CN106146874B - A kind of supercritical fluid expanded polyolefin material and preparation method thereof - Google Patents
A kind of supercritical fluid expanded polyolefin material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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Abstract
The present invention provides a kind of supercritical fluid expanded polyolefin material and preparation method thereof, the supercritical fluid expanded polyolefin material is prepared using following steps：Polyolefin sheets are prepared, the fusing point of the polyolefine material is Tm；Crosslinking with radiation is carried out to polyolefin sheets；Obtained cross-linked polyolefin sheet material is put into pressure vessel, high pressure nitrogen dipping, the dipping temperature T are carried out1For Tm+（30~120）℃；Then fast pressure relief is nucleated in 0.5 ~ 15s, nucleation temperature T2=Tm-（50~80）℃：Then low-pressure heating foaming, blowing temperature T are carried out again3For Tm+（20~50）DEG C, and the T3Less than T1.It adopts this technical solution, the crystallinity of material is not also required, substantially reduce the time that gas reaches dissolution saturation state, improve efficiency, the regular foamed material of the fine and smooth shape uniform, that density is lower, mechanical strength is excellent of abscess can be obtained.
Description
Technical field
The invention belongs to foamed material technical field more particularly to a kind of supercritical fluid expanded polyolefin material and its systems
Preparation Method.
Background technique
Foamed material because having the function of heat preservation, heat-insulated, damping, sound insulation etc., be widely used in articles for daily use, the vehicles,
The industries such as building, electric appliance, packaging material, sports facility, high performance foamed plastics can also be used in the tips such as military affairs, aerospace
Field.
It is plastic foamed to be divided into physical blowing method and chemical blowing process two major classes according to the difference of foaming agent used.Chemistry
Foaming is usually to add chemical foaming agent such as azodicarbonamide (AC), azodiisobutyronitrile (AIBN), sodium bicarbonate and carbon
Sour hydrogen ammonium etc., heating make foaming agent decompose generation gas, so that plastic melt is generated abscess and obtain foamed material.Physical blowing method is
First by nitrogen (N2), carbon dioxide (CO2), butane, gases or the low-boiling point liquid freon (CFCs, HCFCs, HFCs) such as pentane
It dissolves in plastics, releases gas by depressurizing or heating, to form stomata in the plastic and foam.In the process of foaming
In, physical blowing agent is only that physical state changes, and the change of chemical composition does not occur.
Currently used chemical foaming agent such as azodicarbonamide (AC) can generate a large amount of in foaming agent production process
To environmentally hazardous substance, environment is polluted.In addition, European Union the study found that AC foaming agent is when being thermally decomposed, can generate may be led
Substance-semicarbazides of carcinogenic disease, this substance can enter food, and the content highest in baby food.Therefore European Union 2005
Forbid AC foaming agent as food packaging or the sale and import of the plastic material and product that contact with food from August 2,.
2010 end of the year European Union start to carry out limit value to by the content of formamide in the foaming product of foaming agent of AC.Common physical blowing
Agent freon can destroy atmospheric ozone layer, it has also become banned substance.In addition, conventional foamed products, some foaming agent high temperature point
The gas that solution generates can pollute atmospheric environment, and the residue after some foaming agents decompose can pollute product, make
The performance of product declines, and product has peculiar smell, which also limits its certain special dimensions application.
Supercritical fluid (Supercritical Fluids, SCF) refer to certain substance be in critical point (critical-temperature,
Critical pressure) more than, with the double grading of gas and liquid.This fluid has unique object different from gas or liquid
Property, the properties such as density, viscosity, solvability and diffusion coefficient change very sensitive with temperature and pressure.Work as carbon dioxide
(CO2) it is in 31.1 DEG C, 7.38MPa or more, nitrogen (N2) be in -147 DEG C, 3.4MPa or more when, entered supercritical state
State.With supercritical CO2Or N2Traditional foaming agent is substituted, foaming process is relatively mild, and foaming agent is derived from environment, after the completion of foaming
Environment is returned again, it, will not compared with traditional foam process (including chemical blowing and using the physical blowing of alkane foaming agent)
Environment and foaming product itself are polluted, the organic solvents bring such as AC foaming agent, fluorochlorohydrocarbon, petroleum ether is completely eliminated
Environmental hazard and safety problem are current most environmentally friendly and safest polymer foaming technologies.But supercritical fluid is solid at present
State batch-foamed technique has the following problems：
(1) current supercritical fluid solid-state batch-foamed technique, usual saturation temperature is lower, and gas saturation process needs several
Even tens hours a hour, the dosage of required supercritical fluid is larger, and equipment land occupation is big, and production efficiency is lower, at
This is higher；
(2) the nucleation sample of the prior art foams under conditions of being higher than dipping temperature and pressure, sample after foaming
It is easily deformed, and is not readily available the regular foamed material of shape.
(3) the abscess aperture of the foamed material obtained and the bad adjusting of cell density, foam cell uniformity is inadequate, and higher
Mechanical strength under expansion ratio is lower；Some also require the crystallinity of material.
Summary of the invention
Against the above technical problems, the invention discloses a kind of supercritical fluid expanded polyolefin material and its preparation sides
Method does not require the crystallinity of material, substantially reduces the time that gas reaches dissolution saturation state, improves efficiency, can
Obtain the regular foamed material of the fine and smooth shape uniform, that density is lower, mechanical strength is excellent of abscess.
In this regard, the technical solution adopted by the present invention is：
A kind of supercritical fluid expanded polyolefin material, is prepared using following steps：
Step S1：Polyolefin sheets are prepared, the fusing point of the polyolefine material is Tm；
Step S2：Crosslinking with radiation, the polyolefin sheets being crosslinked are carried out to polyolefin sheets；
Step S3：The polyolefin sheets of crosslinking obtained in step S2 are put into pressure vessel, the pressure vessel
Temperature is T1, the T1For Tm+ (30~120) DEG C；Then nitrogen or carbon dioxide are injected into pressure vessel, make pressure vessel
Interior pressure P1For 30~70MPa, 0.5~3h of constant temperature and pressure, the polyolefin sheets of crosslinking is made to absorb nitrogen or carbon dioxide；Its
In, temperature T1For dipping temperature；Pressure P1For impregnation pressure；
Step S4：In pressure vessel after 0.5~3h of constant temperature and pressure, the release within the release time of 0.5~15s makes to press
Pressure in force container is reduced to 12~18MPa, makes the cell nucleation in the polyolefin sheets of crosslinking, then that pressure vessel is cooling
To T2After unload and be depressed into atmospheric pressure, take out nucleation sample；Wherein, the T2=Tm(30~80) DEG C；
Step S5：The nucleation sample that step S4 is obtained is put into pressure vessel, 1.5~5MPa is forced into, is i.e. foaming pressure
Power is 1.5~5MPa；Then the temperature of pressure vessel is risen into T3, after 5~20min of heat-insulation pressure keeping, unload to normal pressure, sample expansion
Foaming, wherein the T3For Tm+ (20~80) DEG C, and the T3Less than T1.Wherein, the temperature T3For blowing temperature.
Technical solution of the present invention is nucleated using first fast pressure relief, then the technical process of low-pressure heating foaming, this step
Rapid key benefit is：
1) nucleation separates progress with foaming, convenient for regulation impregnation pressure, dipping temperature, decompression rate, blowing temperature, foaming
Pressure, thus regulate and control nucleation density, the degrees of expansion of sample of nucleation sample, cell density, the bubble of final regulation and control foamed sample
The density and its mechanical performance of hole aperture and foam, can be obtained that abscess is fine and smooth uniformly, density is lower, mechanical strength is excellent
Foamed material.
2) nucleation separates progress with foaming, and sample uses supercritical fluid to be impregnated, accelerates gas at relatively high temperatures
Body diffusion velocity improves gas in the solubility being intended in foamable polymer, substantially reduces gas and reach dissolution saturation state
Time；Nucleation sample foams under conditions of being lower than dipping temperature and impregnation pressure, avoids the change of sample after foaming
The regular foamed material of shape can be obtained in shape.
3) nucleation separates progress with foaming, in the case where obtaining identical size foamed sample, can reduce the body of autoclave
Product reduces the dosage of supercritical fluid, shortens the time heated up and pressurizeed in dipping process, improves the production effect of foamed material
Rate reduces cost.
As a further improvement of the present invention, the dose of radiation of step S2 is 40~80kGy.
As a further improvement of the present invention, crosslinking with radiation is carried out using electron accelerator.
As a further improvement of the present invention, in step S3, the temperature T1For Tm+ (40~50) DEG C.
As a further improvement of the present invention, in step S3, the pressure P1For 40~60MPa.
As a further improvement of the present invention, in step S4, the release in 1~5s；The temperature T2For Tm(60~70)
℃。
As a further improvement of the present invention, in step S5, the temperature T3For Tm+ (20~30) DEG C.
As a further improvement of the present invention, the polyolefin is at least one of LDPE, MDPE, HDPE or LLDPE.
As a further improvement of the present invention, in step S1, polyolefin sheets are prepared using extrusion.
The present invention also provides a kind of preparation methods of supercritical fluid expanded polyolefin material as described above, including with
Lower step：
Step S1：Polyolefin sheets are prepared, the fusing point of the polyolefine material is Tm；
Step S2：Crosslinking with radiation, the polyolefin sheets being crosslinked are carried out to polyolefin sheets；
Step S3：The polyolefin sheets of crosslinking obtained in step S2 are put into pressure vessel, the pressure vessel
Temperature is T1, the T1For Tm+ (30~120) DEG C；Then nitrogen or carbon dioxide are injected into pressure vessel, make pressure vessel
Interior pressure P1For 30~70MPa, 0.5~3h of constant temperature and pressure, the polyolefin sheets of crosslinking is made to absorb nitrogen or carbon dioxide；Its
In, temperature T1For dipping temperature；Pressure P1For impregnation pressure；
Step S4：In pressure vessel after 0.5~3h of constant temperature and pressure, the release within the release time of 0.5~15s makes to press
Pressure in force container is reduced to 12~18MPa, makes the cell nucleation in the polyolefin sheets of crosslinking, then that pressure vessel is cooling
To T2After unload and be depressed into atmospheric pressure, take out nucleation sample；Wherein, the T2=Tm(30~80) DEG C；
Step S5：The nucleation sample that step S4 is obtained is put into pressure vessel, 1.5~5MPa is forced into, is i.e. foaming pressure
Power is 1.5~5MPa；Then the temperature of pressure vessel is risen into T3, after 5~20min of heat-insulation pressure keeping, unload to normal pressure, sample expansion
Foaming, wherein the T3For Tm+ (20~80) DEG C, and the T3Less than T1.Wherein, the temperature T3For blowing temperature.
As a further improvement of the present invention, the dose of radiation of step S2 is 40~80kGy.
As a further improvement of the present invention, crosslinking with radiation is carried out using electron accelerator.
As a further improvement of the present invention, in step S3, the temperature T1For Tm+ (40~50) DEG C.
As a further improvement of the present invention, in step S3, the pressure P1For 40~60MPa.
As a further improvement of the present invention, in step S4, the release in 1~5s；The temperature T2For Tm(60~70)
℃。
As a further improvement of the present invention, in step S5, the temperature T3For Tm+ (20~30) DEG C.
As a further improvement of the present invention, the polyolefin is at least one of LDPE, MDPE, HDPE or LLDPE.
As a further improvement of the present invention, in step S1, polyolefin sheets are prepared using extrusion.
Compared with prior art, beneficial effects of the present invention are：
First, using technical solution of the present invention, be higher than melting point polymer at a temperature of, using supercritical fluid to desire
Foamable polymer is impregnated, and gas diffusion velocity is accelerated, and improves gas in the solubility being intended in foamable polymer, thus
The time that gas reaches dissolution saturation state is substantially reduced, the crystallinity of material is not also required, it is more environmentally-friendly, and improve
Efficiency.
Second, the present invention improves the melt strength of polymer by way of crosslinking with radiation, so that polymer is molten at it
It can remaining dimensionally-stable property on point；And nucleation sample foams under conditions of being lower than dipping temperature and pressure, avoids
The deformation of sample, can be obtained the regular foamed material of shape after foaming.
Nucleation and foaming are separated progress using technical solution of the present invention by third, convenient for regulation impregnation pressure, dipping
Temperature, decompression rate, blowing temperature, blow pressure, to regulate and control nucleation density, the degrees of expansion of sample of nucleation sample, most
It is fine and smooth that abscess can be obtained in the density and its mechanical performance of the cell density of regulation foamed sample, abscess aperture and foam eventually
Foamed material even, density is lower, mechanical strength is excellent.
4th, using technical solution of the present invention, nucleation separates progress with foaming, is obtaining the foamed sample of identical size
In the case where, the volume of autoclave can be reduced, reduce the dosage of supercritical fluid, shorten heat up in dipping process and pressurization when
Between, improve the production efficiency of foamed material.
Detailed description of the invention
Fig. 1 is the process flow chart of an embodiment of the present invention.
Fig. 2 is the SEM figure of the radiant crosslinked polyethylene foamed material of the embodiment of the present invention 3.
Specific embodiment
Preferably embodiment of the invention is described in further detail below.
Embodiment 1
The technical process of radiant crosslinked polyethylene foamed material is carried out according to the process flow chart of Fig. 1, including following step
Suddenly：
1) LDPE sheet material extrusion molding：Using extruder extrusion molding LPDE sheet material, wherein the fusing point T of LPDEmIt is 111
℃。
2) crosslinking with radiation LDPE：Crosslinking with radiation LDPE is obtained using high-energy electron beam irradiation LDPE sheet material, wherein irradiating agent
Amount is 40kGy.
3) high pressure nitrogen dipping process：Autoclave is raised to set temperature, then puts above-mentioned crosslinking with radiation LDPE print
Enter in autoclave, after with high-pressure pump inject nitrogen, make crosslinking with radiation LDPE print in the leaching of 180 DEG C of dipping temperature, 40.1MPa
Heat-insulation pressure keeping 1h in autoclave under stain pressure makes crosslinking with radiation LDPE print absorb enough nitrogen.
4) fast pressure relief nucleation process：Crosslinking with radiation LDPE print is in autoclave after heat-insulation pressure keeping 1h, the 15s release time
Interior unload rapidly is depressed into 15.1MPa, makes cell nucleation in sample, and sample is slightly expanded, unloaded after autoclave is then cooled to 65 DEG C
It is depressed into atmospheric pressure, taking-up has been nucleated sample.
5) low-pressure heating foaming process：Obtained nucleation sample is put into low pressure kettle, under the blow pressure of 5.0MPa
Again 160 DEG C are warming up to, i.e. blowing temperature is 160 DEG C, after heat-insulation pressure keeping 10min, is unloaded to normal pressure, sample is expanded foamed to be steeped
The closed-cell foam material of hole exquisiteness.
Embodiment 2
On the basis of embodiment 1, the irradiation dose of this example LDPE sheet material is 60kGy, impregnation pressure 50MPa, dipping
Temperature is 200 DEG C, and the release time is 10s, and blowing temperature is 150 DEG C, blow pressure 3MPa.
Embodiment 3
On the basis of embodiment 1, the irradiation dose of this example LDPE sheet material is 80kGy, impregnation pressure 30MPa, dipping
Temperature is 220 DEG C, and the release time is 5s, and blowing temperature is 180 DEG C, blow pressure 1.5Mpa.
Comparative example 1
On the basis of embodiment 1, for the LDPE sheet material of this example without crosslinking with radiation, blowing temperature is 190 DEG C, foaming pressure
Power is 5Mpa.But LDPE sheet material is very poor without crosslinking progress foaming effect, obtained foamed material shape is irregular, no
It can use.
The material of obtained 1~embodiment of embodiment 3 is tested for the property, the results are shown in Table 1,
The results of property table of 1 1~embodiment of embodiment 3 of table, comparative example 1
By the data of table 1 as it can be seen that the coefficient of foaming of the sample of 1~embodiment of embodiment 3 is all at 20 times or more, embodiment 1
Expansion ratio reach 26.4, and the sample of 1~embodiment of embodiment 3 still maintains higher hardness and compressive strength.
The SEM of the sample of embodiment 3 schemes as shown in Fig. 2, from Figure 2 it can be seen that about 120 microns of abscess average pore size, and abscess is equal
It is even.
Embodiment 4
On the basis of embodiment 1, the impregnation pressure of this example is 50MPa, and dipping temperature is 230 DEG C, and the release time is
10s, blowing temperature is 190 DEG C, blow pressure 3MPa.
Embodiment 5
On the basis of embodiment 1, the impregnation pressure of this example is 30MPa, and dipping temperature is 220 DEG C, and the release time is 5s,
Blowing temperature is 180 DEG C, blow pressure 1.5MPa.
Embodiment 6
On the basis of embodiment 1, in this example, the irradiation dose of LDPE sheet material is 80kGy.The LDPE print of crosslinking with radiation
The heat-insulation pressure keeping 1h in autoclave under 160 DEG C of dipping temperature, the impregnation pressure of 40.1MPa inhales crosslinking with radiation LDPE print
Receive enough nitrogen；Then fast pressure relief then cools down autoclave, when temperature is reduced to 63 DEG C, unloads and be pressed onto greatly to 15.1MPa
It is taken out after air pressure and has been nucleated sample；Then sample is put into low pressure kettle, is warming up to 150 DEG C, heat preservation again under 5.0MPa pressure
After pressure maintaining 10min, foam is unloaded.
4~embodiment of embodiment 6 obtains the regular foamed material of shape, to the material progressive of 4~embodiment of embodiment 6
It can test, the results are shown in Table 2,
The results of property table of 2 4~embodiment of embodiment 6 of table
By the data of table 2 as it can be seen that the coefficient of foaming of the sample of 4~embodiment of embodiment 6 is all at 20 times or more, embodiment 4
Expansion ratio reach 31.3, and the sample of 4~embodiment of embodiment 6 still maintains higher hardness and compressive strength.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (10)
1. a kind of supercritical fluid expanded polyolefin material, it is characterised in that：It is prepared using following steps：
Step S1：Polyolefin sheets are prepared, the fusing point of the polyolefine material is Tm；
Step S2：Crosslinking with radiation, the polyolefin sheets being crosslinked are carried out to polyolefin sheets；
Step S3：The polyolefin sheets of crosslinking obtained in step S2 are put into pressure vessel, the temperature of the pressure vessel
For T1, the T1For Tm+（30~120）℃；Then nitrogen or carbon dioxide are injected into pressure vessel, make the pressure in pressure vessel
Power P1For 30 ~ 70MPa, 0.5 ~ 3h of constant temperature and pressure, the polyolefin sheets of crosslinking is made to absorb nitrogen or carbon dioxide；
Step S4：In pressure vessel after 0.5 ~ 3h of constant temperature and pressure, the release in 0.5 ~ 15s makes the pressure drop in pressure vessel
For 12 ~ 18MPa, makes the cell nucleation in the polyolefin sheets of crosslinking, pressure vessel is then cooled to T2After unload and be depressed into atmosphere
Pressure takes out nucleation sample；Wherein, the T2=Tm-（30~80）℃；
Step S5：The nucleation sample that step S4 is obtained is put into pressure vessel, 1.5 ~ 5MPa is forced into, then by pressure vessel
Temperature rise to T3, after 5 ~ 20min of heat-insulation pressure keeping, unload to normal pressure, sample is expanded foamed, wherein the T3For Tm+（20~80）
DEG C, and the T3Less than T1；The polyolefin is polyethylene.
2. supercritical fluid expanded polyolefin material according to claim 1, it is characterised in that：The dose of radiation of step S2
For 40 ~ 80 kGy.
3. supercritical fluid expanded polyolefin material according to claim 2, it is characterised in that：Using electron accelerator into
Row crosslinking with radiation.
4. supercritical fluid expanded polyolefin material according to claim 2, it is characterised in that：In step S3, the temperature
Spend T1For Tm+（50~80）℃.
5. supercritical fluid expanded polyolefin material according to claim 2, it is characterised in that：In step S3, the pressure
Power P1For 40 ~ 60MPa.
6. supercritical fluid expanded polyolefin material according to claim 2, it is characterised in that：In step S4, in 1 ~ 5s
Interior release；The temperature T2For Tm-（60~70）℃.
7. supercritical fluid expanded polyolefin material according to claim 2, it is characterised in that：In step S5, the temperature
Spend T3For Tm+（20~30）℃.
8. supercritical fluid expanded polyolefin material described in any one according to claim 1 ~ 7, it is characterised in that：It is described poly-
Alkene is at least one of LDPE, MDPE, HDPE or LLDPE.
9. supercritical fluid expanded polyolefin material according to claim 8, it is characterised in that：In step S1, using crowded
Polyolefin sheets are prepared out.
10. a kind of preparation method of supercritical fluid expanded polyolefin material as described in claim 1, it is characterised in that：Packet
Include following steps：
Step S1：Polyolefin sheets are prepared, the fusing point of the polyolefine material is Tm；
Step S2：Crosslinking with radiation, the polyolefin sheets being crosslinked are carried out to polyolefin sheets；Wherein, dose of radiation is 40 ~ 80
kGy；
Step S3：The polyolefin sheets of crosslinking obtained in step S2 are put into pressure vessel, the temperature of the pressure vessel
For T1, the T1For Tm+（30~120）℃；Then nitrogen or carbon dioxide are injected into pressure vessel, make the pressure in pressure vessel
Power P1For 30 ~ 70MPa, 0.5 ~ 3h of constant temperature and pressure, the polyolefin sheets of crosslinking is made to absorb nitrogen；
Step S4：In pressure vessel after 0.5 ~ 3h of constant temperature and pressure, the release in 0.5 ~ 15s makes the pressure drop in pressure vessel
For 12 ~ 18MPa, makes the cell nucleation in the polyolefin sheets of crosslinking, pressure vessel is then cooled to T2After unload and be depressed into atmosphere
Pressure takes out nucleation sample；Wherein, the T2= Tm-（30~80）℃；
Step S5：The nucleation sample that step S4 is obtained is put into pressure vessel, 1.5 ~ 5MPa is forced into, then by pressure vessel
Temperature rise to T3, after 5 ~ 20min of heat-insulation pressure keeping, unload to normal pressure, sample is expanded foamed, wherein the T3For Tm+（20~80）
DEG C, and the T3Less than T1。
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