CN105693929A - Norbornene, styrene and nikasol ternary polymerization catalyst and ternary polymerization method - Google Patents
Norbornene, styrene and nikasol ternary polymerization catalyst and ternary polymerization method Download PDFInfo
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- CN105693929A CN105693929A CN201610153707.5A CN201610153707A CN105693929A CN 105693929 A CN105693929 A CN 105693929A CN 201610153707 A CN201610153707 A CN 201610153707A CN 105693929 A CN105693929 A CN 105693929A
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- 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
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- C08F212/00—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 an aromatic carbocyclic ring
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- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
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Abstract
The invention relates to a norbornene, styrene and nikasol ternary polymerization catalyst and a ternary polymerization method. The preparation method of the catalyst comprises the steps that (pentamethyl cyclopentadiene) iridium chloride, aluminum alkyl and a ligand are dissolved into a first solvent in a dry three-mouth flask in the inertia atmosphere, stirring is performed at the constant temperature of 20-50 DEG C at the speed of 110-130 rpm for 20-50 min, and an iridium-aluminum complex catalyst is obtained. The polymerization method comprises the steps that a norbornene monomer, a styrene monomer and a nikasol monomer are taken and added into a reaction kettle, and a second solvent is added for dissolution; then, the iridium-aluminum complex catalyst is added, a reaction is performed under the certain stable pressure, and the product is washed to obtain the terpolymer. Catalytic activity can be generated at low temperature, norbornene, styrene and nikasol ternary polymerization is catalyzed, the reaction temperature is low, the catalysis efficiency is high, the copolymer yield is high, and the terpolymer is good in photoetching performance.
Description
Technical field
The present invention relates to high polymer synthetic catalyst and high polymer synthesis, refer specifically to a kind of norborene class, styrene and vinylacetate ternary polymerization catalyst and method for ternary polymerization。
Background technology
Polynorbornene is a kind of special polymer, has excellent mechanical property, thermostability, solubility in organic solvent and the transparency, can be used for 193nm ultraviolet light photoetching。This material major downside is that fragility, viscosity difference and molecular weight are low etc.。Improve caking property and the solubility of polymer usually by the copolymerization with other material, and reduce the absorptance of material itself。
The preparation method of current norbornene copolymer mainly has the methods such as free radical, living radical, metallic catalyst。If A.E.Feiring and Q.Feng etc. is by norborene and tetrafluoroethene, styrene, acrylate free radical method carries out quarternary copolymerized, the synthesis of photoetching material disclosed in ProceedingsofSPIEVol.5039 (2003) the 80th～92 page have employed the peroxide catalyst as radical polymerization, the synthesis of photoetching material disclosed in ProceedingsofSPIEVol.4690 (2002) the 127th～135 page have employed the AINB (azodiisobutyronitrile) catalyst as radical polymerization, norborene and styrol copolymer photoetching material disclosed in PolymersVol.6 (2014) 565-582 page have employed the synthesis of free radical method。
The shortcomings such as existing synthetic method all exists response time length, copolymer yield is low, molecular weight of copolymer is little, copolymer alternate degree is low。
Summary of the invention
The technical problem to be solved is that the present situation offer for prior art is a kind of can reduce reaction temperature, raising catalytic efficiency and the norborene class of copolymer yield, styrene and vinylacetate ternary polymerization catalyst。
Another technical problem to be solved by this invention is to provide a kind of method of reaction temperature is relatively low, catalytic efficiency is high and copolymer yield is high norborene class, styrene and vinylacetate ternary polymerization。
This invention address that the technical scheme that above-mentioned technical problem adopts is: this norborene class, styrene and vinylacetate ternary polymerization catalyst, it is characterised in that the preparation method of this catalyst is as follows:
In the there-necked flask of dry inert atmosphere, (pentamethylcyclopentadiene) iridium chloride, alkyl aluminum and part are dissolved in the first solvent, stir 20-50 minute with the speed constant temperature of 110-130rpm at 20-50 DEG C, obtain iridium-aluminum complex catalyst；
The mol ratio of described (pentamethylcyclopentadiene) iridium chloride and described part is 1: 8～8: 1, and the mol ratio of described (pentamethylcyclopentadiene) iridium chloride and described alkyl aluminum is 1: 12～12: 1；
Described alkyl aluminum is selected from triisobutyl aluminium or triethyl aluminum；
Described part be selected from oxine, α, α '-bipyridyl, orthophenanthroline, isoquinolin, quinoline, porphyrin, pentanedione；
Described first solvent is selected from benzene, toluene, oxolane, petroleum ether, methyl phenyl ethers anisole, 1,4-dioxane, 1,2-dichloroethanes, hexamethylene or Ketohexamethylene；The ratio of the consumption of described solvent and described (pentamethylcyclopentadiene) iridium chloride, alkyl aluminum and part three's total amount is 10 milliliters: 0.003～0.030 mole。
The mol ratio of described (pentamethylcyclopentadiene) iridium chloride, alkyl aluminum and part three is preferably 1: 8: 4。
Preferably, described part and described first solvent are first dried before use；Solid-state part in wherein said part dry is first to purify then vacuum drying by recrystallization way；The dry of liquid part in described part is to dry with calcium hydride or metallic sodium, and described solvent adopts calcium chloride or calcium hydride to dry。
Use above-mentioned norborene class, styrene and vinylacetate ternary polymerization catalyst norborene class, styrene and vinylacetate method for ternary polymerization, it is characterised in that comprise the steps:
Take in the reactor that Norbornene derivative, styrene and Vinyl Acetate Monomer join repeatedly evacuation, nitrogen charging according to mol ratio 1: 1: 1, add the second solvent and dissolve；It is subsequently adding described iridium-aluminum complex catalyst, at 30～150 DEG C, reacts 1～6 hour under 0.1-10MPa pressure；
Being poured into by the product being obtained by reacting in the alcoholic solution containing 4-5wt% hydrochloric acid, the precipitates washed with EtOH obtained, to neutral, namely obtains norborene class, styrene and vinylacetate terpolymer after vacuum drying；
The consumption of described iridium-aluminum complex catalyst is calculated as the 0.01%-1.5% of norborene class, styrene and vinylacetate three's gross weight by the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst；
Described second solvent is selected from benzene, toluene, oxolane, petroleum ether, methyl phenyl ethers anisole, 1,4-dioxane, 1,2-dichloroethanes, hexamethylene or Ketohexamethylene；The amount ratio of the molal quantity sum of each polymerization single polymerization monomer and described second solvent is 0.03 mole: 20 milliliters。
Described Norbornene derivative can be selected from bicyclo-[2, 2, 1] hept-2-ene", 1-methyl bicyclic [2, 2, 1] hept-2-ene", 5-methyl bicyclic [2, 2, 1] hept-2-ene", 7-methyl bicyclic [2, 2, 1] hept-2-ene", 1-ethyl bicyclo-[2, 2, 1] hept-2-ene", 5-ethyl bicyclo-[2, 2, 1] hept-2-ene", 5, 5-dimethyl bicyclo-[2, 2, 1] hept-2-ene", 1-phenyl bicyclo-[2, 2, 1] hept-2-ene", 5-phenyl bicyclo-[2, 2, 1] hept-2-ene", 5-vinyl bicyclo-[2, 2, 1] hept-2-ene", bicyclo-[2, 2, 1] hept-2-ene"-5-methyl formate or bicyclo-[2, 2, 1] hept-2-ene"-5-formic acid spy's butyl ester。
Compared with prior art, catalyst provided by the invention is a kind of Novel iridium-aluminum complex catalyst mixture, catalyst raw material is cheap and easy to get, catalysis activity can be produced under relatively low temperature, catalysis norborene class, styrene and vinylacetate ternary polymerization, reaction temperature is relatively low, and catalytic efficiency is high, and product is easy to washing and separates, copolymer yield is high；The resistance to corrosion of prepared norborene class, styrene and vinylacetate terpolymer substrate is high, and lithography performance is good, and the caking property of material, solubility and toughness are further enhanced。
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail。
The preparation process of catalyst in following embodiment, if no special instructions, has all carried out dried to part therein and solvent。Specifically: the solid ligand in part dry is first to purify then vacuum drying by recrystallization way；The dry of liquid part in part is to dry with calcium hydride or dry with metallic sodium。The dry of solvent is to dry with calcium chloride or calcium hydride。
Embodiment 1
In the there-necked flask of dry inert atmosphere, rub 0.001 (pentamethylcyclopentadiene) iridium chloride, 0.001 mole of triisobutyl aluminium and 0.001 mole of oxine is dissolved in 10 milliliters of benzene, stir 20 minutes with constant temperature at 120 turns, 20 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of bicyclo-[2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml benzene and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 0.01% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 80 DEG C, reacts 5 hours under 0.1MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains bicyclo-[2,2,1] hept-2-ene", styrene, vinylacetate terpolymer。Calculating reaction yield is 42.2%。
The computational methods of reaction yield are terpolymer weight/comonomer gross weight × 100%。Yield computational methods in following each embodiment are identical with this。
Embodiment 2
In the there-necked flask of dry inert atmosphere, rub (pentamethylcyclopentadiene) iridium chloride, 0.012 mole of triethyl aluminum and 0.006 mole of α by 0.001, α '-bipyridyl is dissolved in 10 milliliters of toluene, stir 50 minutes with constant temperature at 120 turns, 50 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of 1-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml toluene and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 1.5% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 120 DEG C, reacts 6 hours under 8MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains 1-methyl bicyclic [2,2,1] hept-2-ene", styrene, vinylacetate terpolymer。Calculating reaction yield is 70.9%。
Embodiment 3
In the there-necked flask of dry inert atmosphere, rub 0.001 (pentamethylcyclopentadiene) iridium chloride, 0.006 mole of triisobutyl aluminium and 0.008 mole of orthophenanthroline is dissolved in 10 milliliters of oxolanes, stir 40 minutes with constant temperature at 120 turns, 30 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of 5-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml oxolane and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 0.5% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 150 DEG C, reacts 4 hours under 10MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains 5-methyl bicyclic [2,2,1] hept-2-ene", styrene, vinylacetate terpolymer。Calculating reaction yield is 63.9%。
Embodiment 4
In the there-necked flask of dry inert atmosphere, rub 0.001 (pentamethylcyclopentadiene) iridium chloride, 0.003 mole of triisobutyl aluminium and 0.004 mole of isoquinolin is dissolved in 10 milliliters of petroleum ether, stir 30 minutes with constant temperature at 120 turns, 40 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of 7-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml petroleum ether dissolution。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 0.2% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 140 DEG C, reacts 4 hours under 0.6MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains 7-methyl bicyclic [2,2,1] hept-2-ene", styrene, vinylacetate terpolymer。Calculating reaction yield is 58.5%。
Embodiment 5
In the there-necked flask of dry inert atmosphere, rub (pentamethylcyclopentadiene) iridium chloride, 0.008 mole of triisobutyl aluminium and 0.004 mole of α by 0.001, α '-bipyridyl is dissolved in 10 milliliters of toluene, stir 40 minutes with constant temperature at 120 turns, 40 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of bicyclo-[2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml toluene and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 0.2% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature is (here should 140) DEG C 140, reacts 5 hours under 8MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains bicyclo-[2,2,1] hept-2-ene", styrene, vinylacetate terpolymer。Calculating reaction yield is 87.3%。
Embodiment 6
In the there-necked flask of dry inert atmosphere, rub 0.012 (pentamethylcyclopentadiene) iridium chloride, 0.001 mole of triisobutyl aluminium and 0.002 mole of quinoline is dissolved in 10 milliliters of methyl phenyl ethers anisoles, stir 40 minutes with constant temperature at 120 turns, 40 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of 1-ethyl bicyclo-[2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml methyl phenyl ethers anisole and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 1.2% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 100 DEG C, reacts 2 hours under 0.4MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains 1-ethyl bicyclo-[2,2,1] hept-2-ene", styrene, vinylacetate terpolymer。Calculating reaction yield is 51.4%。
Embodiment 7
In the there-necked flask of dry inert atmosphere, rub 0.008 (pentamethylcyclopentadiene) iridium chloride, 0.003 mole of triethyl aluminum and 0.001 mole of porphyrin is dissolved in 10 milliliter 1, in 4-dioxane, stir 40 minutes with constant temperature at 120 turns, 30 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of 5-ethyl bicyclo-[2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml1,4-dioxane and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 0.05% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 70 DEG C, reacts 4 hours under 0.9MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains 5-ethyl bicyclo-[2,2,1] hept-2-ene", styrene, vinylacetate terpolymer。Calculating reaction yield is 62.7%。
Embodiment 8
In the there-necked flask of dry inert atmosphere; rub 0.008 (pentamethylcyclopentadiene) iridium chloride, 0.006 mole of triethyl aluminum and 0.003 mole of pentanedione is dissolved in 10 milliliter 1; in 2-dichloroethanes; stir 40 minutes with constant temperature at 120 turns, 20 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of 5,5-dimethyl bicyclo-[2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml1,2-dichloroethanes and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 0.08% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 50 DEG C, reacts 6 hours under 0.4MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains 5,5-dimethyl bicyclo-[2,2,1] hept-2-ene"s, styrene, vinylacetate terpolymer。Calculating reaction yield is 52.4%。
Embodiment 9
In the there-necked flask of dry inert atmosphere, rub 0.001 (pentamethylcyclopentadiene) iridium chloride, 0.006 mole of triisobutyl aluminium and 0.003 mole of oxine is dissolved in 10 milliliters of hexamethylene, stir 50 minutes with constant temperature at 120 turns, 20 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of 1-phenyl bicyclo-[2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml hexamethylene and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 0.1% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 90 DEG C, reacts 6 hours under 7MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains 1-phenyl bicyclo-[2,2,1] hept-2-ene", styrene, vinylacetate terpolymer。Calculating reaction yield is 75.1%。
Embodiment 10
In the there-necked flask of dry inert atmosphere, rub 0.001 (pentamethylcyclopentadiene) iridium chloride, 0.002 mole of triethyl aluminum and 0.005 mole of orthophenanthroline is dissolved in 10 milliliters of Ketohexamethylene, stir 20 minutes with constant temperature at 120 turns, 50 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of 5-phenyl bicyclo-[2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml Ketohexamethylene and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 0.4% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 110 DEG C, reacts 1 hour under 2MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains 5-phenyl bicyclo-[2,2,1] hept-2-ene", styrene, vinylacetate terpolymer。Calculating reaction yield is 45.5%。
Embodiment 11
In the there-necked flask of dry inert atmosphere, rub 0.001 (pentamethylcyclopentadiene) iridium chloride, 0.005 mole of triethyl aluminum and 0.005 mole of isoquinolin is dissolved in 10 milliliters of benzene, stir 30 minutes with constant temperature at 120 turns, 40 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of 5-vinyl bicyclo-[2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml benzene and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 0.7% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 50 DEG C, reacts 2 hours under 10MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains 5-vinyl bicyclo-[2,2,1] hept-2-ene", styrene, vinylacetate terpolymer。Calculating reaction yield is 51.3%。
Embodiment 12
In the there-necked flask of dry inert atmosphere, rub 0.001 (pentamethylcyclopentadiene) iridium chloride, 0.011 mole of triisobutyl aluminium and 0.004 mole of isoquinolin is dissolved in 10 milliliters of toluene, stir 40 minutes with constant temperature at 120 turns, 40 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of bicyclo-[2,2,1] hept-2-ene"-5-methyl formate, 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml toluene and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 0.9% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 80 DEG C, reacts 4 hours under 8MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains bicyclo-[2,2,1] hept-2-ene"-5-methyl formate, styrene, vinylacetate terpolymer。Calculating reaction yield is 71.1%。
Embodiment 13
In the there-necked flask of dry inert atmosphere, rub 0.001 (pentamethylcyclopentadiene) iridium chloride, 0.010 mole of triisobutyl aluminium and 0.007 mole of quinoline is dissolved in 10 milliliters of toluene, stir 40 minutes with constant temperature at 120 turns, 30 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of bicyclo-[2,2,1] hept-2-ene"-5-formic acid spy's butyl ester, 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml toluene and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 1.1% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 110 DEG C, reacts 4 hours under 9MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains bicyclo-[2,2,1] hept-2-ene"-5-formic acid spy's butyl ester, styrene, vinylacetate terpolymer。Calculating reaction yield is 66.2%。
Embodiment 14
In the there-necked flask of dry inert atmosphere, rub 0.001 (pentamethylcyclopentadiene) iridium chloride, 0.007 mole of triethyl aluminum and 0.003 mole of porphyrin is dissolved in 10 milliliters of petroleum ether, stir 40 minutes with constant temperature at 120 turns, 35 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of 7-methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml petroleum ether dissolution。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 0.3% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 100 DEG C, reacts 5 hours under 7MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains 7-methyl bicyclic [2,2,1] hept-2-ene", styrene, vinylacetate terpolymer。Calculating reaction yield is 69.8%。
Embodiment 15
In the there-necked flask of dry inert atmosphere; rub 0.006 (pentamethylcyclopentadiene) iridium chloride, 0.003 mole of triisobutyl aluminium and 0.012 mole of pentanedione is dissolved in 10 milliliters of methyl phenyl ethers anisoles; stir 35 minutes with constant temperature at 110 turns, 45 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of bicyclo-[2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml methyl phenyl ethers anisole and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 0.6% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 60 DEG C, reacts 6 hours under 0.6MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains bicyclo-[2,2,1] hept-2-ene", styrene, vinylacetate terpolymer。Calculating reaction yield is 54.4%。
Embodiment 16
In the there-necked flask of dry inert atmosphere, rub (pentamethylcyclopentadiene) iridium chloride, 0.001 mole of triisobutyl aluminium and 0.014 mole of α by 0.003, α '-bipyridyl is dissolved in 10 milliliters of methyl phenyl ethers anisoles, stir 25 minutes with constant temperature at 130 turns, 25 DEG C per minute, obtain iridium-aluminum complex catalyst。
0.01 mole of bicyclo-[2,2,1] hept-2-ene", 0.01 mole of styrene and 0.01 molar acetate vinyl acetate are joined repeatedly in evacuation, nitrogen charging autoclave, adds 20ml methyl phenyl ethers anisole and dissolve。By the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst be calculated as norborene, styrene, vinylacetate three's gross weight 0.2% take above-mentioned iridium-aluminum complex catalyst, inject in above-mentioned mixture with syringe。Constant temperature, at 70 DEG C, reacts 6 hours under 0.6MPa pressure。Product is poured in the alcoholic solution containing 5wt% hydrochloric acid and makes copolymer precipitate, and precipitates washed with EtOH, to neutrality, vacuum drying, namely obtains bicyclo-[2,2,1] hept-2-ene", styrene, vinylacetate terpolymer。Calculating reaction yield is 44.1%。
Claims (5)
1. norborene class, styrene and vinylacetate ternary polymerization catalyst, it is characterised in that the preparation method of this catalyst is as follows:
In the there-necked flask of dry inert atmosphere, (pentamethylcyclopentadiene) iridium chloride, alkyl aluminum and part are dissolved in the first solvent, stir 20-50 minute with the speed constant temperature of 110-130rpm at 20-50 DEG C, obtain iridium-aluminum complex catalyst；
The mol ratio of described (pentamethylcyclopentadiene) iridium chloride and described part is 1: 8～8: 1, and the mol ratio of described (pentamethylcyclopentadiene) iridium chloride and described alkyl aluminum is 1: 12～12: 1；
Described alkyl aluminum is selected from triisobutyl aluminium or triethyl aluminum；
Described part be selected from oxine, α, α '-bipyridyl, orthophenanthroline, isoquinolin, quinoline, porphyrin, pentanedione；
Described first solvent is selected from benzene, toluene, oxolane, petroleum ether, methyl phenyl ethers anisole, 1,4-dioxane, 1,2-dichloroethanes, hexamethylene or Ketohexamethylene；The ratio of the consumption of described solvent and described (pentamethylcyclopentadiene) iridium chloride, alkyl aluminum and part three's total amount is 10 milliliters: 0.003～0.030 mole。
2. catalyst according to claim 1, it is characterised in that the mol ratio of described (pentamethylcyclopentadiene) iridium chloride, alkyl aluminum and part three is 1: 8: 4。
3. catalyst according to claim 1 and 2, it is characterised in that described part and described first solvent are first dried before use；Solid-state part in wherein said part dry is first to purify then vacuum drying by recrystallization way；The dry of liquid part in described part is to dry with calcium hydride or metallic sodium, and described solvent adopts calcium chloride or calcium hydride to dry。
4. use norborene class as described in claims 1 to 3 any claim, styrene and vinylacetate ternary polymerization catalyst norborene class, styrene and vinylacetate method for ternary polymerization, it is characterised in that comprise the steps:
Take in the reactor that Norbornene derivative, styrene and Vinyl Acetate Monomer join repeatedly evacuation, nitrogen charging according to mol ratio 1: 1: 1, add the second solvent and dissolve；It is subsequently adding described iridium-aluminum complex catalyst, at 30～150 DEG C, reacts 1～6 hour under 0.1-10MPa pressure；
Being poured into by the product being obtained by reacting in the alcoholic solution containing 4-5wt% hydrochloric acid, the precipitates washed with EtOH obtained, to neutral, namely obtains norborene class, styrene and vinylacetate terpolymer after vacuum drying；
The consumption of described iridium-aluminum complex catalyst is calculated as the 0.01%-1.5% of norborene class, styrene and vinylacetate three's gross weight by the amount of (pentamethylcyclopentadiene) iridium chloride in catalyst；
Described second solvent is selected from benzene, toluene, oxolane, petroleum ether, methyl phenyl ethers anisole, 1,4-dioxane, 1,2-dichloroethanes, hexamethylene or Ketohexamethylene；The amount ratio of the molal quantity sum of each polymerization single polymerization monomer and described second solvent is 0.03 mole: 20 milliliters。
5. method for ternary polymerization according to claim 4, it is characterized in that described Norbornene derivative is selected from bicyclo-[2, 2, 1] hept-2-ene", 1-methyl bicyclic [2, 2, 1] hept-2-ene", 5-methyl bicyclic [2, 2, 1] hept-2-ene", 7-methyl bicyclic [2, 2, 1] hept-2-ene", 1-ethyl bicyclo-[2, 2, 1] hept-2-ene", 5-ethyl bicyclo-[2, 2, 1] hept-2-ene", 5, 5-dimethyl bicyclo-[2, 2, 1] hept-2-ene", 1-phenyl bicyclo-[2, 2, 1] hept-2-ene", 5-phenyl bicyclo-[2, 2, 1] hept-2-ene", 5-vinyl bicyclo-[2, 2, 1] hept-2-ene", bicyclo-[2, 2, 1] hept-2-ene"-5-methyl formate or bicyclo-[2, 2, 1] hept-2-ene"-5-formic acid spy's butyl ester。
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