CN114106315B - Preparation method of narrow-distribution triethanolamine block polyether, block polyether and application of block polyether - Google Patents
Preparation method of narrow-distribution triethanolamine block polyether, block polyether and application of block polyether Download PDFInfo
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- 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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- 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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- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
Abstract
The invention discloses a preparation method of narrow-distribution triethanolamine block polyether, which comprises the step of carrying out polymerization reaction on triethanolamine serving as an initiator, ethylene oxide and propylene oxide in the presence of a certain amount of phosphazene composite catalyst to obtain the triethanolamine block polyether. According to the invention, a certain amount of phosphazene composite catalyst is added, so that the prepared triethanolamine block polyether has the performance characteristics of short preparation period, narrow distribution, low pour point, low foam and good emulsification effect, and compared with the traditional amine ether, the amine ether catalyst prepared by the method is low in dosage, does not need a refining process of post-treatment, greatly reduces the raw material cost and the production cost, and obtains better technical effect.
Description
Technical Field
The invention belongs to the field of nonionic surfactants, and particularly relates to a preparation method and application of narrow-distribution triethanolamine block polyether.
Background
The block copolymer of Ethylene Oxide (EO) and Propylene Oxide (PO) is a high molecular polyether surfactant, and is a nonionic surfactant which is generally generated by the addition polymerization of a compound containing active hydrogen atoms as an initiator and Ethylene Oxide (EO) and Propylene Oxide (PO) in sequence. In the molecular structure, a polyoxyethylene group (PEO) part is a hydrophilic group, a polyoxypropylene group (PPO) part is a hydrophobic group due to hydrophobicity caused by the existence of methyl, the performance of the PPO part is different according to the relative molecular mass, an initiator, the mixing ratio of EO and PO, the reaction temperature and the like, and the structure of the PPO part is rich in designability. In recent years, block polyethers have been developed rapidly and have penetrated almost every field, such as metal processing, defoaming, emulsification, extraction, biochemical separation, tissue engineering, and pharmaceutical and cosmetic fields.
Most of the prior triethanolamine polyethers are singly processed into polyoxyethylene ether or polyoxypropylene ether, and the only triethanolamine block polyether (patent CN101240062A) has the defects of wide molecular weight distribution, long reaction time, need of a large amount of adsorbent post-treatment and the like. Common catalysts for conventional block polyethers are typically basic materials such as alkali metal methanol/ethoxides, alkali (earth) metal hydroxides, etc., with minor proportions of phosphazene catalysts, which are expensive, or bimetallic DMC catalysts, which are more critical in terms of primer and environmental selection, being the primary reason for their limited use. The most common catalysts used industrially for economic reasons are KOH, NaOH, CH 3 OK、CH 3 ONa and the like, but the molecular weight distribution of the block polyether synthesized by the traditional basic substance catalyst is generally wider, and the influence on the application of the block polyether is larger. In addition, the traditional catalyst has low catalytic efficiency and large catalyst consumption, a neutralization filtration or coalescence separation process is generally adopted in the post-treatment refining link, the application range of a coalescence separator is narrow, the surfactant polyether has good compatibility with water and is not applicable, the neutralization filtration process needs to increase the cost, and a large amount of solid waste is generated.
The prior Chinese patents CN106084199A, CN102924707A and CN 110922580A improve the polyether catalyst, but also have the problems of large catalyst dosage, wide molecular weight distribution (the lowest PDI is 1.35, 1.15 and 1.19 respectively) and the like. The molecular weight distribution PDI of the block polyether prepared by the prior art is generally more than 1.1, which affects the performance of polyether products to a certain extent and also brings about the problems of post-treatment refining links. In addition, the PDI of the block polyethers is difficult to achieve even lower based on the methods of the prior art.
Therefore, a new preparation method of narrow distribution block polyether is still needed, so that the PDI of the prepared block polyether product is less than 1.05 and at least 1.023, the product performance is improved, and meanwhile, the post-treatment refining link is simplified.
Disclosure of Invention
The invention aims to provide a preparation method of novel narrow-distribution triethanolamine block polyether, which enables the PDI of the prepared block polyether product to be at least 1.023 and greatly improves the performance of the polyether product.
It is another object of the present invention to provide a narrow distribution triethanolamine block polyether product prepared by this method.
The invention further aims to provide the application of the narrow-distribution triethanolamine block polyether product in the fields of medicines, cosmetics, fibers, washing, lubrication and polyurethane.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of novel narrow-distribution triethanolamine block polyether is characterized in that triethanolamine is used as an initiator to carry out polymerization reaction with ethylene oxide and propylene oxide in the presence of a certain amount of phosphazene composite catalyst to prepare the triethanolamine block polyether.
In a specific embodiment, the preparation method of the novel narrow distribution triethanolamine block polyether comprises the following steps:
(1) mixing triethanolamine and a phosphazene composite catalyst, and removing moisture and impurity monomers after purging and displacement by using nitrogen;
(2) adding epoxy ethane (propane) into a catalyst-containing triethanolamine initiator, reacting, and aging to obtain an intermediate product;
(3) and adding epoxypropane (ethyl) alkane into the intermediate product, reacting and aging to obtain the final product triethanolamine block polyether.
In a specific embodiment, the phosphazene composite catalyst is a mixture prepared by compounding an alkali catalyst, a crown ether and a phosphazene catalyst in a ratio of 1-6: 2-10: 2-40 by mass, preferably 1: 2-8: 6 to 30.
In a specific embodiment, the addition amount of the phosphazene composite catalyst is 0.001-1% of the total mass of the triethanolamine, the ethylene oxide and the propylene oxide; preferably, the reaction molar ratio of the triethanolamine to the ethylene oxide and the propylene oxide is 1: m: n, wherein m and n are selected from integers of 0-200, but at least one of m and n is not 0; more preferably, the triethanolamine block polyether has a molecular weight distribution coefficient of less than 1.05.
In a specific embodiment, the phosphazene catalyst is any one or a mixture of a phosphazene compound, a phosphazene salt and a phosphazene oxide.
In a specific embodiment, the base catalyst is any one or a mixture of sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium methoxide and sodium methoxide.
In a particular embodiment, the crown ether is any one or a mixture of 12-crown-4, 15-crown (ether) -5, 18-crown (ether) -6.
In a specific embodiment, the polymerization reaction temperature in the steps (2) and (3) is 90-180 ℃, the reaction pressure is 0.1-0.6 MPa, and the reaction time is 1-20 hours.
In another aspect of the present invention, a novel narrow distribution triethanolamine block polyether prepared by the foregoing method has a reaction formula:
wherein m is an integer of 0 to 200, n is an integer of 0 to 200, and at least one of m and n is not 0; the molecular weight distribution coefficient of the triethanolamine block polyether is lower than 1.05.
In another aspect of the present invention, the novel narrow distribution triethanolamine block polyether belongs to the field of nonionic surfactants, and is used in the fields of medicine, cosmetics, fiber, washing, lubrication and polyurethane.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the novel narrow-distribution triethanolamine block polyether adopts a novel phosphazene composite catalyst, takes triethanolamine as an initiator, and carries out polymerization reaction with ethylene oxide and propylene oxide to prepare the triethanolamine block polyether. The complex is formed by crown ether and potassium ions in the special phosphazene composite catalyst, so that the reaction rate of a PO section is greatly accelerated, the product presents the characteristic of narrow distribution due to larger steric hindrance of the phosphazene catalyst, the phosphazene catalytic efficiency is higher under the alkaline condition, and the reaction time is greatly shortened.
(2) According to the preparation method, the catalyst dosage of the whole process is 10% of that of the catalyst in the conventional process, the raw material cost is greatly reduced, the sodium and potassium dosages are less, additional refining treatment such as adsorption is not needed, and the production cost is greatly reduced.
(3) The block polyether prepared by the method has small molecular weight distribution coefficient, and the hydroxyl value is closer to the design value, which shows that the method of the invention is easy to customize polyether products with different foam heights and emulsifying performances according to the requirements of customers, and only needs to adjust the molar ratio of EO/PO on the basis of the method of the invention.
(4) The block polyether prepared by the method has low impurity content, small molecular weight distribution coefficient (lower than 1.05) and can reach 1.023 at least, so that the polyether product has the advantages of high transparency, low pour point, low foam, good emulsifying property and the like, and has good application prospect in the fields of daily chemical products, metal cleaning, coatings, oil field industry and the like.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
A novel narrow distribution triethanolamine block polyether having the following reaction formula:
wherein m is an integer of 0 to 200, n is an integer of 0 to 200, and at least one of m and n is not 0; preferably, m is an integer of 2-100 and/or n is an integer of 1-100; more preferably, m is an integer of 3 to 60 and/or n is an integer of 3 to 45. Namely, the triethanolamine, the ethylene oxide and the propylene oxide in the reaction system are mixed according to the proportion of 1: m: n, wherein m and n are selected from the integers which are not 0 at the same time.
Wherein, the molecular weight distribution coefficient (PDI) of the novel narrow-distribution triethanolamine block polyether is lower than 1.05, and can be as low as 1.023, and compared with the prior art which is generally higher than 1.1, the narrow-distribution triethanolamine block polyether has remarkable progress.
The preparation method of the novel narrow-distribution triethanolamine block polyether comprises the following steps:
(1) mixing triethanolamine and a phosphazene composite catalyst, and removing moisture and impurity monomers after purging and displacement by using nitrogen;
(2) adding ethylene oxide (propylene) alkane into an initiator containing a catalyst, reacting and aging to obtain an intermediate product;
(3) adding epoxypropane (ethyl) alkane into the intermediate product, reacting and aging to obtain a final product;
the phosphazene composite catalyst is a mixture of an alkali catalyst, crown ether and a phosphazene catalyst, and is prepared by compounding the alkali catalyst, the crown ether and the phosphazene catalyst according to the mass ratio of 1-6: 2-10: 2-40, preferably 1: 2-8: 6-30. The addition amount of the phosphorus-nitrile composite catalyst is 0.001-1% of the total mass of the triethanolamine, the ethylene oxide and the propylene oxide, and the preferable content of the catalyst is 0.02-0.3% of the total mass of the triethanolamine, the ethylene oxide and the propylene oxide.
The phosphazene catalyst is a phosphazene catalyst, is selected from one or more of a phosphazene compound, a phosphazene salt and phosphonitrile oxide, and is preferably a phosphazene compound; specifically, the phosphazene compound includes, for example, but not limited to, hexachlorocyclotriphosphazene, phosphonitrilic trimer chloride, and the like; the phosphazene salt includes, for example, but is not limited to [ (C) 6 H 11 )CH 3 N] 4 P + BF 4 - Etc.; examples of said phosphonitrilic oxide include, but are not limited to, hexaphenoxycyclotriphosphazene, methoxyphosphazene, guanidino-substituted phosphonitrilic oxide [ (NMe) 2 ) 2 C＝N] 3 PO, and the like.
The alkali catalyst is selected from one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium methoxide and sodium methoxide, and is preferably potassium hydroxide, potassium methoxide and sodium methoxide; the crown ether is selected from any one or more of 12-crown-4, 15-crown (ether) -5 and 18-crown (ether) -6, and is preferably 18-crown (ether) -6. The alkali catalyst, the crown ether and the phosphazene catalyst in the phosphazene composite catalyst adopt high-purity reagents sold in the market, and do not need to be prepared into solution or other pretreatment.
Adding the triethanolamine and phosphazene composite catalyst into a high-temperature high-pressure reaction kettle, sealing the reaction kettle, purging and replacing twice with nitrogen before heating, heating to 80-100 ℃, keeping the temperature of the reaction kettle at 80-100 ℃, and vacuumizing for 1-3 hours to remove water and impurity monomers in a reaction system.
And (2) after the dehydration is finished, keeping the temperature of the reaction kettle at 90-180 ℃, starting to add ethylene oxide (propylene) into the reaction kettle, controlling the pressure of the reaction kettle to be 0.1-0.6 MPa, finishing the addition of the ethylene oxide (propylene) for 0.5-8 h, and aging for a period of time until the pressure is unchanged for 20min after the material is added. The preferable reaction temperature is 100-140 ℃, and the preferable pressure is not more than 0.3 MPa.
And (3) specifically, adding epoxypropane (ethyl) alkane into the aged intermediate product, controlling the temperature of the reaction kettle to be 90-180 ℃, the pressure to be 0.1-0.6 MPa, and finishing the addition within 0.5-8 h, and after the material is added, aging for a period of time until the pressure is unchanged for 20 min. Cooling to about 80 ℃ to remove unreacted monomers. Adding organic acid (such as acetic acid and lactic acid) according to the molar weight of 1-1.05 times of the catalyst, neutralizing for 1h at the temperature of 80-90 ℃, dehydrating and deacidifying for 0.5h, and discharging. The preferable reaction temperature is 100-140 ℃, and the preferable pressure is not more than 0.3 MPa. Wherein, the operations of removing single, dehydrating, deacidifying, discharging and the like can refer to the prior art. For example, the operation of removing the single, dehydrating and deacidifying is specifically to adjust the rotating speed of a stirring paddle of the reaction kettle to 200-300 r/min, the temperature is 80-90 ℃, and the vacuum pumping is continuously carried out; the discharging operation is specifically to open a bottom valve of the reaction kettle and an atmospheric communication valve at about 60 ℃, and hold the product by a reagent bottle.
The order of adding ethylene oxide and propylene oxide in the above step (2) and step (3) is not limited at all, for example, ethylene oxide may be added in step (2), and in this case, propylene oxide is added correspondingly in step (3); similarly, when propylene oxide is added in the step (2), in this case, ethylene oxide is correspondingly added in the step (3), and the conditions of reaction temperature, pressure and the like in the reactor are still performed according to the conditions defined in the step (2) and the step (3) regardless of the addition sequence.
The polymerization reaction of the block polyether can be carried out in any known reactor, as long as the corresponding temperature and pressure can be satisfied and the vacuum condition can be provided, for example, the reaction vessel is any one of a tubular reactor, a stirred tank, a loop reactor and a jet reactor, but is not limited thereto.
The molecular weight distribution coefficient (PDI) of the novel narrow-distribution triethanolamine block polyether prepared by the method is lower than 1.05, and can be as low as 1.023; the molecular weight of the triethanolamine block polyether can be 400-6000 g/mol; wherein, the relative molecular weight of the ethylene oxide in the molecular chain of the triethanolamine block polyether can be 5-95%.
The invention overcomes the problems of low general activity and small reaction steric hindrance of the catalyst in the prior art, and avoids the inherent defects that EO/PO randomly reacts with a substrate and cannot preferentially and selectively generate short-chain reaction. The technical purpose of the invention is realized by the high-efficiency and high-selectivity phosphazene composite catalyst and the accurate control of the reaction process. The invention also thoroughly solves the problems that the residual of the bottom alcohol in the finished product of the polyether with small molecular weight and the PDI are generally more than 1.1, and also avoids the unfavorable situations that the yield of the product is reduced and the PDI is increased because the EO and PO isomeric acetaldehyde and acrolein or formaldehyde and other byproducts are generated by reacting with oxygen due to overlong reaction time and the airtightness of the device does not reach 0 oxygen.
Through analysis and comparison of the existing synthesis method of the triethanolamine polyether product, a two-step synthesis route of adding epoxy ethane (propane) firstly and then adding epoxy propane (ethane) for polymerization is adopted, and through optimized catalyst proportion and repeated experimental study, technological parameters and conditions such as raw material proportion, catalyst dosage, polymerization reaction temperature, time and the like are reasonably determined, the reaction condition is mild, the reaction time is short, and the control is easy, the adjustable molecular weight range of the prepared triethanolamine block polyether is 400-6000 g/mol, the hydroxyl value is 28.05-420.75 mgKOH/g, the molecular weight distribution coefficient is generally lower than 1.05 and can be as low as 1.023, the appearance color is light and the transparency is high, the sodium and potassium ion content is low, no post-treatment is needed, the cost is low, the three wastes are few, and the method has a good application prospect in the field of surfactants, and is particularly used for medicines, cosmetics, fibers, washing, lubrication and the like, In the field of polyurethanes.
The invention is further illustrated by the following more specific examples, which are given by way of illustration only and are not to be construed as limiting the invention in any way.
The following examples used the following sources of starting materials:
18-crown (ether) -6: an Aladdin reagent with the purity of 99 percent;
15-crown (ether) -5: an Aladdin reagent with the purity of 97 percent;
12-crown (ether) -4: an alatin reagent with the purity of 98 percent;
sodium methoxide: an alatin reagent, a 30% pure methanol solution;
KOH: 95% for industrial use;
potassium methoxide: an Aladdin reagent with the purity of 99 percent;
anhydrous lithium hydroxide: an Aladdin reagent with the purity of 99.99 percent;
phosphazene: qike phosphazene catalyst (40% ethanol solution);
glacial acetic acid: the purity of the traditional Chinese medicine reagent is 99.9%;
EO/PO were produced by itself using a Wanhua apparatus.
The hydroxyl value in the present invention is measured according to the benzene blending method described in national Standard GB 12008.3-89 "method for measuring hydroxyl value in polyether polyol".
The molecular weight distribution of the polyether is determined by Gel Permeation Chromatography (GPC), and the molecular weight distribution coefficient PDI can be obtained simultaneously in a GPC chart.
The content of sodium and potassium ions is measured by adopting a flame photometer, potassium and sodium ions of a sample to be measured are diluted to 0-100 ppm by 70% ethanol, and data can be directly read and multiplied by the dilution factor.
The appearance is determined by visual observation after the glass is placed for 2 hours at constant temperature.
Method for measuring emulsifying property: 40mL of a sample with a mass fraction of 0.1% and the same volume of liquid paraffin were vigorously stirred at 25 ℃ for 1min in a 250mL beaker, poured into a 100mL graduated cylinder, and the time(s) for 10mL of the aqueous phase to separate was recorded.
Example 1
The preparation method of triethanolamine polyoxypropylene polyoxyethylene ether comprises the following specific steps:
149.19g (1mol) of triethanolamine and a phosphazene composite catalyst which is equivalent to 0.02 percent of the total mass of the triethanolamine, PO and EO are added into a self-priming stirring reaction kettle. After the reaction kettle is sealed, nitrogen is used for replacing the reaction kettle for 3 times, and the reaction kettle is vacuumized for 1 hour after being heated to 80 ℃ to remove water and methanol. The composition of the phosphazene composite catalyst is KOH: 18-crown-6 ether and phosphazene is 1:2: 7. And after dehydration is finished, keeping the temperature of the reaction kettle at 120-125 ℃, adding 2610g of propylene oxide, controlling the pressure below 0.3MPa, finishing the addition for 5 hours, and continuing to react and age until the pressure is not reduced any more. Cooling to below 60 ℃ because the capacity of the kettle is limited, taking out part of the intermediate, leaving 689.8g of the intermediate in the reaction kettle, replacing 3 times with nitrogen, heating to 120 ℃, introducing 330g of ethylene oxide, controlling the pressure to be below 0.3MPa, finishing the addition within 2h, continuing the aging reaction for a period of time until the pressure is not reduced, cooling to 75-80 ℃, removing the monomer for 1h, adding a proper amount of acetic acid into the product to neutralize the pH to about 7, removing the water and the unreacted acetic acid, and discharging. The hydroxyl value, molecular weight distribution coefficient, sodium and potassium ion content, appearance, emulsifying property and the like of the product are measured.
Examples 2 to 7
The rest of the process is the same as the process of example 1, except that the amount of the catalyst, the compounding ratio of the catalyst, the reaction time, and the molar ratio of triethanolamine to PO and EO are different, and the specific ratios and parameters are shown in table 1, wherein comparative examples 1 to 3 are control groups. The parameter indexes and the detection of the polyether products prepared in the examples and the comparative examples are shown in the table 2.
Table 1 table of process parameters of the examples
TABLE 2 product parameter Performance Table
From the results, compared with the ordinary catalyst or the single phosphazene catalyst in the comparative example, when the number of EO/PO is the same, the usage amount of the phosphazene composite catalyst in the example 1 is only 10% of that in the comparative example, and the reaction time is shortened by about half, which shows that the method of the invention has the obvious advantages of high reaction rate and high catalytic efficiency. The comparison of the five groups of 0.2 percent sodium methoxide catalysis in the comparative example 1, 0.2 percent phosphonitrile catalysis in the comparative example 2 and 0.2 percent KOH catalysis in the comparative example 3 shows that the hydroxyl value of the block polyether prepared by the phosphonitrile composite catalyst is closer to the designed value and the molecular weight is closer to the designed value when the number of grafted EO/PO is the same under the catalytic reaction condition of lower composite catalyst dosage in the examples 1 and 2, and the specific expression is that the molecular weight distribution coefficient is closer to the ideal value 1. Meanwhile, compared with the catalyst used in the embodiment 1, the catalyst used in the embodiment 2 is slightly larger, the hydroxyl value of the final product is closer to the designed value, and the molecular weight distribution coefficient is narrower. The invention can realize high catalytic efficiency by adjusting the proportion and the dosage of the phosphazene composite catalyst, has low molecular weight distribution coefficient, particularly the molecular weight distribution coefficient can reach 1.025 and 1.023 in examples 1 and 2, has the most direct influence that the product has high content of effective components, low content of high molecular weight components and low pour point, and can be compared from the product form at 10 ℃, and the block polyether product with narrow molecular weight distribution obtained by the invention is liquid, thereby providing convenience for the application of the product in winter, particularly the application in the north.
The foam height and the emulsifying property of the product are mainly related to the molar ratio of EO/PO, and when the EO occupation ratio is high, namely the hydrophilic group content is high, the foam height is large; PO is lipophilic, can effectively reduce the surface tension of the formed foam surface, causes the foam to break and disappear, and has obvious defoaming effect. High foam and low foam have different requirements in different fields, and low foam is better in the fields of industrial cleaning and lubrication, but in some fields, the opposite is true, such as daily chemicals, bath lotion, facial cleanser and the like, the pursuit is that much foam and fine foam are obtained; the narrow distribution product can more easily meet the corresponding foam requirement according to the corresponding design value. The low foaming properties are more pronounced, as are the emulsifying properties. Generally, the emulsifiability is related to the EO amount, the EO content is high, the emulsifying property is good, precise adjustment is needed for obtaining products with good emulsifying and foaming properties, and the products in examples 3 and 4 have lower foam height and better emulsifying property, so that the products have certain advantages in application. The block polyether based on the invention has narrower molecular weight distribution coefficient, and the hydroxyl value is closer to the theoretical design value, so that the performance of the product can meet the requirements of different customers by adjusting the EO/PO molar ratio on the basis, and even can be customized according to the requirements; the molecular weight distribution coefficient of the prior art is generally higher than 1.15, and the prior art cannot be customized according to requirements. From the comparison between example 2 and comparative examples 1, 2 and 3, it can be seen that the phosphazene composite catalyst product has certain advantages in emulsification and low foam with other catalyst products. In addition, theoretically, when the crown ether and the alkali are in equal molar quantity, the sodium and potassium ions are completely complexed, the catalytic efficiency is higher, and the proportion of the phosphazene catalyst is properly adjusted on the basis of the complete complexation of the sodium and potassium, so that the purposes of reducing the sodium and potassium content and improving the catalytic efficiency can be achieved, and the product design scheme is optimized to match different customer requirements. According to the invention, in the presence of an alkali catalyst, crown ether and a phosphazene catalyst of a phosphazene composite catalyst, according to a preferred scheme 1: 2-8: 6-30, the sum of the sodium content and the potassium content of the obtained block polyether product is less than 50ppm, so that the block polyether product can be directly used without refining post-treatment, and the production cost is greatly reduced.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (12)
1. A preparation method of narrow-distribution triethanolamine block polyether is characterized in that triethanolamine is used as an initiator to carry out polymerization reaction with ethylene oxide and propylene oxide in the presence of a certain amount of phosphazene composite catalyst to prepare triethanolamine block polyether; the phosphazene composite catalyst is a mixture formed by compounding an alkali catalyst, crown ether and a phosphazene catalyst in a ratio of 1-6: 2-10: 2-40 by mass; the alkali catalyst is any one or a mixture of several of sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium methoxide and sodium methoxide.
2. The method for preparing narrow distribution triethanolamine block polyethers according to claim 1, comprising the following steps:
(1) mixing triethanolamine and a phosphazene composite catalyst, and removing moisture and impurity monomers after purging and displacement by using nitrogen;
(2) adding ethylene oxide into a triethanolamine initiator containing a catalyst, reacting and aging to obtain an intermediate product;
(3) adding propylene oxide into the intermediate product, reacting and aging to obtain a final product triethanolamine block polyether;
or adding propylene oxide in the step (2), and correspondingly adding ethylene oxide in the step (3).
3. The preparation method of narrow-distribution triethanolamine block polyether according to claim 1 or 2, wherein the weight ratio of the base catalyst to the crown ether to the phosphazene catalyst in the phosphazene composite catalyst is 1: 2-8: 6 to 30.
4. The preparation method of the narrow-distribution triethanolamine block polyether as claimed in claim 3, wherein the amount of the phosphazene composite catalyst is 0.001% -1% of the total mass of triethanolamine, ethylene oxide and propylene oxide.
5. The method for preparing narrow distribution triethanolamine block polyethers according to claim 4, wherein the reaction molar ratio of triethanolamine to ethylene oxide and propylene oxide is 1: m: n, wherein m and n are selected from integers of 0-200, but both m and n are not 0.
6. The method of claim 5, wherein the triethanolamine block polyether has a molecular weight distribution coefficient of less than 1.05.
7. The method for preparing narrow distribution triethanolamine block polyether of claim 3, wherein the phosphazene catalyst is a phosphazene compound.
8. The method for preparing narrow distribution triethanolamine block polyether of claim 3, wherein the phosphazene catalyst is one or more of phosphazene salt and phosphazene oxide.
9. The method for preparing narrow distribution triethanolamine block polyethers according to claim 3, wherein the crown ethers are any one or a mixture of several of 12-crown-4, 15-crown-5, 18-crown-6.
10. The method for preparing narrow-distribution triethanolamine block polyether according to claim 2, wherein the polymerization temperature in the steps (2) and (3) is 90-180 ℃, the reaction pressure is 0.1-0.6 MPa, and the reaction time is 1-20 hours.
11. A narrow distribution triethanolamine block polyether prepared by the process according to one of claims 1 to 10, the triethanolamine is reacted with ethylene oxide and propylene oxide in a molar ratio of 1: m: n, m is an integer of 0-200, n is an integer of 0-200, and both m and n are not 0; the molecular weight distribution coefficient of the block polyether is lower than 1.05.
12. The narrow triethanolamine block polyether according to claim 11, which is a nonionic surfactant used in the fields of pharmaceuticals, cosmetics, fibers, detergents, lubricants and polyurethanes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101240062A (en) * | 2007-12-21 | 2008-08-13 | 王伟松 | Synthetic method for triethanolamine block polyether |
| CN107573499A (en) * | 2017-09-15 | 2018-01-12 | 延安大学 | A kind of preparation method of crude oil demulsifier |
| JP2018178100A (en) * | 2017-04-05 | 2018-11-15 | 三洋化成工業株式会社 | Polyol composition for manufacturing polyurethane foam, and polyurethane foam |
| CN110922580A (en) * | 2019-12-12 | 2020-03-27 | 山东一诺威新材料有限公司 | Preparation method of high molecular weight high activity polyether polyol |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240062A (en) * | 2007-12-21 | 2008-08-13 | 王伟松 | Synthetic method for triethanolamine block polyether |
| JP2018178100A (en) * | 2017-04-05 | 2018-11-15 | 三洋化成工業株式会社 | Polyol composition for manufacturing polyurethane foam, and polyurethane foam |
| CN107573499A (en) * | 2017-09-15 | 2018-01-12 | 延安大学 | A kind of preparation method of crude oil demulsifier |
| CN110922580A (en) * | 2019-12-12 | 2020-03-27 | 山东一诺威新材料有限公司 | Preparation method of high molecular weight high activity polyether polyol |
Non-Patent Citations (1)
| Title |
|---|
| 环氧化合物开环聚合催化剂的研究进展;陈华等;《化学工业与工程技术》;20080430;第29卷(第2期);40-45 * |
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