CN108148191B - Branched polyether, intermediate and preparation method thereof - Google Patents
Branched polyether, intermediate and preparation method thereof Download PDFInfo
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- CN108148191B CN108148191B CN201611110467.7A CN201611110467A CN108148191B CN 108148191 B CN108148191 B CN 108148191B CN 201611110467 A CN201611110467 A CN 201611110467A CN 108148191 B CN108148191 B CN 108148191B
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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
- C08G65/2606—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 containing hydroxyl groups
- C08G65/2609—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 containing hydroxyl groups containing aliphatic hydroxyl groups
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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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
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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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
Abstract
The invention discloses a branched polyether, an intermediate and a preparation method thereof. The preparation method comprises the following steps: (1) mixing a monofunctional initiator and a catalyst under an inert atmosphere, heating, gradually adding an epoxide for reaction, and then curing to obtain an intermediate A; (2) mixing the intermediate A with a monobasic strong alkaline substance, reacting to obtain alkoxide, adding 2-chloroglycerin and/or 3-chloroglycerin for capping to obtain a branched polyether intermediate B with the functionality of 2; the molar ratio of the intermediate A to the monobasic strong alkaline substance is 1: 1.05-1: 1.15; (3) and mixing the branched chain polyether intermediate B with a catalyst in an inert atmosphere, heating to 60-120 ℃, gradually introducing an epoxide for reaction, and curing to obtain the branched chain polyether. The branched chain length of the branched chain polyether can be designed by self, the proportion of the branched chain to the main chain is adjustable, the hydrophily and lipophilicity can be designed, the activity of the chain segment can be adjusted, and the branched chain polyether has good damping performance and high-strength energy absorption effect.
Description
Technical Field
The invention relates to a branched polyether, an intermediate and a preparation method thereof.
Background
The conventional polyethers are mainly prepared by using conventional initiators, such as: 1, 2-propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, glycerol, trimethylolpropane and the like, and the polyether polyol with a certain number average molecular weight is obtained by carrying out propoxylation reaction on the polyether polyol, wherein the structure of the polyether polyol is usually a bifunctional straight chain or a trifunctional degree, and after the polyether polyol reacts with isocyanate, the polyether molecular chain has damping performance and energy absorption effect by utilizing the matching of a hard section and a soft section in a macromolecule.
Therefore, how to increase the length of the polyether branch chain, improve the damping performance and the energy absorption function of the polyether becomes an important research topic in the field.
Disclosure of Invention
The invention provides a branched polyether, an intermediate and a preparation method thereof, aiming at overcoming the defects that the conventional branched polyether has no branched chain or has single branched chain group, short length and can not be freely designed.
The invention adopts polyether end capping technology on the basis of the traditional polyether synthesis method, more importantly adopts a special end capping agent which blocks the activity of monofunctional hydroxyl, more importantly introduces dihydroxyl as the main chain of polyether, and the other key point is that the length of a branched chain, the length of the main chain and the proportion of the branched chain and the main chain are freely designed by utilizing the traditional polyether synthesis method, and more importantly, the hydrophilic and lipophilic properties of the branched chain and the main chain can also be freely designed by utilizing the types of epoxides.
The branched chain length of the branched chain polyether synthesized by the method can be designed by self (the conventional polyether branched chain is only a group with a single structure and is extremely short), the proportion of the branched chain and the main chain can be designed, the chain segment structure of the polyether branched chain and the main chain can be designed freely, the hydrophilic and lipophilic properties can be designed, and the activity of the chain segment can also be adjusted. The macromolecular branched polyether with the special structure has excellent damping performance and high-strength energy absorption function, can be widely used in polyurethane soft foam and high-elastomer products, and has excellent high elasticity, good sound insulation, sound absorption, shock absorption, impact resistance and other performances.
The present invention solves the above technical problems by the following technical solutions.
The invention provides a preparation method of branched polyether, which comprises the following steps:
(1) under the inert atmosphere, mixing a monofunctional initiator and a catalyst, heating, gradually adding an epoxide for reaction, and then curing to obtain an intermediate A;
(2) mixing the intermediate A with a monobasic strong alkaline substance, reacting to obtain alkoxide, and adding an end capping agent to cap to obtain an intermediate B with the functionality of 2; the molar ratio of the intermediate A to the monobasic strong alkaline substance is 1: 1.05-1: 1.15; the end-capping agent is 2-chloroglycerol and/or 3-chloroglycerol;
(3) and mixing the intermediate B with a catalyst in an inert atmosphere, heating to 60-120 ℃, gradually introducing an epoxide according to a set amount for reaction, and curing to obtain the catalyst.
In step (1), the monofunctional initiator may be a monofunctional initiator conventionally used in the art, and is generally a monohydric alcohol, the number of carbon atoms of which may not be limited, and preferably, the monohydric alcohol is one or more of methanol, ethanol and butanol.
In the step (1), the catalyst may be a catalyst conventionally used in the art, preferably, the catalyst is an alkali metal compound and/or an alkaline earth metal compound, and more preferably, the catalyst is one or more of potassium hydroxide, sodium hydroxide, potassium methoxide, sodium hydride, and metallic sodium.
In the step (1), the temperature of the temperature rise can be set according to a conventional temperature in the field, preferably, the temperature rise is to 60 to 120 ℃, and more preferably, the temperature rise is to 60 to 70 ℃.
In step (1), the epoxide may be an epoxide conventionally used in the art, preferably ethylene oxide and/or propylene oxide. The amount of the epoxide to be added can be selected by the person skilled in the art according to the actual desired ratio of branches to backbone.
In the step (1), the reaction temperature is preferably controlled to be 105-120 ℃, and the reaction pressure is preferably controlled to be below 0.5 MPa.
In the step (1), the curing time may be a curing time conventionally used in the art, and is preferably 1 to 2.5 hours, and more preferably 1.5 to 2.0 hours.
In step (1), the mass ratio of the monofunctional initiator, the catalyst and the epoxide can be selected by a person skilled in the art according to the self-designed main chain structure and length of the branched polyether and the ratio of the main chain to the branched chain. For example, in a preferred embodiment of the present invention, the mass ratio of the monofunctional initiator, the catalyst and the epoxide can be selected from (30-50): 1-5): 950-970, according to the self-designed structure of the branched polyether of glycerol polyoxyethylene polyoxypropylene ether monomethyl ester (GD4002) and the ratio of the branched chain to the main chain.
In the step (1), the hydroxyl value of the intermediate a can be designed by a person skilled in the art according to the self-designed main chain structure and length of the branched polyether and the ratio of the main chain to the branched chain. For example, in a preferred embodiment of the present invention, the hydroxyl value of the intermediate a can be designed to be 54.0-58.0 mgKOH/g according to the structure of the self-designed GD4002 branched polyether and the ratio of the branches to the main chain.
In step (1), the inert atmosphere may be an inert atmosphere conventionally used in the art, preferably a nitrogen atmosphere or an argon atmosphere.
In step (2), the monobasic strong alkaline substance is a monobasic strong alkaline substance conventionally used in the field, one mole of the monobasic strong alkaline substance can completely react with water and generate one mole of hydroxide ions, and the monobasic strong alkaline substance is generally a hydride of monobasic strong alkaline metal and/or monobasic strong alkaline metal; preferably, the monobasic strong basic substance is sodium hydride and/or metallic sodium.
In the step (2), the mixing temperature may be a conventional mixing temperature in the art, and is preferably 60 to 80 ℃. Wherein, the mixing temperature is within the range of 60-80 ℃, the reaction of the step can be accelerated, and the intermediate B can be ensured not to be damaged.
In the step (2), the mixing time may be a mixing time conventionally used in the art, preferably 4 to 8 hours, and more preferably 6 to 8 hours.
In step (2), the reaction is generally carried out under stirring.
In the step (2), the molar ratio of the intermediate A, the monobasic strong alkaline substance and the end capping agent is preferably 1 (1.05-1.15) to 1.15. For example, in a preferred embodiment of the present invention, according to the self-designed structure of the GD4002 branched polyether and the ratio of the branches to the main chain, the mass ratio of the monofunctional initiator, the catalyst and the epoxide selected in step (1) is (30-50), (1-5), (950-970), and the mass ratio of the intermediate a, the monobasic strong alkaline substance and the blocking agent is (967-1039), (26.5-28.8), (121.6-132.6).
In step (2), the intermediate B is known to those skilled in the art as a capped polyether intermediate B, both in light of the procedures described herein and with common general knowledge in the art. Wherein, the hydroxyl value of the intermediate B is determined by the intermediate A designed by the person skilled in the art. For example, in a preferred embodiment of the present invention, the hydroxyl value of intermediate A is 54.0-58.0 mgKOH/g, and thus the hydroxyl value of the resulting capped polyether intermediate B is 96.5-102.7 mgKOH/g, based on the self-designed structure of the GD4002 branched polyether and the ratio of the branches to the main chain.
In the step (3), before the mixing, the intermediate B is preferably further subjected to vacuum dehydration to reduce the residual amount of moisture, thereby reducing product impurities. The vacuum dehydration can be carried out by a vacuum pump conventional in the art, such as an oil pump, and the vacuum degree of the vacuum dehydration is generally-0.095 to-0.100 MPa.
In the step (3), the catalyst may be a catalyst conventionally used in the art, preferably, the catalyst is an alkali metal compound and/or an alkaline earth metal compound, and more preferably, the catalyst is one or more of potassium hydroxide, sodium hydroxide, potassium methoxide, sodium methoxide and sodium metal.
In the step (3), the temperature of the temperature rise can be set according to a conventional temperature in the field, preferably, the temperature rise is to 60 to 120 ℃, and more preferably, the temperature rise is to 100 to 120 ℃.
In step (3), the epoxide may be an epoxide conventionally used in the art, preferably ethylene oxide and/or propylene oxide. The amount of the epoxide to be added can be selected by the person skilled in the art according to the actual desired ratio of branches to backbone. For example, in a preferred embodiment of the present invention, the mass ratio of the intermediate B, the catalyst and the epoxide can be selected from 1120 (6-9): 2900 according to the ratio of the branch chain to the main chain of the self-designed GD4002 branched polyether.
In the step (3), the curing time may be a curing time conventional in the art, and is preferably 1 to 2.5 hours.
In the step (3), preferably, the refining and purification are further performed after the aging. The purification method and conditions may be performed according to conventional methods and conditions in the art. The purification typically includes neutralization, adsorption and dehydration steps.
Wherein the neutralization can be carried out according to the conventional operation in the field, and the neutralization is generally carried out by adding a neutralizing agent. The neutralizing agent is a neutralizing agent conventionally used in the art, preferably phosphoric acid. The temperature of the neutralization is preferably 60 to 120 ℃, more preferably 80 to 110 ℃. The amount of the neutralizing agent is not particularly limited, as long as the neutralizing agent can neutralize the cured material to make the PH of the system be 5-6, for example, in a preferred embodiment of the present invention, the mass ratio of the cured material to the neutralizing agent may be 4000:152 according to the self-designed GD4002 branched polyether.
Wherein the adsorption can be carried out according to the conventional operation in the field, and the adsorption is carried out by adding a solvent and an adsorbent. The solvent may be a solvent conventionally used in the art, such as water, which is typically deionized water. The adsorbent is an adsorbent conventionally used in the art, preferably one or more of magnesium silicate, aluminum silicate and magnesium aluminum silicate. The adsorption mode is generally stirring adsorption, and the adsorption time can be selected according to the actual situation, such as 60 min. The amount of the solvent and the adsorbent used is not particularly limited as long as the content of metal ions and the chromaticity in the material obtained by aging can meet the specified requirements after filtration, for example, in a preferred embodiment of the present invention, the mass ratio of the material obtained by aging, the solvent and the adsorbent can be 4000:160:12 according to the self-designed GD4002 branched polyether, and the content of metal ions and the chromaticity in the material obtained by aging can meet the requirements specified in the national standard GB/T12008.4-2009 after adsorption and filtration.
Wherein, the dehydration can be carried out according to the conventional operation in the field, generally, the temperature rise and the vacuum pumping dehydration are adopted, and the colorless to pale yellow transparent filtrate obtained after the dehydration and the filtration is the refined branched polyether.
In step (3), the inert atmosphere may be an inert atmosphere conventionally used in the art, preferably a nitrogen atmosphere or an argon atmosphere.
In the present invention, the preparation of the branched polyether is carried out in equipment conventional in the art.
The invention also provides the branched polyether prepared by the preparation method.
The branched chain length of the branched chain polyether can be designed by self, and the ratio of the branched chain to the main chain can be adjusted. Taking the example of the epoxide as ethylene oxide and/or propylene oxide, the branched polyether obtained has the following structural formula:
in the formula, n1、m1、n2、m2、n3And m3Can be designed according to the actual needed use performance, and can be realized by adjusting the amount of the added ethylene oxide and propylene oxide.
The invention also provides a preparation method of the branched polyether intermediate, which comprises the following steps:
(1) under the inert atmosphere, mixing a monofunctional initiator and a catalyst, heating, gradually adding an epoxide for reaction, and then curing to obtain an intermediate A;
(2) mixing the intermediate A with a monobasic strong alkaline substance, reacting to prepare alkoxide, and adding a capping agent to cap to obtain a branched polyether intermediate with the functionality of 2; the molar ratio of the intermediate A to the monobasic strong alkaline substance is 1: 1.05-1: 1.15; the blocking agent is 2-chloroglycerin and/or 3-chloroglycerin.
In step (1), the monofunctional initiator may be a monofunctional initiator conventionally used in the art, and is generally a monohydric alcohol, the number of carbon atoms of which may not be limited, and preferably, the monohydric alcohol is one or more of methanol, ethanol and butanol.
In step (1), the catalyst may be a catalyst conventionally used in the art, preferably, the catalyst is an alkali metal compound and/or an alkaline earth metal compound, and more preferably, the catalyst is one or more of potassium hydroxide, sodium hydroxide, potassium methoxide, sodium methoxide and sodium metal.
In the step (1), the temperature of the temperature rise can be set according to a conventional temperature in the field, preferably, the temperature rise is to 60 to 120 ℃, and more preferably, the temperature rise is to 60 to 70 ℃.
In step (1), the epoxide may be an epoxide conventionally used in the art, preferably ethylene oxide and/or propylene oxide. The amount of the epoxide to be added can be selected by the person skilled in the art according to the actual desired ratio of branches to backbone.
In the step (1), the reaction temperature is preferably controlled to be 105-120 ℃, and the reaction pressure is preferably controlled to be below 0.5 MPa.
In the step (1), the curing time may be a curing time conventionally used in the art, and is preferably 1 to 2.5 hours, and more preferably 1.5 to 2.0 hours.
In step (1), the mass ratio of the monofunctional initiator, the catalyst and the epoxide can be selected by a person skilled in the art according to the self-designed main chain structure and length of the branched polyether and the ratio of the main chain to the branched chain. For example, in a preferred embodiment of the present invention, the mass ratio of the monofunctional initiator, the catalyst and the epoxide can be selected from (30-50): 1-5): 950-970, according to the self-designed structure of the GD4002 branched polyether and the ratio of the branched chain to the main chain.
In the step (1), the hydroxyl value of the intermediate a can be designed by a person skilled in the art according to the self-designed main chain structure and length of the branched polyether and the ratio of the main chain to the branched chain. For example, in a preferred embodiment of the present invention, the hydroxyl value of the intermediate a can be designed to be 54.0-58.0 mgKOH/g according to the structure of the self-designed GD4002 branched polyether and the ratio of the branches to the main chain.
In step (1), the inert atmosphere may be an inert atmosphere conventionally used in the art, preferably a nitrogen atmosphere or an argon atmosphere.
In step (2), the monobasic strong alkaline substance is a monobasic strong alkaline substance conventionally used in the field, one mole of the monobasic strong alkaline substance can completely react with water and generate one mole of hydroxide ions, and the monobasic strong alkaline substance is generally a hydride of monobasic strong alkaline metal and/or monobasic strong alkaline metal; preferably, the monobasic strong basic substance is sodium hydride and/or metallic sodium.
In the step (2), the mixing temperature may be a conventional mixing temperature in the art, and is preferably 60 to 80 ℃. Wherein, the mixing temperature is within the range of 60-80 ℃, the reaction of the step can be accelerated, and the branched chain polyether intermediate can be ensured not to be damaged.
In the step (2), the mixing time may be a mixing time conventionally used in the art, preferably 4 to 8 hours, and more preferably 6 to 8 hours.
In step (2), the reaction is generally carried out under stirring.
In the step (2), the molar ratio (the ratio of the amount of the substances) of the intermediate A, the monobasic strong basic substance and the end capping agent is preferably 1 (1.05-1.15): 1.15. For example, in a preferred embodiment of the present invention, according to the self-designed structure of the GD4002 branched polyether and the ratio of the branches to the main chain, the mass ratio of the monofunctional initiator, the catalyst and the epoxide selected in step (1) is (30-50), (1-5), (950-970), and the mass ratio of the intermediate a, the monobasic strong alkaline substance and the blocking agent is (967-1039), (26.5-28.8), (121.6-132.6).
In step (2), the branched polyether intermediate is known to those skilled in the art as a capped polyether intermediate, both in light of the procedures described herein and with common general knowledge in the art. Wherein the hydroxyl value of the branched polyether intermediate is determined by intermediate A, which is designed by the person skilled in the art. For example, in a preferred embodiment of the present invention, the hydroxyl value of the intermediate A is 54.0-58.0 mgKOH/g according to the self-designed structure of GD4002 branched polyether and the ratio of the branches to the main chain, so that the hydroxyl value of the obtained capped polyether intermediate is 96.5-102.7 mgKOH/g.
The invention also provides a branched polyether intermediate prepared by the preparation method.
In the present invention, the aging is a term of art, and means that the reaction is continued by maintaining the reaction conditions after the addition of the materials is completed.
In the present invention, the pressures involved are gauge pressures.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the branched chain length of the branched chain polyether can be designed by self, the proportion of the branched chain to the main chain can be adjusted, the hydrophilic and oleophilic properties can be designed, the chain segment activity can be adjusted, the macromolecular branched chain polyether with the special structure has excellent damping performance and high-strength energy absorption function, can be widely used in polyurethane soft foam, and obtains excellent high elasticity, good sound insulation and absorption, shock absorption and impact resistance and other properties.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The reagents and starting materials used in the following examples are commercially available.
In the following examples, the parts used are parts by mass.
The GD4002 branched polyether is taken as an example and is prepared by the following preparation method:
example 1
(1) Mixing 32 parts of methanol and 2.5 parts of sodium methoxide, adding the mixture into a high-pressure reaction kettle, replacing air in the reaction kettle with nitrogen for three times, heating the mixture to 60-70 ℃, gradually introducing 970 parts of propylene oxide, controlling the reaction temperature to be 105-120 ℃ and the pressure to be below 0.5MPa until the propylene oxide is completely added, and then curing the mixture for 1.5 hours to obtain an intermediate A, wherein the hydroxyl value of the intermediate A is 56.80 mgKOH/g;
(2) mixing 1000 parts of the intermediate A with 27 parts of sodium hydride at the temperature of 60-80 ℃, continuously stirring for reacting for 6 hours to prepare alkoxide, measuring the base number to be higher than 1.1mgKOH/g, then adding 132.6 parts of 3-chloroglycerin for capping to prepare a capped polyether intermediate B with the functionality of 2, wherein the hydroxyl value of the intermediate B is 100.5 mgKOH/g;
(3) mixing 1120 parts of the intermediate B and 9 parts of sodium hydroxide in a high-pressure reaction kettle, replacing with nitrogen, heating to 100-120 ℃, vacuumizing and dehydrating, introducing 2400 parts of propylene oxide and 500 parts of ethylene oxide according to the set amount when the water content of the mixture is lower than 0.03%, and curing for 1.5 hours to obtain an intermediate C;
(4) putting 4000 parts of the intermediate C into a reaction kettle, heating to 80-90 ℃, adding 152 parts of phosphoric acid, stirring for 30min, adding 160 parts of deionized water after neutralization, stirring for 30min, then adding 6 parts of magnesium silicate and 6 parts of aluminum silicate, stirring for 60min, finally heating, vacuumizing, dehydrating, and filtering when the water content is qualified to obtain colorless to pale yellow transparent filtrate, namely the needed product glycerol polyoxyethylene polyoxypropylene ether monomethyl ester (GD4002-1 #).
Example 2
(1) Mixing 30 parts of methanol and 5 parts of sodium methoxide, adding the mixture into a high-pressure reaction kettle, replacing air in the reaction kettle with nitrogen for three times, heating the mixture to 60-70 ℃, gradually introducing 970 parts of propylene oxide, controlling the reaction temperature to be 105-120 ℃ and the pressure to be below 0.5MPa until the propylene oxide is completely added, and then curing the mixture for 1.5 hours to obtain an intermediate A, wherein the hydroxyl value of the intermediate A is 57.2 mgKOH/g;
(2) mixing 967 parts of the intermediate A and 26.5 parts of sodium hydride at the temperature of 60-80 ℃, continuously stirring for reacting for 6 hours to prepare alkoxide, measuring the base number to be higher than 1.1mgKOH/g, adding 121.6 parts of 3-chloroglycerol for capping to prepare a capped polyether intermediate B with the functionality of 2, wherein the hydroxyl value of the intermediate B is 102.1 mgKOH/g;
(3) mixing 1120 parts of the intermediate B and 9 parts of sodium hydroxide in a high-pressure reaction kettle, replacing with nitrogen, heating to 100-120 ℃, vacuumizing and dehydrating, gradually introducing 2300 parts of propylene oxide and 600 parts of ethylene oxide according to a set amount when the water content of the mixture is lower than 0.03%, and curing for 2.0 hours to obtain an intermediate C;
(4) putting 4000 parts of the intermediate C into a reaction kettle, heating to 80-90 ℃, adding 152 parts of phosphoric acid, stirring for 30min, adding 160 parts of deionized water after neutralization, stirring for 30min, adding 12 parts of magnesium silicate, stirring for 60min, heating, vacuumizing, dehydrating, and filtering when the water content is qualified to obtain colorless to light yellow transparent filtrate, namely the needed product, namely glycerol polyoxyethylene polyoxypropylene ether monomethyl ester (GD4002-2 #).
Example 3
(1) Mixing 50 parts of methanol and 1 part of sodium methoxide, adding the mixture into a high-pressure reaction kettle, replacing air in the reaction kettle with nitrogen for three times, heating the mixture to 60-70 ℃, gradually introducing 950 parts of propylene oxide, controlling the reaction temperature to be 105-120 ℃ and the pressure to be below 0.5MPa until the propylene oxide is completely added, and then curing the mixture for 1.5 hours to obtain an intermediate A, wherein the hydroxyl value of the intermediate A is 57.5 mgKOH/g;
(2) mixing 1039 parts of the intermediate A and 28.5 parts of sodium hydride at 60-80 ℃, continuously stirring for reaction for 6 hours to prepare alkoxide, measuring the base number to be higher than 1.1mgKOH/g, then adding 132.6 parts of 3-chloroglycerol for end capping to prepare an end-capped polyether intermediate B with the functionality of 2, wherein the hydroxyl value of the intermediate B is 99.8 mgKOH/g;
(3) mixing 1120 parts of the intermediate B and 6 parts of sodium hydroxide in a high-pressure reaction kettle, replacing with nitrogen, heating to 100-120 ℃, vacuumizing and dehydrating, gradually introducing 2000 parts of propylene oxide and 900 parts of ethylene oxide according to a set amount when the water content of the mixture is lower than 0.03%, and curing for 2.5 hours to obtain an intermediate C;
(4) putting 4000 parts of the intermediate C into a reaction kettle, heating to 80-90 ℃, adding 152 parts of phosphoric acid, stirring for 30min, adding 160 parts of deionized water after neutralization, stirring for 30min, then adding 6 parts of magnesium silicate and 6 parts of aluminum silicate, stirring for 60min, finally heating, vacuumizing, dehydrating, and filtering when the water content is qualified to obtain colorless to pale yellow transparent filtrate, namely the needed product glycerol polyoxyethylene polyoxypropylene ether monomethyl ester (GD4002-3 #).
Example 4
(1) Mixing 32 parts of methanol and 5 parts of sodium methoxide, adding the mixture into a high-pressure reaction kettle, replacing air in the reaction kettle with nitrogen for three times, heating the mixture to 60-70 ℃, gradually introducing 970 parts of propylene oxide, controlling the reaction temperature to be 105-120 ℃ and the pressure to be below 0.5MPa until the propylene oxide is completely added, and then curing the mixture for 1.5 hours to obtain an intermediate A, wherein the hydroxyl value of the intermediate A is 55.9 mgKOH/g;
(2) mixing 1000 parts of the intermediate A with 28 parts of sodium hydride at the temperature of 60-80 ℃, continuously stirring for reacting for 6 hours to prepare alkoxide, measuring the base number to be higher than 1.1mgKOH/g, adding 132 parts of 3-chloroglycerin for capping to prepare a capped polyether intermediate B with the functionality of 2, wherein the hydroxyl value of the intermediate B is 100.4 mgKOH/g;
(3) mixing 1120 parts of the intermediate B and 9 parts of sodium hydroxide in a high-pressure reaction kettle, replacing with nitrogen, heating to 100-120 ℃, vacuumizing and dehydrating, gradually introducing 2450 parts of propylene oxide and 450 parts of ethylene oxide according to a set amount when the water content of the mixture is lower than 0.03%, and curing for 1 hour after the addition is finished to obtain an intermediate C;
(4) putting 4000 parts of the intermediate C into a reaction kettle, heating to 80-90 ℃, adding 152 parts of phosphoric acid, stirring for 30min, adding 160 parts of deionized water after neutralization, stirring for 30min, adding 12 parts of magnesium silicate, stirring for 60min, heating, vacuumizing, dehydrating, and filtering when the water content is qualified to obtain colorless to light yellow transparent filtrate, namely the needed product, namely glycerol polyoxyethylene polyoxypropylene ether monomethyl ester (GD4002-4 #).
Example 5
(1) Mixing 50 parts of methanol and 5 parts of sodium methoxide, adding the mixture into a high-pressure reaction kettle, replacing air in the reaction kettle with nitrogen for three times, heating the mixture to 60-70 ℃, gradually introducing 950 parts of propylene oxide, controlling the reaction temperature to be 105-120 ℃ and the pressure to be below 0.5MPa until the propylene oxide is completely added, and then curing the mixture for 1.5 hours to obtain an intermediate A, wherein the hydroxyl value of the intermediate A is 56.5 mgKOH/g;
(2) mixing 1000 parts of the intermediate A with 20 parts of sodium hydride at 60-80 ℃, continuously stirring for reacting for 6 hours to prepare alkoxide, measuring the base number to be higher than 0.86mgKOH/g, then adding 100 parts of 3-chloroglycerin for end capping to prepare a capped polyether intermediate B with the functionality of 2, wherein the capped polyether intermediate B also contains the intermediate A, and the measured hydroxyl value of the mixture is 95.1 mgKOH/g;
(3) mixing 1120 parts of the intermediate B and 9 parts of sodium hydroxide in a high-pressure reaction kettle, replacing with nitrogen, heating to 100-120 ℃, vacuumizing and dehydrating, gradually introducing 2300 parts of propylene oxide and 600 parts of ethylene oxide according to a set amount when the water content of the mixture is lower than 0.03%, and curing for 1.5 hours to obtain an intermediate C;
(4) putting 4000 parts of the intermediate C into a reaction kettle, heating to 80-90 ℃, adding 152 parts of phosphoric acid, stirring for 30min, adding 160 parts of deionized water after neutralization, stirring for 30min, adding 12 parts of magnesium silicate, stirring for 60min, heating, vacuumizing, dehydrating, and filtering when the water content is qualified to obtain colorless to light yellow transparent filtrate, namely the needed product, namely glycerol polyoxyethylene polyoxypropylene ether monomethyl ester (GD4002-5 #).
Example 6
(1) Mixing 32 parts of methanol and 5 parts of sodium methoxide, adding the mixture into a high-pressure reaction kettle, replacing air in the reaction kettle with nitrogen for three times, heating the mixture to 60-70 ℃, gradually introducing 970 parts of propylene oxide, controlling the reaction temperature to be 105-120 ℃ and the pressure to be below 0.5MPa until the propylene oxide is completely added, and then curing the mixture for 1.5 hours to obtain an intermediate A, wherein the hydroxyl value of the intermediate A is 56.2 mgKOH/g;
(2) mixing 1000 parts of the intermediate A with 28.5 parts of sodium hydride at 60-80 ℃, continuously stirring for reacting for 6 hours to prepare alkoxide, measuring the base number to be higher than 1.1mgKOH/g, then adding 130 parts of 3-chloroglycerin for capping to prepare a capped polyether intermediate B with the functionality of 2, wherein the capped polyether intermediate B also contains redundant 3-chloroglycerin, and the measured hydroxyl value of the mixture is 100.6 mgKOH/g;
(3) mixing 1120 parts of the intermediate B and 9 parts of sodium hydroxide in a high-pressure reaction kettle, replacing with nitrogen, heating to 100-120 ℃, vacuumizing and dehydrating, gradually introducing 2400 parts of propylene oxide and then 500 parts of ethylene oxide according to a set amount when the water content of the mixture is lower than 0.03%, and curing for 1.5 hours to obtain an intermediate C;
(4) putting 4000 parts of the intermediate C into a reaction kettle, heating to 80-90 ℃, adding 152 parts of phosphoric acid, stirring for 30min, adding 160 parts of deionized water after neutralization, stirring for 30min, then adding 6 parts of magnesium silicate and 6 parts of aluminum silicate, stirring for 60min, finally heating, vacuumizing, dehydrating, and filtering when the water content is qualified to obtain colorless to pale yellow transparent filtrate, namely the needed product glycerol polyoxyethylene polyoxypropylene ether monomethyl ester (GD4002-6 #).
Effects of the embodiment
Glycerol polyoxyethylene polyoxypropylene ether monomethyl ester GD4002 obtained in examples 1 to 6 was subjected to external applicationWater content, pH value, hydroxyl value, acid value, K+Content and Na+The content characterization and the specific detection results are shown in the following table.
From the above table of test data and product application, it can be seen that:
1. the amount of alkali used for preparing alkoxide in the synthesis process of the branched polyether GD4002 must be sufficient, otherwise the end capping is incomplete (as shown in example 5);
2. in the synthesis process of the branched polyether GD4002, a proper amount of the blocking agent is required, otherwise, a large amount of the blocking agent remains after the blocking is completed, and a large amount of byproducts are formed (as shown in example 6);
3. it can be seen from the comparison of examples 1-4 with the comparative example that the branched polyether GD-4002 can be completely used in polyurethane flexible foam.
Claims (10)
1. A preparation method of branched polyether is characterized by comprising the following steps:
(1) under the inert atmosphere, mixing a monofunctional initiator and a catalyst, heating, gradually adding an epoxide for reaction, and then curing to obtain an intermediate A;
(2) mixing the intermediate A with a monobasic strong alkaline substance, reacting to obtain alkoxide, and adding an end capping agent to cap to obtain an intermediate B with the functionality of 2; the molar ratio of the intermediate A to the monobasic strong alkaline substance is 1: 1.05-1: 1.15; the end-capping agent is 2-chloroglycerol and/or 3-chloroglycerol;
(3) and mixing the intermediate B with a catalyst in an inert atmosphere, heating to 60-120 ℃, gradually introducing an epoxide according to a set amount for reaction, and curing to obtain the catalyst.
2. The method according to claim 1, wherein in the step (1), the monofunctional initiator is a monohydric alcohol;
and/or, in the step (1), the catalyst is an alkali metal compound and/or an alkaline earth metal compound;
and/or in the step (1), heating to 60-120 ℃;
and/or in the step (1), the temperature of the reaction is controlled to be 105-120 ℃, and the pressure of the reaction is controlled to be below 0.5 MPa;
and/or in the step (1), the curing time is 1-2.5 h;
and/or, in the step (1), the inert atmosphere is nitrogen atmosphere or argon atmosphere;
and/or, in the step (2), the monobasic strong alkaline substance is sodium hydride and/or metallic sodium;
and/or in the step (2), the mixing temperature is 60-80 ℃;
and/or in the step (2), the mixing time is 4-8 h;
and/or in the step (2), the molar ratio of the intermediate A, the monobasic strong alkaline substance and the end capping agent is 1 (1.05-1.15): 1.15;
and/or, in the step (3), before the mixing, the intermediate B is also subjected to vacuum dehydration;
and/or, in the step (3), the catalyst is an alkali metal compound and/or an alkaline earth metal compound;
and/or in the step (3), heating to 60-120 ℃;
and/or, in step (3), the epoxide is ethylene oxide and/or propylene oxide;
and/or in the step (3), the curing time is 1-2.5 h;
and/or, in the step (3), the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
3. The method according to claim 2, wherein in the step (1), the monohydric alcohol is one or more of methanol, ethanol and butanol;
and/or, in the step (1), the catalyst is one or more of potassium hydroxide, sodium hydroxide, potassium methoxide, sodium hydride and metallic sodium;
and/or in the step (1), heating to 60-70 ℃;
and/or in the step (1), the curing time is 1.5-2.0 h;
and/or in the step (2), the mixing time is 6-8 h;
and/or, in the step (3), the catalyst is one or more of potassium hydroxide, sodium hydroxide, potassium methoxide, sodium hydride and metallic sodium;
and/or in the step (3), raising the temperature to 100-120 ℃.
4. The method according to claim 1, wherein in the step (3), the aging is followed by purification, and the purification comprises neutralization, adsorption, dehydration and filtration.
5. The method according to claim 4, wherein the neutralization is carried out by adding a neutralizing agent;
and/or the temperature of neutralization is 60-120 ℃;
and/or adding a solvent and an adsorbent for adsorption.
6. The method of claim 5, wherein the neutralizing agent is phosphoric acid;
and/or, the solvent is water;
and/or the adsorbent is one or more of magnesium silicate, aluminum silicate and magnesium aluminum silicate.
7. A branched polyether prepared by the method of any one of claims 1 to 6.
8. A preparation method of a branched polyether intermediate is characterized by comprising the following steps:
(1) under the inert atmosphere, mixing a monofunctional initiator and a catalyst, heating, gradually adding an epoxide for reaction, and then curing to obtain an intermediate A;
(2) mixing the intermediate A with a monobasic strong alkaline substance, reacting to prepare alkoxide, and adding a capping agent to cap to obtain a branched polyether intermediate with the functionality of 2; the molar ratio of the intermediate A to the monobasic strong alkaline substance is 1: 1.05-1: 1.15; the blocking agent is 2-chloroglycerin and/or 3-chloroglycerin.
9. The method according to claim 8, wherein in the step (1), the monofunctional initiator is one or more of methanol, ethanol and butanol;
and/or, in the step (1), the catalyst is one or more of potassium hydroxide, sodium hydroxide, potassium methoxide, sodium hydride and metallic sodium;
and/or in the step (1), heating to 60-120 ℃;
and/or, in step (1), the epoxide is ethylene oxide and/or propylene oxide;
and/or in the step (1), the temperature of the reaction is controlled to be 105-120 ℃, and the pressure of the reaction is controlled to be below 0.5 MPa;
and/or in the step (1), the curing time is 1-2.5 h;
and/or, in the step (1), the inert atmosphere is nitrogen atmosphere or argon atmosphere;
and/or, in the step (2), the monobasic strong alkaline substance is sodium hydride and/or metallic sodium;
and/or in the step (2), the mixing temperature is 60-80 ℃;
and/or in the step (2), the mixing time is 4-8 h;
and/or in the step (2), the molar ratio of the intermediate A, the monobasic strong alkaline substance and the end capping agent is 1 (1.05-1.15) to 1.15.
10. A branched polyether intermediate obtainable by the process of claim 8 or 9.
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