CN1587105A - Process for preparing polyurethane base biological fixnig carrier - Google Patents
Process for preparing polyurethane base biological fixnig carrier Download PDFInfo
- Publication number
- CN1587105A CN1587105A CNA2004100625771A CN200410062577A CN1587105A CN 1587105 A CN1587105 A CN 1587105A CN A2004100625771 A CNA2004100625771 A CN A2004100625771A CN 200410062577 A CN200410062577 A CN 200410062577A CN 1587105 A CN1587105 A CN 1587105A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- water
- gac
- carrier
- technology
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 15
- 239000004814 polyurethane Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920001661 Chitosan Polymers 0.000 claims abstract description 27
- 238000005187 foaming Methods 0.000 claims abstract description 12
- 229920003023 plastic Polymers 0.000 claims abstract description 8
- 239000004033 plastic Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000004132 cross linking Methods 0.000 claims abstract description 3
- 239000006260 foam Substances 0.000 claims description 21
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- -1 halogenated alkyl phosphate Chemical compound 0.000 claims description 10
- 238000009775 high-speed stirring Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 229920002545 silicone oil Polymers 0.000 claims description 10
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000005189 flocculation Methods 0.000 claims description 8
- 230000016615 flocculation Effects 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000002594 sorbent Substances 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 6
- 230000006196 deacetylation Effects 0.000 claims description 5
- 238000003381 deacetylation reaction Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 229940106681 chloroacetic acid Drugs 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000013598 vector Substances 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002984 plastic foam Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention discloses the preparation process of one kind of chitosan cross-linked active carbon and polyurethane biological immobile carrier for water treating bioreaction. During synthesizing foamed polyurethane plastic, chitosan and powdered active carbon are added, and through further foaming, pelletizing, perforating and cross-linking, the biological immobile carrier is prepared. The present invention has the advantages of simple operation, reliable quality, low cost, high performance, etc. and the prepared carrier may be used widely in water treatment, especially in sewage treating system.
Description
Technical field
The present invention relates to a kind of technology that is used to prepare the biological fixing carrier of polyurethane-base, more specifically, the present invention relates to a kind of like this preparation technology: its be used for preparing a kind of be used in the water-treatment biological reaction, Polyurethane cross-linked chitosan and bag knitting the biological fixing carrier of gac.
Background technology
At present, along with improving constantly in the requirement aspect environmental protection and the Sustainable development, the multiple mode that waste water is recycled of being used for occurred, a kind of approach wherein is the water-treatment biological reaction, and the water-treatment biological reaction just need be used the biological respinse carrier.
In the prior art, polyurethane foam plastic has obtained certain application as microorganism carrier, still, its exist specific surface little, do not have that fine aperture, adsorptive power are not high, chemical stability is not good enough and the defective of facile hydrolysis.In water treatment procedure, prior art also adopts chitosan and gac as sorbent material and flocculation agent (for example can referring to Chinese patent open file CN 1280104A), but uses these materials then to have easy obstruction, easily run off and the high problem of running cost separately.
Thereby, occurred some in the prior art sorbent material or flocculation agent have been attached to precedent on the urethane carrier, for example in Chinese patent application open file CN 2294253Y, disclose gac is bonded in scheme on the Foam Plastic Surface, No. 4983299 United States Patent (USP) and Chinese patent application open file CN 1105649A have disclosed the scheme that has added gac when polyurethane foam plastic foams, these prior aries can improve the adsorptive power of carrier, but it is little to can't resolve specific surface, there is not fine aperture, chemical stability is not good enough, facile hydrolysis, gac and other additives combine insecure with the Polyurethane matrix, the shortcoming that intensity is relatively poor.
Japanese document spy opens and discloses a kind of precedent that is coated with chitosan on the surface of biological culture carrier among the flat 5-268960, but up to now, in water treatment field, do not appear at as yet in the polyurethane foam plastic building-up process and to add chitosan and gac to form the technology of new and effective carrier.
As for the production technique of urethane foam, there are pre-polymerization method, quasi-prepolymer method and three kinds of modes of single stage method in the prior art.The pre-polymerization method is excessive isocyanic ester and polyhydric alcohol polymer to be made the prepolymer of isocyanate terminated base earlier, and then with chainextender or the reaction of remaining polyhydric alcohol polymer.Quasi-prepolymer method and pre-polymerization method are similar, and just the level of response of prepolymer is lower.In enormous quantities continuous foamed or model foaming need be used single stage method.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of technology that is used to prepare the polyurethane base biological fixing carrier of chitosan crosslinked gac, the water-treatment biological reaction carriers that can utilize this technology to make to have excellent properties, that this technology has is simple to operation, dependable performance, low cost and other advantages.
A kind of technology for preparing the water-treatment biological fixation support has realized above-mentioned purpose, and this technology comprises step:
In the raw material of synthetic vectors porous plastics matrix, add sorbent material and flocculation agent; And
Batch mixing is carried out foaming, granulation, perforate and crosslinking Treatment, and flocculation agent is mutually crosslinked with body material, also bag is being knitted the described carrier of sorbent material.
According to a feature of the present invention, described porous plastics is a polyurethane material.
According to a feature of the present invention, described sorbent material is a gac.
According to a feature of the present invention, described flocculation agent is a chitosan.
According to an aspect of the present invention, the application provides a kind of technology for preparing polyurethane base biological fixing carrier, and it comprises step:
When the Polyurethane flex foam is synthetic, add chitosan and powdered carbon; And
Knit through foaming, granulation, perforate, crosslinked generation Polyurethane macroporous network and bag that the chitosan of gac and glutaraldehyde, epoxy chloropropane or Mono Chloro Acetic Acid are crosslinked to form the polymkeric substance that microporous network interweaves.
According to a further aspect in the invention, the application provides a kind of technology for preparing chitosan crosslinked gac urethane biological fixing carrier, and it comprises step:
By the mass ratio prescription water, polyethers 3010, silicone oil, triethylenediamine, stannous octoate, alkanolamine, halogenated alkyl phosphate, gac and chitosan are put into reactor, high-speed stirring 10 minutes, add the TDI80 high-speed stirring again after 2 minutes, be poured in the foam box that scribbles remover, in 40 ℃ environment, placed 24 hours or place at normal temperatures more than 36 hours, obtain foam;
Foam is cut into 10-30mm
3Particle;
Expanded beads is placed in the reactor,, washes with water to neutrality with 10% sodium carbonate solution reaction after 6-12 hour, soak 6-12 hour with 2% acetum then after, wash with water to neutrality again, press dry;
The hole-opening foaming particle is reacted in 2.5% glutaraldehyde or 10% epoxy chloropropane or 10% chloroacetic acid solution, and reaction is 12-3 hour under 16 ℃-60 ℃ condition, press dry, and reclaims solution, washes with water to neutrality.
According to a feature of the present invention, the raw materials used quality proportioning that foams is:
Polyethers 3010 (hydroxyl value 56) 100
TDI80 35-46
Gac 3-8
Chitosan 3-11
Silicone oil 0.3-0.5
Triethylenediamine 0.15
Alkanolamine 1.5
Stannous octoate 0.1
Halogenated alkyl phosphate 2.0
Water 2-4.5
According to a feature of the present invention, the granularity of used gac is between the 200-400 order among the preparation technology, and the deacetylation of chitosan is more than 90%.
Embodiment
Hereinafter will the present invention will be described in detail in conjunction with concrete embodiment, but these descriptions only are exemplary, those skilled in the art can figure out: in claims institute restricted portion, multiple other embodiment can also be arranged, and all based on the embodiment of design philosophy of the present invention all within the scope of the invention.
First embodiment according to preparation technology of the present invention is as follows:
(1) foaming:
Support material mass ratio prescription is:
Polyethers 3010 (hydroxyl value 56) 100
TDI80 38
Gac (granularity 300 orders) 5
Chitosan (deacetylation is more than 90%) 7
Silicone oil 0.3
Triethylenediamine 0.15
Alkanolamine 1.5
Stannous octoate 0.1
Halogenated alkyl phosphate 2.0
Water 3
By above-mentioned prescription water, polyethers 3010, silicone oil, triethylenediamine, stannous octoate, alkanolamine, halogenated alkyl phosphate, gac and chitosan are put into reactor, high-speed stirring 10 minutes, add the TDI80 high-speed stirring again after 2 minutes, be poured in the foam box that scribbles remover, placement is taken out after 24 hours and is obtained the thing that foams in 40 ℃ environment.
(2) granulation: the thing that will foam cuts into the particle of 15mm3.
(3) perforate: above-mentioned particle in reactor, with 10% sodium carbonate solution reaction 6 hours, is washed with water to neutrality; Soaked 12 hours with 2% acetum again, wash with water, press dry to neutrality.
(4) crosslinked: the carrier after the perforate is reacted in 2.5% glutaraldehyde solution, and 20 ℃ were reacted 10 hours, pressed dry, and reclaimed glutaraldehyde solution, and water is washed till neutrality with carrier, obtains the finished product carrier.
Preparation technology's of the present invention second embodiment is:
(1) foaming:
Support material mass ratio prescription is:
Polyethers 3010 (hydroxyl value 56) 100
TDI80 41
Gac (granularity 250 orders) 4
Chitosan (deacetylation is more than 90%) 8
Silicone oil 0.45
Triethylenediamine 0.15
Alkanolamine 1.5
Stannous octoate 0.1
Halogenated alkyl phosphate 2.0
Water 4
By prescription water, polyethers 3010, silicone oil, triethylenediamine, stannous octoate, alkanolamine, halogenated alkyl phosphate, gac and chitosan are put into reactor, high-speed stirring 10 minutes, add the TDI80 high-speed stirring again after 2 minutes, be poured in the foam box that scribbles remover, placement is taken out after 24 hours and is obtained the thing that foams in 40 ℃ environment.
(2) granulation: it is stand-by that the thing that will foam cuts into the particle of 20mm3.
(3) perforate: above-mentioned particle in reactor, with 10% sodium carbonate solution reaction 6 hours, is washed with water to neutrality, with 2% acetum immersion 12 hours, wash with water again, press dry stand-by to neutrality.
(4) crosslinked: the carrier after the perforate is reacted in 10% epoxy chloropropane solution, and reaction is 3 hours under 60 ℃ condition, press dry carrier, reclaims epoxy chloropropane solution, and water is washed till neutrality with carrier and obtains the finished product carrier.
Preparation technology's of the present invention second embodiment is:
(1) foaming:
Support material mass ratio prescription is:
Polyethers 3010 (hydroxyl value 56) 100
TDI80 40
Gac (granularity 400 orders) 7
Chitosan (deacetylation is more than 90%) 10
Silicone oil 0.3
Triethylenediamine 0.15
Alkanolamine 1.5
Stannous octoate 0.1
Halogenated alkyl phosphate 2.0
Water 2.5
Foaming preparation: water, polyethers 3010, silicone oil, triethylenediamine, stannous octoate, alkanolamine, halogenated alkyl phosphate, gac and chitosan are put into reactor by prescription, high-speed stirring 10 minutes, add the TDI80 high-speed stirring again after 2 minutes, be poured in the foam box that scribbles remover, place at normal temperatures after 36 hours to take out and obtain the thing that foams.
(2) granulation: it is stand-by that the thing that will foam cuts into the particle of 25mm3.
(3) perforate: above-mentioned particle in reactor, with 10% sodium carbonate solution reaction 6 hours, is being washed with water to neutrality, with 2% acetum immersion 12 hours, washing with water again, pressing dry stand-by to neutrality.
(4) crosslinked: the carrier after the perforate is reacted in 10% chloroacetic acid solution, and reaction is 6 hours under 30 ℃ condition, press dry, and reclaims chloroacetic acid solution, and water is washed till neutrality with carrier and obtains the finished product carrier.
Claims (8)
1, a kind of technology for preparing the water-treatment biological fixation support, it comprises step:
In the raw material of synthetic vectors porous plastics matrix, add sorbent material and flocculation agent; And
Batch mixing is carried out foaming, granulation, perforate and crosslinking Treatment, and flocculation agent is mutually crosslinked with body material, also bag is being knitted the described carrier of sorbent material to prepare.
2, technology according to claim 1 is characterized in that: described porous plastics is a polyurethane material.
3, technology according to claim 1 and 2 is characterized in that: described sorbent material is a gac.
4, technology according to claim 3 is characterized in that: described flocculation agent is a chitosan.
5, a kind of technology for preparing polyurethane base biological fixing carrier, it comprises step:
When the Polyurethane flex foam is synthetic, add chitosan and powdered carbon; And
Knit through foaming, granulation, perforate, crosslinked generation Polyurethane macroporous network and bag that the chitosan of gac and glutaraldehyde, epoxy chloropropane or Mono Chloro Acetic Acid are crosslinked to form the polymkeric substance that microporous network interweaves.
6, a kind of technology for preparing chitosan crosslinked gac urethane biological fixing carrier, it comprises step:
By the mass ratio prescription water, polyethers 3010, silicone oil, triethylenediamine, stannous octoate, alkanolamine, halogenated alkyl phosphate, gac and chitosan are put into reactor, high-speed stirring 10 minutes, add the TDI80 high-speed stirring again after 2 minutes, be poured in the foam box that scribbles remover, in 40 ℃ environment, placed 24 hours or place at normal temperatures more than 36 hours, obtain foam;
Foam is cut into 10-30mm
3Particle;
Expanded beads is placed in the reactor,, washes with water to neutrality with 10% sodium carbonate solution reaction after 6-12 hour, soak 6-12 hour with 2% acetum then after, wash with water to neutrality again, press dry;
The hole-opening foaming particle is reacted in 2.5% glutaraldehyde or 10% epoxy chloropropane or 10% chloroacetic acid solution, and reaction is 12-3 hour under 16 ℃-60 ℃ condition, press dry, and reclaims solution, washes with water to neutrality.
7, technology according to claim 6 is characterized in that the quality proportioning that foams raw materials used is:
Polyethers 3,010 100
TDI80 35-46
Gac 3-8
Chitosan 3-11
Silicone oil 0.3-0.5
Triethylenediamine 0.15
Alkanolamine 1.5
Stannous octoate 0.1
Halogenated alkyl phosphate 2.0
Water 2-4.5
8, technology according to claim 7 is characterized in that: the granularity of used gac is between the 200-400 order among the preparation technology, and the deacetylation of chitosan is more than 90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100625771A CN1261373C (en) | 2004-07-02 | 2004-07-02 | Process for preparing polyurethane base biological fixnig carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100625771A CN1261373C (en) | 2004-07-02 | 2004-07-02 | Process for preparing polyurethane base biological fixnig carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1587105A true CN1587105A (en) | 2005-03-02 |
| CN1261373C CN1261373C (en) | 2006-06-28 |
Family
ID=34603728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100625771A Expired - Fee Related CN1261373C (en) | 2004-07-02 | 2004-07-02 | Process for preparing polyurethane base biological fixnig carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1261373C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781396A (en) * | 2010-03-30 | 2010-07-21 | 上海交通大学 | Chitosan-polyurethane composite rigid closed-cell foam material and preparation method thereof |
| CN102531149A (en) * | 2010-12-10 | 2012-07-04 | 新奥科技发展有限公司 | Packing for bearing microorganism |
| CN102935354A (en) * | 2012-05-25 | 2013-02-20 | 高巍 | Novel open micropore molecule carrier and preparation method thereof |
| CN103450687A (en) * | 2012-05-31 | 2013-12-18 | 上海日多高分子材料有限公司 | Manufacturing method of foaming agent for realizing compact and uniform foam pore arrangement |
| CN111892248A (en) * | 2020-08-05 | 2020-11-06 | 张建东 | Biological treatment system for removing pollutants in flue gas desulfurization wastewater |
| CN112158945A (en) * | 2020-10-09 | 2021-01-01 | 北京华明广远环境科技有限公司 | Preparation and strengthening method of biological filter filler for industrial wastewater treatment |
| CN114940817A (en) * | 2022-06-27 | 2022-08-26 | 烟台辰宇汽车部件有限公司 | Polyurethane for thrust rod and preparation method thereof |
-
2004
- 2004-07-02 CN CNB2004100625771A patent/CN1261373C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781396A (en) * | 2010-03-30 | 2010-07-21 | 上海交通大学 | Chitosan-polyurethane composite rigid closed-cell foam material and preparation method thereof |
| CN102531149A (en) * | 2010-12-10 | 2012-07-04 | 新奥科技发展有限公司 | Packing for bearing microorganism |
| CN102531149B (en) * | 2010-12-10 | 2015-09-02 | 新奥科技发展有限公司 | A kind of filler of bearing microorganism |
| CN102935354A (en) * | 2012-05-25 | 2013-02-20 | 高巍 | Novel open micropore molecule carrier and preparation method thereof |
| CN102935354B (en) * | 2012-05-25 | 2015-05-13 | 高巍 | Novel open micropore molecule carrier and preparation method thereof |
| CN103450687A (en) * | 2012-05-31 | 2013-12-18 | 上海日多高分子材料有限公司 | Manufacturing method of foaming agent for realizing compact and uniform foam pore arrangement |
| CN111892248A (en) * | 2020-08-05 | 2020-11-06 | 张建东 | Biological treatment system for removing pollutants in flue gas desulfurization wastewater |
| CN111892248B (en) * | 2020-08-05 | 2022-08-05 | 张建东 | Biological treatment system for removing pollutants in flue gas desulfurization wastewater |
| CN112158945A (en) * | 2020-10-09 | 2021-01-01 | 北京华明广远环境科技有限公司 | Preparation and strengthening method of biological filter filler for industrial wastewater treatment |
| CN114940817A (en) * | 2022-06-27 | 2022-08-26 | 烟台辰宇汽车部件有限公司 | Polyurethane for thrust rod and preparation method thereof |
| CN114940817B (en) * | 2022-06-27 | 2023-11-21 | 烟台辰宇汽车部件有限公司 | Polyurethane for thrust rod and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1261373C (en) | 2006-06-28 |
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Granted publication date: 20060628 |
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