CN104231393A - Bimetallic catalyst porous carrier and preparation method and use thereof - Google Patents
Bimetallic catalyst porous carrier and preparation method and use thereof Download PDFInfo
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- CN104231393A CN104231393A CN201410452101.2A CN201410452101A CN104231393A CN 104231393 A CN104231393 A CN 104231393A CN 201410452101 A CN201410452101 A CN 201410452101A CN 104231393 A CN104231393 A CN 104231393A
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- bimetallic catalyst
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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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
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a bimetallic catalyst porous carrier which is prepared through reaction among three ingredients A, B and C, wherein the material A is polyolefin thermoplastic resin; the material B is inorganic packing; the material C is a compatilizer; and the molar ratio of A to B to C is (18-85) to (10-90) to (0.5-10). After the reaction is ended, the catalyst carrier can be cleaned to recover a catalyst, and thus the catalyst is easy to filter and recover, recycling of the catalyst is achieved, the expensive catalyst can be used many times, repeated utilization of resources is achieved, the production cost is reduced, and the environmental pollution is reduced.
Description
Technical field
The present invention relates to support of the catalyst field, be specifically related to a kind of bimetallic catalyst porous support.
Background technology
Polyether glycol be with low molecular weight polyols, polyamine or containing the compound of reactive hydrogen for initiator, form with olefin oxide ring-opening polymerization under catalyst action, low-molecular-weight polyvalent alcohol is under the effect of bimetallic catalyst (DMC), addition is carried out, obtained polyethers finished product with epoxy compounds.This method due to catalyst levels little, therefore do not need to carry out refinement treatment, thus shorten reaction time, the molecular weight distribution of product is narrower, product properties is better, be the most popular method of producing polyether glycol at present, but its shortcoming is to environment and the harm not treated entered environment of title complex that is micro-, nanometer zinc hexacyanocobaltate low mass molecule alcohol in confused situation and daily life.This is because after the completion of reaction, granules of catalyst is because particle diameter little (nano level), be difficult to filtered and recycled, release with emulsion, both great waste had been caused, increasing production cost, again because all containing the environmentally hazardous substance such as cyanogen, cobalt in bimetallic catalyst, after discharge, very large harm being caused to environment.
Therefore people wish to use support of the catalyst to carry bimetallic catalyst, but containing the bimetallic catalyst of cobalt element as zinc hexacyanocobaltate etc., easily poisoning under alkaline environment; Inorganic support of the catalyst its basic material in building-up process often makes poisoning of catalyst, so cannot apply.A kind of carrier how can be found to carry bimetallic catalyst, and realize the difficult problem successfully reclaiming catalyzer or a puzzlement insider.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art; a kind of bimetallic catalyst porous support is provided; this support of the catalyst can realization response terminate after reclaim catalyzer like a cork, reach reduce production cost, resource regeneration, protection of the environment object.
For achieving the above object, technical scheme of the present invention is, a kind of bimetallic catalyst porous support, and described bimetallic catalyst porous support is reacted by A, B and C tri-kinds of compositions to be made, and wherein, materials A is olefin hydrocarbons thermoplasticity resin; Material B is mineral filler, and material C is compatilizer, and three's mass percent is A: B: C=18 ~ 85: 10 ~ 90: 0.5 ~ 10.
Wherein, three's mass percent is A: B: C=47.5: 47.5: 5.
Wherein, described materials A be the homopolymer of alpha-olefin or cycloolefin, multipolymer one or more.Alpha-olefin includes but not limited to ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cycloolefin includes but not limited to cyclopropylene, cyclobutene, cyclopentenes and tetrahydrobenzene.
Wherein, described material B is one or more in talcum powder, potter's clay, mica, wollastonite, calcium carbonate, titanium dioxide, aluminium hydroxide, carbon black, flyash, wood powder, bamboo fibers, flaxen fiber, shell powder, oyster shell whiting, zinc oxide, antimonous oxide.
Wherein, described material C is one or more in PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH, PP-g-MAH.
The present invention also provides a kind of preparation method of bimetallic catalyst porous support, and described preparation method has following steps:
The first step, by materials A and material C pre-mixing;
Second step, the first step resulting materials and material B are dropped into twin screw simultaneously react mixing extruder, high-temperature fusion, hybrid reaction;
3rd step, the material reacted completely is extruded formation material strip, enter in acid storage and soak;
4th step, material article take out in acid storage, are washed by washing bath, after elimination moisture, enter granulator granulation.
Acid solution refers to the conventional acid such as dilute hydrochloric acid, dilute sulphuric acid solution.
Wherein, granulator granulation is the hollow circular cylinder goods of diameter × length=3 × 3mm.Concrete size can require to adjust according to concrete adsorptive power, specific surface area.Shape is also not limited in right cylinder, take hollow as the best.
In preparation method of the present invention, the material bar extruded is put into acid storage and soaks, diluted acid carries out surface corrosion to material bar, makes material bar form porous insert structure, thus enables support of the catalyst by distinctive bigger serface adsorptive catalyst.
The present invention also provides a kind of purposes of bimetallic catalyst porous support, and described bimetallic catalyst porous support can be used as solid carrier absorption bimetallic catalyst, is applied in the polyether polyols alcohol synthesis reaction of bimetallic catalyst participation.
Preferably, described bimetallic catalyst is the composite compound of low mass molecule alcohol of zinc hexacyanocobaltate.
Bimetallic catalyst zinc hexacyanocobaltate is easily poisoning under alkaline environment, and inorganic support of the catalyst (carrier) often makes poisoning of catalyst at building-up process neutral and alkali material.And the present invention selects the polyolefine good to the chemical stability of bimetallic catalyst toxicological harmless effect, just solve this problem.
Polyolefin porous carrier prepared by the present invention with suitable hole by the absorption of the bimetallic catalyst of micro/nano level wherein, by distinctive bigger serface adsorptive catalyst, after the completion of reaction, can clean support of the catalyst, then by carrier and catalyst separating, reclaim catalyzer, just solve the recovery of catalyzer and the residue problem in polyethers.Catalyzer is the invention enables to be easy to filter and reclaim, solve the not reproducible use of catalyzer in bimetallic catalyst process for production of polyether polyols, the difficult difficult problem be separated, accomplish to recycle, expensive catalyzer is repeatedly used, realize the recycling of resource, save production cost, reduce environmental pollution.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read content of the present invention, these equivalent form of values fall within the application's limited range equally.
Embodiment 1
Mass ratio according to 47.5: 47.5: 5 takes polyethylene, talcum powder, PE-g-ST, then prepares according to the following steps:
The first step, by polyethylene and PE-g-ST pre-mixing;
Second step, the first step resulting materials and talcum powder are dropped into twin screw simultaneously react mixing extruder, high-temperature fusion, hybrid reaction;
3rd step, the material reacted completely is extruded formation material strip, enter in dilute sulphuric acid liquid bath and soak;
4th step, material article take out in acid storage, are washed by washing bath, after elimination moisture, enter granulator granulation.Granulation goes out the right cylinder goods of 3 × 3mm.
Embodiment 2
Mass ratio according to 18: 72: 10 takes polypropylene, diatomite, PP-g-ST, then prepares according to the following steps:
The first step, by polypropylene and PP-g-ST pre-mixing;
Second step, the first step resulting materials and diatomite are dropped into twin screw simultaneously react mixing extruder, high-temperature fusion, hybrid reaction;
3rd step, the material reacted completely is extruded formation material strip, enter in dilute sulphuric acid liquid bath and soak;
4th step, material article take out in acid storage, are washed by washing bath, after elimination moisture, enter granulator granulation.Granulation goes out the right cylinder goods of 3 × 3mm.
Embodiment 3
Mass ratio according to 85: 14: 1 takes polycyclic butylene, bamboo fibers, ABS-g-MAH, then prepares according to the following steps:
The first step, by polycyclic butylene and ABS-g-MAH pre-mixing;
Second step, the first step resulting materials and bamboo fibers are dropped into twin screw simultaneously react mixing extruder, high-temperature fusion, hybrid reaction;
3rd step, the material reacted completely is extruded formation material strip, enter in dilute sulphuric acid liquid bath and soak;
4th step, material article take out in acid storage, are washed by washing bath, after elimination moisture, enter granulator granulation.Granulation goes out the right cylinder goods of 4 × 4mm.
Embodiment 4
Mass ratio according to 46: 46: 8 takes mixing, the PP-g-MAH of poly 1-butene, shell powder and oyster shell whiting, then prepares according to the following steps:
The first step, by poly 1-butene and ABS-g-MAH pre-mixing;
Second step, the mixture of the first step resulting materials and shell powder and oyster shell whiting is dropped into twin screw simultaneously react mixing extruder, high-temperature fusion, hybrid reaction;
3rd step, the material reacted completely is extruded formation material strip, enter in dilute sulphuric acid liquid bath and soak;
4th step, material article take out in acid storage, are washed by washing bath, after elimination moisture, enter granulator granulation.Granulation goes out the right cylinder goods of 4 × 4mm.
The production of polyether glycol is used for after porous catalyst carrier absorption hexacyanocobaltate acid zinc catalyst the present invention prepared, after production process completes, support of the catalyst is cleaned, by carrier and catalyst separating, reclaim catalyzer, then with flame spectrophotometer, the metal content in the emulsion of releasing is measured.Result shows, and in emulsion, cobalt ion content is not for detect, and namely cobalt contents is lower than the detection limit 0.1ppm of flame spectrophotometer.And in industry polyether glycol produce in discharge emulsion in, cobalt ion content generally at 3 ~ 6ppm, high reached at 8ppm.Visible, the invention solves the recovery of hexacyanocobaltate acid zinc catalyst and the residue problem in emulsion, hexacyanocobaltate acid zinc catalyst is repeatedly utilized, not only achieve reusing of resource, complete the requirement of qualified discharge, reach the standard of green circulation economy, and greatly reduce production cost (1kg bimetallic catalyst price about 5000 yuan), there is huge benefit to enterprise and society, achieve the two up to standard of economic benefit and environmental benefit.
Be more than the description to the embodiment of the present invention, by the above-mentioned explanation to the disclosed embodiments, professional and technical personnel in the field realized or uses the present invention.To the multiple amendment of these embodiments will be for those skilled in the art apparent, as defined herein-as principle can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (8)
1. a bimetallic catalyst porous support, is characterized in that, described bimetallic catalyst porous support is reacted by A, B, C tri-kinds of compositions to be made, and wherein, materials A is polyolefins thermoplastic resin; Material B is weighting material, and material C is compatilizer, and three's mass percent is A: B: C=18 ~ 85: 10 ~ 90: 0.5 ~ 10.
2. bimetallic catalyst porous support as claimed in claim 1, it is characterized in that, described mass percent is A: B: C=47.5: 47.5: 5.
3. bimetallic catalyst porous support as claimed in claim 1 or 2, is characterized in that, described materials A be the homopolymer of alpha-olefin or cycloolefin, multipolymer one or more.
4. bimetallic catalyst porous support as claimed in claim 1 or 2, it is characterized in that, described material B is one or more in talcum powder, potter's clay, mica, wollastonite, calcium carbonate, titanium dioxide, aluminium hydroxide, carbon black, flyash, wood powder, bamboo fibers, flaxen fiber, shell powder, oyster shell whiting, zinc oxide, antimonous oxide.
5. bimetallic catalyst porous support as claimed in claim 1 or 2, is characterized in that, described material C is one or more in PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH, PP-g-MAH.
6. the preparation method of a kind of bimetallic catalyst porous support as described in Claims 1 to 5, it is characterized in that, described preparation method has following steps:
The first step, by materials A and material C pre-mixing;
Second step, the first step resulting materials and material B are dropped into twin screw simultaneously react mixing extruder, high-temperature fusion, hybrid reaction;
3rd step, the material reacted completely is extruded formation material strip, enter in acid storage and soak;
4th step, material article take out in acid storage, are washed by washing bath, after elimination moisture, enter granulator granulation.
7. a purposes for bimetallic catalyst porous support, is characterized in that, described bimetallic catalyst porous support can be used as solid carrier absorption bimetallic catalyst, is applied in the polyether polyols alcohol synthesis reaction of bimetallic catalyst participation.
8. the purposes of bimetallic catalyst porous support as claimed in claim 7, it is characterized in that, described bimetallic catalyst is the composite compound of low mass molecule alcohol of zinc hexacyanocobaltate.
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| CN201410452101.2A CN104231393A (en) | 2014-09-05 | 2014-09-05 | Bimetallic catalyst porous carrier and preparation method and use thereof |
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| CN201410452101.2A CN104231393A (en) | 2014-09-05 | 2014-09-05 | Bimetallic catalyst porous carrier and preparation method and use thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111468503A (en) * | 2020-03-21 | 2020-07-31 | 镇平县含笑再生资源有限公司 | Waste supporting ball recovery processing method |
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| EP0830385B1 (en) * | 1995-06-07 | 2000-12-27 | W.R. Grace & Co.-Conn. | Halogenated supports and supported activators |
| CN1293208A (en) * | 1999-10-19 | 2001-05-02 | 中国科学院长春应用化学研究所 | Metallocene catalyst with shell-nuclear compounded carrier and its preparing process |
| CN1306010A (en) * | 2000-12-27 | 2001-08-01 | 中国科学院长春应用化学研究所 | Metallocene catalyst with nm-class hybridized composite organic-inorganic carrier and styrene polymerization |
| CN101010385A (en) * | 2004-08-31 | 2007-08-01 | 埃克森美孚研究工程公司 | Structured bodies with siliceous binder |
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2014
- 2014-09-05 CN CN201410452101.2A patent/CN104231393A/en active Pending
Patent Citations (5)
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| CN1033059A (en) * | 1987-10-28 | 1989-05-24 | 住友化学工业株式会社 | The ingredient of solid catalyst that is used for olefinic polymerization |
| EP0830385B1 (en) * | 1995-06-07 | 2000-12-27 | W.R. Grace & Co.-Conn. | Halogenated supports and supported activators |
| CN1293208A (en) * | 1999-10-19 | 2001-05-02 | 中国科学院长春应用化学研究所 | Metallocene catalyst with shell-nuclear compounded carrier and its preparing process |
| CN1306010A (en) * | 2000-12-27 | 2001-08-01 | 中国科学院长春应用化学研究所 | Metallocene catalyst with nm-class hybridized composite organic-inorganic carrier and styrene polymerization |
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| Title |
|---|
| 朱吕民等: "《聚氨酯泡沫塑料》", 31 January 2005, 化学工业出版社 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111468503A (en) * | 2020-03-21 | 2020-07-31 | 镇平县含笑再生资源有限公司 | Waste supporting ball recovery processing method |
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