CN105001512B - A kind of open cell polymer foams and preparation method thereof - Google Patents
A kind of open cell polymer foams and preparation method thereof Download PDFInfo
- Publication number
- CN105001512B CN105001512B CN201510392373.2A CN201510392373A CN105001512B CN 105001512 B CN105001512 B CN 105001512B CN 201510392373 A CN201510392373 A CN 201510392373A CN 105001512 B CN105001512 B CN 105001512B
- Authority
- CN
- China
- Prior art keywords
- open cell
- polymer foams
- cell polymer
- filling material
- perforated filling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- 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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- 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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
The present invention provides a kind of preparation method of open cell polymer foams, and it comprises the following steps：A weighs the weight portion of polypropylene 100, the weight portion of nucleator 0.5~5, the weight portion of alkene containing ethylene-like polymer 10~100, the weight portion of perforated filling material 1~30；The polypropylene, nucleator, alkene containing ethylene-like polymer and perforated filling material are uniformly mixed to get mixture by b, add the mixture in extruder again, and the carbon dioxide of above-critical state is passed through at the 1/5~1/3 of the screw rod of extruder, extrude and foamed, the open cell polymer foams containing perforated filling material are obtained, the open cell polymer foams for containing perforated filling material include multiple first perforates；C immerses in an etching solution open-cell foam materials containing perforated filling material, the perforated filling material is etched to form multiple second perforates, obtains open cell polymer foams.The present invention also provides a kind of open cell polymer foams.The open cell polymer foams have the advantages that percent opening is high, oil suction multiplying power is good.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of open cell polymer foams and its preparation side
Method.
Background technology
As developing rapidly for industry is constantly improved with the living standard of people, oil leak in oil exploitation and transportation
Event and a large amount of oil-containing industrial waters increase year by year, and oily pollution problem is increasingly severe, seriously destroy the life of the Nature
State is balanced.The oil 30% of these pollution environment comes from industrial wastewater discharge, and 45% leaks from deepwater oil carrier.Offshore oilfield
Exploitation leakage, can cause large stretch of oceanic area to pollute, and marine ecology is threatened, and huge harm is brought to environment.
At present treatment marine oil pollution main method have combustion in situ oil slick method, with oil skimmer and vacuum pump set to oil slick
Salvaged, waste oil is condensed reprocessing with oil dispersant and precipitating reagent reduction oil meter face tension force, oil is carried out using microorganism
Degrade and using oil absorption material oil suction etc..Preceding four kinds of methods can cause the secondary pollution of environment, and oil removal efficiency is low, valency
Lattice are expensive, take long.Had using the method for oil absorption material oil suction and reclaim convenient, free of contamination advantage and attract attention.
Oil absorption material includes natural oil absorption material and synthesis oily material.Common natural oil absorption material has：String,
Organic clay, rice husk, expanded perlite, expanded graphite and staple etc..But natural oil absorption material exist oil-water selectivity it is poor,
Oil suction efficiency is low and oil suction after compression oil leak the shortcomings of.Common synthesis oil absorption material has polyurethane foam and polypropylene oil suction
Blanket etc..The Chinese patent application of such as Publication No. CN102492099A discloses a kind of polyurethane foam oil suction of hydrophobically modified
The preparation method of material.The method using by polyurethane foam toluene of the immersion containing initiator, live by the lower stirring that heats up of nitrogen protection
Change, add reaction monomers and crosslinking agent and react in a nitrogen atmosphere and obtain hydrophobically modified polyurethane foam.But its technique mistake
In complexity, cost is of a relatively high, post-processes also cumbersome.
Polypropylene (PP) oil suction rug prepared by meltblown, although material has oleophilic drainage characteristic, but due to hole
Rate is low, causes oil suction multiplying power low, and there are problems that pressurization when using.
Document (A.Rizvi, R.K.M.Chu, J.H.Lee, C.B.Park, Superhydrophobic and
Oleophilic Open-Cell Foams from Fibrillar Blends of Polypropylene and
Polytetrafluoroethylene,ACS Applied Materials&Interfaces,2014,6(23):21131-
21140.) polytetrafluoroethyl/ne /ne polypropylene (PTFE/PP) foam oil absorption material is prepared for by the method for continuous extrusion foaming.But
The expansion multiplying power of the foam oil absorption material is low, causes oil suction multiplying power low, and high cost.
Notification number discloses a kind of preparation method of polypropylene foam for the Chinese patent of CN101044195B.The polypropylene
The intrinsic open cell content of foam is 40%, but the open cell content of foam is too low, it is difficult to used as oil absorption material.
It can be seen that, the percent opening of existing oil absorption material is relatively low, and is difficult to oil suction multiplying power high, also, prepares work
Skill is more complicated.
The content of the invention
Regarding to the issue above, it is an object of the invention to provide one kind there is high opening rate and the perforate of high oil absorption multiplying power to be polymerized
Thing foamed material and preparation method thereof, to solve technical problem of the prior art.
The present invention provides a kind of preparation method of open cell polymer foams, and it comprises the following steps：
A weighs the weight portion of polypropylene 100, the weight portion of nucleator 0.5~5, the weight portion of alkene containing ethylene-like polymer 10~100,
The weight portion of perforated filling material 1~30；
The polypropylene, nucleator, alkene containing ethylene-like polymer and perforated filling material are uniformly mixed to get a mixture by b, then
Add the mixture in an extruder, and the carbon dioxide of above-critical state be passed through at the 1/5~1/3 of the screw rod of extruder,
Extrude and foamed, obtain the open cell polymer foams containing perforated filling material, this contains the open cell polymer bubble of perforated filling material
Foam material includes multiple first perforates；
C immerses in an etching solution open-cell foam materials containing perforated filling material, makes the opening containing perforated filling material
Perforated filling material in the foamed material of hole is etched to form multiple second perforates, obtains open cell polymer foams.
The particle diameter of perforated filling material described in step a is 100 nanometers~1 millimeter.
Polypropylene described in step a is HOPP, block copolymerization polypropylene or both with being total to that arbitrary proportion mixes
Mixed thing, the polyacrylic melt index is 0.1g/10min~20g/10min.
Perforated filling material described in step a be calcium carbonate, sodium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, potassium carbonate in extremely
Few one kind, the alkene containing ethylene-like polymer be in LLDPE, low density polyethylene (LDPE), polyolefin elastomer at least
One kind, the nucleator is at least one in calcium carbonate, nanoclay, talcum powder, mica, calcium oxide, kaolin, carbon black.
The weight portion of perforated filling material 1~20 in step a.
In step b, the temperature in the first half area of screw rod is 180 DEG C~210 DEG C, the temperature in the later half area of screw rod for 150 DEG C~
180℃。
The quality of the carbon dioxide of above-critical state described in step b accounts for the 5%~15% of the gross mass of the mixture, institute
The injection pressure for stating the carbon dioxide of above-critical state is 8MPa~25Mpa.
Etching solution described in step c is at least one in dilute sulfuric acid, watery hydrochloric acid, phosphoric acid,diluted, nitric acid, acetic acid, described
Mole solubility of etching solution is 1.5mol/L~4.0mol/L.
The soak time that the open-cell foam materials containing perforated filling material are immersed in the etching solution described in step c is small for 1
When~24 hours, etching process is carried out at room temperature.
The present invention also provides a kind of open cell polymer foams obtained using above-mentioned preparation method, the perforate polymerization
Thing foamed material includes multiple perforates, the pore size of the perforate on the surface of the open cell polymer foams for 1 micron~
600 microns, the pore size of the perforate of the inside of open cell polymer foams is 50 microns~150 microns.
Compared to prior art, this preparation method carries out secondary perforate by two kinds of different perforate mechanism, forms perforate
Polymer foams.Specifically, in step a that polypropylene (PP), nucleator, alkene containing ethylene-like polymer and perforated filling material is equal
Even mixing so that the perforated filling material is uniformly distributed in mixture.In stepb, PP and the shape of polyolefin blend containing vinyl
Into PP enrichment phases and the enrichment phase of alkene containing ethylene-like polymer, because the crystallization temperature of PP is higher than alkene containing ethylene-like polymer, when to screw rod
1/5~1/3 at be passed through the carbon dioxide of above-critical state after, now screw rod later half area's temperature reduction, PP is prior to containing vinyl
Polyolefin crystallization, forms the hard phases of PP and the phase of polyolefine soft containing vinyl.When the head by extruder, because pressure declines,
Above-critical state it is carbon dioxide expanded, escape, gas can break through in steep that wall and cool down the slower phase of polyolefine soft containing vinyl and shape
Into multiple first perforates.It is appreciated that the part surface of perforated filling material can be exposed by the plurality of first perforate.Step
In c, fully reacted with perforated filling material by etching solution so that equally distributed perforated filling material is etched, form multiple second
Perforate.The open cell polymer foams include multiple perforates (general designation of the first perforate and the second perforate), and the perforate gathers
The pore size of the perforate on the surface of polymer foam is 1 micron~600 microns, the inside of open cell polymer foams
The pore size of perforate is 50 microns~150 microns.This has height by the open cell polymer foams that secondary perforate is obtained
Percent opening (80%~98%).The pore size of the perforate is moderate (below 1 millimeter), is conducive to oil suction, the open cell polymer
The oil suction multiplying power of foamed material is up to 20g/g~55g/g, and oleophilic drainage performance is excellent, can be used as oil absorption material application.The method
Process is simple, energy consumption are low, low cost, are adapted to industrialized production.
Brief description of the drawings
Fig. 1 is the scanning electron microscopic picture of open cell polymer foams prepared by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscopic picture of open cell polymer foams prepared by the embodiment of the present invention 2.
Specific embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is carried out clearly
Chu, it is fully described by, it is clear that described implementation method is only a part of implementation method of the invention, rather than whole realities
Apply mode.Based on the implementation method in the present invention, those of ordinary skill in the art institute under the premise of creative work is not made
The every other implementation method for obtaining, belongs to the scope of protection of the invention.
The invention provides a kind of preparation method of open cell polymer foams, it comprises the following steps：
A weighs the weight portion of polypropylene 100, the weight portion of nucleator 0.5~5, the weight portion of alkene containing ethylene-like polymer 10~100,
The weight portion of perforated filling material 1~30；
The polypropylene, nucleator, alkene containing ethylene-like polymer and perforated filling material are uniformly mixed to get a mixture by b, then
Add the mixture in an extruder, and the carbon dioxide of above-critical state be passed through at the 1/5~1/3 of the screw rod of extruder,
Extrude and foamed, obtain the open cell polymer foams containing perforated filling material, this contains the open cell polymer bubble of perforated filling material
Foam material includes multiple first perforates；
C immerses in an etching solution open-cell foam materials containing perforated filling material, makes the opening containing perforated filling material
Perforated filling material in the foamed material of hole is etched to form multiple second perforates, obtains open cell polymer foams.
In step a, the polypropylene is that HOPP, block copolymerization polypropylene or both are mixed with arbitrary proportion
Blend.The polyacrylic melt index is 0.1g/10min~20g/10min (test condition is 2.16kg/230 DEG C).Institute
It is at least one in LLDPE, low density polyethylene (LDPE), polyolefin elastomer to state alkene containing ethylene-like polymer.It is described
Nucleator is at least one in calcium carbonate, nanoclay, talcum powder, mica, calcium oxide, kaolin, carbon black.The perforate is filled out
Expect to be at least one in calcium carbonate, sodium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, potassium carbonate.
The particle diameter of the perforated filling material is 100 nanometers~1 millimeter.Preferably, the particle diameter of the perforated filling material be 1 micron~
100 microns.
Preferably, the weight portion of perforated filling material 1~20.
In stepb, can be by the way that high-speed mixer is by the polypropylene (PP), nucleator, alkene containing ethylene-like polymer and opens
Hole filler carries out dry mixed and obtains the mixture.Perforated filling material is dispersed in the mixture.
The mixture can be added in extruder from the charging aperture of extruder.In the screw rod by the extruder,
PP forms PP enrichment phases and the enrichment phase of alkene containing ethylene-like polymer with polyolefin blend containing vinyl.Because the crystallization temperature of PP is higher than
Alkene containing ethylene-like polymer, after the carbon dioxide of above-critical state is passed through, now later half area's temperature reduction of screw rod, PP is prior to containing second
Alkenes polyolefin crystallization, forms the hard phases of PP and the phase of polyolefine soft containing vinyl.The carbon dioxide for being passed through above-critical state act as
The carbon dioxide of above-critical state is set to be uniformly distributed in the hard phases of PP and the phase of polyolefine soft containing vinyl, it is uniform in order to be subsequently formed
First perforate of distribution.When the head by extruder, because pressure declines, carbon dioxide expanded, the escape of above-critical state,
Gas can break through in steep that wall and cool down the slower phase of polyolefine soft containing vinyl and form multiple first perforates.Now, the perforate
The part surface of filler can be exposed by the plurality of first perforate.
The temperature in the first half area of the screw rod of the extruder is 180 DEG C~210 DEG C, and the temperature in the later half area of screw rod is 150
DEG C~180 DEG C.The quality of the carbon dioxide of the above-critical state accounts for the 5%~15% of the gross mass of the mixture, described super
The injection pressure of the carbon dioxide of critical state is 8MPa~25Mpa.The purity of the carbon dioxide of the above-critical state is 99.9%.
Preferably, the carbon dioxide of above-critical state is passed through at the 1/4 of the screw rod of extruder, the screw rod of the extruder
The temperature in first half area is 190 DEG C~200 DEG C, and the temperature in the later half area of screw rod is 150 DEG C~170 DEG C, the two of the above-critical state
The quality of carbonoxide accounts for the 8%~12% of the gross mass of the mixture, the injection pressure of the carbon dioxide of the above-critical state
It is 15MPa~20Mpa.,
In step c, because the part surface of perforated filling material is exposed by the multiple first perforate, thus work as institute
When stating the open-cell foam materials containing perforated filling material into etching solution, the etching solution can via the first perforate with it is described
Perforated filling material is contacted or directly the perforated filling material with the outer surface of the open-cell foam materials containing perforated filling material is contacted, and goes forward side by side
Row reaction, and cause that the perforated filling material is etched, and ultimately forms multiple second perforates.Equivalent to the mistake for having carried out perforate twice
Journey.Because the perforated filling material is uniformly distributed, after it is etched, multiple second perforates for obtaining also are to be uniformly distributed.
First perforate and the second perforate unification are summarised as perforate, the surface of the open cell polymer foams
The pore size of perforate is 1 micron~600 microns, and the pore size of the perforate of the inside of open cell polymer foams is 50 micro-
Rice~150 microns.
The etching solution is preferably acid solution, such as dilute sulfuric acid, watery hydrochloric acid, phosphoric acid,diluted, nitric acid, acetic acid etc..It is described
Mole solubility of etching solution is 1.5mol/L~4.0mol/L.The open-cell foam materials containing perforated filling material immerse the quarter
Soak time in erosion solution is 1 hour~24 hours.The etching reaction can be carried out at room temperature.
The present invention also provides one kind and obtains open cell polymer foams using above-mentioned preparation method.The open cell polymer
Foamed material includes multiple perforates.The pore size of the perforate on the surface of the open cell polymer foams is 1 micron~600
Micron, the pore size of the perforate of the inside of open cell polymer foams is 50 microns~150 microns.The open cell polymer
The percent opening of foamed material is 80%~98%, and oil suction multiplying power is 20g/g~55g/g.It is appreciated that the open cell polymer bubble
Foam material includes multiple perforates, and the quantity of the plurality of perforate is the summation of above-mentioned first perforate and the second perforate.
Compared to prior art, this preparation method carries out secondary perforate by two kinds of different perforate mechanism, forms perforate
Polymer foams.Specifically, in step a that polypropylene (PP), nucleator, alkene containing ethylene-like polymer and perforated filling material is equal
Even mixing so that the perforated filling material is uniformly distributed in mixture.In stepb, PP and the shape of polyolefin blend containing vinyl
Into PP enrichment phases and the enrichment phase of alkene containing ethylene-like polymer, because the crystallization temperature of PP is higher than alkene containing ethylene-like polymer, when to screw rod
1/5~1/3 at be passed through the carbon dioxide of above-critical state after, now screw rod later half area's temperature reduction, PP is prior to containing vinyl
Polyolefin crystallization, forms the hard phases of PP and the phase of polyolefine soft containing vinyl.When the head by extruder, because pressure declines,
Above-critical state it is carbon dioxide expanded, escape, gas can break through in steep that wall and cool down the slower phase of polyolefine soft containing vinyl and shape
Into multiple first perforates.It is appreciated that the part surface of perforated filling material can be exposed by the plurality of first perforate.Step
In c, fully reacted with perforated filling material by etching solution so that equally distributed perforated filling material is etched, form multiple second
Perforate.The open cell polymer foams include multiple perforates (general designation of the first perforate and the second perforate), and the perforate gathers
The pore size of the perforate on the surface of polymer foam is 1 micron~600 microns, the inside of open cell polymer foams
The pore size of perforate is 50 microns~150 microns.This has height by the open cell polymer foams that secondary perforate is obtained
Percent opening (80%~98%).The pore size of the perforate is moderate (below 1 millimeter), is conducive to oil suction, the open cell polymer
Foamed material oil suction multiplying power is up to 20g/g~55g/g, and oleophilic drainage performance is excellent, can be used as oil absorption material application.The method work
Skill is simple, energy consumption is low, low cost, is adapted to industrialized production.
The preparation method of open cell polymer foams of the invention is illustrated with reference to specific embodiment：
Embodiment 1：
Weigh 100 parts by weight of polypropylene, 0.5 weight portion talcum powder, 30 weight portion LLDPEs and 5 weight portions
Calcium carbonate.
By above-mentioned each raw material it is dry-mixed after be added in extruder；Wherein, screw speed is set to 30rad/min, before screw rod
Half area's temperature is set to 190 DEG C, and later half area's temperature of screw rod is set to 165 DEG C；10 weight portion above-critical states are injected at the 1/4 of screw rod
Carbon dioxide, injection pressure is set to 15MPa, and extrusion foaming obtains the open cell polymer foams containing perforated filling material.
The open cell polymer foams containing perforated filling material are immersed in the dilute sulfuric acid that molar concentration is 1.5mol/L again molten
16 hours are etched in liquid, open cell polymer foams are obtained.
Embodiment 2：
Weigh 100 parts by weight of polypropylene, 0.7 weight portion nanoclay, 80 weight portion LLDPEs and 10 weights
Amount part magnesium carbonate.
By above-mentioned each raw material it is dry-mixed after be added in extruder；Wherein, screw speed is set to 50rad/min, before screw rod
Half area's temperature is set to 210 DEG C, and later half area's temperature of screw rod is set to 155 DEG C；12 weight portion above-critical states are injected at the 1/4 of screw rod
Carbon dioxide, injection pressure is set to 18MPa, and extrusion foaming obtains the open cell polymer foams containing perforated filling material.
The open cell polymer foams containing perforated filling material are immersed in the salpeter solution that molar concentration is 3.5mol/L again
20 hours of middle etching, obtain open cell polymer foams.
Embodiment 3：
Weigh 100 parts by weight of polypropylene, 1.5 parts by weight mica, 60 weight portion LLDPEs and 20 weight portions
Sodium carbonate.
By above-mentioned each raw material it is dry-mixed after be added in extruder；Wherein, screw speed is set to 70rad/min, before screw rod
Half area's temperature is set to 200 DEG C, and later half area's temperature of screw rod is down to 168 DEG C；14 weight portion above-critical states are injected at the 1/5 of screw rod
Carbon dioxide, injection pressure is set to 20MPa, and extrusion foaming obtains the open cell polymer foams containing perforated filling material.
The open cell polymer foams containing perforated filling material are immersed in the watery hydrochloric acid that molar concentration is 2.3mol/L again molten
8 hours are etched in liquid, open cell polymer foams are obtained.
Embodiment 4：
Weigh 100 parts by weight of polypropylene, 2.5 parts by weight kaolin clay, 100 weight portion LLDPEs and 5 weight
Part sodium carbonate.
By above-mentioned each raw material it is dry-mixed after be added in extruder, wherein, screw speed is set to 40rad/min, before screw rod
Half area's temperature is set to 190 DEG C, and later half area's temperature of screw rod is set to 150 DEG C；15 weight portion above-critical states are injected at the 1/3 of screw rod
Carbon dioxide, injection pressure is set to 18MPa, and extrusion foaming obtains the open cell polymer foams containing perforated filling material.
The open cell polymer foams containing perforated filling material are immersed in the dilute sulfuric acid that molar concentration is 3.1mol/L again molten
18 hours are etched in liquid, open cell polymer foams are obtained.
Embodiment 5：
Weigh 100 parts by weight of polypropylene, 3 weight portion talcum powder, 40 weight portion LLDPEs and 15 weight portions
Potassium carbonate.
By above-mentioned each raw material it is dry-mixed after be added in extruder；Wherein, screw speed is set to 50r/min, the first half of screw rod
Area's temperature is set to 190 DEG C, and later half area's temperature of screw rod is down to 160 DEG C；10 weight portion above-critical states are injected at the 1/4 of screw rod
Carbon dioxide, injection pressure is set to 20MPa, and extrusion foaming obtains the open cell polymer foams containing perforated filling material.
The open cell polymer foams containing perforated filling material are immersed in the watery hydrochloric acid that molar concentration is 1.8mol/L again molten
10 hours are etched in liquid, open cell polymer foams are obtained.
Embodiment 6：
Weigh 100 parts by weight of polypropylene, 4 parts by weight mica, 30 weight portion LLDPEs and 10 weight portion carbon
Sour potassium.
By above-mentioned each raw material it is dry-mixed after be added in extruder；Wherein, screw speed is set to 70rad/min, before screw rod
Half area's temperature is set to 180 DEG C, and later half area's temperature of screw rod is down to 150 DEG C；12 weight portion above-critical states are injected at the 1/5 of screw rod
Carbon dioxide, injection pressure is set to 15MPa, and extrusion foaming obtains the open cell polymer foams containing perforated filling material.
The open cell polymer foams containing perforated filling material are immersed in the dilute sulfuric acid that molar concentration is 3.5mol/L again molten
18 hours are etched in liquid, open cell polymer foams are obtained.
Comparative example 1：
Weigh 100 parts by weight of polypropylene and 0.5 weight portion talcum powder.
By above-mentioned each raw material it is dry-mixed after be added in extruder；Wherein, screw speed is set to 50rad/min, before screw rod
Half area's temperature is set to 190 DEG C, and later half area's temperature of screw rod is down to 160 DEG C；10 weight portion above-critical states are injected at the 1/4 of screw rod
Carbon dioxide, injection pressure be set to 18MPa, continuous extrusion foaming obtains open cell polymer foams.
Comparative example 2：
Weigh 100 parts by weight of polypropylene and 1 weight portion nanoclay；
By above-mentioned each raw material it is dry-mixed after be added in extruder；Wherein, screw speed is set to 30rad/min, before screw rod
Half area's temperature is set to 200 DEG C, and later half area's temperature of screw rod is down to 155 DEG C；12 weight portion above-critical states are injected at the 1/4 of screw rod
Carbon dioxide, injection pressure be set to 15MPa, continuous extrusion foaming obtains open cell polymer foams.
Open cell polymer foams obtained by embodiment 1 to 6, comparative example 1 and 2 are entered with line density and oil suction multiplying power is surveyed
Examination, the results are shown in Table 1.Wherein, density measurement：It is the density balance of BT224S to use model specification；Oil suction multiplying power is tested：Using type
Number specification is the electronic balance of AL204101.
Table 1
From table 1, relative to comparative example 1 and 2, the expansion times of the open cell polymer foams that embodiment 1 to 6 is obtained
Rate and oil suction multiplying power are greatly improved.It is excellent that this illustrates that the open cell polymer foams that the preparation method is obtained have
Oil absorbency, is conducive to commercial application.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (9)
1. a kind of preparation method of open cell polymer foams, it comprises the following steps：
A weighs the weight portion of polypropylene 100, the weight portion of nucleator 0.5~5, the weight portion of alkene containing ethylene-like polymer 10~100, perforate
The weight portion of filler 1~30, wherein the perforated filling material is in calcium carbonate, sodium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, potassium carbonate
At least one；
The polypropylene, nucleator, alkene containing ethylene-like polymer and perforated filling material are uniformly mixed to get a mixture by b, then should
Mixture is added in an extruder, and the carbon dioxide of above-critical state is passed through at the 1/5~1/3 of the screw rod of extruder, extrusion
And foamed, the open cell polymer foams containing perforated filling material are obtained, this contains the open celled polymeric foam material of perforated filling material
Material includes multiple first perforates, wherein, the temperature in the first half area of screw rod is 180 DEG C~210 DEG C, and the temperature in the later half area of screw rod is
150 DEG C~180 DEG C；
C immerses in an etching solution open cell polymer foams containing perforated filling material, makes described containing perforated filling material
Perforated filling material in open cell polymer foams is etched to form multiple second perforates, obtains open celled polymeric foam material
Material.
2. a kind of preparation method of open cell polymer foams as claimed in claim 1, it is characterised in that institute in step a
The particle diameter for stating perforated filling material is 100 nanometers~1 millimeter.
3. a kind of preparation method of open cell polymer foams as claimed in claim 1, it is characterised in that institute in step a
The blend that polypropylene is mixed for HOPP, block copolymerization polypropylene or both with arbitrary proportion is stated, it is described polyacrylic
Melt index is 0.1g/10min~20g/10min, and wherein test condition is 2.16kg, 230 DEG C.
4. a kind of preparation method of open cell polymer foams as claimed in claim 1, it is characterised in that institute in step a
It is at least one in LLDPE, low density polyethylene (LDPE), polyolefin elastomer to state alkene containing ethylene-like polymer, described
Nucleator is at least one in calcium carbonate, nanoclay, talcum powder, mica, calcium oxide, kaolin, carbon black.
5. a kind of preparation method of open cell polymer foams as claimed in claim 1, it is characterised in that opened in step a
The weight portion of hole filler 1~20.
6. a kind of preparation method of open cell polymer foams as claimed in claim 1, it is characterised in that institute in step b
State the carbon dioxide of above-critical state quality account for the mixture gross mass 5%~15%, the dioxy of the above-critical state
The injection pressure for changing carbon is 8MPa~25Mpa.
7. a kind of preparation method of open cell polymer foams as claimed in claim 1, it is characterised in that institute in step c
It is at least one in dilute sulfuric acid, watery hydrochloric acid, phosphoric acid,diluted, nitric acid, acetic acid, mole solubility of the etching solution to state etching solution
It is 1.5mol/L~4.0mol/L.
8. a kind of preparation method of open cell polymer foams as claimed in claim 1, it is characterised in that institute in step c
The soak time stated in the open cell polymer foams immersion etching solution containing perforated filling material is 1 hour~24 hours,
Etching process is carried out at room temperature.
9. a kind of using the open cell polymer foams that such as claim 1 to 8 any one preparation method is obtained, its feature exists
In the open cell polymer foams include multiple perforates, the hole of the perforate on the surface of the open cell polymer foams
Footpath size is 1 micron~600 microns, and the pore size of the perforate of the inside of open cell polymer foams is 50 microns~150
Micron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510392373.2A CN105001512B (en) | 2015-07-01 | 2015-07-01 | A kind of open cell polymer foams and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510392373.2A CN105001512B (en) | 2015-07-01 | 2015-07-01 | A kind of open cell polymer foams and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105001512A CN105001512A (en) | 2015-10-28 |
| CN105001512B true CN105001512B (en) | 2017-06-27 |
Family
ID=54374395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510392373.2A Active CN105001512B (en) | 2015-07-01 | 2015-07-01 | A kind of open cell polymer foams and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105001512B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433002A (en) * | 2016-09-21 | 2017-02-22 | 苏州佰思科节能环保科技有限公司 | Compound oil-absorbing material with flame retardant property and preparation method thereof |
| CN106832588A (en) * | 2017-02-17 | 2017-06-13 | 哈尔滨工程大学 | Ultralight buoyant material and its supercritical CO can be processed2Fretting map preparation method |
| CN109078509B (en) * | 2017-06-14 | 2020-10-23 | 宁波绿色方舟环境科技有限公司 | Fluorinated ethylene propylene hollow fiber membrane and preparation method thereof |
| CN109078500B (en) * | 2017-06-14 | 2020-10-20 | 宁波绿色方舟环境科技有限公司 | Fluorine-containing polymer flat membrane and preparation method thereof |
| CN109929135A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院宁波材料技术与工程研究所 | Polymer bimodal cell material and preparation method thereof |
| US20190193052A1 (en) * | 2017-12-26 | 2019-06-27 | The Procter & Gamble Company | Fluid etched foam |
| CN109705465B (en) * | 2018-12-29 | 2021-03-05 | 中国科学院宁波材料技术与工程研究所 | Hollow polyolefin foam material and preparation method thereof |
| JP7383266B2 (en) * | 2021-01-29 | 2023-11-20 | プライムプラネットエナジー＆ソリューションズ株式会社 | Method for producing porous olefin resin material |
| CN112980098A (en) * | 2021-03-23 | 2021-06-18 | 南京旭智材料科技有限公司 | High-resilience antistatic polyolefin oil absorption foam and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1861368A (en) * | 2006-06-09 | 2006-11-15 | 北京化工大学 | Method for producing non-cross-linking PP foam material |
| CN101538387A (en) * | 2008-03-17 | 2009-09-23 | 中国科学院宁波材料技术与工程研究所 | Polypropylene foaming material and production method thereof |
| CN101735474A (en) * | 2009-12-23 | 2010-06-16 | 中国石油天然气股份有限公司 | Hydrophilic polyethene microporous membrane and preparation method thereof |
| CN102989328A (en) * | 2011-09-15 | 2013-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Polypropylene film with nano-pore structure, and preparation method thereof |
| CN103435836A (en) * | 2013-07-30 | 2013-12-11 | 四川大学 | Preparation method of polymer foam material in open pore structure |
| CN104592543A (en) * | 2015-02-02 | 2015-05-06 | 四川大学 | Porous polymer material with dual-peak pore structure and preparation method thereof |
| CN104629176A (en) * | 2015-01-22 | 2015-05-20 | 浙江新恒泰新材料有限公司 | Open-celled polypropylene microcellular foaming sheet and production method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010037367A (en) * | 2008-07-31 | 2010-02-18 | Asahi Fiber Glass Co Ltd | Polyolefin resin foam and production method thereof |
| JP2011006626A (en) * | 2009-06-29 | 2011-01-13 | Tosoh Corp | Polyethylene open-cell foam and process for producing the same |
| JP2011219678A (en) * | 2010-04-13 | 2011-11-04 | Tosoh Corp | Polyethylene-based resin composition, foam, and method for manufacturing the same |
-
2015
- 2015-07-01 CN CN201510392373.2A patent/CN105001512B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1861368A (en) * | 2006-06-09 | 2006-11-15 | 北京化工大学 | Method for producing non-cross-linking PP foam material |
| CN101538387A (en) * | 2008-03-17 | 2009-09-23 | 中国科学院宁波材料技术与工程研究所 | Polypropylene foaming material and production method thereof |
| CN101735474A (en) * | 2009-12-23 | 2010-06-16 | 中国石油天然气股份有限公司 | Hydrophilic polyethene microporous membrane and preparation method thereof |
| CN102989328A (en) * | 2011-09-15 | 2013-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Polypropylene film with nano-pore structure, and preparation method thereof |
| CN103435836A (en) * | 2013-07-30 | 2013-12-11 | 四川大学 | Preparation method of polymer foam material in open pore structure |
| CN104629176A (en) * | 2015-01-22 | 2015-05-20 | 浙江新恒泰新材料有限公司 | Open-celled polypropylene microcellular foaming sheet and production method thereof |
| CN104592543A (en) * | 2015-02-02 | 2015-05-06 | 四川大学 | Porous polymer material with dual-peak pore structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Effect of Polytetrafluoroethylene on the Foaming Behaviors of Linear Polypropylene in Continuous Extrusion;Kun Wang et al.;《Journal of Applied polymer Science》;20130115;2253-2260 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105001512A (en) | 2015-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105001512B (en) | A kind of open cell polymer foams and preparation method thereof | |
| CN104974424B (en) | A kind of open cell polymer foams and preparation method thereof | |
| CN103525387B (en) | Foamed cement slurry system and composition | |
| CN105037954A (en) | Overpressure-resistant polypropylene thermal insulation material, preparation method and applications thereof | |
| CN105419753A (en) | novel leakage-preventing while drilling agent for oil-based drilling fluid and application | |
| CN110172176B (en) | Polyurethane reticular foam leaking stoppage reinforcing agent for drilling fluid, preparation method and application thereof | |
| CN104164224B (en) | A kind of inverse emulsion drilling fluid and its preparation method and application | |
| CN103087367A (en) | High-performance water swellable rubber and preparation method thereof | |
| Pang et al. | Kinetics study of oil sorption with open‐cell polypropylene/polyolefin elastomer blend foams prepared via continuous extrusion foaming | |
| CN109904451A (en) | A kind of graphene composite material and its preparation method and application | |
| CN107082610A (en) | A kind of silane-modified concrete and preparation method thereof | |
| CN105331352B (en) | A kind of preparation method of seawater-based fracturing fluid and seawater-based fracturing fluid | |
| Guo et al. | Supercritical CO2 assisted construction of carbon black/polypropylene composite foams with bioinspired open-cell micro-nano hierarchical structure and outstanding performance for oil/water separation | |
| CN110078986A (en) | A kind of preparation method of difunctional expanded elastomers material | |
| CN103951866A (en) | Foamed polyolefin composition and polyolefin foamed material, preparation method of foamed polyolefin composition as well as product prepared by adopting foamed polyolefin composition | |
| CN104004259A (en) | Foamed polyolefin composition, polyolefin foamed material, preparation method thereof and product prepared from composition | |
| CN107987813A (en) | A kind of Polymer-supported type coagulant and preparation method thereof and cement mortar | |
| CN111548777B (en) | Sea area natural gas hydrate drilling fluid and preparation method and application thereof | |
| CN112980098A (en) | High-resilience antistatic polyolefin oil absorption foam and preparation method thereof | |
| CN103203226A (en) | Graphite powder-butyl rubber composite frozen gel oil absorption material and preparation method thereof | |
| CN109593545A (en) | A kind of compounding desulfurizing agent and preparation method thereof suitable for high oil content oil well | |
| CN102492228B (en) | Foamed rubber and preparation method thereof | |
| CN111534001B (en) | High oil absorption polypropylene material and preparation method thereof | |
| CN112662081B (en) | Preparation method of waterproof sealing gasket material for submarine shield tunnel | |
| CN115505070A (en) | High-temperature-resistant expansion fiber resin plugging material, preparation method thereof and application thereof in leak prevention and plugging of well cementation cement slurry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |