CN108690310A - A method of preparing low VOC foaming grafted olefin polymers using supercritical technology - Google Patents
A method of preparing low VOC foaming grafted olefin polymers using supercritical technology Download PDFInfo
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- CN108690310A CN108690310A CN201810378448.5A CN201810378448A CN108690310A CN 108690310 A CN108690310 A CN 108690310A CN 201810378448 A CN201810378448 A CN 201810378448A CN 108690310 A CN108690310 A CN 108690310A
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- olefin polymers
- grafted olefin
- foaming
- low voc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention relates to the preparation methods of foaming grafted olefin polymers, disclose a kind of method preparing low VOC foaming grafted olefin polymers using supercritical technology.The method includes the steps of:1)By common grafted olefin polymers moulding, crude product is obtained;2)Crude product is put into entrainer, 1-8h is impregnated;3)Grafted olefin polymers product is placed in supercritical CO2In extraction kettle, CO is injected2, it is forced into supercriticality, heated sealed, extraction;4)Slowly shed CO2Pressure, release time 10-20min is to get low VOC foaming grafted olefin polymers.The preparation method technological process is simple, environmentally protective, and gained foaming grafted olefin polymers VOC content is extremely low, has no irritating odor and black, Huang Dian, and coefficient of foaming is high, and the strength of materials is good, can be widely applied for food and medicine and packs contour sanitary standard field.
Description
Technical field
The present invention relates to the preparation methods of foaming grafted olefin polymers more particularly to a kind of utilization supercritical technology to prepare
The method of low VOC foaming grafted olefin polymers.
Background technology
Graft-modified polyolefin product is as one kind important in functional polymer material, matrix general-purpose plastics polyolefin
Have the advantages that yield big, wide application and quality-high and inexpensive, by the other monomers of reactive grafting, improves its polarity, dyeability, viscous
Connecing property, antistatic property, hydrophily can be widely applied to the fields such as electronics, biology, the energy.However graft-modified polyolefin product
It is relatively low often to there is grafting rate, it is functional poor;Non-grafted level of residual monomers is big, carry penetrating odor the shortcomings that, make product root
Originally food packaging applications can not be applied to;The more stain of generally existing, Huang Dian, limit in domestic grafted polyolefin products
The application of product.In addition, when some special occasions need to use frothing function material, material need to be carried out at second time of foaming
Reason, increases process.
Application No. is 200580015501.6 Chinese patents to disclose a kind of method from graft polyolefin extracting impurities,
By azeotropic solvent extracting impurities, and do not make graft polymers tacky, improves the color and adhesiveness of graft polyolefin, but should
Method needs to use a large amount of organic solvents, and uneconomical environmental protection, safety is poor, and extraction time is long, needs second time of foaming.
Application No. is 200610030070.7 Chinese patent disclose a kind of super critical CO 2 technology prepare it is siliceous
The method of polypropylene nano foaming material is improved to be foamed using universal isotactic homopolypropylene as raw material by blending and modifying
Polyacrylic performance, and utilize supercritical CO2Technology prepares expanded polypropylene, obtains the siliceous polypropylene nano hair of structure-controllable
Foam material.But this method needs to be suitable for foaming to raw material additional modifications, and material is not purified, remove VOC.
Invention content
In order to solve the above technical problem, the present invention provides a kind of low VOC foaming grafting is prepared using supercritical technology
The method of olefin polymer, method is simple, safety and environmental protection, products therefrom very high purity, the good excellent performance of color, and coefficient of foaming is high,
It is a kind of low VOC foaming grafted olefin of functional high-purity for being applicable to food and medicine and packing contour sanitary standard field
Polymer.
The specific technical solution of the present invention is:The method includes the steps of:
The method includes the steps of:
1)By common grafted olefin polymers moulding, crude product is obtained;
2)Crude product is put into entrainer, 1-8h is impregnated;
3)Crude product after immersion is placed in supercritical CO2In extraction kettle, CO is injected2, it is forced into supercriticality, sealing adds
Heat, extraction;
4)Slowly shed CO2Pressure, release time 10-20min is to get low VOC foaming grafted olefin polymers.
Tradition utilizes supercritical CO2Abstraction purification polymer does not heat generally, polymer beads is directly extracted, in of the invention
It is extracted after raw material is heated, carbon dioxide can be penetrated into effectively in grafted olefin polymers, residual in grafted olefin polymers
The volatile organic matter stayed is diffused into carbon dioxide, keeps slow release after a certain period of time, volatile organic matter is with titanium dioxide
Carbon is discharged together, while reducing VOC, foaming after polymer is fully swollen, without adding foaming agent.Conventional Supercritical two
In carbonoxide foam process, carbon dioxide low temperature quick pressure releasing, although expansion ratio is high, easily there is supersaturated body in abscess
System and hypersaturated state and make abscess destroy, to greatly reduce the intensity of foam polyolefin material, influence its use,
Inorganic nano-particle need to be added as heterogeneous nucleation agent.The present invention after extraction using in the slow release of high temperature, carbon dioxide and waving
Hair property organic matter expands, rate of discharge reduces and relatively stable, and abscess aperture is smaller, and system is not easy supersaturation, and products obtained therefrom is pure
Degree is high, and aperture is small, and intensity is high.
Preferably, the step 1)Middle formative method can be injection molding, molding, squeeze out, one kind in blowing.
Preferably, the step 2)Middle entrainer is acetone, water, dichloromethane, chloroform, methanol, ethyl alcohol, pyrrole
One or more of pyridine, tetrahydrofuran mix.
Grafted olefin polymers product is put into entrainer, polymer can be made to have certain swelling, is conducive to expand VOC
In high molecular channel, be conducive to its abjection.And supercritical CO2For nonpolar solvent, if volatile organic matter polarity is larger,
It is not easy diffusion discharge, polar solvent is added as entrainer, the extraction efficiency of volatile organic matter can be improved.Folder is added simultaneously
Band agent can also help to foam, and obtain the product of different foaming structures.
Preferably, the step 3)Middle heated sealed temperature is on polymer glass temperature under fusing point.
Heating temperature is too low, and grafted olefin polymers are solid, is unfavorable for and carbon dioxide is miscible and volatile organic matter
Diffusion, be also unfavorable for the discharge of carbon dioxide after release;Heating temperature is excessively high, and polymer is difficult to be nucleated, and can not foam, and
Cost is higher, and safety reduces, and is easy to cause phenomena such as graft decomposes, influences polymer performance.
Preferably, the step 3)Middle pressure is 8-45Mpa.
Preferably, the step 3)Middle extraction time is 10-60min.
Extraction time is long to be unfavorable for carbon dioxide discharge, and extraction time is too short, is unfavorable for the diffusion of volatile organic matter
Discharge.
Preferably, the step 1)In common grafted olefin polymers be PP-g-MAH, PP-g-GMA, PE-g-MAH,
One or more of PE-g-GMA, POE-g-MAH, POE-g-GMA are mixed.
Preferably, the step 4)CO is quickly shed before2Then pressure re-injects CO2, it is forced into supercritical state
State, heated sealed, extraction repeat 1-5 times.
Due to the limitation of extraction time, if single extraction, the residual quantity of volatile organic matter is undesirable, can be multiple
It repeats, further increases polymer purity.
Preferably, the heated sealed temperature is on polymer glass temperature under fusing point, the release time is 1-
5s, extraction time 10-60min.
Preferably, injection CO2While also inject entrainer.
It is compared with the prior art, the beneficial effects of the invention are as follows:The preparation method technological process is simple, environmentally protective, institute
The grafted olefin polymers VOC content that must foam is extremely low, has no irritating odor and black, Huang Dian, and coefficient of foaming is high, and the strength of materials is good,
It can be widely applied for food and medicine and pack contour sanitary standard field.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Embodiment 1
After taking the light new material Science and Technology Co., Ltd. trade mark POE-g-GMA product compression moldings of the Ningbo 100g energy, it is placed in
8h is impregnated in chloroform, then is placed in supercritical CO2In extraction kettle, injection 50g chloroforms inject CO as entrainer2To pressure
Power 10Mpa, obtains supercritical CO2, heated sealed to 60oC keeps 15min;Slowly shed CO2Pressure, release time is
20min, obtained product are analyzed using TGA, and before unpurified, the product volatile substances containing small molecule are up to 2.30%, after purification
It is down to 0.03%, illustrates the effect that the method for the present invention has superior removing VOC to prepare high-purity grafted olefin polymers, foaming times
Number is 5.5 times.
Embodiment 2
After taking the light new material Science and Technology Co., Ltd. trade mark PP-g-MAH product compression moldings of the Ningbo 100g energy, it is placed in water
1h is impregnated, then is placed in supercritical CO2In extraction kettle, injection 100g water injects CO as entrainer2To pressure 15Mpa, surpassed
Critical CO2, heated sealed to 100oC keeps 30min;Slowly shed CO2Pressure, release time are 10min, obtain product use
TGA is analyzed, and before unpurified, which is down to 0.05% up to 0.22% after purification, illustrates this
Inventive method has the effect that superior removing VOC prepares high-purity grafted olefin polymers.Its coefficient of foaming is 3.2 times.
Embodiment 3
After taking the light new material Science and Technology Co., Ltd. trade mark PP-g-MAH product compression moldings of the Ningbo 100g energy, it is placed in acetone
Middle immersion 4h, then it is placed in supercritical CO2In extraction kettle, injection 50g acetone injects CO as entrainer2To pressure 8Mpa, obtain
Supercritical CO2, heated sealed to 100oC keeps 60min;Slowly shed CO2Pressure, release time are 15min, obtain product and adopt
It is analyzed with TGA, before unpurified, which is down to 0.02%, explanation up to 0.22% after purification
The method of the present invention has the effect that superior removing VOC prepares high-purity grafted olefin polymers.Its coefficient of foaming is 3.0 times.
Embodiment 4
After taking the light new material Science and Technology Co., Ltd. trade mark PP-g-MAH product compression moldings of the Ningbo 100g energy, it is placed in quality
Than 1:4h is impregnated in 1 acetone/chloroform, then is placed in supercritical CO2In extraction kettle, injection 25g acetone/25g chloroforms
As entrainer, CO is injected2To pressure 45Mpa, supercritical CO is obtained2, heated sealed to 100oC keeps 30min;Slowly shed
CO2Pressure, release time are 20min, obtain product and are analyzed using TGA, before unpurified, which easily waves containing small molecule
Substance is sent out up to 0.22%, 0.02% is down to after purification, it is poly- to illustrate that the method for the present invention has superior removing VOC to prepare high-purity grafted olefin
Close the effect of object.Its coefficient of foaming is 3.1 times.
Embodiment 5
After taking the light new material Science and Technology Co., Ltd. trade mark PP-g-GAH product compression moldings of the Ningbo 100g energy, it is placed in acetone
Middle immersion 4h, then it is placed in supercritical CO2In extraction kettle, injection 50g acetone injects CO as entrainer2To pressure 15Mpa, obtain
Supercritical CO2, heated sealed to 100oC keeps 30min;Again CO is reinjected after 5s fast pressure reliefs2To 15Mpa, it is heated to
100oC keeps 30min;Slowly shed CO2Pressure, the release time be 20min, obtain product using TGA analysis, it is unpurified it
Before, which is down to 0.01% up to 0.12% after purification, and it is superior to illustrate that the method for the present invention has
Removing VOC prepares the effect of high-purity grafted olefin polymers.Its coefficient of foaming is 3.5 times.
Embodiment 6
Take light new material Science and Technology Co., Ltd. trade mark POE-g-GMA and PP-g-GMA the product mixture mould of the Ningbo 100g energy
It after molded, be placed in chloroform and impregnate 2h, then be placed in supercritical CO2In extraction kettle, injection 50g chloroforms are as entrainment
CO is injected in agent2To pressure 10Mpa, supercritical CO is obtained2, heated sealed to 60oC keeps 15min;Again after 1s fast pressure reliefs again
Inject CO2To 10Mpa, it is heated to 60oC keeps 15min;Repeat the release, pressure process 4 times;Slowly shed CO2Pressure,
The release time is 10min, obtains product and is analyzed using TGA, before unpurified, which reaches
0.50%, it is down to 0.02% after purification, illustrates the effect that the method for the present invention has superior removing VOC to prepare high-purity grafted olefin polymers
Fruit.Its coefficient of foaming is 5.1 times.
Embodiment 7
After taking the light new material Science and Technology Co., Ltd. trade mark POE-g-MAH product compression moldings of the Ningbo 100g energy, it is placed in three
2h is impregnated in chloromethanes, then is placed in supercritical CO2In extraction kettle, injection 50g chloroforms inject CO as entrainer2To pressure
10Mpa obtains supercritical CO2, heated sealed to 60oC keeps 15min;Again CO is reinjected after 3s fast pressure reliefs2To 10Mpa, add
Heat is to 60oC keeps 15min;Repeat the release, pressure process 2 times;Slowly shed CO2Pressure, release time are 10min, are obtained
It is analyzed to product using TGA, before unpurified, which is down to up to 1.06% after purification
0.02%, illustrate the effect that the method for the present invention has superior removing VOC to prepare high-purity grafted olefin polymers.Its coefficient of foaming is
5.0 again.
The processing method and effect of remaining common grafted olefin polymers raw material are similar to the above embodiments, no longer arrange one by one
It lifts, it is better for the different raw material selection corresponding entrainers of polarity, also it will not enumerate.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field;In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not imposed any restrictions to the present invention, every according to the present invention
Technical spirit still falls within the technology of the present invention side to any simple modification, change and equivalent transformation made by above example
The protection domain of case.
Claims (10)
1. a kind of method preparing low VOC foaming grafted olefin polymers using supercritical technology, it is characterised in that:This method packet
Containing following steps:
1)By common grafted olefin polymers moulding, crude product is obtained;
2)Crude product is put into entrainer, 1-8h is impregnated;
3)Crude product after immersion is placed in supercritical CO2In extraction kettle, CO is injected2, it is forced into supercriticality, heated sealed,
Extraction;
4)Slowly shed CO2Pressure, release time 10-20min is to get low VOC foaming grafted olefin polymers.
2. the method for preparing low VOC foaming grafted olefin polymers using supercritical technology as described in claim 1, feature
It is, the step 3)Middle heated sealed temperature is on polymer glass temperature under fusing point.
3. the method for preparing low VOC foaming grafted olefin polymers using supercritical technology as claimed in claim 1 or 2,
It is characterized in that, the step 3)Middle pressure is 8-45Mpa.
4. the method for preparing low VOC foaming grafted olefin polymers using supercritical technology as claimed in claim 1 or 2,
It is characterized in that, the step 3)Middle extraction time is 10-60min.
5. the method for preparing low VOC foaming grafted olefin polymers using supercritical technology as described in claim 1, feature
It is, the step 1)In common grafted olefin polymers be PP-g-MAH, PP-g-GMA, PE-g-MAH, PE-g-GMA, POE-
One or more of g-MAH, POE-g-GMA are mixed.
6. the method for preparing low VOC foaming grafted olefin polymers using supercritical technology as described in claim 1 or 5,
It is characterized in that, the step 1)Middle formative method is injection molding, molding, squeezes out, one kind in blowing.
7. the method for preparing low VOC foaming grafted olefin polymers using supercritical technology as described in claim 1, feature
It is, the step 2)Middle entrainer is in acetone, water, dichloromethane, chloroform, methanol, ethyl alcohol, pyridine, tetrahydrofuran
One or more of mixing.
8. the method for preparing low VOC foaming grafted olefin polymers using supercritical technology as described in claim 1, feature
It is, the step 4)CO is quickly shed before2Then pressure re-injects CO2, it is forced into supercriticality, heated sealed,
Extraction repeats 1-5 times.
9. the method for preparing low VOC foaming grafted olefin polymers using supercritical technology as claimed in claim 8, feature
It is, the heated sealed temperature is on polymer glass temperature under fusing point, and the release time is 1-5s, and extraction time is
10-60min。
10. the method for preparing low VOC foaming grafted olefin polymers using supercritical technology as claimed in claim 8, special
Sign is, injects CO2While also inject entrainer.
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| CN201810378448.5A CN108690310A (en) | 2018-04-25 | 2018-04-25 | A method of preparing low VOC foaming grafted olefin polymers using supercritical technology |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109575354A (en) * | 2018-11-16 | 2019-04-05 | 浙江大学 | A method of with volatile organic matter in super/subcritical fluids removing sponge |
| CN110498945A (en) * | 2019-06-27 | 2019-11-26 | 华东理工大学 | A kind of supercritical fluid foaming method of polypropylene material |
| CN114729148A (en) * | 2019-12-18 | 2022-07-08 | 旭化成株式会社 | Method for producing polyamide resin foamed particles |
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2018
- 2018-04-25 CN CN201810378448.5A patent/CN108690310A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575354A (en) * | 2018-11-16 | 2019-04-05 | 浙江大学 | A method of with volatile organic matter in super/subcritical fluids removing sponge |
| EP3878899A4 (en) * | 2018-11-16 | 2022-01-12 | Zhejiang University | Method for using super/subcritical fluid to remove volatile compounds from foam |
| JP2022506669A (en) * | 2018-11-16 | 2022-01-17 | 浙江大学 | Method for removing volatile organic compounds in sponge using supercritical / subcritical fluid |
| JP7248253B2 (en) | 2018-11-16 | 2023-03-29 | 浙江大学 | Method for Removing Volatile Organics in Sponges Using Supercritical/Subcritical Fluids |
| CN115873300A (en) * | 2018-11-16 | 2023-03-31 | 浙江大学 | Method for removing volatile organic compounds in sponge by using supercritical/subcritical fluid |
| CN110498945A (en) * | 2019-06-27 | 2019-11-26 | 华东理工大学 | A kind of supercritical fluid foaming method of polypropylene material |
| CN114729148A (en) * | 2019-12-18 | 2022-07-08 | 旭化成株式会社 | Method for producing polyamide resin foamed particles |
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