CN105367737B - The preparation method for the reticulated polyurethane microbe carrier that multi-walled carbon nanotube is modified - Google Patents
The preparation method for the reticulated polyurethane microbe carrier that multi-walled carbon nanotube is modified Download PDFInfo
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- CN105367737B CN105367737B CN201510924379.XA CN201510924379A CN105367737B CN 105367737 B CN105367737 B CN 105367737B CN 201510924379 A CN201510924379 A CN 201510924379A CN 105367737 B CN105367737 B CN 105367737B
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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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
- C08G2270/00—Compositions for creating interpenetrating networks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention belongs to microbe carrier preparation method technical fields, are related to a kind of preparation method for the reticulated polyurethane microbe carrier that multi-walled carbon nanotube is modified, by vinyl polyether polyalcohol, polyether polyol, polyester polyol, H2O, silicone oil, tin catalyst, amines catalyst, olefinic monomer are added in reaction kettle and are stirred evenly, and are added in multi-walled carbon nanotube and are stirred evenly and keep the temperature as component 1；By isocyanates, radical polymerization initiator, add in reaction kettle and stir evenly as component 2；Component 1 and 2 is mixed evenly, foaming obtains soft polyurethane foam；Soft polyurethane foam is subjected to networking processing by dipping by lye or explosion method, obtains the reticulated polyurethane microbe carrier with inierpeneirating network structure；Olefin polymer is introduced in reticulated polyurethane carrier inside by inierpeneirating network structure, enhances the hydrolysis of carrier and resistance to biological degradability, enhances the compatibility of polyurethane component and olefin polymer components.
Description
Technical field
The invention belongs to microbe carrier preparation method technical field, specifically, being related to a kind of with interpenetrating networks knot
The preparation method for the reticulated polyurethane microbe carrier that the multi-walled carbon nanotube of structure is modified.
Background technology
With the fast development of China's industrial or agricultural and the continuous quickening of urbanization process, city domestic sewage is treated as reality
Existing China's sustainable development of socio-economy, the harmonious home of structure ecology primarily solve the problems, such as.Using activated sludge as the life of representative
Object treated sewage technology is widely used in the processing of city and trade effluent.However, traditional activated sludge technology is dropping
It need to be further improved in terms of low sewage effluents total nitrogen ability, while a large amount of excess sludges generated also become secondary dirt
Dye source.Moving bed biofilm reactor (MBBR) technique, has used the basic principle of biofilm sewage disposal, and make full use of
The advantages of activated sludge process, works well in terms of sewage effluents total nitrogens and excess sludge reduction is reduced.
By introducing microbe carrier, a large amount of attachment site can be provided for sewage disposal microorganism, in carrier surface
The nitration reaction rate that aerobic environment improves nitrobacteria is provided, provides anaerobic environment in carrier inside to improve denitrifying bacteria
Anti-nitration reaction rate, the final ability for improving processing total nitrogen；Meanwhile microbe carrier also is able to promote the original of excess sludge
Position is decomposed, and realizes residual sludge reduction.
At present, high molecular material is most widely used bio-carrier, mainly includes polyolefins and polyurethanes.
In practical application, simple polymer biological carrier filler hydrophily and biological adhesiveness are poor, lead to microorganism colonization
Speed is slower, reduces sewage treating efficiency, and hydrolysis and microbic resolvability are poor, service life is short, and use cost is opposite
It is higher.
Invention content
It is an object of the invention to overcome shortcoming of the existing technology, seek to design what a kind of multi-walled carbon nanotube was modified
The preparation method of reticulated polyurethane microbe carrier with inierpeneirating network structure improves the hydrolysis of carrier and resistance to biodegradation
Property, increase the biomass of polyurethane bio-carrier absorption, improve Sewage Biological Treatment ability.
To achieve these goals, the technical solution adopted by the present invention is：A kind of multi-walled carbon nanotube is modified netted poly-
The preparation method of urethane microbe carrier, includes the following steps：
Step 1：By 5~15 parts of vinyl polyether polyalcohol, 50~120 parts of polyether polyol, polyester polyol 0~30
Part, H2O5~8 part, 1~3 part of silicone oil, 0.05~0.2 part of tin catalyst, 0.1~0.8 part of amines catalyst, olefinic monomer 5
In~50 parts of addition reaction kettles, stir evenly；0.1~1 part of multi-walled carbon nanotube (MWCNTS) is added in, is stirred evenly, and keep the temperature
To 35~45 DEG C, as component 1；Above-mentioned number is mass parts；
Step 2：By 120~140 parts of isocyanates, 0.01~0.15 part of radical polymerization initiator, reaction kettle is added in, is stirred
It mixes uniformly, as component 2；Above-mentioned number is mass parts；
Preferably, the vinyl polyether polyalcohol is vinyl polyoxypropylene polyol or vinyl polycyclic oxygen second
Alkane polyalcohol；
Preferably, the polyether polyol for ethylene glycol polyether polyol, ethylene glycol tetrahydrofuran polyether polyalcohol or
Propylene oxide polyether polyol；
Preferably, the polyester polyol is adipate polyester polyalcohol or aromatic polyester polyol；
Preferably, the tin catalyst is stannous octoate or dibutyl tin dilaurate, and amines catalyst is three second
One kind in alkene diamines, triethanolamine, triethylamine or N-ethylmorpholine, tin class and amines catalyst for be catalyzed isocyanates with
Polyether polyol, polyester polyol reaction, adjust polyurethane foam reactivity.
Preferably, the radical polymerization initiator is benzoyl peroxide (BPO), azodiisobutyronitrile, azo two
One kind in different heptonitrile, for causing the Raolical polymerizable of olefinic monomer and vinyl polyether polyalcohol.
Preferably, the olefinic monomer is styrene or divinylbenzene, and vinyl monomer is made in radical polymerization initiator
With lower from coalescence and vinyl polyether polyol reaction, inierpeneirating network structure is generated inside polyurethane.
Preferably, the isocyanates is methyl diphenylene diisocyanate MDI.
Vinyl polyether polyalcohol contains carbon-carbon double bond and hydroxyl Liang Zhong functional groups, can respectively with double bond containing alkene list
Body and isocyanates reaction, introduce inierpeneirating network structure in polyurethane system.Polyether polyol provides great amount of hydroxy group, with isocyanide
Acid esters reaction generation polyurethane.
Step 3：Component 1 and component 2 are mixed, foaming 12~for 24 hours is poured into mold after stirring evenly, is sent out at room temperature
Bubble, obtains soft polyurethane foam；
Step 4：Soft polyurethane foam prepared by step 3 is subjected to networking processing by dipping by lye or explosion method, is cut
The reticulated polyurethane microbe carrier being modified to multi-walled carbon nanotube.
Preferably, the dipping by lye method is that soft polyurethane foam is immersed in lye, immersion treatment 12~for 24 hours, and alkali
Liquid forms：NaOH aqueous solutions that mass fraction is 40%, isopropanol, propylene glycol by volume 4:1~3:1 be made into mixing it is molten
Liquid；Then it is washed with distilled water 2~3 times.
Preferably, the explosion method is that the soft polyurethane foam of preparation is put into treatment reactor, is first vacuumized, backlash
Enter the explosive gas of certain pressure, spread igniting blasting after a period of time, obtain the soft polyurethane foam of networking processing.
The reticulated polyurethane microbe carrier that multi-walled carbon nanotube is modified is used for the biochemical treatment of city domestic sewage.
Beneficial effects of the present invention are：
(1) olefin polymer is introduced in reticulated polyurethane carrier inside by inierpeneirating network structure, carrier can be enhanced
Hydrolysis and resistance to biological degradability improve service life；The compatibility of polyurethane component and olefin polymer components can be enhanced,
And retain the characteristic of each component；The raw materials for production cost of carrier filler can be reduced；
(2) the reticulated polyurethane microbe carrier that multi-walled carbon nanotube is modified has high-specific surface area and biological adhesiveness
Can, conducive to the attachment and growth of microorganism, shorten the biofilm time；With excellent absorption property, polyurethane biology can be increased
The biomass of carrier adsorption improves Sewage Biological Treatment ability；With nano tubular structure, be conducive to gas inside Polyurethane carrier
The mass transfer of body and other substances improves sewage treating efficiency；
(3) using isocyanates of the MDI as synthetic vectors filler, safe, bioaffinity is good.
(4) bio-carrier prepared by this method has porosity and hydrophily, is provided for sewage disposal microorganism a large amount of attached
Site and good aerobic, anaerobiosis environment, microorganism colonization speed is fast, and biomass is big, thin for nitrification on filler surface
Bacterium provides aerobic environment to improve nitration reaction rate, and anaerobic environment is provided for denitrifying bacteria to improve anti-nitre inside filler
Change reaction rate, biological treatment effect and stability can be significantly improved, reduce total nitrogen, realize residual sludge reduction.
Specific embodiment
Below by specific embodiment, the invention will be further described：
Embodiment 1
The preparation method for the reticulated polyurethane microbe carrier that the multi-walled carbon nanotube of the present embodiment is modified, including following step
Suddenly：
Step 1：By 10 parts of vinyl polyoxypropylene polyol, 80 parts of ethylene glycol polyether polyol, H25 parts of O, silicone oil 1
Part, 0.1 part of tin catalyst stannous octoate, 0.3 part of amines catalyst triethylene diamine, 20 parts of olefinic monomer styrene add in instead
It answers in kettle, stirs evenly；0.2 part of multi-walled carbon nanotube (MWCNTS) is added in, is stirred evenly, and is kept the temperature to 40 DEG C, as component
1；Above-mentioned number is mass parts；
Step 2：By 125 parts of methyl diphenylene diisocyanate (MDI), radical polymerization initiator benzoyl peroxide
(BPO) 0.08 part, reaction kettle is added in, is stirred evenly, as component 2；Above-mentioned number is mass parts；
Step 3：Component 1 and component 2 are mixed, foaming 12~for 24 hours is poured into mold after stirring evenly, is sent out at room temperature
Bubble, obtains soft polyurethane foam；
Step 4：Soft polyurethane foam prepared by step 3 is subjected to networking processing by dipping by lye method, by soft polyurethane foam
It is immersed in lye, immersion treatment 12h, lye composition is：The NaOH aqueous solutions, isopropanol, propylene glycol that mass fraction is 40%
By volume 4:1:1 is made into mixed solution；Then it is washed with distilled water 2 times；Cutting obtains the netted of multi-walled carbon nanotube modification
Polyurethane microbe carrier.
Embodiment 2
The preparation method for the reticulated polyurethane microbe carrier that the multi-walled carbon nanotube of the present embodiment is modified, including following step
Suddenly：
Step 1：By 15 parts of vinyl polyethylene oxide polyol, 100 parts of ethylene glycol tetrahydrofuran polyether polyalcohol, oneself two
1 part of polyester polyols, H26 parts of O, 2 parts of silicone oil, 0.15 part of tin catalyst stannous octoate, amines catalyst triethylene diamine
0.5 part, in 15 parts of addition reaction kettles of olefinic monomer styrene, stir evenly；0.5 part of multi-walled carbon nanotube (MWCNTS) is added in,
It stirs evenly, and keeps the temperature to 40 DEG C, as component 1；Above-mentioned number is mass parts；
Step 2：By 130 parts of methyl diphenylene diisocyanate (MDI), radical polymerization initiator azodiisobutyronitrile
0.06 part, reaction kettle is added in, is stirred evenly, as component 2；Above-mentioned number is mass parts；
Step 3：Component 1 and component 2 are mixed, pours into mold and is foamed for 24 hours after stirring evenly, foamed at room temperature,
Obtain soft polyurethane foam；
Step 4：Soft polyurethane foam prepared by step 3 is subjected to networking processing by explosion method, by the flexible polyurethane of preparation
Bubble is put into treatment reactor, is first vacuumized, after pour the explosive gas of certain pressure, spread to light a fire after a period of time and draw
It is quick-fried, obtain the soft polyurethane foam of networking processing；Cutting obtains the reticulated polyurethane microbe carrier of multi-walled carbon nanotube modification.
Embodiment 3
The preparation method for the reticulated polyurethane microbe carrier that the multi-walled carbon nanotube of the present embodiment is modified, including following step
Suddenly：
Step 1：By 5 parts of vinyl polyethylene oxide polyol, 70 parts of polyether polyol, aromatic polyester polyol 15
Part, H28 parts of O, 2 parts of silicone oil, 0.05 part of tin catalyst dibutyl tin dilaurate, 0.8 part of amines catalyst triethylamine, alkene
In 5 parts of addition reaction kettles of hydrocarbon monomer divinylbenzene, stir evenly；0.1 part of multi-walled carbon nanotube (MWCNTS) is added in, stirring is equal
It is even, and keep the temperature to 35 DEG C, as component 1；Above-mentioned number is mass parts；
Step 2：By 120 parts of methyl diphenylene diisocyanate (MDI), radical polymerization initiator benzoyl peroxide
(BPO) 0.01 part, reaction kettle is added in, is stirred evenly, as component 2；Above-mentioned number is mass parts；
Step 3：Component 1 and component 2 are mixed, foaming 12~for 24 hours is poured into mold after stirring evenly, is sent out at room temperature
Bubble, obtains soft polyurethane foam；
Step 4：Soft polyurethane foam prepared by step 3 is subjected to networking processing by dipping by lye method, by soft polyurethane foam
It is immersed in lye, immersion treatment 18h, lye composition is：The NaOH aqueous solutions, isopropanol, propylene glycol that mass fraction is 40%
By volume 4:3:1 is made into mixed solution；Then it is washed with distilled water 3 times；Cutting obtains the netted of multi-walled carbon nanotube modification
Polyurethane microbe carrier.
Embodiment 4
The preparation method for the reticulated polyurethane microbe carrier that the multi-walled carbon nanotube of the present embodiment is modified, including following step
Suddenly：
Step 1：By 12 parts of vinyl polyether polyalcohol, 120 parts of propylene oxide polyether polyol, aromatic polyester polyol
30 parts, H27 parts of O, 3 parts of silicone oil, 0.2 part of tin catalyst dibutyl tin dilaurate, 0.1 part of amines catalyst triethanolamine,
In 50 parts of addition reaction kettles of olefinic monomer divinylbenzene, stir evenly；1 part of multi-walled carbon nanotube (MWCNTS) is added in, stirring is equal
It is even, and keep the temperature to 45 DEG C, as component 1；Above-mentioned number is mass parts；
Step 2：By 140 parts of methyl diphenylene diisocyanate (MDI), radical polymerization initiator azobisisoheptonitrile
0.15 part, reaction kettle is added in, is stirred evenly, as component 2；Above-mentioned number is mass parts；
Step 3：Component 1 and component 2 are mixed, the 20h that foams in mold is poured into after stirring evenly, is foamed at room temperature,
Obtain soft polyurethane foam；
Step 4：Soft polyurethane foam prepared by step 3 is subjected to networking processing by explosion method, by the flexible polyurethane of preparation
Bubble is put into treatment reactor, is first vacuumized, after pour the explosive gas of certain pressure, spread to light a fire after a period of time and draw
It is quick-fried, obtain the soft polyurethane foam of networking processing；Cutting obtains the reticulated polyurethane microbe carrier of multi-walled carbon nanotube modification.
Claims (6)
1. a kind of preparation method for the reticulated polyurethane microbe carrier that multi-walled carbon nanotube is modified, which is characterized in that including with
Lower step：
Step 1：By 5~15 parts of vinyl polyether polyalcohol, 50~120 parts of polyether polyol, 0~30 part of polyester polyol,
H2O5~8 part, 1~3 part of silicone oil, 0.05~0.2 part of tin catalyst, 0.1~0.8 part of amines catalyst, olefinic monomer 5~50
In part addition reaction kettle, stir evenly；0.1~1 part of multi-walled carbon nanotube (MWCNTS) is added in, is stirred evenly, and is kept the temperature to 35
~45 DEG C, as component 1；Above-mentioned number is mass parts；
Step 2：By 120~140 parts of isocyanates, 0.01~0.15 part of radical polymerization initiator, reaction kettle is added in, stirring is equal
It is even, as component 2；Above-mentioned number is mass parts；
Step 3：Component 1 and component 2 are mixed, foaming 12~for 24 hours is poured into mold after stirring evenly, is foamed at room temperature,
Obtain soft polyurethane foam；
Step 4：Soft polyurethane foam prepared by step 3 is subjected to networking processing by dipping by lye or explosion method, cutting obtains more
The reticulated polyurethane microbe carrier that wall carbon nano tube is modified；
The olefinic monomer is styrene or divinylbenzene.
2. the preparation method for the reticulated polyurethane microbe carrier that multi-walled carbon nanotube according to claim 1 is modified,
It is characterized in that, the tin catalyst is stannous octoate or dibutyl tin dilaurate, and amines catalyst is triethylene diamine, three
One kind in ethanol amine, triethylamine or N-ethylmorpholine.
3. the preparation method for the reticulated polyurethane microbe carrier that multi-walled carbon nanotube according to claim 1 is modified,
It is characterized in that, the radical polymerization initiator is one in benzoyl peroxide, azodiisobutyronitrile, azobisisoheptonitrile
Kind.
4. the preparation method for the reticulated polyurethane microbe carrier that multi-walled carbon nanotube according to claim 1 is modified,
It is characterized in that, the isocyanates is methyl diphenylene diisocyanate.
5. according to the preparation for the reticulated polyurethane microbe carrier that claim 1-4 any one of them multi-walled carbon nanotube is modified
Method, which is characterized in that the dipping by lye method is that soft polyurethane foam is immersed in lye, immersion treatment 12~for 24 hours, lye
It forms and is：NaOH aqueous solutions that mass fraction is 40%, isopropanol, propylene glycol by volume 4:1~3:1 is made into mixed solution；
Then it is washed with distilled water 2~3 times.
6. according to the preparation for the reticulated polyurethane microbe carrier that claim 1-4 any one of them multi-walled carbon nanotube is modified
Method, which is characterized in that the explosion method is that the soft polyurethane foam of preparation is put into treatment reactor, is first vacuumized, backlash
Enter the explosive gas of certain pressure, spread igniting blasting after a period of time, obtain the soft polyurethane foam of networking processing.
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| CN108178840B (en) * | 2017-12-28 | 2020-07-24 | 南京理工大学 | Preparation method and application of intelligent temperature control metal-organic nanotube sponge material |
| CN112390378B (en) * | 2020-11-13 | 2022-08-09 | 浙江工商大学 | Biological filler with denitrification function, preparation method and application thereof |
| CN115897245B (en) * | 2022-12-28 | 2023-05-16 | 海泰纺织（苏州）有限公司 | Preparation method of antistatic finishing agent for fabric |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251596A (en) * | 1997-04-02 | 2000-04-26 | 三洋化成工业株式会社 | Polyurethane foam, process for producing same and foam forming composition |
| CN101560016A (en) * | 2009-05-07 | 2009-10-21 | 浙江省环境保护科学设计研究院 | Preparation method for water treatment microbe immobilization carrier |
| TW201036998A (en) * | 2009-03-11 | 2010-10-16 | Asahi Glass Co Ltd | Method for producing microorganism carrier made from soft polyurethane foam and microorganism carrier made of soft polyurethane foam |
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| JP2006346551A (en) * | 2005-06-15 | 2006-12-28 | Inoac Corp | Microorganism carrier for water treatment |
| JP2010265419A (en) * | 2009-05-18 | 2010-11-25 | Inoac Corp | Polyurethane foam used as carrier for water treatment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251596A (en) * | 1997-04-02 | 2000-04-26 | 三洋化成工业株式会社 | Polyurethane foam, process for producing same and foam forming composition |
| TW201036998A (en) * | 2009-03-11 | 2010-10-16 | Asahi Glass Co Ltd | Method for producing microorganism carrier made from soft polyurethane foam and microorganism carrier made of soft polyurethane foam |
| CN101560016A (en) * | 2009-05-07 | 2009-10-21 | 浙江省环境保护科学设计研究院 | Preparation method for water treatment microbe immobilization carrier |
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