CN111471134A - Active hydrogen tolerant catalyst, preparation method thereof and ultra-low molecular weight poly (carbonate-ether) polyol - Google Patents

Active hydrogen tolerant catalyst, preparation method thereof and ultra-low molecular weight poly (carbonate-ether) polyol Download PDF

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CN111471134A
CN111471134A CN202010411262.2A CN202010411262A CN111471134A CN 111471134 A CN111471134 A CN 111471134A CN 202010411262 A CN202010411262 A CN 202010411262A CN 111471134 A CN111471134 A CN 111471134A
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carbonate
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CN111471134B (en
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曹瀚
张若禹
周庆海
王献红
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Changchun Institute of Applied Chemistry of CAS
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    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
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    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
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Abstract

The invention provides an active hydrogen tolerant catalyst of formula (I); also provided is a method of preparing an ultra-low molecular weight poly (carbonate-ether) polyol, comprising: under the action of the active hydrogen tolerant catalyst or the active hydrogen tolerant catalyst prepared by the preparation method, carbon dioxide, epoxy compound and initiator carry out chain transfer polymerization reaction to obtain the ultra-low molecular weight poly (carbonate-ether) polyol. The active hydrogen tolerant catalyst is an alternative multi-center Lewis acid-base pair catalyst; has high proton tolerance, so that the method is not limited by the concentration of a starter any more, and can prepare the carbon dioxide polyol with ultra-low molecular weight. The molecular weight of the ultra-low molecular weight poly (carbonic ester-ether) polyol is 500-1000 g/mol, and the molecular weight distribution is 1.07-1.15; a carbonate segment and an ether segment exist on a main chain at the same time, and the functionality is 2-10; the content of cyclic carbonate as a by-product is less than 1%.

Description

Active hydrogen tolerant catalyst, preparation method thereof and ultra-low molecular weight poly (carbonate-ether) polyol
Technical Field
The invention relates to the technical field of polymers, in particular to an active hydrogen tolerant catalyst, a preparation method thereof and ultra-low molecular weight poly (carbonate-ether) polyol.
Background
Polyether polyols are one of the important raw materials for polyurethane preparation, and due to the large amount of polyurethane used, the production of polyols brings about a large increase in the carbon footprint. In recent years, the environmental pressure of the polyurethane industry has been greatly slowed by the route of preparing polycarbonate-ether polyols by substituting part of the petroleum-based monomer with carbon dioxide. Meanwhile, chinese patent CN105566597A reports that the aqueous polyurethane prepared from carbon dioxide polyol has more comprehensive hydrolysis/oxidation resistance compared with polyether-based polyurethane. However, researchers have found that as the amount of carbon dioxide inserted increases, the viscosity and glass transition temperature of the polyol increase, which leads to problems of decreased mass transfer capability and poor compatibility in the production of polyurethane, and further affects the product properties of polyurethane (T.E. Mueller, et al; Macromolecules2016,49, 8995-9003). One solution to circumvent the negative impact of carbon dioxide insertion while retaining the performance advantages of carbonate units is to control the molecular weight of the polyol. If the carbon dioxide polyol can be prepared into the ultra-low molecular weight polyol, namely the molecular weight is reduced to below 1000g/mol, the glass transition temperature is low, the viscosity is low, the polyol compatibility is good, the urethane content of a polymerization product is high, and the application performance is further improved.
However, the synthesis of carbon dioxide polyol with ultra-low molecular weight has great challenges, and no literature and patent reports exist so far about the efficient and controllable synthesis of high carbon dioxide content polyol with the molecular weight of 1000g/mol or less. Using propylene oxide/carbon dioxide copolymer polyols (PPC polyols) as an example, formula for calculating theoretical molecular weight of carbon dioxide polyolIs Mpolyol＝Mstarter+([PO]/[starter]) Conv (102 CU% +58 (1-CU)), wherein starter is initiator, MstarterAs starter molar mass PO is propylene oxide, conv. is propylene oxide conversion, CU% is carbonate unit content. Therefore, achieving the preparation of ultra-low molecular weight polyols requires a substantial increase in the amount of chain transfer initiator. However, high concentrations of starter present compatibility problems with the catalyst. In the field of carbon dioxide polyols, the zinc-cobalt double metal cyanide catalysts (Zn-Co DMC) are currently the most widely used catalysts. The catalyst has low proton tolerance, and under the existence of active protons such as high-concentration hydroxyl, carboxyl and the like, the catalyst is inactivated due to irreversible coordination, so that the polymerization reaction is uncontrollable, and the ultra-low molecular weight polyol is difficult to synthesize. Chinese patent CN102617844A discloses a method for preparing polycarbonate-ether polyol, in which the catalyst used is rare earth doped modified double metal cyanide catalyst (Re-DMC), and although the catalytic activity is improved, the catalyst is deactivated at high initiator dosage (5-10 mol ratio of propylene oxide/initiator).
Therefore, it is very necessary to develop a catalyst having high proton tolerance and to synthesize an ultra-low molecular weight carbon dioxide polyol.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an active hydrogen tolerant catalyst, which has high proton tolerance and can synthesize ultra-low molecular weight polyol.
The invention provides an active hydrogen tolerant catalyst of formula (I), comprising:
Figure BDA0002493334610000021
the above-mentioned
Figure BDA0002493334610000022
Is a linking group, is independently selected from the structures of a formula b, a formula c or a formula d, L A is a metalloporphyrin complex with the structure of a formula (II), LB is Lewis base with the structure of formula (e) to formula (g);
Figure BDA0002493334610000023
Figure BDA0002493334610000031
wherein n is polymerization degree and is 4-40, and m is 4-12; o, p and q are the number of methylene groups, the value is 1-7, E1、E2Independently selected from alkyl of C1-C10; e3Is C5-C20 alkyl; y is a quaternary ammonium anion; m is a trivalent metal ion, R1、R2、R3、R4、R5、R6、R7、R8、R9Each independently is one of hydrogen, halogen, amino, nitro, cyano, C1-C10 aliphatic group, substituted C1-C10 aliphatic group, C6-C30 aryl or substituted C6-C30 aryl; x is selected from halogen, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3P-methylbenzoyl, o-nitrophenol oxygen, p-nitrophenol oxygen, m-nitrophenol oxygen, 2, 4-dinitrophenol oxygen, 3-5-dinitrophenol oxygen, 2,4, 6-trinitrophenol oxygen, 3, 5-dichlorophenol oxygen, 3, 5-difluorophenol oxygen, 3, 5-bis-trifluoromethylphenol oxygen or pentafluorophenol oxygen anion.
Preferably, said E1、E2Independently selected from alkyl of C1-C6; e3Is C10-C15 alkyl; y is selected from halogen atoms, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3P-methylbenzoyl, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanionIons, 3, 5-dichlorophenol oxyanions, 3, 5-difluorophenol oxyanions, 3, 5-bistrifluoromethylphenol oxyanions or pentafluorophenol oxyanions.
Preferably, M is selected from one or more of Al, Co, Mn, Fe or Ti.
Preferably, the active hydrogen tolerant catalyst is specifically formula 101, formula 102, formula 103 or formula 104;
Figure BDA0002493334610000032
Figure BDA0002493334610000041
the invention provides a preparation method of an active hydrogen tolerant catalyst shown in a formula (I), which comprises the following steps:
A) reacting p-hydroxybenzaldehyde, substituted benzaldehyde and pyrrole under the condition of propionic acid reflux, and performing column chromatography separation to obtain monohydroxy substituted asymmetric porphyrin;
performing dehydration reaction on maleimide and halogenated alkyl alcohol under the conditions of diisopropyl azodicarboxylate and triphenylphosphine to obtain halogenated alkyl chain-substituted maleimide,
B) reacting the halogenated alkyl chain-substituted maleimide and monohydroxy-substituted porphyrin under an alkaline condition to synthesize ether, so as to prepare a maleimide porphyrin monomer;
C) carrying out asymmetric addition reaction on divinyl ether and hydrogen bromide to obtain an intermediate with a structure shown in a formula (h), and then reacting with TBD or salinizing quaternary ammonium to obtain a vinyl ether monomer;
D) performing alternate copolymerization reaction on maleimide porphyrin monomers and vinyl ether monomers, and then reacting with diethyl aluminum chloride to obtain an active hydrogen tolerant catalyst shown in a formula (I);
Figure BDA0002493334610000042
the invention provides a preparation method of ultra-low molecular weight poly (carbonate-ether) polyol, which comprises the following steps:
under the action of the active hydrogen tolerant catalyst of any one of claims 1 to 4 or the active hydrogen tolerant catalyst prepared by the preparation method of claim 5, carbon dioxide, an epoxy compound and an initiator perform chain transfer polymerization reaction to obtain the ultra-low molecular weight poly (carbonate-ether) polyol.
Preferably, the epoxide is selected from one or more of ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide, cyclohexene oxide, cyclopentane epoxide, epichlorohydrin glycidyl methacrylate ether, methyl glycidyl ether, phenyl glycidyl ether, styrene alkylene oxide, 4-vinyl-1, 2-cyclohexene oxide and vinyl propylene oxide.
Preferably, the initiator is selected from one or more of water, small molecule alcohols, phenols, thiols, carboxylic acids, hydroxy acids and hydroxyl-containing oligomers; the hydroxyl-containing oligomer of the present invention is preferably polyglycerol (polyglycerol-06 and polyglycerol-10).
Wherein the small molecular alcohol is ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, octanediol, sebacic acid diol, dipropylene glycol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylolethane, trimethylolpropane, glycerol, 1,2, 4-butanetriol, polyestertriol, pentaerythritol, xylitol, sorbitol, tripentaerythritol or polyglycidyl oligomers;
the phenol is catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 4 '-ethylidene biphenol and 4,4' - (2-methylpropylidene) biphenol; 4,4- (2-ethylhexyl) biphenol, 2 '-methylenebiphenol or 2,2' - (1, 2-cyclohexanediyl-dinitrosopolylene) biphenol;
the carboxylic acid is preferably malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, terephthalic acid, phthalic acid, isophthalic acid, maleic acid, trimesic acid, pyromellitic acid or oleic acid;
the hydroxy acid is lactic acid, hydroxybutyric acid, hydroxyvaleric acid, malic acid, tartaric acid, citric acid or salicylic acid.
Preferably, the polymerization reaction temperature is 25-150 ℃; the pressure of the polymerization reaction is 0.1-6 MPa; the time of the polymerization reaction is 0.5-24 h.
The invention also provides an ultra-low molecular weight poly (carbonate-ether) polyol prepared by any one of the preparation methods.
Compared with the prior art, the invention provides an active hydrogen tolerant catalyst shown in formula (I); also provided is a method of preparing an ultra-low molecular weight poly (carbonate-ether) polyol, comprising: under the action of the active hydrogen tolerant catalyst or the active hydrogen tolerant catalyst prepared by the preparation method, carbon dioxide, epoxy compound and initiator carry out chain transfer polymerization reaction to obtain the ultra-low molecular weight poly (carbonate-ether) polyol. The active hydrogen tolerant catalyst is an alternative multi-center Lewis acid-base pair catalyst; has high proton tolerance and is therefore no longer limited by starter concentration, and can be self-contained with ultra-low molecular weight carbon dioxide polyols. The molecular weight of the ultra-low molecular weight poly (carbonic ester-ether) polyol is 500-1000 g/mol, and the molecular weight distribution is 1.07-1.15; a carbonate segment and an ether segment exist on a main chain at the same time, and the functionality is 2-10; the content of cyclic carbonate as a by-product is less than 1%.
Drawings
FIG. 1 is a GPC characterization chart of the product of example 5 of the present invention;
FIG. 2 is a graph of theoretical molecular weight versus relative molecular weight (GPC) for the product of example 5 of the present invention;
FIG. 3 shows the theoretical molecular weight and absolute molecular weight of the product of example 5 of the present invention: (1H NMR);
FIG. 4 is a graph of the product of example 5 of the present invention1H NMR spectrum;
FIG. 5 is a graph of glass transition temperature versus molecular weight for the product of example 5 of the present invention.
Detailed Description
The invention provides an active hydrogen tolerant catalyst, a preparation method thereof and an ultra-low molecular weight poly (carbonate-ether) polyol, and can be realized by appropriately improving process parameters by taking the contents of the catalyst as reference by a person skilled in the art. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention provides an active hydrogen tolerant catalyst of formula (I), comprising:
Figure BDA0002493334610000061
wherein n is polymerization degree, the value is 4-40, preferably 4-35,
the above-mentioned
Figure BDA0002493334610000062
Is a linking group; independently selected from the structures of formula b, formula c or formula d, may be the same or different, preferably different. When the difference is different, the name "chain b" or "chain c" can be used.
Figure BDA0002493334610000063
m is 4-12; in particular, it may be 4, 5, 6, 7, 8, 9, 10, 11 or 12.
Preferably, chain B is attached to L B and chain c is attached to L A.
L A of the invention is a metalloporphyrin complex with a structure of formula (II);
Figure BDA0002493334610000071
wherein, M is trivalent metal ion, preferably one or more selected from Al, Co, Mn, Fe or Ti.
E1、E2Independently selected from alkyl of C1-C10; preferably C1-C6 alkyl; can be methyl, ethyl, propyl, butyl; preferably methyl;
E3is C5-C20 alkyl; preferably C10-C15 alkyl; particularly preferably C12H25；
R1、R2、R3、R4、R5、R6、R7、R8、R9Each independently is one of hydrogen, halogen, amino, nitro, cyano, C1-C10 aliphatic group, substituted C1-C10 aliphatic group, C6-C30 aryl or substituted C6-C30 aryl; preferably, the compound is one selected from hydrogen, halogen, amino, nitro, cyano, aliphatic groups of C1-C6, substituted aliphatic groups of C1-C6, aryl groups of C6-C30 or substituted aryl groups of C6-C30; wherein the aryl of C6-C30 is preferably the aryl with 1-3 benzene rings; the substituted aryl of C6-C30 is preferably substituted aryl with 1-3 benzene rings.
X is selected from halogen, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3P-methylbenzoyl, o-nitrophenol oxygen, p-nitrophenol oxygen, m-nitrophenol oxygen, 2, 4-dinitrophenol oxygen, 3-5-dinitrophenol oxygen, 2,4, 6-trinitrophenol oxygen, 3, 5-dichlorophenol oxygen, 3, 5-difluorophenol oxygen, 3, 5-bis-trifluoromethylphenol oxygen or pentafluorophenol oxygen anion;
the metalloporphyrin complex with the structure of the formula (II) can be preferably a compound of the formula (II-1) or a compound of the formula (II-2);
Figure BDA0002493334610000081
the L B is Lewis base with a structure from a formula (e) to a formula (g), in particular to one or more of an organic base 157-triazabicyclo (4.4.0) dec-5-ene group (TBD) with a structure shown in a formula e, a pyridine group with a structure shown in a formula f and quaternary ammonium salt with a structure shown in a formula g;
Figure BDA0002493334610000082
wherein o, p and q are the number of methylene groups, the value is 1-7, and can be 1,2, 3, 4, 5, 6 or 7; preferably 5.
Y is a quaternary ammonium anion; said Y is preferably selected from halogen atoms, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3P-methylbenzoyl, o-nitrophenol oxyanions, p-nitrophenol oxyanions, m-nitrophenol oxyanions, 2, 4-dinitrophenol oxyanions, 3, 5-dinitrophenol oxyanions, 2,4, 6-trinitrophenol oxyanions, 3, 5-dichlorophenol oxyanions, 3, 5-difluorophenol oxyanions, 3, 5-bistrifluoromethylphenol oxyanions or pentafluorophenol oxyanions; more preferably a halide ion, most preferably chlorine; namely, the quaternary ammonium salt group structure is preferably n-hexyl ammonium chloride.
According to the invention, the active hydrogen tolerant catalyst is specifically formula 101, formula 102, formula 103 or formula 104;
Figure BDA0002493334610000091
the invention provides a preparation method of an active hydrogen tolerant catalyst shown in a formula (I), which comprises the following steps:
A) reacting p-hydroxybenzaldehyde, substituted benzaldehyde and pyrrole under the condition of propionic acid reflux, and performing column chromatography separation to obtain monohydroxy substituted asymmetric porphyrin;
performing dehydration reaction on maleimide and halogenated alkyl alcohol under the conditions of diisopropyl azodicarboxylate and triphenylphosphine to obtain halogenated alkyl chain-substituted maleimide,
B) reacting the halogenated alkyl chain-substituted maleimide and monohydroxy-substituted porphyrin under an alkaline condition to synthesize ether, so as to prepare a maleimide porphyrin monomer;
C) carrying out asymmetric addition reaction on divinyl ether and hydrogen bromide to obtain an intermediate with a structure shown in a formula (h), and then reacting with TBD or salinizing quaternary ammonium to obtain a vinyl ether monomer;
D) performing alternate copolymerization reaction on maleimide porphyrin monomers and vinyl ether monomers, and then reacting with diethyl aluminum chloride to obtain an active hydrogen tolerant catalyst shown in a formula (I);
Figure BDA0002493334610000092
the preparation method of the active hydrogen tolerant catalyst shown in the formula (I) provided by the invention comprises the steps of firstly reacting p-hydroxybenzaldehyde, substituted benzaldehyde and pyrrole under the condition of propionic acid reflux, and performing column chromatography separation to obtain monohydroxy substituted asymmetric porphyrin.
The preferable concrete is as follows: p-hydroxybenzaldehyde, substituted benzaldehyde and pyrrole are subjected to one-pot reaction under the condition of propionic acid reflux, and a second color band is collected by a column chromatography separation technology to obtain monohydroxy substituted asymmetric porphyrin.
The molar ratio of the hydroxybenzaldehyde, the substituted benzaldehyde and the pyrrole is preferably 1:3:4, and the temperature of the reflux reaction is 165 ℃. . . The time is 2 h. The column chromatography is specifically eluted and separated by a silica gel column with eluting agent of chloroform/methanol (50: 1), and the second color band is collected.
And (3) carrying out dehydration reaction on maleimide and halogenated alkyl alcohol under the conditions of diisopropyl azodicarboxylate and triphenylphosphine to obtain the halogenated alkyl chain substituted maleimide.
The mole ratio of the maleimide, the halogenated alkyl alcohol, the diisopropyl azodicarboxylate and the triphenylphosphine is preferably 1: 1.5: 1: 1. . . The temperature of the dehydration reaction is preferably 25 ℃. . . The time is preferably 10 h. The halogenated alkyl alcohol may specifically be 6-chloro-1-hexanol.
Then the maleimide and monohydroxy substituted porphyrin are subjected to ether synthesis reaction under alkaline conditions to prepare a maleimide porphyrin monomer;
the molar ratio of maleimide to monohydroxy-substituted porphyrin is preferably 1.2: 1. the temperature of the reaction is preferably 100 ℃; the time is preferably 12 h.
Carrying out asymmetric addition reaction on divinyl ether and hydrogen bromide to obtain an intermediate with a structure shown in a formula (h), and then reacting with TBD or salinizing quaternary ammonium to obtain a vinyl ether monomer; the method specifically comprises the following steps: the divinyl ether and hydrogen bromide are subjected to equivalent asymmetric addition reaction to obtain
Figure BDA0002493334610000101
The intermediate can react with TBD under the condition of potassium carbonate to obtain vinyl ether TBD monomer, or the intermediate quaternary ammonium salt is salinized to obtain vinyl ether quaternary ammonium salt monomer.
The above divinyl ether/hydrogen bromide/TBD molar ratio was (1: 1: 1.1). The temperature of the reaction is preferably 60 ℃; the time is preferably 2 d.
And (2) carrying out alternate copolymerization reaction on the maleimide porphyrin monomer and the vinyl ether monomer, and then reacting with diethyl aluminum chloride to obtain the active hydrogen tolerant catalyst shown in the formula (I).
Under the condition of taking trithioester as a chain transfer agent, carrying out RAFT polymerization on a maleimide monomer and a vinyl ether monomer, wherein the reactivity ratios of the maleimide monomer and the vinyl ether monomer accord with an alternating copolymerization behavior, so that the obtained polymer is an alternating copolymer with a side chain of porphyrin and quaternary ammonium salt or TBD, and finally, the polymer is reacted with diethylaluminum chloride in dichloromethane to finally obtain the catalyst with the structure of the formula II.
The copolymerization technology adopts a reversible addition-fragmentation chain transfer polymerization (RAFT) technology, belongs to active free radical polymerization, and has controllable polymerization degree and narrow molecular weight distribution.
chain b has the ability to control the carbon dioxide polyol carbonate/ether ratio, formula b tends to form ether units, preferably with the structure n-hexyloxy; formula d tends to form carbonate units;
the specific implementation mode of chain b access is a Mitsunobu reaction, namely, maleimide and halogenated alkyl alcohol are subjected to a dehydration reaction under the conditions of diisopropyl azodicarboxylate and triphenylphosphine;
the specific embodiment of chain c access is obtained by asymmetric addition reaction of equivalent weight of divinyl ether and hydrogen bromide
Figure BDA0002493334610000111
The intermediate can be reacted with TBD under the condition of potassium carbonate to connect TBD to L B, and can also be directly quaternized to connect quaternary ammonium salt group to L B.
The key point of preparing the carbon dioxide polyalcohol with the ultra-low molecular weight lies in solving the problem that the catalyst is easy to inactivate under the condition of high active proton concentration. The invention provides a preparation method of a catalyst with high proton tolerance, which is a polymer with Lewis acid base pairs on side chains alternately existing.
The invention provides a preparation method of ultra-low molecular weight poly (carbonate-ether) polyol, which comprises the following steps:
under the action of the active hydrogen tolerant catalyst or the active hydrogen tolerant catalyst prepared by the preparation method in any one of the technical schemes, carbon dioxide, epoxy compound and initiator carry out chain transfer polymerization reaction to obtain the ultra-low molecular weight poly (carbonate-ether) polyol.
The preparation method of the ultra-low molecular weight poly (carbonate-ether) polyol firstly provides the active hydrogen tolerant catalyst or the active hydrogen tolerant catalyst prepared by the preparation method in any one of the technical schemes.
The specific structure and composition of the catalyst and the preparation method of the catalyst are clearly described above, and are not repeated herein.
Under the action of the catalyst, carrying out chain transfer polymerization reaction on carbon dioxide, an epoxy compound and an initiator, wherein the reaction is shown as a formula i;
Figure BDA0002493334610000112
in the formula i, the reaction mixture is,
Figure BDA0002493334610000113
is an epoxide, and is prepared by reacting a compound of the formula,
Figure BDA0002493334610000114
as initiator and catalyst.
According to the invention, the epoxide is selected from one or more of ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide, cyclohexene oxide, cyclopentane epoxide, epichlorohydrin glycidyl methacrylate ether, methyl glycidyl ether, phenyl glycidyl ether, styrene alkylene oxide, 4-vinyl-1, 2-cyclohexene oxide and vinyl propylene oxide.
The initiator is selected from one or more of water, small molecule alcohol, phenol, thiol, carboxylic acid, hydroxy acid and oligomer containing hydroxyl; the hydroxyl-containing oligomer of the present invention is preferably polyglycerol (polyglycerol-06 and polyglycerol-10). . . .
Wherein the small molecular alcohol is ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, octanediol, sebacic acid diol, dipropylene glycol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylolethane, trimethylolpropane, glycerol, 1,2, 4-butanetriol, polyestertriol, pentaerythritol, xylitol, sorbitol, tripentaerythritol or polyglycidyl oligomers;
the phenol is catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 4 '-ethylidene biphenol and 4,4' - (2-methylpropylidene) biphenol; 4,4- (2-ethylhexyl) biphenol, 2 '-methylenebiphenol or 2,2' - (1, 2-cyclohexanediyl-dinitrosopolylene) biphenol;
the carboxylic acid is preferably malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, terephthalic acid, phthalic acid, isophthalic acid, maleic acid, trimesic acid, pyromellitic acid or oleic acid;
the hydroxy acid is lactic acid, hydroxybutyric acid, hydroxyvaleric acid, malic acid, tartaric acid, citric acid or salicylic acid.
The sources of the above components are not limited in the present invention and are well known to those skilled in the art.
The molar ratio of the catalyst, the epoxy compound and the initiator according to the invention is preferably 50000: 1: (5-10).
The polymerization reaction temperature is 25-150 ℃; more preferably 30 ℃ to 130 ℃; most preferably 40 ℃ to 120 ℃; the pressure of the polymerization reaction is 0.1-6 MPa, namely the pressure of the carbon dioxide; more preferably 0.5 to 5.0 MPa; the time of the polymerization reaction is preferably 0.5-24 h; more preferably 0.5h to 20 h; most preferably 1 to 15 hours.
The key point of the preparation technology of the ultra-low molecular weight carbon dioxide polyol provided by the invention is to provide a catalyst with a structure shown in a formula I. The catalyst is prepared by an 'activity'/controllable free radical technology, and the polymerization degree of the catalyst is highly controllable, so the catalyst is soluble in a reaction system and belongs to a homogeneous catalyst; the comonomer utilized in the catalyst preparation is maleimide monomer of bond chain Lewis acid and vinyl ether monomer of bond chain Lewis base, and the reactivity ratio of the maleimide monomer and the vinyl ether monomer accords with a complete alternating copolymerization mode, so that the Lewis acid and the Lewis base naturally exist in an alternating form in the structure of the obtained polymer catalyst; the Lewis acid is a metalloporphyrin complex group, wherein the central metal M has the functions of coordinating epoxide and initiator, and the co-ligand X has the function of deprotonation, so that the monomer and the initiator can be simultaneously stabilized and activated; lewis bases have the effect of opening the epoxide ring, and since the Lewis acid-base pair is present in 1:1 alternation, the activation of the monomer, initiator and ring opening of the monomer proceeds in a close, precise, synergistic fashion. In such a synergistic mode, the initiator does not participate in the reaction by chain transfer, but directly deprotonates and directly promotes the insertion polymerization of epoxide and carbon dioxide in the form of an initiator; thus, unlike conventional catalysts such as DMC, the Lewis acid base having the structure of formula II has a high degree of proton tolerance to alternating polymer catalysts and is therefore no longer limited by starter concentration, enabling efficient, controlled synthesis of ultra-low molecular weight carbon dioxide polyols.
The invention also provides an ultra-low molecular weight poly (carbonate-ether) polyol prepared by any one of the preparation methods.
The molecular weight of the ultra-low molecular weight oligomeric (carbonic ester-ether) polyol product is 500-1000 g/mol, and the molecular weight distribution is 1.07-1.15; a carbonate segment and an ether segment exist on a main chain at the same time, and the functionality is 2-10; the content of cyclic carbonate as a by-product is less than 1%.
The invention provides an active hydrogen tolerant catalyst of formula (I); also provided is a method of preparing an ultra-low molecular weight poly (carbonate-ether) polyol, comprising: under the action of the active hydrogen tolerant catalyst or the active hydrogen tolerant catalyst prepared by the preparation method, carbon dioxide, epoxy compound and initiator carry out chain transfer polymerization reaction to obtain the ultra-low molecular weight poly (carbonate-ether) polyol. The active hydrogen tolerant catalyst is an alternative multi-center Lewis acid-base pair catalyst; has high proton tolerance and is therefore no longer limited by starter concentration, and can be self-contained with ultra-low molecular weight carbon dioxide polyols. The molecular weight of the ultra-low molecular weight poly (carbonic ester-ether) polyol is 500-1000 g/mol, and the molecular weight distribution is 1.07-1.15; a carbonate segment and an ether segment exist on a main chain at the same time, and the functionality is 2-10; the content of cyclic carbonate as a by-product is less than 1%.
To further illustrate the present invention, an active hydrogen tolerant catalyst, a method of making the same, and an ultra low molecular weight poly (carbonate-ether) polyol, provided herein are described in detail below with reference to the examples.
Example 1
Figure BDA0002493334610000141
Triphenylphosphine (1.35g,5.15mmol) was dissolved in 20ml of water-removed THF solution, the reaction was set to-78 ℃ using a dry ice/acetone bath, diisopropyl azodicarboxylate DIAD (1.01ml,5.15mmol) was added dropwise over a period of about 2min, the solution was yellow after completion of the addition, after stirring for 10 minutes, 6-chloro-1-hexanol (1.16g,8.5mmol) was added dropwise, maleimide (0.5g,5.15mmol) was added after 5 minutes, the reaction was allowed to return to room temperature for 10h, the reaction was dark gray, the crude product was chromatographed on a silica gel column (eluent n-hexane/ethyl acetate 2/1), product E L1 was a pale yellow solid, yield 66%.1HNMR(300MHz,CDCl3)＝6.72,3.68,3.37,2.15～2.07,1.75～1.71MS(ESI):[C10H14ClNO2],m/z＝215.7[M+H]+(calcd.215.7)。
Adding p-hydroxybenzaldehyde (13.2g,108mmol), p-bromobenzaldehyde (59.74g,324mmol) and propionic acid 500m L, heating to 130 deg.C, adding pyrrole (30m L, 432mmol), heating to 160 deg.C, refluxing for 2h, cooling to room temperature after reaction, adding methanol, cooling overnight in refrigerator, filtering to obtain product, and performing silica gel column chromatography (CHCl)3/CH3OH) purification the second color band was collected to yield the product E L2 in about 12% yield.1H NMR(300MHz,CDCl3)＝8.91,8.10,7.92,7.15,-2.82MS(MALDI-ToF):[C44H27Br3N4O],m/z＝863.9[M+H]+(calcd.863.9)。
Under the protection of nitrogen, E L1 (0.26g,1.2mmol), E L2 (0.86g,1mmol), anhydrous potassium carbonate (0.28g,2mmol) and a catalytic amount of potassium iodide (10mg) are dissolved in 50ml of dehydrated DMF, the reaction is carried out at 100 ℃ for 12h, after the reaction is finished, potassium salt is removed by filtration, DMF is evaporated by rotation, the crude product is dissolved in dichloromethane and washed with water for three times, an organic phase is dried by anhydrous magnesium sulfate, and the solid product is separated and purified by a silica gel chromatographic column (eluent dichloromethane) to obtain purple solid E L3 with the yield of 85%.1HNMR(300MHz,CDCl3)＝8.91,8.10,7.92,7.15,6.75,3.61,3.37,2.13,1.73,-2.82MS(MALDI-ToF):[C54H40Br3N5O3],m/z＝1046[M+H]+(calcd.1046)。
Adding potassium hydroxide (0.47g, 8.4mmol) into anhydrous ethylene glycolAfter the system was evacuated to a negative pressure, the temperature was raised to 80 ℃ and dissolved by heating, dichlorodiethyl ether (0.3g, 2.1mmol) was added dropwise to the system using a constant pressure low liquid funnel, and the condensed liquid E L4 was collected and the reaction was stopped when no liquid was condensed, with a yield of 35%.1H NMR(300MHz,CDCl3)＝6.50,4.24,4.16,4.08,3.97MS(ESI):[C4H7ClO],m/z＝106.5[M+H]+(calcd.106.5)。
E L5 is an alternating copolymer of E L3 and E L4, and is prepared by RAFT polymerization technology, dissolving E L3 (2.1g,2mmol), E L4 (0.21g,2mmol), 2- (dodecyltrithiocarbonate) -2-methylpropanoic acid (DDMAT) (36mg,0.1mmol) and Azobisisobutyronitrile (AIBN) (8mg,0.05mmol) in 50ml of water-removed THF, freezing to remove oxygen for 3 times, introducing nitrogen, reacting at 65 deg.C for 24h, quenching with liquid nitrogen, precipitating with cold ether, collecting precipitate, repeatedly dissolving with dichloromethane-cold ether, centrifuging for 5 times, vacuum drying to obtain oligomeric porphyrin ligand E L5, yield 49%, gel permeation chromatography (GPC, PS standard, CH) to obtain oligomeric porphyrin ligand E L2Cl2):Mn＝14700,PDI＝1.49。
In a glove box, E L5 is dissolved in dichloromethane, diethyl aluminum chloride (2 mol/L n-hexane solution) with equivalent weight of porphyrin ring is added dropwise, the mixture is stirred and reacted for 3 hours at room temperature, a crude product is purified by neutral alumina column chromatography (eluent dichloromethane), a metallization product is dried in vacuum, 0.4g of the metallization product is dissolved in 5ml of purified trichloromethane and 5ml of purified acetonitrile mixed solvent, 5.4g of trihexylamine (20mmol) is added, the mixture is refluxed for 3 days in dark environment, after the reaction is finished, the mixture is cooled to room temperature, the solvent is removed under reduced pressure, redundant tributylamine is removed by a dropper, the obtained solid is crushed and washed in ether for three times, and residual trace tributylamine is removed, namely CAT1 with the yield of 89 percent is obtained.
Example 2
Figure BDA0002493334610000161
Adding p-hydroxybenzaldehyde (13.2g,108mmol), 2, 4-dichlorobenzaldehyde (56.8g,324mmol) and 500m of L propionic acid, heating to 130 deg.C, adding pyrrole (30m L, 432mmol), and heating to 130 deg.CReflux-reacting at 160 deg.C for 2h, cooling to room temperature after reaction, adding methanol, cooling in refrigerator overnight, filtering to obtain product, and performing silica gel column chromatography (CHCl)3/CH3OH) purification the second color band was collected to yield the product E L6 in about 9% yield.1H NMR(300MHz,CDCl3)＝8.89,8.13,7.92,7.10,-2.82MS(MALDI-ToF):[C44H24Br6N4O],m/z＝837.4[M+H]+(calcd.837.4)。
Under the protection of nitrogen, E L1 (0.26g,1.2mmol), E L6 (0.84g,1mmol), anhydrous potassium carbonate (0.28g,2mmol) and a catalytic amount of potassium iodide (10mg) are dissolved in 50ml of dehydrated DMF, the reaction is carried out at 100 ℃ for 12h, after the reaction is finished, potassium salt is removed by filtration, DMF is evaporated by rotation, the crude product is dissolved in dichloromethane and washed with water for three times, an organic phase is dried by anhydrous magnesium sulfate, and the solid product is separated and purified by a silica gel chromatographic column (eluent dichloromethane) to obtain purple solid E L7 with the yield of 81%.1HNMR(300MHz,CDCl3)＝8.91,8.11,7.89,7.11,6.75,3.61,3.37,2.13～2.10,1.73～1.71,-2.82MS(MALDI-ToF):[C54H37Cl6N5O3],m/z＝1016.6[M+H]+(calcd.1016.6)。
Under nitrogen protection, a dry 50ml three-necked round bottom flask was charged with E L4 (0.11g,1mmol), 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (TBD) (0.15g,1.1mmol) and anhydrous potassium carbonate (0.28g,2mmol), dissolved in 20ml of dehydrated DMF, reacted at 60 ℃ for 2d, the solvent was distilled off under reduced pressure, the crude product was chromatographed on a neutral alumina column, unreacted TBD and residual DMF were first removed with pure dichloromethane, and then purified by silica gel column chromatography (eluent dichloromethane/methanol ═ 1/1) to obtain E L8 with a yield of 95%.1H NMR(300MHz,DMSO)＝6.51,4.37,4.13,3.95,3.73,3.51,3.44,1.96,1.71；MS(ESI):[C11H19N3O],m/z＝209.3[M+H]+(calcd.209.3)。
E L9 is an alternating copolymer of two monomers E L7 and E L8, prepared by RAFT polymerization technique in glove box by dissolving E L7 (2.0g,2mmol), E L8 (0.42g,2mmol), 2- (dodecyltrithiocarbonate) -2-methylpropanoic acid (DDMAT) (36mg,0.1mmol), Azobisisobutyronitrile (AIBN) (8mg,0.05mmol) in 50ml water-removed THF, freezing to remove oxygen for 3 times, charging nitrogen gas, reacting at 65 deg.C for 24h, quenching with liquid nitrogen, precipitating with cold etherCollecting precipitate after precipitation, repeatedly dissolving with dichloromethane-cold diethyl ether, centrifuging for 5 times, and vacuum drying to obtain oligomeric porphyrin ligand E L9 with yield of 41%2Cl2):Mn＝12900,PDI＝1.31。
Dissolving E L5 in dichloromethane in a glove box, dropwise adding diethyl aluminum chloride (2 mol/L n-hexane solution) with the equivalent of porphyrin ring, stirring at room temperature for reaction for 3 hours, purifying the crude product by neutral alumina column chromatography (eluent dichloromethane), and vacuum drying the metallization product to obtain CAT2 with the yield of 93%.
Example 3
Figure BDA0002493334610000171
Figure BDA0002493334610000181
Triphenylphosphine (1.35g,5.15mmol) was dissolved in 20ml of water-removed THF solution, and the reaction was set to-78 ℃ using a dry ice/acetone bath, diisopropyl azodicarboxylate DIAD (1.01ml,5.15mmol) was added dropwise over a period of about 2min, the solution was yellow after completion of the addition, after 10 minutes of stirring, 4' -dimethyloldiphenyl (1.82g,8.5mmol) was added dropwise, maleimide (0.5g,5.15mmol) was added after 5 minutes, the reaction was allowed to return to room temperature and reacted for 10h, the reaction was dark gray, after rotary evaporation of the solvent, the crude product was isolated by silica gel column chromatography (eluent n-hexane/ethyl acetate 1/1), product E L10 was a brown solid with a yield of 41%.1H NMR(300MHz,DMSO)＝7.41,7.37,6.79,5.31,3.85,3.40MS(ESI):[C18H15NO3],m/z＝293.3[M+H]+(calcd.293.3)。
Under the protection of nitrogen, E L10 (2.93g,10mmol), pyridine tribromide (4.0g,12.5mmol) and Hexamethyldisilane (HDMS) (1.83g,12.5mmol) are dissolved in 25ml of dehydrated chloroform, the mixture is stirred at room temperature, heat is released in the system, insoluble salt appears, a T L C point plate (developer n-hexane) monitors whether the reaction is finished (about 30 minutes), after the reaction is finished, 50ml of diethyl ether is added, the mixture is washed for 5 times to completely remove the pyridine salt, anhydrous sodium sulfate is dried, the solvent is dried in vacuum, and the reaction product is obtainedE L11 in 95% yield, E L11 (0.43g,1.2mmol), E L2 (0.86g,1mmol), anhydrous potassium carbonate (0.28g,2mmol) and a catalytic amount of potassium iodide (10mg) are dissolved in 50ml of dehydrated DMF under the protection of nitrogen, the reaction is carried out at 100 ℃ for 12h, after the reaction is finished, the potassium salt is removed by filtration, after the DMF is evaporated by rotary evaporation, the crude product is dissolved in dichloromethane, washed with water for three times, the organic phase is dried by anhydrous magnesium sulfate, and the solid product is separated and purified by a silica gel chromatographic column (eluent dichloromethane) to obtain E L12 as a purple solid in 83% yield.1H NMR(300MHz,CDCl3)＝8.94,8.31,8.05,7.89,7.62,7.26,6.31,6.19,5.94,5.62,4.28,-2.74MS(MALDI-ToF):[C62H38Br3N5O3],m/z＝1142.8[M+H]+(calcd.1142.8)。
Dissolving E L12 (2.3g,2mmol), E L8 (0.42g,2mmol), 2- (dodecyl trithiocarbonate) -2-methylpropionic acid (DDMAT) (36mg,0.1mmol) and Azobisisobutyronitrile (AIBN) (8mg,0.05mmol) in 50ml of water-removed THF, freezing to remove oxygen for 3 times, introducing nitrogen, reacting at 65 deg.C for 36h, quenching with liquid nitrogen, precipitating with cold ether, collecting precipitate, repeatedly dissolving with dichloromethane-cold ether, centrifuging for 5 times, and vacuum drying to obtain oligomeric porphyrin ligand with yield of 41%2Cl2) In a glove box, an oligomeric porphyrin ligand (Mn 17200, PDI 1.44) was dissolved in dichloromethane, diethylaluminum chloride (2 mol/L n-hexane solution) equivalent to the porphyrin ring was added dropwise, the reaction was stirred at room temperature for 3 hours, the crude product was purified by neutral alumina column chromatography (eluent dichloromethane), and the metalized product was vacuum-dried to obtain CAT3 with a yield of 93%.
Example 4
Figure BDA0002493334610000191
Figure BDA0002493334610000201
Triphenylphosphine (1.35g,5.15mmol) was dissolved in 20ml of the water-depleted THF solution and the reaction was set to-78 ℃ using a dry ice/acetone bath. Dropwise adding azodicarbonic acid diisocynatePropyl ester DIAD (1.01ml,5.15mmol) was added dropwise over about 2min, the solution was yellow after the addition was completed, after stirring for 10 minutes, p-xylene glycol (1.17g,8.5mmol) was added dropwise, after 5 minutes, maleimide (0.5g,5.15mmol) was added, the reaction was allowed to return to room temperature and reacted for 10 hours, the reaction system was dark gray, and after rotary evaporation of the solvent, the crude product was chromatographed over silica gel (eluent n-hexane/ethyl acetate: 1/1) to give E L13 with 53% yield.1H NMR(300MHz,DMSO)＝7.44,7.37,6.71,5.28,3.85,3.39 MS(ESI):[C12H11NO3],m/z＝217.2[M+H]+(calcd.217.2)。
Under the protection of nitrogen, E L13 (2.17g,10mmol), pyridine tribromide (4.0g,12.5mmol) and Hexamethyldisilane (HDMS) (1.83g,12.5mmol) are dissolved in 25ml of dehydrated chloroform, stirring is carried out at room temperature, heat is released in a system, insoluble salt appears, a T L C point plate (developing agent n-hexane) monitors whether the reaction is finished (about 30 minutes), after the reaction is finished, 50ml of diethyl ether is added, the pyridine salt is completely removed by washing with water for 5 times, anhydrous sodium sulfate is dried, after the solvent is dried in a spinning mode, vacuum drying is carried out to obtain E L14, the yield is 95%, then under the protection of nitrogen, E L14 (0.34g,1.2mmol), E L2 (0.86g,1mmol), anhydrous potassium carbonate (0.28g,2mmol) and a catalytic amount of potassium iodide (10mg) are dissolved in 50ml of DMF, after the reaction is finished at 100 ℃, the potassium salt is removed by filtration, after the evaporation, the crude DMF is dissolved, the product is washed in a spinning column, the dichloromethane is separated by water, the yield is separated by a purple silica gel column, and the product is purified by a purple solid phase, and the yield is obtained by removing water, and the purple silica gel is L15%.1H NMR(300MHz,CDCl3)＝8.97,8.32,8.05,7.87,7.62,6.31,6.19,5.94,5.62,4.28,3.72,-2.74 MS(MALDI-ToF):[C56H36Br3N5O3],m/z＝1066.7[M+H]+(calcd.1066.7)。
Adding potassium hydroxide (0.47g, 8.4mmol) into anhydrous ethylene glycol, pumping the system to negative pressure, raising the temperature to 80 ℃ for heating and dissolving, dropwise adding dibromodiethyl ether (0.49g, 2.1mmol) into the system by using a constant-pressure low-liquid funnel, collecting condensed liquid E L16, stopping the reaction when no liquid is condensed, and obtaining the yield of 35%.1H NMR(300MHz,CDCl3)＝6.47,4.21,4.13,4.08,3.94 MS(ESI):[C4H7BrO],m/z＝151.0[M+H]+(calcd.151.0)。
In a glove box, willE L (2.1g,2mmol), E L (0.30g,2mmol), 2- (dodecyltrithiocarbonate) -2-methylpropanoic acid (DDMAT) (36mg,0.1mmol), Azobisisobutyronitrile (AIBN) (8mg,0.05mmol) were dissolved in 50ml of water-removed THF, after 3 times of freezing and oxygen removal, nitrogen gas was charged, reaction was carried out at 65 ℃ for 36h, liquid nitrogen quenching was carried out, precipitate was collected after precipitation with cold ether, and after repeated dissolution and centrifugation with dichloromethane-cold ether for 5 times, after vacuum drying, the oligomeric porphyrin ligand was obtained, the yield was 43%2Cl2) Mn ═ 16800, PDI ═ 1.36. in a glove box, the oligomeric porphyrin ligand (Mn ═ 17200, PDI ═ 1.44) was dissolved in dichloromethane, diethylaluminum chloride (2 mol/L n-hexane solution) equivalent to the porphyrin ring was added dropwise, the reaction was stirred at room temperature for 3 hours, the crude product was purified by neutral alumina column chromatography (eluent dichloromethane), and then the metalated product was dried under vacuum to give E L17 in 93% yield.
0.42g E L17 is dissolved in 5ml of dehydrated chloroform and 5ml of dehydrated acetonitrile mixed solvent, then 3.7g of tributylamine (20mmol) is added, then the mixture is refluxed for 3d in dark environment, after the reaction is finished, the mixture is cooled to room temperature, the solvent is removed under reduced pressure, the redundant tributylamine is removed by a dropper, the obtained solid is crushed and washed in ether for three times, and the residual trace tributylamine is removed, namely CAT 4 is obtained, wherein the yield is 90%.
Example 5
In this embodiment, taking propylene oxide as a reaction monomer, sebacic acid as an initiator, and CAT1 as a catalyst as an example, it is demonstrated that, at a high initiator concentration, the molecular weight of the polyol product can still be effectively controlled under the control of lewis acid and base provided by the present invention on the catalyst, and good living polymerization characteristics are reflected. The specific embodiment is that the molar ratio of the sebacic acid to the propylene oxide is adjusted from 1/7-1-10, the molecular weight is controlled within 600-900g/mol, the molecular weight distribution is narrow, and the proportion of the byproduct cyclic carbonate is extremely low (the specific result is summarized in Table 1); at the same time, the theoretical molecular weight,1The absolute molecular weight measured by H NMR and the relative molecular weight measured by GPC have very good fitting relationship, R2>0.99 (FIGS. 1-3), FIG. 1 is a GPC characterization of the product of example 5 of the present invention; FIG. 2 is a graph of theoretical molecular weight versus relative molecular weight (GPC) for the product of example 5 of the present invention) A relationship diagram of (1); FIG. 3 shows the theoretical molecular weight and absolute molecular weight of the product of example 5 of the present invention: (1H NMR); the accuracy and adjustability of the reaction height are reflected.
Figure BDA0002493334610000211
entry 1: propylene oxide (150m L, 2.14mol), sebacic acid (61.83g,306mmol, [ PO ]]/[SA]In a molar ratio of 7/1) and CAT1(0.052g,0.043mmol [ Al ] prepared in example 1]I.e., [ PO ]]/[Al]50000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through2The supply line is filled with CO in the kettle2The reaction was stirred for 8 hours while controlling the temperature at 80 ℃ until the pressure was 2.5 MPa. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, thereby obtaining 182g of poly (carbonate-ether) diol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 600g/mol, with a molecular weight distribution of 1.11;1H-NMR analysis showed that the cyclic carbonate by-product was 0.9%, the carbonate unit content in the polymer was about 39.1%, based on the CH directly attached to the carbonyl group in sebacic acid2Integral area of the characteristic peaks (A2.3), the absolute molecular weight of the polymer being 600 g/mol.
entry 2: the amount of sebacic acid was 43.3g (214mmol, i.e. [ PO ]]/[SA]10/1) was added to the reaction mixture, and the remaining reaction conditions were not changed to obtain 195g of a poly (carbonate-ether) diol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 900g/mol, with a molecular weight distribution of 1.08;1H-NMR analysis showed that the cyclic carbonate by-product was 0.6%, the carbonate unit content in the polymer was about 49.2%, based on the CH directly attached to the carbonyl group in sebacic acid2Integral area of the characteristic peaks (A2.3), the absolute molecular weight of the polymer being 900 g/mol. FIG. 4 is a graph of the product of example 5 of the present invention1H NMR spectrum; FIG. 5 shows the glass transition temperature and composition of the product of example 5 of the present inventionGraph of relationship of the quantum.
Meanwhile, in order to research the relationship between the molecular weight and the PO/SA, experiments of PO/SA-15/1, 30/1,50/1 and 75/1 are supplemented, the molecular weight of a product is 1200,2300,3800,5700 respectively, and the theoretical molecular weight of the series of chain transfer polymerization reactions, namely the molecular weight,1The absolute molecular weight measured by H NMR and the relative molecular weight measured by GPC have very good fitting relationship, R2>0.99, the polymer embodies good living polymerization characteristics, has highly controllable molecular weight and is accurate in synthesis.
TABLE 1 reaction results of inventive example 5
Figure BDA0002493334610000221
Example 6
Propylene oxide (150m L, 2.14mol), sebacic acid (43.3g,214mmol, [ PO ]]/[SA]10/1) and CAT3(0.061g,0.043mmol [ Al ] prepared in example 3]I.e., [ PO ]]/[Al]50000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through2The supply line is filled with CO in the kettle2The reaction was stirred at 80 ℃ for 12 hours while the pressure was 4 MPa. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, thereby obtaining 197g of poly (carbonate-ether) diol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 1000g/mol, with a molecular weight distribution of 1.11;1H-NMR analysis showed that the cyclic carbonate by-product was 0.7%, the carbonate unit content in the polymer was about 75.9%, based on the CH directly attached to the carbonyl group in sebacic acid2Integral area of the characteristic peaks (A2.3), the absolute molecular weight of the polymer being 1000 g/mol.
Example 7
Figure BDA0002493334610000231
Propylene oxide (150)m L, 2.14mol), dipropylene glycol (28.7g,214mmol, i.e. [ PO ]]/[DPG]In a molar ratio of 10/1) and CAT1(0.052g,0.043mmol [ Al ] prepared in example 1]I.e., [ PO ]]/[Al]50000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through2The supply line is filled with CO in the kettle2The reaction was stirred at 80 ℃ for 10 hours while the pressure was 4 MPa. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, thereby obtaining 177g of poly (carbonate-ether) diol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 800g/mol, with a molecular weight distribution of 1.09;1H-NMR analysis showed that the cyclic carbonate by-product was 0.9% and the carbonate unit content in the polymer was about 43.7%.
Example 8
Figure BDA0002493334610000232
Propylene oxide (150m L, 2.14mol), trimesic acid (45.0g,214mmol, [ PO ]]/[TMA]In a molar ratio of 10/1) and CAT1(0.052g,0.043mmol [ Al ] prepared in example 1]I.e., [ PO ]]/[Al]50000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through2The supply line is filled with CO in the kettle2The reaction was stirred at 80 ℃ for 12 hours while the pressure was 3 MPa. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, thereby obtaining 180g of poly (carbonate-ether) triol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 900g/mol, with a molecular weight distribution of 1.11;1H-NMR analysis showed that 0.9% of cyclic carbonate by-product and about 42.0% of carbonate units in the polymer were present, based on the CH directly attached to the carbonyl group in trimesic acid2Integral area of characteristic peaks (A8.8), absolute of the polymerThe molecular weight is 1000 g/mol.
Example 9
Propylene oxide (150m L, 2.14mol), pyromellitic acid (54.4g,214mmol, [ PO ]]/[BTC]In a molar ratio of 10/1) and CAT1(0.052g,0.043mmol [ Al ] prepared in example 1]I.e., [ PO ]]/[Al]50000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through2The supply line is filled with CO in the kettle2The reaction was stirred at 80 ℃ for 12 hours while the pressure was 3 MPa. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 189g of poly (carbonate-ether) tetrahydric alcohol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 900g/mol, with a molecular weight distribution of 1.13;1H-NMR analysis showed that 0.7% of cyclic carbonate by-product and about 40.5% of carbonate units in the polymer were present, based on the CH directly attached to the carbonyl group in pyromellitic acid2Integral area of the characteristic peaks (A8.2), the absolute molecular weight of the polymer being 900 g/mol.
Example 10
Propylene oxide (150m L, 2.14mol), xylitol (21.8g,143mmol, [ PO ]]/[SA]In a molar ratio of 15/1) and CAT 2(0.055g,0.043mmol [ Al ] prepared in example 2]I.e., [ PO ]]/[Al]50000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through2The supply line is filled with CO in the kettle2The reaction was stirred at 80 ℃ for 18 hours while the pressure was 4 MPa. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, carbon dioxide is slowly discharged, and the obtained product is vacuum-dried to remove unreacted propylene oxide, so that 182g of poly (carbonate-ether) pentahydric alcohol is obtained. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 900g/mol, with a molecular weight distribution of 1.15;1H-NMR analysis showed that the cyclic carbonate by-product was 0.6% and the carbonate unit content in the polymer was about 39.7%.
Example 11
Propylene oxide (150m L, 2.14mol), sorbitol (26.1g,143mmol, [ PO ]]/[SA]In a molar ratio of 15/1) and CAT 2(0.055g,0.043mmol [ Al ] prepared in example 2]I.e., [ PO ]]/[Al]50000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through2The supply line is filled with CO in the kettle2The reaction was stirred at 80 ℃ for 18 hours while the pressure was 4 MPa. After the polymerization reaction, the reaction kettle is cooled to room temperature, carbon dioxide is slowly discharged, and the obtained product is vacuum-dried to remove unreacted propylene oxide, so that 179g of poly (carbonate-ether) pentahydric alcohol is obtained. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 1000g/mol, with a molecular weight distribution of 1.15;1H-NMR analysis showed 1.6% cyclic carbonate by-product and about 37.3% carbonate units in the polymer.
Example 12
Cyclohexane epoxide (150m L, 1.48mol), 1, 2-cyclohexanediol (24.6g,212mmol, [ CHO ]]/[CHDO]In a molar ratio of 7/1) and CAT 4 prepared in example 4(0.112g,0.086mmol [ Al ]]I.e., [ CHO]/[Al]25000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through2The supply line is filled with CO in the kettle2The reaction was stirred at 80 ℃ for 12 hours while the pressure was adjusted to 2 MPa. After the polymerization reaction is finished, cooling the reaction kettle to room temperature, slowly discharging carbon dioxide, adding a certain amount of dichloromethane into the kettle to dissolve a polymerization product, dropwise adding the solution into cold methanol for precipitation, washing with n-hexane, and drying in vacuum to obtain 160g of polycarbonate diol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 600g/mol, with a molecular weight distribution of 1.09;1H-NMR analysis results show that no cyclic carbonate by-product exists, and the content of carbonate units in the polymer is more than 99%.
Example 13
Epoxy cyclohexane (150m L, 1.48mol),Trimesic acid (31.1g,148mmol, [ CHO ]]/[TMA]In a molar ratio of 10/1) and CAT 4 prepared in example 4(0.112g,0.086mmol [ Al ]]I.e., [ CHO]/[Al]25000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through2The supply line is filled with CO in the kettle2The reaction was stirred for 15 hours at a pressure of 2MPa and a temperature of 80 ℃. After the polymerization reaction is finished, cooling the reaction kettle to room temperature, slowly discharging carbon dioxide, adding a certain amount of dichloromethane into the kettle to dissolve a polymerization product, dropwise adding the solution into cold methanol for precipitation, washing with n-hexane, and drying in vacuum to obtain 164g of polycarbonate triol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 1000g/mol, with a molecular weight distribution of 1.13;1H-NMR analysis results show that no cyclic carbonate by-product exists, and the content of carbonate units in the polymer is more than 99%.
Example 14
Butylene oxide (190m L, 2.14mol), dipropylene glycol (28.7g,214mmol, i.e. [ BO ]]/[DPG]In a molar ratio of 10/1) and CAT1(0.052g,0.043mmol [ Al ] prepared in example 1]I.e., [ BO]/[Al]50000/1) is added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO with the pressure regulation function is rapidly passed through2The supply line is filled with CO in the kettle2The reaction was stirred for 8 hours while controlling the temperature at 80 ℃ until the pressure was 3 MPa. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted butylene oxide, thereby obtaining 201g of poly (carbonate-ether) diol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 1000g/mol, with a molecular weight distribution of 1.08;1H-NMR analysis showed that the cyclic carbonate by-product was 0.8% and the carbonate unit content in the polymer was about 53.9%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. An active hydrogen tolerant catalyst of formula (I) comprising:
Figure FDA0002493334600000011
the above-mentioned
Figure FDA0002493334600000012
Is a linking group and is independently selected from the structures of formula B, formula c or formula d, L A is a metalloporphyrin complex with the structure of formula (II), L B is Lewis base with the structures of formula (e) to formula (g);
Figure FDA0002493334600000013
wherein n is polymerization degree and is 4-40, and m is 4-12; o, p and q are the number of methylene groups, the value is 1-7, E1、E2Independently selected from alkyl of C1-C10; e3Is C5-C20 alkyl; y is a quaternary ammonium anion; m is a trivalent metal ion; r1、R2、R3、R4、R5、R6、R7、R8、R9Each independently is one of hydrogen, halogen, amino, nitro, cyano, C1-C10 aliphatic group, substituted C1-C10 aliphatic group, C6-C30 aryl or substituted C6-C30 aryl; x is selected from halogen, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3P-methylbenzoyl, o-nitrophenol oxygen, p-nitrophenol oxygen, m-nitrophenol oxygen, 2, 4-dinitrophenol oxygen, 3-5-dinitrophenol oxygen, 2,4, 6-trinitrophenol oxygen, 3, 5-dichlorophenol oxygen, 3, 5-difluorophenol oxygen, 3, 5-bis-trifluoromethylphenol oxygen or pentafluorophenol oxygen anion.
2. The catalyst of claim 1, wherein E is1、E2Independently selected from alkyl of C1-C6; e3Is C10-C15 alkyl; y is selected from halogen atoms, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3P-methylbenzoyl, o-nitrophenol oxyanions, p-nitrophenol oxyanions, m-nitrophenol oxyanions, 2, 4-dinitrophenol oxyanions, 3, 5-dinitrophenol oxyanions, 2,4, 6-trinitrophenol oxyanions, 3, 5-dichlorophenol oxyanions, 3, 5-difluorophenol oxyanions, 3, 5-bistrifluoromethylphenol oxyanions, or pentafluorophenol oxyanions.
3. The catalyst according to claim 1, wherein M is selected from one or more of Al, Co, Mn, Fe or Ti.
4. The catalyst of claim 1, wherein the active hydrogen tolerant catalyst is specifically of formula 101, formula 102, formula 103, or formula 104;
Figure FDA0002493334600000021
Figure FDA0002493334600000031
5. a process for the preparation of an active hydrogen tolerant catalyst of formula (I) as claimed in any one of claims 1 to 4, comprising:
A) reacting p-hydroxybenzaldehyde, substituted benzaldehyde and pyrrole under the condition of propionic acid reflux, and performing column chromatography separation to obtain monohydroxy substituted asymmetric porphyrin;
performing dehydration reaction on maleimide and halogenated alkyl alcohol under the conditions of diisopropyl azodicarboxylate and triphenylphosphine to obtain halogenated alkyl chain-substituted maleimide,
B) reacting the halogenated alkyl chain-substituted maleimide and monohydroxy-substituted porphyrin under an alkaline condition to synthesize ether, so as to prepare a maleimide porphyrin monomer;
C) carrying out asymmetric addition reaction on divinyl ether and hydrogen bromide to obtain an intermediate with a structure shown in a formula (h), and then reacting with TBD or salinizing quaternary ammonium to obtain a vinyl ether monomer;
D) performing alternate copolymerization reaction on maleimide porphyrin monomers and vinyl ether monomers, and then reacting with diethyl aluminum chloride to obtain an active hydrogen tolerant catalyst shown in a formula (I);
Figure FDA0002493334600000032
6. a method for preparing an ultra-low molecular weight poly (carbonate-ether) polyol, comprising:
under the action of the active hydrogen tolerant catalyst of any one of claims 1 to 4 or the active hydrogen tolerant catalyst prepared by the preparation method of claim 5, carbon dioxide, an epoxy compound and an initiator perform chain transfer polymerization reaction to obtain the ultra-low molecular weight poly (carbonate-ether) polyol.
7. The process according to claim 6, wherein the epoxide is selected from one or more of ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide, cyclohexene oxide, cyclopentane epoxide, glycidyl epichlorohydrin methacrylate, methyl glycidyl ether, phenyl glycidyl ether, styrene alkylene oxide, 4-vinyl-1, 2-epoxycyclohexane and vinyl propylene oxide.
8. The process of claim 6, wherein the starter is selected from one or more of water, small molecule alcohols, phenols, thiols, carboxylic acids, hydroxy acids, and hydroxyl group-containing oligomers; the hydroxyl-containing oligomer is polyglycerol (polyglycerol-06 and polyglycerol-10);
wherein the small molecular alcohol is ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, octanediol, sebacic acid diol, dipropylene glycol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylolethane, trimethylolpropane, glycerol, 1,2, 4-butanetriol, polyestertriol, pentaerythritol, xylitol, sorbitol, tripentaerythritol or polyglycidyl oligomers;
the phenol is catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 4 '-ethylidene biphenol and 4,4' - (2-methylpropylidene) biphenol; 4,4- (2-ethylhexyl) biphenol, 2 '-methylenebiphenol or 2,2' - (1, 2-cyclohexanediyl-dinitrosopolylene) biphenol;
the carboxylic acid is preferably malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, terephthalic acid, phthalic acid, isophthalic acid, maleic acid, trimesic acid, pyromellitic acid or oleic acid;
the hydroxy acid is lactic acid, hydroxybutyric acid, hydroxyvaleric acid, malic acid, tartaric acid, citric acid or salicylic acid.
9. The method according to claim 6, wherein the polymerization temperature is 25 to 150 ℃; the pressure of the polymerization reaction is 0.1-6 MPa; the time of the polymerization reaction is 0.5-24 h.
10. An ultra-low molecular weight poly (carbonate-ether) polyol, characterized in that it is prepared by the process of any one of claims 6 to 9.
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