CN104226366B - Titanium series catalyst and its preparation method and application - Google Patents
Titanium series catalyst and its preparation method and application Download PDFInfo
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- CN104226366B CN104226366B CN201410441097.XA CN201410441097A CN104226366B CN 104226366 B CN104226366 B CN 104226366B CN 201410441097 A CN201410441097 A CN 201410441097A CN 104226366 B CN104226366 B CN 104226366B
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Abstract
This application provides Titanium series catalyst of the one kind with structure shown in formula (I), the catalyst is capable of the copolymerization of efficiently catalysis epoxidation compound and carbon dioxide, selectively good；Additionally, it is nontoxic by the makrolon that obtains of catalyst preparation that the present invention is provided, can be applied to food, medical package field.
Description
Technical field
The present invention relates to catalyst field, more particularly to Titanium series catalyst and preparation method and application.
Background technology
Carbon dioxide is the predominant gas for causing greenhouse effects, while being again one of carbon source most abundant on the earth, is also
A kind of cheap carbon oxygen resource.Carbon dioxide is synthesizing large basic chemical, fuel and macromolecular material as carbon oxygen resource
Aspect is an important research topic.Wherein, with carbon dioxide and epoxides as raw material, the combined polymerization under catalyst action
Into fatty poly-ester carbonate be a kind of Full degradation type macromolecular material, with the good transparency, excellent blocking oxygen and
The performance of water, can serve as engineering plastics, biodegradable nonpollution material, a sex medicine and packaging material for food, gluing
Agent and composite etc., and also have a wide range of applications potentiality in the field such as food and medical package.
Since Inoue realizes carbon dioxide and propylene oxide copolymer first within 1969, zinc alkyl/active hydrogen has been occurred in that in succession
Catalyst system and catalyzing, zinc polycarboxylate system, DMC catalysts, rare-earth ternary catalyst, catalysis of metalloporphyrin agent, phenol zincum salts
A series of catalyst system and catalyzings such as catalyst system and catalyzing and diimine zinc class catalyst, the research and development of these catalyst system and catalyzings is complete for synthesizing
Biodegradable aliphatic polycarbonates have a larger impetus, and some systems have been used to industrialized production, but more than
System is still present that catalysis activity is low, reaction time problem long.
Four tooth schiff bases cobalt complex (Selen) the CoX catalyst system and catalyzings for starting for 2003 to occur quickly grow, and successively occur
The double-component catalyst system and collection active site and steric hindrance being made up of with quaternary ammonium salt or quaternary alkylphosphonium salt (Selen) CoX complexs have
In the one-component bifunctional catalysis system of one, this two classes catalyst activity reaches 106 grams of polymer/mole catalysts to machine base groups
Agent.But cobalt is strictly limited as a kind of toxic metals in various international standards so that it is poly- that cobalt system catalyst system and catalyzing is produced
Carbonate material is difficult to be applied to food, medical package field, therefore this kind of four tooth schiff bases cobalts with greater activity
Composition catalyst cannot be applied to actual industrial production always.
The content of the invention
In view of this, the technical problems to be solved by the invention be provide a kind of Titanium series catalyst and preparation method thereof and
Using, the Titanium series catalyst energy effective catalyst that the present invention is provided can efficient catalytic carbon dioxide and epoxide copolymerization,
And the polyester that obtains is nontoxic.
The invention provides a kind of Titanium series catalyst, as shown in formula (I),
Formula (I),
Wherein, R1It is the alkylidene of C1-C20, the alkylene oxide group of C1-C20, C6~C20 arlydene, C6~C20 substitutions
Arlydene；
R2, R3, R4Independent is selected from：The C1-C20 alkyl of the alkyl of H, C1-C20, the alkoxy of C1-C20 or fluorine substitution,
Or R2And R3And its carbon adjacent with them is collectively forming the ring of closing,
Or R3And R4And its carbon adjacent with them is collectively forming the ring of closing；
X is halogen ,-NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3, to methylbenzene
Formate, p-methyl benzenesulfonic acid root, o-nitrophenol oxygen, p-nitrophenol oxygen, metanitrophenol oxygen, 2,4-DNP
Oxygen, 3,5- dinitrophenol oxygen, 2,4,6- trinitrophenol oxygen, 3,5- chlorophenesic acids oxygen, 3,5- difluorophenols oxygen, 3,5- bis--
Trifloro methyl phenol oxygen or pentafluranol negative oxygen ion.
Preferably, the R2And R3And its carbon adjacent with them be collectively forming the ring of closing for C6~C20 aromatic rings, C6~
C20 substitutions aromatic ring, C3~C20 alicyclic rings, C3~C20 substitutions alicyclic ring, C3~C20 heterocycles or C3~C20 substituted heterocycles；
The R3And R4And its carbon adjacent with them is collectively forming the ring of closing for C6~C20 aromatic rings, C6~C20 replace
Aromatic ring, C3~C20 alicyclic rings, C3~C20 substitutions alicyclic ring, C3~C20 heterocycles or C3~C20 substituted heterocycles.
Preferably, the catalyst has formula (I-a) structure,
Formula (I-a)；
Wherein, the alkyl selected from H, C1-C20 of a, b, c, d independence, the aryl of C6-C20, the alkyl of the C1-C20 of substitution
Or the aryl of the C6-C20 of substitution.
Preferably, the R1It is formula (II), formula (III), formula (IV) or formula (V) structure,Formula (II)；Formula
(III)；Formula (IV)；Formula (V)；
Wherein, * represents link position,
R5, R6It is independently selected from H, CH3、CH2CH3、CH(CH3)2、C(CH3)3、OCH3、OCH2CH3, Cl, Br or NO2,
N is 1~6 integer.
Present invention also offers a kind of preparation method of Titanium series catalyst, including：
1) by aldehyde compound shown in formula (VI-a) and diamine reactant shown in formula (VI-b), four tooth bis-Schiff bases are obtained and is matched somebody with somebody
Body；
Formula (VI-a),Formula (VI-b)；
Wherein, R1It is the alkylidene of C1-C20, the alkylene oxide group of C1-C20, C6~C20 arlydene, C6~C20 substitutions
Arlydene；
R2, R3, R4Independent is selected from：The C1-C20 alkyl of the alkyl of H, C1-C20, the alkoxy of C1-C20 or fluorine substitution,
Or R2And R3And its carbon adjacent with them is collectively forming the ring of closing；
Or R3And R4And its carbon adjacent with them is collectively forming the ring of closing；
2) by four tooth bis-Schiff base parts and TiCl3.(THF)3React in the presence of a base, obtain Titanium series catalyst.
Preferably, the step 2) alkali be NaH, KH, Rli, RONa or ROK,
Wherein, R is the alkyl of C1~C6.
Preferably, the TiCl3.(THF)3Prepare in accordance with the following methods：
By ten dichloro Tritanium/Trititanium aluminium (3TiCl3.AlCl3) slurrying in toluene is dissolved to, added under the conditions of -20 DEG C~-78 DEG C
Tetrahydrofuran reacts, and obtains TiCl3.(THF)3。
Preferably, aldehyde compound shown in the formula (VI-a) and the mol ratio of diamines shown in formula (VI-b) are (2~3)：
1。
Present invention also offers a kind of preparation method of makrolon, including：
The catalyst that the present invention is provided and the reaction of epoxide, co-catalyst and carbon dioxide mix, obtain poly- carbon
Acid esters.
Preferably, the cation in the co-catalyst is quaternary ammonium salt or quaternary phosphine salt.
Compared with prior art, the invention provides Titanium series catalyst of the one kind with structure shown in formula (I), the catalyst
It is capable of the copolymerization of efficiently catalysis epoxidation compound and carbon dioxide, selectivity is good, test result indicate that, provided by the application
The polymer that obtains of catalyst in carbonate unit content higher than 95%, cyclic carbonate accessory substance is less than 1.0%, and
Catalyst amount only needs the one thousandth of epoxide；Additionally, the poly- carbon obtained by the catalyst preparation that the present invention is provided
Acid esters is nontoxic, can be applied to food, medical package field.
Specific embodiment
The invention provides a kind of Titanium series catalyst, as shown in formula (I),
Formula (I),
Wherein, R1It is the alkylidene of C1-C20, the alkylene oxide group of C1-C20, C6~C20 arlydene, C6~C20 substitutions
Arlydene；
R2, R3, R4Independent is selected from：The C1-C20 alkyl of the alkyl of H, C1-C20, the alkoxy of C1-C20 or fluorine substitution,
Or R2And R3And its carbon adjacent with them is collectively forming the ring of closing,
Or R3And R4And its carbon adjacent with them is collectively forming the ring of closing；
X is halogen ,-NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3, to methylbenzene
Formate, p-methyl benzenesulfonic acid root, o-nitrophenol oxygen, p-nitrophenol oxygen, metanitrophenol oxygen, 2,4-DNP
Oxygen, 3,5- dinitrophenol oxygen, 2,4,6- trinitrophenol oxygen, 3,5- chlorophenesic acids oxygen, 3,5- difluorophenols oxygen, 3,5- bis--
Trifloro methyl phenol oxygen or pentafluranol negative oxygen ion.
According to the present invention, the R1The preferably alkylidene of C1-C8, the alkylene oxide group of C1-C8, C6~C12 arlydene, C6
~C12 replaces arlydene；More preferably the alkylidene of C1-C6, the alkylene oxide group of C1-C6, C6~C8 arlydene, C6~C10 take
For arlydene；Wherein, the substitution base preferably-CH on the alkylidene, alkylene oxide group, substitution arlydene3、-CH2CH3、-CH
(CH3)2、-C(CH3)3、-OCH3、-OCH2CH3,-Cl ,-CN, Br- or NO2-, the R1Most preferably there is formula (II), formula
(III), formula (IV) or formula (V) structure,
Formula (II)；Formula (III)；Formula (IV)；Formula (V)；
Wherein, * represents link position,
R5, R6It is independently selected from H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-OCH3、-OCH2CH3, Cl-, Br- or-
NO2, n is 1~6 integer, more preferably 1 or 2, the group on formula (III) structure, two chiral centre is configured as
(R, R), (S, S), (R, S) or (S, R).
The R2The C1-C8 alkyl that preferably alkyl of H, C1-C8, the alkoxy of C1-C8 or fluorine replace, more preferably H
Or the alkyl of C1-C4；The R3Preferably the C1-C8 alkyl of the alkyl of H, C1-C8, the alkoxy of C1-C8 or fluorine substitution, more excellent
Elect the alkyl of H or C1-C4 as；The R4The C1-C8 alkane that preferably alkyl of H, C1-C8, the alkoxy of C1-C8 or fluorine replace
The alkyl of base, more preferably H or C1-C4；
Or the R2With the R3And its carbon adjacent with them be collectively forming the ring of closing preferably C6~C20 aromatic rings,
C6~C20 substitutions aromatic ring, C3~C20 alicyclic rings, C3~C20 substitutions alicyclic ring, C3~C20 heterocycles or C3~C20 substituted heterocycles, it is more excellent
Elect the aromatic ring of C6~C12 aromatic rings or C6~C12 substitutions, most preferably phenyl ring or substituted phenyl ring as；On the substitution aromatic ring
Substitution base is preferably the C1-C20 alkyl of the alkyl of C1-C20, the alkoxy of C1-C20 or fluorine substitution, the more preferably alkane of C1-C8
It is the C1-C8 alkyl of base, the alkoxy of C1-C8 or fluorine substitution, most preferably methyl, ethyl, n-propyl, isopropyl, normal-butyl, different
Butyl, the tert-butyl group, methoxyl group, ethyoxyl or amyl group；
Or the R3With the R4And its carbon adjacent with them be collectively forming the ring of closing preferably C6~C20 aromatic rings,
C6~C20 substitutions aromatic ring, C3~C20 alicyclic rings, C3~C20 substitutions alicyclic ring, C3~C20 heterocycles or C3~C20 substituted heterocycles, it is more excellent
Elect the aromatic ring of C6~C12 aromatic rings or C6~C12 substitutions, most preferably phenyl ring or substituted phenyl ring as；On the substitution aromatic ring
Substitution base is preferably the C1-C20 alkyl of the alkyl of C1-C20, the alkoxy of C1-C20 or fluorine substitution, the more preferably alkane of C1-C8
It is the C1-C8 alkyl of base, the alkoxy of C1-C8 or fluorine substitution, most preferably methyl, ethyl, n-propyl, isopropyl, normal-butyl, different
Butyl, the tert-butyl group, methoxyl group, ethyoxyl or amyl group.
The X is preferably Cl-, Br- ,-NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-
N3, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, o-nitrophenol oxygen, p-nitrophenol oxygen, metanitrophenol oxygen, 2,4-
Dinitrophenol oxygen, 3,5- dinitrophenol oxygen, 2,4,6- trinitrophenol oxygen, 3,5- chlorophenesic acids oxygen, 3,5- difluorophenols
Oxygen, 3,5- di-trifluoromethyl phenol oxygen or pentafluranol negative oxygen ion.
Specifically, the catalyst preferably has formula (II) structure,
Formula (II)；
Wherein, R1、R2, X restriction it is the same,
The alkyl selected from H, C1-C20 of a, b, c, d independence, the aryl of C6-C20, the alkyl of the C1-C20 of substitution or substitution
C6-C20 aryl, the C1-C8 alkyl of the more preferably independent alkyl selected from C1-C8, the alkoxy of C1-C8 or fluorine substitution,
It is most preferably independent selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, methoxyl group, ethyoxyl
Or amyl group.
More specifically, the catalyst is preferably with formula (VII)~the complex of structure shown in formula (XV)：
Formula (VII)；Formula (VIII)；
Formula (IX)；Formula (X)；
Formula (XI)；Formula (XII)；
Formula (XIII)；
Formula (XIV)；Formula (XV).
Present invention also offers a kind of preparation method of Titanium series catalyst, including：
1) by aldehyde compound shown in formula (VI-a) and diamine reactant shown in formula (VI-b), four tooth bis-Schiff bases are obtained and is matched somebody with somebody
Body；
Formula (VI-a),Formula (VI-b)；
Wherein, R1It is alkylidene, the alkylene oxide group of C1-C20, C6~C20 arlydene, C6~C20 substitutions of C1-C20
Arlydene；
R2, R3, R4Independent is selected from：The C1-C20 alkyl of the alkyl of H, C1-C20, the alkoxy of C1-C20 or fluorine substitution,
Or R2And R3And its carbon adjacent with them is collectively forming the ring of closing；
Or R3And R4And its carbon adjacent with them is collectively forming the ring of closing；
2) by four tooth bis-Schiff base parts and TiCl3.(THF)3React in the presence of a base, obtain Titanium series catalyst.
According to the present invention, by aldehyde compound shown in formula (VI-a) and diamine reactant shown in formula (VI-b), four teeth are obtained double
Schiff base ligand；Wherein, the R in aldehyde compound shown in formula (VI-a)2、R3、R4Restriction and titanium sub-group compound in R2、R3、R4
Restriction it is identical, the R in diamines shown in formula (VI-b)1Restriction and titanium sub-group compound in R1Restriction it is identical, the formula (VI-a)
Shown aldehyde compound is preferably (2~3) with the mol ratio of diamines shown in formula (VI-b):1, more preferably 2:1；The reaction
Solvent is preferably alcohol compound, more preferably methyl alcohol or ethanol；The temperature of the reaction is preferably back flow reaction.
According to the present invention, by four tooth bis-Schiff base parts and TiCl3.(THF)3React in the presence of a base, obtain the catalysis of titanium system
Agent；The four teeth bis-Schiff base part and the TiCl3.(THF)3Mol ratio be preferably 1：(1~1.2), more preferably 1:1；
The alkali is preferably NaH, KH, Rli, RONa or ROK, wherein, R is the alkyl of C1~C6；The alkali and the double Schiffs of four tooth
The mol ratio of aar ligand is preferably 1：(3~8), more preferably 1：(3~5).
Can be good at carrying out to react, the present invention preferably first reacts four tooth bis-Schiff base parts and alkali, Ran Houzai
TiCl is added under the conditions of -20~-78 DEG C3.(THF)3Reaction, obtains Titanium series catalyst.
Additionally, the present invention is to TiCl3.(THF)3Source be not particularly limited, TiCl of the present invention3.(THF)3It is excellent
Choosing is prepared in accordance with the following methods：
By ten dichloro Tritanium/Trititanium aluminium (3TiCl3.AlCl3) slurrying in toluene is dissolved to, added under the conditions of -20 DEG C~-78 DEG C
Tetrahydrofuran reacts, and obtains TiCl3.(THF)3。
Specifically, the present invention is first by ten dichloro Tritanium/Trititanium aluminium (3TiCl3.AlCl3) be dissolved to slurrying in toluene, then-
To THF is added in the solution after slurrying under the conditions of 60~-80 DEG C, after completion of dropping, 70 DEG C are to slowly warm up to, and it is anti-in the temperature
Answer 15~30 hours, obtain TiCl3.(THF)3；The amount ratio of the ten dichloros Tritanium/Trititanium aluminium and the toluene for 5mmol~
8mmol：1mL；The toluene is preferably the toluene after refining, and the refined method is process for purification well known in the art
, the tetrahydrofuran is preferably refined tetrahydrofuran, and the refined method is essence well known to those skilled in the art
Method processed；Source to ten dichloro Tritanium/Trititanium aluminium is not particularly limited, commercially available.
Present invention also offers a kind of preparation method of makrolon, including：
The catalyst that the present invention is provided and the reaction of epoxide, co-catalyst and carbon dioxide mix, obtain poly- carbon
Acid esters.
According to the present invention, catalyst and epoxide, co-catalyst and carbon dioxide mix that just the present invention is provided
Reaction, obtains makrolon；The epoxide is preferably the epoxide of C1-C20, more preferably oxirane, ring
Ethylene Oxide, 1,2- epoxy butanes, 7-oxa-bicyclo[4.1.0, cyclopentane epoxide, epoxychloropropane, methyl propenoic acid glycidyl ether, first
One or more in base glycidol ether, phenyl glycidyl ether and styrene epoxyalkane；Sun in the co-catalyst
Ion is preferably quaternary ammonium salt or quaternary phosphine salt, and the quaternary ammonium salt or quaternary alkylphosphonium salt are preferably [R '4N]+,[R’4P]+,[R’3P=N=
PR’3]+Or [P [NR '3]3]+, wherein R ' is alkyl, the alkoxy of C1-C20, C6-C20 aryl or the C6-C20 substitutions of C1-C20
Aryl；Anion in the co-catalyst is preferably halogen ,-NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、
BPh4-、-CN、-N3, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, o-nitrophenol oxygen, p-nitrophenol oxygen, m-nitro
Phenol oxygen, 2,4-DNP oxygen, 3-5 dinitrophenol oxygen, 2,4,6- trinitrophenol oxygen, 3,5- chlorophenesic acids oxygen, 3,5-
Difluorophenol oxygen, 3,5- di-trifluoromethyl phenol oxygen or pentafluranol negative oxygen ion.
In the present invention, the catalyst and the mol ratio of the epoxides are 1：(500~10000)；The reaction
Temperature be preferably 0~150 DEG C, the time of the reaction is preferably 0.5~48 hour, and the pressure of the reaction is preferably 0.1
~5MPa；The present invention does not have particular/special requirement to the device for reacting, and is carried out preferably in autoclave.
The Titanium series catalyst that the present invention is provided has catalysis activity and catalytic selectivity high, can efficiently be catalyzed epoxy
The copolymerization of compound and carbon dioxide, copolymerization is selectively good, test result indicate that, the catalyst provided by the application is obtained
To polymer in carbonate unit content be higher than 95%, cyclic carbonate accessory substance is less than 10.0%, and catalyst amount is only
Need 5 hundred to one a ten thousandths of epoxide；Additionally, the makrolon obtained by the catalyst preparation that the present invention is provided
It is nontoxic, can be applied to food, medical package field.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, it is clear that described implementation
Example is only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model of present invention protection
Enclose.
Embodiment 1：Titanous tetrahydrofuran complex TiCl3.(THF)3Preparation
The 3TiCl of 5.0g (25mmol) purple is added in 100mL single-necked flasks3.AlCl3, the toluene slurrying refined with 4mL,
It is put into the bath of -78 DEG C of dry ice-propanone, is slowly dropped into the refined THF of 5mL.Rear system is dripped to be to slowly warm up to 70 DEG C times
Stream 20h, after backflow is finished, is cooled to room temperature, filters, and filter residue is washed three times with refined n-hexane, and residual solvent is removed under reduced pressure,
Obtain nattier blue solid product 7.59g, yield 82%.
By elemental analyser, the TiCl prepared to embodiment 13.(THF)3It is analyzed, its elementary analysis result is：C,
38.55, H, 6.64；Results of calculation is：C, 38.68, H, 6.50；It can be seen that, prepared by embodiment be really TiCl3.(THF)3。
Embodiment 2：The preparation of the complex of formula (VII) structure.
4.68g 3,5- di-tert-butyl salicylaldehyde (20mmol) are dissolved in 100mL drying ethanols, 1.08g, 1,2- benzene two
Amine (10mmol) is dissolved in the drying ethanol of 20mL.Then under agitation, the ethanol solution of 1,2- o-phenylenediamines is dripped
It is added in the ethanol solution of 3,5- di-t-butyl water aldehyde, after being heated to reflux and stirring 14h, cooling reactant mixture to room temperature, rotation
Turn evaporation and remove volatile material, obtain solid, by after the solid ethyl alcohol recrystallization and after vacuum drying, obtain yellow
The tooth bis-Schiff base ligand i II5.05g of needle-like four, yield is 93%.
Four tooth bis-Schiff base ligand i II；
Above-mentioned four teeth bis-Schiff base ligand i II is dissolved in refined 20mLTHF, 0 DEG C of NaH of 4 equivalents of addition is cooled to
(60% is dispersed in mineral oil), system is gradually increased to room temperature, continues to react 4h, is filtered to remove excessive NaH, and filtrate is cooled to
0 DEG C, it is slowly added to the TiCl of 1 equivalent3.(THF)3, after adding, reaction system is gradually increased to room temperature, continues to react 12h.Cross and filter
The NaCl of dereaction generation, filter vacuum removes solvent, obtains the complex with formula (VII) structure of yellow green, yield
98%.
The complex with formula (VII) structure prepared to embodiment by mass spectrograph detected, as a result shown,
MALDI-TOF-MS(m/z)Calcd for[C36H46ClN2O2Ti]+：621.3.
Embodiment 3：The preparation of formula (VIII) structural coordination compound
The complex of 0.062g formulas (VII) structure is dissolved in refined dichloromethane/acetone (volume ratio 1:1) mixed solvent
In, add the AgNO of 2 equivalents3, lucifuge reaction 12h, is removed under reduced pressure mixed solvent at room temperature, again molten with refined dichloromethane
Solution, filtering removes the AgCl and unreacted AgNO of generation3, removal of solvent under reduced pressure obtains blackish green with formula (VIII) knot
The complex of structure.
The complex with formula (VIII) structure prepared to embodiment by mass spectrograph detected, as a result table
It is bright, MALDI-TOF-MS (m/z) Calcd for [C36H46ClN2O2Ti]+：648.3.
Embodiment 4：The preparation of formula (IX) structural coordination compound
The complex of 0.062g formulas (VII) structure is dissolved in refined dichloromethane/acetone (volume ratio 1:1) mixed solvent
In, the AgOAc of 2 equivalents is added, lucifuge reaction 12h, is removed under reduced pressure mixed solvent at room temperature, again molten with refined dichloromethane
Solution, filtering removes the AgCl and unreacted AgOAc of generation.Removal of solvent under reduced pressure, obtains blackish green with formula (IX) structure
Complex.
The complex with formula (IX) structure prepared to embodiment by mass spectrograph detected, as a result shown,
MALDI-TOF-MS(m/z)Calcd for[C36H46ClN2O2Ti]+：645.3.
Embodiment 5：The preparation of formula (X) structural coordination compound
The complex of 0.062g formulas (VII) structure is dissolved in refined dichloromethane/acetone (volume ratio 1:1) mixed solvent
In, the AgOTs of 2 equivalents is added, lucifuge reaction 12h, is removed under reduced pressure mixed solvent at room temperature, again molten with refined dichloromethane
Solution, filtering removes the AgCl and unreacted AgOTs of generation.Removal of solvent under reduced pressure, obtains blackish green with formula (X) structure
Complex.
The complex with formula (X) structure prepared to embodiment by mass spectrograph detected, as a result shown,
MALDI-TOF-MS(m/z)Calcd for[C36H46ClN2O2Ti]+：757.3.
Embodiment 6：The preparation of formula (XI) structural coordination compound
4.68g 3,5- di-tert-butyl salicylaldehydes (20mmol) are dissolved in 100mL drying ethanols, 1.14g, (R, R)-
1,2- cyclohexanediamine (10mmol) is dissolved in the drying ethanol of 20mL.Then under agitation, (R, R) -1,2- hexamethylenes
The ethanol solution of diamines is added drop-wise in the ethanol solution of 3,5- di-t-butyl water aldehyde, after being heated to reflux and stirring 14h, cooling reaction
Mixture to room temperature, rotary evaporation removes volatile material, yellow solid is obtained, after gained solids ethyl alcohol recrystallization
And after being vacuum dried, four tooth bis-Schiff base ligand i V5.15g being obtained, yield is 95%.
Four tooth bis-Schiff base ligand i V；
The tooth bis-Schiff base ligand i V of 0.54g (1mmol) four are dissolved in refined 20mLTHF, 0 DEG C are cooled to and are added 4 to work as
The NaH (60% is dispersed in mineral oil) of amount, system is gradually increased to room temperature, continues to react 4h.Excessive NaH is filtered to remove, is filtered
Liquid is cooled to 0 DEG C, is slowly added to the TiCl of 1 equivalent3.(THF)3, system is gradually increased to room temperature, continues to react 12h.It is filtered to remove
The NaCl of generation is reacted, filter vacuum removes solvent, obtains the blackish green complex with formula (XI) structure, and yield is
98%.
The complex with formula (XI) structure prepared to embodiment by mass spectrograph detected, as a result shown,
MALDI-TOF-MS(m/z)Calcd for[C36H46ClN2O2Ti]+：627.3.
Embodiment 7：The preparation of formula (XII) structural coordination compound
A) 4.68g 3,5- di-tert-butyl salicylaldehydes (20mmol) are dissolved in 100mL drying ethanols, 1.02g, and 2,2- bis-
Methyl propane diamine (10mmol) is dissolved in the drying ethanol of 20mL.Then under agitation, 2,2- dimethylated propyl diethylenetriamines
Ethanol solution be added drop-wise in the ethanol solution of 3,5- di-t-butyl water aldehyde, after being heated to reflux and stirring 14h, cooling reaction mixing
Thing to room temperature, rotary evaporation removes volatile material, obtains yellow solid, after gained solids ethyl alcohol recrystallization and true
After sky is dried, four tooth bis-Schiff base part V4.75g are obtained, yield is 89%.
Four tooth bis-Schiff base part V；
The tooth bis-Schiff base part V of 0.53g (1mmol) four are dissolved in refined 20mL THF, 0 DEG C are cooled to and are added 4 to work as
The NaH (60% is dispersed in mineral oil) of amount, system is gradually increased to room temperature, continues to react 4h.Excessive NaH is filtered to remove, is filtered
Liquid is cooled to 0 DEG C, is slowly added to the TiCl of 1 equivalent3.(THF)3, system is gradually increased to room temperature, continues to react 12h.It is filtered to remove
The NaCl of generation is reacted, filter vacuum removes solvent, obtains the blackish green complex with formula (XII) structure, yield 98%.
The complex with formula (XII) structure prepared to embodiment by mass spectrograph detected, as a result shown,
MALDI-TOF-MS(m/z)Calcd for[C36H46ClN2O2Ti]+：615.3.
Embodiment 8：The preparation of formula (XIII) structural coordination compound
4.68g 3,5- di-tert-butyl salicylaldehyde (20mmol) are dissolved in 100mL drying ethanols, 0.88g, 1,1- diformazan
Base ethylenediamine (10mmol) is dissolved in the drying ethanol of 20mL.Then under agitation, 1,1- dimethyl-ethylenediamines
Ethanol solution is added drop-wise in the ethanol solution of 3,5- di-t-butyl water aldehyde, after being heated to reflux and stirring 14h, cools down reactant mixture
To room temperature, rotary evaporation removes volatile material, obtains yellow solid, simultaneously vacuum after gained solids ethyl alcohol recrystallization
After drying, the tooth bis-Schiff base part VI of yellow needles four is obtained, 4.42g, yield is 85%.
Four tooth bis-Schiff base part VI；
The tooth bis-Schiff base part VI of 0.52g (1mmol) yellow needles four is dissolved in refined 20mLTHF, 0 DEG C is cooled to
The NaH (60% is dispersed in mineral oil) of 4 equivalents is added, system is gradually increased to room temperature, continue to react 4h, be filtered to remove excessive
NaH, filtrate is cooled to 0 DEG C, is slowly added to the TiCl of 1 equivalent3.(THF)3, system is gradually increased to room temperature, continues to react 12h.Cross
The NaCl of dereaction generation is filtered, filter vacuum removes solvent, obtains blackish green formula (XIII) structural coordination compound, yield
99%.
The complex with formula (XIII) structure prepared to embodiment by mass spectrograph detected, as a result table
It is bright, MALDI-TOF-MS (m/z) Calcd for [C36H46ClN2O2Ti]+：601.3.
Embodiment 9：The preparation of formula (XIV) structural coordination compound
The 4.16g 3- tert-butyl group -5- methoxysalicyl aldehydes (20mmol) is dissolved in 100mL drying ethanols, 1.08g, 1,2-
Phenylenediamine (10mmol) is dissolved in the drying ethanol of 20mL.Then under agitation, it is the ethanol of 1,2- o-phenylenediamines is molten
Drop is added in the ethanol solution of the 3- tert-butyl group -5- methoxysalicyl aldehydes, after being heated to reflux and stirring 14h, cooling reaction mixing
Thing to room temperature, rotary evaporation removes volatile material, obtains yellow solid, after gained solids ethyl alcohol recrystallization and true
After sky is dried, the tooth bis-Schiff base part VII of yellow needles yellow needles four is obtained, 4.25g, yield is 87%.
Four tooth bis-Schiff base part VII；
The tooth bis-Schiff base part VII of 0.49g (1mmol) four are dissolved in refined 20mLTHF, 0 DEG C are cooled to and are added 4 to work as
The NaH (60% is dispersed in mineral oil) of amount, system is gradually increased to room temperature, continues to react 4h.Excessive NaH is filtered to remove, is filtered
Liquid is cooled to 0 DEG C, is slowly added to the TiCl of 1 equivalent3.(THF)3, system is gradually increased to room temperature, continues to react 12h.It is filtered to remove
The NaCl of generation is reacted, filter vacuum removes solvent, obtains blackish green formula (XIV) structural coordination compound, yield 99%.
The complex with formula (XIV) structure prepared to embodiment by mass spectrograph detected, as a result shown,
MALDI-TOF-MS(m/z)Calcd for[C36H46ClN2O2Ti]+：569.2.
Embodiment 10：The preparation of formula (XIV) structural coordination compound
4.68g 3, the 5- tert-butyl group salicylide (20mmol) are dissolved in 100mL drying ethanols, 1.77g, and 3,4- bis- chloro- 1,
2- phenylenediamines (10mmol) are dissolved in the drying ethanol of 20mL.Then under agitation, chloro- 1, the 2- phenylenediamines of 3,4- bis-
Ethanol solution be added drop-wise in the ethanol solution of the 3- tert-butyl group -5- methoxysalicyl aldehydes, after being heated to reflux and stirring 14h, cooling
Reactant mixture to room temperature, rotary evaporation removes volatile material, obtains yellow solid, gained solids ethanol is tied again
After crystalline substance and after vacuum drying, the tooth bis-Schiff base part VIII of yellow needles four is obtained, 5.36g, yield is 88%.
Four tooth bis-Schiff base part VIII；
The tooth bis-Schiff base part VIII of 0.61g tetra- are dissolved in refined 20mL THF, 0 DEG C are cooled to and are added 4 equivalents
NaH (60% is dispersed in mineral oil), system is gradually increased to room temperature, continues to react 4h.Excessive NaH is filtered to remove, filtrate is cold
But to 0 DEG C, it is slowly added to the TiCl of 1 equivalent3.(THF)3, system is gradually increased to room temperature, continues to react 12h.It is filtered to remove reaction
The NaCl of generation, filter vacuum removes solvent, obtains blackish green formula (XV) structural coordination compound, yield 98%.
The complex with formula (XV) structure prepared to embodiment by mass spectrograph detected, as a result shown,
MALDI-TOF-MS(m/z)Calcd for[C36H46ClN2O2Ti]+：689.2.
Embodiment 11
In glove box, complex prepared by 0.075mmol embodiments 2,0.075mmol [PPN] Cl and 75mmol do
Dry 7-oxa-bicyclo[4.1.0 be added to it is pre- first pass through water removal, deoxygenation treatment 15mL autoclaves in, autoclave is taken out into gloves
The CO with pressure adjusting function is run through after case2Supply line in kettle to being filled with CO2To 1.0MPa, by temperature control 120
DEG C, pressure is risen into 4.0MPa, react 1 hour, after polymerisation terminates, reactor is cooled to room temperature, slowly bleed off titanium dioxide
Carbon, the complete 7-oxa-bicyclo[4.1.0 of unreacted is taken out in room temperature in vacuum drying chamber, and the makrolon for obtaining of weighing is 5.9g.
It is 557h by the TOF values for calculating the catalyst system and catalyzing-1。
The molecular weight of the makrolon obtained to embodiment by GPC is measured, and its result measures number-average molecular weight and is
5400, molecular weight distribution 1.14,
Pass through1H-NMR detects, as a result shows that cyclic carbonate accessory substance is few to the makrolon that embodiment is obtained
In 1.0%, carbonate unit content is higher than 99% in polymer.
Embodiment 12
In glove box, complex prepared by 0.075mmol embodiments 3,075mmol [PPN] Cl and 75mmol are dried
7-oxa-bicyclo[4.1.0 be added to it is pre- first pass through water removal, deoxygenation treatment 15mL autoclaves in, autoclave is taken out into glove box
The CO with pressure adjusting function is run through afterwards2Supply line in kettle to being filled with CO2To 1.0MPa, by temperature control at 120 DEG C,
Pressure is risen into 4.0MPa, by temperature control at 120 DEG C stirring reaction 1 hour.After polymerisation terminates, reactor is cooled to
Room temperature, slowly bleeds off carbon dioxide, and the complete 7-oxa-bicyclo[4.1.0 of unreacted is taken out in room temperature in vacuum drying chamber, weigh obtain it is poly-
Carbonic ester is 4.8g.
It is 450h by the TOF values for calculating the catalyst system and catalyzing-1。
The molecular weight of the makrolon obtained to embodiment by GPC is measured, and its result measures number-average molecular weight and is
5100, molecular weight distribution 1.12,
Pass through1H-NMR detects, as a result shows that cyclic carbonate accessory substance is few to the makrolon that embodiment is obtained
In 1.0%, carbonate unit content is higher than 99% in polymer.
Embodiment 13
In glove box, complex and 75mmol, 0.075mmol [PPN] Cl prepared by 0.075mmol embodiments 4 does
Dry 7-oxa-bicyclo[4.1.0 be added to it is pre- first pass through water removal, deoxygenation treatment 15mL autoclaves in, autoclave is taken out into gloves
The CO with pressure adjusting function is run through after case2Supply line in kettle to being filled with CO2To 1.0MPa, by temperature control 120
DEG C, pressure is risen into 4.0MPa, by temperature control at 120 DEG C stirring reaction 1 hour.After polymerisation terminates, by reactor
It is cooled to room temperature, slowly bleeds off carbon dioxide, the complete 7-oxa-bicyclo[4.1.0 of unreacted is taken out in room temperature in vacuum drying chamber, weighs and obtain
Makrolon be 5.07g.
It is 476h by the TOF values for calculating the catalyst system and catalyzing-1。
The molecular weight of the makrolon obtained to embodiment by GPC is measured, and its result measures number-average molecular weight and is
5200, molecular weight distribution 1.13,
Pass through1H-NMR detects, as a result shows that cyclic carbonate accessory substance is few to the makrolon that embodiment is obtained
In 1.0%, carbonate unit content is higher than 99% in polymer.
Embodiment 14
In glove box, complex prepared by 0.075mmol embodiments 5, (DNP is referred to 0.075mmol [PPN] [DNP]
2,4- dinitrophenol dinitrophenolates oxygen) and the dry 7-oxa-bicyclo[4.1.0s of 75mmol be added to it is pre- first pass through water removal, deoxygenation treatment 15mL high pressures
In reactor, the CO with pressure adjusting function is run through after autoclave is taken out into glove box2Supply line in kettle to being filled with CO2
To 1.0MPa, by temperature control at 120 DEG C, pressure is risen into 4.0MPa, by temperature control at 120 DEG C stirring reaction 1 hour.
After polymerisation terminates, reactor is cooled to room temperature, slowly bleeds off carbon dioxide, unreacted is taken out in room temperature in vacuum drying chamber
Complete 7-oxa-bicyclo[4.1.0, the makrolon for obtaining of weighing is 5.77g.
It is 541h by the TOF values for calculating the catalyst system and catalyzing-1。
The molecular weight of the makrolon obtained to embodiment by GPC is measured, and its result measures number-average molecular weight and is
5200, molecular weight distribution 1.11,
Pass through1H-NMR detects, as a result shows that cyclic carbonate accessory substance is few to the makrolon that embodiment is obtained
In 1.0%, carbonate unit content is higher than 99% in polymer.
Embodiment 15
In glove box, complex prepared by 0.075mmol embodiments 6,0.075mmol [PPN] Cl and 75mmol do
Dry expoxy propane be added to it is pre- first pass through water removal, deoxygenation treatment 15mL autoclaves in, autoclave is taken out into glove box
The CO with pressure adjusting function is run through afterwards2Supply line in kettle to being filled with CO2To 1.0MPa, by temperature control at 60 DEG C, will
Pressure rises to 3.0MPa, by temperature control at 60 DEG C stirring reaction 3 hours.After polymerisation terminates, reactor is cooled to room
Temperature, slowly bleeds off carbon dioxide, and the complete expoxy propane of unreacted is taken out in room temperature in vacuum drying chamber, the poly- carbonic acid for obtaining of weighing
Ester is 1.73g.
It is 84h by the TOF values for calculating the catalyst system and catalyzing-1。
The molecular weight of the makrolon obtained to embodiment by GPC is measured, and its result measures number-average molecular weight and is
13000, molecular weight distribution 1.15,
Pass through1H-NMR detects, as a result shows that cyclic carbonate accessory substance is few to the makrolon that embodiment is obtained
In 10.0%, carbonate unit content is higher than 95% in polymer.
Embodiment 16
In glove box, complex prepared by 0.075mmol embodiments 7,0.075mmol [PPN] Cl and 75mmol do
Dry styrene oxide be added to it is pre- first pass through water removal, deoxygenation treatment 15mL autoclaves in, autoclave is taken out into gloves
The CO with pressure adjusting function is run through after case2Supply line in kettle to being filled with CO2To 1.0MPa, by temperature control at 80 DEG C,
Pressure is risen into 4.0MPa, by temperature control at 80 DEG C stirring reaction 5 hours.After polymerisation terminates, reactor is cooled to
Room temperature, slowly bleeds off carbon dioxide, and the complete styrene oxide of unreacted is taken out in room temperature in vacuum drying chamber, weigh obtain it is poly-
Carbonic ester is 3.32g.
It is 430h by the TOF values for calculating the catalyst system and catalyzing-1。
The molecular weight of the makrolon obtained to embodiment by GPC is measured, and its result measures number-average molecular weight and is
12000, molecular weight distribution 1.14,
Pass through1H-NMR detects, as a result shows that cyclic carbonate accessory substance is few to the makrolon that embodiment is obtained
In 1.0%, carbonate unit content is higher than 99% in polymer.
Embodiment 17
In glove box, complex prepared by 0.075mmol embodiments 8,0.075mmol [PPN] Cl and 75mmol do
Dry furfuryl glycidyl ether be added to it is pre- first pass through water removal, deoxygenation treatment 15mL autoclaves in, autoclave is taken out
The CO with pressure adjusting function is run through after glove box2Supply line in kettle to being filled with CO2To 1.0MPa, temperature control is existed
60 DEG C, pressure is risen into 3.0MPa, by temperature control at 60 DEG C stirring reaction 5 hours.After polymerisation terminates, by reactor
It is cooled to room temperature, slowly bleeds off carbon dioxide, the complete furfuryl glycidyl ether of unreacted is taken out in room temperature in vacuum drying chamber, claims
The makrolon for restoring is 2.61g.
It is 50h by the TOF values for calculating the catalyst system and catalyzing-1。
The molecular weight of the makrolon obtained to embodiment by GPC is measured, and its result measures number-average molecular weight and is
5100, molecular weight distribution 1.15,
Pass through1H-NMR detects, as a result shows that cyclic carbonate accessory substance is few to the makrolon that embodiment is obtained
In 5.0%, carbonate unit content is higher than 99% in polymer.
Embodiment 18
In glove box, complex prepared by 0.037mmol embodiments 2,0.037mmol [PPN] Cl and 75mmol do
Dry 7-oxa-bicyclo[4.1.0 be added to it is pre- first pass through water removal, deoxygenation treatment 15mL autoclaves in, autoclave is taken out into gloves
The CO with pressure adjusting function is run through after case2Supply line in kettle to being filled with CO2To 1.0MPa, by temperature control 120
DEG C, pressure is risen into 4.0MPa, react 1 hour.After polymerisation terminates, reactor is cooled to room temperature, slowly bleeds off titanium dioxide
Carbon, the complete 7-oxa-bicyclo[4.1.0 of unreacted is taken out in room temperature in vacuum drying chamber, and the makrolon for obtaining of weighing is, 6.3g.
It is 594h by the TOF values for calculating the catalyst system and catalyzing-1。
The molecular weight of the makrolon obtained to embodiment by GPC is measured, and its result measures number-average molecular weight and is
5800, molecular weight distribution 1.14,
Pass through1H-NMR detects, as a result shows that cyclic carbonate accessory substance is few to the makrolon that embodiment is obtained
In 1.0%, carbonate unit content is higher than 99% in polymer.
Embodiment 19
In glove box, complex prepared by 0.037mmol embodiments 2,0.037mmol [PPN] [NO3] and 75mmol
Dry 7-oxa-bicyclo[4.1.0 be added to it is pre- first pass through water removal, deoxygenation treatment 15mL autoclaves in, autoclave is taken out into hand
The CO with pressure adjusting function is run through after casing2Supply line in kettle to being filled with CO2To 1.0MPa, by temperature control 80
DEG C, pressure is risen into 4.0MPa, react 3 hours.After polymerisation terminates, reactor is cooled to room temperature, slowly bleeds off titanium dioxide
Carbon, the complete 7-oxa-bicyclo[4.1.0 of unreacted is taken out in room temperature in vacuum drying chamber, and the makrolon for obtaining of weighing is 5.7g.
It is 180h by the TOF values for calculating the catalyst system and catalyzing-1。
The molecular weight of the makrolon obtained to embodiment by GPC is measured, and its result measures number-average molecular weight and is
6400, molecular weight distribution 1.13,
Pass through1H-NMR detects, as a result shows that cyclic carbonate accessory substance is few to the makrolon that embodiment is obtained
In 1.0%, carbonate unit content is higher than 99% in polymer.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (9)
1. a kind of Titanium series catalyst, as shown in formula (I),
Wherein,
R1It is formula (II) or formula (V) structure,
Wherein, * represents link position,
R5, R6It is independently selected from H, CH3、CH2CH3、CH(CH3)2、C(CH3)3、OCH3、OCH2CH3, Cl, Br or NO2；
R2, R3, R4Independent is selected from：The C1-C20 alkyl of the alkyl of H, C1-C20, the alkoxy of C1-C20 or fluorine substitution,
Or R2And R3And its carbon adjacent with them is collectively forming the ring of closing,
Or R3And R4And its carbon adjacent with them is collectively forming the ring of closing；
X is halogen ,-NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3, p-methylbenzoic acid
Root, p-methyl benzenesulfonic acid root, o-nitrophenol oxygen, p-nitrophenol oxygen, metanitrophenol oxygen, 2,4-DNP oxygen, 3,
5- dinitrophenol oxygen, 2,4,6- trinitrophenol oxygen, 3,5- chlorophenesic acids oxygen, 3,5- difluorophenols oxygen, 3,5-, bis--fluoroforms
Base phenol oxygen or pentafluranol negative oxygen ion.
2. catalyst according to claim 1, it is characterised in that the R2And R3And its carbon common shape adjacent with them
Into closing ring be C6~C20 aromatic rings, C6~C20 substitutions aromatic ring, C3~C20 alicyclic rings, alicyclic ring, C3~C20 are miscellaneous for C3~C20 substitutions
Ring or C3~C20 substituted heterocycles；
The R3And R4And its carbon adjacent with them be collectively forming the ring of closing for C6~C20 aromatic rings, C6~C20 substitutions aromatic ring,
C3~C20 alicyclic rings, C3~C20 substitutions alicyclic ring, C3~C20 heterocycles or C3~C20 substituted heterocycles.
3. catalyst according to claim 1, it is characterised in that the catalyst has formula (I-a) structure,
Wherein, the alkyl selected from H, C1-C20 of a, b, c, d independence, the aryl of C6-C20, substitution C1-C20 alkyl or take
The aryl of the C6-C20 in generation.
4. a kind of preparation method of Titanium series catalyst, including：
1) by aldehyde compound shown in formula (VI-a) and diamine reactant shown in formula (VI-b), four tooth bis-Schiff base parts are obtained；
Wherein,
R1It is formula (II) or formula (V) structure,
Wherein, * represents link position,
R5, R6It is independently selected from H, CH3、CH2CH3、CH(CH3)2、C(CH3)3、OCH3、OCH2CH3, Cl, Br or NO2；
R2, R3, R4Independent is selected from：The C1-C20 alkyl of the alkyl of H, C1-C20, the alkoxy of C1-C20 or fluorine substitution,
Or R2And R3And its carbon adjacent with them is collectively forming the ring of closing；
Or R3And R4And its carbon adjacent with them is collectively forming the ring of closing；
2) by four tooth bis-Schiff base parts and TiCl3.(THF)3React in the presence of a base, obtain Titanium series catalyst.
5. preparation method according to claim 4, it is characterised in that the step 2) alkali be NaH, KH, Rli, RONa
Or ROK,
Wherein, R is the alkyl of C1~C6.
6. preparation method according to claim 4, it is characterised in that the TiCl3.(THF)3Prepare in accordance with the following methods：
By ten dichloro Tritanium/Trititanium aluminium (3TiCl3.AlCl3) slurrying in toluene is dissolved to, add tetrahydrochysene under the conditions of -20 DEG C~-78 DEG C
Furans reacts, and obtains TiCl3.(THF)3。
7. preparation method according to claim 4, it is characterised in that aldehyde compound and formula shown in the formula (VI-a)
(VI-b) mol ratio of diamines shown in is (2~3)：1.
8. a kind of preparation method of makrolon, including：
By the preparation method system described in the catalyst described in claims 1 to 3 any one or claim 4~7 any one
The standby catalyst for obtaining and the reaction of epoxide, co-catalyst and carbon dioxide mix, obtain makrolon.
9. preparation method according to claim 8, it is characterised in that cation in the co-catalyst for quaternary ammonium salt or
Quaternary phosphine salt.
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| Truly Catalytic and Enantioselective Pinacol Coupling of Aryl Aldehydes Mediated by Chiral Ti(III) Complexes;A. Chatterjee et al.;《J. Org. Chem》;20031206;第68卷(第14期);第5668-5671页 * |
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