fiber, stainless steel powder, no
One of rust steel fibre, nickel powder, nickel fiber, silver powder, silver fiber, bronze, golden fiber, wood powder, bamboo powder, powdered rice hulls, straw powder
Or several mixture.
4. the preparation method of non-polar polymer negative poisson's ratio foamed material according to claim 1, which is characterized in that institute
Stating non-polar polymer is polyethylene, ethylene copolymer, polypropylene, propylene copolymer, polybutene, butylene copolymer, polyphenyl second
One of alkene, polybutadiene, polyisoprene, olefin hydrocarbons thermoplasticity elastic body, styrene analog thermoplastic polymer are a variety of
Mixture；
The hydrophile is hydrophilic macromolecule, hydrophilic organics hydrophilicity, water absorbing inorganic object powder, one in solvable inorganic salts
Kind or a variety of mixtures.
5. the preparation method of non-polar polymer negative poisson's ratio foamed material according to claim 4, which is characterized in that institute
Stating olefin hydrocarbons thermoplasticity elastic body is ethylene propylene diene rubber-polypropylene thermoplastic vulcanized rubber, ethylene propylene diene rubber-polyethylene heat
Plasticity vulcanized rubber, natural rubber-polypropylene thermoplastic vulcanized rubber, natural rubber-polythene thermoplastic vulcanized rubber, isoamyl
Diene-polypropylene thermoplastic vulcanized rubber, isoprene-polythene thermoplastic vulcanized rubber, butadiene rubber-polypropylene thermoplastic
One of vulcanized rubber, butadiene rubber-polythene thermoplastic vulcanized rubber or a variety of mixtures；
The styrene analog thermoplastic polymer is styrene-butadiene block copolymer, s-B-S is embedding
Section copolymer, styrene-isoprene-styrene block copolymer, in styrene-ethylene/butylene-styrene block copolymer
One or more mixtures；
The hydrophilic macromolecule is polyethylene glycol, ethylene-vinyl acetate copolymer, polypropylene glycol, polyvinyl acetate, poly- third
Acrylamide, poly- (methyl) acrylic acid, poly- (methyl) acrylate, poly- (methyl) acrylates, starch, cellulose, polypropylene-are poly-
Ethylene glycol graft copolymer, polypropylene-polyethyleneglycol block copolymer, polyethylene-polyethylene alcohol graft copolymer, polyethylene-
Polyvinyl alcohol block copolymer, polystyrene-poly ethylene glycol graft copolymer, in polystyrene-poly ethylene glycol block copolymer
One or more mixtures；
The hydrophilic organics hydrophilicity is ethylene glycol, propylene glycol, glycerol, pentaerythrite, stearic acid, stearic acid sodium salt, potassium stearate
Salt, stearic acid calcium salt, stearic acid zinc salt, palmitic acid, palmitic acid sodium salt, palmitin acid potassium salt, palmitin acid calcium salt, palmitic acid zinc salt,
Adipic acid, adipic acid sodium salt, adipic acid sylvite, adipic acid calcium salt, adipic acid zinc salt, suberic acid, suberic acid sodium salt, suberic acid potassium
Salt, suberic acid calcium salt, suberic acid zinc salt, decanedioic acid, decanedioic acid sodium salt, decanedioic acid calcium salt, decanedioic acid zinc salt, hexamethylene diamine, pungent two
Amine, melamine, oleamide, erucyl amide, cetyl trimethylammonium bromide, dodecyl polyoxyethylene ether, the tetradecane
Base polyoxyethylene ether, cetyl polyoxyethylene ether, Steareth, alkyl phenol polyoxyethylene ether, palmitic acid are sweet
Grease, tristerin, department Pan's series of surfactants, TWEEN Series surfactant, bromide sixteen alkyls pyridine, bromo
Dococylpyridinium, lauryl sodium sulfate, neopelex, hexadecanyl phosphate, in octadecyl phosphate
One or more mixtures；
The water absorbing inorganic object powder be expanded perlite, expanded vermiculite, sepiolite, montmorillonite, diatomite, attapulgite,
One of bentonite, sepiolite, zeolite, molecular sieve or a variety of mixtures；
The solvable inorganic salts are sulfate, the sodium of the borate of sodium, the carbonate of sodium, the nitrate of sodium, the phosphate of sodium, sodium
Chloride salt, the bromide salt of sodium, the borate of potassium, the carbonate of potassium, the nitrate of potassium, the phosphate of potassium, potassium sulfuric acid
Salt, the chloride salt of potassium, the bromide salt of potassium, the borate of magnesium, the carbonate of magnesium, the nitrate of magnesium, the phosphate of magnesium, magnesium
Sulfate, the chloride salt of magnesium, the bromide salt of magnesium, the borate of calcium, the carbonate of calcium, the nitrate of calcium, calcium phosphate,
The sulfate of calcium, the chloride salt of calcium, the bromide salt of calcium, the borate of aluminium, the carbonate of aluminium, the nitrate of aluminium, aluminium phosphorus
Hydrochlorate, the sulfate of aluminium, the chloride salt of aluminium, the bromide salt of aluminium, the borate of iron, the carbonate of iron, the nitrate of iron, iron
Phosphate, the sulfate of iron, the chloride salt of iron, the bromide salt of iron, ferrous borate, ferrous carbonate, ferrous iron
Nitrate, ferrous phosphate, ferrous sulfate, ferrous chloride salt, ferrous bromide salt, copper borate,
The carbonate of copper, the nitrate of copper, the phosphate of copper, the sulfate of copper, the chloride salt of copper, the bromide salt of copper, zinc boron
Hydrochlorate, the carbonate of zinc, the nitrate of zinc, the phosphate of zinc, the sulfate of zinc, the chloride salt of zinc, zinc bromide salt in
One or more mixtures.
6. the preparation method of non-polar polymer negative poisson's ratio foamed material according to claim 1, which is characterized in that institute
It states in composite material, hydrophile accounts for 2wt%~20wt%.
7. the preparation method of non-polar polymer negative poisson's ratio foamed material according to claim 1, which is characterized in that institute
Stating compound method is that addition mixer is compound or addition extruder is compound, and the molding method is extruding pelletization, is extruded into
Type, calendering formation, compression molding or injection molding.
8. the preparation method of non-polar polymer negative poisson's ratio foamed material according to claim 1, which is characterized in that institute
Stating physical blowing agent is CO2、N2, butane, one or more of pentane mixture.
9. the preparation method of non-polar polymer negative poisson's ratio foamed material according to claim 1, which is characterized in that institute
Stating saturation temperature is 90~170 DEG C, and saturation pressure is 5~16MPa, and saturation time is 0.5~10h；The quick pressure releasing is let out
Pressure speed is 2~50MPa/s.
10. prepared by the preparation method of non-polar polymer negative poisson's ratio foamed material described in claim 1~9 any one
Non-polar polymer negative poisson's ratio foamed material.
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