CN111393630B - Polymer polyol and preparation method thereof - Google Patents

Polymer polyol and preparation method thereof Download PDF

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CN111393630B
CN111393630B CN202010411257.1A CN202010411257A CN111393630B CN 111393630 B CN111393630 B CN 111393630B CN 202010411257 A CN202010411257 A CN 202010411257A CN 111393630 B CN111393630 B CN 111393630B
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曹瀚
周庆海
王献红
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a preparation method of polymer polyol, which comprises the following steps of carrying out ring-opening (co) polymerization on one or more of epoxide, carbon dioxide, cyclic ester and cyclic anhydride under the action of a non-heavy metal center catalytic system to obtain the polymer polyol; the non-heavy metal center catalytic system comprises an aluminum porphyrin oligomer catalyst (with a structure shown in a formula I) and an initiator; the polymer polyol is polyether polyol, polyester-polyether polyol, poly (carbonate-ether) polyol and a multipolymer polyol thereof, wherein the molecular weight of the polymer polyol is 1200-10000, the functionality of the polymer polyol is 2-10, and the main chain structure of the polymer polyol is adjustable. The method can realize the high-efficiency preparation of the poly (carbonate-ether) polyol with different carbonate unit contents (20-80 percent of carbonate content), and the content of the cyclic carbonate by-product in the product is lower than 1 percent, thereby reducing the problems of separation energy consumption and cost in the production process from the source.

Description

Polymer polyol and preparation method thereof
Technical Field
The invention relates to the technical field of materials, in particular to polymer polyol and a preparation method thereof.
Background
The polyurethane is a high molecular compound with a main chain containing a repeating unit of a carbamate group, is a large amount of high molecular materials, is widely applied to the fields of buildings, traffic, furniture, daily necessities and the like, and has the global annual consumption of more than 2000 million tons. The polyurethane is mainly prepared by reacting polyisocyanate and polyol containing terminal hydroxyl. Wherein, the mass fraction of the polyol is 60-80 percent, which is a core raw material in the polyurethane industry. The traditional polyol is mainly polyester or polyether polyol, the polyurethane material based on the polyester polyol generally has the characteristics of good mechanical property, good oxidation resistance, oil resistance, wear resistance and the like, and the polyurethane material based on the polyether polyol generally has the characteristics of good low-temperature flexibility, outstanding hydrolysis resistance and the like.
In the production methods of a plurality of polyols, the ring-opening (co) polymerization route of the oxygen-containing monomer has the advantages of high atom economy, abundant monomer sources, mild reaction conditions and high efficiency, and the obtained polyols have multiple varieties and good molecular regularity. The high-efficiency catalyst is the core technology in ring-opening polymerization reaction.
At present, the catalyst with the widest application range is zinc-cobalt double metal cyanide (Zn-Co DMC), and has the advantages of high activity, controllable molecular weight, low unsaturation degree and the like in the preparation of polyether polyol, and more importantly, the DMC catalyst can realize the preparation of novel carbon dioxide-based poly (carbonate-ether) polyol. WO/2013/010987 discloses a method for preparing high carbonate content poly (carbonate-ether) polyols by activating DMC catalysts. However, DMC-catalyzed poly (carbonate-ether) polyols typically contain greater than 5 wt% cyclic carbonates as by-products, the presence of which can affect the material properties of the later polyurethanes. CN201510470795 reports a method using carboxylic acid as chain transfer agent and pre-activation to reduce the formation of cyclic by-products, but its content of cyclic carbonate is still higher than 4%. Meanwhile, the catalyst contains toxic substances such as cobalt metal, cyano and the like, and the removal of the catalyst after production is also necessary. The method has obvious high separation energy consumption problem because the by-products and the catalyst need to be removed simultaneously in the product post-treatment. Therefore, the development of a novel efficient environment-friendly catalytic system has the characteristic of high selectivity, and is a research hotspot in the field of polyol synthesis.
Therefore, an all-round catalytic system is developed, ring-opening (co) polymerization reaction of various other oxygen-containing monomers including lactone, lactide, cyclic anhydride and the like can be realized simultaneously, and the method has important significance for controlling the structure of a polyol product and enriching the variety of the polyol product. The revolutionary new technology can strongly promote the further development of the polyurethane field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing polymer polyol, and the catalyst system provided by the present invention has good activity, selectivity and control capability on telomerization reaction for preparing polymer polyol.
The invention provides a preparation method of polymer polyol, which comprises the following steps:
under the action of a non-heavy metal center catalytic system, performing ring-opening (co) polymerization on one or two of epoxide, carbon dioxide, cyclic ester and cyclic anhydride to obtain polymer polyol;
the non-heavy metal center catalytic system comprises an aluminum catalyst and an initiator;
the aluminum catalyst is an aluminum porphyrin oligomer catalyst and has a structure shown in formula I:
Figure GDA0003375137520000021
in the formula I, the C1 is a main chain structure shown in a formula (II); c2 is a bond chain group, the bond chain group has a structure of a formula III, a formula IV or a formula V, and por-Al is an aluminum porphyrin complex with a formula VI:
Figure GDA0003375137520000022
Figure GDA0003375137520000031
wherein Z is selected from formula a or formula b, and Ra and Rb are independently selected from hydrogen, halogen, aliphatic substituted aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl; the R iscSelected from C1-C12 alkyl, preferably C12; q is 0 or 1; the R isdAlkyl selected from C1-C12; r' is independently selected from formula c; the m is chain length or polymerization degree and takes the value of 4-20;
in the formula VI, Nu is quaternary ammonium salt anion with the ability of initiating polymerization, and x is Nu number, and the value is 0-3; the R is1、R2、R3Is a functional substituent or a quaternary ammonium salt of a porphyrin complexIon, X is selected from halogen radical, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bistrifluoromethylphenol oxyanion, or pentafluorophenol oxyanion, preferably from chlorine.
The initiator is selected from one or more of water, small molecule alcohol, phenol, mercaptan, carboxylic acid, hydroxy acid and oligomer containing hydroxyl
Preferably, Nu is halide ion, 2,4, 6-trinitrophenol oxyanion, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3；
The functional substituent is selected from hydrogen, halogen or quaternary ammonium salt cation; the quaternary ammonium salt cation is selected from tetra-n-butylammonium, tetra-isobutylammonium, tetra-n-hexylammonium and tetra-n-decylammonium.
Preferably, the aluminoporphyrin oligomer catalyst is specifically represented by formula 101, formula 102, formula 103, formula 104, formula 105 or formula 106:
Figure GDA0003375137520000041
preferably, the ring-opening (co) polymerization of one or two of the epoxide, carbon dioxide, cyclic ester, and cyclic anhydride includes ring-opening polymerization of epoxide, ring-opening polymerization of cyclic ester, ring-opening copolymerization of epoxide and cyclic anhydride, and ring-opening copolymerization of epoxide and carbon dioxide;
the polymer polyol is selected from polyether polyol, polyester-ether polyol, poly (carbonate-ether) polyol or their multipolymer polyol.
Preferably, the epoxide comprises 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 cyclic ester is selected from one or more of L-lactide, DL-lactide, beta-butyrolactone, delta-valerolactone and epsilon-caprolactone;
the cyclic anhydride is selected from one or more of maleic anhydride, phthalic anhydride, cyclobutane-1, 2-dicarboxylic anhydride, methylnadic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, succinic anhydride, hexahydrophthalic anhydride, itaconic anhydride, cyclopentane-1, 2-formic anhydride, dodecenyl succinic anhydride, allyl butyric anhydride, methyl tetrahydrophthalic anhydride, glutaric anhydride, trimethyl glutaric anhydride, 3-oxabicyclo [3.1.0] hexane-2, 4-dione, beta- (4-chlorophenyl) glutaric anhydride and 3, 3-dimethyl glutaric anhydride.
Preferably, the molar ratio of the metal center to the reactive monomer is 1 (2000-200000); the molar ratio of the monomer to the initiator is 100 (1-12).
Preferably, the initiator is selected from one or more of water, small molecule alcohols, phenols, thiols, carboxylic acids, hydroxy acids and hydroxyl-containing oligomers;
preferably, the small molecular alcohol is ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, octanediol, decanediol, 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 and 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 copolymerization reaction temperature is 25-150 ℃; the pressure of the copolymerization reaction is 0.1-6 MPa; the time of the copolymerization reaction is 0.5-48 h.
The invention provides a polymer polyol prepared by the preparation method of any one of the technical schemes.
Compared with the prior art, the invention provides a preparation method of polymer polyol, which comprises the following steps: under the action of a non-heavy metal center catalytic system, performing ring-opening (co) polymerization on one or two of epoxide, carbon dioxide, cyclic ester and cyclic anhydride to obtain polymer polyol; the non-heavy metal center catalytic system comprises an aluminum catalyst and an initiator; the aluminum catalyst is an aluminum porphyrin oligomer catalyst and has a structure shown in a formula I. The non-heavy metal center catalytic system can catalyze ring-opening (co) polymerization of a plurality of oxygen-containing monomers such as epoxide, carbon dioxide, lactone, lactide, cyclic anhydride and the like, and can prepare polyether polyol, polyester-polyether polyol and poly (carbonate-ether) polyol with molecular weight of 300-10000, functionality of 2-10 and adjustable main chain structure with high activity and high selectivity. For the most difficult controlled carbon dioxide/propylene oxide telomerization reaction, the method can realize the high-efficiency preparation of poly (carbonate-ether) polyols with different carbonate unit contents (carbonate content of 20-80%), and the content of cyclic carbonate byproducts in the product is lower than 1%, so that the problems of separation energy consumption and cost in the production process are reduced from the source.
Detailed Description
The invention provides a polymer polyol and a preparation method thereof, and a person skilled in the art can use the content for reference and appropriately improve the process parameters to realize the purpose. 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 a preparation method of polymer polyol, which comprises the following steps:
under the action of a non-heavy metal center catalytic system, performing ring-opening (co) polymerization on one or two of epoxide, carbon dioxide, cyclic ester and cyclic anhydride to obtain polymer polyol;
the non-heavy metal center catalytic system comprises an aluminum catalyst and an initiator;
the aluminum catalyst is an aluminum porphyrin oligomer catalyst and has a structure shown in formula I:
Figure GDA0003375137520000071
in the formula I, the C1 is a main chain structure shown in a formula (II);
Figure GDA0003375137520000072
formula II; specifically, the structure may be represented by the formula (II-1);
Figure GDA0003375137520000073
z is selected from formula a or formula b: wherein Ra and Rb are independently selected from hydrogen, halogen, aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaliphaticAn aryl group;
m is 4-20, preferably 10-20, and more preferably 13.
Figure GDA0003375137520000074
The R iscAlkyl selected from C1-C12; preferably C1-C10 alkyl; may also be specifically-CH3、-CH2CH3、-(CH2)3CH3。
Figure GDA0003375137520000075
Q is 0 or 1; said R isdAlkyl selected from C1-C12; preferably C1-C10 alkyl; more preferably a C1-C5 alkyl group;
r' is selected from formula c
Figure GDA0003375137520000076
The m is chain length or polymerization degree and takes the value of 4-20; preferably 4-16;
in formula I, C2 is a linker group having a structure of formula III, formula IV, or formula V:
Figure GDA0003375137520000081
the bond chain groups with different steric hindrance sizes have the capability of changing the selectivity of chemical reaction, so that the chain segment composition of a polymerization product is regulated and controlled, for example, the chain segment containing the formula III is prone to generating an ether chain segment, and the chain segment containing the formula IV is prone to generating a carbonate chain segment.
The por-Al is a catalytic center consisting of a metal complex and a nucleophilic group, the metal complex is a functionalized aluminum porphyrin compound, and the nucleophilic group is an ionic quaternary ammonium salt, and specifically, the por-Al is an aluminum porphyrin complex with a formula VI:
Figure GDA0003375137520000082
in formula VI, Nu is quaternary ammonium salt anion with polymerization initiating capability, preferably halide ion, 2,4, 6-trinitrophenol oxyanion and-NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3(ii) a The x is Nu number, the value is 0-3, namely, the number can be 0, 1,2 or 3, and 1 is preferred.
The R is1、R2、R3Is a functional substituent of porphyrin complex or a quaternary ammonium salt cation, and the ratio of the substituent to the quaternary ammonium salt cation is preferably one of 0/3, 1/2, 2/1 and 3/0. The functional substituent is preferably selected from hydrogen and halogen, most preferably bromine; the quaternary ammonium salt cation is preferably selected from tetra-n-butylammonium, tetra-isobutylammonium, tetra-n-hexylammonium or tetra-n-decylammonium, and most preferably tetra-n-hexylammonium;
x is selected from halo, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2, 4-dinitrophenol oxyanion, 3, 5-dinitrophenol oxyanion, 2,4, 6-trinitrophenol oxyanion, 3, 5-dichlorophenol oxyanion, 3, 5-difluorophenol oxyanion, 3, 5-bistrifluoromethylphenol oxyanion or pentafluorophenol oxyanion.
The initiator is selected from one or more of water, small molecule alcohol, phenol, thiol, carboxylic acid, hydroxy acid and oligomer containing hydroxyl; in the present invention, the aluminoporphyrin oligomer catalyst is specifically represented by formula 101, formula 102, formula 103, formula 104, formula 105 or formula 106:
Figure GDA0003375137520000091
the aluminum porphyrin oligomer catalyst with the structure shown in the formula I is preferably prepared by the following method:
the catalyst with the structure shown in the formula I is a polymer catalyst, the oligomerization degree and the polymerization degree distribution are well controlled during synthesis, and the polymerization degree is controlled to be between 4 and 20 by adopting a reversible addition-fragmentation chain transfer polymerization (RAFT) technology, so that the soluble state of the catalyst in a polymerization reaction is maintained. The basic preparation of the catalyst comprises four steps of preparing porphyrin monomers, RAFT polymerization, metallization and quaternization, and the sequence is not interchangeable. If the metallation is prior to RAFT polymerization, the metal and the co-ligand interfere with radical polymerization during RAFT polymerization, and the preparation fails.
The aluminum porphyrin complex of formula VI is preferably prepared by propionic acid one-pot method, namely, p-hydroxybenzaldehyde, substituted benzaldehyde and pyrrole are reacted in one-pot method under the condition of propionic acid reflux to obtain 6 kinds of porphyrin, and after the reaction is finished, a second color band is collected by column chromatography separation technology to obtain monohydroxy substituted porphyrin. The connection of C2 and porphyrin ring adopts acylation reaction, Williams' synthesis ether and other conventional organic reactions, the former is the substitution reaction of hydroxyl and acyl chloride in THF solution under alkaline condition, the latter is the reaction of halogen and hydroxyl under high temperature condition with potassium carbonate/potassium iodide as catalyst, and DMF as solvent.
The basic steps of RAFT polymerisation are: under the anhydrous and anaerobic conditions, dissolving porphyrin monomer, RAFT reagent trithioester and initiator Azobisisobutyronitrile (AIBN) in THF, wherein the dosage of the initiator is 1/2 of the trithioester, and the molar ratio of the porphyrin monomer to the trithioester is 10/1-20/1. Three times of freeze-drying and oxygen removal treatment are required before polymerization, and after polymerization is finished, the reaction bottle is placed in liquid nitrogen to quench free radicals. The separation of monomer and oligomer is carried out by centrifugal method, and the ether solution is light pink after dissolving cold ether-dichloromethane precipitate for three times.
The basic operation steps of the metallization reaction are that oligomeric porphyrin ligand is dissolved in dichloromethane in a glove box, a normal hexane solution of diethylaluminum chloride is dripped to react for 3 hours at normal temperature, and after the reaction is finished, column chromatography separation and purification are carried out. The basic procedure of the quaternization reaction is to dissolve the metalized aluminum porphyrin oligomer into a chloroform/acetonitrile 1:1 mixed solvent under the protection of nitrogen, and reflux the reaction for 3 days in a dark environment although alkylamine is added.
The preparation method of the polymer polyol comprises the step of firstly carrying out ring-opening (co) polymerization on one or two of epoxide, carbon dioxide, cyclic ester and cyclic anhydride under the action of a non-heavy metal center catalytic system to obtain the polymer polyol.
The reaction apparatus of the present invention is not limited, and an autoclave known to those skilled in the art may be used.
The non-heavy metal center catalytic system comprises an aluminum catalyst and an initiator; preferably, the initiator is selected from one or more of water, small molecule alcohol, phenol, thiol, carboxylic acid, hydroxy acid and oligomer containing hydroxyl group, and the initiator is selected from one or more of water, small molecule alcohol, phenol, thiol, carboxylic acid, hydroxy acid and oligomer containing hydroxyl group; the small molecular alcohol is preferably ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 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 and polyglycidyl oligomers;
the phenol is preferably catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 4 '-ethylidene biphenol, 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 preferably lactic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxysuccinic acid, tartaric acid, citric acid or salicylic acid.
The aluminum-based catalyst with the structure of formula I has been described clearly in the present invention, and is not described herein again.
According to the present invention, the ring-opening (co) polymerization of one or both of the epoxide, carbon dioxide, cyclic ester and cyclic anhydride preferably specifically includes ring-opening polymerization of epoxide, ring-opening polymerization of cyclic ester, ring-opening copolymerization of epoxide and cyclic anhydride, and ring-opening copolymerization of epoxide and carbon dioxide.
In the present invention, the polymer polyol is selected from polyether polyol, polyester-ether polyol or poly (carbonate-ether) polyol.
The epoxide preferably comprises one or more of ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide, cyclohexene oxide, cyclopentane epoxide, epichlorohydrin glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, styrene alkylene oxide, 4-vinyl-1, 2-cyclohexene oxide and vinyl propylene oxide;
the cyclic ester is preferably selected from one or more of L-lactide, DL-lactide, beta-butyrolactone, delta-valerolactone, epsilon-caprolactone;
the cyclic anhydride is preferably one or more selected from maleic anhydride, phthalic anhydride, cyclobutane-1, 2-dicarboxylic anhydride, methylnadic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, succinic anhydride, hexahydrophthalic anhydride, itaconic anhydride, cyclopentane-1, 2-carboxylic anhydride, dodecenyl succinic anhydride, allyl butyric anhydride, methyl tetrahydrophthalic anhydride, glutaric anhydride, trimethyl glutaric anhydride, 3-oxabicyclo [3.1.0] hexane-2, 4-dione, beta- (4-chlorophenyl) glutaric anhydride, and 3, 3-dimethyl glutaric anhydride.
In the invention, the molar ratio of the metal center to the reactive monomer is preferably 1 (2000-200000); more preferably 1 (5000-180000); in a particular embodiment of the invention, the molar ratio of the metal center to the reactive monomer is in particular 1:50000
The molar ratio of the monomers to the starter is preferably (15-70):1
The copolymerization reaction temperature is preferably 25-150 ℃; more preferably 30-120 ℃; most preferably 30-100 ℃; in a specific embodiment of the invention, the copolymerization temperature is specifically 80 ℃.
The pressure of the copolymerization reaction is preferably 0.1-6 MPa; more preferably 1-5 MPa; in a specific embodiment of the invention, the pressure of the copolymerization reaction is specifically 4MPa
The time of the copolymerization reaction is preferably 0.5-48 h; more preferably 1-40 h; most preferably 1-20 h; in the specific embodiment of the invention, the time of the copolymerization reaction is specifically 1.5-8 h.
The invention provides a polymer polyol prepared by the preparation method of any one of the technical schemes.
The invention provides a preparation method of polymer polyol, which comprises the following steps: under the action of a non-heavy metal center catalytic system, performing ring-opening (co) polymerization on one or two of epoxide, carbon dioxide, cyclic ester and cyclic anhydride to obtain polymer polyol; the non-heavy metal center catalytic system comprises an aluminum catalyst and an initiator; the aluminum catalyst is an aluminum porphyrin oligomer catalyst and has a structure shown in a formula I. The non-heavy metal center catalytic system can catalyze the ring-opening (co) polymerization reaction of a plurality of oxygen-containing monomers such as epoxide, carbon dioxide, lactone, lactide, cyclic anhydride and the like, and can prepare polyether polyol, polyester-polyether polyol and poly (carbonate-ether) polyol with molecular weight of 300-10000, functionality of 2-10 and adjustable main chain structure with high activity and high selectivity. Among them, for the most difficult controlled telomerization reaction of carbon dioxide/propylene oxide, the invention can realize the high-efficiency preparation of poly (carbonate-ether) polyols with different carbonate unit contents (carbonate content is 20-80%), and the content of cyclic carbonate by-products in the product is lower than 0.5%, thereby reducing the problems of separation energy consumption and cost in the production process from the source.
In order to further illustrate the present invention, a polymer polyol and a method for preparing the same according to the present invention will be described in detail with reference to the following examples.
Example 1
Figure GDA0003375137520000131
Adding p-hydroxybenzaldehyde (13.2g,108mmol), p-bromobenzaldehyde (59.74g,324mmol) and propionic acid 500mL, heating to 130 deg.C, adding pyrrole (30mL,432mmol) dropwise, heating to 160 deg.C, refluxing 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 to yield the second color band as product EL1 in about 12% yield.1H NMR(300MHz,CDCl3)δ＝8.91,8.10,7.92,7.15,-2.82MS(MALDI-ToF):[C44H27Br3N4O],m/z＝863.9[M+H]+(calcd.863.9)。
EL1(0.86g,1mmol), triethylamine (0.12g,1.2mmol) and anhydrous tetrahydrofuran were added to a 100ml reaction flask, which was cooled in an ice-water bath. Methacryloyl chloride (0.124g,1.2mmol) was dissolved in 10mL of anhydrous tetrahydrofuran and added dropwise to the reaction flask and stirred at room temperature overnight. After the reaction, the reaction mixture was filtered, dried, dissolved in dichloromethane, washed 3 times with a sodium chloride solution, dried over anhydrous magnesium sulfate, and the crude product was subjected to column chromatography using dichloromethane to obtain EL2 in 88.2% yield.1H NMR(300MHz,CDCl3)δ＝8.93,8.23,7.93,7.58,6.59,5.94,2.13,-2.83.MS(MALDI-ToF):[C48H31Br3N4O2],m/z＝935.5[M+H]+(calcd.935.5)。
EL2(0.56g,0.6mmol), 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid (DDMAT) (44mg,0.12mmol), AIBN (10mg,0.06mmol) and 25mL tetrahydrofuran were added into a Schlenk reaction tube, after 3 times of oxygen removal by freezing, nitrogen gas was charged, reaction was carried out at 65 ℃ for 24h, quenching was carried out with liquid nitrogen, precipitate was collected after precipitation with cold ether, and after repeated dissolution and centrifugation with dichloromethane-cold ether for 5 times, after vacuum drying, oligoporphyrin ligand EL3 was obtained with a yield of 45%. Gel permeation chromatography (GPC, PS standard, CH)2Cl2):Mn＝6700,PDI＝1.34。
The ligand EL3 was dissolved in dichloromethane, and an equivalent amount of AlEt was added dropwise2Cl (diethylaluminum chloride) (2mol in hexane), the reaction was stirred at room temperature for 2 h. The solvent was drained in vacuo and dried to give the desired catalyst 1.
Example 2
Figure GDA0003375137520000141
The reaction equation is the same as in example 1, with a change only in step three, i.e. the molecular weight is increased by changing the ratio of porphyrin monomer to trithioester DDMAT in the RAFT polymerization and extending the reaction time appropriately. The method comprises the following specific steps: EL2(0.56g,0.6mmol), 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid (DDMAT) (22mg,0.06mmol), AIBN (5mg,0.03mmol) and 25mL tetrahydrofuran were added into a Schlenk reaction tube, after 3 times of oxygen removal by freezing, nitrogen gas was charged, reaction was carried out at 65 ℃ for 32h, quenching was carried out with liquid nitrogen, precipitate was collected after precipitation with cold ether, and after repeated dissolution and centrifugation with dichloromethane-cold ether, vacuum drying was carried out to obtain the desired oligoporphyrin ligand EL4 with a yield of 67%. Gel permeation chromatography (GPC, PS standard, CH)2Cl2) Mn is 13600 and PDI is 1.67. Dissolving the ligand in dichloromethane, and dropwise adding equivalent AlEt2Cl (diethylaluminum chloride) (2mol in hexane), stirred at room temperature for 2 h. The solvent was drained in vacuo and dried to give the desired catalyst 2.
Example 3
Figure GDA0003375137520000151
Figure GDA0003375137520000161
Adding p-hydroxybenzaldehyde (13.2g,108mmol), p-chlorobenzaldehyde (45.39g,324mmol) and 500mL propionic acid, heating to 130 deg.C, adding pyrrole (30mL,432mmol), heating to 160 deg.C, refluxing, and reactingCooling to room temperature after reaction for 2h, adding methanol, cooling in refrigerator overnight, filtering to obtain product, and performing silica gel column chromatography (CHCl)3/CH3OH) purification to yield the second color band as product EL5 in about 12% yield.1H NMR(300MHz,DMSO)δ＝10.07,8.90,8.29,8.04,7.83,7.26,-2.95.MS(MALDI-ToF):[C44H27Cl3N4O],m/z＝734.08[M+H]+(calcd.734.08)。
Triethylamine (10.12g, 0.1mol), 6-chloro-1-hexanol (13.66g, 0.1mol) was added to 200ml of chloroform at 0 ℃ under nitrogen protection, methacryloyl chloride (10.45g, 0.1mol) was slowly added dropwise, and the system was stirred at room temperature overnight after completion of the dropwise addition. Washing the obtained product with 30ml water for three times, taking the organic phase and using anhydrous Na2SO4After drying, the solvent was removed to give EL6 as a yellow liquid.1H NMR(300MHz,CDCl3)δ＝6.09,5.54,4.14,3.53,1.93,1.78,1.69,1.44
EL5(2.00g, 2.7mmol) and EL6(0.71g, 3.5mmol) were dissolved in anhydrous DMF under nitrogen protection and K was added2CO3(0.22g, 1.54mmol) and KI (10mg) were reacted at 100 ℃ for 24 hours, and the porphyrin product EL7 was obtained by column chromatography with a yield of 80%.1H NMR(300MHz,CDCl3)δ＝8.94,8.05,7.89,7.26,6.19,5.62,4.28,2.17,2.03,1.32,-2.78.MS(MALDI-ToF):[C54H43Cl3N4O3],m/z＝902.31[M+H]+(calcd.902.31)。
EL7(0.54g,0.6mmol), 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid (DDMAT) (22mg,0.06mmol), AIBN (5mg,0.03mmol) and 25mL tetrahydrofuran were added into a Schlenk reaction tube, after 3 times of oxygen removal by freezing, nitrogen gas was charged, reaction was carried out at 65 ℃ for 32h, quenching was carried out with liquid nitrogen, precipitate was collected after precipitation with cold ether, and after repeated dissolution and centrifugation with dichloromethane-cold ether, vacuum drying was carried out to obtain the desired oligomeric porphyrin ligand EL8 with a yield of 47%. Gel permeation chromatography (GPC, PS standard, CH)2Cl2):Mn＝6600,PDI＝1.19。
The ligand EL8 was dissolved in dichloromethane, and an equivalent amount of AlEt was added dropwise2Cl (diethylaluminum chloride) (2mol in hexane), stirred at room temperature for 2 h. The solvent was drained in vacuo and dried to give the desired catalyst 3.
Example 4
Figure GDA0003375137520000171
42.8g (0.2mol) of 4' -hydroxybiphenyl-4-carboxylic acid and 1.6g (0.4mol) of NaOH are dissolved in 1L of water, placed in a three-necked flask, 25.0(0.24mol) of methacryloyl chloride is dissolved in 300ml of anhydrous dichloromethane and added dropwise at 5 ℃ over 2h, the mixture is left at room temperature and the reaction is continued for 3 h. The solid was filtered, dissolved in ethyl acetate, washed with water and hydrochloric acid solution several times, and the solid was rotary-distilled to give product EL 9.1H NMR(DMSO,ppm)：13.22，8.21，7.71，7.20，6.30，5.94，2.02；
Under the protection of nitrogen, 7.0g (0.025mol) of compound EL9 is dissolved in dry THF, 1.5g (0.0125mol) of oxalyl chloride is added dropwise under a water bath at 0 ℃,0.2 ml of DMF is added after the end of the addition, the room temperature is recovered and the reaction is carried out for 6h, and the product EL10 is obtained after the solvent is removed under reduced pressure;
3.0g (0.01mol) of EL10 and 8.7g (0.01mol) of EL1 are dissolved in 200ml of DMF under nitrogen protection, 0.12g (0.012mol) of triethylamine is added, reaction is carried out for 24h at 50 ℃, after solvent removal, the obtained solid is dissolved in dichloromethane, washing is carried out for three times in sodium chloride solution and then dried by anhydrous sodium sulfate, the crude product is subjected to column chromatography by dichloromethane to obtain the product EL11,1H NMR(300MHz,CDCl3)δ＝8.94,8.31,8.05,7.89,7.62,7.26,6.31,6.19,5.94,5.62,4.28,2.17,2.03,1.32,-2.78.MS(MALDI-ToF):：1131.7，found：1132.0；
RAFT polymerisation procedure was similar to example 1: EL11(1.15g,1mmol), 18mg of 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid (DDMAT) (36mg,0.1mmol), AIBN (8mg,0.05mmol) and 50mL of tetrahydrofuran are added into a Schlenk reaction tube, oxygen is removed by freezing for 3 times, nitrogen is filled, reaction is carried out for 12 hours at 65 ℃, liquid nitrogen is quenched, precipitates are collected after precipitation by cold ether, dichloromethane-cold ether is used for repeated dissolution and centrifugation for 5 times, and after vacuum drying, the oligomeric porphyrin ligand EL12 is obtained, wherein the yield is 42%. Gel permeation chromatography (GPC, CH)2Cl2):Mn＝4700,PDI＝1.26。
Dissolving the ligand EL12In dichloromethane, an equivalent amount of AlEt is added dropwise2Cl (diethylaluminum chloride) (2mol in hexane), stirred at room temperature for 2 h. The solvent was drained in vacuo and dried to give the desired catalyst 4.
Example 5
Figure GDA0003375137520000191
2.12g of benzaldehyde (20mmol) and 104ml of purified pyrrole (1.5mol) were added to a dry 250ml three-necked round bottom flask under nitrogen. Followed by the addition of 0.4g of InCl3Reacting at room temperature for 2h, adding 8.0g of 50-mesh sodium hydroxide powder, then continuing stirring for 45min, filtering, distilling the filtrate under reduced pressure, recovering the redundant pyrrole, and obtaining a brown solid crude product. The crude product obtained is triturated in a mortar and washed three times with n-hexane to remove the residual pyrrole, then chromatographed on a petroleum ether/dichloromethane column and purified to give a pale grey solid. The grey solid (0.24g,1mmol), triethylamine (0.12g,1.2mmol) was dissolved in 30ml of anhydrous tetrahydrofuran under nitrogen protection and cooled in an ice-water bath. A solution of methacryloyl chloride (0.124g,1.2mmol) in tetrahydrofuran was then added dropwise and stirred at room temperature overnight. After the reaction is finished, the mixture is filtered, dried by spinning, redissolved in dichloromethane and washed by sodium chloride for 3 times to obtain the EL13, wherein the yield is 65%.
1H NMR(CDCl3):δ7.93,7.18-7.35,6.72,6.57,6.18,6.00,5.92,5.49,2.13
MS(ESI):[C19H18N2O2],m/z＝306.14[M+H]+(calcd.306.14)
P-hydroxybenzaldehyde (12.2g,0.1mol) and 1, 6-dibromohexane (24.4g,0.1mol) were dissolved in anhydrous DMF under nitrogen protection, potassium carbonate (69.1g,0.5mol) and a catalytic amount of potassium iodide (50mg) were added to react at 50 ℃ for 48 hours, and the mixture was filtered, distilled under reduced pressure, washed with water for 3 times, and the crude product was subjected to n-heptane/ethyl acetate column chromatography to obtain a pale yellow oily liquid. The obtained oily liquid and purified pyrrole were subjected to a dipyrrolidation reaction in the same manner as in EL 13. The dipyrrolidine (10mmol) was dissolved in 200mL of purified toluene in a 500mL three-necked round bottom flask under argon. 50ml of ethyl magnesium bromide (1M in THF) were slowly added dropwise at room temperature, and after the addition was complete, stirring was continued for 3 min. A toluene solution (25mmol) of p-bromobenzoyl chloride was slowly added dropwise over 10min, after which the reaction was continued for 1 h. The reaction solution was quenched by pouring it into 200ml of a saturated ammonium chloride solution, followed by extraction with 150ml of ethyl acetate. The organic phase was washed with saturated sodium chloride solution and deionized water, dried over anhydrous Na2SO4, filtered, and the solvent was removed under reduced pressure. The residual solid was dissolved in 20ml of purified methylene chloride under an argon atmosphere, and then 4.18ml of triethylamine (30mmol) and 3.04g of di-t-butyltin chloride (10.0mmol) were added to the solution to react at room temperature for 30 min. The solvent and excess triethylamine were removed under reduced pressure and purified by column chromatography on silica gel (dichloromethane as eluent). Taking 2mmol of the obtained solid, dissolving the solid with a mixed solvent of 20ml of THF and 10ml of methanol, adding 1.52g of sodium borohydride (40mmol) in batches, slowly heating to 35-45 ℃, reacting for 1.5h, pouring the reaction solution into 100ml of saturated ammonium chloride solution, extracting with 100ml of 2-methylene chloride, washing an organic phase with deionized water, drying with anhydrous sodium sulfate, filtering, and removing the solvent under reduced pressure to obtain EL 14. 2mmol of the compound EL13 and 150ml of anhydrous acetonitrile were directly charged into a reaction flask containing EL14, 1.85ml of trifluoroacetic acid (24mmol) was slowly added dropwise, and after 5min of reaction, 1.36g of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) (6mmol) was added, and the reaction was continued at room temperature for 1 h. Filtering to remove precipitate, then distilling under reduced pressure to remove the solvent, and purifying the crude product by petroleum ether/dichloromethane neutral alumina column chromatography to obtain pure purple solid, namely the compound EL15 with the yield of 31%.
1H NMR(CDCl3):δ8.75,8.11,8.02,7.57-7.67,7.42,6.59,5.97,3.49,2.95,2.32,2.10,-2.84.
MS(MALDI):[C54H43Br3N4O3],m/z＝1035.7[M+H]+(calcd.1035.7)
The RAFT polymerisation and metallisation step followed the protocol of example 1 to give EL16 and will not be described in detail. Gel permeation chromatography (GPC, CH2Cl2) determined the molecular weight of the oligomeric porphyrin ligand to be: mn6800 and PDI 1.39. 0.40g of EL16 was dissolved in 5ml of purified chloroform and 5ml of purified chloroformAcetonitrile, followed by 3.7g of trihexylamine (20mmol) and reflux in the dark for 3 d. After the reaction was completed, the reaction mixture was cooled to room temperature, the solvent was removed under reduced pressure, and the excess trihexylamine was removed with a dropper. The resulting solid was washed by grinding in ether three times to remove the residual traces of tributylamine, to obtain catalyst 5 in 92% yield.
Example 6
Figure GDA0003375137520000211
Figure GDA0003375137520000221
Parahydroxybenzaldehyde (12.2g,0.1mol) and 1, 6-dibromohexane (12.7g,0.1mol) were dissolved in anhydrous DMF under nitrogen protection, potassium carbonate (69.1g,0.5mol) and a catalytic amount of potassium iodide (50mg) were added to react at 50 ℃ for 48 hours, and the mixture was filtered, distilled under reduced pressure, washed with water for 3 times, and the crude product was subjected to column chromatography with n-heptane/ethyl acetate to obtain a colorless oily liquid. 3 equivalents of this colorless oily liquid, 1 equivalent of p-hydroxybenzaldehyde and 4 equivalents of pyrrole were added to 500mL of propionic acid, and reacted under reflux for 2 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, methanol was added thereto and the mixture was cooled overnight in a refrigerator, and the product obtained by filtration was purified by silica gel column chromatography (CHCl3/CH3OH) to collect a second color band and obtain a product EL17 in a yield of about 3%.
1H NMR(300MHz,DMSO)δ＝10.03,9.01–8.70,8.22,8.01,7.83,7.21,3.53,1.93,1.78,1.44-2.93.
MS(MALDI-ToF):[C56H51Cl3N4O],m/z＝902.4[M+H]+(calcd.902.4)
EL17(2.44g, 2.7mmol) and EL6(0.71g, 3.5mmol) were dissolved in anhydrous DMF under nitrogen, K2CO3(0.22g, 1.54mmol) and KI (10mg) were added and reacted at 100 ℃ for 24h, and the porphyrin product EL18 was isolated by column chromatography in 80% yield.
1H NMR(300MHz,CDCl3)δ＝8.94,8.05,7.89,7.26,6.19,5.62,4.28,2.17,2.03,1.32,-2.78
MS(MALDI-ToF):[C66H67Cl3N4O3],m/z＝1070.4[M+H]+(calcd.1070.4)
RAFT polymerisation, metallisation procedure as in example 1, gel permeation chromatography (GPC, CH2Cl2) determined the molecular weight of the oligomeric porphyrin ligand: mn7700 and PDI 1.35. The quaternization step was the same as in example 4, with only the trihexylamine being changed to tributylamine, to finally obtain catalyst 6.
Example 7
Catalyst 1 prepared in example 1(0.35g,0.43mmol [ Al ]]) Tris (diphenylphosphinyl) ammonium chloride (0.13g,0.21mmol), dipropylene glycol (5.74g,42.8mmol) and propylene oxide (150mL,2.14mol) were charged into a 500mL autoclave previously subjected to water removal and oxygen removal, and rapidly passed through CO having a pressure regulating function2The supply line is filled with CO in the kettle2The reaction was stirred for 1.5 hours while controlling the temperature at 80 ℃ until 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 107g of poly (carbonate-ether) polyol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 1500g/mol, with a molecular weight distribution of 1.08;1H-NMR analysis showed 0.5% by-product of cyclic carbonate and about 49% carbonate units in the polymer.
Example 8
Catalyst 4 prepared in example 4(0.042g,0.043mmol [ Al ]]) Tris (diphenylphosphinyl) ammonium chloride (0.013g,0.021mmol), sebacic acid (8.66g,42.8mmol) and propylene oxide (150mL,2.14mol) were added to a 500mL autoclave previously subjected to water removal and oxygen removal, and rapidly passed through CO having a pressure adjusting function2The supply line is filled with CO in the kettle2The reaction was stirred for 6 hours while controlling the temperature at 80 ℃ until 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 154g of poly (carbonate-ether) polyol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 2700g/mol, with a molecular weight distribution of 1.09;1H-NMR analysis showed that the compound is cyclicCarbonate by-product 0.3% and carbonate units in the polymer about 70%. Thus, the polyol carbonate/ether ratio can be manipulated by varying the oligomerization structure of the procatalyst.
Example 9
Catalyst 3 prepared in example 3(0.043g,0.043mmol [ Al ]]) 0.020mmol of tris (diphenylphosphinyl) ammonium chloride (0.013g,0.021mmol), sebacic acid (8.66g,42.8mmol) and propylene oxide (150mL,2.14mol) were added to a 500mL autoclave previously subjected to water removal and oxygen removal, and rapidly passed through CO having a pressure regulating function2The supply line is filled with CO in the kettle2The reaction was stirred for 6 hours while controlling the temperature at 80 ℃ until the pressure was 0.2 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 86g of poly (carbonate-ether) polyol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 2100g/mol, with a molecular weight distribution of 1.11;1H-NMR analysis showed 0.5% by-product of cyclic carbonate and about 21% carbonate units in the polymer. Thus, the polyol carbonate/ether ratio can also be regulated by varying the carbon dioxide pressure.
Example 10
Catalyst 5 prepared in example 5(0.043g,0.043mmol [ Al ]]) Tris (diphenylphosphinyl) ammonium chloride (0.013g,0.021mmol), sebacic acid (14.41g,71.4mmol) and propylene oxide (150mL,2.14mol) were added to a 500mL autoclave previously subjected to water removal and oxygen removal, and rapidly passed through CO having a pressure adjusting function2The supply line is filled with CO in the kettle2The reaction was stirred for 5 hours while controlling the temperature at 80 ℃ until 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 115g of poly (carbonate-ether) polyol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 1600g/mol, with a molecular weight distribution of 1.07;1H-NMR analysis results showed that the cyclic carbonate0.9% by-product and a content of carbonate units in the polymer of about 51%.
Example 11
Catalyst 5 prepared in example 5(0.043g,0.043mmol [ Al ]]) Tris (diphenylphosphinyl) ammonium chloride (0.013g,0.021mmol), trimesic acid (14.98g,71.3mmol) and propylene oxide (150mL,2.14mol) were added to a 500mL autoclave previously subjected to water removal and oxygen removal, and rapidly passed through CO having a pressure adjusting function2The supply line is filled with CO in the kettle2The reaction was stirred for 8 hours at a pressure of 4MPa and a temperature of 80 ℃. 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 122g of poly (carbonate-ether) polyol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 1700g/mol, with a molecular weight distribution of 1.10;1H-NMR analysis showed that the cyclic carbonate by-product was 0.9% and the carbonate unit content in the polymer was about 47%.
Example 12
Catalyst 5 prepared in example 5(0.043g,0.043mmol [ Al ]]) Tris (diphenylphosphinyl) ammonium chloride (0.013g,0.021mmol), pyromellitic acid (18.11g,71.3mmol) and propylene oxide (150mL,2.14mol) were added to a 500mL autoclave previously subjected to water removal and oxygen removal, and rapidly passed through CO having a pressure-regulating function2The supply line is filled with CO in the kettle2The reaction was stirred for 8 hours at a pressure of 4MPa and a temperature of 80 ℃. 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 119g of poly (carbonate-ether) polyol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 1600g/mol, with a molecular weight distribution of 1.07;1H-NMR analysis showed 0.8% by-product of cyclic carbonate and about 48% carbonate units in the polymer.
Example 13
Catalyst 5 prepared in example 5(0.043g,0.043mmol [ Al ]])、0.020mmol of tris (diphenylphosphinyl) ammonium chloride (0.013g,0.021mmol), dipentaerythritol (18.11g,71.3mmol) and propylene oxide (150mL,2.14mol) were charged in a 500mL autoclave previously subjected to water removal and oxygen removal, and rapidly passed through CO having a pressure regulating function2The supply line is filled with CO in the kettle2The reaction was stirred for 8 hours at a pressure of 4MPa and a temperature of 80 ℃. 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 107g of poly (carbonate-ether) polyol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 1400g/mol, with a molecular weight distribution of 1.07;1H-NMR analysis showed 1.1% by-product of cyclic carbonate and about 48% carbonate units in the polymer.
Example 14
Catalyst 6 prepared in example 6(0.043g,0.043mmol [ Al ]]) 0.020mmol of tris (diphenylphosphinyl) ammonium chloride (0.013g,0.021mmol), pyromellitic acid (36.2g,142.6mmol) and propylene oxide (300mL,4.28mol) were charged in a 500mL autoclave which had been previously subjected to water removal and oxygen removal. The reaction was stirred for 3 hours with the temperature controlled at 80 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, and the obtained product was vacuum-dried to remove unreacted propylene oxide, thereby obtaining 177g of polyether polyol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The polymer was found to have a number average molecular weight of 1300g/mol and a molecular weight distribution of 1.13.
Example 15
Catalyst 6 prepared in example 6(0.081g,0.1mmol [ Al ]]) Tris (diphenylphosphinyl) ammonium chloride (0.029g,0.05mmol), sorbitol (0.73g,4mmol), L-lactide (14.41g,0.1mol) and anhydrous toluene (100mL) were added to a Schlenk reaction flask which had been previously subjected to water removal and oxygen removal treatment, and the reaction was stirred while controlling the temperature at 100 ℃. The reaction solution was taken out by means of an injector,1H-NMR monitored monomer conversion. Precipitating the mixed solution with frozen mixed solvent of methanol and diethyl ether (1: 1, volume ratio), centrifuging, and vacuum drying for 24 hr to obtain polyester14g of polyol. By gel permeation chromatography (GPC, PS standard, CH)2Cl2) The polymer was found to have a number average molecular weight of 3700g/mol and a molecular weight distribution of 1.23.
Example 16
Catalyst 6 prepared in example 6(0.081g,0.1mmol [ Al ]]) Tris (diphenylphosphinyl) ammonium chloride (0.029g,0.05mmol), tripentaerythritol (2.23g,6mmol) caprolactone (11.41g,0.1mol) and anhydrous toluene (100mL) were added to a Schlenk reaction flask which had been previously subjected to water removal and oxygen removal, and the reaction was stirred while controlling the temperature at 100 ℃. The reaction solution was taken out by means of an injector,1H-NMR monitored monomer conversion. After the reaction is completed, the mixed solution is precipitated by using a frozen methanol-ether mixed solvent (1: 1, volume ratio), and is centrifugally separated and dried for 24 hours under vacuum, so that 13g of polyester polyol is obtained. By gel permeation chromatography (GPC, PS standard, CH)2Cl2) It was found that the number average molecular weight of the polymer was 2400g/mol, and the molecular weight distribution was 1.19.
Example 17
Catalyst 6 prepared in example 6(81mg,0.1mmol [ Al ]]) Tris (diphenylphosphinyl) ammonium chloride (29mg,0.05mmol), tripentaerythritol (0.75g,2mmol) caprolactone (11.41g,0.1mol) and anhydrous toluene (100mL) were added to a Schlenk reaction flask which had been previously subjected to water removal and oxygen removal treatment, and the reaction was stirred while controlling the temperature at 100 ℃. The reaction solution was taken out by means of an injector,1H-NMR monitored monomer conversion. After the reaction is completed, the mixed solution is precipitated by using a frozen methanol-ether mixed solvent (1: 1, volume ratio), centrifugally separated and dried for 24 hours under vacuum, and 12g of polyester polyol is obtained. By gel permeation chromatography (GPC, PS standard, CH)2Cl2) The polymer was found to have a number average molecular weight of 8300g/mol and a molecular weight distribution of 1.24.
Example 18
Catalyst 6 prepared in example 6(0.042g,0.043mmol [ Al ]]) Tris (diphenylphosphinyl) ammonium chloride (0.053g,0.086mmol), 1, 3-propanediol (3.26g,42.8mmol), phthalic anhydride (63.39g,0.43mol) and propylene oxide (150mL,2.14mol) were charged into a 500mL autoclave which had been previously subjected to water removal and oxygen removal. The reaction was stirred for 3.5 hours with the temperature controlled at 110 ℃.After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, and the obtained product was vacuum-dried to remove unreacted propylene oxide, thereby obtaining 102g of polyester-ether polyol. By gel permeation chromatography (GPC, PS standard, CH)2Cl2) The polymer was found to have a number average molecular weight of 2900g/mol and a molecular weight distribution of 1.17.1H-NMR analysis showed that the polymer contained about 71% of ester units.
Example 19
Catalyst 6 prepared in example 5 (0.059g,0.059mmol [ Al ]]) Tris (diphenylphosphinyl) ammonium chloride (0.068g,0.119mmol), xylitol (2.25g,14.8mmol), succinic anhydride (14.84g,148mmol), epoxycyclohexane (30mL,297mmol) and anhydrous toluene (60mL) were added to a Schlenk reaction flask which had been previously subjected to water and oxygen removal treatment, and the reaction was stirred at 100 ℃ for 80 min. After the reaction is completed, the Schlenk reaction bottle is cooled to room temperature, the mixed solution is precipitated by using a frozen methanol-ether mixed solvent (1: 1, volume ratio), and is centrifugally separated and dried under vacuum for 24 hours to obtain 34g of polyester-ether polyol. By gel permeation chromatography (GPC, PS standard, CH)2Cl2) The polymer was found to have a number average molecular weight of 2600g/mol and a molecular weight distribution of 1.15.1H-NMR analysis showed that the polymer contained about 83% of ester units.
Example 20
Catalyst 5 prepared in example 5(0.043g,0.043mmol [ Al ]]) Tris (diphenylphosphinyl) ammonium chloride (0.013g,0.021mmol), sebacic acid (10.82g,53.5mmol), phthalic anhydride (15.85g,107mmol) and propylene oxide (150mL,2.14 mmol) were added to a 500mL autoclave previously subjected to water removal and oxygen removal treatment, and rapidly passed through CO having a pressure adjusting function2The supply line is filled with CO in the kettle2The reaction was stirred for 3 hours while controlling the temperature at 80 ℃ until 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 131g of poly (ester-carbonate-ether) polyol. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) The number average molecular weight of the polymer was found to be 2700g/mol, with a molecular weight distribution of 1.08;1H-Nthe results of MR analysis showed 0.6% cyclic carbonate by-product, about 43% carbonate units in the polymer, 17% ester segments and 40% ether segments.
Comparative example 1
The inventor utilizes the following catalysts to carry out carbon dioxide/propylene oxide telomerization reaction under the same reaction conditions to prepare the carbon dioxide polyol, and compares the differences of the three in activity, selectivity and telomerization reaction control capacity. The catalyst is catalyst 2 of patent example 2 and the catalyst reported in ACS Catal.2019,9,8669-8676.
The reaction conditions and operation were as follows: adding a catalyst, tris (diphenylphosphinyl) ammonium chloride (equimolar with the catalyst aluminum center), sebacic acid (8.66g,42.8mmol) and propylene oxide (150mL,2.14mol) into a 500mL high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and rapidly passing through CO with a pressure regulation function2The supply line is filled with CO in the kettle2The reaction is stirred for a certain time at 80 ℃ until the pressure is 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 poly (carbonate-ether) polyol is obtained, wherein the reaction results are shown in the following table. By gel permeation chromatography (GPC, PEG standard, CH)2Cl2) Measuring the molecular weight and molecular weight distribution of the poly (carbonate-ether) polyol product;1H-NMR analysis shows the propylene oxide conversion (conv. of PO%) and the proportion of cyclic carbonate by-products (W)PCwt%) and the content of carbonate units (CU%) in the polymer.
As shown in the table below, catalyst 2 of the present disclosure can regulate the polymerization reaction at low catalyst concentration (PO/[ a1] ═ 50000/1), with activity measured as the transition frequency (TOF), which can reach 9600 per hour; in the aspect of selectivity, the Wpc% is controlled to be 0.5%, and an extremely low level without post-treatment is achieved; the control molecular weight is about 2000, the molecular weight distribution is extremely low, and the experimental molecular weight is identical with the theoretical molecular weight; the comparative catalyst CAT 'does not have PO conversion after reacting for 3 hours under the catalyst concentration, so the dosage of the catalyst CAT' needs to be increased by 10 times, the TOF value is 900 per hour under the concentration of PO/[ A1] (5000/1), the Wpc% is 2.9%, the activity and the selectivity have a large difference with the catalyst 2 of the patent, and the molecular weight is controlled to be 2700 and higher than the theoretical molecular weight, which shows that the control on telomerization reaction capability is weaker than that of the catalyst 2 of the patent.
Figure GDA0003375137520000281
Figure GDA0003375137520000291
Catalyst CAT 'to be compared'
ACS Catal.2019,9,8669-8676
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 (6)

1. A method of making a polymer polyol, comprising:
under the action of a non-heavy metal center catalytic system, performing ring-opening copolymerization on one or more of epoxide, carbon dioxide, cyclic ester and cyclic anhydride to obtain polymer polyol;
the non-heavy metal center catalytic system comprises an aluminum catalyst and an initiator;
the aluminum catalyst is an aluminum porphyrin oligomer catalyst; the aluminum porphyrin oligomer catalyst is specifically represented by formula 103, formula 104, formula 105 or formula 106:
Figure FDA0003575080790000011
the initiator is selected from one or more of water, small molecule alcohols, phenols, thiols, carboxylic acids, hydroxy acids, and hydroxyl-containing oligomers.
2. The method of claim 1, wherein the ring-opening copolymerization of one or two of the epoxide, carbon dioxide, cyclic ester, and cyclic anhydride comprises ring-opening polymerization of epoxide, ring-opening polymerization of cyclic ester, ring-opening copolymerization of epoxide and cyclic anhydride, and ring-opening copolymerization of epoxide and carbon dioxide;
the polymer polyol is selected from polyether polyol, polyester-ether polyol, poly (carbonate-ether) polyol or their multipolymer polyol.
3. The method of claim 2, wherein the epoxide comprises one or more of ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide, cyclohexene oxide, cyclopentane oxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, styrene alkylene oxide, 4-vinyl-1, 2-epoxycyclohexane, and vinyl propylene oxide;
the cyclic ester is selected from one or more of L-lactide, DL-lactide, beta-butyrolactone, delta-valerolactone and epsilon-caprolactone;
the cyclic anhydride is selected from one or more of maleic anhydride, phthalic anhydride, cyclobutane-1, 2-dicarboxylic anhydride, methyl nadic anhydride, cyclohexanedicarboxylic anhydride, succinic anhydride, hexahydrophthalic anhydride, itaconic anhydride, dodecenyl succinic anhydride, methyl tetrahydrophthalic anhydride, glutaric anhydride, trimethyl glutaric anhydride, 3-oxabicyclo [3.1.0] hexane-2, 4-dione, beta- (4-chlorophenyl) glutaric anhydride and 3, 3-dimethyl glutaric anhydride.
4. The preparation method according to claim 1, wherein the molar ratio of the metal center to the reactive monomer is 1 (2000-200000); the molar ratio of the monomer to the initiator is 100 (1-12).
5. The method according to claim 1, wherein the small molecule alcohol is ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, octanediol, decanediol, 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, trimethylolpropane, or mixtures thereof, Xylitol, sorbitol, tripentaerythritol and 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-cycloadipyl-dinitrosopolylene) biphenol; the carboxylic acid is 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.
6. The preparation method according to claim 1, wherein the copolymerization reaction temperature is 25 to 150 ℃; the pressure of the copolymerization reaction is 0.1-6 MPa; the time of the copolymerization reaction is 0.5-48 h.
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