CN111393630A - Polymer polyol and preparation method thereof - Google Patents

Polymer polyol and preparation method thereof Download PDF

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CN111393630A
CN111393630A CN202010411257.1A CN202010411257A CN111393630A CN 111393630 A CN111393630 A CN 111393630A CN 202010411257 A CN202010411257 A CN 202010411257A CN 111393630 A CN111393630 A CN 111393630A
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anhydride
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polyol
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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 a plurality of polyol production methods, the ring-opening (co) polymerization route of the oxygen-containing monomer has the advantages of high atom economy, rich monomer sources, mild reaction conditions and high efficiency, and the obtained polyol has a plurality of 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 polymer polyol prepared by the catalytic system provided by the present invention has good activity, selectivity and control capability on telomerization reaction.
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 BDA0002493339080000021
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 BDA0002493339080000022
Figure BDA0002493339080000031
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 polymerization initiating capability, and x is the number of Nu, and the value is 0-3; the R is1、R2、R3Is a functional substituent of porphyrin complex or a quaternary ammonium salt cation, and X is selected from halogen group, -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 BDA0002493339080000041
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, D L-lactide, β -butyrolactone, -valerolactone and-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, β - (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 BDA0002493339080000071
in the formula I, the C1 is a main chain structure shown in a formula (II);
Figure BDA0002493339080000072
formula II; specifically, the structure may be represented by the formula (II-1);
Figure BDA0002493339080000073
formula (II-1); 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 heteroaryl;
m is 4-20, preferably 10-20, and more preferably 13.
Figure BDA0002493339080000074
Formula a, RcAlkyl selected from C1-C12; preferably C1-C10 alkyl; may also be specifically-CH3、-CH2CH3、-(CH2)3CH3。
Figure BDA0002493339080000075
Formula b, wherein q is 0 or 1; the R isdAlkyl selected from C1-C12; preferably C1-C10 alkyl; more preferably a C1-C5 alkyl group;
r' is selected from formula c
Figure BDA0002493339080000076
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 BDA0002493339080000077
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 generate an ether chain segment, and the chain segment containing the formula IV is prone to generate 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 BDA0002493339080000081
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 0/3, 1/2, 2/1 or 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, p-nitrophenol oxyanion, m-nitrophenol oxyanion, p-nitrobenzoate oxyanion, p-nitrobenzophenone oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion,3, 5-bis-trifluoromethylphenol 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 BDA0002493339080000091
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 monomer, RAFT polymerization, metallization and quaternary ammonium salinization, and the sequence is not changeable. 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, D L-lactide, β -butyrolactone, -valerolactone, -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, β - (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 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. 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 BDA0002493339080000131
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 L1 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)。
E L1 (0.86g,1mmol), triethylamine (0.12g,1.2mmol) and anhydrous tetrahydrofuran were added to a 100ml reaction flask, the reaction flask was placed in an ice-water bath to cool, methacryloyl chloride (0.124g,1.2mmol) was dissolved in 10m L of anhydrous tetrahydrofuran and added dropwise to the reaction flask, the reaction was stirred at room temperature overnight, after the reaction was over, filtered, dissolved in dichloromethane, washed 3 times with sodium chloride solution and dried over anhydrous magnesium sulfate, and the crude product was chromatographed over dichloromethane to give E L2 in 88.2% yield.1H NMR(300MHz,CDCl3)＝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)。
Adding E L2 (0.56g,0.6mmol), 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid (DDMAT) (44mg,0.12mmol), AIBN (10mg,0.06mmol) and 25m L tetrahydrofuran into a Schlenk reaction tube, freezing to remove oxygen for 3 times, filling nitrogen, reacting at 65 ℃ for 24 hours, quenching with liquid nitrogen, precipitating with cold diethyl ether, collecting precipitate, repeatedly dissolving with dichloromethane-cold diethyl ether, centrifuging for 5 times, and vacuum drying to obtain oligomeric porphyrin ligand E L3, wherein the yield is 45%2Cl2):Mn＝6700,PDI＝1.34。
The ligand E L3 is dissolved in dichloromethane, and an equivalent amount of AlEt is added dropwise2Cl (diethylaluminum chloride) (2mol of inhexane) 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 BDA0002493339080000141
The reaction equation is the same as in example 1, but 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 specific steps are that E L2 (0.56g,0.6mmol), 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid (DDMAT) (22mg,0.06mmol), AIBN (5mg,0.03mmol) and 25m L tetrahydrofuran are added into a Schlenk reaction tube, after 3 times of freezing and oxygen removal, nitrogen is charged, reaction is carried out at 65 ℃ for 32h, liquid nitrogen is quenched, precipitate is collected after precipitation with cold ether, and repeated dissolution and centrifugation with dichloromethane-cold ether for 5 times, vacuum drying is carried out to obtain the desired oligomeric porphyrin ligand E L4, yield is 67%. gel permeation chromatography (GPC, PSstandard, CH2Cl2) 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 BDA0002493339080000151
Adding p-hydroxybenzaldehyde (13.2g,108mmol), p-chlorobenzaldehyde (45.39g,324mmol) and 500m L of propionic acid, heating to 130 ℃, dropwise adding pyrrole (30m L, 432mmol), continuously heating to 160 ℃, refluxing for reaction for 2h, cooling to room temperature after the reaction is finished, adding methanol, cooling in a refrigerator overnight, filtering to obtain a product, and performing silica gel column chromatography (CHCl)3/CH3OH) purification to yield the second color band as product E L5 in about 12% yield.1H NMR(300MHz,DMSO)＝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 E L6 as a yellow liquid.1H NMR(300MHz,CDCl3)＝6.09,5.54,4.14,3.53,1.93,1.78,1.69,1.44
Dissolving E L5 (2.00g, 2.7mmol) and E L6 (0.71g, 3.5mmol) in anhydrous DMF under nitrogen protection, adding K2CO3(0.22g, 1.54mmol) and KI (10mg) were reacted at 100 ℃ for 24 hours, and the porphyrin product E L7 was obtained by column chromatography with a yield of 80%.1H NMR(300MHz,CDCl3)＝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)。
Adding E L7 (0.54g,0.6mmol), 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid (DDMAT) (22mg,0.06mmol), AIBN (5mg,0.03mmol) and 25m L tetrahydrofuran into a Schlenk reaction tube, freezing to remove oxygen for 3 times, filling nitrogen, reacting at 65 ℃ for 32 hours, quenching with liquid nitrogen, precipitating with cold diethyl ether, collecting precipitate, repeatedly dissolving with dichloromethane-cold diethyl ether, centrifuging for 5 times, and vacuum drying to obtain the desired oligomeric porphyrin ligand E L8, wherein the yield is 47%2Cl2):Mn＝6600,PDI＝1.19。
The ligand E L8 is dissolved in dichloromethane, and an equivalent amount of AlEt is added dropwise2Cl (diethylaluminum chloride) (2mol of inhexane) was stirred at room temperature for 2 h. The solvent was drained in vacuo and dried to give the desired catalyst 3.
Example 4
Figure BDA0002493339080000161
Figure BDA0002493339080000171
42.8g (0.2mol) of 4' -hydroxybiphenyl-4-carboxylic acid and 1.6g (0.4mol) of NaOH are dissolved in 1L water, the solution is placed in a three-neck flask, 25.0(0.24mol) of methacryloyl chloride is dissolved in 300ml of anhydrous dichloromethane, dropwise addition is carried out at 5 ℃ within 2h, the mixture is placed in room temperature, the reaction is continued for 3h, solids are filtered out, the solids are dissolved by ethyl acetate, washed by water and hydrochloric acid solution for several times, and the solids are evaporated by rotation to obtain the product E L9.1H 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 E L9 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 restored and the reaction is carried out for 6h, and the product E L10 is obtained after the solvent is removed under reduced pressure;
dissolving 3.0g (0.01mol) of E L10 and 8.7g (0.01mol) of E L1 in 200ml of DMF under the protection of nitrogen, adding 0.12g (0.012mol) of triethylamine, reacting at 50 ℃ for 24h, removing the solvent to obtain a solid, dissolving the solid in dichloromethane, washing the solid with sodium chloride solution for three times, drying the solid with anhydrous sodium sulfate, and carrying out column chromatography on the crude product with dichloromethane to obtain a product E L11,1H NMR(300MHz,CDCl3)＝8.94,8.31,8.05,7.89,7.62,7.26,6.31,6.19,5.94,5.62,4.28,2.17,2.03,1.32,-2.78.MS(MALDI-ToF):：1131.7，found：1132.0；
RAFT polymerisation procedure similar to example 1, E L11 (1.15g,1mmol), 18mg 2- (dodecyltrithiocarbonate) -2-methylpropanoic acid (DDMAT) (36 mg)0.1mmol), AIBN (8mg,0.05mmol) and 50m L tetrahydrofuran were added to a Schlenk reaction tube, after 3 times of oxygen removal by freezing, nitrogen gas was charged, reaction was carried out at 65 ℃ for 12 hours, 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, oligomeric porphyrin ligand E L12 was obtained after vacuum drying, yield 42%, gel permeation chromatography (GPC, CH, etc.) was used, and the oligomeric porphyrin ligand E L was obtained2Cl2):Mn＝4700,PDI＝1.26。
The ligand E L12 is dissolved in dichloromethane, and an equivalent amount of AlEt is added dropwise2Cl (diethylaluminum chloride) (2mol of inhexane) was stirred at room temperature for 2 h. The solvent was drained in vacuo and dried to give the desired catalyst 4.
Example 5
Figure BDA0002493339080000181
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 InCl3The reaction is carried out at room temperature for 2 hours, 8.0g of 50-mesh sodium hydroxide powder is added, then the stirring is continued for 45min, the filtration is carried out, the filtrate is decompressed and distilled, the redundant pyrrole is recovered, and a brown solid crude product is obtained, the obtained crude product is ground by a mortar and washed by n-hexane for three times, the residual pyrrole is removed, then petroleum ether/dichloromethane column chromatography is carried out, the purification is carried out to obtain a light gray solid, under the protection of nitrogen, the gray solid (0.24g and 1mmol) and triethylamine (0.12g and 1.2mmol) are dissolved in 30ml of anhydrous tetrahydrofuran, the cooling is carried out in an ice water bath, then a tetrahydrofuran solution of methacryloyl chloride (0.124g and 1.2mmol) is added dropwise, the stirring is carried out at room temperature for overnight, after the reaction is finished, the filtration, the rotary drying and the redissolution in dichloromethane are washed by sodium chloride for 3 times, and the yield of E L13.
1H NMR(CDCl3):7.93,7.18-7.35,6.72,6.57,6.18,6.00,5.92,5.49,2.13
MS(ESI):[C19H18N2O2],m/z＝306.14[M+H]+(calcd.306.14)
Under the protection of nitrogen, p-hydroxybenzaldehyde (12.2g,0.1mol), 1, 6-dibromohexane (24.4g,0.1mol) are dissolved in anhydrous DMF, potassium carbonate (69.1g,0.5mol) and catalytic amount of potassium iodide (50mg) are added, reaction is carried out for 48h at 50 ℃, filtration and reduced pressure distillation are carried out, then washing is carried out for 3 times, the crude product is chromatographically separated by n-heptane/ethyl acetate column to obtain light yellow oily liquid, the obtained oily liquid and refined pyrrole are subjected to dipyrrole reaction of E L, under the protection of argon, the dipyrrole product (10mmol) is dissolved in 200ml of refined toluene in a 500ml three-neck round bottom flask, 50ml of ethylmagnesium bromide (1M THF solution) is slowly added at room temperature, after that addition is finished, stirring is continued for 3min, toluene solution of p-bromobenzoyl chloride (25mmol) is slowly added, after that dropping, reaction is finished, the reaction is carried out by pouring into 200ml of saturated ammonium chloride solution, then 150ml of ethyl acetate is slowly dropped, after that ethyl acetate is added, after that the ethyl acetate is added, the reaction solution is washed by 150 mmol, after the saturated ethyl acetate, the reaction is removed, the saturated ethyl acetate, the reaction is dried, the reaction is carried out, after the reaction is carried out, after the reaction is carried out, after the reaction is carried out, after the temperature is carried out, the reaction is carried out, the temperature is carried out, the saturated solvent is 10mmol is carried out, 2mmol is carried out, the saturated solvent is carried out, 2mmol is carried out, the saturated ammonium chloride is carried out.
1H NMR(CDCl3):8.75,8.11,8.02,7.57-7.67,7.42,6.59,5.97,3.49,2.95,2.32,2.10,-2.84.
MS(MALDI):[C54H43Br3N4O3],m/z＝1035.7[M+H]+(calcd.1035.7)
RAFT polymerization and metallation procedures following the protocol of example 1 gave E L16, no further details.gel permeation chromatography (GPC, CH2Cl2) determined the molecular weight of the oligomeric porphyrin ligand Mn6800 and PDI 1.39, 0.40g E L16 was dissolved in 5ml of a mixed solvent of purified chloroform and 5ml of purified acetonitrile, 3.7g of trihexylamine (20mmol) was added, and the mixture was refluxed in the dark for 3d, after the reaction was completed, the mixture was cooled to room temperature, the solvent was removed under reduced pressure, excess trihexylamine was removed with a dropper, and the resulting solid was crushed and washed three times in ether to remove residual trace of tributylamine, to obtain catalyst 5 in 92% yield.
Example 6
Figure BDA0002493339080000201
Figure BDA0002493339080000211
Under the protection of nitrogen, p-hydroxybenzaldehyde (12.2g,0.1mol) and 1, 6-dibromohexane (12.7g,0.1mol) are dissolved in anhydrous DMF, potassium carbonate (69.1g,0.5mol) and a catalytic amount of potassium iodide (50mg) are added to react for 48h at 50 ℃, the mixture is filtered, distilled under reduced pressure and washed with water for 3 times, the crude product is subjected to column chromatography by n-heptane/ethyl acetate to obtain colorless oily liquid, 3 equivalents of the colorless oily liquid, 1 equivalent of p-hydroxybenzaldehyde and 4 equivalents of pyrrole are added to 500m L propionic acid to perform reflux reaction for 2h, the mixture is cooled to room temperature after the reaction is finished, methanol is added to the mixture and cooled in a refrigerator overnight, and the product obtained by filtration is purified by silica gel column chromatography (CHCl3/CH3OH) to obtain a second colored band product E L17 with the yield of about 3%.
1H NMR(300MHz,DMSO)＝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)
E L17 (2.44g, 2.7mmol) and E L6 (0.71g, 3.5mmol) were dissolved in anhydrous DMF under nitrogen protection, K2CO3(0.22g, 1.54mmol) and KI (10mg) were added, reaction was carried out at 100 ℃ for 24h, and porphyrin product E L18 was obtained by column chromatography in 80% yield.
1H NMR(300MHz,CDCl3)＝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 (150m L, 2.14mol) were charged into a 500ml autoclave preliminarily subjected to water removal and oxygen removal treatment, 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 (150m L, 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 is finished, the reaction mixture is stirred,the reaction vessel was cooled to room temperature, carbon dioxide was slowly vented, and the resulting product was vacuum dried to remove unreacted propylene oxide, yielding 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 0.3% by-product of cyclic carbonate and about 70% carbonate units in the polymer. 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 (150m L, 2.14mol) were added to a 500ml autoclave previously subjected to water removal and oxygen removal, and rapidly passed through a CO-containing reactor 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 (150m L, 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 is finished, the reaction is carried outThe pot was cooled to room temperature, carbon dioxide was slowly vented, and the resulting product was vacuum dried to remove unreacted propylene oxide, yielding 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 showed 0.9% by-product of cyclic carbonate and about 51% carbonate units in the polymer.
Example 11
Catalyst 5 prepared in example 5(0.043g,0.043mmol [ Al ]]) Adding tris (diphenylphosphinyl) ammonium chloride (0.013g,0.021mmol), trimesic acid (14.98g,71.3mmol) and propylene oxide (150m L, 2.14mol) into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal treatment in advance, and rapidly passing through CO with 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 0.9% by-product of cyclic carbonate and about 47% carbonate units in the polymer.
Example 12
Catalyst 5 prepared in example 5(0.043g,0.043mmol [ Al ]]) Adding tris (diphenyl phosphoranylidene) ammonium chloride (0.013g,0.021mmol), pyromellitic acid (18.11g,71.3mmol) and propylene oxide (150m L, 2.14mol) into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal treatment in advance, and rapidly passing through CO with 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 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 (150m L, 2.14mol) were added to a 500ml autoclave previously subjected to water removal and oxygen removal, and rapidly passed through a CO-containing reactor 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 (diphenylphosphino) ammonium chloride (0.013g,0.021mmol), pyromellitic acid (36.2g,142.6mmol) and propylene oxide (300m L, 4.28mol) were added to a 500ml autoclave previously subjected to water removal and oxygen removal treatment, the temperature was controlled at 80 ℃ and the reaction was stirred for 3 hours, after completion of the polymerization reaction, the autoclave was cooled to room temperature, the resulting product was vacuum-dried to remove unreacted propylene oxide, and 177g of polyether polyol was obtained, and 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) andanhydrous toluene (100m L) was added to a Schlenk reaction flask which had been previously subjected to water removal and oxygen removal treatment, the temperature was controlled at 100 ℃ and the reaction was stirred, the reaction solution was taken out by a syringe,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 14g 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 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 (100m L) were added to a Schlenk reaction flask which had been previously subjected to water removal and oxygen removal treatment, the temperature was controlled at 100 ℃ and the reaction was stirred, the reaction solution was taken out by syringe,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) The polymer was found to have a number average molecular weight of 2400g/mol and a molecular weight distribution of 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 (100m L) were added to a Schlenk reaction flask which had been previously subjected to water removal and oxygen removal treatment, the temperature was controlled at 100 ℃ and the reaction was stirred, the reaction solution was taken out by a syringe,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 (150m L, 2.14mol) were charged into a 500ml autoclave which had been previously subjected to water removal and oxygen removal treatment, the temperature was controlled at 110 ℃ and the reaction was stirred for 3.5 hours, after the polymerization was completed, the autoclave was cooled to room temperature, the obtained product was vacuum-dried to remove unreacted propylene oxide, and polyester-ether polyol 102g was obtained, which was subjected to gel permeation chromatography (GPC, PSstandard, 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 ]]) Adding tris (diphenylphosphinyl) ammonium chloride (0.068g,0.119mmol), xylitol (2.25g,14.8mmol), succinic anhydride (14.84g,148mmol), cyclohexene oxide (30m L, 297mmol) and anhydrous toluene (60m L) into a Schlenk reaction bottle which is subjected to water removal and oxygen removal in advance, controlling the temperature at 100 ℃ and stirring for reaction for 80min, cooling the Schlenk reaction bottle to room temperature after the reaction is completed, precipitating the mixed solution by using a frozen methanol-ether mixed solvent (1: 1, volume ratio), centrifuging and drying for 24h under vacuum to obtain polyester-polyether polyol (34 g), and performing gel permeation chromatography (GPC, PS standard, CH) to obtain polyester-polyether polyol2Cl2) 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 (150m L, 2.14 mmol) were charged into 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 pressure is 4MPa, the temperature is controlled to be 80 ℃, and the stirring reaction is carried out for 3 hours. 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, PEGstandard, 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-NMR analysis showed that the cyclic carbonate by-product was 0.6%, the content of carbonate units in the polymer was about 43%, the content of ester segments was 17%, and the content of ether segments was 40%.
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 the catalyst, tris (diphenylphosphinyl) ammonium chloride (equimolar to the catalyst aluminium centre), sebacic acid (8.66g,42.8mmol) and propylene oxide (150m L, 2.14mol) to a 500ml autoclave previously subjected to water removal and oxygen removal treatment, and rapidly passing CO with 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 3 hours of reaction at the catalyst concentration, so the dosage of the catalyst CAT' needs to be increased by 10 times, the TOF value is 900 per hour and the Wpc% is 2.9% at the concentration of PO/[ A1] ═ 5000/1, the activity and selectivity have a large difference with the catalyst 2 of the patent, and the molecular weight is controlled to be 2700 which is 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 BDA0002493339080000271
Figure BDA0002493339080000272
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. A method of making a polymer polyol, comprising:
under the action of a non-heavy metal center catalytic system, performing ring-opening (co) polymerization 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 and has a structure shown in formula I:
Figure FDA0002493339070000011
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 FDA0002493339070000012
Figure FDA0002493339070000021
wherein Ra and Rb are independently selected from hydrogen, halogen, aliphatic substituted aliphatic, substituted heteroaliphatic, aryl, substituted aryl, or substituted heteroaryl; z is selected from formula a or formula b, RcAlkyl selected from C1-C12; q is 0 or 1; the R isdAlkyl selected from C1-C12; r' is 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 polymerization initiating capability, and x is the number of Nu, and the value is 0-3; the R is1、R2、R3Is a functional substituent of porphyrin complex or a quaternary ammonium salt cation, and X is selected from halogen group, -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 alcohols, phenols, thiols, carboxylic acids, hydroxy acids, and hydroxyl-containing oligomers.
2. The method according to claim 1, wherein Nu is a halide ion or a2, 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.
3. The method of claim 1, wherein the aluminoporphyrin oligomer catalyst is represented by formula 101, formula 102, formula 103, formula 104, formula 105, or formula 106:
Figure FDA0002493339070000031
4. the method of claim 1, wherein the ring-opening (co) polymerization of one or both 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.
5. The method of claim 4, wherein the epoxide comprises one or more of ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide, cyclohexene oxide, cyclopentane oxide, glycidyl epichlorohydrin 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, D L-lactide, β -butyrolactone, -valerolactone and-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, β - (4-chlorophenyl) glutaric anhydride and 3, 3-dimethyl glutaric anhydride.
6. 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).
7. The method of claim 1, wherein the initiator is selected from one or more of water, small molecule alcohols, phenols, thiols, carboxylic acids, hydroxy acids, and hydroxyl-containing oligomers.
8. The method according to claim 7, 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, sebacic glycol, 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-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 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.
10. A polymer polyol produced by the production method according to any one of claims 1 to 9.
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