CN102352069A - Beta crystal polypropylene tensile expandable material and preparation method thereof - Google Patents
Beta crystal polypropylene tensile expandable material and preparation method thereof Download PDFInfo
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- CN102352069A CN102352069A CN 201110249094 CN201110249094A CN102352069A CN 102352069 A CN102352069 A CN 102352069A CN 201110249094 CN201110249094 CN 201110249094 CN 201110249094 A CN201110249094 A CN 201110249094A CN 102352069 A CN102352069 A CN 102352069A
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Abstract
The invention discloses a beta crystal polypropylene tensile expandable material and a preparation method thereof. N,N'-dicyclohexyl-2,6-naphthalenedicarboxamide (DCNDCA) is used as a single beta crystal nucleating agent of isotactic polypropylene, and the adding amount of the DCNDCA is more than 0 and not more than 2 percent of the mass of the isotactic polypropylene. The nucleating agent and the isotactic polypropylene are blended by multiple modes of melt blending, solution blending and the like, so that the nucleating agent is uniformly dispersed in the polypropylene material. The material shows tensile expandable property in a certain strain range; and the tensile expandable property of the material is conveniently and flexibly controlled by formation control of polypropylene beta crystal, so that an alternative raw material with flexibility, convenience for making and high economical efficiency, isotropy and mechanical strength is provided for design and manufacture of more tensile expandable material products, the category of the domestic tensile expandable material is enriched, and support is provided for wider application of the tensile expandable material.
Description
Technical field
The present invention relates to a kind of polypropylene material and preparation method thereof, more particularly, relating to a kind of is the auxetic materials and preparation method thereof of main body with the polypropylene.
Background technology
The drawn expanded material; Or be called negative poisson's ratio material; Sometimes abbreviate auxetic materials as; Be usually for for the common material that people were familiar with respect to some; Like common rubber material; Its Poisson's ratio (being defined as the ratio of negative transvrsal strain and axial strain) is about 1/2, and during the stretching on receiving a certain direction (or compression), this type common material can shrink (or expansion) with it on the vertical direction.The drawn expanded material then has remarkable difference or opposite characteristics, and its Poisson's ratio is a negative value, during the stretching on receiving a certain direction (or compression), can expand (or contraction) with it on the vertical direction.
In fact, according to theory of elasticity, the Poisson's ratio of isotropic material can be between-1 and 1/2, and common material generally has the Poisson's ratio near 1/3, and Poisson's ratio is that the material of negative value is very rare.Early than 1987; R.S.Lakes has reported a kind of polyurethane foamed material with drawn expanded characteristic on Science; People find gradually and have developed some drawn expanded materials based on polymer gel, polymer molecular structure, polymer porous structure and polymer blending or composite structure subsequently, and some have the metallic substance (like cadmium, arsenic etc.) and the ceramic (like polycrystalline α-cristobalite, pyrolyzing graphite material etc.) of drawn expanded characteristics.The scientific research personnel of the Wang Wanlu of domestic Wei Gaoyuan like Peking University, University Of Chongqing, the Yang Mingbo of Sichuan University etc. and some other units is all doing a lot of valuable work aspect the drawn expanded material, and the summary introduction of some summary property has been arranged.
The drawn expanded material of having found has at present been contained polymer materials, metallic substance and ceramic; But can notice; The characteristics of the drawn expanded that it had also do not rely on the ownership of certain specific material in this three big material, and relevant with the special construction that is had.Described special construction comprises:
(1) belongs to grand, is situated between and sees the re-entrant angle porous trellises such as bi-dimensional cellular structure, measurements of the chest, waist and hips foamy structure and little vesicular structure of category.Being Poisson's ratio like R.S.Lakes in the drawn expanded structural foam of report in 1987 is-0.6 isotropy re-entrant angle porous structure material; Take special preparation technology can prepare isotropic foam copper material, its Poisson's ratio is about-0.8; Has the wideer little grid foam materials of anisotropy and Poisson's ratio span; It like Poisson's ratio little porous polyethylene material of-1.24; Its drawn expanded characteristic maybe be relevant with the special perk structure of microfilament fiber in this little grid material, and this structure has the characteristics of similar re-entrant angle porous trellis.Other also belongs to this type drawn expanded material like have expanded microporous polytetra fluoroethylene-EPTEE material, the micropore superhigh molecular weight polyethylene material etc. that obtain through special methods.Domestic Pan Zelin etc. have prepared the drawn expanded material (ZL200510130683.3) of this type of unlike material with the core that is controlled to be of special foamy structure.
(2) belong to the crystalline structure of Jie, microcosmic category.Metallic substance, ceramic and polymer materials all relate to the crystalline structure material.The characteristics of its constituting atom interphase interaction during based on body-centered cubic or face-centered cubic lattice distortion, a lot of materials demonstrate the characteristics that have negative poisson ' s ratio along crystal plane direction, and then show as the drawn expanded material on the macroscopic view.Can on a certain direction, show Poisson's ratio like cadmium and be about-0.4 character, other all belongs to the drawn expanded material of this type like materials such as arsenic, antimony, bismuth and basic metal, α-cristobalite, pyrolytic graphite, crystal gel, plasma crystals.About above-mentioned these metals and inorganic non-metallic drawn expanded material, a lot of bibliographical informations have been arranged.About the crystalline structure material of polymer class, its drawn expanded characteristic seldom has report, and only the refined grade of Li Liang has been reported the brilliant drawn expanded characteristic of the height-oriented α of uniaxial extension isotatic polypropylene at present, and has analyzed the brilliant architecture basics of its hinge type primary and secondary.
(3) belong to composite structure and the polymer blending structure that Jie sees category.Some are by the matrix material of anisotropy fiber filled; Its mechanical property isotropy on two dimension or three-dimensional; But have multilayered structure, the inner cross section of formation easily is star, the microvoid structure unit with interior re-entrant angle, shows the drawn expanded characteristic thus.Some multilayer hollow fibers are filled reinforced composite materials, and when the tubular fibre loading level reached certain volume fraction, this matrix material can show as the drawn expanded material.Wei Gaoyuan etc. think also can have negative poisson ' s ratio at isotropic spherical embedding thing through theoretical analysis.The special polyolefin blends (Vilaterm and polypropylene blend) of blend such as Yang Mingbo preparation; Poisson's ratio is-1.4; Its drawn expanded characteristic is attributed to the formation of blend material pore space structure in drawing process, and the modulus of material and intensity improve a lot than some porous negative poisson's ratio materials.Fu Zengli etc. then reported the research that the stretching volume expansion behavior to polypropylene/high density polyethylene(HDPE), polypropylene/high density polyethylene(HDPE)/SBS, polypropylene/SBS carries out; But do not provide the negative poisson ' s ratio data of material or the evidence of typical drawn expanded behavioral trait, being difficult to clearly define is typical drawn expanded material.
(4) belong to the special molecular structure of microcosmic category.The structure that has the type like the polymer gel material on the molecular level, polymer liquid crystal material etc.On molecular level, carry out similar cellular inner recess structure Design and structure, as being the backbone molecule structure with the liquid crystalline polymers, the molecular cell with club shaped structure is a side chain simultaneously, can realize the design and the structure of the drawn expanded performance of material.
(5) other ad hoc structure.The drawn expanded material also possibly have some other ad hoc structure basis.
More than be based on the simple division that the structure on the different scale is carried out the drawn expanded material.Someone tends to think; These all drawn expanded materials all have the architecture basics of hinge type, and under stretching action, this hinge arrangement is opened; Make bill of material reveal the drawn expanded characteristic, so the drawn expanded characteristic of material and hinge-type structure characteristic are closely related.However, carry out the design of specific drawn expanded material and the practice that structure still needs people constantly to make great efforts intensification understanding and pay.Certainly, the drawn expanded Development of Materials drives and also be unable to do without cognition, expectation and the constantly pursuit of people to its excellent properties.
The excellent part of drawn expanded material is, based on its specific structure basis, can make material have a lot of performances of significantly improving, as improving shearing modulus, anti-breach and the ability of anti-fracture and the resilience toughness of material; Through influence elastic force in the hole or the distribution in slit influence the transmission and the reflection characteristic of elastic wave; Can reduce impulse force better to be used as buffer protection material or mechanical resistance damping material; Have special elasticity and sound absorbing power and be used as sound-proof material etc.Particularly, can use some vibroshocks of drawn expanded made, air filter, nose cone, road traffic protective grating, bullet-proof vest and wrister, fistfight clothing or the armor, sealing equipment etc.This shows that drawn expanded material extensively model is applied to national economy field and national defence fields such as aerospace, electronics and computer, safety precaution, medical science.But must notice that also different Application Areass is concrete and discrepant to the requirement of drawn expanded material, and various drawn expanded material also have separately characteristics and corresponding suitability.On the low side like some based on the intensity of the drawn expanded material of micro polymer foam structure; And some drawn expanded materials that constitute based on the metallic substance of foam structure or crystalline texture or non-metallic material is flexible not enough, through polymer blending or compound some drawn expanded materials that obtain often because the existence at interface causes the relative reduction of mechanics of materials intensity.In addition, should also be noted that some drawn expanded anisotropy of material characteristic can limit it and use, and the technology of preparing of a lot of drawn expanded materials is also more numerous and diverse.
Summary of the invention
Based on the above-mentioned background technology; The objective of the invention is to; A kind of beta-crystal polypropylene drawn expanded material and preparation method thereof is provided; This material shows the drawn expanded characteristic in certain range of strain; And can regulate and control easily and flexibly its drawn expanded characteristic through the brilliant formation control of polypropylene beta; The design and the manufacturing of stretching the expanding material goods for Duola more provides a kind of flexibility thus; Simple for production and economical; Isotropy; The alternative starting material that mechanical strength is higher; To enrich the kind of domestic drawn expanded material, use more widely for the drawn expanded material and to provide support.
The object of the invention is achieved through following technical proposals:
Adopt N, N '-dicyclohexyl-2,6-aphthalimide (DCNDCA) be as the brilliant nucleator of the single β of isotatic polypropylene, its molecular structure as shown in Figure 1, its addition is greater than zero and be not more than 2% of isotatic polypropylene quality.Through multiple modes such as melt blending, solution blendings, nucleator and isotatic polypropylene are carried out blend, so that nucleator homodisperse in polypropylene material.
As adopt the mode of melt blending, the temperature of melt blending to select but be not limited to temperature condition commonly used on the industrial production, as 170 ℃～270 ℃.When the mode nucleator through melt blending and the blend of polypropylene material, concrete applicable banburying, open multiple compounding process such as refining, double-screw extruding pelletizing.
The homodisperse polypropylene material crystallization at room temperature that mixing back obtains, for example 20-25 ℃ Tc.
In the technical scheme of the present invention; The β crystal structure that under the effect of the brilliant nucleator of described β, in polypropylene, forms; Compare with the plain polypropylene material; Has the drawn expanded characteristic; And can be in the amount ranges of the brilliant nucleator of said this β; Through adjusting its actual amount and corresponding crystallization condition is regulated and control its crystalline texture, and then regulate and control the drawn expanded characteristic of this material flexibly and easily.
Polypropylene material of the present invention; In drawing process, show the behavioral trait of drawn expanded; Be the polypropylene material that contains the brilliant nucleator DCNDCA of β tensile stress strain curve like accompanying drawing 2 at 30 ℃; Wherein 0034; 0036; 0037 grade is labeled as the different stretch strain constantly; Scheming perpendicular to the WAXD on the draw direction corresponding to these different stretch strains material constantly; As shown in Figure 3; Compare with initial 0034; Material extending to 0036 obviously increases with 0037 o'clock long period; Confirmed that material has the marked inflation behavior on perpendicular to draw direction, promptly show the drawn expanded behavioral trait.
Polypropylene material of the present invention shows the drawn expanded characteristic under different temperature; Be (1wt%) polypropylene material of containing the brilliant nucleator DCNDCA of β tensile stress strain curve like accompanying drawing 4 at 60 ℃; Wherein 116,119,222 etc. be labeled as the different stretch strain constantly; Scheming perpendicular to the SAXS on the draw direction corresponding to these different stretch strains material constantly; As shown in Figure 5; Compare with initial 116; Material extending to 119 obviously increases with 222 o'clock long period, has confirmed that 60 ℃ of following materials are perpendicular to the drawn expanded behavioral trait on the draw direction.
All show the drawn expanded characteristic in the range of strain before the thin at a certain temperature neck of polypropylene material of the present invention occurs; Like Fig. 6 (1wt%) polypropylene material of containing the brilliant nucleator DCNDCA of β at 100 ℃ tensile stress strain curve; Wherein 0398; 0401; 0404 grade is labeled as the different stretch strain constantly; Corresponding to these different stretch strains material constantly perpendicular to the SAXS on the draw direction; As shown in Figure 7; Compare with initial 0398; Certain strain before the material extending to 0407 constantly; Pairing long period all has increase; And increasing degree appears increases the characteristic that afterwards reduces earlier, and showing before 100 ℃ of thin necks of following material production has the drawn expanded behavioral trait that strengthens afterwards to weaken earlier on perpendicular to draw direction.
Polypropylene material of the present invention is compared with the drawn expanded material based on metallic substance or non-metallic material, owing to be the main body with the polypropylene material of flexibility, obviously has flexible light weight and isotropic characteristics; Compared to the drawn expanded material of polymer foams base, avoided foam structure to cause the loss of mechanical strength, thereby mechanical strength is more excellent relatively; Drawn expanded material compared to some polymer blendings or composite material base; Interface brilliant by β and that amorphous portion constitutes is better than the interface in polymer blending or the matrix material; Reduced the defective that is easy to generate at the interface, integral material has more strong and unyielding equilibrium and more excellent mechanical strength relatively.
Use a kind of beta-crystal polypropylene drawn expanded material provided by the invention; Compare with the plain polypropylene material; Have the drawn expanded characteristic, thereby have other excellent properties such as ability and good power, sound, mechanical wave damping characteristic of higher shearing modulus, anti-breach and anti-fracture; Compare with the drawn expanded material of existing metallic substance and non-metallic material base, have flexible light weight and isotropic characteristics; Compare with foam of polymers type drawn expanded material and to have more excellent mechanical strength; Compare with matrix material with polymer blending, have stronger and more unyielding isostatic characteristics and more excellent mechanical strength relatively.Use a kind of beta-crystal polypropylene drawn expanded material provided by the invention; Can overcome prior art in the difficulty that is difficult to take into account simultaneously flexible and two aspects of mechanical strength aspect the drawn expanded material preparation; And prepare easy and economical; Can enrich the kind of domestic drawn expanded material, for more design and manufacturings with drawn expanded material product of premium properties provide a kind of suitable alternative starting material more.
Description of drawings
Fig. 1 N, N '-dicyclohexyl-2, the molecular chemistry formula of 6-aphthalimide (DCNDCA).
The polypropylene material that Fig. 2 contains the brilliant nucleator DCNDCA of β is at 30 ℃ tensile stress strain curve.
Fig. 3 contains the materials in polypropylene material different moment on 30 ℃ tensile stress strain curve of the brilliant nucleator DCNDCA of β is scheming (small angle X ray scattering) perpendicular to the SAXS on the draw direction.
The polypropylene material that Fig. 4 contains the brilliant nucleator DCNDCA of β is at 60 ℃ tensile stress strain curve.
Fig. 5 contains the material in polypropylene material different stretch strain moment on 60 ℃ tensile stress strain curve of the brilliant nucleator DCNDCA of β to scheme perpendicular to the SAXS on the draw direction.
The polypropylene material that Fig. 6 contains the brilliant nucleator DCNDCA of β is at 100 ℃ tensile stress strain curve.
Fig. 7 contains the material in polypropylene material different stretch strain moment on 100 ℃ tensile stress strain curve of the brilliant nucleator DCNDCA of β to scheme perpendicular to the SAXS on the draw direction.
The polypropylene material that Fig. 8 contains the brilliant nucleator DCNDCA of β is at 80 ℃ tensile stress strain curve.
Fig. 9 contains the material in polypropylene material different stretch strain moment on 80 ℃ tensile stress strain curve of the brilliant nucleator DCNDCA of β to scheme perpendicular to the SAXS on the draw direction.
The dumb bell sample size of Figure 10 tensile stress-strain test usefulness.
Embodiment
Further specify technical scheme of the present invention below in conjunction with embodiment.
Take by weighing 100kg isotactic polypropylene (trade mark T1701); Amount according to its mass percent 0.1% takes by weighing DCNDCA nucleator 100g; With the polypropylene that taken by weighing and DCNDCA nucleator at room temperature through mixed at high speed evenly after; Send into the loading hopper of double-screw extruding pelletizing unit; Unit mixer temperature is set at 210 ℃; Head temperature is set at 190 ℃; Obtain containing the PP GRANULES of DCNDCA nucleator mass percent 0.1% through extruding pelletization; With extrusion molding sheet material after this particulate material fusion; The crystallization control temperature is room temperature (25 ℃); It is brilliant to contain polyacrylic β in the sheet material products that obtains, and this sheet material has the drawn expanded characteristic.
Utilize miniature mechanical test machine to carry out tensile property test, be the TST350 of the Linkam company hot platform that stretches.The data of SAXS are to utilize the synchrotron radiation laboratory to accomplish test, and the sample that uses is dumb-bell shape, and like Figure 10, thickness is 0.5mm, and A is 1 ± 0.1mm, and B is 2mm, and rate of extension is 2mm/min.
Like Fig. 8 is the stress strain curve of this material under 80 ℃; Wherein 0303,0305,0309 etc. be labeled as the different stretch strain constantly; Scheming as shown in Figure 9 perpendicular to the SAXS on the draw direction corresponding to these different stretch strains material constantly; Compare with initial 0303; Material extending all had increase to other pairing long period of strain moment before 0313; And increasing degree appears increases the characteristic that afterwards reduces earlier, and showing before 80 ℃ of thin necks of following material production has the drawn expanded behavioral trait that strengthens afterwards to weaken earlier on perpendicular to draw direction.
Embodiment 2
Take by weighing 50g isotatic polypropylene (trade mark T1701); Amount according to its mass percent 0.1% takes by weighing DCNDCA nucleator 0.05g; The polypropylene and the DCNDCA nucleator that are taken by weighing are added in the chamber body of mixer that is set at 190 ℃; Set rotating speed 60rpm; Shut down and take out material behind the 8min; In blocks in 190 ℃ of hot pressing, obtain containing the brilliant print (Tc is 20 ℃ of room temperatures) of polyacrylic β with postcooling, have the described drawn expanded characteristic of similar Fig. 8 and Fig. 9.
Embodiment 3
Take by weighing 50g isotatic polypropylene (trade mark T1701); Amount according to its mass percent 1% takes by weighing DCNDCA nucleator 0.5g; The polypropylene and the DCNDCA nucleator that are taken by weighing are added in the chamber body of mixer that is set at 200 ℃; Set rotating speed 30rpm; Shut down and take out material behind the 10min; In blocks in 200 ℃ of hot pressing, obtain containing the brilliant print (Tc is 20 ℃ of room temperatures) of polyacrylic β with postcooling, have the described drawn expanded characteristic of similar Fig. 2 and Fig. 3.
Be the polypropylene material that contains the brilliant nucleator DCNDCA of β tensile stress strain curve like accompanying drawing 2 at 30 ℃; Wherein 0034,0036,0037 etc. be labeled as the different stretch strain constantly; Scheming perpendicular to the SAXS on the draw direction corresponding to these different stretch strains material constantly; As shown in Figure 3; Compare with initial 0034; Material extending to 0036 obviously increases with 0037 o'clock long period; Confirmed that material has the marked inflation behavior on perpendicular to draw direction, promptly show the drawn expanded behavioral trait.
More than the present invention has been done exemplary description; Should be noted that; Under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (8)
1. a beta-crystal polypropylene drawn expanded material is characterized in that, adopts N, and N '-dicyclohexyl-2,6-aphthalimide (DCNDCA) be as the brilliant nucleator of the single β of isotatic polypropylene, and its addition is greater than zero and be not more than 2% of isotatic polypropylene quality.Through multiple modes such as melt blending, solution blendings; Nucleator and isotatic polypropylene are carried out blend; So that nucleator homodisperse in polypropylene material; The homodisperse polypropylene material crystallization at room temperature that mixing back obtains, the material of acquisition produces the drawn expanded behavioral trait on perpendicular to draw direction.
2. a kind of beta-crystal polypropylene drawn expanded material according to claim 1 is characterized in that Tc is 20-25 ℃ under the said room temperature.
3. a kind of beta-crystal polypropylene drawn expanded material according to claim 1 is characterized in that, adopts the mode of melt blending, and the temperature of melt blending can be selected but be not limited to temperature condition commonly used on the industrial production, as 170 ℃～270 ℃.
4. a kind of beta-crystal polypropylene drawn expanded material according to claim 1 is characterized in that, when the mode nucleator through melt blending and the blend of polypropylene material, concrete applicable banburying, opens multiple compounding process such as refining, double-screw extruding pelletizing.
5. method for preparing beta-crystal polypropylene drawn expanded material; It is characterized in that, adopt N, N '-dicyclohexyl-2; 6-aphthalimide (DCNDCA) is as the brilliant nucleator of the single β of isotatic polypropylene, and its addition is greater than zero and be not more than 2% of isotatic polypropylene quality.Through multiple modes such as melt blending, solution blendings, nucleator and isotatic polypropylene are carried out blend, so that nucleator homodisperse in polypropylene material, the homodisperse polypropylene material crystallization at room temperature that mixing back obtains.
6. a kind of method for preparing beta-crystal polypropylene drawn expanded material according to claim 5 is characterized in that Tc is 20-25 ℃ under the said room temperature.
7. a kind of method for preparing beta-crystal polypropylene drawn expanded material according to claim 5 is characterized in that, adopts the mode of melt blending, and the temperature of melt blending can be selected but be not limited to temperature condition commonly used on the industrial production, as 170 ℃～270 ℃.
8. a kind of method for preparing beta-crystal polypropylene drawn expanded material according to claim 5; It is characterized in that; When the mode nucleator through melt blending and the blend of polypropylene material, concrete applicable banburying, open multiple compounding process such as refining, double-screw extruding pelletizing.
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| CN102875900A (en) * | 2012-10-17 | 2013-01-16 | 四川大学 | Preparation method capable of toughening and reinforcing polypropylene product |
| CN103689898A (en) * | 2014-01-14 | 2014-04-02 | 北京航空航天大学 | Novel backpack shoulder strap with stretch-expansion material liner |
| CN105001622A (en) * | 2015-07-29 | 2015-10-28 | 国家纳米科学中心 | Negative-Poisson ratio multifunctional sponge and preparation method thereof |
| CN105566743A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Beta-crystal-form polypropylene strip and preparation method thereof |
| WO2019093470A1 (en) * | 2017-11-10 | 2019-05-16 | 積水化学工業株式会社 | Separator for electricity storage devices, and electricity storage device |
| CN109776961A (en) * | 2019-01-22 | 2019-05-21 | 中国科学院长春应用化学研究所 | A kind of non-polar polymer negative poisson's ratio foamed material and preparation method thereof |
| JP2019091549A (en) * | 2017-11-10 | 2019-06-13 | 積水化学工業株式会社 | Power storage device separator and power storage device |
| JP2019091548A (en) * | 2017-11-10 | 2019-06-13 | 積水化学工業株式会社 | Power storage device separator and power storage device |
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| CN102875900A (en) * | 2012-10-17 | 2013-01-16 | 四川大学 | Preparation method capable of toughening and reinforcing polypropylene product |
| CN103689898A (en) * | 2014-01-14 | 2014-04-02 | 北京航空航天大学 | Novel backpack shoulder strap with stretch-expansion material liner |
| CN105566743A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Beta-crystal-form polypropylene strip and preparation method thereof |
| CN105001622A (en) * | 2015-07-29 | 2015-10-28 | 国家纳米科学中心 | Negative-Poisson ratio multifunctional sponge and preparation method thereof |
| CN105001622B (en) * | 2015-07-29 | 2018-02-02 | 国家纳米科学中心 | A kind of negative poisson's ratio Multifunctional sponge and preparation method thereof |
| WO2019093470A1 (en) * | 2017-11-10 | 2019-05-16 | 積水化学工業株式会社 | Separator for electricity storage devices, and electricity storage device |
| JP2019091549A (en) * | 2017-11-10 | 2019-06-13 | 積水化学工業株式会社 | Power storage device separator and power storage device |
| JP2019091548A (en) * | 2017-11-10 | 2019-06-13 | 積水化学工業株式会社 | Power storage device separator and power storage device |
| CN111201635A (en) * | 2017-11-10 | 2020-05-26 | 积水化学工业株式会社 | Separator for electricity storage device and electricity storage device |
| CN109776961A (en) * | 2019-01-22 | 2019-05-21 | 中国科学院长春应用化学研究所 | A kind of non-polar polymer negative poisson's ratio foamed material and preparation method thereof |
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Application publication date: 20120215 |