CN119285922A - A synthesis process of high molecular weight unsaturated polyether - Google Patents
A synthesis process of high molecular weight unsaturated polyether Download PDFInfo
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Abstract
The invention provides a synthesis process of high molecular weight unsaturated polyether, which comprises the steps of (1) adding a first initiator into a reaction system, adding an alkaline catalyst, carrying out reaction to enable the alkaline catalyst to be completely dissolved, adding a second initiator, (2) adding a first epoxy monomer at a first reaction temperature, continuing to react until the reaction is complete after the addition is finished to obtain first low molecular weight polyether, (3) sequentially carrying out water adding and heating reaction, neutralization, moisture removal and first refining on the first low molecular weight polyether, (4) mixing a solution of the second low molecular weight polyether and an acid auxiliary catalyst, (5) introducing the epoxy monomer for curing, and then cooling and vacuum degassing. The invention synthesizes the high molecular weight unsaturated polyether through a two-step process, and finally obtains the high molecular weight unsaturated polyether with narrower molecular weight distribution, higher double bond retention rate and fewer impurities.
Description
Technical Field
The invention relates to the technical field of polyether, in particular to a synthesis process of high molecular weight unsaturated polyether.
Background
Unsaturated polyethers are mainly classified into two types according to applications, wherein the polyoxyethylene unsaturated polyether is used in a large amount, and is mainly produced by ring-opening polymerization of alcohol containing unsaturated double bonds and ethylene oxide, and is used for manufacturing carboxylic acid water reducer and nonionic surfactant. And the other is to react special groups with unsaturated bonds to produce products with special properties, such as hydrogen-containing silicone oil to produce special silicone oil, for example, straight-chain polyether with two ends capped by double bonds can be used as a main raw material of the silane-terminated polyether sealant.
The production process of polyether with double-bond end-capped at two sides mainly comprises the steps of propylene glycol polyether glycol double-bond end-capped and preparing polyether monol double-bond end-capped by alcohol containing unsaturated double bonds. The process for end capping the polyether prepared by taking unsaturated alcohol as an initiator has higher double bond retention rate, and meets the requirement of silane modified polyether sealant.
When the double metal cyanide complex catalyst (DMC) is used for preparing polyether with higher molecular weight through catalysis, the side reaction occurrence rate is extremely low, the retention degree of the polyether structure is higher, the original double bond structure of the polyether can not be damaged, and the double metal cyanide complex catalyst (DMC) has higher practical value when the polyether is used as a raw material for synthesizing the sealant. Meanwhile, the post-treatment of the crude polyether is also particularly important, and influences important indexes such as metal ion and moisture content, pH value, chromaticity and the like of the polyether product. So the polyether post-treatment technology level is improved, the structure of polyether can be maintained to a great extent, and the quality of polyether products is also improved. Based on the prior art, how to prepare a high molecular weight unsaturated polyether product with narrower molecular weight distribution, higher double bond retention rate and fewer impurities is a technical problem to be solved at present.
Disclosure of Invention
In view of the above, the present invention provides a process for synthesizing high molecular weight unsaturated polyether.
The invention provides a synthesis process of high molecular weight unsaturated polyether, which comprises the following steps:
(1) Adding a first initiator into a reaction system, replacing with inert gas, adding an alkaline catalyst, performing a reaction to completely dissolve the alkaline catalyst, and adding a second initiator;
(2) Continuously replacing inert gas, feeding a first epoxy monomer at a first reaction temperature, and continuously reacting until the reaction is complete after the feeding is finished to obtain first low molecular weight polyether;
(3) Sequentially carrying out water adding and heating reaction, neutralization, water removal and first refining on the first low molecular weight polyether, discharging and filtering solid residues to obtain second low molecular weight polyether;
(4) Mixing the second low molecular weight polyether with the solution of the acid auxiliary catalyst, adding the double metal cyanide complex catalyst, and starting heating, stirring and vacuum;
(5) Closing vacuum, controlling the second reaction temperature, introducing epoxy monomers for curing, cooling and vacuum degassing.
Optionally, step (5) yields a crude polyether, and the synthesis process further comprises the following steps after step (5):
(6) And cooling the crude polyether, sequentially carrying out alkalization, second refining, heating dehydration and filtration to obtain the high molecular weight unsaturated polyether.
Optionally, the acid promoter catalyst in step (4) is fluosilicic acid and/or fluoboric acid.
Optionally, in the step (4), the mass fraction of the solution of the acid auxiliary catalyst is 5-15%, and the solution dosage of the acid auxiliary catalyst is 1-10 ppm of the total designed mass of the high molecular weight unsaturated polyether;
the dosage of the double metal cyanide complex catalyst is 15-65 ppm of the total designed mass of the high molecular weight unsaturated polyether.
Optionally, in the step (4), mixing the solution of the second low molecular weight polyether and the acid auxiliary catalyst for 20-60 min, and then adding the double metal cyanide complex catalyst.
Optionally, curing the epoxy monomer in the step (5) includes the following steps sequentially:
And (3) introducing a second epoxy monomer, performing first curing, introducing a third epoxy monomer, performing second curing, introducing a fourth epoxy monomer, and performing third curing.
Optionally, each of the first epoxy monomer in step (2), the second epoxy monomer in step (5), the third epoxy monomer, and the fourth epoxy monomer is ethylene oxide and/or propylene oxide.
Optionally, the first epoxy monomer in the step (2) is propylene oxide, the second epoxy monomer in the step (5) is propylene oxide, the third epoxy monomer is a mixture of ethylene oxide and propylene oxide, and the fourth epoxy monomer is propylene oxide;
And taking the total design mass of the high molecular weight unsaturated polyether as a reference, wherein the feeding mass ratio of the ethylene oxide in the third epoxy monomer is 0-35%.
Optionally, in step (1), the first initiator and the second initiator are each one or more selected from allyl alcohol, methallyl alcohol, N-methallylamine, 3-buten-1-ol;
The molecular weight of the first initiator accounts for 0.05-0.75% of the molecular weight of the high-molecular-weight unsaturated polyether, and the molecular weight of the second initiator accounts for 0.02-1.00% of the molecular weight of the high-molecular-weight unsaturated polyether, based on 5000-15000 of the molecular weight of the high-molecular-weight unsaturated polyether.
Optionally, in step (1), the first initiator is allyl alcohol and the second initiator is 3-buten-1-ol.
Optionally, the filtration in step (6) is filter-pressed with a glass fiber filter membrane.
Optionally, the alkaline catalyst in the step (1) is one or more selected from metallic potassium, metallic sodium, sodium methoxide, potassium hydroxide and sodium hydroxide;
the amount of the alkaline catalyst in the step (1) is 0.05-1.00% of the total mass of the second low molecular weight polyether charge obtained in the step (3).
The beneficial effects are that:
The invention synthesizes high molecular weight unsaturated polyether through a two-step process, firstly adopts alkaline catalysis to synthesize low molecular weight polyether and refines, then adopts an acid auxiliary catalyst to be matched with a double metal cyanide complex catalyst to further polymerize the low molecular weight polyether, and finally obtains the high molecular weight unsaturated polyether with narrower molecular weight distribution, higher double bond retention rate and fewer impurities.
Detailed Description
The present application will be described in further detail by way of examples. The features and advantages of the present application will become more apparent from the description.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
In the present invention, the term "total mass of the high molecular weight unsaturated polyether design" means the mass sum of all the initiator and the epoxy monomer in terms of the charge at the time of synthesizing the high molecular weight unsaturated polyether.
In addition, the technical features described below in the different embodiments of the present application may be combined with each other as long as they do not collide with each other.
The invention provides a synthesis process of high molecular weight unsaturated polyether, which comprises the following steps:
(1) Adding a first initiator into a reaction system, replacing with inert gas, adding an alkaline catalyst, performing a reaction to completely dissolve the alkaline catalyst, and adding a second initiator;
(2) Continuously replacing inert gas, feeding a first epoxy monomer at a first reaction temperature, and continuously reacting until the reaction is complete after the feeding is finished to obtain first low molecular weight polyether;
(3) Sequentially carrying out water adding and heating reaction, neutralization, water removal and first refining on the first low molecular weight polyether, discharging and filtering solid residues to obtain second low molecular weight polyether;
(4) Mixing the second low molecular weight polyether with the solution of the acid auxiliary catalyst, adding the double metal cyanide complex catalyst, and starting heating, stirring and vacuum;
(5) Closing vacuum, controlling the second reaction temperature, introducing epoxy monomers for curing, cooling and vacuum degassing.
In one embodiment of the foregoing synthesis process of the present invention, step (5) results in a crude polyether, the synthesis process further comprising the following steps after step (5):
(6) And cooling the crude polyether, sequentially carrying out alkalization, second refining, heating dehydration and filtration to obtain the high molecular weight unsaturated polyether.
In another embodiment of the foregoing synthesis process of the present invention, the acid promoter catalyst in step (4) is fluosilicic acid and/or fluoboric acid.
The invention synthesizes high molecular weight unsaturated polyether through a two-step process, firstly synthesizes low molecular weight polyether by adopting an alkaline catalyst, carries out neutralization refining, then uses fluosilicic acid and/or fluoboric acid as an acid auxiliary catalyst to be mutually matched and catalyzed with a double metal cyanide complex catalyst (DMC catalyst), further polymerizes the low molecular weight polyether into finished polyether, and carries out refining to finally obtain the high molecular weight unsaturated polyether.
Specifically, the preparation of the initiator solution and the intermediate crude polyether is completed through the steps (1) and (2), a first initiator can be added into a closed reaction kettle with a cooling coil, industrial N 2 is used for replacing 3-5 times, an alkaline catalyst which is cut into small blocks is added, part of gas in the reaction kettle can be removed after the alkaline catalyst is completely dissolved, and a second initiator is added. And after the temperature is raised to the required temperature, adding a certain amount of first epoxy monomer and completely reacting the first epoxy monomer to obtain a crude polyether intermediate, namely first low molecular weight polyether.
And (3) finishing refining the crude polyether intermediate, transferring the crude polyether intermediate, namely the first low molecular weight polyether, to a neutralization reaction kettle (which can be a normal pressure glass reaction kettle), adding a proper amount of deionized water, heating for reacting for a certain time, adding a neutralizing agent for neutralization, removing water in a system, adding a refining agent for further absorbing trace metal ions in the polyether, and filtering out solid residues in the system to obtain the polyether intermediate, namely the second low molecular weight polyether.
And (3) synthesizing high molecular weight unsaturated polyether in the steps (4) and (5), transferring the second low molecular weight polyether into a clean reaction kettle, adding the DMC catalyst after adding the solution of the acid cocatalyst, mixing for a certain time, heating to a pre-reaction temperature in vacuum, closing the vacuum, adding quantitative epoxy monomer, and removing trace volatile components in the system in vacuum after the monomer feeding is finished and the reaction is completed, so as to obtain the high molecular weight crude polyether.
And (6) refining the crude polyether with high molecular weight, transferring the crude polyether to a refining reaction kettle (which can be a glass neutralization reaction kettle), adding NaOH aqueous solution, alkalizing for half an hour, adding polyether refining agent, heating and removing water in the polyether, and finally filtering to obtain the finished polyether. The high molecular weight unsaturated polyether produced by the process has narrower molecular weight distribution, higher double bond retention rate and total metal ion measured value less than 3ppm, and completely meets the requirements of the end-capping process.
In the two-step synthesis process, after the intermediate is prepared by alkaline catalysis, DMC catalyst is used for synthesizing finished polyether, in order to reduce the influence on the finished polyether product, after the intermediate is prepared, the solution of acid auxiliary catalyst is added before DMC catalyst is added in the step (4), so that the stabilizer is used, trace alkali brought in the polyether polymerization process is neutralized, certain metal catalysts are deactivated, the stabilizing effect is achieved, high molecular weight unsaturated polyether with excellent synthesis performance is achieved, especially fluosilicic acid and/or fluoboric acid is used as acid auxiliary catalyst, the acid auxiliary catalyst can synergistically enhance the performance of the polyether product in multiple aspects, the high molecular weight unsaturated polyether product with narrower molecular weight distribution, higher double bond retention rate and fewer impurities is finally prepared, and the molecular weight of the polyether product can be between 1000-20000.
In one embodiment of the above synthesis process, the mass fraction of the solution of the acid auxiliary catalyst in the step (4) is 5-15%, and the solution dosage of the acid auxiliary catalyst is 1-10 ppm of the total designed mass of the high molecular weight unsaturated polyether;
the dosage of the double metal cyanide complex catalyst is 15-65 ppm of the total designed mass of the high molecular weight unsaturated polyether.
The mass fraction of the solution of the acid auxiliary catalyst may be specifically 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc., the solution of the acid auxiliary catalyst may be 1 to 20ppm of the total mass of the high molecular weight unsaturated polyether design, specifically 2ppm、3ppm、4ppm、5ppm、6ppm、7ppm、8ppm、9ppm、10ppm、11ppm、12ppm、13ppm、14ppm、15ppm、16ppm、17ppm、18ppm、19ppm、20ppm% of the total mass of the high molecular weight unsaturated polyether design, etc., and the DMC catalyst may preferably be 15ppm, 20ppm, 25ppm, 30ppm, 35ppm, 40ppm, 45ppm, 50ppm, 55ppm, 60ppm, 65ppm of the total mass of the high molecular weight unsaturated polyether design.
In the synthesis process, the high molecular weight unsaturated polyether with better performance is prepared by controlling the mass fraction and the dosage of the solution of the acid auxiliary catalyst and the dosage of the DMC catalyst, so that the molecular weight distribution of the polyether product is narrower, the double bond retention rate is higher, and the impurities are fewer.
In another embodiment of the above synthesis process of the present invention, in the step (4), the solution of the second low molecular weight polyether and the acid auxiliary catalyst is mixed for 20 to 60 minutes, and then the double metal cyanide complex catalyst is added.
It should be noted that, through research and development experiments for many years, the inventor discovers that when fluosilicic acid and/or fluoboric acid is used as an acid auxiliary catalyst, the mixing time of the second low molecular weight polyether and the acid auxiliary catalyst solution has an important influence on the molecular weight distribution, double bond retention rate and the like of the finally synthesized polyether product, if the mixing time of the second low molecular weight polyether and the acid auxiliary catalyst solution is too short or too long, the DMC catalyst with the same dosage is added, the performance of the finally obtained finished polyether is reduced, the DMC catalyst is added after the mixing of the second low molecular weight polyether and the acid auxiliary catalyst solution is controlled to be 20-60 min, and finally the obtained polyether product has narrower molecular weight distribution, higher double bond retention rate and fewer impurities.
In one embodiment of the above synthesis process of the present invention, the curing by introducing the epoxy monomer in the step (5) includes the following steps sequentially:
And (3) introducing a second epoxy monomer, performing first curing, introducing a third epoxy monomer, performing second curing, introducing a fourth epoxy monomer, and performing third curing.
It should be noted that the second epoxy monomer, the third epoxy monomer, and the fourth epoxy monomer may be the same or different epoxy monomers.
In one embodiment of the above-described synthesis process of the present invention, each of the first epoxy monomer in step (2), the second epoxy monomer in step (5), the third epoxy monomer, and the fourth epoxy monomer is ethylene oxide and/or propylene oxide.
It should be noted that when the first epoxy monomer in the step (2) is propylene oxide, the step (3) obtains propylene oxide polyether (polypropylene oxide), and when the first epoxy monomer in the step (2) is ethylene oxide, the step (3) obtains ethylene oxide polyether (polyethylene oxide). If the first epoxy monomer, the second epoxy monomer, the third epoxy monomer and the fourth epoxy monomer are the same epoxy monomer, if the first epoxy monomer, the second epoxy monomer, the third epoxy monomer and the fourth epoxy monomer are ethylene oxide, the polyether product is ethylene oxide polyether, and if the first epoxy monomer, the second epoxy monomer, the third epoxy monomer and the fourth epoxy monomer are propylene oxide polyether. The first epoxy monomer, the second epoxy monomer, the third epoxy monomer and the fourth epoxy monomer can be different monomers, and various polyether products such as random copolymerization, block copolymerization and the like can be prepared by adjusting the monomer and the feeding sequence.
In a preferred embodiment of the above synthesis process of the present invention, the first epoxy monomer in step (2) is propylene oxide, the second epoxy monomer in step (5) is propylene oxide, the third epoxy monomer is a mixture of ethylene oxide and propylene oxide, and the fourth epoxy monomer is propylene oxide;
And taking the total design mass of the high molecular weight unsaturated polyether as a reference, wherein the feeding mass ratio of the ethylene oxide in the third epoxy monomer is 0-35%.
In this preferred embodiment, the ethylene oxide in the third epoxy monomer may be added in a mass ratio of specifically 5%, 10%, 15%, 20%, 25%, 30%, 35%. The structure of the high molecular weight unsaturated polyether can be an ABA type structure, after the initiator is subjected to ring-opening polymerization reaction with propylene oxide to form propylene oxide polyether with certain molecular weight, the propylene oxide polyether is sequentially mixed with two catalysts in the step (4), the propylene oxide polyether is polymerized and cured with propylene oxide monomer in the step (5) until the reaction is complete, then the propylene oxide polyether is subjected to random copolymerization and curing with a mixture of propylene oxide and ethylene oxide, finally the propylene oxide polyether is subjected to ring-opening polymerization and curing with propylene oxide monomer to obtain a block-type structure polyether product of PO- (EO/PO) -PO, PO represents a polymerization chain segment after the ring opening of propylene oxide, EO represents a polymerization chain segment after the ring opening of ethylene oxide, and EO/PO represents an intermediate chain segment of mixed polymerization (random copolymerization) after the ring opening of ethylene oxide and propylene oxide. The molecular weight of the finally obtained polyether product can be, but is not limited to, 5000-12000, and the finally obtained polyether product can be used as a polyether raw material for preparing sealant.
In the synthesis process of the invention, the polyether product with the specific chain segment structure mainly comprising propylene oxide has very good performance, narrower molecular weight distribution, higher double bond retention rate and fewer impurities by controlling the monomer types of the first epoxy monomer, the second epoxy monomer, the third epoxy monomer and the fourth epoxy monomer and feeding the monomers in sequence.
In yet another embodiment of the above synthetic process of the present invention, each of the first initiator and the second initiator in step (1) is one or more selected from allyl alcohol, methallyl alcohol, N-methallylamine, 3-buten-1-ol;
The molecular weight of the first initiator accounts for 0.05-0.75% of the molecular weight of the high-molecular-weight unsaturated polyether, and the molecular weight of the second initiator accounts for 0.02-1.00% of the molecular weight of the high-molecular-weight unsaturated polyether, based on 5000-15000 of the molecular weight of the high-molecular-weight unsaturated polyether.
The first initiator and the second initiator in step (1) may each be an unsaturated alcohol or amine containing a double bond selected from the above.
In a preferred embodiment of the above synthetic process of the present invention, the first initiator in step (1) is allyl alcohol and the second initiator is 3-buten-1-ol.
The starter of the polyether is generally a small molecule alcohol with unsaturated double bonds, and from the aspects of performance and cost, allyl alcohol and 3-butene-1-alcohol are selected as a first starter and a second starter respectively. In view of the fact that the final polyether product may be used as a raw material of a silane modified polyether sealant, a high double bond retention rate and double bond reactivity are required, allyl alcohol and 3-buten-1-ol are preferably used as the initiators of unsaturated polyethers, and the prepared polyether product has a high double bond retention rate and high reactivity in the process of preparing the sealant.
As a variant embodiment, the first initiator and the second initiator can be the same and can be allyl alcohol, and the finally prepared polyether product has low reactivity in the process of preparing the sealant although the molecular weight distribution is narrow, the double bond retention rate is high and the impurity content is low. In the synthesis process of the invention, in the step (1), allyl alcohol is used as a first initiator added firstly, 3-butene-1-ol is used as a second initiator added later, the two initiators are matched for use, and according to the subsequent steps in the synthesis process of the invention, fluosilicic acid and/or fluoboric acid are used as acid auxiliary catalysts to be matched with DMC catalysts, so that the finally obtained polyether product has the advantages of narrow molecular weight distribution, high double bond retention rate, low impurity content and high reaction activity in the process of preparing the sealant.
In yet another embodiment of the above synthesis process of the present invention, the filtration in step (6) is filter-pressed with a glass fiber filter membrane.
After the polyether product is synthesized, catalyst components in the polyether product need to be removed, and the subsequent synthesis is not affected if the impurity content in the product is extremely low. For polyether with a certain high molecular weight, the ordinary filtering mode is difficult to achieve good filtering effect due to the restriction of viscosity and the like. The glass fiber filter membrane can be a high-purity glass fiber filter membrane and the like, and has high porosity and good filtering performance, so that insoluble impurities can be removed better, and the purity of polyether is improved. And the high-purity glass fiber filter membrane can show good chemical stability and thermal stability when filtering high-molecular-weight polyether with certain viscosity, can resist certain temperature and chemical environment, and can not bring any negative influence to polyether, so that the high-purity glass fiber filter membrane has higher applicability when treating organic compounds such as polyether. Therefore, the high-purity glass fiber filter membrane is adopted for filtering, so that trace catalyst residues and other impurities in the product can be well filtered, and the polyether maintains excellent performance, and finally, the finished polyether with narrower molecular weight distribution, higher double bond retention rate and fewer impurities is obtained.
In one embodiment of the above synthesis process of the present invention, the basic catalyst in step (1) is one or more selected from the group consisting of metallic potassium, metallic sodium, sodium methoxide, potassium hydroxide, sodium hydroxide;
the amount of the alkaline catalyst in the step (1) is 0.05-1.00% of the total mass of the second low molecular weight polyether charge obtained in the step (3).
It should be noted that, in the step (1), the alkaline catalyst may be one or more selected from the simple substance, oxide, hydroxide and alcoholate of alkali metal and alkaline earth metal, and particularly preferably is potassium metal, and the feeding amount of the alkaline catalyst is preferably 0.10-0.25% of the total mass of the second low molecular weight polyether fed in the step (3). When the alkaline catalyst in the step (1) is preferably metal potassium and the dosage is controlled as above, the metal potassium has higher catalytic activity and fewer reaction treatment procedures, and the metal potassium is used as the alkaline catalyst and is synthesized according to the synthesis process of the invention, so that the performance of the synthesized polyether product can be further improved, the molecular weight distribution of the polyether product is narrower, the double bond retention rate is higher, and the impurities are fewer.
In the step (3), the water-adding and temperature-increasing reaction may be performed as follows:
Adding water, heating to 75-95 ℃ for reaction for 40 min-2 h, wherein the mass of the added water accounts for 1-15% of the mass of the first low molecular weight polyether obtained in the step (2) in terms of the discharging material;
For propylene oxide polyether with molecular weight of about 400, deionized water accounting for 10% can be added for reaction at 90 ℃ for 1 hour.
The neutralization process in step (3) may be performed as follows:
the neutralizing agent is added for neutralization, and the neutralizing agent can be one or more selected from sulfuric acid, phosphoric acid, pyrophosphoric acid and adipic acid, or can also be one or more selected from acid salts of sulfuric acid, phosphoric acid, pyrophosphoric acid and adipic acid, and generally phosphoric acid or adipic acid aqueous solution is used as the neutralizing agent, and the neutralization can be carried out at 75-100 ℃ for 1-2 h.
The removal of water in step (3) may be performed as follows:
The dehydration can be carried out at 105-125 ℃ in vacuum to ensure that the moisture content is less than 0.02%, the dehydration process can be generally carried out at a temperature rise after the neutralization reaction is completed, the dehydration temperature is not too high, the dehydration efficiency can be improved by bubbling high-purity nitrogen at the bottom of the reaction kettle in the later stage of dehydration, and the moisture content is less than 0.02% due to the requirement of the DMC catalyst catalysis process in the step (4).
In step (3), the first refining may be performed as follows:
Adding a first refining agent to perform first refining, wherein the first refining agent can be magnesium silicate and/or aluminum silicate, the weight of the first refining agent in the total weight of the high molecular weight unsaturated polyether discharging meter obtained in the step (6) can be 0.01-1.0%, and the first refining can be performed at 105-125 ℃ such as 120 ℃ for 1.5-3 hours.
In step (3), the solid residue may be filtered as follows:
Various types of filters can be selected in the filtering process, solid residues in polyether are required to be completely filtered, the filtered polyether intermediate is required to be slightly acidic, and the pH value can be between 6 and 7. The solid residue is filtered to obtain an intermediate, namely second low molecular weight polyether, wherein the molecular weight of the intermediate can be, but is not limited to, 200-600, preferably about 200, 400, 500 and the like, and the molecular weight design of the intermediate is related to the reaction kettle mode and the material growth ratio in the design polymerization process.
The water is added in the step (3) to perform the reaction at a temperature rising, the neutralization and the water removal are performed, the solid residues are filtered, and the polyether intermediate is subjected to the refining process.
In step (6), the alkalization may be performed as follows:
Adding an alkalizing reagent solution for alkalizing, wherein the alkalizing reagent solution can be an aqueous NaOH solution and/or an aqueous KOH solution, the consumption of the alkalizing reagent solution can be 10-1000 ppm of the designed total mass of the high molecular weight unsaturated polyether, the alkalizing can be carried out at 25-95 ℃ for 0.5-1.5 h, the mass fraction of the alkalizing reagent solution used during the alkalizing can be generally 1-15%, and 10% of the aqueous solution can be added according to 20ppm、30ppm、50ppm、70ppm、90ppm、100ppm、200ppm、300ppm、400ppm、500ppm、600ppm、700ppm、800ppm、900ppm、1000ppm of the designed total mass of the high molecular weight unsaturated polyether.
In the step (6), the second purification may be performed as follows:
The second refining agent can be added for second refining for 0.5-2.0 hours, preferably 1.0-1.5 hours, or the second refining agent can be directly dehydrated after being added, so that the end of the refining process can be considered after the moisture content is qualified, and the dosage of the second refining agent can be 50-500 ppm of the total mass of the high molecular weight unsaturated polyether design.
And (3) when the temperature is increased and the dehydration is carried out in the step (6), nitrogen bubbling can be started at 110-125 ℃ to remove the moisture in the water.
The present invention will be further described in detail by way of examples, which are not intended to limit the scope of the invention. In the examples below, the laboratory apparatus and the raw materials involved are commercially available products, unless otherwise specified.
The high purity glass fiber filter membrane used in the following examples was a QM-TN #1650 high purity ultrafine quartz fiber filter cartridge of Qingdao Bao blue technology Co., ltd.
Example 1
Unsaturated polyether with molecular weight of 10000 is prepared in a 5L polymerization reaction kettle, and the method comprises the following steps:
(1) 325g of allyl alcohol is added into a clean reaction kettle, stirring is started, 5g of metal potassium is added after N 2 is replaced for 3 times, the metal potassium is fully reacted to be completely dissolved, and when the temperature of the material is rapidly increased or exceeds 85 ℃, cooling water can be properly started to reduce the temperature of the reactant, and 135g of 3-butene-1-ol is added.
(2) And continuing to replace N 2 for 2 times, maintaining the pressure in the reaction kettle to be slightly higher than the normal pressure, introducing propylene oxide 2540g at the moment, maintaining the reaction temperature at 110 ℃, feeding for 5 hours, and continuing to react for 2.5 hours after the feeding is finished until the reaction is complete.
(3) And completely transferring the materials to a 5L normal pressure glass reaction kettle, adding 300g of deionized water into the reaction kettle, heating to 90 ℃ for reaction for 1 hour, adding 25g of 85% phosphoric acid, maintaining the temperature for neutralization for 1.5 hours, heating to 120 ℃, completely removing the moisture in the system in vacuum, breaking vacuum by using N 2 after the analysis moisture is less than 0.02%, adding 5g of magnesium silicate refining agent into the reaction kettle for refining for 2 hours at the maintained temperature, discharging, and filtering solid residues by using a plate-type circulating filter or a Buchner funnel with filter paper to obtain the polyether intermediate.
(4) 120G of polyether intermediate and 0.01g of 10% fluosilicic acid aqueous solution are put into a clean reaction kettle for half an hour of mixing, then 0.125g of DMC catalyst is put into the reaction kettle after being completely mixed, and the temperature is raised to 145 ℃ by starting heating, stirring and vacuum.
(5) And closing vacuum, controlling the reaction temperature to 140-145 ℃, firstly introducing 480g of propylene oxide, feeding for 1 hour, curing for 0.5 hour, then introducing a mixture of 450g of ethylene oxide and 1350g of propylene oxide, feeding for 3 hours, curing for 0.5 hour after feeding is completed, finally adding 600g of propylene oxide, feeding for 1.5 hours, curing for 1 hour, cooling to 110 ℃, opening vacuum degassing for 30 minutes, and removing unreacted volatile components to obtain crude polyether.
(6) Transferring the crude polyether into a glass neutralization reaction kettle, cooling to below 60 ℃, adding 0.5g of 10% NaOH aqueous solution, maintaining the reaction at 50-60 ℃ for 1 hour for alkalization, adding 0.6g of magnesium silicate refining agent, heating to 110 ℃ for dehydration until the water content of the material is lower than 0.02%, and performing filter pressing by using a high-purity glass fiber filter membrane to obtain the finished polyether.
Example 2
An unsaturated polyether was prepared as in example 1, except that:
the fluosilicic acid aqueous solution in the step (4) is replaced by fluoboric acid aqueous solution.
Unsaturated polyether with molecular weight of 10000 is prepared in a 5L polymerization reaction kettle, and the method comprises the following steps:
(1) 325g of allyl alcohol is added into a clean reaction kettle, stirring is started, 5g of metal potassium is added after N 2 is replaced for 3 times, the metal potassium is fully reacted to be completely dissolved, and when the temperature of the material is rapidly increased or exceeds 85 ℃, cooling water can be properly started to reduce the temperature of the reactant, and 135g of 3-butene-1-ol is added.
(2) And continuing to replace N 2 for 2 times, maintaining the pressure in the reaction kettle to be slightly higher than the normal pressure, introducing propylene oxide 2540g at the moment, maintaining the reaction temperature at 110 ℃, feeding for 5 hours, and continuing to react for 2.5 hours after the feeding is finished until the reaction is complete.
(3) And completely transferring the materials to a 5L normal pressure glass reaction kettle, adding 300g of deionized water into the reaction kettle, heating to 90 ℃ for reaction for 1 hour, adding 25g of 85% phosphoric acid, maintaining the temperature for neutralization for 1.5 hours, heating to 120 ℃, completely removing the moisture in the system in vacuum, breaking vacuum by using N 2 after the analysis moisture is less than 0.02%, adding 5g of magnesium silicate refining agent into the reaction kettle for refining for 2 hours at the maintained temperature, discharging, and filtering solid residues by using a plate-type circulating filter or a Buchner funnel with filter paper to obtain the polyether intermediate.
(4) 120G of polyether intermediate and 0.01g of 10% fluoboric acid aqueous solution are put into a clean reaction kettle for half an hour of mixing, then 0.125g of DMC catalyst is put into the reaction kettle after being completely mixed, and the temperature is raised to 145 ℃ by starting heating, stirring and vacuum.
(5) And closing vacuum, controlling the reaction temperature to 140-145 ℃, firstly introducing 480g of propylene oxide, feeding for 1 hour, curing for 0.5 hour, then introducing a mixture of 450g of ethylene oxide and 1350g of propylene oxide, feeding for 3 hours, curing for 0.5 hour after feeding is completed, finally adding 600g of propylene oxide, feeding for 1.5 hours, curing for 1 hour, cooling to 110 ℃, opening vacuum degassing for 30 minutes, and removing unreacted volatile components to obtain crude polyether.
(6) Transferring the crude polyether into a glass neutralization reaction kettle, cooling to below 60 ℃, adding 0.5g of 10% NaOH aqueous solution, maintaining the reaction at 50-60 ℃ for 1 hour for alkalization, adding 0.6g of magnesium silicate refining agent, heating to 110 ℃ for dehydration until the water content of the material is lower than 0.02%, and performing filter pressing by using a high-purity glass fiber filter membrane to obtain the finished polyether.
Example 3
An unsaturated polyether was prepared as in example 1, except that:
And (3) replacing the filter pressing of the high-purity glass fiber filter membrane in the step (6) with glass sand core filtering.
Unsaturated polyether with molecular weight of 10000 is prepared in a 5L polymerization reaction kettle, and the method comprises the following steps:
(1) 325g of allyl alcohol is added into a clean reaction kettle, stirring is started, 5g of metal potassium is added after N 2 is replaced for 3 times, the metal potassium is fully reacted to be completely dissolved, if the temperature of the material is rapidly increased or exceeds 85 ℃, cooling water can be properly started to reduce the temperature of the reactant, and 135g of 3-butene-1-ol is added.
(2) And continuing to replace N 2 for 2 times, maintaining the pressure in the reaction kettle to be slightly higher than the normal pressure, introducing propylene oxide 2540g at the moment, maintaining the reaction temperature at 110 ℃, feeding for 5 hours, and continuing to react for 2.5 hours after the feeding is finished until the reaction is complete.
(3) And completely transferring the materials to a 5L normal pressure glass reaction kettle, adding 300g of deionized water into the reaction kettle, heating to 90 ℃ for reaction for 1 hour, adding 25g of 85% phosphoric acid, maintaining the temperature for neutralization for 1.5 hours, heating to 120 ℃, completely removing the moisture in the system in vacuum, breaking vacuum by using N 2 after the analysis moisture is less than 0.02%, adding 5g of magnesium silicate refining agent into the reaction kettle for refining for 2 hours at the maintained temperature, discharging, and filtering solid residues by using a plate-type circulating filter or a Buchner funnel with filter paper to obtain the polyether intermediate.
(4) 120G of polyether intermediate and 0.01g of 10% fluosilicic acid aqueous solution are put into a clean reaction kettle for half an hour of mixing, then 0.125g of DMC catalyst is put into the reaction kettle after being completely mixed, and the temperature is raised to 145 ℃ by starting heating, stirring and vacuum.
(5) And closing vacuum, controlling the reaction temperature to 140-145 ℃, firstly introducing 480g of propylene oxide, feeding for 1 hour, curing for 0.5 hour, then introducing a mixture of 450g of ethylene oxide and 1350g of propylene oxide, feeding for 3 hours, curing for 0.5 hour after feeding is completed, finally adding 600g of propylene oxide, feeding for 1.5 hours, curing for 1 hour, cooling to 110 ℃, opening vacuum degassing for 30 minutes, and removing unreacted volatile components to obtain crude polyether.
(6) Transferring the crude polyether into a glass neutralization reaction kettle, cooling to below 60 ℃, adding 0.5G of 10% NaOH aqueous solution, maintaining the reaction at 50-60 ℃ for 1 hour for alkalization, adding 0.6G of magnesium silicate refining agent, heating to 110 ℃ for dehydration until the water content of the material is lower than 0.02%, and carrying out suction filtration twice by using a G4 sand core funnel, wherein the filtering speed is lower, and the material liquid needs to be kept warm in the filtering process to obtain the finished polyether.
Example 4
An unsaturated polyether was prepared as in example 1, except that:
the polyether structure adopts full random copolymerization.
Unsaturated polyether with molecular weight of 10000 is prepared in a 5L polymerization reaction kettle, and the method comprises the following steps:
(1) 325g of allyl alcohol is added into a clean reaction kettle, stirring is started, 5g of metal potassium is added after N 2 is replaced for 3 times, the metal potassium is fully reacted to be completely dissolved, if the temperature of the material is rapidly increased or exceeds 85 ℃, cooling water can be properly started to reduce the temperature of the reactant, and 135g of 3-butene-1-ol is added.
(2) And continuing to replace N 2 for 2 times, maintaining the pressure in the reaction kettle slightly higher than normal pressure, introducing a mixture of 2159g of propylene oxide and 381g of ethylene oxide, maintaining the reaction temperature at 110 ℃, and continuing to react for 2.5 hours after the feeding is finished until the reaction is complete.
(3) And completely transferring the materials to a 5L normal pressure glass reaction kettle, adding 400g of deionized water into the reaction kettle, heating to 90 ℃ for reaction for 1 hour, adding 25g of 85% phosphoric acid, maintaining the temperature for neutralization for 1.5 hours, heating to 120 ℃, completely removing the moisture in the system in vacuum, breaking vacuum by using N 2 after the analysis moisture is less than 0.02%, adding 5g of magnesium silicate refining agent into the reaction kettle for refining for 2 hours at the maintained temperature, discharging, and filtering solid residues by using a plate-type circulating filter or a Buchner funnel with filter paper to obtain the polyether intermediate.
(4) 120G of polyether intermediate and 0.01g of 10% fluosilicic acid aqueous solution are put into a clean reaction kettle for half an hour of mixing, then 0.125g of DMC catalyst is put into the reaction kettle after being completely mixed, and the temperature is raised to 145 ℃ by starting heating, stirring and vacuum.
(5) And closing vacuum, controlling the reaction temperature to be 140-145 ℃, introducing a mixture of 2450g of propylene oxide and 430g of ethylene oxide, feeding for 7.5 hours, curing for 1.5 hours, cooling to 110 ℃, opening vacuum for degassing for 30 minutes, and removing unreacted volatile components to obtain crude polyether.
(6) Transferring the crude polyether into a glass neutralization reaction kettle, cooling to below 60 ℃, adding 0.5g of 10% NaOH aqueous solution, maintaining the reaction at 50-60 ℃ for 1 hour for alkalization, adding 0.6g of magnesium silicate refining agent, heating to 110 ℃ for dehydration until the water content of the material is lower than 0.02%, and performing filter pressing by using a high-purity glass fiber filter membrane to obtain the finished polyether.
Comparative example 1
An unsaturated polyether was prepared as in example 1, except that:
The initiator in step (1) was only 435g of allyl alcohol.
Unsaturated polyether with molecular weight of 10000 is prepared in a 5L polymerization reaction kettle, and the method comprises the following steps:
(1) 435g of allyl alcohol is added into a clean reaction kettle, stirring is started, 5g of metal potassium is added after N 2 is replaced for 3 times, and the metal potassium is fully reacted to be completely dissolved, and at the moment, if the temperature of the materials is rapidly increased or exceeds 85 ℃, cooling water can be properly started to reduce the temperature of the reactants.
(2) And continuing to replace N 2 for 2 times, maintaining the pressure in the reaction kettle to be slightly higher than the normal pressure, introducing propylene oxide 2540g at the moment, maintaining the reaction temperature at 110 ℃, feeding for 5 hours, and continuing to react for 2.5 hours after the feeding is finished until the reaction is complete.
(3) And completely transferring the materials to a 5L normal pressure glass reaction kettle, adding 300g of deionized water into the reaction kettle, heating to 90 ℃ for reaction for 1 hour, adding 25g of 85% phosphoric acid, maintaining the temperature for neutralization for 1.5 hours, heating to 120 ℃, completely removing the moisture in the system in vacuum, breaking vacuum by using N 2 after the analysis moisture is less than 0.02%, adding 5g of magnesium silicate refining agent into the reaction kettle for refining for 2 hours at the maintained temperature, discharging, and filtering solid residues by using a plate-type circulating filter or a Buchner funnel with filter paper to obtain the polyether intermediate.
(4) 120G of polyether intermediate and 0.01g of 10% fluosilicic acid aqueous solution are put into a clean reaction kettle for half an hour of mixing, then 0.125g of DMC catalyst is put into the reaction kettle after being completely mixed, and the temperature is raised to 145 ℃ by starting heating, stirring and vacuum.
(5) And closing vacuum, controlling the reaction temperature to 140-145 ℃, firstly introducing 480g of propylene oxide, feeding for 1 hour, curing for 0.5 hour, then introducing a mixture of 450g of ethylene oxide and 1350g of propylene oxide, feeding for 3 hours, curing for 0.5 hour after feeding is completed, finally adding 600g of propylene oxide, feeding for 1.5 hours, curing for 1 hour, cooling to 110 ℃, opening vacuum degassing for 30 minutes, and removing unreacted volatile components to obtain crude polyether.
(6) Transferring the crude polyether into a glass neutralization reaction kettle, cooling to below 60 ℃, adding 0.5g of 10% NaOH aqueous solution, maintaining the reaction at 50-60 ℃ for 1 hour for alkalization, adding 0.6g of magnesium silicate refining agent, heating to 110 ℃ for dehydration until the water content of the material is lower than 0.02%, and performing filter pressing by using a high-purity glass fiber filter membrane to obtain the finished polyether.
Test case
The polyether prepared in the above examples and comparative examples was tested for molecular weight, molecular weight distribution coefficient, double bond retention, and impurity content in the product, and the results are shown in Table 1 below.
The detection of the molecular weight and the molecular weight distribution coefficient is determined by GB/T31816-2015;
Detecting double bond retention rate by measuring iodine value with GB/T13892-2020, and converting;
The content of metal impurities in the product is detected by ICP analysis.
TABLE 1
The double bond retention rate has obvious advantages when the allyl alcohol is used as an initiator to prepare polyether, but the reactivity is low in the process of preparing the sealant, so that the compound initiator can be selected in consideration of the balance of the double bond retention rate and the reactivity. The acid promoter catalyst is selected from acids which are acidic and which are free of chemical oxidation and reduction, but organic acids should be avoided as much as possible to reduce side reactions during the polymerization. The high-purity glass fiber filter membrane has the advantages of high filtering speed and capability of absorbing trace metal ions, for example, the conventional glass sand core filtering is adopted, trace metal ions in polyether are required to be re-absorbed by superfine microporous silica before filtering, and then the filtering is carried out for multiple times to ensure that the metal ion content in the polyether meets the raw material requirement of the sealant, so that the process is complex.
In the description of the present application, it should be noted that the directions or positional relationships indicated by the terms "upper", "lower", "inner", "outer", "front", "rear", "left", "right", etc. are directions or positional relationships based on the operation state of the present application are merely for convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements to be referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present application.
In the description of the present application, it should be noted that the terms "mounted," "connected," and "connected" are to be construed broadly, unless otherwise specifically defined and limited. The specific meaning of the above terms in the present application will be understood in specific cases by those of ordinary skill in the art.
The application has been described above in connection with preferred embodiments, which are, however, exemplary only and for illustrative purposes. On this basis, the application can be subjected to various substitutions and improvements, and all fall within the protection scope of the application.
Claims (12)
1. A synthesis process of high molecular weight unsaturated polyether is characterized by comprising the following steps:
(1) Adding a first initiator into a reaction system, replacing with inert gas, adding an alkaline catalyst, performing a reaction to completely dissolve the alkaline catalyst, and adding a second initiator;
(2) Continuously replacing inert gas, feeding a first epoxy monomer at a first reaction temperature, and continuously reacting until the reaction is complete after the feeding is finished to obtain first low molecular weight polyether;
(3) Sequentially carrying out water adding and heating reaction, neutralization, water removal and first refining on the first low molecular weight polyether, discharging and filtering solid residues to obtain second low molecular weight polyether;
(4) Mixing the second low molecular weight polyether with the solution of the acid auxiliary catalyst, adding the double metal cyanide complex catalyst, and starting heating, stirring and vacuum;
(5) Closing vacuum, controlling the second reaction temperature, introducing epoxy monomers for curing, cooling and vacuum degassing.
2. The synthetic process of claim 1 wherein step (5) yields a crude polyether, the synthetic process further comprising the following steps after step (5):
(6) And cooling the crude polyether, sequentially carrying out alkalization, second refining, heating dehydration and filtration to obtain the high molecular weight unsaturated polyether.
3. The synthetic process of claim 1 wherein the acid promoter catalyst in step (4) is fluosilicic acid and/or fluoboric acid.
4. The synthesis process according to claim 2, wherein in the step (4), the mass fraction of the solution of the acid auxiliary catalyst is 5-15%, and the solution amount of the acid auxiliary catalyst is 1-10 ppm of the total designed mass of the high molecular weight unsaturated polyether;
the dosage of the double metal cyanide complex catalyst is 15-65 ppm of the total designed mass of the high molecular weight unsaturated polyether.
5. The synthesis process according to claim 1, wherein in step (4), the double metal cyanide complex catalyst is added after mixing the solution of the second low molecular weight polyether and the acid promoter catalyst for 20 to 60 minutes.
6. The synthetic process of claim 2 wherein said curing of said epoxy monomer in step (5) comprises the steps of, in sequence:
And (3) introducing a second epoxy monomer, performing first curing, introducing a third epoxy monomer, performing second curing, introducing a fourth epoxy monomer, and performing third curing.
7. The synthesis process according to claim 6, wherein the first epoxy monomer in step (2), the second epoxy monomer in step (5), the third epoxy monomer, and the fourth epoxy monomer are each ethylene oxide and/or propylene oxide.
8. The synthesis process according to claim 7, wherein the first epoxy monomer in step (2) is propylene oxide, the second epoxy monomer in step (5) is propylene oxide, the third epoxy monomer is a mixture of ethylene oxide and propylene oxide, and the fourth epoxy monomer is propylene oxide;
And taking the total design mass of the high molecular weight unsaturated polyether as a reference, wherein the feeding mass ratio of the ethylene oxide in the third epoxy monomer is 0-35%.
9. The synthetic process of claim 2 wherein in step (1) the first initiator and the second initiator are each one or more selected from the group consisting of allyl alcohol, methallyl alcohol, N-methallylamine, 3-buten-1-ol;
The molecular weight of the first initiator accounts for 0.05-0.75% of the molecular weight of the high-molecular-weight unsaturated polyether, and the molecular weight of the second initiator accounts for 0.02-1.00% of the molecular weight of the high-molecular-weight unsaturated polyether, based on 5000-15000 of the molecular weight of the high-molecular-weight unsaturated polyether.
10. The synthetic process of claim 9 wherein in step (1) the first initiator is allyl alcohol and the second initiator is 3-buten-1-ol.
11. The synthetic process of claim 2 wherein the filtration in step (6) is a filter press using a glass fiber filter.
12. The synthesis process according to claim 1, wherein the basic catalyst in step (1) is one or more selected from the group consisting of metallic potassium, metallic sodium, sodium methoxide, potassium hydroxide, sodium hydroxide;
the amount of the alkaline catalyst in the step (1) is 0.05-1.00% of the total mass of the second low molecular weight polyether charge obtained in the step (3).
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