CN105504113B - The preparation method of the catalyst of synthesis of trans Isosorbide-5-Nitrae polyisoprene - Google Patents
The preparation method of the catalyst of synthesis of trans Isosorbide-5-Nitrae polyisoprene Download PDFInfo
- Publication number
- CN105504113B CN105504113B CN201610046965.3A CN201610046965A CN105504113B CN 105504113 B CN105504113 B CN 105504113B CN 201610046965 A CN201610046965 A CN 201610046965A CN 105504113 B CN105504113 B CN 105504113B
- Authority
- CN
- China
- Prior art keywords
- mgcl
- sio
- preparation
- catalyst
- synthesis
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/08—Isoprene
-
- 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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/645—Component covered by group C08F4/64 with a metal or compound covered by group C08F4/44, not provided for in a single group of groups C08F4/642 - C08F4/643
- C08F4/6452—Component of C08F4/64 containing at least two different metals
- C08F4/6455—Component of C08F4/64 containing at least two different metals containing magnesium
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
- C08F4/6465—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a kind of preparation method of the catalyst of synthesis of trans Isosorbide-5-Nitrae polyisoprene, by by MgCl2It is dissolved in a large amount of organic solvents, and SiO is repeatedly poured under the conditions of anhydrous and oxygen-free2In powder, each addition can be quickly by SiO2Absorption, can not only avoid MgCl2Autoprecipitation form irregular thing, and SiO2Duct will not be deposited blocking, it is often more important that load to SiO2The MgCl on surface2More uniformly, follow-up TiCl is advantageous to4The uniformity of load.Simple to operate, Load Balanced of the invention, beneficial to industrialized production.
Description
Technical field
The present invention relates to catalyst preparation technical field, and in particular to a kind of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene catalysis
The preparation method of agent.
Background technology
Trans-l, 4- polyisoprene (TPI) are also known as synthetic guttapercha, with stress at definite elongation is big, hardness is high, anti-wear performance
Well, the advantages that good fatigue durability and high tensile strength, can be used as matching somebody with somebody glue in tyre industry, to improve the resistance to of tire
Cryogenic property, wet-sliding resistant performance and low-rolling-resistance, and the processing characteristics and resistance to cold flow energy of rubber can be improved, it is the high property of development
The preferable sizing material of energy radial.
The mankind are earliest since natural guttapercha using TPI, and it is the skin, leaf, the extract of seed of gutta-percha tree.Cause
Limited for content, application is severely limited.After the Ziegler-Natta catalyst stereospecfic polymerization discovery fifties, people
Work synthesis TPI is possibly realized.Foreign countries synthesis TPI patent is published in nineteen fifty-five earliest.The beginning of the sixties, Canadian Borland mountain are public
The Deng Lupu companies of department and Britain realize industrialization in succession, and Kuraray company has also built up a set of 200t/a dress within 1974
Put, these patents and device are to employ vanadium system or vanadium/titanium mixed catalyst system.In the 1990s, patent
ZL95110352.0 proposes to use MgCl2Supported titanium-AlR3 systems catalysis isoprene bulk precipitation polymerization synthesis TPI.China
Patent publication No. CN1255442C is disclosed using load TiCl4/MgCl2/X-AlR3Low average molecular in going out for catalyst preparation
Quality anti-form-1,4- polyisoprene Waxes.For these loaded catalysts using anhydrous magnesium chloride as carrier, ball milling destroys α-MgCl2
Crystal structure, it is set to be changed into the δ-MgCl for having fault of construction2, crystal grain diminishes, while MgCl2With TiC4Have an effect, carry
The activation of body synchronously completes with carrying titanium, and the method technique is simple, but the more difficult control of form of catalyst, particle size distribution are wide.Change
It is first MgCl to learn reaction method2It is dissolved in electron donor solvent（Such as alcohol, ester, ether）Complex solution is formed, then with heat
Processing removing, evaporation solvent, make MgCl2Recrystallization, or make MgCl with condensation and chloride precipitation2Again separate out and pass through spy
Different technique prepares spherical carrier, then uses TiCl4Processing both obtains MgCl2Carried catalyst.
In order to improve the uniformity of the porosity of Ziegler-Natta catalyst carrier and catalyst, SiO is utilized2It is porous
Property, load MgCl2Form MgCl2/SiO2Complex carrier is most widely used.MgCl2/SiO2Complex carrier can both be kept
MgCl2The characteristics of carrier, SiO is maintained again2Porous, high-specific surface area and good particle shape and mobility.It is main at present
The preparation method wanted is by SiO2Powder is added to high concentration MgCl2In electronics liquid solution, cooling makes MgCl2Precipitation loads to
SiO2Surface forms complexes carrier.But the MgCl largely separated out in the prior art2Solid not only easily blocks SiO2Carrier hole
Road, and autoprecipitation is easily formed, influence the uniformity of catalyst granules.
The content of the invention
To make up the deficiencies in the prior art, the present invention provides a kind of excellent catalytic effect, and synthesis of trans-Isosorbide-5-Nitrae of Load Balanced-
The preparation method of the catalyst of polyisoprene.
The present invention is achieved through the following technical solutions：
A kind of preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene, it is characterized in that：Including following
Step：
（1）Under inert gas shielding, by anhydrous MgCl2It is added in organic solvent, is warming up to 40-150 DEG C, makes MgCl2It is molten
Solution forms the solution of water white transparency, is incubated 0.5-12h at this temperature；
（2）By SiO20.5-12h is calcined at 300-800 DEG C, room temperature is cooled under inert gas shielding, sealing is standby；
（3）By step（2）In treat SiO2It is put into two-mouth bottle, inert gas replacement 1-30min, by step（1）
In MgCl2Solution 30-400ml is added to SiO under agitation2In carrier, after being sufficiently stirred, heat and vacuumize removing
Solvent, repeat this step and obtain MgCl2/SiO2Complex carrier；
（4）By step（3）The MgCl of preparation2/SiO2Complex carrier is added to TiCl under inert gas shielding4In, in
80-200 DEG C of backflow 0.5-12 h, filters and removes excessive TiCl4, repeat this step 1-5 times；
（5）By TiCl under inert gas shielding4The carrier of processing washs 1-10 times in organic solvent, is removed under vacuum condition
Organic solvent is gone to obtain catalyst.
The preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene of the present invention, step（1）To step（5）In
The inert gas is one kind in nitrogen, helium, argon gas, hydrogen.
The preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene of the present invention, step（1）Middle organic solvent is
Methanol, ethanol, propyl alcohol, isopropanol, ether, tetrahydrofuran, butanol, amylalcohol, hexanol, enanthol, toluene, N, N- dimethyl formyls
Amine, chloroform, dichloromethane, one kind of hexane, preferably use tetrahydrofuran.
The preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene of the present invention, step（1）Middle preparation
MgCl2The concentration of solution is 0.1-10 g/100 ml, preferably 0.3-1 g/100 ml.
The preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene of the present invention, step（3）Middle preparation
MgCl2/SiO2MgCl in complex carrier2 : SiO2Mass ratio is 1:0.5-30, preferably 1:1-20.
The preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene of the present invention, step（3）Middle MgCl2Solution
Each addition is 5-50 ml/g SiO2, preferably 10-35 ml/g SiO2。
The preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene of the present invention, step（4）Repeat number
It is preferred that 1-3 times.
The preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene of the present invention, step（5）It is middle by TiCl4Place
The carrier of reason washs 2-5 times in organic solvent.
The preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene of the present invention, step（5）Middle organic solvent is
Ethanol, toluene, tetrahydrofuran, n-hexane, DMF, CS2, one kind in hexamethylene, preferably n-hexane.
The beneficial effects of the invention are as follows：Complex carrier Ziegler-Natta catalyst prepared by the present invention is simple to operation,
SiO can not only be promoted2Carrier surface loads MgCl2And follow-up TiCl4Uniformity, moreover it is possible to effectively avoid conventional chemical
MgCl in method2The generation of autoprecipitation, has given play to SiO2The porous sexual clorminance and MgCl of carrier2The importance of carrier.Successfully application
In the synthesis of high trans-Isosorbide-5-Nitrae-polyisoprene rubber, and the support type TiCl for first preparing chemical method4/MgCl2Catalysis
Agent is applied to this field, will be anti-form-1, and the commercial application of 4- polyisoprene rubbers makes important value.
Embodiment
With reference to embodiment, the present invention is further detailed explanation.
Embodiment 1
The preparation of complex carrier：Under nitrogen protection, by the anhydrous MgCl of 2.198 g2It is added in 700 ml tetrahydrofurans,
MgCl is back in 80 DEG C2It is completely dissolved, is incubated 2 h.By SiO26 h are calcined in 550 DEG C of tube furnaces, nitrogen protection drops to
Magnesium chloride solution, with nitrogen displacement 3 times, 350 ml is pipetted extremely under stirring condition by room temperature, the g of transferase 12 1.373 into two-mouth bottle
SiO2In flask, removing solvent is vacuumized after stirring, is repeated twice, the MgCl of preparation2/SiO2MgCl in complex carrier2 :
SiO2Mass ratio is 1:10.
The preparation of catalyst：The carrier of above-mentioned processing is weighed in the titanium tetrachloride solution that 5.29 g pour into -20 DEG C, stirred
120 DEG C, the h of back flow reaction 1 are to slowly warm up under the conditions of mixing, filters and removes remaining titanium tetrachloride solution.Repeat this step 1
It is secondary, washed 2 times with the n-hexane of excess.Dry catalyst is vacuumized under heating condition.
The synthesis of trans isoamyl glue：500 ml single port bottles are cleaned, dry, vacuumized, use high-purity N2Displacement for several times, adds
250 ml isoprene monomers, then sequentially add the g of catalyst 0.36 and the ml of triisobutyl aluminium 7.2, hydrogen ftercompction to 0.04
MPa.20 h are reacted in 20 DEG C, is terminated and polymerize with a small amount of deionized water, it is vacuum dried to obtain the g of loose particles product 66.01, turn
The % of rate 38.3, product anti-form-1, the % of 4- polyisoprene contents 98.2, Mooney 32.5.
Embodiment 2
The preparation of complex carrier：Under nitrogen protection, 1 g anhydrous magnesium chlorides are added in 200 ml tetrahydrofurans, in
80 DEG C are back to MgCl2It is completely dissolved, is incubated 1 h.By SiO26 h are calcined in 550 DEG C of Muffle furnaces, room is down in nitrogen protection
Temperature, it is transferred in two-mouth bottle, nitrogen displacement 3 times, the ml of magnesium chloride solution 100 to SiO is pipetted under stirring condition2In flask, stirring
Vacuumize, be repeated once, the MgCl of complex carrier processed after uniformly2/SiO2=1:10。
The preparation of catalyst：The carrier of above-mentioned processing is weighed in the titanium tetrachloride solution that 5.29 g pour into -20 DEG C, stirred
120 DEG C, the h of back flow reaction 1 are to slowly warm up under the conditions of mixing, filters and removes remaining titanium tetrachloride solution.Repeat this step 1
It is secondary, washed 2 times with the n-hexane of excess.Dry catalyst is vacuumized under heating condition.
The synthesis of trans isoamyl glue：500 ml single port bottles are cleaned, dry, vacuumized, use high-purity N2Displacement for several times, adds
250 ml isoprene monomers, then sequentially add the g of catalyst 0.36 and the ml of triisobutyl aluminium 7.2.20 are reacted in 20 DEG C
H, terminated and polymerize with a small amount of deionized water, vacuum dried the g of loose particles product 54, the % of conversion ratio 31.8, product is trans-
The % of Isosorbide-5-Nitrae-polyisoprene contents 97.9, Mooney 152.9.
Claims (5)
- A kind of 1. preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene, it is characterised in that：Comprise the following steps：（1）Under inert gas shielding, by anhydrous MgCl2It is added in organic solvent, is warming up to 40-150 DEG C, makes MgCl2Dissolve shape Into the solution of water white transparency, MgCl2The concentration of solution is 0.1-10 g/100 ml, is incubated 0.5-12h at this temperature；It is described Inert gas is one kind in nitrogen, helium, argon gas, hydrogen；（2）By SiO20.5-12h is calcined at 300-800 DEG C, room temperature is cooled under inert gas shielding, sealing is standby；（3）By step（2）In treat SiO2It is put into two-mouth bottle, inert gas replacement 1-30min, by step（1）In MgCl2Solution 30-400ml is added to SiO under agitation2In carrier, after being sufficiently stirred, heat and vacuumize removing solvent, This step is repeated to the load capacity needed, obtains MgCl2/SiO2Complex carrier, MgCl2/SiO2MgCl in complex carrier2 : SiO2Mass ratio is 1:0.5-30；（4）By step（3）The MgCl of preparation2/SiO2Complex carrier is added to TiCl under inert gas shielding4In, in 80-200 DEG C backflow 0.5-12 h, filter and remove excessive TiCl4, repeat this step 1-5 times；（5）By TiCl under inert gas shielding4The carrier of processing washs 1-10 times in organic solvent, is removed under vacuum condition Organic solvent.
- 2. a kind of preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene according to claim 1, its feature It is：Step（1）Middle organic solvent is methanol, ethanol, propyl alcohol, isopropanol, ether, tetrahydrofuran, butanol, amylalcohol, hexanol, heptan Alcohol, toluene, DMF, chloroform, one kind of hexane.
- 3. a kind of preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene according to claim 1, its feature It is：Step（4）Number is repeated as 1-5 times.
- 4. a kind of preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene according to claim 1, its feature It is：Step（5）It is middle by TiCl4The carrier of processing washs 2-5 times in organic solvent.
- 5. a kind of preparation method of the catalyst of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene according to claim 1 or 4, its It is characterised by：Step（5）Middle organic solvent is ethanol, toluene, tetrahydrofuran, n-hexane, DMF, CS2, ring One kind in hexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610046965.3A CN105504113B (en) | 2016-01-25 | 2016-01-25 | The preparation method of the catalyst of synthesis of trans Isosorbide-5-Nitrae polyisoprene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610046965.3A CN105504113B (en) | 2016-01-25 | 2016-01-25 | The preparation method of the catalyst of synthesis of trans Isosorbide-5-Nitrae polyisoprene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105504113A CN105504113A (en) | 2016-04-20 |
| CN105504113B true CN105504113B (en) | 2018-01-26 |
Family
ID=55712456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610046965.3A Expired - Fee Related CN105504113B (en) | 2016-01-25 | 2016-01-25 | The preparation method of the catalyst of synthesis of trans Isosorbide-5-Nitrae polyisoprene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105504113B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057467A (en) * | 1990-06-22 | 1992-01-01 | 蒙特代普公司 | The method for preparing ethene (being total to) polymerization solid catalyst component |
| CN103265654A (en) * | 2013-05-29 | 2013-08-28 | 浙江大学 | Method and catalyst for preparing high trans-polyisoprene by adopting gaseous phase polymerization |
-
2016
- 2016-01-25 CN CN201610046965.3A patent/CN105504113B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057467A (en) * | 1990-06-22 | 1992-01-01 | 蒙特代普公司 | The method for preparing ethene (being total to) polymerization solid catalyst component |
| CN103265654A (en) * | 2013-05-29 | 2013-08-28 | 浙江大学 | Method and catalyst for preparing high trans-polyisoprene by adopting gaseous phase polymerization |
Non-Patent Citations (2)
| Title |
|---|
| Polymerization of dienes with titanium-magnesium catalysts;Mushina, EA et al;《VYSOKOMOLEKULYARNYE SOEDINENIYA SERIYA A & SERIYA》;19961231;第38卷(第3期);全文 * |
| 负载催化剂合成 s-PB/TPB/TPI 釜内共混物及其结构性能;李皓;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20120715;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105504113A (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107486157B (en) | Multi-walled carbon nanotube/metal organic framework composite material and preparation method | |
| Otsuka et al. | Decomposition and regeneration of methane in the absence and the presence of a hydrogen-absorbing alloy CaNi5 | |
| CN105536660B (en) | A kind of preparation method of nano-silver loaded oil-tea camellia husks pyrolysis carbosphere | |
| CN106423287A (en) | Supported mercury-free catalyst, preparation method thereof and application of supported mercury-free catalyst in preparation of vinyl chloride through ethyne hydrochlorination | |
| CN103571044A (en) | Preparation method of high-impact-strength polypropylene kettle internal alloy | |
| CN102676860B (en) | Preparation method of carbon nanotube reinforced Al-matrix composite | |
| CN105504113B (en) | The preparation method of the catalyst of synthesis of trans Isosorbide-5-Nitrae polyisoprene | |
| JP2000327703A (en) | Suspension polymerization of conjugated diene | |
| Guo et al. | Selectively catalytic hydrogenation of styrene-butadiene rubber over Pd/g-C3N4 catalyst | |
| CN102336855B (en) | Ethylene in-situ copolymerization catalytic system | |
| CN114471471A (en) | Adsorbent for removing residual metal in polyolefin, preparation method and application thereof | |
| Chen et al. | Synthesis of Co3O4 nanoparticles with controllable size and their catalytic properity | |
| Zhang et al. | Immobilization of highly active Pd nano-catalysts on functionalized mesoporous silica supports using mercapto groups as anchoring sites and their catalytic performance for phenol hydrogenation | |
| US5958820A (en) | Gas-phase polymerisation of conjugated dienes in the presence of rare earth allyl compounds | |
| JP3616371B2 (en) | Method for producing polyolefin polymerization catalyst | |
| CN109535393B (en) | Preparation method of microporous organic polymer nano-microspheres and product thereof | |
| CN108976330B (en) | Process for preparing metallocene ethylene polymer | |
| CN112409539A (en) | Butadiene-isoprene copolymer and preparation method thereof | |
| CN113912915B (en) | High-strength anti-aging rubber material and preparation method thereof | |
| CN112940158B (en) | Supported metallocene catalyst and preparation method and application thereof | |
| CN108889302A (en) | CO and CO2Cu base catalyst of synthesizing methanol by hydrogenating and its preparation method and application | |
| CN112194748B (en) | Polyisoprene and preparation method thereof | |
| CN109651546B (en) | Polymer carrier loaded trans-1, 4-polyisoprene titanium catalyst and use method thereof | |
| CN107602737B (en) | Application of chromium-series metal organic framework material in olefin polymerization | |
| CN105418810B (en) | The preparation method and applications of neodymium series isoprene polymerization rubber rare earth catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160926 Address after: 274500 Shandong city of Heze province Dongming County wusheng Qiao Xiang Yu Huang Miao Xing Zheng Cun Yu Huang Miao Village No. 92 Applicant after: Wang Jinshu Address before: 274512 Shandong city of Heze province Dongming County wusheng Industrial Development Zone Applicant before: SHANDONG YUHUANG CHEMICAL Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20161222 Address after: 274000 Changjiang Road, Heze Development Zone, Shandong, China, No. 4666 Applicant after: Jade Emperor flourishing age chemical Inc. Shandong Address before: 274500 Shandong city of Heze province Dongming County wusheng Qiao Xiang Yu Huang Miao Xing Zheng Cun Yu Huang Miao Village No. 92 Applicant before: Wang Jinshu |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180126 Termination date: 20220125 |