CN111286017B - Cyclic polyether diester, preparation method thereof and application of catalyst - Google Patents

Cyclic polyether diester, preparation method thereof and application of catalyst Download PDF

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CN111286017B
CN111286017B CN201811495653.6A CN201811495653A CN111286017B CN 111286017 B CN111286017 B CN 111286017B CN 201811495653 A CN201811495653 A CN 201811495653A CN 111286017 B CN111286017 B CN 111286017B
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anhydride
cyclic
ethylene oxide
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calcium
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CN111286017A (en
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朱建民
刘兆滨
董振鹏
赵春雨
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Liaoning Oxiranchem Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2651—Alkaline earth metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2654—Aluminium or boron; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
    • C08G2650/24—Polymeric initiators

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Abstract

The invention provides a cyclic polyether diester, a preparation method thereof and application of a catalyst, wherein the preparation method comprises the steps of carrying out ring-opening polymerization on ethylene oxide by taking cyclic anhydride as an initiator under the action of the catalyst to prepare the cyclic polyether diester; wherein the catalyst comprises one or more of a group IIA metal composite oxide, an alkyl compound, an alkoxy compound and a carboxylate, a group IIA metal and aluminum composite oxide, a zinc carboxylate and an alkyl compound. The method of the embodiment of the invention prepares the cyclic polyether diester by a one-step method, and has the advantages of simple process flow and high yield.

Description

Cyclic polyether diester, preparation method thereof and application of catalyst
Technical Field
The invention relates to polyether diester, in particular to cyclic polyether diester and a preparation method thereof.
Background
Polyether diesters are generally obtained by esterification of a polyether with an acid or transesterification of a polyether with an ester. The esterification and ester exchange reactions are a kind of reversible chemical reactions, one of them is usually selected to be excessive in order to improve the product yield, and the product in the reaction process is continuously distilled and removed to promote the reaction to go forward.
Since the boiling point of the polyether is usually higher than that of the acid or ester, the acid or ester is often selected in excess when controlling the reaction direction, and if the acid and ester are required to be recycled after the reaction, a separation unit is required to separate the product and the acid (ester), thereby prolonging the reaction period and increasing the production cost.
Disclosure of Invention
The invention provides a preparation method of cyclic polyether diester, which comprises the steps of under the action of a catalyst, using cyclic anhydride as an initiator to carry out ring-opening polymerization of ethylene oxide to prepare the cyclic polyether diester;
wherein the catalyst comprises one or more of a group IIA metal composite oxide, an alkyl compound, an alkoxy compound and a carboxylate, a group IIA metal and aluminum composite oxide, a zinc carboxylate and an alkyl compound.
According to an embodiment of the invention, the cyclic anhydride is selected from one or more of phenylsuccinic anhydride, 2,3-pyridinedicarboxylic anhydride, 2-methylsuccinic anhydride, maleic anhydride, 2,3-dimethylmaleic anhydride, 2,3-dichloromaleic anhydride, 3-fluorophthalic anhydride, succinic anhydride, citraconic anhydride, phthalic anhydride.
According to one embodiment of the present invention, the molar ratio of the cyclic acid anhydride to the ethylene oxide is 1 (2 to 150).
According to one embodiment of the present invention, the ring-opening polymerization is carried out at a reaction temperature of 80 to 180 ℃ and a reaction pressure of 0.1 to 0.5MPa.
According to one embodiment of the invention, the catalyst comprises one or more of magnesium aluminum composite oxide, magnesium aluminum calcium composite oxide, an alkoxide compound of calcium, an alkyl compound of calcium, an acetate salt of calcium, an alkoxide compound of barium, an alkyl compound of zinc, and an acetate salt of zinc.
According to an embodiment of the present invention, the mass of the catalyst is 0.05% to 5% of the total mass of the cyclic acid anhydride and the ethylene oxide.
One embodiment of the present invention further provides a cyclic polyether diester, having a structural formula:
Figure BDA0001896825070000021
wherein n is 1 +n 2 N, n represents the average addition number of ethylene oxide;
R 1 、R 2 independently selected from phenyl, methyl or hydrogen;
R 3 、R 4 independently selected from methyl, chlorine or hydrogen, or R 3 、R 4 Together forming one of the following structures:
Figure BDA0001896825070000022
one embodiment of the present invention further provides a cyclic polyether diester prepared by ring-opening polymerization of a cyclic anhydride and ethylene oxide.
An embodiment of the present invention further provides a use of a catalyst in a ring-opening polymerization reaction of a cyclic acid anhydride and ethylene oxide, wherein the catalyst comprises one or more of a group iia metal complex oxide, an alkyl compound, an alkoxy compound, a carboxylate, a group iia metal and aluminum complex oxide, and a zinc carboxylate, an alkyl compound.
According to the method provided by the embodiment of the invention, the cyclic polyether diester is prepared through one-step reaction, and the method has the advantages of simple process flow and high yield.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below. It is to be understood that the invention is capable of other and different embodiments and its several details are capable of modification without departing from the scope of the invention, and that the description is intended to be illustrative in nature and not to be construed as limiting the invention.
The invention provides a preparation method of cyclic polyether diester, which comprises the steps of under the action of a catalyst, using cyclic anhydride as an initiator to carry out ring-opening polymerization on ethylene oxide to prepare cyclic polyether diester; wherein the catalyst comprises one or more of a group IIA metal composite oxide, an alkyl compound, an alkoxy compound and a carboxylate, a group IIA metal and aluminum composite oxide, a zinc carboxylate and an alkyl compound.
According to the method provided by the embodiment of the invention, the cyclic polyether diester is generated through one-step reaction, and compared with the traditional esterification (ester exchange) method, the method provided by the invention avoids multi-step separation and shortens the process flow.
In one embodiment, the cyclic anhydride may be phenylsuccinic anhydride, 2,3-pyridinedicarboxylic anhydride, 2-methylsuccinic anhydride, maleic anhydride, 2,3-dimethylmaleic anhydride, 2,3-dichloromaleic anhydride, 3-fluorophthalic anhydride, succinic anhydride, citraconic anhydride, phthalic anhydride, or the like.
In one embodiment, the molar ratio of cyclic anhydride to ethylene oxide is 1 (2 to 150), for example 1.
In one embodiment, the ring-opening polymerization of ethylene oxide is carried out using phthalic anhydride as the initiator to produce polyethylene glycol bisphthalate, according to the following equation:
Figure BDA0001896825070000031
wherein n = n 1 +n 2 (ii) a n represents the average addition number of ethylene oxide, and may be: 2. Ltoreq. N.ltoreq.150, for example 10, 50, 75, 100, etc.
In one embodiment, the catalyst may be a C1-C4 alkyl, alkoxy, or carboxylate salt of a group IIA metal (e.g., magnesium, calcium), or a C1-C4 alkoxy or carboxylate salt of zinc.
In one embodiment, the catalyst may be magnesium aluminum (Mg-Al) composite oxide, magnesium aluminum calcium (Mg-Al-Ca) composite oxide, calcium alkoxide, calcium alkyl, calcium acetate, barium alkoxide, zinc alkyl, zinc acetate, and the like, and may specifically be one or more of Mg-Al oxide, calcium methoxide, calcium acetate, zinc acetate, and diethyl zinc, for example.
In one embodiment, the preparation method of the metal composite oxide used as the catalyst may be a coprecipitation method, for example, an aqueous solution of two soluble salts is used as a precursor, sodium hydroxide, sodium carbonate or ammonia water is used as a pH regulator, and after the reaction is finished, the catalyst is obtained through multiple times of washing, drying and roasting.
In one embodiment, the mass of the catalyst is 0.05 to 5% of the total mass of the cyclic acid anhydride and ethylene oxide, for example, 0.06%, 0.07%, 0.08%, 0.10%, 0.14%, and the like.
In one embodiment, the reaction temperature for the ring-opening polymerization of ethylene oxide is 80 to 180 ℃, preferably 150 to 170 ℃, and the reaction pressure is 0.1 to 0.5MPa.
In one embodiment, a method of preparing a cyclic polyether diester comprises: adding cyclic anhydride into a reaction kettle, then adding a catalyst, sealing the reaction kettle, carrying out air tightness detection, replacing 3-5 times with nitrogen after the detection is qualified, then starting to heat up, introducing a small amount of ethylene oxide into the reaction kettle after the temperature is raised to 140 ℃, continuously introducing the rest of ethylene oxide after the pressure is lowered and the temperature is raised, controlling the reaction temperature to be 150-170 ℃, continuing to cure for 30-50 minutes after the reaction is finished, cooling to 70 ℃, and taking out the material.
According to the embodiment of the invention, the cyclic polyether diester is obtained through ethoxylation reaction by using the anhydride as the initiator through a one-step method under the action of the specific catalyst, the synthetic process is short, the production cost is low, and the product yield is high.
The preparation method of the cyclic polyether diester provided by the embodiment of the invention has the advantages of simple steps, convenience in operation, easiness in directly realizing industrialization and capability of directly obtaining a high-purity product.
The preparation method of the cyclic polyether diester provided by the embodiment of the invention does not use a solvent, saves energy, has no washing step, avoids the generation of three wastes, and is beneficial to environmental protection; meanwhile, no solvent is used, so that the special smell of the product is avoided.
One embodiment of the present invention further provides a cyclic polyether diester, having a structural formula:
Figure BDA0001896825070000051
wherein n is 1 +n 2 N, n represents the average number of additions of ethylene oxide, and can be: 2. Ltoreq. N.ltoreq.150, for example 10, 50, 75, 100, etc.
R 1 、R 2 Independently selected from phenyl, methyl or hydrogen;
R 3 、R 4 independently selected from methyl, chlorine or hydrogen, or R 3 、R 4 Together forming one of the following structures:
Figure BDA0001896825070000052
in one embodiment, R 1 Is phenyl, R 2 Is hydrogen.
In one embodiment, R 1 Is methyl, R 2 Is hydrogen.
In one embodiment, R 1 、R 2 Are all hydrogen.
In one embodiment, R 3 、R 4 Are all methyl.
In one embodiment, R 3 、R 4 All are chlorine.
In one embodiment, R 3 、R 4 Are all hydrogen.
In one embodiment, R 3 Is methyl, R 4 Is hydrogen.
One embodiment of the present invention further provides a cyclic polyether diester obtained by ring-opening polymerization of a cyclic acid anhydride and ethylene oxide.
Hereinafter, the preparation of the cyclic polyether diester according to one embodiment of the present invention will be described in detail with reference to specific examples. Wherein, the hydroxyl value of the synthetic sample is determined according to GB/T7384-1996 acetic anhydride method for determining the hydroxyl value of the polyethoxylated derivative of the nonionic surfactant, the acid value of the synthetic sample is determined according to GB/T7304-2014 potentiometric titration method for determining the acid value of the petroleum product, and the hydroxyl value and the acid value are both 0, which indicates that no impurity is generated. The saponification value is measured by using a method of HG/T3505-2000 & lt & gt determination of saponification value of surfactant & lt & gt, aiming at characterizing the number average molecular weight of the product; the yield of the product is calculated by the following formula: product yield = actual discharge × 100%/theoretical discharge.
The preparation method of the magnesium-aluminum composite oxide of the embodiment is as follows: respectively configuring 1mol/L of Mg (NO) 3 ) 2 Aqueous solution and 1mol/L Al (NO) 3 ) 3 Aqueous solution, naOH and Na with pH value of 10-11 2 CO 3 The three solutions are respectively heated to 50 ℃, and Mg (NO) with the volume ratio of 1:1 or 2:1 is added at 50 DEG C 3 ) 2 With Al (NO) 3 ) 3 The solution is respectively dropwise added into NaOH and Na 2 CO 3 After the addition, the reaction was continued at 50 ℃ for 12 hours. Washing with water and alcohol, drying at 110 ℃, and then roasting at 500 ℃ for 3h to finally obtain the composite metal oxide with the corresponding Mg/Al ratio.
The catalysts in examples, such as calcium methoxide, calcium acetate, and diethyl zinc, were commercially available.
Example 1
148g of phthalic anhydride is added into a reaction kettle, 0.18g of Mg-Al oxide with the Mg/Al molar ratio of 2:1 is then added, the reaction kettle is sealed, nitrogen is used for replacing for 3-5 times after the airtightness detection is qualified, then the temperature is raised, 5g of ethylene oxide is introduced after the temperature is raised to 140 ℃, 83g of ethylene oxide is continuously introduced after the pressure is reduced and the temperature is raised, the reaction temperature is controlled to be 150-170 ℃, the reaction pressure is controlled to be 0.1-0.5 MPa, after the reaction is finished, the aging is continuously carried out for 30-50 minutes, the temperature is reduced to 70 ℃, the materials are taken out, and the weight of the materials is weighed to be 234.5g. The hydroxyl value and the acid value of the test sample are both 0, so that the sample is proved to have no hydroxyl or carboxyl, and the synthesized sample can be judged to be the target sample. Detecting the saponification value of the product, wherein the saponification value of the product is as follows: 477.2, the yield of the product is 99.4%.
Example 2
Adding 148g of phthalic anhydride into a reaction kettle, then adding 0.22g of Mg-Al oxide with the Mg/Al molar ratio of 1:1, sealing the reaction kettle, replacing 3-5 times with nitrogen after passing the airtightness detection, then starting to heat up, heating up to 140 ℃, introducing 5g of ethylene oxide, continuously introducing 83g of ethylene oxide after the pressure is reduced and the temperature is increased, controlling the reaction temperature to be 150-170 ℃, the reaction pressure to be 0.1-0.5 MPa, after the reaction is finished, continuously curing for 30-50 minutes, cooling to 70 ℃, taking out the material, and weighing 233.9g of the material. The hydroxyl value and the acid value of the test sample are both 0, so that the sample is proved to have no hydroxyl or carboxyl, and the synthesized sample can be judged to be the target sample. Detecting the saponification value of the product, wherein the saponification value of the product is as follows: 478.2, product yield 99.0%.
Example 3
Adding 100g of succinic anhydride into a reaction kettle, then adding 0.26g of calcium methoxide, sealing the reaction kettle, replacing 3-5 times with nitrogen after the air tightness is detected to be qualified, then starting to heat up, introducing 5g of ethylene oxide after the temperature is raised to 140 ℃, continuously introducing 83g of ethylene oxide after the temperature is lowered and raised, controlling the reaction temperature to be 150-170 ℃ and the reaction pressure to be 0.1-0.5 MPa, after the reaction is finished, continuously curing for 30-50 minutes, cooling to 70 ℃, taking out the material, and weighing 186.3g of the material. The hydroxyl value and the acid value of the test sample are both 0, so that no hydroxyl group or carboxyl group exists in the sample, and the synthesized sample can be judged to be a target sample. Detecting the saponification value of the product, wherein the saponification value of the product is as follows: 598.6, product yield 99.1%.
Example 4
Adding 176g of phenyl succinic anhydride into a reaction kettle, then adding 0.60g of diethyl zinc, sealing the reaction kettle, replacing 3-5 times with nitrogen after the air tightness is qualified, then starting to heat up, introducing 5g of ethylene oxide after the temperature is raised to 80 ℃, continuously introducing 435g of ethylene oxide after the pressure is lowered and the temperature is raised, controlling the reaction temperature to be 100-110 ℃ and the reaction pressure to be 0.1-0.5 MPa, after the reaction is finished, continuously curing for 30-50 minutes, cooling to 70 ℃, taking out the material, and weighing 612.8g of the material. The hydroxyl value and the acid value of the test sample are both 0, so that the sample is proved to have no hydroxyl or carboxyl, and the synthesized sample can be judged to be the target sample. Detecting the saponification value of the product, wherein the saponification value of the product is as follows: 184.9, the yield of the product is 99.5 percent.
Example 5
Adding 114g of 2-methylsuccinic anhydride into a reaction kettle, then adding 0.40g of calcium methoxide and 0.4g of diethyl zinc, sealing the reaction kettle, replacing 3-5 times by nitrogen after the airtightness detection is qualified, then starting to heat up, introducing 5g of ethylene oxide after the temperature is raised to 80 ℃, continuously introducing 435g of ethylene oxide after the pressure is lowered and the temperature is raised, controlling the reaction temperature to be 100-110 ℃ and the reaction pressure to be 0.1-0.5 MPa, continuously curing for 30-50 minutes after the reaction is finished, cooling to 70 ℃, taking out the material, and weighing 551.3g of the material. The hydroxyl value and the acid value of the test sample are both 0, so that the sample is proved to have no hydroxyl or carboxyl, and the synthesized sample can be judged to be the target sample. Detecting the saponification value of the product, wherein the saponification value of the product is as follows: 204.1, and the product yield is 99.5 percent.
Example 6
Adding 148g of phthalic anhydride into a reaction kettle, then adding 1.40g of calcium acetate and 1.4g of diethyl zinc, sealing the reaction kettle, replacing 3-5 times with nitrogen after passing the airtightness detection, then starting to heat up, introducing 5g of ethylene oxide after the temperature is raised to 140 ℃, continuously introducing 2195g of ethylene oxide after the pressure is reduced and the temperature is raised, controlling the reaction temperature to be 150-170 ℃, continuing to cure for 30-50 minutes after the reaction is finished, cooling to 70 ℃, taking out the material, and weighing 2337.5g of the material. The hydroxyl value and the acid value of the test sample are both 0, so that the sample is proved to have no hydroxyl or carboxyl, and the synthesized sample can be judged to be the target sample. Detecting the saponification value of the product, wherein the saponification value of the product is as follows: 48.6, the yield of the product is 99.6%.
Example 7
Adding 74g of phthalic anhydride into a reaction kettle, then adding 1.40g of calcium acetate, 1.4g of diethyl zinc and 1.5g of calcium methoxide, sealing the reaction kettle, replacing 3-5 times with nitrogen after the air tightness is detected to be qualified, then starting to heat up, introducing 5g of ethylene oxide after the temperature is raised to 140 ℃, continuously introducing 3295g of ethylene oxide after the pressure is reduced and the temperature is raised, controlling the reaction temperature to be 150-170 ℃, continuing to cure for 30-50 minutes after the reaction is finished, cooling to 70 ℃, taking out the material, and weighing 3358.6g of the material. The hydroxyl value and the acid value of the test sample are both 0, so that the sample is proved to have no hydroxyl or carboxyl, and the synthesized sample can be judged to be the target sample. Detecting the saponification value of the product, wherein the saponification value of the product is as follows: 17.8, the yield of the product is 99.5%.
Comparative example
Adding 148g of phthalic anhydride into a reaction kettle, then adding 0.60g of sodium methoxide, sealing the reaction kettle, replacing 3-5 times with nitrogen after the air tightness is detected to be qualified, then starting to heat up, introducing 5g of ethylene oxide after the temperature is raised to 80 ℃, wherein the pressure is 0.15MPa, after the temperature is lowered and the temperature is raised, the pressure is not obviously changed after 2 hours, raising the temperature to 100-110 ℃, raising the pressure to 0.25MPa, keeping the pressure not lowered after 2 hours, continuing to heat up to 150-170 ℃, raising the pressure to 0.55MPa, and after 2hours, lowering the temperature and discharging, wherein the material quality is 148.5g, and comprehensively judging that the ethylene oxide is not reacted.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.

Claims (7)

1. A preparation method of cyclic polyether diester comprises the steps of carrying out ring-opening polymerization of ethylene oxide by taking cyclic anhydride as an initiator under the action of a catalyst to prepare the cyclic polyether diester;
wherein, the catalyst comprises one or more of a group IIA metal composite oxide, an alkyl compound, an alkoxy compound and a carboxylate, a group IIA metal and aluminum composite oxide, a zinc carboxylate and an alkyl compound;
the preparation method comprises the following steps: adding cyclic anhydride into a reaction kettle, adding a catalyst, sealing the reaction kettle, carrying out air tightness detection, replacing 3-5 times with nitrogen after the detection is qualified, then starting to heat up, introducing a small amount of ethylene oxide into the reaction kettle after the temperature is raised to 140 ℃, continuously introducing the rest of ethylene oxide after the pressure is reduced and the temperature is raised, controlling the reaction temperature to be 150-170 ℃, continuing to cure for 30-50 minutes after the reaction is finished, cooling to 70 ℃, and taking out the material;
the molar ratio of the cyclic acid anhydride to the ethylene oxide is 1 (2-150).
2. The method of claim 1, wherein the cyclic anhydride is selected from one or more of phenylsuccinic anhydride, 2,3-pyridinedicarboxylic anhydride, 2-methylsuccinic anhydride, maleic anhydride, 2,3-dimethylmaleic anhydride, 2,3-dichloromaleic anhydride, 3-fluorophthalic anhydride, succinic anhydride, citraconic anhydride, phthalic anhydride.
3. The method of claim 1, wherein the catalyst comprises one or more of magnesium aluminum composite oxide, magnesium aluminum calcium composite oxide, an alkoxide of calcium, an alkyl of calcium, an acetate of calcium, an alkoxide of barium, an alkyl of zinc, and an acetate of zinc.
4. The method according to claim 1, wherein the mass of the catalyst is 0.05 to 5% of the total mass of the cyclic acid anhydride and the ethylene oxide.
5. A cyclic polyether diester having the structural formula:
Figure FDA0003949180630000011
wherein n is 1 +n 2 N, n represents the average addition number of ethylene oxide;
R 1 、R 2 independently selected from phenyl, methyl or hydrogen;
R 3 、R 4 independently selected from methyl, chlorine or hydrogen, or R 3 、R 4 Together forming one of the following structures:
Figure FDA0003949180630000021
6. a cyclic polyether diester, which is prepared by ring-opening polymerization reaction of cyclic anhydride and ethylene oxide;
the ring-opening polymerization reaction is carried out under the action of a catalyst, wherein the catalyst comprises one or more of magnesium-aluminum composite oxide, magnesium-aluminum-calcium composite oxide, an alkoxy compound of calcium, an alkyl compound of calcium, acetate of calcium, an alkoxide of barium, an alkyl compound of zinc and acetate of zinc;
the molar ratio of the cyclic acid anhydride to the ethylene oxide is 1 (2-150).
7. The cyclic polyether diester of claim 6 wherein the cyclic anhydride is selected from one or more of phenylsuccinic anhydride, 2,3-pyridinedicarboxylic anhydride, 2-methylsuccinic anhydride, maleic anhydride, 2,3-dimethylmaleic anhydride, 2,3-dichloromaleic anhydride, 3-fluorophthalic anhydride, succinic anhydride, citraconic anhydride, phthalic anhydride.
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