CN109608610A - A kind of graphene modified aqueous polyurethane-epoxy resin and preparation method thereof - Google Patents
A kind of graphene modified aqueous polyurethane-epoxy resin and preparation method thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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Abstract
The present invention relates to a kind of graphene modified aqueous polyurethane-epoxy resin and preparation method thereof, by weight, consisting of: 8.0~20.0 parts of polyisocyanates, 2.0~6.0 parts of polyalcohol, 0.5~2.0 part of polynary amine chain extender, 4.0~10.0 parts of oligomer polyether polyol, 1.5~4.5 parts of dihydromethyl propionic acid, 4.0~15.0 parts of epoxy resin, 0.01~0.1 part of dibutyl tin dilaurate, 0.5~2.5 part of graphene, 4.0~10.0 parts of acetone, 1.0~3.0 parts of neutralizer, 48.0~68.0 parts of distilled water；Graphene modified aqueous polyurethane-epoxy resin produced by the present invention has the characteristics that good adhesive force, corrosion-resistant, water resistance, alkali resistance, wearability, antistatic, high rigidity, it is widely used in marine field, iron component, woodwork coating, anti-static coatings, conductive coating, antifouling water-repellent paint, application potential is all very huge.
Description
Technical field
The present invention relates to a kind of preparation method of modified aqueous polyurethane-epoxy resin, more particularly to one kind are multi-functional
Graphene modified aqueous polyurethane-epoxy resin and preparation method thereof, belong to water-base resin synthesis technical field.
Background technique
The advantages of polyurethane system, is to have binary acid abundant, dihydric alcohol polymerized monomer available, mainly by alcohol
It is reacted with isocyanates, reaction raw materials and technological factor have a significant impact to polyurethane material form, therefore being capable of basis
Different requirements organically combine soft segment, hard section, to achieve the purpose that design.But polyurethane resin presence is easy in case of wet
Blistering, the problems such as resistance to acid and alkali is poor, general polyurethane insulating is high, easy to produce static electricity, make its special dimension application by
To limitation.And epoxy resin is since it is with excellent physical and chemical performance, and its solidfied material has that mechanical performance is high, chemistry is steady
The advantages that qualitative good, cure shrinkage is low and processing performance is good, is widely used in aerospace, communications and transportation and civilian
Facility field.
Graphene has excellent comprehensive performance, such as high conductivity, thermal conductivity, high intensity characteristic, and graphene is
Most thin, the most hard nano material in known world.Graphene is referred to as " dark fund ", is " king of new material ", scientist is even
Foretell that graphene " will thoroughly change for 21st century ".Very likely start the subversiveness new technology NPD projects to have swept the globe a leather
Life can improve the anti-corrosive properties of coating, electrical and thermal conductivity and anti-flammability and mechanical property, world's model by adding graphene
There are many documents and patent report graphene enhancing composite material in enclosing.Chinese patent CN104140639 discloses one kind
Graphene/epoxy resin composite material: compared with pure epoxy resin, tensile strength improves 34.9%~124.8%, impact
Intensity improves 15.4%~105.1%, and glass transition temperature improves 5 DEG C~19 DEG C, but based on graphene in aqueous body
It is easy to happen reunion in system and settles, limits its application.
Chinese patent CN104762051A disclose transformer core end face graphene/epoxy resin composite adhesive and
Production method: by graphene dispersion into epoxy monomer solution, endurable active toughener, reactive diluent, solvent is added.It is adopted
Graphene is added in epoxy resin with physical mixed, stability is poor.
In order to integrate the excellent performance of polyurethane and graphene, the prior art forms the method performance of composite material to the two
It has conducted extensive research.The anti-corrosive properties of coating, electrical and thermal conductivity and anti-flammability and mechanics can be improved by adding graphene
Performance, but reunion is easy to happen in water-based system based on graphene and is settled, its application is limited, therefore, using chemical method
General character graphene and polyurethane resin become trend.
The present invention is chemically reacted using the hydroxyl of graphene oxide, the specific groups of epoxy resin and polyurethane, is adopted
It is connected with chemical bond, has taken into account the property of graphene and epoxy resin, effectively improved polyurethane resin, epoxy resin
Mechanical strength, anti-corrosion, heat resistance, UV resistant, resistance to oxidation degradation and the performances such as easy to produce static electricity that insulate of material.
Summary of the invention
In order to solve technical problem described above, the present invention is in polyurethane resin with chemical bond form on molecular structure
It introduces epoxy resin to be modified, modified polyurethane resin has that anticorrosion is good, adhesive force is good and the performances such as resistance to ozone；
Polyether polyol is introduced simultaneously, effectively improves the problems such as polyurethane-epoxy resin hydrolytic resistance is poor.
Special graphite alkene is introduced in polyurethane-epoxy resin and carries out chemical modification, and graphene is aoxidized via strong oxidizer
After can be prepared into graphite oxide, oxidized graphite flake layer contains a large amount of oxygen-containing polar group, such as hydroxyl, carboxyl, epoxy group,
Specific surface area with higher, graphene are destroyed through peroxidating, the pi-conjugated structure of π-, and lamella is easily peeled off, this is stone
Black alkene modified aqueous polyurethane-epoxy resin provides natural endowment, and modified polyurethane-epoxy resin has good lead
Electrical property and antistatic performance, and graphene is connected with polyurethane-epoxy resin by chemical bond, and physical mixed is efficiently solved
When be also easy to produce aggregation and the problems such as settle.
The purpose of the present invention is intended to provide a kind of graphene modified aqueous polyurethane-epoxy resin of high comprehensive performance.
Another object of the present invention is to provide a kind of preparation methods of graphene modified aqueous polyurethane-epoxy resin.
Graphene modified aqueous polyurethane-epoxy resin solve graphene physical mixed be also easy to produce aggregation and occur sedimentation and it is aqueous
The problems such as polyurethane and epoxy resin compatibility are poor remains the good antiseptic property of epoxy resin and excellent anti-of graphene
Antistatic property.
In order to solve technical problem described above, the present invention takes following technical scheme: the present invention relates to a kind of graphite
Alkene modified aqueous polyurethane-epoxy resin, by weight, consisting of: 8.0~20.0 parts of polyisocyanates, polyalcohol 2.0
~6.0 parts, 0.5~2.0 part of polynary amine chain extender, 4.0~10.0 parts of oligomer polyether polyol, dihydromethyl propionic acid 1.5
~4.5 parts, 4.0~15.0 parts of epoxy resin, 0.01~0.1 part of dibutyl tin dilaurate, 0.5~2.5 part of graphene, acetone
4.0~10.0 parts, 1.0~3.0 parts of neutralizer, 48.0~68.0 parts of distilled water.
The polyalcohol is ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, Diethylene Glycol, a contracting
Dipropylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 2,4- diethyl -1,5- pentanediol, 2- ethyl -1,3- hexylene glycol, three
The combination of one or more of hydroxymethyl-propane, glycerol, trimethylolethane, pentaerythrite, xylitol, sorbierite.
The oligomer polyether polyol is polytetrahydrofuran ether glycol of the molecular weight between 1000~4000, polyethers
The combination of one or both of dihydric alcohol.
The graphene be hydroxyl graphene oxide, by Hummers method, Staudemaier method, electrochemical process or
The preparation of Brodie method；It further, is the graphene oxide of Hummers method preparation.
The neutralizer is the combination of one or more of triethylamine, ammonium hydroxide, dimethylethanolamine.
The polynary amine chain extender is the combination of one or more of ethylenediamine, hydrazides, hydrazine hydrate.
The polyisocyanates is toluene di-isocyanate(TDI) TDI, isophorone diisocyanate IPDI, hexa-methylene two
Isocyanates HDI, benzene dimethylene diisocyanate XDI, cyclohexanedimethyleterephthalate diisocyanate H6XDI, durol two
The combination of one or more of methylene diisocyanate TMXDI.
Graphene modified aqueous polyurethane-epoxy resin preparation method, comprising the following steps:
A, equipped with thermometer, condenser pipe, blender four mouthfuls of reactors in, by the parts by weight of formula sequentially add polyalcohol,
Oligomer polyether polyol, dihydromethyl propionic acid are heated to 1.5~2.0h of vacuum dehydration between 100 DEG C~110 DEG C；
B, 70 DEG C~75 DEG C are cooled to, is vacuumized, nitrogen pressure release is passed through, epoxy resin, graphene is added, polyisocyanic acid is added dropwise
Ester, 0.5~1h are added dropwise to complete.Then be added dropwise formula ratio dibutyl tin dilaurate, be warming up to 80 DEG C~82 DEG C reaction 2~
2.5h supplements acetone depending on system viscosity, nco value is measured, until it is consistent with design value；
C, continue stirring and cool the temperature to 35 DEG C hereinafter, neutralizer is slowly added dropwise, continue to be stirred to react 10~20 min, meter is added
The distilled water that 10 DEG C~20 DEG C of calculation amount continues to be stirred to react 15 min of dispersion, polynary amine chain extender is added under agitation,
High-speed stirred disperses 1h, then stirs at low speed dispersion 0.5h, takes off acetone to get graphene modified aqueous polyurethane-epoxy resin.
The present invention provides a kind of function admirable, non-environmental-pollution, VOC content extremely low graphene modified aqueous polyurethane-
Epoxy resin and preparation method thereof.Graphene modified aqueous polyurethane-epoxy resin produced by the present invention has good attachment
The features such as power, corrosion-resistant, water resistance, alkali resistance, wearability, antistatic, high rigidity, is widely used in marine field, iron component, wood
Device coating, anti-static coatings, conductive coating, antifouling water-repellent paint, application potential are all very huge.
Specific embodiment
Present invention combination following instance is described further the preparation of graphene modified aqueous polyurethane-epoxy resin.
It is understood that specific embodiment described herein is used only for explaining related invention, rather than the restriction to the invention.
Embodiment 1
A kind of graphene modified aqueous polyurethane-epoxy resin, preparation process are as follows:
A, in four mouthfuls of reactors that thermometer, condenser pipe, blender are housed, fourth two is sequentially added by the weight percent of formula
3.0 parts of alcohol, 1.5 parts of trimethylolpropane, 6.0 parts of polytetrahydrofuran ether glycol, 2.6 parts of dihydromethyl propionic acid, are heated to
1.5~2.0h of vacuum dehydration between 100 DEG C~110 DEG C；
B, 70 DEG C~75 DEG C are cooled to, is vacuumized, nitrogen pressure release is passed through, 1.5 parts of graphene, 8.0 parts of epoxy resin, drop is added
Add 14.0 parts of hexamethylene diisocyanate, 0.5~1h is added dropwise to complete.Then formula ratio dibutyl tin dilaurate 0.05 is added dropwise
Part, 80~82 DEG C of 2~2.5h of reaction are warming up to, 6.0 parts of acetone is supplemented depending on system viscosity, nco value is measured, when itself and design value one
Until cause；
C, continue stirring and cool the temperature to 35 DEG C hereinafter, be slowly added dropwise 1.9 parts of neutralizer triethylamine, continue to be stirred to react 10~20
54.25 parts of distilled water of 10 DEG C~20 DEG C of calculation amount are added in min, continue to be stirred to react 15 min of dispersion, under agitation plus
Enter 1.2 parts of ethylenediamine, high-speed stirred disperses 1h, then stirs at low speed dispersion 0.5h, it is poly- to get graphene modified water-soluble to take off acetone
Urethane-epoxy resin.
Embodiment 2
A kind of graphene modified aqueous polyurethane-epoxy resin, preparation process are as follows:
A, in four mouthfuls of reactors that thermometer, condenser pipe, blender are housed, butanediol is sequentially added by the parts by weight of formula
2.5 parts, 1.5 parts of glycerol, 7.0 parts of polytetrahydrofuran ether glycol, 2.8 parts of dihydromethyl propionic acid, are heated to 100 DEG C~110
1.5~2.0h of vacuum dehydration between DEG C；
B, 70 DEG C~75 DEG C are cooled to, is vacuumized, nitrogen pressure release is passed through, 1.5 parts of graphene, 4.0 parts of epoxy resin, drop is added
Add 16.0 parts of isophorone diisocyanate, 0.5~1h is added dropwise to complete.Then formula ratio dibutyl tin dilaurate 0.05 is added dropwise
Part, 80~82 DEG C of 2~2.5h of reaction are warming up to, 6.0 parts of acetone is supplemented depending on system viscosity, nco value is measured, when itself and design value one
Until cause；
C, continue stirring and cool the temperature to 35 DEG C hereinafter, be slowly added dropwise 2.1 parts of neutralizer triethylamine, continue to be stirred to react 10~
55.55 parts of distilled water of 10 DEG C~20 DEG C of calculation amount are added in 20 min, continue to be stirred to react 15 min of dispersion, in stirring condition
Lower 1.0 parts of addition ethylenediamine, high-speed stirred disperses 1h, then stirs at low speed dispersion 0.5h, takes off acetone to get graphene modified water
Property polyurethane-epoxy resin.
Embodiment 3
A kind of graphene modified aqueous polyurethane-epoxy resin, preparation process are as follows:
A, in four mouthfuls of reactors that thermometer, condenser pipe, blender are housed, new penta is sequentially added by the weight percent of formula
2.2 parts of glycol, 1.2 parts of trimethylolpropane, 6.5 parts of polyether Glycols, 2.4 parts of dihydromethyl propionic acid, are heated to 100 DEG C
1.5~2.0h of vacuum dehydration between~110 DEG C；
B, 70 DEG C~75 DEG C are cooled to, is vacuumized, nitrogen pressure release is passed through, 1.6 parts of graphene, 9.0 parts of epoxy resin, drop is added
Add 14.0 parts of toluene di-isocyanate(TDI), 0.5~1h is added dropwise to complete.Then it is added dropwise 0.05 part of formula ratio dibutyl tin dilaurate,
80~82 DEG C of 2~2.5h of reaction are warming up to, 6.5 parts of acetone is supplemented depending on system viscosity, nco value is measured, when it is consistent with design value
Until；
C, continue stirring and cool the temperature to 35 DEG C hereinafter, be slowly added dropwise 2.0 parts of neutralizer triethylamine, continue to be stirred to react 10~20
52.95 parts of distilled water of 10 DEG C~20 DEG C of calculation amount are added in min, continue to be stirred to react 15 min of dispersion, under agitation plus
Enter 1.6 parts of ethylenediamine, high-speed stirred disperses 1h, then stirs at low speed dispersion 0.5h, it is poly- to get graphene modified water-soluble to take off acetone
Urethane-epoxy resin.
According to relevant criterion, graphene modified aqueous polyurethane-epoxy resin of preparation of the embodiment of the present invention is examined
It surveys, performance indicator is as shown in table 1.
Table 1: graphene modified aqueous polyurethane-Properties of Epoxy Resin index
| Detection project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Appearance | Grey is semi-transparent | Grey is semi-transparent | Grey is semi-transparent |
| Storage stability | It is outstanding | It is outstanding | It is outstanding |
| Pencil hardness | 1H | 1H | 1H |
| Adhesive force | 0 | 0 | 0 |
| Bend test/mm | 1 | 1 | 1 |
| Impact resistance/50cm | Paint film is normal | Paint film is normal | Paint film is normal |
| Water resistance | 480h paint film is normal | 480h paint film is normal | 480h paint film is normal |
| Alkali resistance (50g/L NaOH) | 10d paint film is normal | 10d paint film is normal | 10d paint film is normal |
| Acid resistance (50g/L H2SO4) | 10d paint film is normal | 10d paint film is normal | 10d paint film is normal |
| Oil resistivity (93#Gasoline) | 10d paint film is normal | 10d paint film is normal | 10d paint film is normal |
| Salt fog resistance | 1000h paint film is normal | 1000h paint film is normal | 1000h paint film is normal |
| Antistatic performance | Well | Well | Well |
| Anticorrosive property | Well | Well | Well |
Above description is only the preferred embodiment of the application and the explanation to institute's application technology principle；Those skilled in the art answer
Work as understanding, invention scope involved in the application, however it is not limited to technical solution made of the specific combination of above-mentioned technical characteristic,
It should also cover in the case where not departing from the inventive concept simultaneously, carry out any group by above-mentioned technical characteristic or its equivalent feature
The other technical solutions closed and formed.Such as features described above and (but being not limited to) disclosed herein have the skill of similar functions
Art feature is replaced mutually and the technical solution that is formed.
Claims (8)
1. a kind of graphene modified aqueous polyurethane-epoxy resin, it is characterised in that: by weight, consisting of: polyisocyanate cyanogen
8.0~20.0 parts of acid esters, 2.0~6.0 parts of polyalcohol, 0.5~2.0 part of polynary amine chain extender, oligomer polyether polyol 4.0
~10.0 parts, 1.5~4.5 parts of dihydromethyl propionic acid, 4.0~15.0 parts of epoxy resin, dibutyl tin dilaurate 0.01~0.1
Part, 0.5~2.5 part of graphene, 4.0~10.0 parts of acetone, 1.0~3.0 parts of neutralizer, 48.0~68.0 parts of distilled water.
2. a kind of graphene modified aqueous polyurethane-epoxy resin as described in claim 1, it is characterised in that: described is more
First alcohol is ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, Diethylene Glycol, dipropylene glycol, 2- butyl-
2- ethyl -1,3- propylene glycol, 2,4- diethyl -1,5- pentanediol, 2- ethyl -1,3- hexylene glycol, trimethylolpropane, glycerol,
The combination of one or more of trimethylolethane, pentaerythrite, xylitol, sorbierite.
3. a kind of graphene modified aqueous polyurethane-epoxy resin as described in claim 1, it is characterised in that: described is low
Polymers polyether polyol be one of polytetrahydrofuran ether glycol of the molecular weight between 1000~4000, polyether Glycols or
Two kinds of combination.
4. a kind of graphene modified aqueous polyurethane-epoxy resin as described in claim 1, it is characterised in that: the stone
Black alkene is hydroxyl graphene oxide, is prepared by Hummers method, Staudemaier method, electrochemical process or Brodie method；Further
Ground, for the graphene oxide of Hummers method preparation.
5. a kind of graphene modified aqueous polyurethane-epoxy resin as described in claim 1, it is characterised in that: in described
It is the combination of one or more of triethylamine, ammonium hydroxide, dimethylethanolamine with agent.
6. a kind of graphene modified aqueous polyurethane-epoxy resin as described in claim 1, it is characterised in that: described is more
First amine chain extender is ethylenediamine, two hydrazine of adipic acid, hydrazine hydrate, N, one or more of N- dihydroxy (diisopropyl) aniline
Combination.
7. a kind of graphene modified aqueous polyurethane-epoxy resin as described in claim 1, it is characterised in that: described is more
Isocyanates is toluene di-isocyanate(TDI) TDI, isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI, benzene two
Methylene diisocyanate XDI, cyclohexanedimethyleterephthalate diisocyanate H6XDI, tetramethylxylylene diisocyanate
The combination of one or more of TMXDI.
8. the preparation method of graphene modified aqueous polyurethane-epoxy resin as described in claim 1, it is characterised in that: institute
The preparation method stated, preparation process are as follows:
A, equipped with thermometer, condenser pipe, blender four mouthfuls of reactors in, by the parts by weight of formula sequentially add polyalcohol,
Oligomer polyether polyol, dihydromethyl propionic acid are heated to 1.5~2.0h of vacuum dehydration between 100 DEG C~110 DEG C；
B, 70 DEG C~75 DEG C are cooled to, is vacuumized, nitrogen pressure release is passed through, epoxy resin, graphene is added, polyisocyanic acid is added dropwise
Ester, 0.5~1h are added dropwise to complete；Then be added dropwise formula ratio dibutyl tin dilaurate, be warming up to 80 DEG C~82 DEG C reaction 2~
2.5h supplements acetone depending on system viscosity, nco value is measured, until it is consistent with design value；
C, continue stirring and cool the temperature to 35 DEG C hereinafter, neutralizer is slowly added dropwise, continue to be stirred to react 10~20 min, meter is added
The distilled water that 10 DEG C~20 DEG C of calculation amount continues to be stirred to react 15 min of dispersion, polynary amine chain extender is added under agitation,
High-speed stirred disperses 1h, then stirs at low speed dispersion 0.5h, takes off acetone to get graphene modified aqueous polyurethane-epoxy resin.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120228560A1 (en) * | 2009-11-05 | 2012-09-13 | Duk San Tekopia Co., Ltd. | Conductive adhesive, method for manufacturing the same, and electronic device including the same |
| CN104693989A (en) * | 2015-03-26 | 2015-06-10 | 东南大学 | Preparation method for graphene modified polyurethane-epoxy resin waterborne damping coating |
| CN104910791A (en) * | 2015-06-29 | 2015-09-16 | 东南大学 | Preparation method of graphene modified polyurethane-epoxy resin water-based damping paint |
| CN106632965A (en) * | 2016-12-30 | 2017-05-10 | 康伦国 | Graphene-organosilicon modified waterborne polyurethane resin |
| CN106832183A (en) * | 2016-12-14 | 2017-06-13 | 武汉科利尔新材料有限公司 | A kind of Graphene modified cathode polyurethane electrophoresis resin and its cataphoresis paint composition |
| CN107699122A (en) * | 2017-10-27 | 2018-02-16 | 安徽海程铁路器材科技有限公司 | A kind of watersoluble closed dose of preparation method of railway elastic bar |
| CN107779077A (en) * | 2017-10-27 | 2018-03-09 | 安徽海程铁路器材科技有限公司 | A kind of railway elastic bar is with watersoluble closed dose |
| CN107880237A (en) * | 2017-12-26 | 2018-04-06 | 海安常州大学高新技术研发中心 | A kind of preparation method of graphene oxide modified aqueous polyurethane anti-corrosion emulsion |
-
2018
- 2018-12-13 CN CN201811527986.2A patent/CN109608610A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120228560A1 (en) * | 2009-11-05 | 2012-09-13 | Duk San Tekopia Co., Ltd. | Conductive adhesive, method for manufacturing the same, and electronic device including the same |
| CN104693989A (en) * | 2015-03-26 | 2015-06-10 | 东南大学 | Preparation method for graphene modified polyurethane-epoxy resin waterborne damping coating |
| CN104910791A (en) * | 2015-06-29 | 2015-09-16 | 东南大学 | Preparation method of graphene modified polyurethane-epoxy resin water-based damping paint |
| CN106832183A (en) * | 2016-12-14 | 2017-06-13 | 武汉科利尔新材料有限公司 | A kind of Graphene modified cathode polyurethane electrophoresis resin and its cataphoresis paint composition |
| CN106632965A (en) * | 2016-12-30 | 2017-05-10 | 康伦国 | Graphene-organosilicon modified waterborne polyurethane resin |
| CN107699122A (en) * | 2017-10-27 | 2018-02-16 | 安徽海程铁路器材科技有限公司 | A kind of watersoluble closed dose of preparation method of railway elastic bar |
| CN107779077A (en) * | 2017-10-27 | 2018-03-09 | 安徽海程铁路器材科技有限公司 | A kind of railway elastic bar is with watersoluble closed dose |
| CN107880237A (en) * | 2017-12-26 | 2018-04-06 | 海安常州大学高新技术研发中心 | A kind of preparation method of graphene oxide modified aqueous polyurethane anti-corrosion emulsion |
Non-Patent Citations (3)
| Title |
|---|
| ZENG CEN，等: "Enhanced thermal and mechanical properties of epoxy composites by mixing noncovalently functionalized graphene sheets", 《POLYMER BULLETIN》 * |
| 孙静: "海洋环境下高耐蚀涂层用水性聚氨酯及其复合材料的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 李俊贤: "《塑料工业手册 聚氨酯》", 31 July 1999, 化学工业出版社 * |
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