CN108383932A - A kind of preparation method of chemical industry synthesis catalyst - Google Patents
A kind of preparation method of chemical industry synthesis catalyst Download PDFInfo
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- CN108383932A CN108383932A CN201810211203.3A CN201810211203A CN108383932A CN 108383932 A CN108383932 A CN 108383932A CN 201810211203 A CN201810211203 A CN 201810211203A CN 108383932 A CN108383932 A CN 108383932A
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- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
Abstract
The invention discloses a kind of preparation method of chemical industry synthesis catalyst, this method adds triethylamine, is slowly warming up to 80 ~ 90 DEG C after stirring 30min, obtains ligand by being cooled to 0 ~ 2 DEG C after 30 ~ 40min is mixed in double diphenylphosphine ethanes, dry toluene；In 150 ~ 180 DEG C, inert gas shielding, airtight vacuum environment, after ligand and 4 Carboxybenzeneboronic acids, diphosphine monoxide are stirred evenly, it is rapidly added chromium compound, after reacting 30 ~ 40min, gained filter residue is main active constituent after reacted constituent is filtered；By main powdered active ingredient and auxiliary agent powder, support powder and binder and pore creating material mixed-forming, dry and roasting obtains the catalyst.Preparation method of the present invention is simple, and catalyst is efficient, for catalyzing and synthesizing for polyolefins, can obtain the polymer of high linear polyethylene, and can obtain the copolymer of polar monomer random distribution in polymer chain.
Description
Technical field
The invention belongs to technical field of chemical synthesis more particularly to a kind of preparation methods of chemical industry synthesis catalyst.
Background technology
It is although widely used as the polyolefins of representative using polyethylene and polypropylene, but is not particularly suited for whole use
On the way.Polyolefins be substantially it is nonpolar, thus the physical property such as cementability, the residual of dyestuff, printing and compatibility compared with
Difference, therefore its serviceability is restricted.It is well known, however, that by introducing function obtained by a small amount of polar functional group in polyolefins
Property polyolefin, these characteristics can significantly improve.
In order to expand the application range of polyolefins, the method for importing polar functional group to polyolefins is reported.These
It is to be copolymerized polar vinyl monomer useful on olefinic monomer and industry among method.Utilize the alkene of transition-metal catalyst
Hydro carbons polymerize with the coordination of polar vinyl monomer insertion（It is coordinated addition polymerization）, as with determining polymer architecture, point
Son is measured the strong synthetic method of the functional polyolefin class of the introduction volume of distribution and comonomer and is advocated.As catalysis alkene
Hydro carbons is inserted into the late transition metal complex polymerizeing with the coordination of polar vinyl monomer, and most successful so far is coordination
The complex of alpha-diimine or phosphine-azochlorosulfonate acid ion.The fine structure of the polymer of highly linear usually can be by being coordinated phosphine-
The palladium and Raney nickel of azochlorosulfonate acid ion obtains.On the other hand, the palladium and Raney nickel seeding height branch of alpha-diimine have been coordinated
The formation of the polymer of change.It reports among both important catalyst types, has been coordinated the catalyst of phosphine-azochlorosulfonate acid ion
Compared with the catalyst for being coordinated alpha-diimine, with vinyl acetate, acrylonitrile, vinyl chloride and vinyl ethers isopolarity second
Very high activity is shown in the copolymerization of alkenyl monomer.However, the transient metal complex of phosphine-azochlorosulfonate acid ion has been coordinated not reach yet
To practical requirement.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of chemical industry synthesis catalyst.
The invention is realized in this way a kind of preparation method of chemical industry synthesis catalyst, this approach includes the following steps：
（1）It is cooled to 0 ~ 2 after 30 ~ 40min is mixed in the double diphenylphosphine ethanes of 1 ~ 2 mass parts, 7 ~ 8 mass parts dry toluenes
DEG C, 3 ~ 4 mass parts triethylamines are added, 80 ~ 90 DEG C is slowly warming up to after stirring 30min, obtains ligand；
（2）In 150 ~ 180 DEG C, inert gas shielding, airtight vacuum environment, by 5 ~ 6 mass parts ligands and 2 ~ 3 mass parts 4- carboxylics
After base phenyl boric acid, 2 ~ 3 mass parts diphosphine monoxides stir evenly, it is rapidly added 1 ~ 2 mass parts chromium compound, reaction 30 ~
After 40min, gained filter residue is main active constituent after reacted constituent is filtered；
（3）By the main powdered active ingredient of 1 ~ 2 mass parts and 5 ~ 6 mass parts auxiliary agent powder, 10 ~ 12 mass parts support powders and
0.5 ~ 1 mass parts binder and 0.3 ~ 0.6 mass parts pore creating material mixed-forming, dry and roasting obtain the catalyst.
Preferably, in step（1）In, double diphenylphosphine ethanes, dry toluene, triethylamine mass ratio be 1 ︰, 8 ︰ 3.
Preferably, in step（2）In, ethyl alcohol is added in filtering in the reacted constituent.
Preferably, in step（2）In, the ligand, 4- Carboxybenzeneboronic acids, diphosphine monoxide, chromium compound quality
Than for 5 ︰, 2 ︰, 3 ︰ 1.
Preferably, in step（2）In, the chromium compound includes Cr2O3、CrO3、CrCl3。
Preferably, in step（3）In, it the main powdered active ingredient, auxiliary agent powder, support powder, binder and makes
The mass ratio of hole agent is 1 ︰, 5 ︰, 10 ︰, 0.8 ︰ 0.5.
Preferably, in step（3）In, the auxiliary agent includes the oxide of Fe, Cu, Ru, K, Zn；The carrier includes
SiO2、Al2O3；The binder includes moulding sand binder.
The present invention further discloses above-mentioned chemical industry synthesis catalyst.Chemical industry synthesis catalyst of the present invention can be preferably as
The catalyst for polymerization of vinyl monomer uses, additionally it is possible to the homopolymerization of nonpolar olefinic is used for, in addition, can be used as non-pole
The copolymerization of property alkene and polar olefin is used with catalyst.
Chemical industry synthesis catalyst of the present invention can be not required to discretely by reaction solution when preparing directly as catalyst group
Object is closed for polymerizeing.
Catalyst of the present invention can be used in the homopolymerization of nonpolar olefinic, as nonpolar olefinic, such as selected from ethylene, third
Alkene, 1- butylene, 2- butylene, isobutene, 1- amylenes, 1- hexenes, 1- heptene, 1- octenes, 1,5- hexadienes, 1,7- octadienes, ring
The alpha-olefins such as pentadiene, norbornadiene and combination thereof, preferred nonpolar olefinic can be ethylene.
Catalyst of the present invention can be used in the copolymerization of above-mentioned nonpolar olefinic and polar olefin, the polar olefin that can be used
For example, it is selected from vinyl formate, vinyl acetate, n Propanoic acid vinyl acetate, vinyl butyrate, vinyl isobutyrate ester, neopentanoic acid second
Enester, Versatic acid（A kind of alkanecarboxylic acid having branch）Vinyl acetate, 2 ethyl hexanoic acid vinyl acetate, vinyl benzoate,
The vinyl esters such as methylvinyl acetate；Vinyl chloride；Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, normal-butyl
The vinyl ethers such as vinyl ethers, isobutyl vinyl ether, tert-Butyl vinyl ether, Vinyl phenyl ether；Methyl acrylate, propylene
The acrylate such as acetoacetic ester, n-propyl, n-butyl acrylate, dodecylacrylate, phenyl acrylate, methyl-prop
E pioic acid methyl ester, ethyl methacrylate, n propyl methacrylate, n-BMA, lauryl base
The methacrylates such as ester, phenyl methacrylate；At least a kind in acrylonitrile etc..
In the present invention, polar olefin can be the allyl compound containing polar group.As containing polar group
Allyl compound example, can enumerate allyl acetate, trifluoroacetic acid allyl ester, allyl alcohol, allyl methyl ether,
Allyl ethyl ether, allyl n-propyl ether, allyl butyl ether, allyl tertbutyl ether, allyl phenyl ether, allyl
Chlorine, allyl bromide, bromoallylene, allyl amine, allylamine hydrochloride, N- allyls aniline, N- tert-butoxycarbonyl-N- allyl amines, N-
Benzyloxycarbonyl-N- allyl amines etc..
In addition, in the present invention, polar olefin can be vinyl ketone monomer.As vinyl ketone, for example,
15 carbene -3- ketone of 1-, 1- teracrylic acids -one, 1- decene -3- ketone, 3- butene-2s -one, 19 carbene -3- ketone of 1-, 1- octenes -3-
Ketone, 1- teracrylic acids -one, 1- hexene-3-ones, 1- penten-3-ones and 1- phenyl -2- propylene -1- ketone.
In the present invention, polar olefin can be N- vinyl monomers, as N- vinyl monomers, can be selected from N- second
Vinyl pyrrolidone, N- caprolactams, N- vinyl formamides；N- vinyl acetamides；N- vinyl O-phthalics
Acid imide；N- methylvinylacetamides；N- caprolactams；5- ethyl -5- methyl -3- vinyl hydantoins；N-
Vinyl pyrrolidone；5- methyl -5- phenyl -3- vinyl hydantoins；N- vinyl carbazoles；N, N- dimethyl allene acyl
Amine；And 5- pentamethylene -3- vinyl hydantoins etc..
In the present invention, polar olefin may be polarity norbornene-type monomers, vinyl phosphonic acid and its ester.
As the polar olefin in the present invention, more preferably vinyl acetate, vinyl benzoate, acrylonitrile, methyl second
Alkene ether, ethyl vinyl ether, butyl vinyl ether, allyl acetate, trifluoroacetic acid allyl ester, allyl alcohol, allyl first
Base ether, allyl ethyl ether, allyl n-propyl ether, allyl butyl ether, allyl tertbutyl ether, allyl phenyl ether,
Allyl chloride, allyl bromide, bromoallylene, allyl amine, allylamine hydrochloride, N- allyls aniline, N- tert-butoxycarbonyl-N- allyls
Base amine, N- benzyloxycarbonyl-N- allyl amines.
The nonpolar olefinic of the present invention can be warm in 20 DEG C~80 DEG C react with the autofrettage of the copolymer of polar olefin
Degree is lower to carry out.The pressure of polymerization changes according to catalyst component activity and nonpolar olefinic and the polar olefin of selection.Allusion quotation
Type, gas shape monomer, such as ethylene need high pressure.Polymerization pressure is the atmospheric pressure of 0.20 atmospheric pressure~100.In turn, this hair
Bright polar olefin monomer used is 20 ︰, 1~500000 ︰ 1 relative to the molar ratio of organometallic complex.About high pressure, spy
Be not certain high pressure, the gas shape monomer of such as 400psi or more, the nonpolar olefinic single phase used in the present invention for
The molar ratio of organometallic complex can be 5,000,000 1 or more ︰, such as 6,000,000 1 or less ︰, 8000000 ︰ 1 with
Under, or be further more than it.In the polymerization of the present invention, for the amount of diluent, with diluent relative to 1 mM
The present invention organometallic complex volume（mL）It indicates, is 0.0~10000.
Catalyst of the present invention can also be supported on carrier and be used to polymerize.Carrier in this case is not limited especially
It is fixed, organic carriers such as the inorganic carriers such as silica gel, aluminium oxide, polystyrene, polyethylene, polypropylene etc. can be enumerated.As metal
Complex supports method, and can enumerate makes the solution of metal complex infiltrate the physical absorption side in the carrier and being dried
Method, with making metal complex and support chemistry in conjunction with and the method etc. that supports.Polymerization is not particularly limited, may be used
Commonly used approach is polymerize.It can be with for Process such as solution polymerization process, suspension polymerization, gaseous polymerizations, especially
It is preferred that solution polymerization process, suspension polymerization.In addition, polymerization methods can be batch-type, or continous way.Furthermore it is possible to
A stage polymerization is carried out, multistage polymerization can also be carried out.
Polymerization time can suitably be adjusted according to technique pattern, polymerization activity etc., can be the short time of a few minutes,
It can also be thousands of hours long reaction time.About the atmosphere gas in polymerization system, the activity of catalyst reduces in order to prevent,
It is preferred that with other than polymerized monomer nitrogen and/or the inert gases such as argon be full of, be not mixed into air, oxygen, moisture etc..Separately
Outside, in the case of a solution polymerization, the atent solvent other than polymerized monomer can be used.Atent solvent is not limited especially
It is fixed, the aliphatic hydrocarbons such as pentane, hexane, heptane can be enumerated；The ester ring type hydrocarbons such as pentamethylene, hexamethylene, cycloheptane；Benzene, toluene, two
The aromatic hydrocarbons such as toluene；The halogenated aliphatics hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride, dichloroethanes, tetrachloroethanes；Chlorine
The halogenated aromatics hydrocarbon such as benzene, dichloro-benzenes, trichloro-benzenes；The aliphatic esters such as methyl acetate, ethyl acetate；Methyl benzoate, benzoic acid
The aromatic esters such as ethyl ester.
After polymerisation, as product（Altogether）Polymer passes through well known operation, processing method（In such as
It is distilled off with solvent extraction, washing, liquid separation, solvent, reprecipitation etc.）It is post-processed and is detached.
Compared with the prior art the shortcomings that and deficiency, the invention has the advantages that：Preparation method of the present invention is simple,
Catalyst can be applicable to the synthesis of polyolefins, and high catalytic efficiency can obtain the polymer of high linear polyethylene, and can obtain pole
The copolymer of property monomer random distribution in polymer chain.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
（1）2 DEG C are cooled to after 40min is mixed in the double diphenylphosphine ethanes of 2 mass parts, 8 mass parts dry toluenes, is added
4 mass parts triethylamines are slowly warming up to 90 DEG C after stirring 30min, obtain ligand；
（2）In 180 DEG C, inert gas shielding, airtight vacuum environment, by 6 mass parts ligands and 3 mass parts 4- carboxyl benzene boron
After acid, 3 mass parts diphosphine monoxides stir evenly, it is rapidly added 2 mass parts Cr2O3, after reacting 40min, by reacted constituent mistake
Gained filter residue is main active constituent after filter；
（3）By the main powdered active ingredient of 2 mass parts and 6 mass parts Fe2O3Auxiliary agent powder, 12 mass parts SiO2Powder and 1 mass
Part moulding sand binder and 0.6 mass parts pore creating material mixed-forming, dry and roasting obtain the catalyst 1.
Embodiment 2
（1）It is cooled to 0 DEG C after 30min is mixed in the double diphenylphosphine ethanes of 1 mass parts, 7 mass parts dry toluenes, is added
3 mass parts triethylamines are slowly warming up to 80 DEG C after stirring 30min, obtain ligand；
（2）In 150 DEG C, inert gas shielding, airtight vacuum environment, by 5 mass parts ligands and 2 mass parts 4- carboxyl benzene boron
After acid, 2 mass parts diphosphine monoxides stir evenly, it is rapidly added 1 mass parts CrO3, after reacting 30min, by reacted constituent mistake
Gained filter residue is main active constituent after filter；
（3）By the main powdered active ingredient of 1 mass parts and 5 mass parts CuO powder, 10 mass parts Al2O3Powder and 0.5 mass parts
Moulding sand binder and 0.3 mass parts pore creating material mixed-forming, dry and roasting obtain the catalyst 2.
Embodiment 3
（1）It is cooled to 0 DEG C after 35min is mixed in the double diphenylphosphine ethanes of 1 mass parts, 8 mass parts dry toluenes, is added
3 mass parts triethylamines are slowly warming up to 85 DEG C after stirring 30min, obtain ligand；
（2）In 160 DEG C, inert gas shielding, airtight vacuum environment, by 5 mass parts ligands and 2 mass parts 4- carboxyl benzene boron
After acid, 3 mass parts diphosphine monoxides stir evenly, it is rapidly added 1 mass parts CrCl3, after reacting 35min, by reacted constituent
Gained filter residue is main active constituent after filtering；Ethyl alcohol is added when filtering to be washed；
（3）By the main powdered active ingredient of 1 mass parts and 5 mass parts ZnO powders, 10 mass parts SiO2Powder and 0.8 mass parts
Moulding sand binder and 0.5 mass parts pore creating material mixed-forming, dry and roasting obtain the catalyst 3.
Effect example
It is measured using 500MHz NMR spectrometer with superconducting magnet1H NMR、13C-NMR and31P NMR、19F NMR.For in polymer
Polar monomer containing ratio and copolymer the degree of branching, be added Cr (acac)3（Acac=Acetylacetonate is levulinic
Ketonates）；CH3COCHCOCH3As moderator, use13C-NMR is quantitative.For molecular weight, will connect in size exclusion chromatography post
Meet TSKgel GMHHR-H（S）HT, after being estimated on the basis of polystyrene, by mark-Huo Wenke parameters and polystyrene（K=
1.75×10-2cm3/ g, α=0.67）, linear low density polyethylene (LDPE)（K=5.90×10-2cm3/ g, α=0.69）Using being repaiied
Just.High resolution mass spectrum（HRMS）Using electro-spray ionization time-of-flight method, surveyed using using polyethylene glycol as standard
It is fixed.
The catalyst that embodiment 1 obtains is dissolved in dichloromethane, catalyst（50mg）With（cod）PdMeCl（cod =
1,5- cyclo-octadiene 80mg, 0.30mmol）Dichloromethane（2mL）After solution mixes 5min at 25 DEG C, be added toluene and
Hexane obtains intermediate o- (Ph2P)C6H4(P(O)Ph2) PdMeCl complexs 175mg.By the solid and 2,6- diformazans
Yl pyridines（0.033mL, 0.28mmol）It is dissolved in 5mL dichloromethane, makes itself and silver hexafluoroantimonate（97mg, 0.28mmol）
10min is reacted at 25 DEG C.Pass through Celite（Celite, a kind of diatomaceous trade name）After being filtered to remove silver chlorate,
Solvent is distilled off, is dissolved in trifluoromethylbenzene, ether is added, collects the precipitation of generation and makes it dry, from dichloromethane
In recrystallized, the compound thus to obtain 175mg as the pale orange crystallization stablized in air and moisture, yield is
68%.The compound1H NMR（CD2Cl2, 500MHz）δ：7.76-7.70（M, 2H）, 7.61-7.29（M, 20H）, 7.24-
7.19（M, 5H）, 3.16（S, 6H）, 0.15（D, J=3.7Hz, 3H）；13C-NMR（CD 2Cl 2, 102MHz）δ 139.59,
136.73（Dd, J=64,10Hz）, 134.51（D, J=12Hz）, 134.05-133.76（m）, 132.60（D, J=
11Hz）, 132.01,131.45（D, J=12Hz）, 129.64-129.41（m）, 128.70,128.46,128.17,123.66
（D, J=9Hz）, 26.94, -0.84；31P NMR（CD2Cl2, 202MHz）δ40.42（D, J=17Hz）, 29.52（D, J=17Hz）
；19F NMR（CD2Cl2, 470MHz）δ-113.93-134.61（m）；HRMS-ESI（m/z）:[M]+Calc’d for
C38H36NOP2Pd：690.1307, Found：690.1313.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (7)
1. a kind of preparation method of chemical industry synthesis catalyst, which is characterized in that this approach includes the following steps：
（1）It is cooled to 0 ~ 2 after 30 ~ 40min is mixed in the double diphenylphosphine ethanes of 1 ~ 2 mass parts, 7 ~ 8 mass parts dry toluenes
DEG C, 3 ~ 4 mass parts triethylamines are added, 80 ~ 90 DEG C is slowly warming up to after stirring 30min, obtains ligand；
（2）In 150 ~ 180 DEG C, inert gas shielding, airtight vacuum environment, by 5 ~ 6 mass parts ligands and 2 ~ 3 mass parts 4- carboxylics
After base phenyl boric acid, 2 ~ 3 mass parts diphosphine monoxides stir evenly, it is rapidly added 1 ~ 2 mass parts chromium compound, reaction 30 ~
After 40min, gained filter residue is main active constituent after reacted constituent is filtered；
（3）By the main powdered active ingredient of 1 ~ 2 mass parts and 5 ~ 6 mass parts auxiliary agent powder, 10 ~ 12 mass parts support powders and
0.5 ~ 1 mass parts binder and 0.3 ~ 0.6 mass parts pore creating material mixed-forming, dry and roasting obtain the catalyst.
2. the preparation method of chemical industry synthesis catalyst as described in claim 1, which is characterized in that in step（1）In, it is described
Double diphenylphosphine ethanes, dry toluene, triethylamine mass ratio be 1 ︰, 8 ︰ 3.
3. the preparation method of chemical industry synthesis catalyst as claimed in claim 2, which is characterized in that in step（2）In, it is described
Ethyl alcohol is added in filtering in reacted constituent.
4. the preparation method of chemical industry synthesis catalyst as claimed in claim 3, which is characterized in that in step（2）In, it is described
Ligand, 4- Carboxybenzeneboronic acids, diphosphine monoxide, chromium compound mass ratio be 5 ︰, 2 ︰, 3 ︰ 1.
5. the preparation method of chemical industry synthesis catalyst as claimed in claim 4, which is characterized in that in step（2）In, it is described
Chromium compound includes Cr2O3、CrO3、CrCl3。
6. the preparation method of chemical industry synthesis catalyst as claimed in claim 5, which is characterized in that in step（3）In, it is described
Main powdered active ingredient, auxiliary agent powder, support powder, binder and pore creating material mass ratio be 1 ︰, 5 ︰, 10 ︰, 0.8 ︰ 0.5.
7. the preparation method of chemical industry synthesis catalyst as claimed in claim 6, which is characterized in that in step（3）In, it is described
Auxiliary agent includes the oxide of Fe, Cu, Ru, K, Zn；The carrier includes SiO2、Al2O3；The binder includes moulding sand binder.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501078A (en) * | 2006-08-15 | 2009-08-05 | 巴塞尔聚烯烃意大利有限责任公司 | Process for preparing catalyst components for the polymerization of olefins |
| CN102597016A (en) * | 2009-10-28 | 2012-07-18 | 埃克森美孚化学专利公司 | Catalyst compounds and use thereof |
| CN104271585A (en) * | 2012-05-11 | 2015-01-07 | 国立大学法人东京大学 | Catalyst for synthesizing polyolefins |
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2018
- 2018-03-14 CN CN201810211203.3A patent/CN108383932A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501078A (en) * | 2006-08-15 | 2009-08-05 | 巴塞尔聚烯烃意大利有限责任公司 | Process for preparing catalyst components for the polymerization of olefins |
| CN102597016A (en) * | 2009-10-28 | 2012-07-18 | 埃克森美孚化学专利公司 | Catalyst compounds and use thereof |
| CN104271585A (en) * | 2012-05-11 | 2015-01-07 | 国立大学法人东京大学 | Catalyst for synthesizing polyolefins |
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Application publication date: 20180810 |