CN104891509B - A kind of A grades of non-combustible silica aerogel and preparation method thereof - Google Patents
A kind of A grades of non-combustible silica aerogel and preparation method thereof Download PDFInfo
- Publication number
- CN104891509B CN104891509B CN201510236100.9A CN201510236100A CN104891509B CN 104891509 B CN104891509 B CN 104891509B CN 201510236100 A CN201510236100 A CN 201510236100A CN 104891509 B CN104891509 B CN 104891509B
- Authority
- CN
- China
- Prior art keywords
- preparation
- aeroge
- alcohol
- aerogel
- mixture
- 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.)
- Active
Links
Abstract
The present invention relates to a kind of A grades of Hydrophobic silica aeroge and aerogel composite and preparation method thereof, preparation method includes step：(1) esters of silicon acis and methylethoxy base silane proportioning liquid are hydrolyzed in alcohol with acid catalyst, obtain colloidal sol；(2) base catalyst is added in colloidal sol, pH value is adjusted to 6 10, obtain alkaline sol, alkaline sol can then form wet gel；Or after obtaining alkaline sol, alkaline sol is combined with inorfil, prepare gelatinous fibre composite；(3) wet gel after ageing or gelatinous fibre composite are placed in CO2It is dried in overcritical device, uses CO2The alcohol in hole is displaced, dry silica aerogel is obtained；(4) silane compound is sprayed onto the surface of dry silica aerogel or oxygen gelatinous fibre composite, and the body of heated oxide silica aerogel or gelatinous fibre composite carries out hydrophobically modified, obtains non-combustible silica hydrophobic aerogel.
Description
Technical field
The present invention relates to aeroge production field, more particularly to a kind of preparation method of A grades of non-combustible silica aerogel
And it is related to the non-combustible silica aerogel product prepared by the method.
Background technology
Aeroge is described as one of following ten most potential big new materials, because its porosity is up to more than 90%, heat conduction
Coefficient and density as little as 0.01 W/m.K and 0.03g/cm3, so have at aspects such as insulation, heat-insulated, noise reduction, sound insulations to look forward to
And advantage, future surely for energy-saving and emission-reduction are contributed share.
Aeroge is silicon source with waterglass, with collosol and gel by Stanford Univ USA's Kistler teaching inventives in 1931
Technique prepares aeroge, but complex process, is not applied.
The sixties in last century, Nicolaon et al. are obtained wet gel, so with silicon alkoxide as presoma with sol gel process
After use supercritical drying（SCFD）Technique is obtained.But the aeroge that these techniques are prepared is hydrophilic, due to surface hydroxyl
A large amount of presence of base so that the material is very easy to the moisture absorption, so that condensation vapor, improves thermal conductivity factor, substantially reduce airsetting
The major functions such as the insulation of glue.
The 80s and 90s, researcher adds silane type organic to carry out hydrophobic modification and is modified aborning, such as Publication No.
Listed in the patent document of CN101318659A the gel after aging has been combined with organo-silicon compound such as trim,ethylchlorosilanes
Material carries out hydrophobic modification and is modified, and is then dried with the mode of constant pressure and dry.The purpose of hydrophobic modification partly in order to
The effect of gel internal capillaries power is reduced, so as to reduce the interface interaction power of hole internal solvent and air surface, this is normal pressure
The step of desiccant gel must be carried out；On the other hand hydrophobic layer is formed, guarantor is reduced to prevent the immersion of moisture during use
Although warm soundproof effect, aeroge prepared by this technique is provided with hydrophobic effect, but is molten because hydrophobic modification is modified
Carried out in agent, in practice it has proved that must assure that organo-silicon compound are attached on bulk material more than the amount of gross mass more than 10%,
Can just realize most capillaries hydrophobic and be unlikely to collapse.So exactly cause the Use out of range of organic compound, one
Aspect causes environmental pollution, it is often more important that such substantial amounts of organic matter can burn at high temperature, it is impossible to reach Ministry of Public Security's public affairs and disappear
2011 No. 65 texts（《Had the right on further clear and definite civil buildings insulation material fire supervision management the notice of requirement》）Will
Ask, the notice request civil buildings heat insulating material for external uses combustibility A grades of material of text.(GB8624-2012《Construction material and
Product burns grading performance》), can be sayed without any advantage compared with the B such as extruded sheet grades of material, especially in energy-conserving and environment-protective situation phase
When under severe overall situation.
In the aeroge porous material preparation method that the patent document of publication No. CN103524111A is listed, also in dry
Organo-silicon compound solution is introduced before dry, due to containing substantial amounts of hydroxyl in wet gel, it is necessary to substantial amounts of silane compound ability
Realize the purpose of hydrophobically modified.Although the aerogel material therefore prepared has hydrophobicity, due to organic compound content
It is exceeded, it is impossible to reach A grades of non-combustible material standard, therefore cannot be widely used in building exterior wall heat preserving industry, limit aeroge
Promote the use of.
The content of the invention
In view of existing aeroge hydrophobically modified and be unable to reach the A grades of problem of non-combustible material standard, the present invention provides a kind of A
The preparation method of level hydrophobic aerogel and aerogel composite, the method comprises the following steps：
（1）Esters of silicon acis and methylethoxy base silane proportioning liquid are fully hydrolyzed in alcohol with acid catalyst, obtain colloidal sol.
（2）Base catalyst is added in colloidal sol, pH value is adjusted to 6-12, the weakly acidic pH or the colloidal sol of alkalescence for obtaining are subsequent
Form wet gel；Or after obtaining the colloidal sol of weakly acidic pH or alkalescence, the colloidal sol of weakly acidic pH or alkalescence and inorfil are combined, make
Standby gelatinous fibre composite；The wet gel that to obtain or or gelatinous fibre composite be aged.
（3）Wet gel after ageing or gelatinous fibre composite are placed in CO2It is dried in overcritical device, uses CO2
The alcohol in hole is displaced, dry silica aerogel is obtained.
（4）Silane compound is sprayed onto the surface of dry silica aerogel or aeroge fibrous composite, and is added
The body of thermal oxidation silicon aeroge or gelatinous fibre composite carries out hydrophobically modified, obtains non-combustible silica aerogel.
Further, step（1）In alcohol, esters of silicon acis, the proportioning of methylethoxy base silane be（Mass fraction）10-20 parts
: 0.2-5 parts: 0.2-5 part；Wherein described alcohol is alcohol of the content more than 90%.
Further, step（1）In methylethoxy base silane be MTES, diformazan diethoxy silicon
Alkane, trimethylethoxysilane or their mixture.
Further, step（1）The esters of silicon acis be a kind of in methyl silicate, tetraethyl orthosilicate, butyl silicate
Or their mixture；The alcohol liquid is one kind or their mixture in methyl alcohol, ethanol, n-butanol, isopropanol；The acid
Catalyst is a kind of or their mixture in hydrochloric acid, sulfuric acid, acetic acid, butyric acid, formic acid；The base catalyst be NaOH,
A kind of or its mixture in potassium hydroxide, ammoniacal liquor, monoethanolamine, diethanol amine, triethanolamine；The silane compound is front three
A kind of or its mixture in base chlorosilane, HMDS, HMDS.
Further, hydrolysis is carried out between pH value is 1-4.
Further, in step（2）In, the inorfil is glass fibre, quartz glass fibre, boron fibre, ceramics
A kind of or their mixture in fiber and metallic fiber.
Further, in step（2）In, wet gel or gel stand with fibrous composite at a temperature of 25-70 DEG C
It is aging 3-24 hours.
Further, in step（4）In, it is sprayed onto the surface of dry silica aerogel or aeroge fibrous composite
Silane compound account for the 0.5-1.5 % of silica aerogel or aeroge fibrous composite this weight（w/w）.
Further, step（4）In hydrophobically modified temperature between 50-100 DEG C.
The present invention also provides a kind of aeroge obtained according to above-mentioned preparation method or aeroge fibrous composite.
Being mainly characterized by for the inventive method is rearmounted by hydrophobically modified step（I.e. hydrophobically modified step is placed on aeroge and does
After dry, and unconventional modified wet gel）, modified gel body or gelatinous fibre composite body is dried interior
Portion the has certain hydrophobic grouping but less aerosil of hydrophobic angle, by the hydroxyl on dried aeroge surface
Group is greatly decreased, and recycles silane compound spraying modified, the use of weight than the silane compound less than 1.5% is that can reach
The effect of hydrophobically modified, makes the content of organics of inorganic oxide silica aerogel reach least limit, fully achieves both hydrophobic
The again not exceeded effect of organic matter.
Colloidal sol configuration phase of the present invention has used mass fraction 0.2-5 parts of Ethoxysilane class compound（First
Ethyl triethoxy silicane alkane, dimethyldiethoxysilane, trimethylethoxysilane）Esters of silicon acis with mass fraction 0.2-5 parts
Proportioning liquid is hydrolyzed.Because the former carries certain methyl hydrophobic grouping, so can form a small amount of hydrophobic inside gel
Key, be behind be modified with minimal amount of hydrophobic modifier and successfully laid good inner base.
The modification mode of aeroge of the present invention or gelatinous fibre composite has greatly innovation.Prior art is in wet gel
Do not carry out after ageing or ripening and be immediately introduced silane compound solution to carry out surface modification or hydrophobically modified, and the present invention
It is to carry out hydrophobically modified after the drying, the variation just for product so in industrialized production is provided convenience condition, if
If hydrophilic product in need, you can packaging is sold, and such as needs hydrophobic product, then be immediately fed into modified facility and be modified；Tradition
Hydrophobically modified mode uses immersion form, and water-repelling agent consumption is big, is directly sprayed onto aeroge surface, consumption using spray pattern now
Decrease a lot.
In addition, preparation method of the invention can greatly save the consumption of modifying agent.Prior art is carried out on wet gel
It is modified, because, containing a large amount of hydroxyl alcoholic solutions, silane compound has the hydroxyl in a great deal of and alcoholic solution in wet gel
There is substitution reaction in base, can so waste several times even more than ten times of silane compound, and the price of silane compound is from per ton
20000-40000 units, the consumption of modifying agent is directly connected to the cost of aeroge finished product.The dry airsetting of present invention selection
Glue is modified, only with a small amount of silane compound（The 0.5-1.5% of aeroge this weight）Hydrophobically modified can be completed.
Preparation method of the present invention can greatly reduce organic compound content, reach A grades of non-combustible standard, environmental protection and safety.
Brief description of the drawings
Fig. 1 shows the Hydrophobic silica aeroge prepared by the method for the present invention；
Fig. 2 shows the Hydrophobic silica aerogel blanket prepared by the method for the present invention；
Fig. 3 shows to prepare the electron microscope of aeroge by the method for the present invention.
Specific embodiment
Embodiment 1
500 grams of the industrial methanol of 90-95% contents is extracted, the aqueous hydrochloric acid solution of 1wt% concentration is instilled, the pH of system is adjusted
It is 1.After stirring, methyl silicate is at the uniform velocity instilled（99%wt）150 grams and 50 grams of mixed liquors of MTES, and
After at the uniform velocity stir about 10-40 minutes, the sodium hydrate aqueous solution heightening pH value of 1% concentration is instilled, stirred, stand 10-60 points
Zhong Hou, that is, form gel.Supercritical drying is carried out by gel is placed in 50 DEG C of environment after aging 5 hours.Will be aging good
Gel be placed in autoclave and close, to being slowly injected into liquid CO in autoclave2, and 60 DEG C or so will be warming up in kettle, this
When kettle in pressure can rise to 10-15 MPa, use CO in the range of this temperature and pressure2Methyl alcohol in displacement kettle, after about 4-6 hours
Methanol content in kettle near less than 0.1%, beginning are discharged at a slow speed CO2, supercritical drying is to complete and prepare aeroge
Grain, then take out aerogel particle weigh, hydrophobicity and thermal conductivity factor detection, testing result is：Quality is 55 grams, aeroge
Particle is slightly hydrophilic, 25 DEG C when thermal conductivity factor be 0.0158 W/m.K.
The aerogel particle that abovementioned steps are prepared is contained in beaker, the trim,ethylchlorosilane for taking aeroge quality 1% changes
Property agent is contained in spray kettle, by silane modifier even spraying to aeroge body surface, then closes beaker, then will be closed
Beaker be put into baking oven, temperature is adjusted to 85 DEG C, heats 2-4 hour, then takes out aerogel particle, weighs, hydrophobicity, leads
Hot coefficient and flammability are tested, and are as a result shown：55.66 grams（Quality increases by 1.2%）, aerogel particle completely hydrophobic, thermal conductivity factor
For 0.0162W/m.K, flammability test result are A grades non-combustible.
Embodiment 2
It is prepared by sol-gel：500 grams of the industrial methanol of 90-95% contents is extracted, the acetic acid for instilling 10wt% concentration is water-soluble
Liquid, by the pH regulations of system to 4.After stirring, methyl silicate is at the uniform velocity instilled（99%wt）150 grams and methyl triethoxy
50 grams of mixed liquors of silane, and after at the uniform velocity stir about 10-40 minutes, the sodium hydrate aqueous solution heightening pH value of 1% concentration is instilled to 8,
Stir and be prepared into Ludox, Ludox injection length is generous respectively：In the fibre glass chopped stand mat of 20cm, 20cm and 1cm,
After standing 10-60 minutes, that is, it is made gel glass blanket.Gel glass blanket is placed in 50 DEG C of environment after aging 5 hours
Carry out supercritical drying.
Supercritical drying：Aging good gel glass blanket is placed in autoclave and closed, to injecting liquid in autoclave
CO2, 60 DEG C or so will be warming up in kettle, now pressure rises to 10-15MPa in kettle, keep in the range of this temperature and pressure, use
CO2Methyl alcohol in kettle is replaced, after about 4-6 hours, in kettle within methyl alcohol surplus 0.1%, beginning discharges at a slow speed CO2, that is, prepare airsetting
Glue glass composite blanket, after tested, this blanket is hydrophilic blanket, and thermal conductivity factor at 25 DEG C is 0.0175W/m.K.
Hydrophobically modified：The HMDS modifying agent for taking aeroge glass blanket quality 1.5% is contained in spray kettle, and
Dried aeroge composite blanket surface is uniformly sprayed on, beaker is then closed, closed beaker is then put into baking oven, temperature is adjusted
To 95 DEG C, 2-4 hour is heated, then takes out aeroge glass composite blanket, do the test of hydrophobicity, thermal conductivity factor and flammability,
Result shows：Aeroge glass composite blanket is completely hydrophobic, and thermal conductivity factor at 25 DEG C is 0.0181 W/m.K, flammability test knot
Fruit is non-combustible for A grades.
Claims (9)
1. a kind of preparation method of Hydrophobic silica aeroge and aerogel composite, the method comprises the following steps：
（1）Esters of silicon acis and methylethoxy base silane proportioning liquid are hydrolyzed in alcohol with acid catalyst, obtain colloidal sol；
（2）Base catalyst is added in colloidal sol, pH values are adjusted to 6-12, the colloidal sol for obtaining weakly acidic pH or alkalescence is subsequently formed
Wet gel；Or after obtaining the colloidal sol of weakly acidic pH or alkalescence, the colloidal sol of weakly acidic pH or alkalescence and inorfil are combined, prepare gas
Gelatinous fibre composite；Then, the wet gel or wet gel fibrous composite that will be obtained stand at a temperature of 25-70 DEG C
Aging 3-24 hours is aged；
（3）Wet gel after ageing or wet gel fibrous composite are placed in CO2 It is dried in overcritical device, uses CO2
The alcohol in hole is displaced, dry silica aerogel or dry aeroge fibrous composite is obtained；
（4）Silane compound is sprayed onto the surface of dry silica aerogel or dry aeroge fibrous composite, so
The body of heated oxide silica aerogel or aeroge fibrous composite carries out hydrophobically modified afterwards, obtains non-combustible Hydrophobic silica gas
Gel or non-combustible Hydrophobic silica aeroge fibrous composite.
2. the preparation method according to claim 1, it is characterised in that step（1）In alcohol, esters of silicon acis, methyl ethoxy
The proportioning of silane is 10-20 by weight parts: 0.2-5 part: 0.2-5 parts；Wherein described alcohol is content more than 90%
Alcohol.
3. the preparation method according to claim 1, it is characterised in that step（1）In methylethoxy base silane be methyl
Triethoxysilane, diformazan diethoxy silane, trimethylethoxysilane or their mixture.
4. the preparation method according to claim 1, it is characterised in that step（1）The esters of silicon acis be positive silicic acid first
A kind of or their mixture in ester, tetraethyl orthosilicate, butyl silicate；The alcohol liquid is methyl alcohol, ethanol, n-butanol, isopropyl
One kind or their mixture in alcohol；The acid catalyst is a kind of in hydrochloric acid, sulfuric acid, acetic acid, butyric acid, formic acid or they
Mixture；The base catalyst is a kind of or their mixture in NaOH, potassium hydroxide, ammoniacal liquor；The silane chemical combination
Thing is a kind of or its mixture in trim,ethylchlorosilane, HMDS, HMDS.
5. the preparation method according to claim 1, it is characterised in that step（1）In the hydrolysis pH values in 1-4
Between.
6. the preparation method according to claim 1, it is characterised in that in step（2）In, the inorfil is glass
A kind of or their mixture in fiber, boron fibre, ceramic fibre and metallic fiber.
7. the preparation method according to claim 1, it is characterised in that in step（4）In, it is sprayed onto dry silica gas
The silane compound on the surface of gel or aeroge fibrous composite accounts for silica aerogel or aeroge fibrous composite
The 0.5-1.5 % of this weight（w/w）.
8. the preparation method according to claim 1, it is characterised in that step（4）In hydrophobically modified temperature in 50-
Between 100 DEG C.
9. the aeroge or airsetting glue fiber that a kind of preparation method according to above claim any one of 1-8 is obtained are multiple
Condensation material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510236100.9A CN104891509B (en) | 2015-05-11 | 2015-05-11 | A kind of A grades of non-combustible silica aerogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510236100.9A CN104891509B (en) | 2015-05-11 | 2015-05-11 | A kind of A grades of non-combustible silica aerogel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104891509A CN104891509A (en) | 2015-09-09 |
| CN104891509B true CN104891509B (en) | 2017-06-06 |
Family
ID=54024548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510236100.9A Active CN104891509B (en) | 2015-05-11 | 2015-05-11 | A kind of A grades of non-combustible silica aerogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104891509B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098354A (en) * | 2016-02-20 | 2017-08-29 | 金承黎 | A kind of preparation method from hydrophobic silicon hydrochlorate aerogel material |
| KR20170104914A (en) * | 2016-03-08 | 2017-09-18 | 주식회사 엘지화학 | Method for preparing aerogel blanket and aerogel blanket prepared by the same |
| CN106745002B (en) * | 2016-12-28 | 2019-07-02 | 伊科纳诺（北京）科技发展有限公司 | A kind of method that co-precursor method constant pressure and dry prepares block aerosil |
| CN113750914B (en) * | 2021-08-05 | 2023-02-14 | 华东理工大学 | Silicon dioxide aerogel modification method |
| CN113828505A (en) * | 2021-10-20 | 2021-12-24 | 河北金纳科技有限公司 | Method for rapidly preparing hydrophobic aerogel composite felt |
| CN116983914A (en) * | 2023-06-21 | 2023-11-03 | 广东埃力生科技股份有限公司 | Hydrophobic aerogel material, preparation method thereof and heat insulation material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB807454A (en) * | 1954-05-06 | 1959-01-14 | Monsanto Chemicals | Surface-modified silica products and silicone rubbers containing the same |
| CN102500314A (en) * | 2011-11-30 | 2012-06-20 | 南京工业大学 | Preparation method for aerogel for adsorbing nitrocompound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HUP1100603A2 (en) * | 2011-10-28 | 2013-06-28 | Debreceni Egyetem | Method and installation for preparation of silicate - alcogels, xerogels, aerogels |
| CN103130231B (en) * | 2011-11-25 | 2015-09-02 | 航天特种材料及工艺技术研究所 | A kind of silica aerogel material and preparation method thereof |
| CN104402395B (en) * | 2014-11-18 | 2017-05-10 | 四川睿光科技有限责任公司 | Fiber-reinforced flexible SiO2 aerogel heat-insulation material and preparation method thereof |
-
2015
- 2015-05-11 CN CN201510236100.9A patent/CN104891509B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB807454A (en) * | 1954-05-06 | 1959-01-14 | Monsanto Chemicals | Surface-modified silica products and silicone rubbers containing the same |
| CN102500314A (en) * | 2011-11-30 | 2012-06-20 | 南京工业大学 | Preparation method for aerogel for adsorbing nitrocompound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104891509A (en) | 2015-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104891509B (en) | A kind of A grades of non-combustible silica aerogel and preparation method thereof | |
| CN107531494B (en) | Method for producing aerogels and aerogel composite materials | |
| CN107140938B (en) | A kind of anti-shedding aeroge complex heat-preservation felt and preparation method thereof | |
| CN108609621B (en) | Preparation method of silicon dioxide aerogel | |
| CN101456569B (en) | Method for quickly preparing aerogel by hydro-thermal synthesis at low cost | |
| CN108658576B (en) | Preparation method of composite silica aerogel felt | |
| CN107263948B (en) | A kind of fire-proof thermal-insulation decoration and preparation method thereof | |
| CN107760065A (en) | A kind of method of modifying of super-hydrophobic filler grain for antifouling flush paint and application | |
| CN106867019A (en) | One kettle way prepares SiO2The method of cellulose composite aerogel material | |
| CN108373316A (en) | A kind of aerogel heat-proof paper and preparation method thereof | |
| CN101633505A (en) | SiO2 nanoscale porous material with aerogel property prepared by microwave reaction and preparation method thereof | |
| CN109265131A (en) | A kind of preparation method of aerogel vacuum thermal insulation plate and its core material | |
| CN104909375A (en) | Method for rapidly preparing hydrophobicsilica aerogel by carbon dioxidesubcritical drying method | |
| CN107089810B (en) | A kind of aeroge modified expanded perlite insulation board and preparation method thereof | |
| CN104876226B (en) | A kind of method for quickly preparing Hydrophobic silica aeroge with the subcritical drying of methanol | |
| CN104497688A (en) | Aerogel thermal insulation coating and preparation method thereof | |
| CN107089818B (en) | A kind of silica aerogel fire prevention, waterproof, environment-friendly insulating cream and preparation method thereof | |
| CN113683343A (en) | High-flexibility aerogel felt and preparation method thereof | |
| CN104843723A (en) | Silicon aerogel material preparation method | |
| CN106752139B (en) | A kind of heat power equipment and pipeline nano-thermal-insulating coating and preparation method thereof | |
| CN108793173A (en) | A method of improved silica aerogel material is prepared using outer circulation mode constant pressure and dry | |
| CN105347351A (en) | Method for preparing TiO2/SiO2 aerogel microspheres by emulsion method | |
| CN109179428A (en) | A kind of enhanced transparent silicon dioxide aerogel and preparation method thereof | |
| US20220275164A1 (en) | Thermally insulating aerogel vacuum composite panel and preparation method thereof | |
| CN107344837A (en) | Method for preparing hydrophobic silica aerogel cement-based thermal insulation material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170724 Address after: 061108 Cangzhou port chemical industry park in Hebei province by the east of the road to four, south of chemical Avenue Patentee after: Epee and new materials Co., Ltd. Address before: 100142 room 810, Xinzhou business building, 58 Fu Cheng Road, Beijing, Haidian District Patentee before: Tian Lei |