CN112791663A - Melamine-based surfactant and preparation method thereof - Google Patents
Melamine-based surfactant and preparation method thereof Download PDFInfo
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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
- C08G65/32—Polymers modified by chemical after-treatment
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Abstract
The invention relates to a melamine-based surfactant and a preparation method thereof, and mainly solves the technical problems of poor emulsifying property and low activity of the surfactant in heavy oil reservoirs in the existing enhanced oil recovery technology. The invention adopts a melamine-based surfactant, which has a molecular general formula as follows: wherein R is1～R6Is H, C1～C50At least one of aliphatic group and/or aromatic group of (a), and R1～R6At least one of the technical schemes is not H, and the novel melamine-based surfactant is adopted, so that the technical problem that the conventional surfactant is poor in thick oil emulsifying capacity is well solved, and the novel melamine-based surfactant can be used in the enhanced oil recovery process of an oil field.
Description
Technical Field
The invention relates to a melamine-based surfactant and a preparation method thereof.
Background
With the increase of world energy demand, the reasonable development and utilization of petroleum have attracted great attention of people, and the requirements on the production quantity and the production efficiency of petroleum are higher and higher. The method realizes the efficient exploitation of oil and gas resources, and has practical significance and important strategic significance for improving the yield of crude oil. Conventional oil recovery methods (primary and secondary methods) generally only recover 1/3, which is the geological reserve of crude oil, and also fail to recover about 2/3 of crude oil, and thus enhanced oil recovery has been a significant issue in oil recovery research. The tertiary oil recovery technology is an effective method for improving the oil recovery rate and can be divided into four categories, namely thermal flooding, steam flooding, in-situ combustion and the like; second, miscible flooding, comprising CO2Miscible phase, hydrocarbon miscible phase and other inert gas miscible phase flooding; thirdly, chemical flooding; and fourthly, microbial oil recovery, including biopolymer and microbial surfactant flooding. Chemical flooding is a very important and large-scale technology implemented in enhanced oil recovery, and includes polymer flooding, surfactant flooding, alkali water flooding, concentrated sulfuric acid flooding and the like, as well as various combination technologies of polymer, alkali and surfactant. The chemical flooding effect is the result of physical action, which is the sweeping action of the displacement fluid, and chemical action, which is the microscopic displacement action of the displacement fluid. The key to the chemical action is to reduce the interfacial tension of the displacement fluid and the crude oil and improve the oil washing efficiency. The surfactant has both oleophilic (hydrophobic) and hydrophilic (oleophobic) properties, so that when the surfactant is dissolved in water, molecules are mainly distributed on an oil-water interface, and the oil-water interface tension can be remarkably reduced. The reduction of the oil-water interfacial tension means the reduction of the work of adhesion, i.e., the crude oil is easily eluted from the surface of the formation, thereby improving the oil washing efficiency. The oil displacement effect of the surfactant is also shown in the effects of reversing the wettability of the oleophilic rock surface, emulsifying crude oil, improving the surface charge density, merging oil drops and the like, which is the reason why the surfactant plays a significant role in the chemical flooding technology.
At present, the most used tertiary oil recovery surfactants at home and abroad are petroleum sulfonate, alkylbenzene sulfonate, olefin sulfonate and other surfactants, and are referred to as CN1203935A, CN1566258A, CN1458219A, CN1426833A and US 2010/0282467. The surfactant has the advantages of wide source, low cost and the like. However, with the increasing depth of the exploitation degree of the oil field and the increasing depth of the oil extraction stratum, the use temperature of the surfactant is higher and higher, and the mineralization degree of water quality is higher and higher. However, the salt tolerance of the surfactant, especially the divalent cation tolerance, is poor, so that the surfactant cannot be applied to high-temperature and high-salinity oil field blocks. Therefore, the development of the novel temperature-resistant salt-resistant surfactant has great significance for the tertiary oil recovery industry.
In recent years, anionic and nonionic surfactants have attracted attention because of their heat resistance of anionic surfactants and salt resistance of nonionic surfactants. The anionic nonionic surfactant mainly comprises alkoxy carboxylate, alkoxy sulfonate, alkoxy sulfate salt and the like. For example, Zhang Yongmin and Zhang Hujun respectively report the performances of anionic and nonionic surfactants such as sodium nonylphenol polyoxyethylene ether sulfonate and sodium fatty alcohol polyoxyethylene ether sulfonate (see: 2009, 26(2), 4-7; oilfield chemistry, 2009, 26(1), 72-75; chemical research and application, 2009, 21(7), 964-968; daily chemical industry, 2008, 38(4), 253-256; CN 201210188897.6). The use of anionic and nonionic surfactants such as alkoxy carboxylates and alkoxy sulfonates in enhanced Oil recovery has also been reported by the university of Texas, Austin division, USA, Oil Chem Technology, BASF, respectively. (see SPE 154256; SPE 154261; US 7,629,299; US 20120120101010; US2011120707A 1; US20140116690A 1). In the above anionic nonionic surfactants, the nonionic moiety is solely ethoxy and/or propoxy. In US20110281779, however, anionic nonionic surfactants R containing a non-ionic segment of butoxy BO, propoxy PO and ethoxy EO are disclosed1-BOx-POy-EOz-X-Ya- a/b Mb+And shows better performance. Wherein R is1From C12-C36 linear or branched fatty alcohols through Guerbet reaction dimerizes.
Disclosure of Invention
The invention relates to a novel melamine-based surfactant, which simultaneously contains melamine group and composite polyether functional groups BO, PO and EO in the molecular structure, thereby solving the technical problems of poor emulsifying property and low activity of the surfactant for heavy oil reservoirs in the prior intensified oil recovery technology.
One of the technical problems to be solved by the invention is to provide a novel melamine-based surfactant aiming at the technical problems of poor emulsifying property and low activity of the heavy oil reservoir surfactant in the prior art.
The second technical problem to be solved by the invention is to provide a preparation method of the melamine-based surfactant. The method has the characteristics of simple process, mild reaction conditions and high product yield.
The invention aims to solve the technical problem of providing the application of the melamine-based surfactant.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a melamine-based surfactant having the general molecular formula:
wherein R is1～R6Independently selected as H, C1～C50And R is at least one of alkyl, alkenyl, aryl or substituted alkyl, alkenyl, aryl of (A), and1～R6at least one of which is not H.
In the above technical scheme, R1～R6Independently preferably H, C1～C30At least one of alkyl, alkenyl, aryl or substituted alkyl, alkenyl, aryl.
In the above technical scheme, R1～R6Independently more preferably H, C1～C20At least one of alkyl, alkenyl, aryl or substituted alkyl, alkenyl, aryl.
In the above technical scheme, R1～R6Preferably two, three, four, five or six are not H.
In the above technical scheme, R which is not H1～R6Also preferably contains at least one of ethoxy, propoxy and butoxy groups.
In the technical scheme, the polymerization degree of the ethoxy, propoxy and butoxy is independently and preferably selected from any one of the number of 0-100 and more than 0; more independently, it is preferably any number selected from 1 to 50.
To solve the second technical problem, the invention adopts the following technical scheme: a preparation method of melamine-based surfactant comprises the following steps:
a) carrying out alkoxylation on an initiator and optional required amount of ethylene oxide, propylene oxide and butylene oxide under the action of a catalyst to obtain polyether polyol nonionic surfactant; wherein the initiator is C with carbon atom number1～ C50Preferably C, at least one of aliphatic alcohol, aromatic alcohol and alkylphenol1～C30More preferably C1～ C20；
b) And c) carrying out substitution reaction on the polyether polyol nonionic surfactant synthesized in the step a) and melamine to obtain the melamine-based surfactant.
In the technical scheme, the reaction temperature of the alkoxylation reaction is preferably 140-200 ℃, and the pressure is preferably 0-5 MPa; the molar ratio of the initiator to the ethylene oxide, the propylene oxide and the butylene oxide is independently preferably 1 (1-50); the catalyst is preferably an alkali metal hydroxide, a DMC (double metal polyether) catalyst or a phosphazene catalyst, and the using amount of the catalyst is preferably 0.001-2.0% of that of the initiator.
In the technical scheme, in the step b), the mole ratio of the polyether polyol nonionic surfactant to the melamine is preferably (1-6): 1; the reaction temperature of the substitution reaction is preferably 150-300 ℃, and the reaction time is preferably 0.5-10 hours; the substitution reaction is preferably carried out using LewisThe acid catalyst may be a Lewis acid catalyst commonly used in the art, such as but not limited to AlCl3、BF3、SbCl5、FeBr3、FeCl3、SnCl4、TiCl4、ZnCl2Phosphoric acid, and the like.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the application of melamine-based surfactant is disclosed, wherein the melamine-based surfactant is the melamine-based surfactant described in any one of the above technical solutions or the melamine-based surfactant prepared by the preparation method described in any one of the above technical solutions.
In the above technical scheme, the application is not particularly limited, for example, but not limited to the application in oil and gas field enhanced oil recovery, for example, the aqueous solution containing the surfactant of the present invention is injected into the underground to enhance oil and gas field recovery, especially for thick oil, including common thick oil, extra thick oil and super thick oil, which can form 10 with underground crude oil at a concentration of more than 0.05%-3The ultra-low interfacial tension of milli-Newton/m, the solubilization parameter reaches more than 8.
The melamine-based surfactant enhances the interaction between the surfactant and the components of the thickened oil and the molecules of the crude oil by introducing the substituent containing alkoxy into the melamine aromatic heterocycle, so that the surfactant has the functions of solubilizing and emulsifying the thickened oil.
The melamine-based surfactant used in the surfactant composition for tertiary oil recovery has the following advantages:
(1) the surfactant has high interfacial activity and strong emulsifying capacity. Aiming at thick oil, including common thick oil, extra thick oil and super thick oil, when the concentration is more than 0.05 percent, the thick oil and underground crude oil can form 10-3The milli-Newton/m ultra-low interfacial tension, the solubilization parameter reaches more than 8, and the emulsifying agent has the advantages of strong emulsifying capacity and high activity to the thickened oil.
(2) High heat resistance and high salt resistance. Because the salt-resistant material contains non-ionic groups such as BO, PO, EO and the like, the salt resistance of the salt-resistant material is obviously improved; different functional groups are connected through C-C bonds or C-O bonds, so that the hydrothermal stability is high.
The invention is further illustrated by the following examples.
Detailed Description
Example 1 Synthesis of methyl polyether Melamine surfactant
Adding a certain amount of methanol and 1% KOH (potassium hydroxide) by mass as a catalyst into a polymerization reaction kettle, heating the system to 200 ℃ under stirring, slowly introducing metered butylene oxide, and controlling the reaction pressure to be less than 5.0MPa to carry out etherification reaction. After the reaction is finished, cooling to 180 ℃, continuously and slowly introducing the calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding the calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), purging the system by using nitrogen, and removing unreacted ethylene oxide to obtain the methyl polyether polyol.
1 percent of aluminum trichloride catalyst and 2 times of H by mass of the product obtained in the previous step2Adding O and melamine (the mol ratio of the melamine to the methyl polyether polyol is 1:2) into a reactor, starting stirring, heating to 280 ℃ and reacting for 5 hours to obtain a target product. The structure is shown in table 1.
Example 2 Synthesis of oleyl polyether melamine surfactant
Adding a certain amount of oleyl alcohol (cis-9-octadecenol), 0.5% of KOH by mass and 30ppm of phosphazene catalyst into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, purging for 3-4 times by using nitrogen to remove air in the system, raising the reaction temperature to 200 ℃, slowly introducing metered butylene oxide, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. After the reaction is finished, cooling to 180 ℃, continuously and slowly introducing the calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding the calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), purging the system by using nitrogen, and removing unreacted ethylene oxide to obtain the oleyl polyether polyol.
The product obtained above was mixed with 2.0% by mass of a phosphoric acid catalyst and 5 times by mass of H2Adding O and melamine (the mol ratio of the melamine to the oleyl alcohol polyether polyol is 1:1) into a reactor, starting stirring, heating to 200 ℃ and reacting for 10 hours to obtain a target product. The structure is shown in table 1.
Example 3 Synthesis of Aniline polyether Melamine surfactant
Adding a certain amount of aniline, 0.5% KOH and 0.01% of bimetallic polyether catalyst (DMC) in terms of mass into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, purging with nitrogen for 3-4 times to remove air in the system, raising the reaction temperature to 200 ℃, slowly introducing metered butylene oxide, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. After the reaction is finished, cooling to 140 ℃, adding a calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system by using nitrogen to remove unreacted ethylene oxide to obtain the aniline polyether polyol.
The product obtained above was mixed with 0.5% by mass of a phosphoric acid catalyst and 4 times by mass of H2Adding O and melamine (the mol ratio of the melamine to the aniline polyether polyol is 1:1) into a reactor, starting stirring, heating to 250 ℃ and reacting for 6 hours to obtain a target product. The structure is shown in table 1.
Example 4 Synthesis of coconut oil diethanolamide polyether Melamine surfactant
Adding a certain amount of coconut oil diethanolamide (C) into a polymerization reaction kettle11H23CON(CH2CH2OH)2) And KOH accounting for 1.0 percent of the mass of the catalyst, heating the system temperature to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, purging with nitrogen for 3-4 times to remove air in the system, raising the reaction temperature to 180 ℃, slowly introducing metered propylene oxide, and controlling the reaction pressure<Etherification reaction is carried out under 2.0 MPa. After the reaction is finished, cooling to 150 ℃, adding the calculated amount of ethylene oxide, and carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged)) And blowing the system by using nitrogen to remove unreacted ethylene oxide to obtain the coconut oil diethanolamide polyether polyol.
The product obtained above was mixed with 1.5% by mass of a phosphoric acid catalyst and 8 times by mass of H2Adding O and melamine (the mol ratio of the melamine to the aniline polyether polyol is 1:1) into a reactor, starting stirring, heating to 180 ℃ and reacting for 10 hours to obtain the target product. The structure is shown in table 1.
[ example 5 ] Synthesis of Ethylamino polyether Melamine surfactant
Certain amount of epoxy butane and ethylene diamine (molar ratio is 1:1) and ZSM-5 catalyst (Si/Al is 80) accounting for 1 wt% of the total raw materials are added into a reaction kettle, the mixture is heated to 170 ℃ for reaction for 6 hours, and the catalyst is filtered out to obtain the product A.
Certain amount of propylene oxide and ethylenediamine (molar ratio is 1:1) and ZSM-5 catalyst (Si/Al is 80) accounting for 1 wt% of the total raw materials are added into a reaction kettle, the mixture is heated to 160 ℃ for reaction for 6 hours, and the catalyst is filtered out to obtain a product B.
Certain amount of ethylene oxide and ethylenediamine (molar ratio is 1:1) and ZSM-5 catalyst (Si/Al is 80) accounting for 1 wt% of the total raw materials are added into a reaction kettle, the mixture is heated to 150 ℃ for reaction for 6 hours, and the catalyst is filtered out to obtain a product C.
Adding a certain amount of ethylamine and 0.5% KOH by mass into a polymerization reaction kettle, heating the system to 200 ℃ under stirring, slowly introducing metered A (the molar ratio of A to the ethylamine is 1:1), and continuously reacting for 5 hours. Then adding B (the mol ratio of B to ethylamine is 1:1), and reacting for 5 hours again; finally, C (the mol ratio of the C to the ethylamine is 1:1) is added, and the reaction is carried out for 8 hours again to obtain an intermediate product D.
The intermediate product D thus obtained was mixed with 2.0% by mass of a phosphoric acid catalyst and 5 times by mass of H2Adding O and melamine (the molar ratio of D to melamine is 3:1) into a reactor, starting stirring, heating to 200 ℃ and reacting for 10 hours to obtain the target product. The structure is shown in table 1.
[ example 6 ] Synthesis of Cardanol polyether sulfonic acid sodium anionic and nonionic surfactant
Certain amount of epoxy butane and ethylene diamine (molar ratio is 1:1) and ZSM-5 catalyst (Si/Al is 80) accounting for 1 wt% of the total raw materials are added into a reaction kettle, the mixture is heated to 170 ℃ for reaction for 6 hours, and the catalyst is filtered out to obtain the product A.
Certain amount of propylene oxide and ethylenediamine (molar ratio is 1:1) and ZSM-5 catalyst (Si/Al is 80) accounting for 1 wt% of the total raw materials are added into a reaction kettle, the mixture is heated to 160 ℃ for reaction for 6 hours, and the catalyst is filtered out to obtain a product B.
Certain amount of ethylene oxide and ethylenediamine (molar ratio is 1:1) and ZSM-5 catalyst (Si/Al is 80) accounting for 1 wt% of the total raw materials are added into a reaction kettle, the mixture is heated to 150 ℃ for reaction for 6 hours, and the catalyst is filtered out to obtain a product C.
Adding a certain amount of aniline and 0.5% KOH by mass into a polymerization reaction kettle, heating the system to 200 ℃ under stirring, slowly introducing metered A (the molar ratio of A to the aniline is 1:1), and continuously reacting for 5 hours. Then adding B (the molar ratio of B to aniline is 1:1), and reacting for 5 hours again; finally, C (molar ratio of C to aniline is 1:1) is added, and the reaction is carried out for 8 hours again, so as to obtain an intermediate product D.
The intermediate product D thus obtained was mixed with 2.0% by mass of a phosphoric acid catalyst and 5 times by mass of H2Adding O and melamine (the molar ratio of D to melamine is 3:1) into a reactor, starting stirring, heating to 200 ℃ and reacting for 10 hours to obtain the target product. The structure is shown in table 1.
[ example 7 ] evaluation of emulsifying Properties of surfactants
The phase evaluation was performed according to the SPE 113313 method to calculate the emulsifying capacity. The method mainly comprises the following steps: the desired volume and concentration of aqueous surfactant solution was added to the glass tube, and then crude oil was added to the solution, with a water-to-oil volume ratio (WOR) of 1.0. Sealing and mixing. It was then placed in a metal bath, heated to a set temperature, and periodically mixed to enhance mass transfer between the phases. Equilibrium is considered to be reached until the visual interface position does not change. Its emulsifying capacity is expressed by the solubilization parameter SP, i.e. the volume or mass of surfactant per unit volume or mass that solubilizes water in oil or oil in water. The results are shown in tables 2 and 3.
[ example 8 ] evaluation of surfactant interfacial Property
And measuring the interfacial tension change between the 0.3 wt% of surfactant and the crude oil by using a TX-500C rotary drop interfacial tension meter or a Dataphysics SVT20 under the conditions of reservoir temperature and rotating speed of 5000 r/min until oil drops are balanced. The results are shown in tables 2 and 3.
[ example 9 ] evaluation of oil-washing Performance of surfactant
Taking a certain amount of oil sand, according to the oil: sand 1: 4 (mass ratio) aging at the oil reservoir temperature for 10 days, and stirring for 5 minutes every 2 hours; the aged oil sand, 5g, was then removed, along with a 0.3 wt% surfactant solution as an oil sand: the mass ratio of the solution is 1: 10, mixing uniformly, aging for 48 hours at the oil reservoir temperature, extracting crude oil in the solution by using petroleum ether, fixing the volume by using a 50ml colorimetric tube, and carrying out colorimetric analysis by using a spectrophotometer at the wavelength of 430 nm. The crude oil concentration in the surfactant solution was calculated using a standard curve. The results are shown in tables 2 and 3.
[ example 10 ] evaluation of oil repellency for surfactant
According to the test of the physical simulated oil displacement effect of the composite oil displacement system in the SY/T6424-2000 composite oil displacement system performance test method, a simulated oil displacement experiment is carried out at the oil reservoir temperature. Firstly, using injected water to drive oil-free, then transferring 0.3PV (core pore volume) of the above-mentioned surfactant, then water-driving again to oil-free so as to raise crude oil recovery ratio. The results are shown in tables 2 and 3.
[ COMPARATIVE EXAMPLE 1 ]
Preparation of C according to CN201210188897.618H37O(CH2CH2O)10CH2CH2COONa, and the results of the performance evaluation are shown in tables 2 and 3.
Table 1 examples 1-6 surfactant compositions and structures
Table 2 examples 1-6 surfactant properties
And (3) testing conditions are as follows:
the mineralization degree is 42,000mg/L, the divalent ion content is 1,000mg/L, crude oil API is 20, the acid value of the crude oil is 2.1mg/g KOH, and the core permeability is 318mD
| Examples | Solubilization parameter | Interfacial tension (mN/m) | Wash oil Performance (%) | Enhanced recovery (%) |
| 1 | 9.8 | 0.00433 | 42 | 6.5 |
| 2 | 10.2 | 0.00329 | 58 | 7.2 |
| 3 | 11.4 | 0.00217 | 72 | 8.9 |
| 4 | 11.0 | 0.00225 | 56 | 7.0 |
| 5 | 12.5 | 0.00207 | 70 | 9.4 |
| 6 | 13.2 | 0.00116 | 74 | 10.3 |
| Comparative example 1 | 4.4 | 0.0208 | 30 | 3.8 |
The surfactant prepared in example 6 was formulated at various concentrations and tested for oil-water interfacial tension with the crude oil described above, and the results are shown in table 3.
TABLE 3 oil-water interfacial tension between surfactant groups of different concentrations and crude oil
The results show that the surfactant disclosed by the invention has high oil-water interfacial activity on the tested thickened oil.
The surfactant of the invention is used for high-temperature high-salinity heavy oil reservoir again, and the oil-water interfacial tension of the surfactant is tested, and the result is shown in table 4. As can be seen from the results in tables 2, 3 and 4, the surfactants prepared by the present invention have excellent properties.
Table 4 examples 1-6 surfactant properties
And (3) testing conditions are as follows:
120 ℃, the degree of mineralization of 260,000mg/L, the content of divalent ions of 10,000mg/L, crude oil API (American Petroleum institute) of 15, the acid value of the crude oil of 2.8mg/g KOH and the permeability of the rock core of 542 mD.
| Examples | Solubilization parameter | Interfacial tension (mN/m) | Wash oil Performance (%) | Enhanced recovery (%) |
| 1 | 8.5 | 0.00621 | 40 | 5.8 |
| 2 | 9.2 | 0.00409 | 53 | 6.3 |
| 3 | 11.3 | 0.00310 | 69 | 9.0 |
| 4 | 10.6 | 0.00281 | 50 | 6.2 |
| 5 | 11.7 | 0.00105 | 70 | 9.1 |
| 6 | 12.3 | 0.00222 | 75 | 9.8 |
| Comparative example 1 | 3.7 | 0.0817 | 30 | 3.0 |
Claims (10)
1. A melamine based surfactant having the following molecular formula:
wherein R is1～R6Is H, C1～C50At least one of aliphatic group and/or aromatic group of (a), and R1～R6At least one of which is not H.
2. The melamine based surfactant according to claim 1, wherein R is1～R6Is H, C1～C30At least one of alkyl, alkenyl, aryl or substituted alkyl, alkenyl, aryl.
3. The melamine based surfactant according to claim 1, wherein R is1～R6Is H, C1～C20At least one of alkyl, alkenyl, aryl or substituted alkyl, alkenyl, aryl.
4. The melamine based surfactant according to claim 1, wherein R which is not H1～R6Also contains at least one of ethoxy, propoxy and butoxy.
5. The melamine-based surfactant according to claim 4, wherein the degree of polymerization of said ethoxy group, propoxy group and butoxy group is independently selected from any one number of 0 to 100 and more than 0.
6. The melamine-based surfactant according to claim 5, wherein the degree of polymerization of said ethoxy group, propoxy group and butoxy group is independently selected from any one number of 1 to 50.
7. A process for preparing a melamine based surfactant according to any one of claims 1 to 6, comprising the steps of:
a) carrying out alkoxylation on an initiator and optional required amount of ethylene oxide, propylene oxide and butylene oxide under the action of a catalyst to obtain polyether polyol nonionic surfactant; wherein the initiator is C with carbon atom number1～C50Preferably C, at least one of aliphatic alcohol, aromatic alcohol and alkylphenol1～C30More preferably C1～C20；
b) And c) carrying out substitution reaction on the polyether polyol nonionic surfactant synthesized in the step a) and melamine to obtain the melamine-based surfactant.
8. The method for preparing a melamine-based surfactant according to claim 7, wherein the alkoxylation reaction is carried out at a reaction temperature of 140 to 200 ℃ and a reaction pressure of 0 to 5 MPa; the molar ratio of the initiator to the ethylene oxide, the propylene oxide and the butylene oxide is independently selected from 1 (1-50); the catalyst is alkali metal hydroxide, DMC (dimethyl formamide) double metal polyether catalyst or phosphazene catalyst, and the using amount of the catalyst is 0.001-2.0% of the weight of the initiator.
9. The method for preparing the melamine-based surfactant according to claim 7, wherein the molar ratio of the polyether polyol nonionic surfactant to the melamine in the substitution reaction is (1-6): 1, the substitution reaction temperature is 150-300 ℃, and the substitution reaction time is 0.5-10 hours.
10. The application of the melamine-based surfactant is characterized in that the melamine-based surfactant is the melamine-based surfactant disclosed in any one of claims 1-6 or the melamine-based surfactant prepared by the preparation method disclosed in any one of claims 7-9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| US20020111457A1 (en) * | 2000-12-18 | 2002-08-15 | Wei Li | Reaction products of melamine and derivatives thereof |
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| CN104877126A (en) * | 2015-06-25 | 2015-09-02 | 淄博德信联邦化学工业有限公司 | Synthetic method for high-activity flame-retardant polyether polyol |
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| US4013655A (en) * | 1972-03-28 | 1977-03-22 | Ciba-Geigy Corporation | Production of alkoxylated n-methylol compounds |
| JPS5543156A (en) * | 1978-09-22 | 1980-03-26 | Toyobo Co Ltd | Method for imparting infusibility to meltable molded article |
| US20020111457A1 (en) * | 2000-12-18 | 2002-08-15 | Wei Li | Reaction products of melamine and derivatives thereof |
| CN101263172A (en) * | 2005-09-07 | 2008-09-10 | 阿克佐诺贝尔国际涂料股份有限公司 | Melamine polyols and coatings thereof |
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