CN110343326A - Supercritical fluid polymer micro foamed and preparation method thereof - Google Patents
Supercritical fluid polymer micro foamed and preparation method thereof Download PDFInfo
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- CN110343326A CN110343326A CN201910761773.4A CN201910761773A CN110343326A CN 110343326 A CN110343326 A CN 110343326A CN 201910761773 A CN201910761773 A CN 201910761773A CN 110343326 A CN110343326 A CN 110343326A
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- polymer micro
- supercritical fluid
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- vulcanized
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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
-
- 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
-
- 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
- C08J2323/08—Copolymers of ethene
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The present invention provides a kind of supercritical fluid polymer micro foamed and preparation method thereof, the critical fluids polymer micro foamed includes following components: 60 ~ 80 parts of polyethylene-vinyl acetate copolymer；20 ~ 40 parts of thermoplastic polyurethane elastomer；5 ~ 20 parts of filler；0.6 ~ 2 part of vulcanizing agent；And 0.5 ~ 1 part of release agent.The embodiment of the present invention is blended by using polyethylene-vinyl acetate copolymer and thermoplastic polyurethane elastomer, to mixing granulation, vulcanization and crosslinking with radiation are carried out again, then it places into reaction kettle and foams, relative to traditional chemical blowing, it is more environmentally-friendly using physical blowing, lightweight, free from extraneous odour；Meanwhile the product abscess after foaming is finer and smoother uniform, more wear resistant to stop loss, impact strength is bigger, has better thermal stability and toughness, lower thermal coefficient and thermal conductivity, can effectively improve the performance of product.
Description
Technical field
The present invention relates to microporous foam object technical field more particularly to a kind of supercritical fluid polymer micro foamed and
Preparation method.
Background technique
Chemical blowing process is plastic foamed to make using chemical method generation gas: to the chemical foaming agent being added in plastics
Heat being allowed to decompose and releases gas and foam;In addition it also can use and mutually chemically reacted between each plastic fraction
The gas that releases and foam.Using chemical foaming agent carry out foamed plastic injection molding technique substantially with general Shooting Technique
It is identical.Heat temperature raising, mixing, plasticizing and the most foaming and intumescing of plastics are completed in injection molding machine.But it is traditional
It learns foamed material needs to foam in mold, low output, fraction defective is high, and energy consumption is high.
Summary of the invention
The present invention in order to solve the technical problem, provides a kind of supercritical fluid polymer micro foamed and its preparation side
Method, the critical fluids polymer micro foamed includes following components:
60 ~ 80 parts of polyethylene-vinyl acetate copolymer；
20 ~ 40 parts of thermoplastic polyurethane elastomer；
5 ~ 20 parts of filler；
0.6 ~ 2 part of vulcanizing agent；And
0.5 ~ 1 part of release agent.
Further, the critical fluids polymer micro foamed includes following components:
65 ~ 75 parts of polyethylene-vinyl acetate copolymer；
25 ~ 35 parts of thermoplastic polyurethane elastomer；
10 ~ 15 parts of filler；
1 ~ 1.5 part of vulcanizing agent；And
0.7 ~ 0.8 part of release agent.
Further, the filler uses rubber filler；The rubber filler include rubber powder, reclaimed rubber,
One of shellac, cellulose, silicon-containing compound, metal salt and metal oxide are a variety of.
Further, the vulcanizing agent uses elementary sulfur, selenium, tellurium, sulfur-containing compound, peroxide, quinones, amine
One of class compound, resinae compound, metal oxide and isocyanates are a variety of.
Further, the release agent uses high polymer release agent, and the high polymer release agent includes silicone oil, polyethylene glycol
And one of low molecular weight polyethylene or a variety of.
On the other hand, the present invention also provides a kind of preparation methods of supercritical fluid polymer micro foamed, including with
Lower step:
Raw material is blended；
It is molded after cooling；
Vulcanized, crosslinking with radiation and cold and detached hot material molding one of or it is a variety of, be cooled and shaped；
Reaction kettle is put into foam；
It is cooled and shaped.
Further, the step " raw material is blended " specifically includes polyethylene-vinyl acetate copolymer, heat
Plastic polyurethane elastomer and filler carry out mixing granulation.
Further, step " vulcanized, crosslinking with radiation and cold and detached hot material molding one of or it is a variety of " specifically include:
Addition vulcanizing agent is vulcanized,
Carry out crosslinking with radiation；Or
Step " vulcanized, crosslinking with radiation and cold and detached hot material molding one of or it is a variety of " specifically include:
Cold pressing sizing is carried out by module, model or template,
Carry out crosslinking with radiation；Or
Step " vulcanized, crosslinking with radiation and cold and detached hot material molding one of or it is a variety of " specifically include:
Addition vulcanizing agent is simultaneously vulcanized by module, model or template.
Further, step " being put into reaction kettle to foam " specifically includes:
It product after cooling will be vulcanized is put into reaction kettle and foam；Blow pressure be 18 ~ 28Mpa, foamed time be 0.5 ~
5h, blowing temperature are 80 ~ 150 DEG C.
Further, the reaction kettle uses circular cone type reaction kettle or flat reaction kettle.
The beneficial effects of the present invention are: the embodiment of the present invention is by using polyethylene-vinyl acetate copolymer and thermoplastic
Property polyurethane elastomer be blended, thus mixing granulation, then carry out vulcanization and crosslinking with radiation, then place into reaction kettle into
Row foaming, more environmentally-friendly using physical blowing relative to traditional chemical blowing, lightweight, free from extraneous odour；Meanwhile after foaming
Product abscess is finer and smoother, and uniformly more wear resistant to stop loss, impact strength is bigger, has better thermal stability and toughness, lower
Thermal coefficient and thermal conductivity, the performance of product can be effectively improved.
Detailed description of the invention
Fig. 1 is the step process of preparation method one embodiment of supercritical fluid polymer micro foamed of the present invention
Figure.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
In the description of the present invention, it is to be understood that, term " center ", " longitudinal direction ", " transverse direction ", " length ", " width ",
" thickness ", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom" "inner", "outside", " up time
The orientation or positional relationship of the instructions such as needle ", " counterclockwise " is to be based on the orientation or positional relationship shown in the drawings, and is merely for convenience of
The description present invention and simplified description, rather than the device or element of indication or suggestion meaning must have a particular orientation, with spy
Fixed orientation construction and operation, therefore be not considered as limiting the invention.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include one or more of the features.In the description of the present invention, the meaning of " plurality " is two or more,
Unless otherwise specifically defined.
In the present invention unless specifically defined or limited otherwise, term " installation ", " connected ", " connection ", " fixation " etc.
Term shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or be integrally connected；It can be machine
Tool connection, is also possible to be electrically connected；It can be directly connected, two members can also be can be indirectly connected through an intermediary
Connection inside part.For the ordinary skill in the art, above-mentioned term can be understood in this hair as the case may be
Concrete meaning in bright.
In the present invention unless specifically defined or limited otherwise, fisrt feature second feature "upper" or "lower"
It may include that the first and second features directly contact, also may include that the first and second features are not direct contacts but pass through it
Between other characterisation contact.Moreover, fisrt feature includes the first spy above the second feature " above ", " above " and " above "
Sign is right above second feature and oblique upper, or is merely representative of first feature horizontal height higher than second feature.Fisrt feature exists
Second feature " under ", " lower section " and " following " include that fisrt feature is directly below and diagonally below the second feature, or is merely representative of
First feature horizontal height is less than second feature.
Below by specific embodiment combination attached drawing, invention is further described in detail.
The present invention provides a kind of supercritical fluid polymer micro foamed and preparation method thereof, the critical fluids are poly-
Closing object microporous foam object includes following components:
60 ~ 80 parts of polyethylene-vinyl acetate copolymer；
20 ~ 40 parts of thermoplastic polyurethane elastomer；
5 ~ 20 parts of filler；
0.6 ~ 2 part of vulcanizing agent；And
0.5 ~ 1 part of release agent.
The embodiment of the present invention is total to by using polyethylene-vinyl acetate copolymer and thermoplastic polyurethane elastomer
It is mixed, thus mixing granulation, then vulcanization and crosslinking with radiation are carried out, it then places into reaction kettle and foams, relative to traditional
Chemical blowing, lightweight more environmentally-friendly using physical blowing, free from extraneous odour；Meanwhile the product abscess after foaming is finer and smoother
Even, more wear resistant to stop loss, impact strength is bigger, has better thermal stability and toughness, lower thermal coefficient and thermal conductivity,
The performance of product can be effectively improved.
In addition, improvement material performance, or energy increase-volume, weight gain can be effectively improved using filler, the cost of material is reduced
Solid matter.No matter natural rubber or synthetic rubber, the additional amount of filler accounts for its gross weight in most rubber processing product
The 10 ~ 50% of amount, the kind of application almost summarise all filler kinds, and the Adding Way of use is mainly kneaded.According to right
The different of requirements such as rubber product abrasion, elongation, hardness tensile strength, permanent deformation, tearing strength, meeting elasticity select difference
Additive and additional amount, improve its performance and economy；
The substance that rubber can be made under certain condition to vulcanize is referred to as vulcanizing agent, and so-called vulcanization is to make rubber linear molecule knot
Structure becomes solid netted mechanism by " bridge formation " of vulcanizing agent, so that the mechanical and physical performance of rubber be made significantly to be changed
It is kind.
Release agent is a kind of functional materials between mold and finished product.Release agent is chemically resistant, with difference
It is not dissolved when chemical analysis (the especially styrene and amine) contact of resin.Release agent also has heat-resisting and stress performance,
It is not easily decomposed or wears；Release agent is adhered on mold and is not transfer on processed product, do not interfere spray painting or other two
Secondary process operation.It is convenient for removing from the mold product using release agent.
In one alternate embodiment, the critical fluids polymer micro foamed includes following components:
65 ~ 75 parts of polyethylene-vinyl acetate copolymer；
25 ~ 35 parts of thermoplastic polyurethane elastomer；
10 ~ 15 parts of filler；
1 ~ 1.5 part of vulcanizing agent；And
0.7 ~ 0.8 part of release agent.
Specifically, 70 parts of the polyethylene-vinyl acetate copolymer；
30 parts of thermoplastic polyurethane elastomer；
15 parts of filler；
1 part of vulcanizing agent；And
0.7 part of release agent.
Or 75 parts of polyethylene-vinyl acetate copolymer；
25 parts of thermoplastic polyurethane elastomer；
10 parts of filler；
1.5 parts of vulcanizing agent；And
0.7 part of release agent.
In one alternate embodiment, the filler uses rubber filler；The rubber filler includes glue
One of powder, reclaimed rubber, shellac, cellulose, silicon-containing compound, metal salt and metal oxide are a variety of.Using filler,
The properties of product can be effectively increased.
In one alternate embodiment, the vulcanizing agent uses elementary sulfur, selenium, tellurium, sulfur-containing compound, peroxide, quinone
One of class compound, aminated compounds, resinae compound, metal oxide and isocyanates are a variety of.Use sulphur
Agent can make rubber linearity molecular structure become solid netted mechanism by " bridge formation " of vulcanizing agent, to make the machine of rubber
Tool physical property is significantly improved.Specifically, the vulcanizing agent uses ethylene propylene diene rubber or polyolefin elastomer；Ternary
EP rubbers is the terpolymer of ethylene, propylene and non-conjugated diene hydrocarbon.The most important characteristic of EPDM is exactly that its is superior
Resistance to oxidation, ozone-resistant and erosion-resistant ability；It has fabulous vulcanization characteristics.In all rubber, EPDM has minimum
Specific gravity, therefore rubber compound that can be cheap with cost of manufacture；Polyolefin elastomer (Polyolefin elastomer)
It (POE) is the thermoplastic elastic being distributed as catalyst with narrow molecular weight distribution and uniform short-chain branch using metallocene
Body；POE molecular structure is similar to ethylene propylene diene rubber (EPDM), therefore POE can also have ageing-resistant, resistance to ozone, chemically-resistant to be situated between
The excellent properties such as matter, by being crosslinked to POE, the heat resisting temperature of material is enhanced, and permanent deformation reduces, and tensile strength is torn
The main mechanical properties such as resistance to spalling all have significant improvement.
In one alternate embodiment, the release agent uses high polymer release agent, and the high polymer release agent includes silicon
One of oil, polyethylene glycol and low molecular weight polyethylene are a variety of.It is convenient for removing from the mold product using release agent.
As shown in Figure 1, on the other hand, the present invention also provides a kind of preparation sides of supercritical fluid polymer micro foamed
Method, comprising the following steps:
Raw material is blended；
It is molded after cooling；
Vulcanized, crosslinking with radiation and cold and detached hot material molding one of or it is a variety of, be cooled and shaped；
Reaction kettle is put into foam；
It is cooled and shaped.
The embodiment of the present invention is total to by using polyethylene-vinyl acetate copolymer and thermoplastic polyurethane elastomer
It is mixed, thus mixing granulation, then vulcanization and crosslinking with radiation are carried out, it then places into reaction kettle and foams, relative to traditional
Chemical blowing, lightweight more environmentally-friendly using physical blowing, free from extraneous odour；Meanwhile the product abscess after foaming is finer and smoother
Even, more wear resistant to stop loss, impact strength is bigger, has better thermal stability and toughness, lower thermal coefficient and thermal conductivity,
The performance of product can be effectively improved.
In one alternate embodiment, the step " raw material is blended " specifically includes polyethylene vinyl acetate
Ester copolymer, thermoplastic polyurethane elastomer and filler carry out mixing granulation.Blending refers to common mixing, is a kind of physics side
Method mixes different materials uniformly, the method to improve material property, industrially with rubber mixing machine by different rubber or rubber and modeling
Material, being equably kneaded into sizing material is typical example, the ingredient of certain properties can also be added in the polymer to change
The performance of polymer such as electric conductivity etc..
In one alternate embodiment, step " vulcanized, crosslinking with radiation and cold and detached hot material molding one of or it is more
Kind " specifically include:
Addition vulcanizing agent is vulcanized,
Carry out crosslinking with radiation；Or
Step " vulcanized, crosslinking with radiation and cold and detached hot material molding one of or it is a variety of " specifically include:
Cold pressing sizing is carried out by module, model or template,
Carry out crosslinking with radiation；Or
Step " vulcanized, crosslinking with radiation and cold and detached hot material molding one of or it is a variety of " specifically include:
Addition vulcanizing agent is simultaneously vulcanized by module, model or template.
In the present embodiment, one of vulcanization, crosslinking with radiation and cold and detached hot material molding or a variety of raising products can be passed through
Performance so that product quality is more preferable.
In one alternate embodiment, step " being put into reaction kettle to foam " specifically includes:
It product after cooling will be vulcanized is put into reaction kettle and foam；Blow pressure be 18 ~ 28Mpa, foamed time be 0.5 ~
5h, blowing temperature are 80 ~ 150 DEG C.
During foaming, the stability and harmony of the temperature and pressure of reaction kettle are the key that prepare foamed material
Factor, likewise, step " raw material is blended " and step " vulcanized, one in the molding of crosslinking with radiation and cold and detached hot material
Kind is a variety of " it is all made of same reaction condition and environment with reaction kettle foaming.
In one alternate embodiment, the reaction kettle uses circular cone type reaction kettle or flat reaction kettle.Use difference
Reaction kettle can produce different types of product, it is simple and convenient.
In the description of this specification, reference term " embodiment ", " some embodiments ", " an implementation
The description of example ", " some embodiments ", " example ", " specific example " or " some examples " etc. means to combine the embodiment or example
Particular features, structures, materials, or characteristics described are included at least one embodiment or example of the invention.In this explanation
In book, schematic expression of the above terms be may not refer to the same embodiment or example.Moreover, the specific spy of description
Sign, structure, material or feature can be combined in any suitable manner in any one or more of the embodiments or examples.
The above content is specific embodiment is combined, further detailed description of the invention, and it cannot be said that this hair
Bright specific implementation is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, it is not taking off
Under the premise of from present inventive concept, a number of simple deductions or replacements can also be made.
Claims (10)
1. a kind of supercritical fluid polymer micro foamed, which is characterized in that the critical fluids polymer micro foamed
Including following components:
60 ~ 80 parts of polyethylene-vinyl acetate copolymer；
20 ~ 40 parts of thermoplastic polyurethane elastomer；
5 ~ 20 parts of filler；
0.6 ~ 2 part of vulcanizing agent；And
0.5 ~ 1 part of release agent.
2. supercritical fluid polymer micro foamed as described in claim 1, which is characterized in that the critical fluids polymerization
Object microporous foam object includes following components:
65 ~ 75 parts of polyethylene-vinyl acetate copolymer；
25 ~ 35 parts of thermoplastic polyurethane elastomer；
10 ~ 15 parts of filler；
1 ~ 1.5 part of vulcanizing agent；And
0.7 ~ 0.8 part of release agent.
3. supercritical fluid polymer micro foamed as described in claim 1, which is characterized in that the filler uses rubber
Glue filler；The rubber filler includes rubber powder, reclaimed rubber, shellac, cellulose, silicon-containing compound, metal salt and gold
Belong to one of oxide or a variety of.
4. supercritical fluid polymer micro foamed as described in claim 1, which is characterized in that the vulcanizing agent is using member
Plain sulphur, selenium, tellurium, sulfur-containing compound, peroxide, quinones, aminated compounds, resinae compound, metal oxide
And one of isocyanates or a variety of.
5. supercritical fluid polymer micro foamed as described in claim 1, which is characterized in that the release agent is using high
Polymers release agent, the high polymer release agent include one of silicone oil, polyethylene glycol and low molecular weight polyethylene or a variety of.
6. a kind of preparation method of such as described in any item supercritical fluid polymer micro foameds of claim 1 ~ 5, special
Sign is, comprising the following steps:
Raw material is blended；
It is molded after cooling；
Vulcanized, crosslinking with radiation and cold and detached hot material molding one of or it is a variety of, be cooled and shaped；
Reaction kettle is put into foam；
It is cooled and shaped.
7. the preparation method of supercritical fluid polymer micro foamed as claimed in claim 6, which is characterized in that the step
Suddenly " raw material is blended " and is specifically included polyethylene-vinyl acetate copolymer, thermoplastic polyurethane elastomer and filling
Agent carries out mixing granulation.
8. the preparation method of supercritical fluid polymer micro foamed as claimed in claim 6, which is characterized in that step
" vulcanized, crosslinking with radiation and cold and detached hot material molding one of or it is a variety of " specifically include:
Addition vulcanizing agent is vulcanized,
Carry out crosslinking with radiation；Or
Step " vulcanized, crosslinking with radiation and cold and detached hot material molding one of or it is a variety of " specifically include:
Cold pressing sizing is carried out by module, model or template,
Carry out crosslinking with radiation；Or
Step " vulcanized, crosslinking with radiation and cold and detached hot material molding one of or it is a variety of " specifically include:
Addition vulcanizing agent is simultaneously vulcanized by module, model or template.
9. the preparation method of supercritical fluid polymer micro foamed as claimed in claim 6, which is characterized in that step
" being put into reaction kettle to foam " specifically includes:
It product after cooling will be vulcanized is put into reaction kettle and foam；Blow pressure be 18 ~ 28Mpa, foamed time be 0.5 ~
5h, blowing temperature are 80 ~ 150 DEG C.
10. the preparation method of supercritical fluid polymer micro foamed as claimed in claim 6, which is characterized in that described
Reaction kettle uses circular cone type reaction kettle or flat reaction kettle.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113527801A (en) * | 2021-07-16 | 2021-10-22 | 福建三盛实业有限公司 | Supercritical fluid polymer microcellular foam and preparation method thereof |
| CN114989570A (en) * | 2022-04-27 | 2022-09-02 | 中山大学 | Crosslinked thermoplastic elastomer micro-foaming coiled material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102338A (en) * | 2018-01-26 | 2018-06-01 | 青岛科技大学 | A kind of foaming midsole |
-
2019
- 2019-08-19 CN CN201910761773.4A patent/CN110343326A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102338A (en) * | 2018-01-26 | 2018-06-01 | 青岛科技大学 | A kind of foaming midsole |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113527801A (en) * | 2021-07-16 | 2021-10-22 | 福建三盛实业有限公司 | Supercritical fluid polymer microcellular foam and preparation method thereof |
| CN114989570A (en) * | 2022-04-27 | 2022-09-02 | 中山大学 | Crosslinked thermoplastic elastomer micro-foaming coiled material and preparation method and application thereof |
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Application publication date: 20191018 |