CN105693928B - Norborneol alkenes, hexafluoropropene and acrylonitrile ternary polymerization catalyst and method for ternary polymerization - Google Patents
Norborneol alkenes, hexafluoropropene and acrylonitrile ternary polymerization catalyst and method for ternary polymerization Download PDFInfo
- Publication number
- CN105693928B CN105693928B CN201610151343.7A CN201610151343A CN105693928B CN 105693928 B CN105693928 B CN 105693928B CN 201610151343 A CN201610151343 A CN 201610151343A CN 105693928 B CN105693928 B CN 105693928B
- Authority
- CN
- China
- Prior art keywords
- cerium
- hept
- ene
- hexafluoropropene
- catalyst
- 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
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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- 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
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/28—Hexyfluoropropene
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- 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
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
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 present invention relates to a kind of norborneol alkenes, hexafluoropropene and acrylonitrile ternary polymerization catalyst, the preparation method of catalyst is：In the three-necked flask of dry inert atmosphere, two (pentamethylcyclopentadiene base) cerium chlorides and part are dissolved in the first solvent, titanium tetrachloride is instilled in above-mentioned solution under stirring, stirred 30 60 minutes in 30 60 DEG C of constant temperature after dripping off, cerium titanium complex catalyst is produced；Take Norbornene derivative, hexafluoropropene and acrylonitrile monemer to be added to repeatedly to vacuumize, in nitrogen charging reactor, add the dissolving of the second solvent；Then described cerium titanium complex catalyst is added, is reacted under certain temperature and pressure, terpolymer is obtained after product washing.Catalyst raw material of the present invention is cheap and easy to get, and catalytic activity can be produced at low temperature, and catalysis norborneol alkenes, hexafluoropropene and acrylonitrile ternary polymerization, reaction temperature are low, and high catalytic efficiency, copolymer yield is high；Copolymer lithography performance is good.
Description
Technical field
The present invention relates to high polymer field, a kind of norborneol alkenes, hexafluoropropene and acrylonitrile ternary polymerization are referred specifically to
Catalyst and method for ternary polymerization.
Background technology
Polynorbornene is a kind of special polymer, with excellent mechanical property, heat resistance, in organic solvent
The soluble and transparency, available for 193nm ultraviolet light photoetching.This material major defect is that fragility, viscosity difference and molecular weight are low
Deng.The caking property and solubility of polymer are generally improved by the copolymerization with other materials, and reduces the extinction of material in itself
Rate.
The preparation method of current norbornene copolymer mainly has the methods such as free radical, living radical, metallic catalyst.
ENB and tetrafluoroethene, styrene, acrylate are carried out four by such as A.E.Feiring and Q.Feng with free based method
First copolymerization, the synthesis of photoetching material disclosed in Proceedings of SPIE Vol.5039 (2003) pages 80~92 is employed
Peroxide is used as the catalyst of radical polymerization, Proceedings of SPIE Vol.4690 (2002) pages 127~135
The synthesis of disclosed photoetching material employs AINB (azodiisobutyronitrile) as the catalyst of radical polymerization, Polymers
The disclosed ENBs of the 565-582 pages of Vol.6 (2014) and styrol copolymer photoetching material employ free based method and closed
Into.
Existing synthetic method has that reaction time length, copolymer yield are low, molecular weight of copolymer is small, copolymer alternating
Spend low shortcoming.
The content of the invention
The technical problems to be solved by the invention be for prior art present situation provide one kind can reduce reaction temperature,
Improve catalytic efficiency and norborneol alkenes, styrene and the vinylacetate ternary polymerization catalyst of copolymer yield.
Another technical problem to be solved by this invention is to provide a kind of relatively low reaction temperature, high catalytic efficiency and copolymerization
Norborneol alkenes, styrene and the method for vinylacetate ternary polymerization of thing high income.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：Norborneol alkenes, hexafluoropropene and the propylene
Nitrile ternary polymerization catalyst, it is characterised in that the preparation method of the catalyst is as follows：
In the three-necked flask of dry inert atmosphere, two (pentamethylcyclopentadiene base) cerium chlorides and part are dissolved in
In first solvent, under 110-130rpm stirrings, titanium tetrachloride is instilled in above-mentioned solution, it is same at 30-60 DEG C after dripping off
Constant temperature is stirred 30-60 minutes under stir speed (S.S.), produces cerium-titanium complex catalyst；
The mol ratio of two (pentamethylcyclopentadiene base) cerium chloride and the part is 1: 10~10: 1, described two
The mol ratio of (pentamethylcyclopentadiene base) cerium chloride and the titanium tetrachloride is 1: 12~12: 1；
The part is selected from 8-hydroxyquinoline, α, α '-bipyridyl, Phen, isoquinolin, quinoline, porphyrin, acetyl group third
Ketone；
First solvent is selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloros
Ethane, hexamethylene or cyclohexanone；
The consumption of the solvent and described two (pentamethylcyclopentadiene base) cerium chlorides, titanium tetrachloride and part three's total amount
Ratio be 10 milliliters：0.003~0.030 mole.
The mol ratio of described two (pentamethylcyclopentadiene base) cerium chlorides, titanium tetrachloride and part three is preferably 1: 3: 4.
Preferably, the part and first solvent are first dried using preceding；Solid-state in wherein described part
The drying of part is first to be purified and then be dried in vacuo with recrystallization method；The drying of liquid part in the part is with hydrogenation
Calcium or metallic sodium are dried, and the solvent is dried using calcium chloride or calcium hydride.
Use above-mentioned norborneol alkenes, the norborneol alkenes of hexafluoropropene and acrylonitrile ternary polymerization catalyst, hexafluoro third
Alkene and acrylonitrile method for ternary polymerization, it is characterised in that comprise the steps：
According to mol ratio 1: 1: 1 take Norbornene derivative, hexafluoropropene and acrylonitrile monemer be added to repeatedly vacuumize,
In nitrogen charging reactor, the dissolving of the second solvent is added；Then described cerium-titanium complex catalyst is added, at 30~120 DEG C,
Reacted 1~6 hour under 0.1-6MPa pressure；
The product that reaction is obtained is poured into the ethanol solution of the hydrochloric acid containing 4-5wt%, obtained precipitates washed with EtOH
To neutral, ENB class, hexafluoropropene and acrylonitrile terpolymer are obtained after vacuum drying；
The consumption of the cerium-titanium complex catalyst presses the gauge of two (pentamethylcyclopentadiene base) cerium chlorides in catalyst
For the 0.01%-1.0% of norborneol alkenes, hexafluoropropene and acrylonitrile three's gross weight；
Second solvent is selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloros
Ethane, hexamethylene or cyclohexanone；The amount ratio of the molal quantity sum of each polymerized monomer and second solvent is 0.03 mole：20
Milliliter.
The Norbornene derivative can be selected from two rings [2,2,1] hept-2-ene", 1- methyl bicyclics [2,2,1] hept- 2-
Alkene, 5- methyl bicyclics [2,2,1] hept-2-ene", 7- methyl bicyclics [2,2,1] hept-2-ene", the ring of 1- ethyls two [2,2,1] hept- 2-
Alkene, the ring of 5- ethyls two [2,2,1] hept-2-ene", the ring of 5,5- dimethyl two [2,2,1] hept-2-ene", the ring of 1- phenyl two [2,2,1] hept-
2- alkene, the ring of 5- phenyl two [2,2,1] hept-2-ene", the ring of 5- vinyl two [2,2,1] hept-2-ene", two rings [2,2,1] hept-2-ene"-
5- methyl formates or the special butyl ester of two rings [2,2,1] hept-2-ene" -5- formic acid.
Compared with prior art, the catalyst that the present invention is provided is a kind of new cerium-titanium complex catalyst mixture, is urged
Agent raw material is cheap and easy to get, can be catalyzed norborneol alkenes, hexafluoropropene and acrylonitrile ternary compared with catalytic activity is produced under low temperature
Copolymerization, reaction temperature is relatively low, high catalytic efficiency, and product is easy to washing separation, and copolymer yield is high；Prepared norborneol
The resistance to corrosions of alkenes, hexafluoropropene and acrylonitrile terpolymer matrix is high, and lithography performance is good, the caking property of material, solvable
Property and toughness are further enhanced.
Embodiment
The present invention is described in further detail with reference to embodiments.
The preparation process of catalyst in following embodiment, unless otherwise instructed, is carried out to part therein and solvent
Drying process.Specifically：The drying of solid ligand in part is first to be purified and then be dried in vacuo with recrystallization method；
The drying of liquid part in part is to be dried or dried with metallic sodium with calcium hydride.The drying of solvent is to use calcium chloride or hydrogen
Change calcium to dry.
Embodiment 1
In the three-necked flask of dry inert atmosphere, by 0.001 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.001 mole of 8-hydroxyquinoline is dissolved in 10 milliliters of benzene, under 120 turns per minute of speed stirring, by 0.001 mole of four chlorination
Titanium is instilled in above-mentioned solution, in constant temperature stirring 30 minutes at same 30 DEG C of stir speed (S.S.) after dripping off, is produced cerium-titanium complex and is urged
Agent.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mol propylene nitrile are added to many
It is secondary to vacuumize, in nitrogen charging autoclave, plus the dissolving of 20ml benzene.By the gauge of in catalyst two (pentamethylcyclopentadiene base) cerium chlorides
0.01% for ENB, hexafluoropropene and acrylonitrile three's gross weight takes above-mentioned cerium-titanium complex catalyst, uses syringe
Inject in above-mentioned mixture.Constant temperature reacts 5 hours under 80 DEG C, 0.1MPa pressure.The ethanol that product is poured into the hydrochloric acid containing 5wt% is molten
Copolymer is precipitated in liquid, precipitates washed with EtOH to neutrality, vacuum drying obtains two rings [2,2,1] hept-2-ene", six
Fluoropropene and acrylonitrile terpolymer.It is 39.3% to calculate reaction yield.
The computational methods of reaction yield are terpolymer weight/comonomer gross weight × 100%.Following each embodiments
In yield computational methods it is identical with this.
Embodiment 2
In the three-necked flask of dry inert atmosphere, by 0.001 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.004 mole of α, α '-bipyridyl is dissolved in 10 milliliters of toluene, under 120 turns per minute of speed stirring, by 0.003 mole four
Titanium chloride is instilled in above-mentioned solution, in constant temperature stirring 40 minutes at same 40 DEG C of stir speed (S.S.) after dripping off, and produces cerium-titanium complexing
Thing catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mol propylene nitrile are added to many
It is secondary to vacuumize, in nitrogen charging autoclave, plus the dissolving of 20ml toluene.By the amount of in catalyst two (pentamethylcyclopentadiene base) cerium chlorides
Be calculated as ENB, hexafluoropropene and acrylonitrile three's gross weight 0.05% takes above-mentioned cerium-titanium complex catalyst, with injection
Device is injected in above-mentioned mixture.Constant temperature reacts 6 hours under 110 DEG C, 2MPa pressure.Product is poured into the ethanol of the hydrochloric acid containing 5wt%
Precipitate copolymer in solution, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain two rings [2,2,1] hept-2-ene",
Hexafluoropropene and acrylonitrile terpolymer.It is 90.5% to calculate reaction yield.
Embodiment 3
In the three-necked flask of dry inert atmosphere, by 0.001 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.010 mole of Phen is dissolved in 10 milliliters of tetrahydrofurans, under 110 turns per minute of speed stirring, by 0.004 mole four
Titanium chloride is instilled in above-mentioned solution, in constant temperature stirring 50 minutes at same 30 DEG C of stir speed (S.S.) after dripping off, and produces cerium-titanium complexing
Thing catalyst.
0.01 mole of 1- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mol propylene nitrile are added
Enter to repeatedly vacuumizing, in nitrogen charging autoclave, plus the dissolving of 20ml tetrahydrofurans.By in catalyst two (pentamethylcyclopentadiene bases)
The amount of cerium chloride is calculated as the 1.0% of ENB, hexafluoropropene and acrylonitrile three's gross weight and takes above-mentioned cerium-titanium complex catalysis
Agent, is injected in above-mentioned mixture with syringe.Constant temperature reacts 1 hour under 120 DEG C, 6MPa pressure.Product is poured into salt containing 5wt%
Copolymer is precipitated in the ethanol solution of acid, precipitates washed with EtOH to neutrality, vacuum drying obtains 1- methyl bicyclics
[2,2,1] hept-2-ene", hexafluoropropene and acrylonitrile terpolymer.It is 71.1% to calculate reaction yield.
Embodiment 4
In the three-necked flask of dry inert atmosphere, by 0.001 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.005 mole of quinoline is dissolved in 10 milliliters of petroleum ethers, under 110 turns per minute of speed stirring, by 0.012 mole of titanium tetrachloride
Instill in above-mentioned solution, in constant temperature stirring 60 minutes at same 50 DEG C of stir speed (S.S.) after dripping off, produce cerium-titanium complex catalysis
Agent.
0.01 mole of 5- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mol propylene nitrile are added
Enter to repeatedly vacuumizing, in nitrogen charging autoclave, plus 20ml petroleum ether dissolutions.By in catalyst two (pentamethylcyclopentadiene base) chlorine
The amount of change cerium is calculated as the 0.03% of ENB, hexafluoropropene and acrylonitrile three's gross weight and takes above-mentioned cerium-titanium complex catalysis
Agent, is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours under 100 DEG C, 4MPa pressure.Product is poured into salt containing 5wt%
Copolymer is precipitated in the ethanol solution of acid, precipitates washed with EtOH to neutrality, vacuum drying obtains 5- methyl bicyclics
[2,2,1] hept-2-ene", hexafluoropropene and acrylonitrile terpolymer.It is 67.1% to calculate reaction yield.
Embodiment 5
In the three-necked flask of dry inert atmosphere, by 0.001 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.006 mole of porphyrin is dissolved in 10 milliliters of methyl phenyl ethers anisoles, under 120 turns per minute of speed stirring, by 0.006 mole of titanium tetrachloride
Instill in above-mentioned solution, in constant temperature stirring 40 minutes at same 60 DEG C of stir speed (S.S.) after dripping off, produce cerium-titanium complex catalysis
Agent.
0.01 mole of 7- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mol propylene nitrile are added
Enter to repeatedly vacuumizing, in nitrogen charging autoclave, plus the dissolving of 20ml methyl phenyl ethers anisoles.By in catalyst two (pentamethylcyclopentadiene base) chlorine
The amount of change cerium is calculated as the 0.06% of ENB, hexafluoropropene and acrylonitrile three's gross weight and takes above-mentioned cerium-titanium complex catalysis
Agent, is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours under 90 DEG C, 3MPa pressure.Product is poured into salt containing 5wt%
Copolymer is precipitated in the ethanol solution of acid, precipitates washed with EtOH to neutrality, vacuum drying obtains 7- methyl bicyclics
[2,2,1] hept-2-ene", hexafluoropropene and acrylonitrile terpolymer.It is 85.4% to calculate reaction yield.
Embodiment 6
In the three-necked flask of dry inert atmosphere, by 0.010 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.001 mole of pentanedione is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, under 120 turns per minute of speed stirring, by 0.006
Mole titanium tetrachloride is instilled in above-mentioned solution, after dripping off at same 30 DEG C of stir speed (S.S.) constant temperature stir 40 minutes, produce cerium-
Titanium complex catalyst.
The 0.01 mole of ring of 1- ethyls two [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mol propylene nitrile are added
Enter to repeatedly vacuumizing, in nitrogen charging autoclave, plus the dissolving of 20ml1,4- dioxane.By in catalyst two (pentamethyl rings penta 2
Alkenyl) amount of cerium chloride is calculated as the 0.09% of ENB, hexafluoropropene and acrylonitrile three's gross weight and takes the complexing of above-mentioned cerium-titanium
Thing catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 3 hours under 60 DEG C, 1MPa pressure.Product, which is poured into, to be contained
Copolymer is precipitated in the ethanol solution of 5wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying obtains 1- second
The ring of base two [2,2,1] hept-2-ene", hexafluoropropene and acrylonitrile terpolymer.It is 45.6% to calculate reaction yield.
Embodiment 7
In the three-necked flask of dry inert atmosphere, by 0.012 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.002 mole of 8-hydroxyquinoline is dissolved in 10 milliliters of Isosorbide-5-Nitrae-dioxane, under 120 turns per minute of speed stirring, by 0.001
Mole titanium tetrachloride is instilled in above-mentioned solution, after dripping off at same 40 DEG C of stir speed (S.S.) constant temperature stir 30 minutes, produce cerium-
Titanium complex catalyst.
The 0.01 mole of ring of 5- ethyls two [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mol propylene nitrile are added
Enter to repeatedly vacuumizing, in nitrogen charging autoclave, plus the dissolving of 20ml1,4- dioxane.By in catalyst two (pentamethyl rings penta 2
Alkenyl) amount of cerium chloride is calculated as the 0.1% of ENB, hexafluoropropene and acrylonitrile three's gross weight and takes the complexing of above-mentioned cerium-titanium
Thing catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 2 hours under 30 DEG C, 0.4MPa pressure.Product, which is poured into, to be contained
Copolymer is precipitated in the ethanol solution of 5wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying obtains 5- second
The ring of base two [2,2,1] hept-2-ene", hexafluoropropene and acrylonitrile terpolymer.It is 32.3% to calculate reaction yield.
Embodiment 8
In the three-necked flask of dry inert atmosphere, by 0.006 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.012 mole of isoquinolin is dissolved in 10 milliliters of 1,2- dichloroethanes, under 120 turns per minute of speed stirring, by 0.001 mole
Titanium tetrachloride is instilled in above-mentioned solution, in constant temperature stirring 50 minutes at same 40 DEG C of stir speed (S.S.) after dripping off, produces cerium-titanium network
Mixture catalyst.
By the 0.01 mole of ring of 5,5- dimethyl two [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mol propylene
Nitrile, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, plus the dissolving of 20ml1,2- dichloroethanes.By in catalyst two (pentamethyl rings
Pentadienyl) amount of cerium chloride is calculated as the 0.2% of ENB, hexafluoropropene and acrylonitrile three's gross weight and takes above-mentioned cerium-titanium
Complex compound catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 hours under 40 DEG C, 0.7MPa pressure.Product inclines
Copolymer is precipitated in the ethanol solution for entering the hydrochloric acid containing 5wt%, precipitates washed with EtOH to neutrality, vacuum drying obtains
The ring of 5,5- dimethyl two [2,2,1] hept-2-ene", hexafluoropropene and acrylonitrile terpolymer.It is 35.1% to calculate reaction yield.
Embodiment 9
In the three-necked flask of dry inert atmosphere, by 0.001 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.008 mole of α, α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, under 120 turns per minute of speed stirring, by 0.008 mole
Titanium tetrachloride is instilled in above-mentioned solution, in constant temperature stirring 50 minutes at same 50 DEG C of stir speed (S.S.) after dripping off, produces cerium-titanium network
Mixture catalyst.
The 0.01 mole of ring of 1- phenyl two [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mol propylene nitrile are added
Enter to repeatedly vacuumizing, in nitrogen charging autoclave, plus the dissolving of 20ml hexamethylenes.By in catalyst two (pentamethylcyclopentadiene base) chlorine
The amount of change cerium is calculated as the 0.6% of ENB, hexafluoropropene and acrylonitrile three's gross weight and takes above-mentioned cerium-titanium complex catalysis
Agent, is injected in above-mentioned mixture with syringe.Constant temperature reacts 6 hours under 80 DEG C, 0.9MPa pressure.Product is poured into containing 5wt%
Copolymer is precipitated in the ethanol solution of hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying obtains the ring of 1- phenyl two
[2,2,1] hept-2-ene", hexafluoropropene and acrylonitrile terpolymer.It is 53.5% to calculate reaction yield.
Embodiment 10
In the three-necked flask of dry inert atmosphere, by 0.001 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.005 mole of α, α '-bipyridyl is dissolved in 10 milliliters of cyclohexanone, under 130 turns per minute of speed stirring, by 0.007 mole
Titanium tetrachloride is instilled in above-mentioned solution, in constant temperature stirring 60 minutes at same 60 DEG C of stir speed (S.S.) after dripping off, produces cerium-titanium network
Mixture catalyst.
The 0.01 mole of ring of 5- phenyl two [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mol propylene nitrile are added
Enter to repeatedly vacuumizing, in nitrogen charging autoclave, plus the dissolving of 20ml cyclohexanone.By in catalyst two (pentamethylcyclopentadiene base) chlorine
The amount of change cerium is calculated as the 0.8% of ENB, hexafluoropropene and acrylonitrile three's gross weight and takes above-mentioned cerium-titanium complex catalysis
Agent, is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours under 70 DEG C, 1MPa pressure.Product is poured into salt containing 5wt%
Copolymer is precipitated in the ethanol solution of acid, precipitates washed with EtOH to neutrality, vacuum drying obtains the ring of 5- phenyl two
[2,2,1] hept-2-ene", hexafluoropropene and acrylonitrile terpolymer.It is 67.7% to calculate reaction yield.
Embodiment 11
In the three-necked flask of dry inert atmosphere, by 0.001 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.007 mole of Phen is dissolved in 10 milliliters of toluene, under 120 turns per minute of speed stirring, by 0.005 mole of four chlorination
Titanium is instilled in above-mentioned solution, in constant temperature stirring 60 minutes at same 50 DEG C of stir speed (S.S.) after dripping off, is produced cerium-titanium complex and is urged
Agent.
By the 0.01 mole of ring of 5- vinyl two [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mol propylene nitrile
It is added to and repeatedly vacuumizes, in nitrogen charging autoclave, plus the dissolving of 20ml toluene.By in catalyst two (pentamethylcyclopentadiene base) chlorine
The amount of change cerium is calculated as the 0.04% of ENB, hexafluoropropene and acrylonitrile three's gross weight and takes above-mentioned cerium-titanium complex catalysis
Agent, is injected in above-mentioned mixture with syringe.Constant temperature reacts 4 hours under 90 DEG C, 4MPa pressure.Product is poured into salt containing 5wt%
Copolymer is precipitated in the ethanol solution of acid, precipitates washed with EtOH to neutrality, vacuum drying obtains the ring of 5- vinyl two
[2,2,1] hept-2-ene", hexafluoropropene and acrylonitrile terpolymer.It is 75.1% to calculate reaction yield.
Embodiment 12
In the three-necked flask of dry inert atmosphere, by 0.001 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.004 mole of isoquinolin is dissolved in 10 milliliters of tetrahydrofurans, under 120 turns per minute of speed stirring, by 0.005 mole of tetrachloro
Change titanium to instill in above-mentioned solution, in constant temperature stirring 30 minutes at same 50 DEG C of stir speed (S.S.) after dripping off, produce cerium-titanium complex
Catalyst.
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- methyl formate, 0.01 mole of hexafluoropropene and 0.01 mole third
Alkene nitrile, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, plus the dissolving of 20ml tetrahydrofurans.By in catalyst two (pentamethyl rings penta
Dialkylene) amount of cerium chloride is calculated as the 0.05% of ENB, hexafluoropropene and acrylonitrile three's gross weight and takes above-mentioned cerium-titanium network
Mixture catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours under 100 DEG C, 4MPa pressure.Product is poured into
Copolymer is precipitated in the ethanol solution of the hydrochloric acid containing 5wt%, precipitates washed with EtOH to neutrality, vacuum drying obtains two
Ring [2,2,1] hept-2-ene" -5- methyl formates, hexafluoropropene and acrylonitrile terpolymer.It is 79.2% to calculate reaction yield.
Embodiment 13
In the three-necked flask of dry inert atmosphere, by 0.012 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.004 mole of quinoline is dissolved in 10 milliliters of petroleum ethers, under 120 turns per minute of speed stirring, by 0.003 mole of titanium tetrachloride
Instill in above-mentioned solution, in constant temperature stirring 30 minutes at same 40 DEG C of stir speed (S.S.) after dripping off, produce cerium-titanium complex catalysis
Agent.
By the special butyl ester of 0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid, 0.01 mole of hexafluoropropene and 0.01 mole
Acrylonitrile, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, plus 20ml petroleum ether dissolutions.By in catalyst two (pentamethyl rings penta
Dialkylene) amount of cerium chloride is calculated as the 0.06% of ENB, hexafluoropropene and acrylonitrile three's gross weight and takes above-mentioned cerium-titanium network
Mixture catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 2 hours under 120 DEG C, 6MPa pressure.Product is poured into
Copolymer is precipitated in the ethanol solution of the hydrochloric acid containing 5wt%, precipitates washed with EtOH to neutrality, vacuum drying obtains two
Ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, hexafluoropropene and acrylonitrile terpolymer.Calculating reaction yield is
49.7%.
Embodiment 14
In the three-necked flask of dry inert atmosphere, by 0.012 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.007 mole of porphyrin is dissolved in 10 milliliters of methyl phenyl ethers anisoles, under 130 turns per minute of speed stirring, by 0.002 mole of titanium tetrachloride
Instill in above-mentioned solution, in constant temperature stirring 30 minutes at same 50 DEG C of stir speed (S.S.) after dripping off, produce cerium-titanium complex catalysis
Agent.
By the special butyl ester of 0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid, 0.01 mole of hexafluoropropene and 0.01 mole
Acrylonitrile, which is added to, repeatedly to be vacuumized, in nitrogen charging autoclave, plus the dissolving of 20ml methyl phenyl ethers anisoles.By in catalyst two (pentamethyl rings penta
Dialkylene) amount of cerium chloride is calculated as the 0.08% of ENB, hexafluoropropene and acrylonitrile three's gross weight and takes above-mentioned cerium-titanium network
Mixture catalyst, is injected in above-mentioned mixture with syringe.Constant temperature reacts 5 hours under 50 DEG C, 5MPa pressure.Product, which is poured into, to be contained
Copolymer is precipitated in the ethanol solution of 5wt% hydrochloric acid, precipitates washed with EtOH to neutrality, vacuum drying obtains two rings
[2,2,1] hept-2-ene" -5- formic acid spy butyl ester, hexafluoropropene and acrylonitrile terpolymer.It is 46.8% to calculate reaction yield.
Embodiment 15
In the three-necked flask of dry inert atmosphere, by 0.001 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.006 mole of α, α '-bipyridyl is dissolved in 10 milliliters of hexamethylenes, under 120 turns per minute of speed stirring, by 0.006 mole
Titanium tetrachloride is instilled in above-mentioned solution, in constant temperature stirring 60 minutes at same 40 DEG C of stir speed (S.S.) after dripping off, produces cerium-titanium network
Mixture catalyst.
0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mol propylene nitrile are added to many
It is secondary to vacuumize, in nitrogen charging autoclave, plus the dissolving of 20ml hexamethylenes.By in catalyst two (pentamethylcyclopentadiene base) cerium chlorides
Amount is calculated as the 0.09% of ENB, hexafluoropropene and acrylonitrile three's gross weight and takes above-mentioned cerium-titanium complex catalyst, with note
Emitter is injected in above-mentioned mixture.Constant temperature reacts 5 hours under 80 DEG C, 4MPa pressure.Product is poured into the ethanol of the hydrochloric acid containing 5wt%
Precipitate copolymer in solution, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain two rings [2,2,1] hept-2-ene",
Hexafluoropropene and acrylonitrile terpolymer.It is 69.9% to calculate reaction yield.
Embodiment 16
In the three-necked flask of dry inert atmosphere, by 0.001 rub two (pentamethylcyclopentadiene base) cerium chlorides and
0.003 mole of 8-hydroxyquinoline is dissolved in 10 milliliters of benzene, under 120 turns per minute of speed stirring, by 0.005 mole of four chlorination
Titanium is instilled in above-mentioned solution, and constant temperature is stirred 50 minutes at same 40 DEG C of stir speed (S.S.) after dripping off, and produces cerium-titanium complex catalysis
Agent.
0.01 mole of 1- methyl bicyclics [2,2,1] hept-2-ene", 0.01 mole of hexafluoropropene and 0.01 mol propylene nitrile are added
Enter to repeatedly vacuumizing, in nitrogen charging autoclave, plus the dissolving of 20ml benzene.By in catalyst two (pentamethylcyclopentadiene base) cerium chlorides
Amount be calculated as the 0.06% of ENB, hexafluoropropene and acrylonitrile three's gross weight and take above-mentioned cerium-titanium complex catalyst, use
Syringe is injected in above-mentioned mixture.Constant temperature reacts 5 hours under 100 DEG C, 5MPa pressure.Product is poured into the hydrochloric acid containing 5wt%
Precipitate copolymer in ethanol solution, precipitates washed with EtOH to neutrality, vacuum drying, that is, obtain 1- methyl bicyclics [2,2,
1] hept-2-ene", hexafluoropropene and acrylonitrile terpolymer.It is 80.6% to calculate reaction yield.
Claims (4)
1. norborneol alkenes, hexafluoropropene and acrylonitrile method for ternary polymerization, it is characterised in that the preparation of used catalyst
Method is as follows：
In the three-necked flask of dry inert atmosphere, two (pentamethylcyclopentadiene base) cerium chlorides and part are dissolved in first
In solvent, under 110 ~ 130rpm stirrings, titanium tetrachloride is instilled in above-mentioned solution, equally stirred at 30-60 DEG C after dripping off
Constant temperature is stirred 30-60 minutes under speed, produces cerium-titanium complex catalyst；
The mol ratio of two (pentamethylcyclopentadiene base) cerium chloride and the part is 1: 10 ~ 10: 1, the two (pentamethyl
Cyclopentadienyl group) mol ratio of cerium chloride and the titanium tetrachloride is 1: 12 ~ 12: 1；
The part is selected from 8-hydroxyquinoline, α, α '-bipyridyl, Phen, isoquinolin, quinoline, porphyrin, pentanedione；
First solvent be selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloroethanes,
Hexamethylene or cyclohexanone；
The consumption of first solvent and described two (pentamethylcyclopentadiene base) cerium chlorides, titanium tetrachloride and part three's total amount
Ratio be 10 milliliters：0.003~0.030 mole；
According to mol ratio 1: 1: 1 take Norbornene derivative, hexafluoropropene and acrylonitrile monemer be added to repeatedly vacuumize, nitrogen charging
In reactor, the dissolving of the second solvent is added；Then described cerium-titanium complex catalyst, at 30 ~ 120 DEG C, 0.1- are added
Reacted 1 ~ 6 hour under 6MPa pressure；
The product that reaction is obtained is poured into the ethanol solution of the hydrochloric acid containing 4-5wt%, and obtained precipitates washed with EtOH is into
Property, obtain ENB class, hexafluoropropene and acrylonitrile terpolymer after vacuum drying；
The consumption of the cerium-titanium complex catalyst is calculated as drop by the amount of in catalyst two (pentamethylcyclopentadiene base) cerium chlorides
The 0.01%-1.0% of borneol alkenes, hexafluoropropene and acrylonitrile three's gross weight；
Second solvent be selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloroethanes,
Hexamethylene or cyclohexanone；The amount ratio of the molal quantity sum of each polymerized monomer and second solvent is 0.03 mole：20 milliliters.
2. method for ternary polymerization according to claim 1, it is characterised in that described two (pentamethylcyclopentadiene base) chlorination
The mol ratio of cerium, titanium tetrachloride and part three is 1: 3: 4.
3. method for ternary polymerization according to claim 1 or 2, it is characterised in that the part and first solvent make
First it is dried with preceding；The drying of solid-state part in wherein described part be first with recrystallization method purify then vacuum do
It is dry；The drying of liquid part in the part is dried with calcium hydride or metallic sodium, first solvent using calcium chloride or
Calcium hydride is dried.
4. method for ternary polymerization according to claim 3, it is characterised in that the Norbornene derivative be selected from two rings [2,
2,1] hept-2-ene", 1- methyl bicyclics [2,2,1] hept-2-ene", 5- methyl bicyclics [2,2,1] hept-2-ene", 7- methyl bicyclics [2,2,
1] hept-2-ene", the ring of 1- ethyls two [2,2,1] hept-2-ene", the ring of 5- ethyls two [2,2,1] hept-2-ene", the ring of 5,5- dimethyl two [2,
2,1] hept-2-ene", the ring of 1- phenyl two [2,2,1] hept-2-ene", the ring of 5- phenyl two [2,2,1] hept-2-ene", the ring of 5- vinyl two [2,
2,1] the special butyl ester of hept-2-ene", two rings [2,2,1] hept-2-ene" -5- methyl formates or two rings [2,2,1] hept-2-ene" -5- formic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610151343.7A CN105693928B (en) | 2016-03-17 | 2016-03-17 | Norborneol alkenes, hexafluoropropene and acrylonitrile ternary polymerization catalyst and method for ternary polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610151343.7A CN105693928B (en) | 2016-03-17 | 2016-03-17 | Norborneol alkenes, hexafluoropropene and acrylonitrile ternary polymerization catalyst and method for ternary polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105693928A CN105693928A (en) | 2016-06-22 |
| CN105693928B true CN105693928B (en) | 2017-08-08 |
Family
ID=56221918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610151343.7A Active CN105693928B (en) | 2016-03-17 | 2016-03-17 | Norborneol alkenes, hexafluoropropene and acrylonitrile ternary polymerization catalyst and method for ternary polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105693928B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432609B (en) * | 2016-09-26 | 2018-08-07 | 宁波工程学院 | The preparation method of norborneol alkenes, styrene and cyclohexene terpolymer |
| CN106632852B (en) * | 2016-12-19 | 2019-02-15 | 宁波工程学院 | Norborneol alkenes, vinylacetate and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization |
| CN106832120B (en) * | 2017-02-17 | 2019-03-29 | 宁波工程学院 | Norborneol alkenes, hexafluoropropene and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization |
| CN106866884A (en) * | 2017-02-20 | 2017-06-20 | 宁波工程学院 | Norborneol alkenes, vinyl cyclohexane and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization |
| CN106832121B (en) * | 2017-02-20 | 2019-07-30 | 宁波工程学院 | Norborneol alkenes, cyclohexene and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914178A (en) * | 2010-07-30 | 2010-12-15 | 宁波镇洋化工发展有限公司 | Preparation method of dutrex-unsaturated nitrile-cyclenes heat-resistant copolymer |
| CN102153701A (en) * | 2011-01-24 | 2011-08-17 | 宁波工程学院 | Catalyst for ternary polymerization of norbornene, acrylate and cyclohexene and preparation method thereof and ternary polymerization method |
| CN102382228A (en) * | 2011-09-02 | 2012-03-21 | 宁波镇洋化工发展有限公司 | SAN (styrene-acrylonitrile copolymer) preparation method |
| CN103626919A (en) * | 2013-11-27 | 2014-03-12 | 宁波工程学院 | Norbornene, maleic anhydride and vinyl acetate ternary polymerization catalyst and ternary polymerization method |
| CN103864990A (en) * | 2014-03-11 | 2014-06-18 | 宁波工程学院 | Norbornene, norbornene and cyclohexene ternary polymerization catalyst and ternary polymerization method |
| CN104262513A (en) * | 2014-10-14 | 2015-01-07 | 宁波工程学院 | Ternary polymerization catalyst and ternary polymerization method for norbornylene, vinylacetate and octafluorocyclopentene |
-
2016
- 2016-03-17 CN CN201610151343.7A patent/CN105693928B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914178A (en) * | 2010-07-30 | 2010-12-15 | 宁波镇洋化工发展有限公司 | Preparation method of dutrex-unsaturated nitrile-cyclenes heat-resistant copolymer |
| CN102153701A (en) * | 2011-01-24 | 2011-08-17 | 宁波工程学院 | Catalyst for ternary polymerization of norbornene, acrylate and cyclohexene and preparation method thereof and ternary polymerization method |
| CN102382228A (en) * | 2011-09-02 | 2012-03-21 | 宁波镇洋化工发展有限公司 | SAN (styrene-acrylonitrile copolymer) preparation method |
| CN103626919A (en) * | 2013-11-27 | 2014-03-12 | 宁波工程学院 | Norbornene, maleic anhydride and vinyl acetate ternary polymerization catalyst and ternary polymerization method |
| CN103864990A (en) * | 2014-03-11 | 2014-06-18 | 宁波工程学院 | Norbornene, norbornene and cyclohexene ternary polymerization catalyst and ternary polymerization method |
| CN104262513A (en) * | 2014-10-14 | 2015-01-07 | 宁波工程学院 | Ternary polymerization catalyst and ternary polymerization method for norbornylene, vinylacetate and octafluorocyclopentene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105693928A (en) | 2016-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105693928B (en) | Norborneol alkenes, hexafluoropropene and acrylonitrile ternary polymerization catalyst and method for ternary polymerization | |
| CN105693929B (en) | Norborneol alkenes, styrene and vinylacetate ternary polymerization catalyst and method for ternary polymerization | |
| CN105111372B (en) | Norborneol alkenes, octafluoro cyclopentene and hexamethylene alkenes ternary polymerization catalyst and method for ternary polymerization | |
| CN105924548B (en) | Norborneol alkenes, acrylonitrile and vinylacetate method for ternary polymerization | |
| CN105924576B (en) | Norborneol alkenes, octafluoro cyclopentene and acrylonitrile ternary polymerization catalyst and method for ternary polymerization | |
| CN104140496B (en) | Norborneol alkenes, vinylacetate and esters of acrylic acid method for ternary polymerization | |
| CN105524218B (en) | Norborneol alkenes, hexafluoropropene and 1 hexene ternary polymerization catalyst and method for ternary polymerization | |
| CN106832122B (en) | Norborneol alkenes, amylene class and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization | |
| CN106832120B (en) | Norborneol alkenes, hexafluoropropene and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization | |
| CN105218709B (en) | Norborneol alkenes, phenylethylene and maleic anhydride tercopolymer catalyst for copolymerization and method for ternary polymerization | |
| CN106749911B (en) | Norborneol alkenes, tetrafluoroethene and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization | |
| CN106832124B (en) | Norborneol alkenes, acrylonitrile and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization | |
| CN106832121B (en) | Norborneol alkenes, cyclohexene and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization | |
| CN106749912B (en) | Norborneol alkenes, vinylacetate and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization | |
| CN106749915B (en) | Norborneol alkenes, esters of acrylic acid and vinylene carbonate ternary polymerization catalyst and method for ternary polymerization | |
| CN104311738B (en) | Norbornylene class, maleic anhydride and octafluoro cyclopentenes terpolymer catalyzer and method for ternary polymerization | |
| CN106832123B (en) | Norborneol alkenes, vinyl ethyl ether and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization | |
| CN106832119B (en) | Norborneol alkenes, tetrafluoroethene and perfluoro methyl vinyl ether ternary polymerization catalyst and method for ternary polymerization | |
| CN106496417B (en) | Norborneol alkenes, styrene and acrylonitrile ternary polymerization catalyst and method for ternary polymerization | |
| CN106749913B (en) | Norborneol alkenes, octafluoro cyclopentene and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization | |
| CN106432609B (en) | The preparation method of norborneol alkenes, styrene and cyclohexene terpolymer | |
| CN106632851B (en) | Norborneol alkenes, hexafluoropropene and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization | |
| CN106832118B (en) | Norborneol alkenes and vinylene carbonate binary copolymerization catalyst and binary copolymerization method | |
| CN106749781B (en) | Norborneol alkenes and perfluoro methyl vinyl ether binary copolymerization catalyst and binary copolymerization method | |
| CN107540788A (en) | Norborneol alkenes, cyclohexene and N phenyl maleimide ternary polymerization catalyst and method for ternary polymerization |
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 |