CN109021009A - Salicylic alidehyde imine metal titanium complex, synthetic method and the application method that a kind of novel phenyl replaces - Google Patents
Salicylic alidehyde imine metal titanium complex, synthetic method and the application method that a kind of novel phenyl replaces Download PDFInfo
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- CN109021009A CN109021009A CN201810651264.1A CN201810651264A CN109021009A CN 109021009 A CN109021009 A CN 109021009A CN 201810651264 A CN201810651264 A CN 201810651264A CN 109021009 A CN109021009 A CN 109021009A
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/28—Titanium compounds
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
The present invention discloses salicylic alidehyde imine metal titanium complex, synthetic method and the application method that a kind of novel phenyl replaces.The salicylic alidehyde imine metal titanium complex H that novel phenyl prepared by the present invention replaces1~H5Not only there is superelevation homopolymerization catalytic activity (to be up to 10 respectively ethylene, methyl methacrylate monomer within the scope of 0 ~ 100 DEG C7 g·PE mol‑1 Ti·h‑1Above, 105 g·PMMA mol‑1 Ti·h‑1More than), and there is superelevation polymerization activity (up to 10 to the copolymerization of ethylene and methyl methacrylate4 g·EMMA mol‑1 Ti·h‑1More than), the molecular weight of gained polyethylene and polymethyl methacrylate is up to 300,000 or more, 1300 respectively, 000 or more, and the molecular weight that the copolymer of ethylene and methyl methacrylate is prepared is greater than 40,000, wherein the insertion rate of methyl methacrylate is greater than 65%.
Description
Technical field
The invention belongs to Nonmetallocene titanium complex catalyst technical fields.It is related to the salicylide that a kind of novel phenyl replaces
Imine metal titanium complex, synthetic method and application method.
Background technique
Polyolefin such as polyethylene, polypropylene are the very excellent polymeric materials of a kind of performance, but they have surface property
Insufficient defect.It is especially bad with the compatibility of the compatibility of polar material and functional material.Methyl methacrylate
The vinyl monomer of a kind of polar functionalities, the polyvinyls of the polar functionalities formed by this kind of monomer stickiness,
In terms of toughness, interfacial property (such as dyeability and printing) and other polymers compatibility, than traditional nonpolar polyethylene
Material has apparent advantage.Therefore, the copolymer for developing both ethylene and methyl methacrylate, becomes vinyl monomer
The hot spot of polymerization studies.
EMMA is ethylene-methylmethacrylate copolymer english abbreviation, than EMA in side chain on molecular structure
On mostly a methyl, be a kind of newer copolymer.The copolymer of vinyl is belonged to, EMMA has than traditional EEA and EVA
The advantage of many protrusions, than the performance of LDPE also it is superior very much.EMMA completely can and direct food contact, health peace
Full performance has already been through FDA certification and the health certification of Japanese health ministry.The heat of the prolonged EMMA under high temperature
Stability will be far superior to EVA.Even if dead angle present in process equipment or temporary localized hyperthermia all will not influence EMM A
Physical property, this to production film and electric wire factory it is particularly important.There is a large amount of methyl-prop in EMMA molecular side chain
E pioic acid methyl ester, these polar groups can make EMMA and PET or PA, and AL has good bonding force.In efficient packaging
On line, packaging linear velocity quickly, waits at all and carries out next process again after being adequately cooled less than closure part, at this time exist
Air expansive force (causing when the article of packaging heat) in gravity or bag can all produce to not yet cooling closure part is in
A raw tension, these active forces open the part just sealed so as to cause waste product.Thoroughly to overcome above-mentioned ask
Topic, it is necessary to which hot sealing layer has good thermal viscosity.I.e. material will still maintain this higher viscosity at high operating temperatures.EMMA
Since there is huge methyl methacrylate groups in its molecular side chain, even if material is in melting or the condition of high temperature
Under, these big groups can also be in and intertwine with each other state so that the melt strength of EMMA is very high, that is to say, that EMMA's
Thermal viscosity is splendid.EMMA with larger side chain not only still very high thermal viscosity at high temperature, but also there is good workability
EMMA be also able to satisfy the requirement of ultra-low temperature heat sealing.
Having reported in literature, (Zhang Danfeng, Zhang Yujun, analogy state is clever, waits salicylic alidehyde imine nickel complex as catalyst ethylene and methyl-prop
Copolyreaction [J] Chemical Journal of Chinese Universities of e pioic acid methyl ester, 2017,38 (11): 2082-2088.) it is taken in No. 3 of salicylide
The complex for subrogating the salicylide nickel for substituent groups such as hydrogen, methyl, propyl can be catalyzed being total to for ethylene and methyl methacrylate
It is poly-, but its catalytic polymerization activity is relatively low, and the molecular weight of copolymer being prepared is low, and the insertion rate of methyl methacrylate is small.And
And nickel metal has toxicity, so, the material application of the salicylide nickel complex as catalyst preparation of this kind of Nonmetallocene is limited.
The present invention utilizes Suzuki coupling reaction, uses bromo salicylide for main starting material, in salicylide main body
No. 3 substitution positions of structure or No. 5 the position of substitution or 3, No. 5 two the position of substitution introduce the phenyl ring with larger steric hindrance, obtain benzene
The salicylide that base replaces is condensed by schiff alkali with aniline or substituted aniline, obtains the salicylidene that series replaces containing phenyl
Imine ligand, then reacted under certain condition with metal titanium compound, obtain the bigcatkin willow of Novel series replaced containing phenyl
The stability of complex can be enhanced in aldimine titanium complex H, the introducing of phenyl ring, improves its catalysis containing vinyl
Monomer polymerization activity.The salicylic alidehyde imine metal titanium complex H that novel phenyl prepared by the present invention replaces1~H50~
Not only there is superelevation homopolymerization catalytic activity (to be up to 10 respectively ethylene, methyl methacrylate monomer within the scope of 100 DEG C7g·PE
mol-1Ti·h-1Above, 105g·PMMA mol-1Ti·h-1More than), and the copolymerization to ethylene and methyl methacrylate
With very high polymerization activity (up to 104g·EMMA mol-1Ti·h-1More than), gained ethylene and methyl methacrylate
The molecular weight of homopolymer is up to 300,000 or more, 1300 respectively, and 000 or more, and molecular weight has been prepared greater than 40,000
The copolymer EMMA of ethylene and methyl methacrylate.Therefore, using catalyst preparation polyethylene of the present invention, polymethylacrylic acid
When methyl esters, poly- (ethylene methyl methacrylate), the amount of catalyst required for unit polymer can be greatly reduced, and be urged
The unit consumption and cost of agent can greatly reduce, and the content of catalyst and co-catalyst in polymerizate can also be greatly
It reduces, can simplify many processes on later period polymer treatment, such as reduce polymer deliming (denitrating catalyst) process, drop
Low process costs greatly reduce the treating capacity of waste water.Resulting copolymer EMMA and nonpolar polyethylene, polypropylene etc. are poly-
Closing object material has good compatibility, also has with the vinyl polymeric materials of other polar functionalities good compatible
Property and compatibility.The polyvinyl EMMA of polar functionalities is in stickiness, toughness, interfacial property such as dyeability and printing etc.
Aspect has excellent performance, and processing, blending and modifying is blended in fluoropolymer resin and increases polymer material dyeability and print
Brush aspect of performance has apparent technical advantage and cost advantage, has a extensive future.
Summary of the invention
It is an object of the invention to propose the salicylic alidehyde imine metal titanium complex of a kind of novel phenyl substitution, synthetic method
And application method.
The salicylic alidehyde imine metal titanium complex that a kind of novel phenyl replaces, it is characterised in that the novel phenyl of one kind takes
The salicylic alidehyde imine metal titanium complex in generation is denoted as H, structural formula are as follows:
Wherein: R1、R2、R3And R4To be each independently selected from one of following substances: hydrogen, methyl, phenyl, isopropyl,
And R1、R2The two at least one be phenyl.
" → ", indicates coordinate bond
The synthetic method for the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces, it is characterised in that the conjunction
At comprising the concrete steps that for method:
Step 1: the synthesis of ligand L.
The structural formula of ligand L are as follows:
Wherein: R1、R2、R3And R4To be each independently selected from one of following substances: hydrogen, methyl, phenyl, isopropyl,
And R1、R2The two at least one be phenyl.
The synthesis of ligand L includes two stages: first stage is the synthesis of novel phenyl substituted salicylic aldehydes；Second rank
Section is that novel phenyl substituted salicylic aldehydes and aniline or substituted aniline are condensed through schiff alkali, obtains ligand L.
The synthesis of novel phenyl substituted salicylic aldehydes: vacuumizing logical nitrogen for the reaction flask of 100mL, after nitrogen is replaced 3 times,
It is separately added into the 3- bromosalicylaldehyde or 5- bromosalicylaldehyde or 3 of 10~20mmol under nitrogen protection, 5- Dibromosalicylaldehyde,
11~44mmol phenyl boric acid, 10~20mmol potassium carbonate, the tetrahydrofuran of 20~30mL and the mixed solvent (V of waterTetrahydrofuran: VWater=
5:1), 0.1~0.2mmol tetrakis triphenylphosphine palladium, after 50~80 DEG C of magnetic agitations react 1~2h, product separation, is done purifying
After dry, 3- phenyl salicylic aldehyde, 5- phenyl salicylic aldehyde, 3,5- diphenyl salicylide are respectively obtained.
Novel phenyl substituted salicylic aldehydes and aniline or substituted aniline are condensed through schiff alkali, obtain ligand L: by 10 mmol 3-
Phenyl salicylic aldehyde or 5- phenyl salicylic aldehyde or 3,5- diphenyl salicylide respectively with the aniline of 10~11mmol or substitution
Aniline is added in the tetrahydrofuran solvent of 50mL, the formic acid of 0.1~0.2mmol is added, magnetic agitation is anti-at 20~50 DEG C
After answering 1~2h, in -10~0 DEG C of cooling precipitation solid, filtering is refiltered, after filter residue is using about 5 DEG C of cold ethanol washings in ethyl alcohol
Middle recrystallization, about 5 DEG C of cold ethyl alcohol wash again/filter obtained solid and obtain ligand L after drying.
Step 2: the synthesis for the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces.
Ligand L described in 1.0~2.0mmol is dissolved in 50mL methylene chloride, at -30 DEG C and under good stirring condition, 1h
It is inside added dropwise by 0.5~1.0mmolTiCl4With the solution of 30mL methylene chloride composition, it is increased to 30~35 DEG C of magnetic agitations
2h is reacted, the triethylamine of 1.0~2.0mmol is then injected with syringe, continues to be stirred to react 2h at 30~35 DEG C, then concentration is anti-
It answers liquid to about 40mL, 30-50mL petroleum ether is added as filtering after precipitating reagent, filter residue is washed 3 times with the cold methylene chloride of 3 × 10mL
Afterwards, resulting solid recrystallizes in methylene chloride after filtering, refilters rear obtained solid and is dried to obtain a kind of novel phenyl and takes
The salicylic alidehyde imine metal titanium complex H in generation.
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
The application method for the salicylic alidehyde imine metal titanium complex that a kind of novel phenyl replaces, specific steps include:
(1) application method for the salicylic alidehyde imine metal titanium complex H catalysis ethylene homo that a kind of novel phenyl replaces.Its
It is characterized in that the specific steps difference of the application method is as follows:
250mL polymeric kettle is vacuumized into water removal deoxygenation, after nitrogen is sufficiently displaced from, then is passed through ethylene displacement nitrogen, and in second
The toluene solvant of 100mL is added under the protection of alkene, is passed through normal pressure ethylene gas to saturation is dissolved, one kind of 1~100 μm of ol is added
The co-catalyst methylaluminoxane of salicylic alidehyde imine metal titanium complex H and corresponding proportion that novel phenyl replaces, co-catalyst:
10~1000:1 of ratio of the amount of the substance for the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces, then proceedes to be passed through second
Alkene, and 0.5~1h of polymerization reaction under the conditions of 0~100 DEG C and 0.1~10MPa magnetic agitation, close the inlet valve of ethylene, will
Polymeric kettle is vented to normal pressure, stops reaction with the ethanol solution containing 10% hydrochloric acid.Material is released from polymeric kettle, is filtered, is obtained
To polymer crude product, successively it is dried in vacuo at 60 DEG C with ethyl alcohol with water washing, obtained solid is distilled, obtains polymeric articles
A。
(2) salicylic alidehyde imine metal titanium complex H Methyl Methacrylate Catalyzed homopolymerization that a kind of novel phenyl replaces
Application method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is passed through pure argon and is sufficiently displaced from air.Add
Enter the salicylic alidehyde imine metal titanium complex H that 10~100mmol methyl methacrylate and the novel phenyl of 1~100 μm of ol replace
With the co-catalyst methylaluminoxane of corresponding proportion, co-catalyst: the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces
Substance amount ratio 10~1000.In 0~100 DEG C of constant temperature oil bath after 0.5~1h of magnetic agitation polymerization reaction, addition contains
The ethanol solution of 10% hydrochloric acid terminates reaction.Then dehydrated alcohol precipitation polymers, filtering are used, then is washed with deionized.Institute
It obtains solid and is dried under vacuum to constant weight at 60 DEG C, obtain polymeric articles B.
(3) salicylic alidehyde imine metal titanium complex H catalysis ethylene and methyl methacrylate that a kind of novel phenyl replaces
Copolymerization application method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is set respectively with argon gas and ethylene after cooling
It changes, under ethylene protection, sequentially adds the salicylic alidehyde imine metal titanium complex H and 10 that the novel phenyl of 1~100 μm of ol replaces
~100mmol methyl methacrylate continues the ethylene gas usually pressed to full conjunction, co-catalyst methylaluminoxane is added, helps
Catalyst: the ratio of the amount of the substance for the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces is 10~1000:1.And it adjusts
Ethylene is to required 0.1~10MPa of pressure, and magnetic agitation reacts 0.5~1h at 0~100 DEG C, with the ethanol solution of 10% hydrochloric acid
Solution terminates reaction, and resulting polymers are filtered, are washed with dehydrated alcohol, and obtained solid is dried under vacuum to constant weight at 60 DEG C,
Obtain polymeric articles C.
Compared with prior art, the present invention having following obvious advantages:
The salicylic alidehyde imine Titanium that the present invention proposes that a kind of excellent novel phenyl of catalytic performance replaces is complex-catalyzed
Agent compares currently and has virose salicylide nickel metal complex, the salicylic alidehyde imine metal titanium complex that novel phenyl replaces
Catalyst is nontoxic, environmentally friendly.The salicylic alidehyde imine Titanium composition catalyst that novel phenyl replaces can not only be catalyzed ethylene, first
Base methyl acrylate polymerization, moreover it is possible to the copolymerization of both less amount of catalyst efficient catalytics.And prepare gained ethylene and methyl
The molecular weight of copolymer of methyl acrylate is high, methyl methacrylate insertion rate is high, therefore, using catalyst preparation of the present invention
When polyethylene, polymethyl methacrylate, polyethylene methacrylic acid methyl esters, the amount of catalyst required for unit polymer
It can greatly reduce, the unit consumption and cost of catalyst can greatly reduce, catalyst and co-catalyst in polymerizate
Content can also greatly reduce, can simplify many processes on later period polymer treatment, it is de- such as to reduce polymer
Grey (denitrating catalyst) process, reduces process costs, greatly reduces the treating capacity of waste water.Resulting copolymer gathers with nonpolar
The polymer materials such as ethylene, polypropylene have good compatibility, also with the vinyl polymeric materials of other polar functionalities
With good compatibility and compatibility.The polyolefine material of higher methyl methacrylate polar monomer insertion rate is glutinous
Property, toughness, interfacial property (such as dyeability and printing) etc. have apparent advantage compared with common polyolefine material,
It has a extensive future.
Detailed description of the invention
Fig. 1 is the ligand L of the embodiment of the present invention 11Mass spectrogram；
Fig. 2 is the ligand L of the embodiment of the present invention 11's1H NMR figure；
Fig. 3 is the complex H of the embodiment of the present invention 11's1H NMR figure；
Fig. 4 is the complex H of the embodiment of the present invention 11It is catalyzed ethylene and the GPC figure of methylmethacrylate copolymer C3.
Example is embodied
Below by specific implementation example, the invention will be further described, but it needs to be emphasized that the present invention is never only
The example for being only limitted to act listed below.In following cases:
Work as R1=phenyl, R2=R3=R4When=hydrogen, corresponding ligand L1, corresponding salicylaldehyde titanium complex is H1；
Work as R2=phenyl, R1=R3=R4When=hydrogen, corresponding ligand L2, corresponding salicylaldehyde titanium complex is H2；
Work as R1=R2=phenyl, R3=R4When=hydrogen, corresponding ligand L3, corresponding salicylaldehyde titanium complex is H3；
Work as R1=R2=phenyl, R3=R4When=methyl, corresponding ligand L4, corresponding salicylaldehyde titanium complex is
H4；
Work as R1=R2=phenyl, R3=R4When=isopropyl, corresponding ligand L5, corresponding salicylaldehyde titanium complex is
H5；
Example 1
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces1, synthetic method and application method.Described one
The salicylic alidehyde imine metal titanium complex H that the novel phenyl of class replaces1Structural formula are as follows:
Wherein " → " indicates coordinate bond.
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces1Synthetic method comprise the concrete steps that:
Step 1: ligand L1Synthesis.
Ligand L1Structural formula are as follows:
Ligand L1Synthesis include two stages: first stage be 3- phenyl salicylic aldehyde synthesis；Second stage is
The synthesis of 3- phenyl salicylic aldehyde and aniline condensation ligand.
The synthesis of 3- phenyl salicylic aldehyde: vacuumizing logical nitrogen for the reaction flask of 50mL, after nitrogen is replaced 3 times, protects in nitrogen
The lower 3- bromosalicylaldehyde that 10mmol is added of shield, 11mmol phenyl boric acid, 10mmol potassium carbonate, the tetrahydrofuran of 20mL and mixing for water
Bonding solvent (VTetrahydrofuran: VWater=5:1), 0.1mmol tetrakis triphenylphosphine palladium, after 75 DEG C of magnetic agitations react 1h, product separates, is pure
After changing, being dry, 3- phenyl salicylic aldehyde is obtained.
The synthesis of 3- phenyl salicylic aldehyde and aniline condensation ligand: by the 3- phenyl salicylic aldehyde of 10mmol and the benzene of 11mmol
Amine is added in 50mL tetrahydrofuran solvent, and the formic acid of 0.2mmol is added, and magnetic agitation reacts 2h at 20 DEG C, cold at -10 DEG C
But solid is precipitated, filters, filter residue is refiltered using after about 5 DEG C of cold ethanol washings, and recrystallization, about 5 DEG C of cold ethyl alcohol are again in ethanol
Washing, filtering obtain ligand L after dry1.Ligand L1The main fragment of mass spectrum are as follows: 273.33,237.22,226.27,
207.19,197.24,168.23,152.23,141.23,115.20,77.13,63.12.Ligand L1's1H NMR analyzes result
Are as follows:1H NMR(600MHz, CDCl3) δ 14.02 (s, 1H, ArOH), 8.64 (s, 1H, C (N) H), 7.62 (t, J=7.6Hz, 2H,
), Ar 7.56 (d, J=2.3Hz, 1H, Ar), 7.52 (d, J=2.3Hz, 1H, Ar), 7.49-7.42 (m, 5H, Ar), 7.39 (d,
J=7.4Hz, 1H, Ar), 7.32 (d, J=7.3Hz, 1H, Ar), 7.29 (d, J=8.0Hz, 2H, Ar).
Step 2: the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces1Synthesis.
By ligand L described in 1.0mmol1Be dissolved in 50mL methylene chloride, at -30 DEG C and under good stirring condition, in 1h by
It is added dropwise to by 0.5mmol TiCl4With the solution of 30mL methylene chloride composition, 35 DEG C of magnetic agitation reaction 2h are increased, needle is then used
Cylinder injects the triethylamine of 1.0mmol, continues magnetic agitation at 35 DEG C and reacts 2h, then concentration of reaction solution about 40mL, 30mL is added
Petroleum ether after precipitating reagent as filtering, and after filter residue washs 3 times with the cold methylene chloride of 3 × 10mL, resulting solid is in methylene chloride
Middle recrystallization filters, is dried to obtain the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces1。
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
Complex H1's1HNMR analyzes result are as follows:1HNMR(600MHz,CDCl3)8.64(s,1H, C(N)H),7.62(t,
J=7.6Hz, 2H, Ar), 7.56 (d, J=2.3Hz, 1H, Ar), 7.52 (d, J=2.3Hz, 1H, Ar), 7.49-7.42 (m,
5H, Ar), 7.39 (d, J=7.4Hz, 1H, Ar), 7.32 (d, J=7.3Hz, 1H, Ar), 7.29 (d, J=8.0Hz, 2H, Ar).
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces1Application method, specific steps include:
(1) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces1It is catalyzed the application method of ethylene homo.
It is characterized in that the specific steps difference of the application method is as follows:
250mL polymeric kettle is vacuumized into water removal deoxygenation, after nitrogen is sufficiently displaced from, then is passed through ethylene displacement nitrogen, and in second
The toluene solvant of 100mL is added under the protection of alkene, is passed through normal pressure ethylene gas to saturation is dissolved, one kind that 10 μm of ol are added is novel
The salicylic alidehyde imine metal titanium complex H that phenyl replaces1And the co-catalyst methylaluminoxane of corresponding proportion, co-catalyst: new
The salicylic alidehyde imine metal titanium complex H that type phenyl replaces1Substance amount ratio 100:1, then proceed to be passed through ethylene, and
Polymerization reaction 0.5h under the conditions of 30 DEG C and 3MPa and magnetic agitation, closes the inlet valve of ethylene, and polymeric kettle is vented to normal pressure, is used
Ethanol solution containing 10% hydrochloric acid stops reaction.Material is released from polymeric kettle, is filtered, is obtained polymer crude product, successively
With ethyl alcohol and distillation water washing, obtained solid is dried in vacuo at 60 DEG C, obtains polymeric articles A1.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces1Catalyzed ethylene polymerization activity is 2.1
×107g·PE mol-1Ti·h-1, obtaining polyethylene number-average molecular weight is 31.3 × 104。
(2) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces1Methyl Methacrylate Catalyzed homopolymerization
Application method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is passed through pure argon and is sufficiently displaced from air.Add
Enter the salicylic alidehyde imine metal titanium complex H that 23.4mmol methyl methacrylate and the novel phenyl of 20 μm of ol replace1With it is corresponding
The co-catalyst methylaluminoxane of ratio, co-catalyst: the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces1Object
The ratio 100:1 of the amount of matter.In 60 DEG C of constant temperature oil baths of magnetic agitation after polymerization reaction 2h, it is molten that the ethyl alcohol containing 10% hydrochloric acid is added
Liquid terminates reaction.Then dehydrated alcohol precipitation polymers, filtering are used, then is washed with deionized.Obtained solid is true at 60 DEG C
Sky is dry to constant weight, obtains polymeric articles B1.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces1Methyl Methacrylate Catalyzed polymerization
Activity is 1.14 × 105g·PMMA mol-1Ti·h-1, obtain polymethyl methacrylate number-average molecular weight be 140.5 ×
104。
(3) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces1It is catalyzed ethylene and methyl methacrylate
Copolymerization application method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is set respectively with argon gas and ethylene after cooling
It changes, under ethylene protection, sequentially adds the salicylic alidehyde imine metal titanium complex H that the novel phenyl of 50 μm of ol replaces1With
47mmol methyl methacrylate continues the ethylene gas usually pressed to full conjunction, co-catalyst methylaluminoxane, co-catalysis is added
Agent: the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces1Substance amount ratio be 150:1.And ethylene is adjusted to institute
Pressure 3MPa is needed, reacts 2h under 45 DEG C of magnetic agitations, reaction is terminated with the ethanol solution solution of 10% hydrochloric acid, gained is polymerize
Object filtering, is washed, obtained solid is dried under vacuum to constant weight at 60 DEG C, obtains polymeric articles C1 with dehydrated alcohol.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces1It is catalyzed ethylene and methyl methacrylate
Ester co-polymeric activity is 1.89 × 104g EMMA mol-1Ti·h-1, obtain ethylene and methylmethacrylate copolymer number be equal
Molecular weight is 4.37 × 104。
Example 2
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces2, synthetic method and application method.Described one
The salicylic alidehyde imine metal titanium complex H that the novel phenyl of class replaces2Structural formula are as follows:
Wherein " → " indicates coordinate bond.
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces2Synthetic method comprise the concrete steps that:
Step 1: ligand L2Synthesis.
Ligand L2Structural formula are as follows:
Ligand L2Synthesis include two stages: first stage be 5- phenyl salicylic aldehyde synthesis；Second stage is
The synthesis of 5- phenyl salicylic aldehyde and aniline condensation ligand.
The synthesis of 5- phenyl salicylic aldehyde: vacuumizing logical nitrogen for the reaction flask of 50mL, after nitrogen is replaced 3 times, protects in nitrogen
The lower 5- bromosalicylaldehyde that 10mmol is added of shield, 11mmol phenyl boric acid, 10mmol potassium carbonate, the tetrahydrofuran of 20mL and mixing for water
Bonding solvent (VTetrahydrofuran: VWater=5:1), 0.1mmol tetrakis triphenylphosphine palladium, after 75 DEG C of magnetic agitations react 1h, product separates, is pure
After changing, being dry, 5- phenyl salicylic aldehyde is obtained.
The synthesis of 5- phenyl salicylic aldehyde and aniline condensation ligand: by the 5- phenyl salicylic aldehyde of 10mmol and the benzene of 11mmol
Amine is added in 50mL tetrahydrofuran solvent, and the formic acid of 0.2mmol is added, and magnetic agitation reacts 2h at 20 DEG C, cold at -10 DEG C
But solid is precipitated, filters, filter residue is refiltered using after about 5 DEG C of cold ethanol washings, and recrystallization, about 5 DEG C of cold ethyl alcohol are again in ethanol
Washing, filtering obtain ligand L after dry2。
Step 2: the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces2Synthesis.
By ligand L described in 1.0mmol2Be dissolved in 50mL methylene chloride, at -30 DEG C and under good stirring condition, in 1h by
It is added dropwise to by 0.5mmol TiCl4With the solution of 30mL methylene chloride composition, 35 DEG C of magnetic agitation reaction 2h are increased, needle is then used
Cylinder injects the triethylamine of 1.0mmol, continues to stir 2h at 35 DEG C, then concentration of reaction solution about 40mL, and 30mL petroleum ether is added and makees
To filter after precipitating reagent, after filter residue washs 3 times with the cold methylene chloride of 3 × 10mL, resulting solid recrystallizes in methylene chloride,
It filters, be dried to obtain the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces2。
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces2Application method, specific steps include:
(1) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces2It is catalyzed the application method of ethylene homo.
It is characterized in that the specific steps difference of the application method is as follows:
250mL polymeric kettle is vacuumized into water removal deoxygenation, after nitrogen is sufficiently displaced from, then is passed through ethylene displacement nitrogen, and in second
The toluene solvant of 100mL is added under the protection of alkene, is passed through normal pressure ethylene gas to saturation is dissolved, one kind that 10 μm of ol are added is novel
The salicylic alidehyde imine metal titanium complex H that phenyl replaces2And the co-catalyst methylaluminoxane of corresponding proportion, co-catalyst: new
The salicylic alidehyde imine metal titanium complex H that type phenyl replaces2Substance amount ratio 100:1, then proceed to be passed through ethylene, and
Polymerization reaction 0.5h under the conditions of 30 DEG C and 3MPa and magnetic agitation, closes the inlet valve of ethylene, and polymeric kettle is vented to normal pressure, is used
Ethanol solution containing 10% hydrochloric acid stops reaction.Material is released from polymeric kettle, is filtered, is obtained polymer crude product, successively
With ethyl alcohol and distillation water washing, obtained solid is dried in vacuo at 60 DEG C, obtains polymeric articles A2.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces2Catalyzed ethylene polymerization activity is 1.7
×107g·PE mol-1Ti·h-1, obtaining polyethylene number-average molecular weight is 30.7 × 104。
(2) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces2Methyl Methacrylate Catalyzed homopolymerization
Application method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is passed through pure argon and is sufficiently displaced from air.Add
Enter the salicylic alidehyde imine metal titanium complex H that 23.4mmol methyl methacrylate and the novel phenyl of 20 μm of ol replace2With it is corresponding
The co-catalyst methylaluminoxane of ratio, co-catalyst: the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces2Object
The ratio 100:1 of the amount of matter.In 60 DEG C of constant temperature oil baths of magnetic agitation after polymerization reaction 2h, it is molten that the ethyl alcohol containing 10% hydrochloric acid is added
Liquid terminates reaction.Then dehydrated alcohol precipitation polymers, filtering are used, then is washed with deionized.Obtained solid is true at 60 DEG C
Sky is dry to constant weight, obtains polymeric articles B2.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces2Methyl Methacrylate Catalyzed polymerization
Activity is 1.05 × 105g·PMMA mol-1Ti·h-1, obtain polymethyl methacrylate number-average molecular weight be 130.7 ×
104。
(3) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces2It is catalyzed ethylene and methyl methacrylate
Copolymerization application method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is set respectively with argon gas and ethylene after cooling
It changes, under ethylene protection, sequentially adds the salicylic alidehyde imine metal titanium complex H that the novel phenyl of 50 μm of ol replaces2With
47mmol methyl methacrylate continues the ethylene gas usually pressed to full conjunction, co-catalyst methylaluminoxane, co-catalysis is added
Agent: the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces2Substance amount ratio be 150:1.And ethylene is adjusted to institute
It needs pressure 3MPa, reacts 2h under 45 DEG C and magnetic agitation, terminate reaction with the ethanol solution solution of 10% hydrochloric acid, gained is polymerize
Object filtering, is washed, obtained solid is dried under vacuum to constant weight at 60 DEG C, obtains polymeric articles C2 with dehydrated alcohol.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces2It is catalyzed ethylene and methyl methacrylate
Ester co-polymeric activity is 1.73 × 104g·EMMA mol-1Ti·h-1, obtain ethylene and methylmethacrylate copolymer number
Average molecular weight is 4.16 × 104。
Example 3
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces3, synthetic method and application method.Described one
The salicylic alidehyde imine metal titanium complex H that the novel phenyl of class replaces3Structural formula are as follows:
Wherein " → " indicates coordinate bond.
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces3Synthetic method comprise the concrete steps that:
Step 1: ligand L3Synthesis.
Ligand L3Structural formula are as follows:
Ligand L3Synthesis include two stages: first stage be 3,5- diphenyl salicylide synthesis；Second rank
Section is the synthesis of 3,5- diphenyl salicylide and aniline condensation ligand.
The synthesis of 3,5- diphenyl salicylides: the reaction flask of 50mL is vacuumized into logical nitrogen, after nitrogen is replaced 3 times, in nitrogen
3, the 5- Dibromosalicylaldehyde of 10mmol, 24mmol phenyl boric acid, 10mmol potassium carbonate, the tetrahydrofuran of 30mL are added under gas shielded
With the mixed solvent (V of waterTetrahydrofuran: VWater=5:1), 0.1mmol tetrakis triphenylphosphine palladium produces after 75 DEG C of magnetic agitations react 1h
After object separation, purifying, drying, 3,5- diphenyl salicylide is obtained.
The synthesis of 3,5- diphenyl salicylide and aniline condensation ligand: by the 3,5- diphenyl salicylide of 10mmol and
The aniline of 11mmol is added in 50mL tetrahydrofuran solvent, and the formic acid of 0.2mmol is added, and magnetic agitation is reacted at 20 DEG C
2h, in -10 DEG C of cooling precipitation solids, filtering refilters after filter residue is using about 5 DEG C of cold ethanol washings, recrystallize in ethanol,
About 5 DEG C of cold ethyl alcohol wash again, and filtering obtains ligand L after dry3。
Step 2: the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces3Synthesis.
By ligand L described in 1.0mmol3Be dissolved in 50mL methylene chloride, at -30 DEG C and under good stirring condition, in 1h by
It is added dropwise to by 0.5mmol TiCl4With the solution of 30mL methylene chloride composition, 35 DEG C of magnetic agitation reaction 2h are increased, needle is then used
Cylinder injects the triethylamine of 1.0mmol, continues to stir 2h at 35 DEG C, then concentration of reaction solution about 40mL, and 30mL petroleum ether is added and makees
To filter after precipitating reagent, after filter residue washs 3 times with the cold methylene chloride of 3 × 10mL, resulting solid recrystallizes in methylene chloride,
It filters, be dried to obtain the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces3。
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces3Application method, specific steps include:
(1) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces3It is catalyzed the application method of ethylene homo.
It is characterized in that the specific steps difference of the application method is as follows:
250mL polymeric kettle is vacuumized into water removal deoxygenation, after nitrogen is sufficiently displaced from, then is passed through ethylene displacement nitrogen, and in second
The toluene solvant of 100mL is added under the protection of alkene, is passed through normal pressure ethylene gas to saturation is dissolved, one kind that 10 μm of ol are added is novel
The salicylic alidehyde imine metal titanium complex H that phenyl replaces3And the co-catalyst methylaluminoxane of corresponding proportion, co-catalyst: new
The salicylic alidehyde imine metal titanium complex H that type phenyl replaces3Substance amount ratio 100:1, then proceed to be passed through ethylene, and
Polymerization reaction 0.5h under the conditions of 30 DEG C and 3MPa and magnetic agitation, closes the inlet valve of ethylene, and polymeric kettle is vented to normal pressure, is used
Ethanol solution containing 10% hydrochloric acid stops reaction.Material is released from polymeric kettle, is filtered, is obtained polymer crude product, successively
With ethyl alcohol and distillation water washing, obtained solid is dried in vacuo at 60 DEG C, obtains polymeric articles A3.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces3Catalyzed ethylene polymerization activity is 2.8
×107g·PE mol-1Ti·h-1, obtaining polyethylene number-average molecular weight is 33.6 × 104。
(2) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces3Methyl Methacrylate Catalyzed homopolymerization
Application method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is passed through pure argon and is sufficiently displaced from air.Add
Enter the salicylic alidehyde imine metal titanium complex H that 23.4mmol methyl methacrylate and the novel phenyl of 20 μm of ol replace3With it is corresponding
The co-catalyst methylaluminoxane of ratio, co-catalyst: the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces3Object
The ratio 100:1 of the amount of matter.In 60 DEG C of constant temperature oil baths of magnetic agitation after polymerization reaction 2h, it is molten that the ethyl alcohol containing 10% hydrochloric acid is added
Liquid terminates reaction.Then dehydrated alcohol precipitation polymers, filtering are used, then is washed with deionized.Obtained solid is true at 60 DEG C
Sky is dry to constant weight, obtains polymeric articles B3.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces3Methyl Methacrylate Catalyzed polymerization
Activity is 1.28 × 105g·PMMA mol-1Ti·h-1, obtain polymethyl methacrylate number-average molecular weight be 155.4 ×
104。
(3) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces3It is catalyzed ethylene and methyl methacrylate
Copolymerization application method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is set respectively with argon gas and ethylene after cooling
It changes, under ethylene protection, sequentially adds the salicylic alidehyde imine metal titanium complex H that the novel phenyl of 50 μm of ol replaces3With
47mmol methyl methacrylate continues the ethylene gas usually pressed to full conjunction, co-catalyst methylaluminoxane, co-catalysis is added
Agent: the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces3Substance amount ratio be 150:1.And ethylene is adjusted to institute
It needs pressure 3MPa, reacts 2h under 45 DEG C and magnetic agitation, terminate reaction with the ethanol solution solution of 10% hydrochloric acid, gained is polymerize
Object filtering, is washed, obtained solid is dried under vacuum to constant weight at 60 DEG C, obtains polymeric articles C3 with dehydrated alcohol.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces3It is catalyzed ethylene and methyl methacrylate
Ester co-polymeric activity is 2.57 × 104g EMMA mol-1Ti·h-1, obtain ethylene and methylmethacrylate copolymer number be equal
Molecular weight is 5.67 × 104。
Example 4
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces4, synthetic method and application method.Described one
The salicylic alidehyde imine metal titanium complex H that the novel phenyl of class replaces4Structural formula are as follows:
Wherein " → " indicates coordinate bond.
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces4Synthetic method comprise the concrete steps that:
Step 1: ligand L4Synthesis.
Ligand L4Structural formula are as follows:
Ligand L4Synthesis include two stages: first stage be 3,5- diphenyl salicylide synthesis；Second rank
Section is 3,5- diphenyl salicylide and 2, and 6- dimethylaniline is condensed the synthesis of ligand.
The synthesis of 3,5- diphenyl salicylide: see embodiment 3.
3,5- diphenyl salicylides and 2,6- dimethylaniline are condensed the synthesis of ligand: by 3, the 5- diphenyl of 10mmol
2, the 6- dimethylaniline of salicylide and 11mmol are added in 50mL tetrahydrofuran solvent, and the formic acid conduct of 0.15mmol is added
The catalyst of condensation reaction is stirred to react 2h at 20 DEG C, and in -10 DEG C of cooling precipitation solids, filtering, filter residue is cold using about 5 DEG C
It after ethanol washing, refilters, recrystallization, about 5 DEG C of cold ethyl alcohol wash again in ethanol, filter, and obtain ligand L after dry4。
Step 2: the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces4Synthesis.
By ligand L described in 1.0mmol4Be dissolved in 50mL methylene chloride, at -30 DEG C and under good stirring condition, in 1h by
It is added dropwise to by 0.5mmol TiCl4With the solution of 30mL methylene chloride composition, 35 DEG C of magnetic agitation reaction 2h are increased, needle is then used
Cylinder injects the triethylamine of 1.0mmol, continues to stir 2h at 35 DEG C, then concentration of reaction solution about 40mL, and 30mL petroleum ether is added and makees
To filter after precipitating reagent, after filter residue washs 3 times with the cold methylene chloride of 3 × 10mL, resulting solid recrystallizes in methylene chloride,
It filters, be dried to obtain the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces4。
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces4Application method, specific steps include:
(1) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces4It is catalyzed the application method of ethylene homo.
It is characterized in that the specific steps difference of the application method is as follows:
250mL polymeric kettle is vacuumized into water removal deoxygenation, after nitrogen is sufficiently displaced from, then is passed through ethylene displacement nitrogen, and in second
The toluene solvant of 100mL is added under the protection of alkene, is passed through normal pressure ethylene gas to saturation is dissolved, one kind that 10 μm of ol are added is novel
The salicylic alidehyde imine metal titanium complex H that phenyl replaces4And the co-catalyst methylaluminoxane of corresponding proportion, co-catalyst: new
The salicylic alidehyde imine metal titanium complex H that type phenyl replaces4Substance amount ratio 100:1, then proceed to be passed through ethylene, and
Polymerization reaction 0.5h under the conditions of 30 DEG C and 3MPa and magnetic agitation, closes the inlet valve of ethylene, and polymeric kettle is vented to normal pressure, is used
Ethanol solution containing 10% hydrochloric acid stops reaction.Material is released from polymeric kettle, is filtered, is obtained polymer crude product, successively
With ethyl alcohol and distillation water washing, obtained solid is dried in vacuo at 60 DEG C, obtains polymeric articles A4.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces4Catalyzed ethylene polymerization activity is 3.3
×107g·PE mol-1Ti·h-1, obtaining polyethylene number-average molecular weight is 36.8 × 104。
(2) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces4Methyl Methacrylate Catalyzed homopolymerization
Application method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is passed through pure argon and is sufficiently displaced from air.Add
Enter the salicylic alidehyde imine metal titanium complex H that 23.4mmol methyl methacrylate and the novel phenyl of 20 μm of ol replace4With it is corresponding
The co-catalyst methylaluminoxane of ratio, co-catalyst: the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces4Object
The ratio 100:1 of the amount of matter.In 60 DEG C of constant temperature oil baths of magnetic agitation after polymerization reaction 2h, it is molten that the ethyl alcohol containing 10% hydrochloric acid is added
Liquid terminates reaction.Then dehydrated alcohol precipitation polymers, filtering are used, then is washed with deionized.Obtained solid is true at 60 DEG C
Sky is dry to constant weight, obtains polymeric articles B4.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces4Methyl Methacrylate Catalyzed polymerization
Activity is 1.36 × 105g·PMMA mol-1Ti·h-1, obtain polymethyl methacrylate number-average molecular weight be 170.6 ×
104。
(3) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces4It is catalyzed ethylene and methyl methacrylate
Copolymerization application method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is set respectively with argon gas and ethylene after cooling
It changes, under ethylene protection, sequentially adds the salicylic alidehyde imine metal titanium complex H that the novel phenyl of 50 μm of ol replaces4With
47mmol methyl methacrylate continues the ethylene gas usually pressed to full conjunction, co-catalyst methylaluminoxane, co-catalysis is added
Agent: the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces4Substance amount ratio be 150:1.And ethylene is adjusted to institute
It needs pressure 3MPa, reacts 2h under 45 DEG C and magnetic agitation, terminate reaction with the ethanol solution solution of 10% hydrochloric acid, gained is polymerize
Object filtering, is washed, obtained solid is dried under vacuum to constant weight at 60 DEG C, obtains polymeric articles C4 with dehydrated alcohol.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces4It is catalyzed ethylene and methyl methacrylate
Ester co-polymeric activity is 2.91 × 104g EMMA mol-1Ti·h-1, obtain ethylene and methylmethacrylate copolymer number be equal
Molecular weight is 5.88 × 104。
Example 5
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces5, synthetic method and application method.Described one
The salicylic alidehyde imine metal titanium complex H that the novel phenyl of class replaces5Structural formula are as follows:
Wherein " → " indicates coordinate bond.
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces5Synthetic method comprise the concrete steps that:
Step 1: ligand L5Synthesis.
Ligand L5Structural formula are as follows:
Ligand L5Synthesis include two stages: first stage be 3,5- diphenyl salicylide synthesis；Second rank
Section is 3,5- diphenyl salicylide and 2, the synthesis of 6- diisopropyl base aniline condensation ligand.
The synthesis of 3,5- diphenyl salicylide: see embodiment 3.
The synthesis of 3,5- diphenyl salicylides and 2,6-DIPA condensation ligand: by 3, the 5- hexichol of 10mmol
The 2,6-DIPA of base salicylide and 11mmol are added in 50mL tetrahydrofuran solvent, are then added 0.15mmol's
Catalyst of the formic acid as condensation reaction, magnetic agitation reacts 2h at 20 DEG C, in -10 DEG C of cooling precipitation solids, filtering, filter residue
It after about 5 DEG C of cold ethanol washings, refilters, recrystallization, about 5 DEG C of cold ethyl alcohol wash again in ethanol, filter, and obtain after dry
Ligand L5。
Step 2: the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces5Synthesis.
By ligand L described in 1.0mmol5Be dissolved in 50mL methylene chloride, at -30 DEG C and under good stirring condition, in 1h by
It is added dropwise to by 0.5mmol TiCl4With the solution of 30mL methylene chloride composition, 35 DEG C of magnetic agitation reaction 2h are increased, needle is then used
Cylinder injects the triethylamine of 1.0mmol, continues to stir 2h at 35 DEG C, then concentration of reaction solution about 40mL, and 30mL petroleum ether is added and makees
To filter after precipitating reagent, after filter residue washs 3 times with the cold methylene chloride of 3 × 10mL, resulting solid recrystallizes in methylene chloride,
It filters, be dried to obtain the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces5。
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
The salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces5Application method, specific steps include:
(1) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces5It is catalyzed the application method of ethylene homo.
It is characterized in that the specific steps difference of the application method is as follows:
250mL polymeric kettle is vacuumized into water removal deoxygenation, after nitrogen is sufficiently displaced from, then is passed through ethylene displacement nitrogen, and in second
The toluene solvant of 100mL is added under the protection of alkene, is passed through normal pressure ethylene gas to saturation is dissolved, one kind that 10 μm of ol are added is novel
The salicylic alidehyde imine metal titanium complex H that phenyl replaces5And the co-catalyst methylaluminoxane of corresponding proportion, co-catalyst: new
The salicylic alidehyde imine metal titanium complex H that type phenyl replaces5Substance amount ratio 100:1, then proceed to be passed through ethylene, and
Polymerization reaction 0.5h under the conditions of 30 DEG C and 3MPa and magnetic agitation, closes the inlet valve of ethylene, and polymeric kettle is vented to normal pressure, is used
Ethanol solution containing 10% hydrochloric acid stops reaction.Material is released from polymeric kettle, is filtered, is obtained polymer crude product, successively
With ethyl alcohol and distillation water washing, obtained solid is dried in vacuo at 60 DEG C, obtains polymeric articles A5.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces4Catalyzed ethylene polymerization activity is 3.5
×107g·PE mol-1Ti·h-1, obtaining polyethylene number-average molecular weight is 44.2 × 104。
(2) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces5Methyl Methacrylate Catalyzed homopolymerization
Application method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is passed through pure argon and is sufficiently displaced from air.Add
Enter the salicylic alidehyde imine metal titanium complex H that 23.4mmol methyl methacrylate and the novel phenyl of 20 μm of ol replace5With it is corresponding
The co-catalyst methylaluminoxane of ratio, co-catalyst: the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces5Object
The ratio 100:1 of the amount of matter.In 60 DEG C of constant temperature oil baths of magnetic agitation after polymerization reaction 2h, it is molten that the ethyl alcohol containing 10% hydrochloric acid is added
Liquid terminates reaction.Then dehydrated alcohol precipitation polymers, filtering are used, then is washed with deionized.Obtained solid is true at 60 DEG C
Sky is dry to constant weight, obtains polymeric articles B5.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces5Methyl Methacrylate Catalyzed polymerization
Activity is 1.89 × 105g·PMMA mol-1Ti·h-1, obtain polymethyl methacrylate number-average molecular weight be 178.7 ×
104。
(3) the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces5It is catalyzed ethylene and methyl methacrylate
Copolymerization application method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is set respectively with argon gas and ethylene after cooling
It changes, under ethylene protection, sequentially adds the salicylic alidehyde imine metal titanium complex H that the novel phenyl of 50 μm of ol replaces5With
47mmol methyl methacrylate continues the ethylene gas usually pressed to full conjunction, co-catalyst methylaluminoxane, co-catalysis is added
Agent: the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces5Substance amount ratio be 150:1.And ethylene is adjusted to institute
It needs pressure 3MPa, reacts 2h under 45 DEG C and magnetic agitation, terminate reaction with the ethanol solution solution of 10% hydrochloric acid, gained is polymerize
Object filtering, is washed, obtained solid is dried under vacuum to constant weight at 60 DEG C, obtains polymeric articles C5 with dehydrated alcohol.
Calculate the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces5It is catalyzed ethylene and methyl methacrylate
Ester co-polymeric activity is 3.34 × 104g EMMA mol-1Ti·h-1, obtain ethylene and methylmethacrylate copolymer number be equal
Molecular weight is 6.41 × 104。
Examples of implementation 1~5 and the comparison of comparative example 6~8 are as shown in table 1.
1 catalytic polymerization result of table and the comparison with document
Comparative example 6 derives from: Liu Guomin, Sun Yue, Wang Xiaoling, wait salicylic alidehyde imine class nickel system complex synthesis and its
Catalyzed ethylene polymerization [J] East China University of Science journal, 2011,37 (3): 293-298.
Comparative example 7 derives from: Lu J, Zhang D, Chen Q, et al.Polymerization ofmethyl
methacrylate catalyzed by mono-/bis-salicylaldiminato nickel(II)complexes
andmethylaluminoxane[J].Frontiers of Chemical Science&Engineering,2011,5(1):
19-25.
Comparative example 8 derives from: Zhang Danfeng, Zhang Yujun, and analogy state is clever, waits salicylic alidehyde imine nickel complex as catalyst ethylene and first
Copolyreaction [J] Chemical Journal of Chinese Universities of base methyl acrylate, 2017,38 (11): 2082-2088.
Al/cat: refer to the ratio of the amount of the substance of co-catalyst and major catalyst.
Mn: refer to the number-average molecular weight of catalysate.
Catalyst D, E, F structural formula is as follows:
D:
E:
F:
Example 1~5 and comparative example comparison are it is found that in No. 3 substitution positions of salicylide or No. 5 substitution positions or No. 3 and 5 from table 1
Number position is replaced to introduce the phenyl ring of larger steric group, than being the smaller steric hindrances such as hydrogen, methyl, propyl in No. 3 substitutions positions of salicylide
The salicylide nickel complex as catalyst activity of substituent group to be whether catalyzed ethylene and methyl methacrylate homopolymerization, still greatly
Both catalysis copolymerization, the former can obtain the polymerizate of higher molecular weight.Product C1~C5 of comparison example 1~5 and comparison
Example 8 is it is found that salicylaldehyde titanium complex provided by the invention catalysis ethylene and methyl methacrylate copolymer, methacrylic acid
Methyl esters insertion rate is bigger.
In conclusion the present invention is with 3- bromosalicylaldehyde cheap and easy to get, 5- bromosalicylaldehyde and 3,5- Dibromosalicylaldehyde
Beginning raw material introduces benzene in No. 3 substitution positions of salicylide or No. 5 substitution positions or No. 3 and No. 5 substitution positions using Suzuki coupling reaction
Cyclosubstituted salicylide, then with aniline or substituted aniline by schiff alkali to be condensed to yield a kind of salicylic alidehyde imine that phenyl replaces new
Type ligand, and reacted with the chloride of transition metals Ti, a kind of salicylic alidehyde imine metal that novel phenyl replaces has successfully been obtained
Titanium complex, the complex with efficient catalytic ethylene, methyl methacrylate and its can mix under the co-catalysis of methylaluminoxane
It closes monomer and polymerization reaction occurs, obtain homopolymerization and the copolymerization product of high molecular weight.It compares currently and has virose salicylide nickel gold
Metal complex, the salicylic alidehyde imine Titanium composition catalyst that novel phenyl replaces are nontoxic, environmentally friendly.The water that novel phenyl replaces
Poplar aldimine Titanium composition catalyst can not only be catalyzed ethylene, methyl methacrylate polymerization, moreover it is possible to less amount of
The copolymerization of both catalyst efficient catalytics.And the molecular weight of copolymer of preparation gained ethylene and methyl methacrylate is high, methyl
The insertion rate of methyl acrylate is high, therefore, using catalyst preparation polyethylene of the present invention, polymethyl methacrylate, poly- (second
Alkene-methyl methacrylate) when, the amount of catalyst required for unit polymer can greatly reduce, the unit consumption of catalyst
It can be greatly reduced with cost, the content of catalyst and co-catalyst in polymerizate can also greatly reduce, the later period
Can simplify many processes on polymer treatment, such as reduce polymer deliming (denitrating catalyst) process, reduce technique at
This, greatly reduces the treating capacity of waste water.This greatly improves resulting polymer and other contain nonpolar vinyl polymerization
The compatibility of the vinyl polymeric materials of object or polar functionalities also increases non-with polyethylene, polypropylene, polyvinyl chloride etc.
Functional material and compatibility with polyester, the functional material of other polar functionalities.Higher methyl methacrylate polarity
The polyolefine material of monomer insertion rate stickiness, toughness, interfacial property (such as dyeability and in terms of printing with common polyene
Hydrocarbon material is compared, and is had apparent advantage, is had a extensive future.
Although preferred embodiments of the present invention have been described, it is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications may be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various modification and variations without departing from the spirit and scope of the present invention.If in this way, these modifications and changes of the present invention
Within the scope of the claims of the present invention and its equivalent technology, then the present invention is also intended to encompass these modification and variations and exists
It is interior.
Claims (6)
1. the salicylic alidehyde imine metal titanium complex that a kind of novel phenyl replaces, it is characterised in that the novel phenyl of one kind replaces
Salicylic alidehyde imine metal titanium complex be denoted as H, structural formula are as follows:
Wherein: R1、R2、R3And R4To be each independently selected from one of following substances: hydrogen, methyl, phenyl, isopropyl, and R1、
R2The two at least one be phenyl.
" → ", indicates coordinate bond.
2. the synthetic method for the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces, it is characterised in that the synthesis
Method comprises the concrete steps that:
Step 1: the synthesis of ligand L.
The structural formula of ligand L are as follows:
Wherein: R1、R2、R3And R4To be each independently selected from one of following substances: hydrogen, methyl, phenyl, isopropyl, and R1、
R2The two at least one be phenyl.
The synthesis of ligand L includes two stages: first stage is the synthesis of novel phenyl substituted salicylic aldehydes；Second stage is
Novel phenyl substituted salicylic aldehydes and aniline or substituted aniline are condensed through schiff alkali, obtain ligand L.
The synthesis of novel phenyl substituted salicylic aldehydes: the reaction flask of 100mL is vacuumized into logical nitrogen, after nitrogen is replaced 3 times, in nitrogen
Protection under be added 10~20mmol 3- bromosalicylaldehyde or 5- bromosalicylaldehyde or 3,5- Dibromosalicylaldehyde, 11~44mmol
Phenyl boric acid, 10~20mmol potassium carbonate, the tetrahydrofuran of 20~30mL and the mixed solvent (V of waterTetrahydrofuran: VWater=5:1), 0.11
~0.2mmol tetrakis triphenylphosphine palladium, after 50~80 DEG C of 1~2h of magnetic agitation back flow reaction, product separation, purifying, drying
Afterwards, 3- phenyl salicylic aldehyde, 5- phenyl salicylic aldehyde, 3,5- diphenyl salicylide are respectively obtained.
Novel phenyl substituted salicylic aldehydes and aniline or substituted aniline are condensed through schiff alkali, obtain ligand L: by the 3- phenyl of 10mmol
Salicylide or 5- phenyl salicylic aldehyde or 3,5- diphenyl salicylide respectively with the aniline of 10~11mmol or substituted aniline
It is added in the tetrahydrofuran solvent of 50mL, the formic acid of 0.1~0.2mmol of addition is as catalyst, the magnetic force at 20~50 DEG C
After being stirred to react 1~2h, in -10~0 DEG C of cooling precipitation solid, filtering refilters after filter residue is using about 5 DEG C of cold ethanol washings,
Ligand L is obtained after recrystallization, about 5 DEG C of cold ethyl alcohol are washed again, filtered in ethanol, solid is dry.
Step 2: the synthesis for the salicylic alidehyde imine metal titanium complex H that a kind of novel phenyl replaces.
Ligand L described in 1.0~2.0mmol is dissolved in 50mL methylene chloride, at -30 DEG C and under good stirring condition, in 1h by
It is added dropwise to by 0.5~1.0mmolTiCl4With the solution of 30mL methylene chloride composition, it is increased to 30~35 DEG C of magnetic agitation reactions
Then 2h injects the triethylamine of 1.0~2.0mmol with syringe, continues to be stirred to react 2h at 30~35 DEG C, then concentration of reaction solution
To about 40mL, 30-50mL petroleum ether is added as filtering after precipitating reagent, after filter residue washs 3 times with the cold methylene chloride of 3 × 10mL,
Resulting solid recrystallizes in methylene chloride, filters, is dried to obtain the salicylic alidehyde imine Titanium that a kind of novel phenyl replaces
Complex H.
Step 2 is carried out under the conditions of anhydrous and oxygen-free.
3. the synthetic method for the salicylic alidehyde imine metal titanium complex H that the novel phenyl of one kind described in claim 2 replaces, wherein taking
It is 2,6- dimethylaniline or 2,6- diisopropyl aniline for aniline.
4. the application method for the salicylic alidehyde imine metal titanium complex H catalysis ethylene homo that a kind of novel phenyl replaces.Its feature
It is that the specific steps difference of the application method is as follows:
250mL polymeric kettle is vacuumized into water removal deoxygenation, after nitrogen is sufficiently displaced from, then is passed through ethylene displacement nitrogen, and in ethylene
The lower toluene solvant that 100mL is added of protection, is passed through normal pressure ethylene gas to saturation is dissolved, one kind that 1 ~ 100 μm of ol is added is novel
The co-catalyst methylaluminoxane of salicylic alidehyde imine metal titanium complex H and corresponding proportion that phenyl replaces, co-catalyst: novel
10 ~ 1000:1 of ratio of the amount of the substance for the salicylic alidehyde imine metal titanium complex H that phenyl replaces, then proceedes to be passed through ethylene, and
0.5 ~ 1h of polymerization reaction under the conditions of 0 ~ 100 DEG C and 0.1 ~ 10MPa and magnetic agitation, closes the inlet valve of ethylene, by polymeric kettle
Emptying stops reaction with the ethanol solution containing 10% hydrochloric acid to normal pressure.Material is released from polymeric kettle, is filtered, is obtained polymer
Crude product is successively dried in vacuo at 60 DEG C with water washing, obtained solid is distilled with ethyl alcohol, obtains polymeric articles A.
5. the user for the salicylic alidehyde imine metal titanium complex H Methyl Methacrylate Catalyzed homopolymerization that a kind of novel phenyl replaces
Method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is passed through pure argon and is sufficiently displaced from air.It is added 10
The salicylic alidehyde imine metal titanium complex H and phase that ~ 100 mmol methyl methacrylates and the novel phenyl of 1 ~ 100 μm of ol replace
The co-catalyst methylaluminoxane of ratio is answered, co-catalyst: the object for the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces
10 ~ 1000:1 of ratio of the amount of matter.In 0 ~ 100 DEG C of constant temperature oil bath after 0.5 ~ 1h of magnetic agitation polymerization reaction, it is added and contains 10% hydrochloric acid
Ethanol solution, terminate reaction.Then dehydrated alcohol precipitation polymers, filtering are used, then is washed with deionized.Obtained solid exists
It is dried under vacuum to constant weight at 60 DEG C, obtains polymeric articles B.
6. the copolymerization of salicylic alidehyde imine metal titanium complex H catalysis ethylene and methyl methacrylate that a kind of novel phenyl replaces
Application method.It is characterized in that the specific steps difference of the application method is as follows:
By the heating of 250mL stainless steel polymeric kettle and vacuum drying removes water deoxygenation, is replaced respectively with argon gas and ethylene after cooling,
Under ethylene protection, the salicylic alidehyde imine metal titanium complex H and 10 ~ 100 that the novel phenyl of 1 ~ 100 μm of ol replaces is sequentially added
Mmol methyl methacrylate continues the ethylene gas usually pressed to full conjunction, co-catalyst methylaluminoxane, co-catalysis is added
Agent: the ratio of the amount of the substance for the salicylic alidehyde imine metal titanium complex H that novel phenyl replaces is 10 ~ 1000:1.And adjust ethylene
To required 0.1 ~ 10 MPa of pressure, magnetic agitation reacts 0.5 ~ 1h at 0 ~ 100 DEG C, is terminated with the ethanol solution solution of 10% hydrochloric acid
Reaction, resulting polymers are filtered, are washed with dehydrated alcohol, obtained solid is dried under vacuum to constant weight at 60 DEG C after filtering, obtains
To polymeric articles C.
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| CN113501909A (en) * | 2021-07-28 | 2021-10-15 | 西北师范大学 | Preparation method of antibacterial microspheres of polypropylene ester-loaded Schiff base metal complex |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199052A (en) * | 1997-04-25 | 1998-11-18 | 三井化学株式会社 | Olefin polymerization catalysts, transition metal compounds, processes for olefin polymerization, and alpha-olefin/conjugated diene copolymers |
| JP2004331965A (en) * | 2003-04-18 | 2004-11-25 | Mitsui Chemicals Inc | Catalyst for olefin polymerization and process for producing olefin polymer |
| CN1697845A (en) * | 2003-01-23 | 2005-11-16 | 三井化学株式会社 | Process for producing ethylene/alpha-olefin/unconjugated polyene copolymer and ethylene/alpha-olefin/unconjugated polyene copolymer |
-
2018
- 2018-06-22 CN CN201810651264.1A patent/CN109021009A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199052A (en) * | 1997-04-25 | 1998-11-18 | 三井化学株式会社 | Olefin polymerization catalysts, transition metal compounds, processes for olefin polymerization, and alpha-olefin/conjugated diene copolymers |
| CN1697845A (en) * | 2003-01-23 | 2005-11-16 | 三井化学株式会社 | Process for producing ethylene/alpha-olefin/unconjugated polyene copolymer and ethylene/alpha-olefin/unconjugated polyene copolymer |
| JP2004331965A (en) * | 2003-04-18 | 2004-11-25 | Mitsui Chemicals Inc | Catalyst for olefin polymerization and process for producing olefin polymer |
Non-Patent Citations (1)
| Title |
|---|
| MICHAEL A. ZHURAVEL ET AL.: "Preparation of 3-aryl-substituted salicylaldehydes via Suzuki coupling", 《TETRAHEDRON LETTERS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113501909A (en) * | 2021-07-28 | 2021-10-15 | 西北师范大学 | Preparation method of antibacterial microspheres of polypropylene ester-loaded Schiff base metal complex |
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