CN108239118B - Cyclic oligomeric phosphazene compound and preparation method and application thereof - Google Patents

Cyclic oligomeric phosphazene compound and preparation method and application thereof Download PDF

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CN108239118B
CN108239118B CN201611219031.1A CN201611219031A CN108239118B CN 108239118 B CN108239118 B CN 108239118B CN 201611219031 A CN201611219031 A CN 201611219031A CN 108239118 B CN108239118 B CN 108239118B
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CN108239118A (en
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李志波
赵娜
任传利
刘绍峰
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Qingdao Boyuan Polymer Materials Research Institute Co., Ltd
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    • C08G77/08—Preparatory processes characterised by the catalysts used

Abstract

The invention discloses a cyclic oligomeric phosphazene compound, and a preparation method and application thereof. The cyclic oligomeric phosphazene compound disclosed by the invention is good in stability, easy to store and transport, free of heavy metal elements and belongs to a green environment-friendly product, and meanwhile, the cyclic oligomeric phosphazene compound disclosed by the invention is simple in synthesis route, easy in raw material obtaining, low in cost and suitable for popularization and application.

Description

Cyclic oligomeric phosphazene compound and preparation method and application thereof
Technical Field
The invention relates to the field of organic chemistry, in particular to a cyclic oligomeric phosphazene compound and a preparation method and application thereof.
Background
Phosphazenes, also known as phosphazenes, are nonpolar, strongly basic compounds containing phosphorus-nitrogen (P ═ N) double bonds and are widely used in organic catalytic reactions. In addition, the phosphazene compound is a high-activity anionic polymerization catalyst and is widely applied to polymerization reaction of monomers such as epoxy compounds, cyclosiloxanes, lactams, cyclic esters, cyclic carbonates, acrylic esters, acrylamides and the like.
In the last 90 s, Schwesinger et al reported the synthesis of a series of phosphazene compounds, including P4([(NMe2)3P＝N]3P ═ NR, superbase, pKa value 42.6 in acetonitrile solvent) and P2([(NMe2)3P＝N]P＝NR(NMe2)2Medium base, pKa value in acetonitrile solvent 33.5), and the like. In addition, the phosphonitrile salt catalyst PZN ({ [ (NR) was developed by Mitsui chemical Co., Japan2)3P＝N]4P}+Z-) The catalyst is successfully applied to ring-opening polymerization of epoxy compounds, the catalytic activity is 450 times of that of potassium hydroxide, the yield of the product polyether can be improved by 30-40% compared with that of the traditional catalyst, and the impurity content in the product is only 1/4 of the traditional polyether.
Although the research of the phosphazene compound has been carried out for many years, the currently common phosphazene compound catalyst has limited types, complex synthesis method and high cost, and is not beneficial to the application in the aspect of large-scale production. Therefore, a novel phosphazene catalyst which is cheap and easy to obtain is deeply researched and developed and popularized and applied as soon as possible, and huge economic and social benefits are certainly generated.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a cyclic oligomeric phosphazene compound and a preparation method and application thereof. The cyclic oligomeric phosphazene compound has the advantages of novel structure, good stability, easy storage and transportation, no heavy metal element and environment-friendly product.
In a first aspect of the invention, the invention features a compound. According to an embodiment of the invention, the compound is a compound of formula (I) or a solvate of a compound of formula (I),
Figure GDA0002174823160000011
wherein the content of the first and second substances,
a is a six-or eight-membered ring formed by- (P ═ N) -,
b is at least one
Figure GDA0002174823160000021
Or halogen, and B is bound to the P atom in A,
r is optionally substituted C1-6Alkyl, optionally substituted C1-6Cycloalkyl, optionally substituted aryl, optionally substituted benzyl, or R forms C with the attached N atom1-6A heterocycloalkyl group.
According to the embodiment of the invention, the compound has high molecular symmetry, good stability, easy storage and transportation and no heavy metal element, and belongs to a green and environment-friendly product.
In some embodiments of the invention, B is at least one
Figure GDA0002174823160000022
Or a combination of Cl and a base,
r is methyl, ethyl, isopropyl, N-butyl, cyclohexyl, phenyl, benzyl, or R forms with the N atom to which it is attached
Figure GDA0002174823160000023
In some embodiments of the invention, the compound is a compound or solvate of a compound represented by at least one of the following:
Figure GDA0002174823160000024
Figure GDA0002174823160000031
in a second aspect of the invention, there is provided a process for the preparation of the compounds of the above embodiments of the invention. According to an embodiment of the invention, the method comprises:
(a) contacting phosphorus pentachloride with a compound represented by formula X and ammonia gas to obtain a compound represented by formula 1;
(b) contacting the compound represented by formula 1 with a base to obtain a compound represented by formula 2;
(c) contacting said compound of formula 2 with hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene to obtain the compound of the above example,
Figure GDA0002174823160000032
wherein R is as previously described.
According to the embodiment of the invention, the raw materials adopted by the method for preparing the compound of the embodiment of the invention are easy to obtain, the cost is low, and the preparation method is simple.
In some embodiments of the invention, in step (a), the contacting is performed in a first nonaqueous solvent.
In some embodiments of the present invention, in step (a), the first nonaqueous solvent includes at least one selected from the group consisting of benzene, toluene, xylene, dichloromethane and tetrahydrofuran, preferably dichloromethane.
In some embodiments of the present invention, in step (a), the contacting is performed at-80 to 0 ℃ for 1 to 6 hours.
In some embodiments of the present invention, in step (a), the contacting of the phosphorus pentachloride and the compound of formula X is performed in a molar ratio of 1 (3-10).
In some embodiments of the invention, in step (b), the base is sodium hydroxide.
In some embodiments of the present invention, in the step (b), the base is a 20 to 70 wt% aqueous sodium hydroxide solution, preferably a 50 wt% aqueous sodium hydroxide solution.
In some embodiments of the invention, in step (c), the contacting is carried out in a second anhydrous solvent in the presence of an acid scavenger.
In some embodiments of the present invention, in step (c), the second anhydrous solvent comprises at least one selected from the group consisting of benzene, toluene, xylene, chlorobenzene and tetrahydrofuran, preferably toluene.
In some embodiments of the present invention, in step (c), the molar ratio of the hexachlorocyclotriphosphazene or the octachlorocyclotetraphosphazene to the compound represented by formula 2 to the acid-binding agent is 1 (1-8) to (1-8).
In some embodiments of the invention, in step (c), the acid scavenger comprises at least one selected from triethylamine, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide, preferably triethylamine.
In some embodiments of the present invention, in step (c), the contacting is performed at 40 to 150 degrees Celsius for 3 to 18 hours.
In a third aspect of the invention, the invention provides a process for the preparation of the compounds of the above embodiments of the invention. According to an embodiment of the invention, the method comprises:
placing phosphorus pentachloride in anhydrous dichloromethane in a nitrogen atmosphere, adding a compound shown as a formula X into the anhydrous dichloromethane at the temperature of-80-0 ℃, and reacting for 1-6 hours to obtain an intermediate;
continuously introducing ammonia gas into the intermediate for 1-6 hours at-80-0 ℃ and filtering to obtain a first filtrate, and distilling the first filtrate to remove the solvent to obtain the compound shown in the formula 1;
mixing the compound shown in the formula 1 with a 50 wt% sodium hydroxide aqueous solution, reacting for 1-5 hours, filtering to obtain a second filtrate, and distilling the second filtrate to remove a solvent to obtain a compound shown in a formula 2;
mixing hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene with the compound of formula 2 and triethylamine in a nitrogen atmosphere, refluxing and reacting in anhydrous toluene for 3-18 hours, then filtering to obtain a third filtrate, distilling the third filtrate to remove the solvent to obtain the compound of any one of claims 1-3,
Figure GDA0002174823160000041
wherein R is as previously described.
According to the embodiment of the invention, the raw materials adopted by the method for preparing the compound of the embodiment of the invention are easy to obtain, the cost is low, and the preparation method is simple.
In a fourth aspect of the invention, the invention proposes the use of the compounds of the above examples of the invention as catalysts in polymerization reactions. According to the embodiment of the invention, the compound of the embodiment of the invention can be used as a catalyst for preparing ester copolymers, ether copolymers, polyester, polyether and polycarbonate copolymers, the prepared polymer product has the advantages of easily regulated structure, abundant varieties, no heavy metal element in the product, low catalyst residue, good biocompatibility, wide application range and high additional value.
In a fifth aspect of the invention, the invention provides a process for preparing a polymer using the compounds of the above examples of the invention as catalysts. The polymer product prepared by the method has the advantages of easy structure regulation and control, rich varieties, no heavy metal element contained in the product, low catalyst residue, good biocompatibility, wide application range and high added value.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
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The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of tris (dimethylamine) phosphazene according to one embodiment of the invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of tris (dimethylamine) phosphazene according to one embodiment of the invention;
FIG. 3 is a nuclear magnetic resonance phosphorous spectrum of tris (dimethylamine) phosphazene according to one embodiment of the invention;
FIG. 4 is a NMR spectrum of hexa [ tris (dimethylamine) phosphazene ] polyphosphazene according to one embodiment of the invention;
FIG. 5 is a nuclear magnetic resonance carbon spectrum of hexa [ tris (dimethylamine) phosphazene ] polyphosphazene according to one embodiment of the present invention;
FIG. 6 is a nuclear magnetic resonance phosphorus spectrum of hexa [ tris (dimethylamine) phosphazene ] polyphosphazene according to one embodiment of the present invention;
FIG. 7 is a high resolution mass spectrum of tris (dimethylamine) phosphazene according to one embodiment of the invention;
FIG. 8 is a high resolution mass spectrum of hexa [ tris (dimethylamine) phosphazene ] triphosphazene according to one embodiment of the invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
Definitions and general terms
Reference will now be made in detail to certain embodiments of the invention, examples of which are illustrated by the accompanying structural and chemical formulas. The invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. Those skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ or contradict this application (including but not limited to defined terminology, application of terminology, described techniques, and the like), this application controls.
It will be further appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.
The articles "a," "an," and "the" as used herein are intended to include "at least one" or "one or more" unless otherwise indicated or clearly contradicted by context. Thus, as used herein, the articles refer to articles of one or more than one (i.e., at least one) object. For example, "a component" refers to one or more components, i.e., there may be more than one component contemplated for use or use in embodiments of the described embodiments.
The term "comprising" is open-ended, i.e. comprising what is specified in the invention, but does not exclude other aspects.
The compounds of the invention may be optionally substituted with one or more substituents, as described herein, in compounds of the general formula above, or as specifically exemplified, sub-classes, and classes of compounds encompassed by the invention.
In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced with a particular substituent. Unless otherwise indicated, a substituted group may have one substituent substituted at each substitutable position of the group. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, then the substituents may be substituted, identically or differently, at each substitutable position.
In various parts of this specification, the invention discloses compoundsThe substituents of (1) are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C1-6Alkyl "means in particular independently disclosed methyl, ethyl, C3Alkyl radical, C4Alkyl radical, C5Alkyl and C6An alkyl group.
In each of the parts of the invention, linking substituents are described. Where the structure clearly requires a linking group, the markush variables listed for that group are understood to be linking groups. For example, if the structure requires a linking group and the markush group definition for the variable recites "alkyl" or "aryl," it is understood that the "alkyl" or "aryl" represents an attached alkylene group or arylene group, respectively.
The term "alkyl" or "alkyl group" as used herein, denotes a saturated straight or branched chain monovalent hydrocarbon radical, wherein the alkyl group may be optionally substituted with one or more substituents as described herein. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in another embodiment, the alkyl group contains 3 to 12 carbon atoms; in another embodiment, the alkyl group contains 1 to 6 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 4 carbon atoms.
Examples of alkyl groups include, but are not limited to, methyl (Me, -CH)3) Ethyl group (Et, -CH)2CH3) N-propyl (n-Pr, -CH)2CH2CH3) Isopropyl group (i-Pr, -CH (CH)3)2) N-butyl (n-Bu, -CH)2CH2CH2CH3) Isobutyl (i-Bu, -CH)2CH(CH3)2) Sec-butyl (s-Bu, -CH (CH)3)CH2CH3) Tert-butyl (t-Bu, -C (CH)3)3) N-pentyl (-CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH)3)CH2CH2CH3) 3-pentyl (-CH (CH)2CH3)2) 2-methyl-2-butyl (-C (CH)3)2CH2CH3) 3-methyl-2-butyl (-CH (CH)3)CH(CH3)2) 3-methyl-1-butyl (-CH)2CH2CH(CH3)2) 2-methyl-1-butyl (-CH)2CH(CH3)CH2CH3) N-hexyl (-CH)2CH2CH2CH2CH2CH3) 2-hexyl (-CH (CH)3)CH2CH2CH2CH3) 3-hexyl (-CH (CH)2CH3)(CH2CH2CH3) 2-methyl-2-pentyl (-C (CH))3)2CH2CH2CH3) 3-methyl-2-pentyl (-CH (CH)3)CH(CH3)CH2CH3) 4-methyl-2-pentyl (-CH (CH)3)CH2CH(CH3)2) 3-methyl-3-pentyl (-C (CH)3)(CH2CH3)2) 2-methyl-3-pentyl (-CH (CH)2CH3)CH(CH3)2) 2, 3-dimethyl-2-butyl (-C (CH)3)2CH(CH3)2) 3, 3-dimethyl-2-butyl (-CH (CH)3)C(CH3)3) N-heptyl, n-octyl, and the like.
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The term "aryl" denotes a monocyclic, bicyclic or tricyclic carbocyclic ring system containing 6 to 14 ring atoms, or 6 to 12 ring atoms, or 6 to 10 ring atoms, wherein at least one ring is aromatic and has one or more attachment points to the rest of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring". In one embodiment, aryl is a carbocyclic ring system consisting of 6 to 10 ring atoms and containing at least one aromatic ring therein. Examples of the aryl group may include phenyl, naphthyl and anthracenyl. Wherein the aryl group may independently be optionally substituted with one or more substituents described herein.
"solvate" of the present invention refers to an association of one or more solvent molecules with a compound of the present invention. Solvents that form solvates include, but are not limited to, water, isopropanol, ethanol, methanol, dimethyl sulfoxide, ethyl acetate, acetic acid, and aminoethanol. The term "hydrate" refers to an association of solvent molecules that is water.
When the solvent is water, the term "hydrate" may be used. In some embodiments, a molecule of a compound of the present invention may be associated with a molecule of water, such as a monohydrate; in other embodiments, one molecule of the compound of the present invention may be associated with more than one molecule of water, such as a dihydrate, and in still other embodiments, one molecule of the compound of the present invention may be associated with less than one molecule of water, such as a hemihydrate. It should be noted that the hydrates of the present invention retain the biological effectiveness of the compound in its non-hydrated form.
In a first aspect of the invention, the invention features a compound. According to an embodiment of the invention, the compound is a compound of formula (I) or a solvate of a compound of formula (I),
Figure GDA0002174823160000071
Figure GDA0002174823160000081
wherein the content of the first and second substances,
a is a six-or eight-membered ring formed by- (P ═ N) -,
b is at least one
Figure GDA0002174823160000082
Or halogen, and B is bound to the P atom in A,
r is optionally substituted C1-6Alkyl, optionally substituted C1-6Cycloalkyl, optionally substituted aryl, optionally substituted benzyl, or R forms C with the attached N atom1-6A heterocycloalkyl group.
In some implementations of the inventionIn the examples, B is at least one
Figure GDA0002174823160000083
Or a combination of Cl and a base,
r is methyl, ethyl, isopropyl, N-butyl, cyclohexyl, phenyl, benzyl, or R forms with the N atom to which it is attached
Figure GDA0002174823160000084
In some embodiments of the invention, the compound is a compound or solvate of a compound represented by at least one of the following:
Figure GDA0002174823160000085
Figure GDA0002174823160000091
according to the embodiment of the invention, the compound has high molecular symmetry, good stability, easy storage and transportation and no heavy metal element, and belongs to a green and environment-friendly product.
In a second aspect of the invention, there is provided a process for the preparation of the compounds of the above embodiments of the invention. According to an embodiment of the invention, the method comprises:
(a) contacting phosphorus pentachloride with a compound represented by formula X and ammonia gas to obtain a compound represented by formula 1;
specifically, phosphorus pentachloride is suspended in a first anhydrous solvent under a nitrogen atmosphere and placed in a low temperature bath with vigorous stirring. And continuously introducing the compound of the formula X into the reaction system, naturally raising the temperature of the system to room temperature after the introduction of the gas is finished, and continuously reacting for 1-6 hours. And placing the system in a low-temperature bath again, introducing ammonia gas until the system is saturated, slowly raising the temperature to the room temperature, and continuously introducing the ammonia gas for 1-6 hours. Insoluble matter was filtered off, and the solvent was distilled off under reduced pressure to obtain the compound represented by formula 1.
The kind of the first nonaqueous solvent is not particularly limited according to an embodiment of the present invention, and may be selected by those skilled in the art according to actual needs, and according to a specific embodiment of the present invention, the first nonaqueous solvent may include at least one selected from the group consisting of benzene, toluene, xylene, dichloromethane, and tetrahydrofuran, preferably dichloromethane. In experiments, the inventor finds that phosphorus pentachloride and the compound shown in the formula X have better solubility in anhydrous dichloromethane, and the reactants can be effectively and fully dissolved by using the anhydrous dichloromethane, thereby improving the efficiency of reaction.
According to the specific embodiment of the invention, phosphorus pentachloride and the compound shown in the formula X are contacted in a molar ratio of 1 (3-10). The inventors found in experiments that, if the compounding ratio of the compound represented by formula X is too low, the chlorine atom in phosphorus pentachloride cannot be efficiently substituted sufficiently, and the compound represented by formula 1 cannot be obtained.
Figure GDA0002174823160000092
Wherein R is as previously described.
According to an embodiment of the present invention, the temperature of the low temperature bath may be-80 to 0 ℃. The inventor finds that if the temperature of the reaction system is too high, the reaction is too violent, and the temperature of the low-temperature bath can be controlled to be-80-0 ℃, so that the reaction is ensured to be stably carried out under the low-temperature condition.
(b) Contacting a compound represented by formula 1 with a base to obtain a compound represented by formula 2;
specifically, the compound shown in the formula 1 is added into an alkali liquor, and the reaction is carried out for 1-5 hours at room temperature. After the reaction, insoluble matter was filtered off, the filtrate was subjected to liquid separation, and the organic phase was depressurized to remove the solvent, so that the compound represented by formula 2 was obtained.
According to a specific embodiment of the invention, the base may be sodium hydroxide.
According to an embodiment of the present invention, the alkali may be a 20 to 70 wt% aqueous sodium hydroxide solution, preferably a 50 wt% aqueous sodium hydroxide solution. Thus, chloride ions in the compound represented by formula 1 can be effectively removed using a 50 wt% aqueous solution of sodium hydroxide and an elimination reaction can be performed with the compound represented by formula 1 to obtain the compound represented by formula 2.
Figure GDA0002174823160000101
Wherein R is as previously described.
(c) The compound of formula 2 is contacted with hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene to obtain the compound of the above example.
Specifically, under the nitrogen atmosphere, dissolving the compound shown in the formula 2, hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene and an acid-binding agent in a second anhydrous solvent, and performing reflux reaction for 3-18 hours. After the reaction, the hydrochloride formed by the chlorine atom in the phosphorus pentachloride and the acid binding agent is filtered, and the obtained filtrate is concentrated, so that the compound of the embodiment of the invention is obtained.
The kind of the second anhydrous solvent is not particularly limited according to the embodiment of the present invention, and may be selected by those skilled in the art according to actual needs, and according to the embodiment of the present invention, the second anhydrous solvent may be at least one selected from benzene, toluene, xylene, chlorobenzene, and tetrahydrofuran, and is preferably toluene. In experiments, the inventor finds that phosphorus pentachloride and the compound shown in the formula X have better solubility in anhydrous chlorobenzene, and the anhydrous chlorobenzene can be used for effectively and fully dissolving reactants, thereby improving the efficiency of reaction.
According to the specific embodiment of the invention, the molar ratio of hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene, the compound shown in formula 2 and the acid-binding agent can be 1 (1-8) to 1-8. In experiments, the inventor finds that the number of the substituted chlorine atoms in the hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene can be controlled by changing the feeding ratio of the hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene to the compound shown in the formula 2 (and correspondingly changing the feeding ratio of the acid-binding agent), so that target compounds substituted by different numbers of phosphazenes can be obtained.
According to the embodiment of the present invention, the kind of the acid scavenger is not particularly limited, and may be selected by a person skilled in the art according to actual needs, and according to the specific embodiment of the present invention, the acid scavenger may include at least one selected from triethylamine, sodium carbonate, sodium bicarbonate, sodium hydroxide, and potassium hydroxide, and preferably triethylamine. The inventor finds that the compound shown in the formula 2 reacts with hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene to generate small-molecule HCl, so that an acid-binding agent is required to be added to react with HCl to obtain hydrochloride, and HCl in the reaction system is removed. According to the embodiment of the invention, the inventor finds that the effect of adopting triethylamine as an acid-binding agent is better, and triethylamine hydrochloride generated by the reaction of triethylamine and HCl has low solubility in an organic solvent and is easy to filter and remove.
According to the specific embodiment of the invention, the compound shown in the formula 2 and hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene react at 40-150 ℃, so that the reaction efficiency can be obviously improved.
Therefore, according to the embodiment of the invention, the compound of the embodiment of the invention can be effectively prepared by the method, the adopted raw materials are easy to obtain, the cost is low, and the preparation method is simple.
In a third aspect of the invention, the invention provides a process for the preparation of the compounds of the above embodiments of the invention. According to an embodiment of the invention, the method comprises:
placing phosphorus pentachloride in anhydrous dichloromethane in a nitrogen atmosphere, adding a compound shown as a formula X into the anhydrous dichloromethane at the temperature of-80-0 ℃, and reacting for 1-6 hours to obtain an intermediate;
continuously introducing ammonia gas into the intermediate for 1-6 hours at-80-0 ℃ and filtering to obtain a first filtrate, and distilling the first filtrate to remove the solvent to obtain the compound shown in the formula 1;
mixing the compound shown in the formula 1 with a 50 wt% sodium hydroxide aqueous solution, reacting for 1-5 hours, filtering to obtain a second filtrate, and distilling the second filtrate to remove a solvent to obtain a compound shown in a formula 2;
mixing hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene with the compound of formula 2 and triethylamine in a nitrogen atmosphere, refluxing and reacting in anhydrous toluene for 3-18 hours, then filtering to obtain a third filtrate, distilling the third filtrate to remove the solvent to obtain the compound of any one of claims 1-3,
Figure GDA0002174823160000111
wherein R is as previously described.
Therefore, according to the embodiment of the invention, the compound of the embodiment of the invention can be effectively prepared by the method, the adopted raw materials are easy to obtain, the cost is low, and the preparation method is simple.
In a fourth aspect of the invention, the invention proposes the use of the compounds of the above examples of the invention as catalysts in polymerization reactions. According to the embodiment of the invention, the compound of the embodiment of the invention can be used as a catalyst for preparing ester copolymers, ether copolymers, polyester, polyether and polycarbonate copolymers, the prepared polymer product has the advantages of easily regulated structure, abundant varieties, no heavy metal element in the product, low catalyst residue, good biocompatibility, wide application range and high additional value.
In a fifth aspect of the invention, the invention provides a process for preparing a polymer using the compounds of the above examples of the invention as catalysts. The polymer product prepared by the method has the advantages of easy structure regulation and control, rich varieties, no heavy metal element contained in the product, low catalyst residue, good biocompatibility, wide application range and high added value.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
Preparation of tris (dimethylamine) phosphazene
Figure GDA0002174823160000121
Phosphorus pentachloride (41.7g,0.2mol,1.0equiv.) was added to a 1L three-necked flask equipped with mechanical stirring, 150mL of anhydrous dichloromethane were added under nitrogen protection, and the mixture was placed in a low temperature bath at-40 ℃ with vigorous stirring. Dimethylamine gas (54g,1.2mol,6.0equiv.) was continuously fed into the reaction system, and the solution temperature was maintained at less than-30 ℃. After the introduction, the temperature of the system was naturally raised to 20 ℃ and the reaction was continued for 1 hour. And reducing the temperature of the system to-20 ℃ again, introducing ammonia gas until the temperature is saturated, raising the temperature to 20 ℃, and continuously introducing the ammonia gas for 3 hours until the stirring is stopped and no precipitate is generated on the surface. Insoluble matter was filtered off, the solvent was distilled off under reduced pressure, and the resulting solid was added to 400mL of an aqueous sodium hydroxide solution (50 wt%) and reacted at room temperature for 1 hour. After the reaction, insoluble matter was filtered off, and the organic phase was vacuum distilled to remove the solvent to give 33g of a colorless liquid with a yield of 93%.
1H NMR(500MHz,CDCl3):2.52(d,18H)。13C NMR(125MHz,CDCl3):81.68。31P NMR(500MHz,CDCl3):43.75。HRMS(ESI)calcd for C6H19N4P[M+H]+,179.1426,found179.1417。
Example 2
Preparation of tris (diethylamine) phosphazene
Figure GDA0002174823160000122
Phosphorus pentachloride (41.7g,0.2mol,1.0equiv.) was added to a 1L three-necked flask equipped with mechanical stirring, 150mL of anhydrous dichloromethane were added under nitrogen protection, and the mixture was placed in a low temperature bath at-40 ℃ with vigorous stirring. Diethylamine (124mL,1.2mol,6.0equiv.) was continuously added dropwise to the reaction system, maintaining the solution temperature below-30 ℃. After the introduction, the temperature of the system was naturally raised to 20 ℃ and the reaction was continued for 2 hours. And reducing the temperature of the system to 0 ℃ again, introducing ammonia gas until the temperature is saturated, raising the temperature to 20 ℃, and continuously introducing the ammonia gas for 3 hours until the stirring is stopped and no precipitate is generated on the surface. Insoluble matter was filtered off, the solvent was distilled off under reduced pressure, and the resulting solid was added to 400mL of an aqueous sodium hydroxide solution (50 wt%) and reacted at room temperature for 1 hour. After the reaction, insoluble matter was filtered off, and the organic phase was vacuum distilled to remove the solvent to give 52.0g of colorless liquid in a yield of 99%.
1H NMR(500MHz,CDCl3):2.58(t,12H),1.08(q,18H)。HRMS(ESI)calcd forC12H31N4P[M+H]+,263.2365,found 263.2359。
Example 3
Preparation of tris (dicyclohexylamine) phosphazenes
Figure GDA0002174823160000131
Phosphorus pentachloride (41.7g,0.2mol,1.0equiv.) was added to a 1L three-necked flask equipped with mechanical stirring, 150mL of anhydrous dichloromethane were added under nitrogen protection, and the mixture was placed in a low temperature bath at-40 ℃ with vigorous stirring. Dicyclohexylamine (239mL,1.2mol,6.0equiv.) was continuously added dropwise to the reaction system, maintaining the solution temperature below-30 ℃. After the introduction, the temperature of the system was naturally raised to 20 ℃ and the reaction was continued for 1 hour. And reducing the temperature of the system to 0 ℃ again, introducing ammonia gas until the temperature is saturated, raising the temperature to 20 ℃, and continuously introducing the ammonia gas for 3 hours until the stirring is stopped and no precipitate is generated on the surface. Insoluble matter was filtered off, the solvent was distilled off under reduced pressure, and the resulting solid was added to 400mL of an aqueous sodium hydroxide solution (50 wt%) and reacted at room temperature for 1 hour. After the reaction was completed, insoluble matter was filtered off, and the organic phase was vacuum distilled to remove the solvent to obtain 88g of colorless liquid with a yield of 75%.
1H NMR(500MHz,CDCl3):2.57(m,6H),1.68-1.07(m,60H)。HRMS(ESI)calcd forC36H67N4P[M+H]+,587.5182,found 587.5173。
Example 4
Preparation of tris (diphenylamine) phosphazenes
Figure GDA0002174823160000132
Phosphorus pentachloride (41.7g,0.2mol,1.0equiv.) was added to a 1L three-necked flask equipped with mechanical stirring, 150mL of anhydrous dichloromethane were added under nitrogen protection, and the mixture was placed in a low temperature bath at-40 ℃ with vigorous stirring. A dichloromethane solution of diphenylamine (containing 203g of diphenylamine, 1.2mol,6equiv.) was continuously added dropwise to the reaction system, maintaining the solution temperature below-30 ℃. After the introduction, the temperature of the system was naturally raised to 20 ℃ and the reaction was continued for 1 hour. And reducing the temperature of the system to-20 ℃ again, introducing ammonia gas until the temperature is saturated, raising the temperature to 20 ℃, and continuously introducing the ammonia gas for 3 hours until the stirring is stopped and no precipitate is generated on the surface. Insoluble matter was filtered off, the solvent was distilled off under reduced pressure, and the resulting solid was added to 400mL of an aqueous sodium hydroxide solution (50 wt%) and reacted at room temperature for 1 hour. After the reaction, insoluble matter was filtered off, and the organic phase was vacuum distilled to remove the solvent to give 79g of a white solid in a yield of 72%.
1H NMR(500MHz,CDCl3):7.45(m,12H),6.98(m,6H),6.77(m,12H)。HRMS(ESI)calcd for C36H31N4P[M+H]+,551.2365,found 551.2352。
Example 5
Preparation of tripyrrole phosphazenes
Figure GDA0002174823160000141
Phosphorus pentachloride (41.7g,0.2mol,1.0equiv.) was added to a 1L three-necked flask equipped with mechanical stirring, 150mL of anhydrous dichloromethane were added under nitrogen protection, and the mixture was placed in a low temperature bath at-40 ℃ with vigorous stirring. Pyrrolidine (99mL,1.2mol,6.0equiv.) was continuously added dropwise to the reaction system, maintaining the solution temperature below-30 ℃. After the introduction, the temperature of the system was naturally raised to 20 ℃ and the reaction was continued for 2 hours. And reducing the temperature of the system to-20 ℃ again, introducing ammonia gas until the temperature is saturated, raising the temperature to 20 ℃, and continuously introducing the ammonia gas for 3 hours until the stirring is stopped and no precipitate is generated on the surface. Insoluble matter was filtered off, the solvent was distilled off under reduced pressure, and the resulting solid was added to 400mL of an aqueous sodium hydroxide solution (50 wt%) and reacted at room temperature for 1 hour. After the reaction, insoluble matter was filtered off, and the organic phase was vacuum distilled to remove the solvent to give 44g of colorless liquid with a yield of 85%.
1H NMR(500MHz,CDCl3):3.17(m,12H),1.68(m,12H)。HRMS(ESI)calcd forC12H25N4P[M+H]+,257.1895,found 257.1888。
Example 6
Preparation of hexa [ tris (dimethylamine) phosphazene ] triphosphazene
Figure GDA0002174823160000142
Under the protection of nitrogen, hexachlorocyclotriphosphazene (0.7g,2.0mmol,1.0equiv.) is dissolved in 4mL of toluene, the mixture is placed in a low-temperature bath at-78 ℃ and stirred uniformly, tris (dimethylamine) phosphazene (2.14g,12.0mmol,6equiv.) is dissolved in 4mL of toluene, the mixture is slowly dripped into the reaction system, and then triethylamine (1.21g, 12.0mmol,6.0equiv.) as an acid-binding agent is added. Heated to reflux and reacted for 12 hours. After the reaction, the reaction mixture was naturally cooled to room temperature, insoluble matter was filtered off, and the filtrate was concentrated to obtain 1.63g of a white solid with a yield of 68%.
1H NMR(500MHz,CDCl3):2.63(d,108H)。13C NMR(125MHz,CDCl3):37.53。31P NMR(500MHz,CDCl3):47.02,34.87。HRMS(ESI)calcd for C36H108N27P9[M+H]+,1198.6998,found 1198.6949。
Example 7
Preparation of hexa [ tris (diethylamine) phosphazene ] triphosphazene
Figure GDA0002174823160000151
Under the protection of nitrogen, hexachlorocyclotriphosphazene (0.7g,2.0mmol,1.0equiv.) is dissolved in 4mL of toluene, the mixture is placed in a low-temperature bath at-78 ℃ and stirred uniformly, tris (diethylamine) phosphazene (3.15g,12.0mmol,6equiv.) is dissolved in 4mL of toluene, the solution is slowly dripped into the reaction system, and then triethylamine (1.21g, 12.0mmol,6.0equiv.) as an acid-binding agent is added. Heated to reflux and reacted for 12 hours. After completion of the reaction, the reaction mixture was naturally cooled to room temperature, insoluble matter was filtered off, and the filtrate was concentrated to obtain 1.74g of a white solid with a yield of 51%.
1H NMR(500MHz,CDCl3):2.65(t,72H),1.11(q,108H)。HRMS(ESI)calcd forC72H180N27P9[M+H]+,1703.2632,found 1703.2609。
Example 8
Preparation of octa [ tris (dimethylamine) phosphazene ] tetraphosphazene
Figure GDA0002174823160000152
Octachlorocyclotetraphosphazene (2.32g,5.0mmol,1.0equiv.) was dissolved in 10mL of toluene under nitrogen protection, placed in a low temperature bath at-78 ℃ and stirred uniformly, tris (dimethylamine) phosphazene (7.13g,40.0mmol,8equiv.) was dissolved in 10mL of toluene, slowly added dropwise to the reaction system, and then acid-binding agent triethylamine (4.05g, 40.0mmol,8.0equiv.) was added. Heated to reflux and reacted for 12 hours. After the reaction was completed, the reaction mixture was naturally cooled to room temperature, insoluble matter was filtered off, and the filtrate was concentrated to obtain 5.75g of a white solid with a yield of 72%.
1H NMR(500MHz,CDCl3):2.68(m,144H)。HRMS(ESI-TOF)calcd for C48H145N36P12[M+H]+,1597.9304,found 1597.9275。
Example 9
Preparation of hexa [ tris (dicyclohexylamine) phosphazene ] triphosphazene
Figure GDA0002174823160000153
Under the protection of nitrogen, hexachlorocyclotriphosphazene (0.7g,2.0mmol,1.0equiv.) is dissolved in 4mL of toluene, the mixture is placed in a low-temperature bath at-78 ℃ and stirred uniformly, tris (dicyclohexylamine) phosphazene (7.04g,12.0mmol,6equiv.) is dissolved in 4mL of toluene, the solution is slowly dripped into the reaction system, and then acid-binding agent triethylamine (1.21g, 12.0mmol,6.0equiv.) is added. Heated to reflux and reacted for 12 hours. After the reaction, the reaction mixture was naturally cooled to room temperature, insoluble matter was filtered off, and the filtrate was concentrated to obtain 4.97g of a white solid with a yield of 68%.
1H NMR(500MHz,CDCl3):2.62(m,36H),1.62-1.09(m,360H)。HRMS(ESI-TOF)calcdfor C216H396N27P9[M+H]+,3650.9601,found 3650.9575。
Example 10
Preparation of hexa [ tris (diphenylamine) phosphazene ] triphosphazene
Figure GDA0002174823160000161
Under the protection of nitrogen, hexachlorocyclotriphosphazene (0.7g,2.0mmol,1.0equiv.) is dissolved in 4mL of toluene, the mixture is placed in a low-temperature bath at-78 ℃ and stirred uniformly, tris (diphenylamine) phosphazene (6.61g,12.0mmol,6equiv.) is dissolved in 4mL of toluene, the mixture is slowly dripped into the reaction system, and then an acid-binding agent triethylamine (1.21g, 12.0mmol,6.0equiv.) is added. Heated to reflux and reacted for 12 hours. After completion of the reaction, the reaction mixture was naturally cooled to room temperature, insoluble matter was filtered off, and the filtrate was concentrated to give 3.64g of a white solid with a yield of 53%.
1H NMR(500MHz,CDCl3):7.39(m,72H),6.88(m,36H),6.72(m,72H)。HRMS(ESI-TOF)calcd for C216H180N27P9[M+H]+,3433.2699,found 3433.2646。
Example 11
Preparation of hexa [ tripyrrole phosphazene ] triphosphazene
Figure GDA0002174823160000162
Under the protection of nitrogen, hexachlorocyclotriphosphazene (0.7g,2.0mmol,1.0equiv.) is dissolved in 4mL of toluene, the mixture is placed in a low-temperature bath at-78 ℃ and stirred uniformly, tripyrrolophosphazene (3.08g,12.0mmol,6equiv.) is dissolved in 4mL of toluene, the solution is slowly dripped into the reaction system, and then triethylamine (1.21g, 12.0mmol,6.0equiv.) as an acid-binding agent is added. Heated to reflux and reacted for 12 hours. After completion of the reaction, the reaction mixture was naturally cooled to room temperature, insoluble matter was filtered off, and the filtrate was concentrated to obtain 1.93g of a white solid with a yield of 58%.
1H NMR(500MHz,CDCl3):3.27(m,72H),1.72(m,72H)。HRMS(ESI)calcd forC72H144N27P9[M+H]+,1666.9815,found 1666.9798。
Example 12
Preparation of penta [ tris (dimethylamine) phosphazene ] monochlorotriphosphazene
Figure GDA0002174823160000171
Under the protection of nitrogen, hexachlorocyclotriphosphazene (0.7g,2.0mmol,1.0equiv.) is dissolved in 4mL of toluene, the mixture is placed in a low-temperature bath at-78 ℃ and stirred uniformly, tris (dimethylamine) phosphazene (1.78g,10.0mmol,5.0equiv.) is dissolved in 4mL of toluene, the mixture is slowly dripped into the reaction system, and then acid-binding agent triethylamine (1.01g, 10.0mmol,5.0equiv.) is added. Heated to reflux and reacted for 12 hours. After the reaction was completed, the reaction mixture was naturally cooled to room temperature, insoluble matter was filtered off, and the filtrate was concentrated to obtain 1.52g of a white solid with a yield of 72%.
1H NMR(500MHz,CDCl3):2.67(d,90H)。HRMS(ESI)calcd for C30H90ClN23P8[M+H]+,1056.5417,found 1056.5399。
Example 13
Preparation of tetrakis [ tris (dimethylamine) phosphazene ] dichlorotriphosphazene
Figure GDA0002174823160000172
Under the protection of nitrogen, hexachlorocyclotriphosphazene (0.7g,2.0mmol,1.0equiv.) is dissolved in 4mL of toluene, the mixture is placed in a low-temperature bath at-78 ℃ and stirred uniformly, tris (dimethylamine) phosphazene (1.43g,8.0mmol,4.0equiv.) is dissolved in 4mL of toluene, the mixture is slowly dripped into the reaction system, and then triethylamine (0.81g, 8.0mmol,4.0equiv.) as an acid-binding agent is added. Heated to reflux and reacted for 12 hours. After the reaction was completed, the reaction mixture was naturally cooled to room temperature, insoluble matter was filtered off, and the filtrate was concentrated to obtain 1.24g of a white solid with a yield of 68%.
1H NMR(500MHz,CDCl3):2.68(d,72H)。HRMS(ESI)calcd for C24H72Cl2N19P7[M+H]+,914.3837,found 914.3819。
Example 14
Preparation of tris [ tris (dimethylamine) phosphazene ] trichlorotriphosphazene
Figure GDA0002174823160000181
Under the protection of nitrogen, hexachlorocyclotriphosphazene (0.7g,2.0mmol,1.0equiv.) is dissolved in 4mL of toluene, the mixture is placed in a low-temperature bath at-78 ℃ and stirred uniformly, tris (dimethylamine) phosphazene (1.07g,6.0mmol,3.0equiv.) is dissolved in 4mL of toluene, the mixture is slowly dripped into the reaction system, and then acid-binding agent triethylamine (0.61g, 6.0mmol,3.0equiv.) is added for reaction at room temperature for 12 hours. After completion of the reaction, insoluble matter was filtered off, and concentrated to obtain 1.20g of a white solid with a yield of 78%.
1H NMR(500MHz,CDCl3):2.67(d,54H)。HRMS(ESI)calcd for C18H54Cl3N15P6[M+H]+,772.2256,found 772.2247。
Example 15
Preparation of bis [ tris (dimethylamine) phosphazene ] tetrachlorotriphosphazene
Figure GDA0002174823160000182
Under the protection of nitrogen, hexachlorocyclotriphosphazene (0.7g,2.0mmol,1.0equiv.) is dissolved in 4mL of toluene, the mixture is placed in a low-temperature bath at-78 ℃ and stirred uniformly, tris (dimethylamine) phosphazene (0.71g,4.0mmol,2.0equiv.) is dissolved in 4mL of toluene, the mixture is slowly dripped into the reaction system, and then triethylamine (0.41g, 4.0mmol,2.0equiv.) as an acid-binding agent is added for reaction at room temperature for 12 hours. After completion of the reaction, insoluble matter was filtered off, and the filtrate was concentrated to obtain 0.98g of a white solid in a yield of 78%.
1H NMR(500MHz,CDCl3):2.67(d,36H)。HRMS(ESI)calcd for C12H36Cl4N11P5[M+H]+,632.0646,found 632.0633。
Example 16
Preparation of [ tris (dimethylamine) phosphazene ] pentachloro triphosphazene
Figure GDA0002174823160000183
Under the protection of nitrogen, hexachlorocyclotriphosphazene (0.7g,2.0mmol,1.0equiv.) is dissolved in 4mL of toluene, the mixture is placed in a low-temperature bath at-78 ℃ and stirred uniformly, tris (dimethylamine) phosphazene (0.36g,2.0mmol,1.0equiv.) is dissolved in 4mL of toluene, the mixture is slowly dripped into the reaction system, and then triethylamine (0.20g,2.0mmol,1.0equiv.) as an acid-binding agent is added for reaction at room temperature for 12 hours. After completion of the reaction, insoluble matter was filtered off, and the mixture was concentrated to obtain 0.67g of a white solid with a yield of 68%.
1H NMR(500MHz,CDCl3):2.68(d,18H)。HRMS(ESI)calcd for C6H18Cl5N7P4[M+H]+,489.9066,found 489.9051。
Example 17
Preparation of Polypropylene oxide with the Hex [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000191
Under the protection of nitrogen, 5.0mL of catalyst solution (0.1mol/L of toluene solution, containing 0.50mmol of catalyst) is added into a 100mL pressure-resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (52 mu L,0.50mmol) and propylene oxide (3.5mL,50.0mmol) are added, the reaction kettle is closed, and the reaction kettle is placed in a preheated 100 ℃ oil bath for reaction until the pressure is reduced to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide 2.85g with the conversion rate of 98%. Mn,GPC＝3 500g mol-1，Mw/Mn＝1.25。
Example 18
Preparation of Polypropylene oxide with the Hex [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000192
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L toluene solution) was takenLiquid containing 0.25mmol of catalyst) is added into a 100mL pressure resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (26 μ L,0.25mmol) and propylene oxide (3.5mL,50.0mmol) are added, the reaction kettle is closed, the reaction kettle is placed in an oil bath preheated to 100 ℃, and the reaction is carried out until the pressure is reduced to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide 2.85g with the conversion rate of 98%. Mn,GPC＝4800g mol-1，Mw/Mn＝1.22。
Example 19
Preparation of Polypropylene oxide with the Hex [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000193
Under the protection of nitrogen, 0.1mL of catalyst solution (0.1mol/L of toluene solution, containing 0.01mmol of catalyst) is added into a 100mL pressure-resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (52 mu L,0.50mmol) and propylene oxide (7.0mL,100.0mmol) are added, the reaction kettle is closed, and the reaction kettle is placed in a preheated 100 ℃ oil bath for reaction until the pressure is reduced to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide 5.72g with the conversion rate of 98%. Mn,GPC＝9 300g mol-1，Mw/Mn＝1.15。
Example 20
Preparation of polyethylene oxide with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000201
Under the protection of nitrogen, 5.0mL of catalyst solution (0.1mol/L toluene solution, containing 0.50mmol of catalyst) was added into a 100mL pressure-resistant reaction vessel, the solvent was removed under high vacuum, benzyl alcohol (52. mu.L, 0.50mmol) and ethylene oxide (2.2g,50.0mmol) were added, the reaction vessel was closed, and the vessel was placed in a preheated 100 ℃ oil bathThe reaction was carried out until the pressure dropped to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polyethylene oxide 2.15g with the conversion rate of 98%. Mn,GPC＝3800g mol-1，Mw/Mn＝1.06。
Example 21
Preparation of propylene oxide ethylene oxide copolymer with Hexakis [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000202
Under the protection of nitrogen, 5.0mL of catalyst solution (0.1mol/L of toluene solution, containing 0.50mmol of catalyst) is added into a 100mL pressure-resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (52 mu L,0.50mmol) and propylene oxide (3.5mL,50.0mmol) are added, the reaction kettle is closed, the reaction kettle is placed in a preheated 100 ℃ oil bath, the pressure is reduced to 0, then ethylene oxide (2.2g,50.0mmol) is added, and the reaction is continued until the pressure is reduced to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final epoxypropane-epoxyethane copolymer 5.01g with the conversion rate of 98%. Mn,GPC＝7500g mol-1，Mw/Mn＝1.11。
Example 22
Preparation of ethylene oxide propylene oxide copolymer with Hexas [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000203
Under the protection of nitrogen, 5.0mL of catalyst solution (0.1mol/L of toluene solution, containing 0.50mmol of catalyst) is added into a 100mL pressure-resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (52 mu L,0.50mmol) and ethylene oxide (2.2g,50.0mmol) are added, the reaction kettle is closed, the reaction kettle is placed in an oil bath preheated to 100 ℃, the pressure is reduced to 0, then propylene oxide (3.5mL,50.0mmol) is added, and the reaction is continued until the pressure is reduced to 0The pressure drop was 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final ethylene oxide propylene oxide copolymer 4.96g with the conversion rate of 97%. Mn,GPC＝7800g mol-1，Mw/Mn＝1.13。
Example 23
Preparation of polycaprolactone with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000211
Under nitrogen protection, 0.5mL of catalyst solution (0.1mol/L toluene solution, containing 0.05mmol of catalyst) was added to a 50mL Schlenk reaction tube, benzyl alcohol (5.2. mu.L, 0.05mmol) was added, and the mixture was reacted at room temperature for 10 minutes, followed by addition of caprolactone (1.11mL,10.0mmol) and reaction at room temperature for 12 hours under nitrogen protection. After the reaction is finished, adding tetrahydrofuran and a little acetic acid, and precipitating for 2 times in 100mL of cold methanol to obtain 1.05g of the final polymer polycaprolactone with the conversion rate of 92%. Mn,GPC＝16 000gmol-1，Mw/Mn＝1.21。
Example 24
Preparation of polylactide Using the hexa [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000212
Under nitrogen protection, 0.5mL of a catalyst solution (0.1mol/L toluene solution, containing 0.05mmol of the catalyst) was added to a 50mL Schlenk reaction tube, benzyl alcohol (5.2. mu.L, 0.05mmol) was added, and the mixture was reacted at room temperature for 10 minutes, followed by addition of lactide (1.44g,10.0mmol) and reaction at room temperature for 12 hours under nitrogen protection. After the reaction, tetrahydrofuran and a little acetic acid were added, and the resulting mixture was precipitated in 100mL of cold methanol for 2 times to obtain 1.35g of the final polymer polylactide, which had a conversion of 94%. Mn,GPC＝16 800gmol-1，Mw/Mn＝1.22。
Example 25
Preparation of polydimethylsiloxane Using the hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000213
Under nitrogen protection, 0.5mL of catalyst solution (0.1mol/L toluene solution, containing 0.05mmol of catalyst) was added to a 50mL Schlenk reaction tube, benzyl alcohol (5.2. mu.L, 0.05mmol) was added, the reaction was carried out at room temperature for 10 minutes, octamethylcyclotetrasiloxane (3.10mL,10.0mmol) was added, and the mixture was placed in a preheated 80 ℃ oil bath and reacted for 20 minutes. After the reaction is finished, tetrahydrofuran and a little triethylamine are added, and the mixture is precipitated for 2 times in 100mL of cold methanol to obtain 2.97g of final polymer polydimethylsiloxane with the conversion rate of 99%. Mn,GPC＝83 900g mol-1，Mw/Mn＝1.06。
Example 26
Preparation of caprolactone-lactide copolymer using hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000221
Under nitrogen protection, 0.5mL of catalyst solution (0.1mol/L toluene solution, containing 0.05mmol of catalyst) was added to a 50mL Schlenk reaction tube, benzyl alcohol (5.2. mu.L, 0.05mmol) was added, and the mixture was reacted at room temperature for 10 minutes, followed by addition of caprolactone (1.11mL,10.0mmol) and reaction at room temperature for 12 hours under nitrogen protection. After completion of the reaction, lactide (1.44g,10.0mmol) was added and the reaction was carried out at room temperature for 30 minutes. After the reaction is finished, tetrahydrofuran and a little acetic acid are added, and the mixture is precipitated for 2 times in 100mL of cold methanol to obtain 2.09g of the final caprolactone-lactide copolymer with the conversion rate of 81%. Mn,GPC＝17 000g mol-1，Mw/Mn＝1.31。
Example 27
Preparation of propylene oxide/caprolactone copolymer with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000222
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L of toluene solution, containing 0.25mmol of catalyst) is added into a 100mL pressure-resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (26 μ L,0.25mmol) and propylene oxide (3.5mL,50.0mmol) are added, the reaction kettle is closed, and the reaction kettle is placed in a preheated 100 ℃ oil bath for reaction until the pressure is reduced to 0. After the reaction, the temperature was reduced to room temperature, 2.5mL of toluene was added, the mixture was stirred uniformly, and caprolactone (1.11mL,10.0mmol) was added and the reaction was carried out at room temperature under nitrogen for 12 hours. After the reaction is finished, tetrahydrofuran and a little acetic acid are added, and the mixture is precipitated for 2 times in 100mL of cold methanol to obtain 3.68g of the final epoxypropane and caprolactone copolymer with the conversion rate of 91%. Mn,GPC＝8 700g mol-1，Mw/Mn＝1.22。
Example 28
Preparation of Polypropylene oxide with the Hex [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000223
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L toluene solution, containing 0.25mmol of catalyst) was added into a 100mL pressure-resistant reaction vessel, the solvent was removed under high vacuum, ethylene glycol (13. mu.L, 0.25mmol) and propylene oxide (3.5mL,50.0mmol) were added, the reaction vessel was closed, placed in a preheated 100 ℃ oil bath, and reacted until the pressure dropped to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide 2.87g with the conversion rate of 99%. Mn,GPC＝5 200g mol-1，Mw/Mn＝1.22。
Example 29
Preparation of Polypropylene oxide with the Hex [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000231
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L of toluene solution, containing 0.25mmol of catalyst) was added into a 100mL pressure-resistant reaction vessel, the solvent was removed under high vacuum, glycerol (18. mu.L, 0.25mmol) and propylene oxide (3.5mL,50.0mmol) were added, the reaction vessel was closed, placed in a preheated 100 ℃ oil bath, and reacted until the pressure dropped to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide 2.76g with the conversion rate of 95%. Mn,GPC＝5 100g mol-1，Mw/Mn＝1.32。
Example 30
Preparation of Polypropylene oxide with the Hex [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000232
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L of toluene solution, containing 0.25mmol of catalyst) is added into a 100mL pressure-resistant reaction kettle, the solvent is removed under high vacuum, propylene oxide (3.5mL,50.0mmol) is added, the reaction kettle is sealed without adding an initiator, and the reaction kettle is placed in an oil bath preheated to 100 ℃ for reaction until the pressure is reduced to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide 2.76g with the conversion rate of 95%. Mn,GPC＝4 500g mol-1，Mw/Mn＝1.56。
Example 31
Preparation of Polypropylene oxide with the Hex [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000233
Taking under the protection of nitrogen2.5mL of a catalyst solution (0.1mol/L of a toluene solution, containing 0.25mmol of a catalyst) was added to a 100mL pressure resistant reaction vessel, the solvent was removed under high vacuum, benzyl alcohol (26. mu.L, 0.25mmol) and propylene oxide (17.5mL,250.0mmol) were added, the reaction vessel was closed, and the reaction vessel was placed in a preheated 100 ℃ oil bath and allowed to react until the pressure dropped to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide 11.91g with the conversion rate of 82%. Mn,GPC＝21 800g mol-1，Mw/Mn＝1.25。
Example 32
Preparation of Polypropylene oxide with the Hex [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000241
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L of toluene solution, containing 0.25mmol of catalyst) is added into a 500mL pressure-resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (26 μ L,0.25mmol) and propylene oxide (175mL,2.5mol) are added, the reaction kettle is closed, and the reaction kettle is placed in a preheated 100 ℃ oil bath for reaction until the pressure is reduced to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide of 76.96g with the conversion rate of 53%. Mn,GPC＝25 500g mol-1，Mw/Mn＝1.21。
Example 33
Preparation of Polypropylene oxide with the Hex [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000242
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L toluene solution, containing 0.25mmol of catalyst) was added to a 500mL pressure-resistant reaction vessel, the solvent was removed under high vacuum, benzyl alcohol (260. mu.L, 2.5mmol) and propylene oxide (175mL,2.5mol) were added, and the vessel was sealedClosing the reaction kettle, putting the reaction kettle in a preheated 100 ℃ oil bath, and reacting until the pressure is reduced to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain 108.91g of final polymer polypropylene oxide with the conversion rate of 75%. Mn,GPC＝23 400g mol-1，Mw/Mn＝1.27。
Example 34
Preparation of Polypropylene oxide with the Hex [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000243
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L of toluene solution, containing 0.25mmol of catalyst) is added into a 500mL pressure-resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (2.6mL,25mmol) and propylene oxide (175mL,2.5mol) are added, the reaction kettle is closed, the reaction kettle is placed in a preheated 100 ℃ oil bath, and the reaction is carried out until the pressure is reduced to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain 113.26g of final polymer polypropylene oxide with the conversion rate of 78%. Mn,GPC＝3 700g mol-1，Mw/Mn＝1.27。
Example 35
Preparation of Polypropylene oxide with the Hex [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000244
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L of toluene solution, containing 0.25mmol of catalyst) is added into a 100mL pressure-resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (26 μ L,0.25mmol) and propylene oxide (3.5mL,50.0mmol) are added, the reaction kettle is closed, and the reaction kettle is placed in a preheated 50 ℃ oil bath to react until the pressure is reduced to 0. Cooling to room temperature after the reaction is finished, adding tetrahydrofuran and a little acetic acid, filtering out insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final productThe final polymer, polypropylene oxide 2.70g, had a conversion of 93%. Mn,GPC＝5 300g mol-1，Mw/Mn＝1.32。
Example 36
Preparation of Polypropylene oxide with the Hex [ tris (dimethylamino) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000251
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L of toluene solution, containing 0.25mmol of catalyst) is added into a 100mL pressure-resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (26 μ L,0.25mmol) and propylene oxide (3.5mL,50.0mmol) are added, the reaction kettle is closed, and the reaction kettle is placed in a preheated 120 ℃ oil bath for reaction until the pressure is reduced to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide 2.76g with the conversion rate of 95%. Mn,GPC＝5 300g mol-1，Mw/Mn＝1.52。
Example 37
Preparation of polycaprolactone with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000252
Under nitrogen protection, 0.5mL of a catalyst solution (0.1mol/L toluene solution, containing 0.05mmol of the catalyst) was added to a 50mL Schlenk reaction tube, ethylene glycol (2.6. mu.L, 0.05mmol) was added, and the mixture was reacted at room temperature for 10 minutes, followed by addition of caprolactone (1.11mL,10.0mmol) and reaction at room temperature for 12 hours under nitrogen protection. After the reaction is finished, adding tetrahydrofuran and a little acetic acid, and precipitating for 2 times in 100mL of cold methanol to obtain 1.02g of the final polymer polycaprolactone with the conversion rate of 90%. Mn,GPC＝16600g mol-1，Mw/Mn＝1.24。
Example 38
Preparation of polycaprolactone with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000253
Under nitrogen protection, 0.5mL of catalyst solution (0.1mol/L toluene solution, containing 0.05mmol of catalyst) was added to a 50mL Schlenk reaction tube, benzyl alcohol (5.2. mu.L, 0.05mmol) was added, and the mixture was reacted at room temperature for 10 minutes, followed by addition of caprolactone (0.55mL,5.0mmol) and reaction at room temperature for 12 hours under nitrogen protection. After the reaction is finished, adding tetrahydrofuran and a little acetic acid, and precipitating for 2 times in 100mL of cold methanol to obtain the final polymer polycaprolactone 0.54g with the conversion rate of 95%. Mn,GPC＝8 700gmol-1，Mw/Mn＝1.25。
Example 39
Preparation of polycaprolactone with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000261
Under nitrogen protection, 0.5mL of catalyst solution (0.1mol/L toluene solution, containing 0.05mmol of catalyst) was added to a 50mL Schlenk reaction tube, benzyl alcohol (5.2. mu.L, 0.05mmol) was added, and the mixture was reacted at room temperature for 10 minutes, followed by addition of caprolactone (5.5mL,50.0mmol) and reaction at room temperature for 24 hours under nitrogen protection. After the reaction is finished, tetrahydrofuran and a little acetic acid are added, and the mixture is precipitated for 2 times in 100mL of cold methanol to obtain the final polymer polycaprolactone 3.13g with the conversion rate of 55%. Mn,GPC＝28 700gmol-1，Mw/Mn＝1.21。
Example 40
Preparation of polycaprolactone with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000262
Under the protection of nitrogen, the nitrogen gas is used for protecting the reaction vessel,0.5mL of a catalyst solution (0.1mol/L of a toluene solution containing 0.05mmol of a catalyst) was added to a 50mL Schlenk reaction tube, caprolactone (1.11mL,10.0mmol) was added without adding an initiator, and the reaction was carried out at room temperature under nitrogen for 12 hours. After the reaction is finished, tetrahydrofuran and a little acetic acid are added, and the mixture is precipitated for 2 times in 100mL of cold methanol to obtain the final polymer polycaprolactone 0.93g with the conversion rate of 82%. Mn,GPC＝16 300g mol-1，Mw/Mn＝1.45。
EXAMPLE 41
Preparation of polycaprolactone with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000263
Under nitrogen protection, 0.5mL of catalyst solution (0.1mol/L toluene solution, containing 0.05mmol of catalyst) was added to a 50mL Schlenk reaction tube, benzyl alcohol (52. mu.L, 0.5mmol) was added, and the mixture was reacted at room temperature for 10 minutes, followed by addition of caprolactone (27.5mL,250.0mmol) and reaction at room temperature for 24 hours under nitrogen protection. After the reaction is finished, tetrahydrofuran and a little acetic acid are added, and the mixture is precipitated for 2 times in 200mL of cold methanol to obtain the final polymer polycaprolactone 7.13g with the conversion rate of 25%. Mn,GPC＝31 700gmol-1，Mw/Mn＝1.18。
Example 42
Preparation of polycaprolactone with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000271
Under the protection of nitrogen, 0.5mL of catalyst solution (0.1mol/L toluene solution, containing 0.05mmol of catalyst) was added into a 50mL Schlenk reaction tube, benzyl alcohol (5.2. mu.L, 0.05mmol) was added, the reaction was carried out at room temperature for 10 minutes, the reaction solution was placed in an ice water bath, and after 10 minutes, -caprolactone (1.11mL,10.0mmol) was added, and the reaction was carried out at 0 ℃ for 12 hours under the protection of nitrogen. After the reaction is finished, adding tetrahydrofuran and a little acetic acid, and precipitating in 100mL of cold methanolAfter 2 times of precipitation, the final polymer polycaprolactone 0.97g was obtained, with a conversion of 85%. Mn,GPC＝17 500g mol-1，Mw/Mn＝1.16。
Example 43
Preparation of polycaprolactone with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000272
Under the protection of nitrogen, 0.5mL of catalyst solution (0.1mol/L of toluene solution, containing 0.05mmol of catalyst) was added into a 50mL Schlenk reaction tube, benzyl alcohol (5.2. mu.L, 0.05mmol) was added, the reaction was carried out at room temperature for 10 minutes, the reaction was carried out in a preheated 50 ℃ oil bath, and caprolactone (1.11mL,10.0mmol) was added after 10 minutes, and the reaction was carried out at 50 ℃ for 12 hours under the protection of nitrogen. After the reaction is finished, adding tetrahydrofuran and a little acetic acid, and precipitating for 2 times in 100mL of cold methanol to obtain 1.08g of the final polymer polycaprolactone with the conversion rate of 95%. Mn,GPC＝16 300g mol-1，Mw/Mn＝1.31。
Example 44
Preparation of polycaprolactone with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000273
Under the protection of nitrogen, 0.5mL of catalyst solution (0.1mol/L of toluene solution, containing 0.05mmol of catalyst) was added into a 50mL Schlenk reaction tube, benzyl alcohol (5.2. mu.L, 0.05mmol) was added, the reaction was carried out at room temperature for 10 minutes, the reaction was carried out in a preheated 100 ℃ oil bath, and caprolactone (1.11mL,10.0mmol) was added after 10 minutes, and the reaction was carried out under the protection of nitrogen at 100 ℃ for 12 hours. After the reaction is finished, adding tetrahydrofuran and a little acetic acid, and precipitating for 2 times in 100mL of cold methanol to obtain 1.12g of the final polymer polycaprolactone with the conversion rate of 99%. Mn,GPC＝15 600g mol-1，Mw/Mn＝1.36。
Example 45
Preparation of polycaprolactone with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000274
Under nitrogen protection, 0.5mL of a catalyst solution (0.1mol/L of a toluene solution, containing 0.05mmol of a catalyst) was added to a 50mL Schlenk reaction tube, the solvent was removed under reduced pressure, 0.5mL of tetrahydrofuran was added, after the catalyst was dissolved, benzyl alcohol (5.2. mu.L, 0.05mmol) was added, the reaction was carried out at room temperature for 10 minutes, and caprolactone (1.11mL,10.0mmol) was added, and the reaction was carried out at room temperature for 12 hours under nitrogen protection. After the reaction is finished, adding tetrahydrofuran and a little acetic acid, and precipitating for 2 times in 100mL of cold methanol to obtain 1.12g of the final polymer polycaprolactone with the conversion rate of 98%. Mn,GPC＝16 800g mol-1，Mw/Mn＝1.25。
Example 46
Preparation of polycaprolactone with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000281
Under nitrogen protection, 0.5mL of a catalyst solution (0.1mol/L toluene solution, containing 0.05mmol of the catalyst) was added to a 50mL Schlenk reaction tube, the solvent was removed under reduced pressure, 0.5mL of methylene chloride was added, after the catalyst was dissolved, benzyl alcohol (5.2. mu.L, 0.05mmol) was added, the reaction was carried out at room temperature for 10 minutes, and caprolactone (1.11mL,10.0mmol) was added, and the reaction was carried out at room temperature for 12 hours under nitrogen protection. After the reaction is finished, tetrahydrofuran and a little acetic acid are added, and the mixture is precipitated for 2 times in 100mL of cold methanol to obtain the final polymer polycaprolactone 0.97g with the conversion rate of 85%. Mn,GPC＝15 300g mol-1，Mw/Mn＝1.28。
Example 47
Preparation of propylene oxide/caprolactone copolymer with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000282
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L toluene solution, containing 0.25mmol of catalyst) was added into a 100mL pressure-resistant reaction vessel, the solvent was removed under high vacuum, ethylene glycol (13. mu.L, 0.25mmol) and propylene oxide (3.5mL,50.0mmol) were added, the reaction vessel was closed, placed in a preheated 100 ℃ oil bath, and reacted until the pressure dropped to 0. After the reaction, the temperature was reduced to room temperature, 2.5mL of toluene was added, the mixture was stirred uniformly, and caprolactone (1.11mL,10.0mmol) was added and the reaction was carried out at room temperature under nitrogen for 12 hours. After the reaction is finished, adding tetrahydrofuran and a little acetic acid, and precipitating for 2 times in 100mL of cold methanol to obtain 3.55g of the final epoxypropane and caprolactone copolymer with the conversion rate of 88%. Mn,GPC＝9 300g mol-1，Mw/Mn＝1.25。
Example 48
Preparation of Polypropylene oxide Using Penta [ tris (dimethylamino) phosphazene ] monochlorotriphosphazene prepared in example 12 as catalyst
Figure GDA0002174823160000291
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L of toluene solution, containing 0.25mmol of catalyst) is added into a 100mL pressure-resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (26 μ L,0.25mmol) and propylene oxide (3.5mL,50.0mmol) are added, the reaction kettle is closed, and the reaction kettle is placed in a preheated 100 ℃ oil bath for reaction until the pressure is reduced to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide 2.70g with the conversion rate of 93%. Mn,GPC＝4 500g mol-1，Mw/Mn＝1.42。
Example 49
Preparation of Polypropylene oxide Using Tetrakis [ tris (dimethylamino) phosphazene ] dichlorotriphosphazene prepared in example 13 as catalyst
Figure GDA0002174823160000292
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L of toluene solution, containing 0.25mmol of catalyst) is added into a 100mL pressure-resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (26 μ L,0.25mmol) and propylene oxide (3.5mL,50.0mmol) are added, the reaction kettle is closed, and the reaction kettle is placed in a preheated 100 ℃ oil bath for reaction until the pressure is reduced to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide 2.75g with the conversion rate of 95%. Mn,GPC＝4 300g mol-1，Mw/Mn＝1.45。
Example 50
Preparation of Polypropylene oxide Using Tri [ tris (dimethylamino) phosphazene ] trichlorotriphosphazene prepared in example 14 as catalyst
Figure GDA0002174823160000293
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L of toluene solution, containing 0.25mmol of catalyst) is added into a 100mL pressure-resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (26 μ L,0.25mmol) and propylene oxide (3.5mL,50.0mmol) are added, the reaction kettle is closed, and the reaction kettle is placed in a preheated 100 ℃ oil bath for reaction until the pressure is reduced to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide 2.76g with the conversion rate of 95%. Mn,GPC＝4 600g mol-1，Mw/Mn＝1.40。
Example 51
Preparation of Polypropylene oxide Using bis [ tris (dimethylamino) phosphazene ] tetrachlorotriphosphazene prepared in example 15 as catalyst
Figure GDA0002174823160000301
Under the protection of nitrogen, 2.5mL of catalyst solution is taken(0.1mol/L toluene solution, containing 0.25mmol of catalyst) is added into a 100mL pressure resistant reaction kettle, the solvent is removed under high vacuum, benzyl alcohol (26. mu.L, 0.25mmol) and propylene oxide (3.5mL,50.0mmol) are added, the reaction kettle is closed, and the reaction kettle is placed in an oil bath preheated to 100 ℃ for reaction until the pressure is reduced to 0. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide 2.55g with the conversion rate of 87%. Mn,GPC＝4 200g mol-1，Mw/Mn＝1.36。
Example 52
Preparation of Polypropylene oxide Using [ Tris (dimethylamine) phosphazene ] pentachloro triphosphazene prepared in example 16 as catalyst
Figure GDA0002174823160000302
Under the protection of nitrogen, 2.5mL of catalyst solution (0.1mol/L of toluene solution, containing 0.25mmol of catalyst) was added into a 100mL pressure-resistant reaction vessel, the solvent was removed under high vacuum, benzyl alcohol (26. mu.L, 0.25mmol) and propylene oxide (3.5mL,50.0mmol) were added, the reaction vessel was closed, and the reaction vessel was placed in a preheated 100 ℃ oil bath for 12 hours. After the reaction is finished, cooling to room temperature, adding tetrahydrofuran and a little acetic acid, filtering insoluble substances, and removing the solvent by reduced pressure distillation to obtain the final polymer polypropylene oxide 2.15g with the conversion rate of 74%. Mn,GPC＝3 400g mol-1，Mw/Mn＝1.32。
Example 53
Preparation of random copolymer of polycaprolactone and lactide with hexa [ tris (dimethylamine) phosphazene ] triphosphazene prepared in example 6 as catalyst
Figure GDA0002174823160000303
Under nitrogen protection, 0.5mL of catalyst solution (0.1mol/L toluene solution, containing 0.05mmol of catalyst) was added to a 50mL Schlenk reaction tube, benzyl alcohol (5.2. mu.L, 0.05mmol) was added, the reaction was carried out at room temperature for 10 minutes, and caprolactone (1.11mL,10 mL, caprolactone)0mmol) and lactide (1.44g,10.0mmol), under nitrogen protection at room temperature for 12 hours. After the reaction is finished, tetrahydrofuran and a little acetic acid are added, and the mixture is precipitated for 2 times in 100mL of cold methanol to obtain 2.21g of the final caprolactone-lactide random copolymer with the conversion rate of 86%. Mn,GPC＝19200g mol-1，Mw/Mn＝1.27。
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (18)

1. A compound, said compound being represented by at least one of:
Figure FDA0002435122460000011
2. a process for preparing the compound of claim 1, comprising:
(a) contacting phosphorus pentachloride with a compound represented by formula X and ammonia gas to obtain a compound represented by formula 1;
(b) contacting the compound represented by formula 1 with a base to obtain a compound represented by formula 2;
(c) contacting said compound of formula 2 with hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene to obtain the compound of claim 1,
NHR2
X
Figure FDA0002435122460000021
wherein R is methyl, ethyl, cyclohexyl, phenyl, or R forms with the N atom to which it is attached
Figure FDA0002435122460000022
3. The method of claim 2, wherein in step (a), the contacting is performed in a first non-aqueous solvent.
4. The method according to claim 3, wherein in step (a), the first nonaqueous solvent is at least one selected from the group consisting of benzene, toluene, xylene, methylene chloride and tetrahydrofuran.
5. The method according to claim 4, wherein the first nonaqueous solvent is dichloromethane.
6. The method of claim 2, wherein in step (a), the contacting is performed at-80 to 0 ℃ for 1 to 6 hours.
7. The method of claim 2, wherein in step (a), the contacting of the phosphorus pentachloride and the compound of formula X is performed in a molar ratio of 1 (3-10).
8. The process of claim 2, wherein in step (b), the base is sodium hydroxide.
9. The method according to claim 8, wherein in the step (b), the alkali is an aqueous solution of sodium hydroxide having a concentration of 20 to 70 wt%.
10. The method of claim 9, wherein the base is an aqueous solution of sodium hydroxide having a concentration of 50 wt%.
11. The process of claim 2, wherein in step (c), the contacting is carried out in a second anhydrous solvent in the presence of an acid scavenger.
12. The method according to claim 11, wherein in step (c), the second anhydrous solvent is selected from at least one of benzene, toluene, xylene, chlorobenzene, and tetrahydrofuran.
13. The method of claim 12, wherein the second anhydrous solvent is toluene.
14. The method of claim 11, wherein in step (c), the molar ratio of the hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene to the compound of formula 2 to the acid-binding agent is 1 (1-8) to (1-8).
15. The process of claim 11, wherein in step (c), the acid scavenger is selected from at least one of triethylamine, sodium carbonate, sodium bicarbonate, sodium hydroxide, and potassium hydroxide.
16. The method of claim 15, wherein the acid scavenger is triethylamine.
17. The method of claim 2, wherein in step (c), the contacting is performed at 40 to 150 degrees Celsius for 3 to 18 hours.
18. A process for preparing the compound of claim 1, comprising:
placing phosphorus pentachloride in anhydrous dichloromethane in a nitrogen atmosphere, adding a compound shown as a formula X into the anhydrous dichloromethane at the temperature of-80-0 ℃, and reacting for 1-6 hours to obtain an intermediate;
continuously introducing ammonia gas into the intermediate for 1-6 hours at-80-0 ℃ and filtering to obtain a first filtrate, and distilling the first filtrate to remove the solvent to obtain the compound shown in the formula 1;
mixing the compound shown in the formula 1 with a 50 wt% sodium hydroxide aqueous solution, reacting for 1-5 hours, filtering to obtain a second filtrate, and distilling the second filtrate to remove a solvent to obtain a compound shown in a formula 2;
mixing hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene with the compound shown in formula 2 and triethylamine in a nitrogen atmosphere, refluxing and reacting in anhydrous toluene for 3-18 hours, then filtering to obtain a third filtrate, distilling the third filtrate to remove the solvent to obtain the compound of claim 1,
NHR2
X
Figure FDA0002435122460000031
wherein R is methyl, ethyl, cyclohexyl, phenyl, or R forms with the N atom to which it is attached
Figure FDA0002435122460000032
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