CN106221042B - A kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity and preparation method thereof - Google Patents
A kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity and preparation method thereof Download PDFInfo
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- CN106221042B CN106221042B CN201610711676.0A CN201610711676A CN106221042B CN 106221042 B CN106221042 B CN 106221042B CN 201610711676 A CN201610711676 A CN 201610711676A CN 106221042 B CN106221042 B CN 106221042B
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- pentene
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- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 239000006260 foam Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 82
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000002708 enhancing effect Effects 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 66
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 29
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 238000005728 strengthening Methods 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 6
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 description 22
- 239000007788 liquid Substances 0.000 description 22
- 238000002604 ultrasonography Methods 0.000 description 16
- 238000007711 solidification Methods 0.000 description 13
- 230000008023 solidification Effects 0.000 description 13
- 238000003760 magnetic stirring Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010792 warming Methods 0.000 description 7
- 239000004620 low density foam Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 229920006389 polyphenyl polymer Polymers 0.000 description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- 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
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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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
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- 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
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
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- C08J2425/06—Polystyrene
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- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/16—Homopolymers or copolymers of alkyl-substituted styrenes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, belongs to polymeric material field, as mass fraction, including poly- 4-methyl-1-pentene 50~99.8% and reinforcing agent 0.2~50%；Reinforcing agent is at least one of polymer intensifier and inorganic enhancing.By the way that reinforcing agent is added in traditional poly- 4-methyl-1-pentene foam of low-density, it will be apparent that improve the frame strength of the poly- 4-methyl-1-pentene foam of low-density, and then improve the processing performance of foam and improve the mechanical property of foam.The present invention also proposes a kind of preparation method of the poly- 4-methyl-1-pentene foam of the low-density of high intensity, the preparation method is easy to operate, process stabilizing, too complicated equipment is not needed, only simple several steps can efficiently obtain the high-intensitive poly- 4-methyl-1-pentene foam of low-density, obtained froth pulp parameters are stablized, and reproducibility is high.
Description
Technical field
The present invention relates to polymeric material fields, in particular to a kind of poly- 4- methyl-1-of low-density of high intensity
Amylene foam (PMP) and preparation method thereof.
Background technique
Low-density polymeric porous material is a kind of excellent functional material, due to many unique physical properties,
Such as high dielectric constant, low thermal conductivity, low-density, high-specific surface area, may be used as catalyst carrier, heat-barrier material, gas
Body filter device, IC substrate etc..Wherein, PMP foamed material ingredient is pure hydrocarbon material, has intensity higher and molding
The advantages that being easy is currently to apply and study most wide low density foam in inertial confinement fusion (ICF) experimental study in the world
One of material.
The hardness and strength of PMP foam and its density are almost in a linear relationship, and in the prior art, density is higher than 30mg/
cm3PMP foam comparatively robust, excipient can be machined.And 30mg/cm is lower than for density3PMP foam, due to gelinite
Be intensity is low, brittleness is big, machining when easily there are a variety of bad phenomenons, bring very high difficulty to machining, and
With this kind of low-density PMP Foam machining, finally product mechanical property obtained is poor.
Summary of the invention
The purpose of the present invention is to provide a kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, more existing skills
The poly- 4-methyl-1-pentene foam of low-density in art has higher mechanical strength, can conveniently be processed into required shape.
Another object of the present invention is to provide a kind of preparations of the poly- 4-methyl-1-pentene foam of the low-density of high intensity
Method, this method is easy to operate, process stabilizing, the equipment of needs are simple, can be efficiently synthesized the high-intensitive poly- 4- first of low-density
Base -1- amylene foam.
The embodiment of the present invention is achieved in that
A kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, which is characterized in that as mass fraction, including
Poly- 4-methyl-1-pentene 50~99.8% and reinforcing agent 0.2~50%；Reinforcing agent is in polymer intensifier and inorganic enhancing
At least one.
A kind of preparation method of the poly- 4-methyl-1-pentene foam of the low-density of high intensity, includes the following steps:
It prepares polymer solution step: solvent, poly- 4-methyl-1-pentene and reinforcing agent being uniformly mixed and heated, is obtained
Polymer solution；
It prepares foam of polymers step: obtaining the poly- 4- methyl-1-pentene of low-density after will be polymer solutions gelled, dry
Alkene foam.
The beneficial effect of the embodiment of the present invention is: a kind of poly- 4- methyl-1-pentene of the low-density of high intensity proposed by the present invention
Reinforcing agent is added in traditional poly- 4-methyl-1-pentene foam of low-density, it will be apparent that improves the poly- 4- of low-density in alkene foam
The frame strength of Methyl-1-pentene foam, and then improve the processing performance of foam and improve the mechanical property of foam.The present invention is also
A kind of preparation method of the poly- 4-methyl-1-pentene foam of low-density of high intensity is proposed, the preparation method is easy to operate, work
Skill is stablized, and too complicated equipment is not needed, and only simple several steps can efficiently obtain the high-intensitive poly- 4- first of low-density
Base -1- amylene foam, obtained froth pulp parameters are stablized, and reproducibility is high.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to a kind of poly- 4-methyl-1-pentene foam of low-density of high intensity of the embodiment of the present invention and its preparation side
Method is specifically described.
The invention proposes a kind of poly- 4-methyl-1-pentene foams of the low-density of high intensity, which is characterized in that presses quality
Score meter, including poly- 4-methyl-1-pentene 50~99.8% and reinforcing agent 0.2~50%；Reinforcing agent be polymer intensifier and
At least one of inorganic enhancing.
Further, in the other preferred embodiments of the present invention, as mass fraction, the poly- 4-methyl-1-pentene of low-density
Foam includes poly- 4-methyl-1-pentene 50~75% and reinforcing agent 25~50%.
Further, in the other preferred embodiments of the present invention, polymer intensifier is polystyrene and poly- 4- tert-butyl
Any one of styrene.Preferably, polystyrene weight average molecular weight is greater than 300,000, poly- 4- t-butyl styrene Weight-average molecular
Amount is greater than 100,000.Contain big and hard side group phenyl ring class formation in polystyrene and the strand of poly- 4- t-butyl styrene, it should
Class reinforcing agent molecule chain rigidity is the poly- 4-methyl-1-pentene of alkyl much larger than side group, is added to as reinforcing agent
The frame strength of poly- 4-methyl-1-pentene foam can be enhanced in poly- 4-methyl-1-pentene, and then improve adding for froth pulp
Work performance and the mechanical property for improving froth pulp.
Further, in the other preferred embodiments of the present invention, inorganic strengthening agent is carbon nanotube.Preferably, carbon nanometer
For length of tube less than 25 μm, the quality of carbon nanotube is the 0.05~0.5% of the quality of poly- 4-methyl-1-pentene.Carbon nanotube tool
There is excellent mechanical property, elasticity modulus adds carbon nanotube as increasing up to 1TPa in poly- 4-methyl-1-pentene foam
Strong agent can be improved the frame strength of poly- 4-methyl-1-pentene foam, and then improve the processing performance and raising of froth pulp
The mechanical property of froth pulp.
The present invention also proposes a kind of preparation method of the poly- 4-methyl-1-pentene foam of the low-density of high intensity, including preparation
Polymer solution step: solvent, poly- 4-methyl-1-pentene and reinforcing agent are uniformly mixed and are heated, polymer solution is obtained.
Further, in the other preferred embodiments of the present invention, reinforcing agent includes inorganic strengthening agent, above-mentioned to prepare polymer
Further include the steps that for solvent and inorganic strengthening agent being pre-mixed in solution step.Specifically, the mode of premixing is in 60~80
10~30min of ultrasonic disperse at DEG C.Enough temperature can keep the mobility of solvent, under the action of ultrasound, make solvent mixed
That closes is more uniform, while allowing the dispersion of inorganic strengthening agent in a solvent more evenly.
Further, in the other preferred embodiments of the present invention, solvent is mixed by suitable solvents and non-solubility solvent
It is made, the quality of suitable solvents is the 30~60% of the quality of solvent.Specifically, suitable solvents are durol, it is non-can
Soluble solvent is naphthalene.Using the solvent of suitable solvents and non-solubility solvent being mixed in a certain ratio, in subsequent step
In rapid, poly- 4-methyl-1-pentene and reinforcing agent can be made to obtain better dispersion effect in a solvent, so that obtaining final
To the poly- 4-methyl-1-pentene foam of low-density in, reinforcing agent can be uniformly distributed, and guarantee power everywhere in foamed material
Learn balancing performance.
Further, in the other preferred embodiments of the present invention, the quality of poly- 4-methyl-1-pentene is polymer solution
Quality 0.87~2.26%.The ratio of poly- 4-methyl-1-pentene and solvent suitably just can guarantee the flowing of polymer solution
Property, poly- 4-methyl-1-pentene could be preferably scattered in polymer solution.The dosage of poly- 4-methyl-1-pentene is excessive
In the case of, foam density is higher than 30mg/cm3, there is preferable processing performance and mechanical property, but it has been not belonging to the present invention
The range of related low density foam can not have to the method and improve its mechanical property.
Further, in other preferred embodiments of the invention, solvent, poly- 4-methyl-1-pentene and reinforcing agent exist
Heating stirring mixes at 150~180 DEG C, obtains polymer solution.Whipping process maintains at such a temperature, solvent can be made to be in
The state all melted, can guarantee the mobility of polymer solution, and avoid occur condensing before stirring evenly from showing
As.
A kind of preparation method of the poly- 4-methyl-1-pentene foam of low-density of high intensity proposed by the present invention further includes system
Standby foam of polymers step: the poly- 4-methyl-1-pentene foam of low-density is obtained after will be polymer solutions gelled, dry.
Further, in other preferred embodiments of the invention, polymer solution also needs to be surpassed before gelation
Sonication.Specifically, ultrasonic treatment needs to maintain 150~180 DEG C, and the time of ultrasonic treatment is 10min.Ultrasonic treatment can be with
It makes polymer solution more uniform, guarantees being sufficiently mixed for the poly- 4-methyl-1-pentene of low-density and inorganic strengthening agent, allow obtain
Froth pulp it is homogeneous, each section mechanical strength is suitable.Ultrasonic treatment also needs to maintain 150~180 DEG C, to prevent
Condensation.
Further, in other preferred embodiments of the invention, polymer solution stands 12 at room temperature~it carries out for 24 hours
Gelation.Enough setting times can allow gel forming better effect, more sufficiently.
Further, in other preferred embodiments of the invention, dry mode uses boulton process.Drying can be with
Solvent is removed, the poly- 4-methyl-1-pentene foam of low-density is obtained.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment proposes that a kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, preparation method are as follows:
20.1g naphthalene is sequentially added in ground flask, 27.1g durol is mixed into solvent, magneton is added into solvent,
And under magnetic stirring oil bath heating to 180 DEG C.The poly- 4-methyl-1-pentene of 0.82g and 0.27g polyphenyl is added into solvent again
Ethylene, stirring 2h is completely dissolved to poly- 4-methyl-1-pentene is made polymer solution.Polymer solution is transferred to preheating
In mold, cooled to room temperature, and 12h is stood at room temperature, until polymer solution solidifies completely, by the polymerization after solidification
Object solution moves to dry removal solvent in vacuum oven, obtains the high-intensitive poly- 4-methyl-1-pentene foam of low-density.
Embodiment 2
The present embodiment proposes that a kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, preparation method are as follows:
20.1g naphthalene is sequentially added in ground flask, 27.1g durol is mixed into solvent, magneton is added into solvent,
And under magnetic stirring oil bath heating to 180 DEG C.The poly- 4-methyl-1-pentene of 0.545g is added into solvent again and 0.545g is poly-
Styrene, stirring 3h is completely dissolved to poly- 4-methyl-1-pentene is made polymer solution.Polymer solution is transferred to preheating
Mold in, cooled to room temperature, and stand 16h at room temperature will be poly- after solidification until polymer solution solidifies completely
Polymer solution moves to dry removal solvent in vacuum oven, obtains the high-intensitive poly- 4-methyl-1-pentene foam of low-density.
Embodiment 3
The present embodiment proposes that a kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, preparation method are as follows:
20.1g naphthalene is sequentially added in ground flask, 27.1g durol is mixed into solvent, magneton is added into solvent,
And under magnetic stirring oil bath heating to 180 DEG C.The poly- 4-methyl-1-pentene of 0.79g and 0.3g polyphenyl second is added into solvent again
Alkene, stirring 2h is completely dissolved to poly- 4-methyl-1-pentene is made polymer solution.Polymer solution is transferred to the mould of preheating
In tool, cooled to room temperature, and stand at room temperature for 24 hours, until polymer solution solidifies completely, by the polymer after solidification
Solution moves to dry removal solvent in vacuum oven, obtains the high-intensitive poly- 4-methyl-1-pentene foam of low-density.
Embodiment 4
The present embodiment proposes that a kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, preparation method are as follows:
33g naphthalene is sequentially added in ground flask, 14.2g durol is mixed into solvent, magneton is added into solvent, and
Oil bath heating is to 150 DEG C under magnetic stirring.The poly- 4-methyl-1-pentene of 0.58g and poly- uncle 4- of 0.51g is added into solvent again
Butylstyrene, stirring 2h is completely dissolved to poly- 4-methyl-1-pentene is made polymer solution.Polymer solution is transferred to
In the mold of preheating, cooled to room temperature, and 18h is stood at room temperature, until polymer solution solidifies completely, after solidification
Polymer solution move in vacuum oven dry removal solvent, obtain the poly- 4-methyl-1-pentene bubble of high-intensitive low-density
Foam.
Embodiment 5
The present embodiment proposes that a kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, preparation method are as follows:
18.8g naphthalene is sequentially added in ground flask, 28.4g durol is mixed into solvent, magneton is added into solvent,
And under magnetic stirring oil bath heating to 170 DEG C.The poly- 4-methyl-1-pentene of 0.6g and the poly- 4- of 0.49g is added into solvent again
T-butyl styrene, stirring 2h is completely dissolved to poly- 4-methyl-1-pentene is made polymer solution.Polymer solution is shifted
Into the mold of preheating, cooled to room temperature, and 18h is stood at room temperature, until polymer solution solidifies completely, will solidify
Polymer solution afterwards moves to dry removal solvent in vacuum oven, obtains the high-intensitive poly- 4-methyl-1-pentene of low-density
Foam.
Embodiment 6
The present embodiment proposes that a kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, preparation method are as follows:
23.1g naphthalene is sequentially added in ground flask, 24.1g durol is mixed into solvent, 0.6mg is added into solvent
Carbon nanotube and magneton, dispersion liquid is made to 80 DEG C in oil bath heating under magnetic stirring.Dispersion liquid is placed in 90 DEG C of hot water
The pre-dispersed 30min of ultrasound.Dispersion liquid after ultrasound is moved in oil bath and is warming up to 180 DEG C, then simultaneously to the dispersion liquid after ultrasound
Oil bath heating is to 180 DEG C under magnetic stirring.The poly- 4-methyl-1-pentene of 1.09g is added into solvent again, stirs 2h to poly- 4-
Methyl-1-pentene, which is completely dissolved, is made polymer solution.Polymer solution is transferred in the mold of preheating, room is naturally cooled to
Temperature, and 18h is stood at room temperature, until polymer solution solidifies completely, the polymer solution after solidification is moved into vacuum drying
Dry removal solvent, obtains the high-intensitive poly- 4-methyl-1-pentene foam of low-density in case.
Embodiment 7
The present embodiment proposes that a kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, preparation method are as follows:
20.1g naphthalene is sequentially added in ground flask, 27.1g durol is mixed into solvent, 1.6mg is added in a solvent
Carbon nanotube and magneton, dispersion liquid is made to 80 DEG C in oil bath heating under magnetic stirring.Dispersion liquid is placed in 90 DEG C of hot water
The pre-dispersed 30min of ultrasound.Dispersion liquid after ultrasound is moved in oil bath and is warming up to 180 DEG C, then into the dispersion liquid after ultrasound
The poly- 4-methyl-1-pentene of 0.84g is added, stirring 2h is completely dissolved to poly- 4-methyl-1-pentene is made polymer solution.It will gather
It is ultrasonically treated 10min at polymer solution and 180 DEG C, is transferred in the mold of preheating, cooled to room temperature, and quiet at room temperature
It sets for 24 hours, until polymer solution solidifies completely, it is molten that the polymer solution after solidification is moved to dry removal in vacuum oven
Agent obtains the high-intensitive poly- 4-methyl-1-pentene foam of low-density.
Embodiment 8
The present embodiment proposes that a kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, preparation method are as follows:
20.1g naphthalene is sequentially added in ground flask, 27.1g durol is mixed into solvent, 0.5mg is added in a solvent
Carbon nanotube and magneton, dispersion liquid is made to 80 DEG C in oil bath heating under magnetic stirring.Dispersion liquid is placed in 90 DEG C of hot water
The pre-dispersed 30min of ultrasound.Dispersion liquid after ultrasound is moved in oil bath and is warming up to 180 DEG C, then into the dispersion liquid after ultrasound
The poly- 4-methyl-1-pentene of 0.63g and 0.21g polystyrene is added, stirring 2h is completely dissolved to poly- 4-methyl-1-pentene to be made
Polymer solution.It will be ultrasonically treated 10min at polymer solution and 180 DEG C, is transferred in the mold of preheating, naturally cools to room
Temperature, and stand at room temperature for 24 hours, until polymer solution solidifies completely, the polymer solution after solidification is moved into vacuum drying
Dry removal solvent, obtains the high-intensitive poly- 4-methyl-1-pentene foam of low-density in case.
Embodiment 9
The present embodiment proposes that a kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, preparation method are as follows:
20.1g naphthalene is sequentially added in ground flask, 27.1g durol is mixed into solvent, 1.1mg is added in a solvent
Carbon nanotube and magneton, dispersion liquid is made to 80 DEG C in oil bath heating under magnetic stirring.Dispersion liquid is placed in 90 DEG C of hot water
The pre-dispersed 30min of ultrasound.Dispersion liquid after ultrasound is moved in oil bath and is warming up to 180 DEG C, then into the dispersion liquid after ultrasound
The poly- 4-methyl-1-pentene of 0.76g and the poly- 4- t-butyl styrene of 0.08g is added, stirring 2h is complete to poly- 4-methyl-1-pentene
Polymer solution is made in fully dissolved.It will be ultrasonically treated 10min at polymer solution and 180 DEG C, is transferred in the mold of preheating, from
It is so cooled to room temperature, and stands at room temperature for 24 hours, until polymer solution solidifies completely, the polymer solution after solidification is moved
Into vacuum oven, dry removal solvent, obtains the high-intensitive poly- 4-methyl-1-pentene foam of low-density.
Embodiment 10
The present embodiment proposes that a kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, preparation method are as follows:
20.6g naphthalene is sequentially added in ground flask, 26.6g durol is mixed into solvent, 4.2mg is added in a solvent
Carbon nanotube and magneton, dispersion liquid is made to 80 DEG C in oil bath heating under magnetic stirring.Dispersion liquid is placed in 90 DEG C of hot water
The pre-dispersed 30min of ultrasound.Dispersion liquid after ultrasound is moved in oil bath and is warming up to 180 DEG C, then into the dispersion liquid after ultrasound
The poly- 4-methyl-1-pentene of 0.84g is added, stirring 2h is completely dissolved to poly- 4-methyl-1-pentene is made polymer solution.It will gather
It is ultrasonically treated 10min at polymer solution and 180 DEG C, is transferred in the mold of preheating, cooled to room temperature, and quiet at room temperature
It sets for 24 hours, until polymer solution solidifies completely, it is molten that the polymer solution after solidification is moved to dry removal in vacuum oven
Agent obtains the high-intensitive poly- 4-methyl-1-pentene foam of low-density.
Embodiment 11
The present embodiment proposes that a kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, preparation method are as follows:
20.1g naphthalene is sequentially added in ground flask, 27.1g durol is mixed into solvent, magneton is added in a solvent,
Oil bath heating is to 180 DEG C under magnetic stirring, then the poly- 4-methyl-1-pentene of 0.42g and 0.42g polyphenyl second are added into solvent
Alkene, stirring 2h is completely dissolved to poly- 4-methyl-1-pentene is made polymer solution.At ultrasonic at polymer solution and 180 DEG C
10min is managed, is transferred in the mold of preheating, cooled to room temperature, and stand 18h at room temperature, until polymer solution is complete
Polymer solution after solidification is moved to dry removal solvent in vacuum oven, it is poly- to obtain high-intensitive low-density by full solidification
4-methyl-1-pentene foam.
Comparative example 1
This comparative example proposes that a kind of poly- 4-methyl-1-pentene foam of low-density, preparation method are as follows:
20.1g naphthalene, 27.1g durol, the poly- 4-methyl-1-pentene of 1.09g and magneton are sequentially added in ground flask
Mixing, is warming up to 180 DEG C in oil bath and stirs 2h polymer solution is made.Polymer solution is transferred to the mold of preheating
In, cooled to room temperature, and stand at room temperature for 24 hours, until polymer solution solidifies completely, the polymer after solidification is molten
Liquid moves to dry removal solvent in vacuum oven, obtains the poly- 4-methyl-1-pentene foam of low-density.
Comparative example 2
This comparative example proposes that a kind of poly- 4-methyl-1-pentene foam of low-density, preparation method are as follows:
20.1g naphthalene, 27.1g durol, the poly- 4-methyl-1-pentene of 0.84g and magneton are sequentially added in ground flask
Mixing, is warming up to 180 DEG C in oil bath and stirs 2h polymer solution is made.Polymer solution is transferred to the mold of preheating
In, cooled to room temperature, and stand at room temperature for 24 hours, until polymer solution solidifies completely, the polymer after solidification is molten
Liquid moves to dry removal solvent in vacuum oven, obtains the poly- 4-methyl-1-pentene foam of low-density.
Test example
Using the poly- 4-methyl-1-pentene foam of low-density provided by embodiment 1~11 and comparative example 1~2, carry out such as
Lower test:
1. after polymer solutions gelled, first pass through lathe process at diameter and height be 1mm cylinder again into
Row drying weighs to the poly- 4-methyl-1-pentene foam of cylindric low-density is obtained, and is calculate by the following formula density: ρ=
4m/πd2H, wherein ρ is density, and m is the quality of the poly- 4-methyl-1-pentene foam of cylindric low-density, and d is diameter (microscope
Measurement), h is height (being measured microscopically), calculates 3 times and is averaged, calculated result is shown in Table 1；
2. drawing out poly- 4- by mechanic property test method (thermal deformation analyzer, pressure pattern) generally in the art
The load-deformation curve of Methyl-1-pentene foam, and Young's modulus is calculated according to the slope of curve start-up portion, calculate knot
Fruit is shown in Table 1.
The poly- 4-methyl-1-pentene foaming properties of 1. low-density of table compare
| Density (mg/cm3) | Young's modulus (MPa) | |
| Embodiment 1 | 25 | 0.90 |
| Embodiment 2 | 25 | 1.00 |
| Embodiment 3 | 25 | 1.20 |
| Embodiment 4 | 26 | 1.30 |
| Embodiment 5 | 25 | 1.10 |
| Embodiment 6 | 24 | 1.00 |
| Embodiment 7 | 19 | 0.13 |
| Embodiment 8 | 20 | 0.16 |
| Embodiment 9 | 20 | 0.17 |
| Embodiment 10 | 19 | 0.14 |
| Embodiment 11 | 21 | 0.24 |
| Comparative example 1 | 25 | 0.20 |
| Comparative example 2 | 20 | 0.10 |
As shown in table 1, the Young's modulus of poly- 4-methyl-1-pentene foam becomes larger with the increase of density, wherein
20mg/cm3It is an apparent turning point, can shows drastically reducing for modulus, therefore by embodiment 1~11 and comparative example
1~2 when being compared, and should be grouped according to density, density is in 25mg/cm3Provided by the Examples 1 to 6 of left and right
The Young's modulus of the poly- 4-methyl-1-pentene foam of low-density can reach 0.90MPa or more, and from the point of view of comparison, density is all 25mg/
cm3The Young's modulus of comparative example 1 be only 0.20MPa, the poly- 4- methyl-1-of low-density provided by the embodiment of the present invention 1~6
Amylene foam is obviously improved in intensity.On the other hand, density is in 20mg/cm3Provided by the embodiment 7~11 of left and right
The Young's modulus of the poly- 4-methyl-1-pentene foam of low-density can reach 0.13MPa or more, can reach 0.24MPa, comparison
From the point of view of, density is all 20mg/cm3The Young's modulus of comparative example 2 be only 0.10MPa, provided by the embodiment of the present invention 7~11
Although it is so obvious that the poly- 4-methyl-1-pentene foam of low-density promotes too late Examples 1 to 6 in intensity, also have certain
The promotion of degree.
In conclusion the poly- 4-methyl-1-pentene foam of low-density provided in an embodiment of the present invention, by adding strand
The rigidity carbon nanometer high much larger than the polystyrene of poly- 4-methyl-1-pentene and poly- 4- t-butyl styrene or elasticity modulus
Pipe has the effect of being more obviously improved as reinforcing agent, to the mechanical strength of poly- 4-methyl-1-pentene foam.The present invention is implemented
The preparation method for the poly- 4-methyl-1-pentene foam of low-density that example uses is easy to operate, and process stabilizing does not need too complicated
Equipment, only simple several steps can efficiently obtain the high-intensitive poly- 4-methyl-1-pentene foam of low-density, obtained bubble
Foam product parameters are stablized, and reproducibility is high, are suitble to commercial introduction.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of poly- 4-methyl-1-pentene foam of the low-density of high intensity, which is characterized in that as mass fraction, including it is poly-
4-methyl-1-pentene 50~99.8% and reinforcing agent 0.2~50%；The reinforcing agent is polymer intensifier and inorganic enhancing
Agent；The density of the poly- 4-methyl-1-pentene foam of low-density is lower than 30mg/cm3；
The inorganic strengthening agent is carbon nanotube；The quality of the carbon nanotube is the quality of the poly- 4-methyl-1-pentene
0.05~0.5%；The polymer intensifier is any one of polystyrene and poly- 4- t-butyl styrene.
2. the poly- 4-methyl-1-pentene foam of low-density according to claim 1, which is characterized in that as mass fraction,
Including the poly- 4-methyl-1-pentene 50~75% and the reinforcing agent 25~50%.
3. a kind of preparation of such as poly- 4-methyl-1-pentene foam of low-density of the described in any item high intensity of claim 1~2
Method characterized by comprising
It prepares polymer solution step: solvent, the poly- 4-methyl-1-pentene and the reinforcing agent is uniformly mixed and is heated,
Obtain polymer solution；
It prepares foam of polymers step: the poly- 4- methyl-of the low-density will be obtained after the polymer solutions gelled, drying
1- amylene foam.
4. preparation method according to claim 3, which is characterized in that the reinforcing agent includes inorganic strengthening agent；Described
It prepares and includes the steps that for the solvent and the inorganic strengthening agent being pre-mixed in polymer solution step.
5. preparation method according to claim 3, which is characterized in that the solvent is mixed by durol and naphthalene,
The quality of the durol is the 30~60% of the quality of the solvent.
6. preparation method according to claim 3, the quality of the poly- 4-methyl-1-pentene is the polymer solution
Quality 0.87~2.26%.
7. preparation method according to claim 3, the solvent, poly- 4-methyl-1-pentene and reinforcing agent are 150~180
Heating stirring mixes at DEG C, obtains the polymer solution.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040805A (en) * | 1988-09-02 | 1990-03-28 | 三井石油化学工业株式会社 | Heat resistant poly-4 methyl pentene l resin composition and moulded products thereof |
| CN1389507A (en) * | 2001-11-24 | 2003-01-08 | 中国工程物理研究院激光聚变研究中心 | Formula and preparation method of poly-4-methyl-1-pentene low-density foam material |
| CN102863668A (en) * | 2012-09-21 | 2013-01-09 | 霍志明 | Foamed plastic with strong sound insulation |
-
2016
- 2016-08-23 CN CN201610711676.0A patent/CN106221042B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040805A (en) * | 1988-09-02 | 1990-03-28 | 三井石油化学工业株式会社 | Heat resistant poly-4 methyl pentene l resin composition and moulded products thereof |
| CN1389507A (en) * | 2001-11-24 | 2003-01-08 | 中国工程物理研究院激光聚变研究中心 | Formula and preparation method of poly-4-methyl-1-pentene low-density foam material |
| CN102863668A (en) * | 2012-09-21 | 2013-01-09 | 霍志明 | Foamed plastic with strong sound insulation |
Non-Patent Citations (2)
| Title |
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| 碳纳米管对聚4-甲基1-戊烯结晶及力学性能的影响;闫怀文等;《合成树脂及塑料》;20150925;第32卷(第5期);13-16 |
| 超低密度聚-4-甲基-1-戊烯泡沫材料的制备技术;刘才林等;《材料导报》;19970415;第11卷(第2期);46-48 |
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