Algae-killing ionic liquid modified polyether polyol as well as preparation method and application thereof

Abstract

The invention relates to algicidal ionic liquid modified polyether polyol as well as a preparation method and application thereof, and mainly solves the problem that in the prior art, common polyether polyol has no algicidal performance when being applied to preparation of filter cotton. According to the technical scheme of the ionic liquid modified polyether polyol and the preparation method thereof, the problems are well solved, and the ionic liquid modified polyether polyol can be used for industrial preparation of filter cotton.

Description

Technical Field

[0001] The invention relates to an algaecidal ionic liquid modified polyether polyol and a preparation method and application thereof. Background Art

[0002] Polyether polyol is one of the main raw materials for synthesizing polyurethane materials. With the increasing demand for various properties of polyurethane products such as antibacterial, anti-mite, algaecide, flame retardant, and antistatic, the modification technology of polyether polyol has been continuously improved, and new polyether polyols have been continuously emerging. The ways to modify polyether polyols are: introducing another monomer into the molecular chain, from the original homopolymerization of a single monomer to the copolymerization of two or more monomers; introducing aliphatic rings into the molecular chain segments; replacing traditional small molecule diols (ethylene glycol, diethylene glycol, propylene glycol, etc.) with new initiators with special structures; introducing other segments into the polyether chain segments to make block polymers. Some even introduce special functional groups into the polyether polyol chain segments to meet special purposes. At present, maleic anhydride, amino resin, melamine, etc. have been used for the modification of polyether polyols, among which the use of "green solvent" ionic liquids has attracted much attention.

[0003] Ionic liquids are a class of substances that are composed of organic cations and inorganic or organic anions and are liquid at room temperature or near room temperature. They have the advantages of low melting point, low volatility, high catalytic efficiency, good thermal stability, adjustable structural properties, and recyclability. More importantly, ionic liquids are highly designable, and specific functions can be given to ionic liquids through anion and cation design to meet different application requirements. The cation part is replaced by traditional small molecule diols, and the anion part is added in the post-reaction to prepare functionalized polyether polyols that have the excellent properties of both ionic liquids and polyether polyols.

[0004] Most filter sponges on the market do not have algaecidal ability and have poor algaecidal effect, which will cause various inconveniences during use. Therefore, we propose an ionic liquid modified polyether polyol with algaecidal performance, which can be used in the preparation of filter sponges. Summary of the invention

[0005] One of the technical problems to be solved by the present invention is that the conventional polyether polyols in the prior art have no algaecidal performance when used to prepare filter cotton, and an algaecidal ionic liquid modified polyether polyol is provided, which has the advantage of good algaecidal performance.

[0006] The second technical problem to be solved by the present invention is to provide a method for preparing algaecidal ionic liquid modified polyether polyol corresponding to the first technical problem to be solved.

[0007] The third technical problem to be solved by the present invention is to provide a use of algicidal ionic liquid modified polyether polyol corresponding to the first technical problem to be solved.

[0008] In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: an algaecidal ionic liquid modified polyether polyol, the general structural formula of which is as follows:

[0009]

[0010] Among them, L1, L2 and L3 are alkanes, and their general formula is (CH2) n CH3, (n≥2), R is one of nitrogen and phosphorus, X is one of fluorine, chlorine and bromine, Y is one of potassium, sodium, zinc and magnesium, and n1 and n2 are positive integers.

[0011] In order to solve the second technical problem mentioned above, the technical solution adopted by the present invention is as follows: a method for preparing an algaecidal ionic liquid modified polyether polyol comprises the following steps in sequence:

[0012] (1) adding an ionic liquid cation as an initiator and a catalyst into a reactor and dehydrating for 1 to 2 hours, then adding alkylene oxide to react, controlling the temperature in the reactor to 90 to 120° C., the reaction pressure ≤ 0.45 MPa, and the internal pressure time to 1 to 4 hours, and obtaining polyether polyol I after the pressure in the reactor drops and stabilizes;

[0013] (2) adding 6-10% water and 1-5% adsorbent to polyether polyol I, based on the mass percentage of polyether polyol I, stirring for 1-5 hours, vacuuming and dehydrating for 2-8 hours, and filtering to obtain polyether polyol II;

[0014] (3) After mixing the halogenated alkane and the polyether polyol II in a molar ratio of 1 to 3:1, the reaction temperature is controlled to be 80 to 130° C. and the reaction is carried out for 3 to 15 hours to obtain the ionic liquid modified polyether polyol III.

[0015] (4) After mixing the ionic liquid modified polyether polyol III and the metal halide at a molar ratio of 1 to 3:1, the reaction temperature is controlled to be 80 to 130° C., and the reaction is carried out for 4 to 15 hours to obtain the ionic liquid modified polyether polyol IV having algaecidal properties.

[0016] In the above technical scheme, in the step (1), the ionic liquid cationic initiator is selected from one of N,N-dimethylethanolamine, N-butyldiethanolamine, N-(3-aminopropyl)diethanolamine, triethanolamine, and triisopropanolamine, and has a molecular weight of 60 to 400 and a functionality of 1 to 4; the temperature in the reactor is 100 to 120° C.; and the internal pressure time is 2 to 4 hours.

[0017] In the above technical solution, the catalyst in step (1) is one of alkaline catalysts such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, etc.

[0018] In the above technical solution, the adsorbent in step (2) is selected from one of magnesium silicate, aluminum silicate or magnesium aluminum silicate.

[0019] In the above technical solution, the halogenated alkane in step (3) is (CH2) a X, (5≤a≤12), X is one of fluorine, chlorine and bromine.

[0020] In the above technical scheme, the molar ratio of the halogenated alkane to the polyether polyol II in the step (3) is 1.2 to 3:1; the reaction temperature is 90 to 120° C., and the reaction time is 9 to 12 hours.

[0021] In the above technical solution, in the step (4), the reaction temperature of the ionic liquid modified polyether polyol and the metal halide is 80 to 120° C., and the reaction time is 6 to 13 hours.

[0022] In the above technical solution, the metal halide in step (4) is one of potassium chloride, potassium bromide, sodium chloride, sodium bromide, zinc chloride and zinc bromide.

[0023] In order to solve the third of the above technical problems, the technical solution adopted by the present invention is as follows: an application of an algicidal ionic liquid modified polyether polyol in the preparation of filter cotton.

[0024] The present invention provides a method for preparing an algaecidal ionic liquid modified polyether polyol, wherein the ionic liquid cation is used to replace the traditional small molecule diol, and then the cationic component is added in the post-reaction, and then the metal halide is added, so as to prepare a functionalized polyether polyol having both the excellent properties of the ionic liquid and the polyether polyol, and the structural designability of the ionic liquid further enriches the types of polyether polyols. The algaecidal ionic liquid modified polyether polyol designed by the present invention has a simple preparation method and a stronger algaecidal effect than ordinary polyether polyols. At the same time, the reactive ionic liquid modified polyether polyol is not easy to be free compared with the additive algaecide, and can be applied to the preparation of algaecidal filter cotton. DETAILED DESCRIPTION

[0025] The following are only preferred implementations of the present invention, and are not intended to limit the scope of protection of the present invention. All technical solutions within the scope of the present invention should fall within the scope of protection of the present invention. For professional and technical personnel in this technical field, minor improvements and modifications to the present invention without departing from the principles of the present invention should also fall within the scope of protection of the present invention.

[0026] Table 1 List of raw materials

[0027] Raw material name Brand and manufacturer Other polyols CHE-307, CHP-2045, CHE-5602, Changhua Chemical Silicone oil 8002, Shanghai Yexing Industrial Co., Ltd. Catalyst 1 A33, Evonik Specialty Chemicals GmbH Catalyst 2 T9, Shanghai Yexing Industrial Co., Ltd. Toluene diisocyanate TDI-80, Wanhua Chemical Algaecide MDL203, Jinan Delan Chemical

[0028] Example 1

[0029] (1) Add 240 g of N, N-dimethylethanolamine and 3 g of potassium hydroxide into a reactor, dehydrate at 110° C. for 2 h, add 960 g of propylene oxide to carry out polymerization reaction, control the temperature in the reactor to be 110° C., and the pressure to be 0.01 MPa. After the reaction is completed, the internal pressure is maintained for 2 h, and after the pressure in the reactor decreases and stabilizes, a polyether polyol I with a functionality of 1 and a molecular weight of 400 is obtained;

[0030] (2) Transferring polyether polyol I into a glass reactor, adding 85 g of water and 21 g of magnesium silicate, stirring for 2 h, performing vacuum negative pressure dehydration for 4 h, and filtering to obtain polyether polyol II;

[0031] (3) The filtered polyether polyol II was transferred to a glass reactor, 558 g of n-butyl chloride was added, the reaction temperature was controlled to be 110° C., and after reacting for 12 h, the residual monomers were removed by vacuum to obtain ionic liquid modified polyether polyol III;

[0032] (4) After mixing the ionic liquid modified polyether polyol III with 146 g of sodium bromide, the reaction temperature was controlled to 90° C. and the reaction was carried out for 8 hours to obtain a polyether polyol having the general structural formula (a).

[0033] Example 2

[0034] (1) Add 290 g of N-butyldiethanolamine and 3.6 g of potassium hydroxide into a reactor, dehydrate at 110° C. for 2 h, add 910 g of propylene oxide to carry out polymerization reaction, control the temperature in the reactor to 105° C. and the pressure to 0.01 MPa, and maintain the internal pressure for 2 h after the reaction is completed. After the pressure in the reactor decreases and stabilizes, polyether polyol I with a functionality of 2 and a molecular weight of 600 is obtained;

[0035] (2) Transferring polyether polyol I into a glass reactor, adding 80 g of water and 20 g of magnesium silicate, stirring for 2 h, performing vacuum negative pressure dehydration for 3 h, and filtering to obtain polyether polyol II;

[0036] (3) The filtered polyether polyol II was transferred to a glass reactor, 279 g of n-butyl chloride was added, the reaction temperature was controlled to be 115° C., and after reacting for 12 h, the residual monomers were removed by vacuum to obtain ionic liquid modified polyether polyol III;

[0037] (4) After mixing the ionic liquid modified polyether polyol III with 104 g of sodium bromide, the reaction temperature was controlled to 90° C. and the reaction was carried out for 8 hours to obtain a polyether polyol having the general structural formula (a).

[0038] Example 3

[0039] (1) Add 175 g of N-(3-aminopropyl)diethanolamine and 4.2 g of potassium hydroxide into a reactor, dehydrate at 110° C. for 2 h, add 1025 g of propylene oxide to carry out polymerization reaction, control the temperature in the reactor to 100° C. and the pressure to 0.01 MPa. After the reaction is completed, the internal pressure is maintained for 2 h. After the pressure in the reactor decreases and stabilizes, polyether polyol I with a functionality of 2 and a molecular weight of 1000 is obtained.

[0040] (2) Transferring polyether polyol I into a glass reactor, adding 84 g of water and 21 g of magnesium silicate, stirring for 2 h, performing vacuum negative pressure dehydration for 3 h, and filtering to obtain polyether polyol II;

[0041] (3) The filtered polyether polyol II was transferred to a glass reactor, 187 g of chloropropane was added, the reaction temperature was controlled to be 100° C., and after reacting for 10 hours, the residual monomers were removed by vacuum to obtain ionic liquid modified polyether polyol III;

[0042] (4) After mixing the ionic liquid modified polyether polyol III with 67 g of sodium bromide, the reaction temperature was controlled to 90° C. and the reaction was carried out for 8 hours to obtain a polyether polyol having the general structural formula (a).

[0043] Example 4

[0044] (1) Add 322 g of triethanolamine and 3 g of potassium hydroxide into a reactor, dehydrate at 110° C. for 2 h, add 878 g of propylene oxide to carry out polymerization reaction, control the temperature in the reactor to be 110° C. and the pressure to be 0.01 MPa, and after the reaction is completed, maintain the internal pressure for 2 h, vacuumize to remove residual monomers, and after the pressure in the reactor drops and stabilizes, obtain polyether polyol I with a functionality of 3 and a molecular weight of 500;

[0045] (2) Transferring polyether polyol I into a glass reactor, adding 90 g of water and 22 g of aluminum silicate, stirring for 2 h, performing vacuum negative pressure dehydration for 3 h, and filtering to obtain polyether polyol II;

[0046] (3) The polyether polyol II obtained by filtration was transferred to a glass reactor, 337 g of chloropropane was added, the reaction temperature was controlled to be 120° C., and after reacting for 12 hours, the residual monomers were removed by vacuum to obtain the ionic liquid modified polyether polyol III;

[0047] (4) After mixing the ionic liquid modified polyether polyol III with 125 g of sodium bromide, the reaction temperature was controlled to be 95° C. and the reaction was carried out for 8 hours to obtain a polyether polyol having the general structural formula (a).

[0048] Example 5

[0049] (1) Add 188 g of triisopropanolamine and 3.6 g of potassium hydroxide into a reactor, dehydrate at 110° C. for 2 h, add 1012 g of propylene oxide to carry out polymerization reaction, control the temperature in the reactor to be 110° C. and the pressure to be 0.01 MPa. After the reaction is completed, the internal pressure is maintained for 2 h, and the residual monomers are removed by vacuum. After the pressure in the reactor drops and stabilizes, polyether polyol I with a functionality of 3 and a molecular weight of 1100 is obtained.

[0050] (2) Transferring polyether polyol I into a glass reactor, adding 88 g of water and 22 g of aluminum silicate, stirring for 2 h, performing vacuum negative pressure dehydration for 3 h, and filtering to obtain polyether polyol II;

[0051] (3) The filtered polyether polyol II was transferred to a glass reactor, 156 g of chloropropane was added, the reaction temperature was set at 120° C., and after reacting for 12 hours, the residual monomers were removed by vacuum to obtain ionic liquid modified polyether polyol III;

[0052] (4) After mixing the ionic liquid modified polyether polyol III with 62 g of sodium bromide, the reaction temperature was controlled to 95° C. and the reaction was carried out for 8 hours to obtain a polyether polyol having the general structural formula (a).

[0053] Example 6

[0054] (1) Prepare the components according to Table 2 (the alginate polyether polyol is prepared in Example 1);

[0055] (2) Stir the components in a mixer at a rotation speed of 3500 rpm for 5 to 10 seconds, quickly pour them into a mold, and then mature them for 30 minutes to obtain a polyurethane foam.

[0056] Embodiments 7 to 10

[0057] Examples 7 to 10 were carried out according to the steps in Example 6, except that the alginate polyether polyols in the formula were prepared by Examples 2 to 5, respectively. The mass fractions of each component are shown in Table 2. The performance index data of the prepared polyurethane foam are shown in Table 4.

[0058] Comparative Example 1

[0059] (1) Prepare the components according to Table 2 (polyether polyol is ordinary polyether polyol of Changhua Chemical);

[0060] (2) Stir the components in a mixer at a rotation speed of 3500 rpm for 5 to 10 seconds, quickly pour them into a mold, and then mature them for 30 minutes to obtain a polyurethane foam.

[0061] Comparative Example 2

[0062] (1) Prepare the components according to Table 2 (the algaecide is a common additive algaecide on the market);

[0063] (2) Stir the components in a mixer at a rotation speed of 3500 rpm for 5 to 10 seconds, quickly pour them into a mold, and then mature them for 30 minutes to obtain a polyurethane foam.

[0064] Table 2 Mass fractions of each component in the polyurethane foaming formula of Examples 6 to 10 and Comparative Examples 1 to 2

[0065]

[0066] Table 3 Index data of polyurethane foams of Examples 6 to 10 and Comparative Examples 1 to 2

[0067]

[0068] From the synthesis method, product structure and data in Table 3, it can be seen that the synthesis method of the algaecidal ionic liquid modified polyether polyol involved in the present invention is simple, the algaecidal property of the product is significantly improved, and the algaecidal rate is increased from 2% to 78%, which better solves the problem that most sponges produced by ordinary polyethers on the market have poor algaecidal effects. At the same time, the algaecidal performance of the additive algaecides on the market gradually fails over time, while the algaecidal performance of the reactive algaecidal ionic liquid modified polyether polyol of the present invention can still reach about 70% after half a year.

Claims

1. An algaecidal ionic liquid modified polyether polyol having the following general structural formula (a): in, L1, L2 and L3 are alkanes, and their general formula is (CH2) n CH3, (n≥2), R is one of nitrogen and phosphorus, Y is one of potassium, sodium, zinc and magnesium, X is one of fluorine, chlorine and bromine, n1 and n2 are positive integers, and YX is compounded in the structure.

2. A method for preparing the algicidal ionic liquid modified polyether polyol according to claim 1, comprising the following steps in sequence: (1) adding an ionic liquid cation as an initiator and a catalyst into a reactor and dehydrating for 1 to 2 hours, then adding alkylene oxide to react, controlling the temperature in the reactor to be 90 to 120° C., the reaction pressure to be ≤0.45 MPa, and the internal pressure time to be 1 to 4 hours, and obtaining polyether polyol I after the pressure in the reactor drops and stabilizes; (2) adding 6-10% water and 1-5% adsorbent to polyether polyol I, based on the mass percentage of polyether polyol I, stirring for 1-5 hours, vacuuming and dehydrating for 2-8 hours, and filtering to obtain polyether polyol II; (3) After mixing the halogenated alkane and the polyether polyol II in a molar ratio of 1 to 3:1, the reaction temperature is controlled to be 80 to 130° C. and the reaction is carried out for 3 to 15 hours to obtain the ionic liquid modified polyether polyol III. (4) After mixing the ionic liquid modified polyether polyol III with the metal halide in a molar ratio of 1 to 3:1, the reaction temperature is controlled to be 80 to 130° C. and the reaction is carried out for 4 to 15 hours to obtain a polyether polyol having the general structural formula (a).

3. The method for preparing the algicidal ionic liquid modified polyether polyol according to claim 2, characterized in that: In the step (1), the ionic liquid cationic initiator is selected from one of N,N-dimethylethanolamine, N-butyldiethanolamine, N-(3-aminopropyl)diethanolamine, triethanolamine and triisopropanolamine, and has a molecular weight of 60 to 400 and a functionality of 1 to 4; the temperature in the reactor is 100 to 120° C.; and the internal pressure time is 2 to 4 hours.

4. The method for preparing the algicidal ionic liquid modified polyether polyol according to claim 2, characterized in that: The catalyst in step (1) is one of alkaline catalysts such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, etc.

5. The method for preparing the algicidal ionic liquid modified polyether polyol according to claim 2, characterized in that: In the step (2), the adsorbent is selected from magnesium silicate, aluminum silicate or magnesium aluminum silicate.

6. The method for preparing the algicidal ionic liquid modified polyether polyol according to claim 2, characterized in that: In the step (3), the halogenated alkane is (CH2) a X, (2≤a≤12), X is one of fluorine, chlorine and bromine.

7. The method for preparing the algicidal ionic liquid modified polyether polyol according to claim 2, characterized in that: In the step (3), the molar ratio of the halogenated alkane to the polyether polyol II is 1.2-3:1; the reaction temperature is 90-120°C, and the reaction time is 9-12 hours.

8. The method for preparing the algicidal ionic liquid modified polyether polyol according to claim 2, characterized in that: In the step (4), the reaction temperature of the ionic liquid modified polyether polyol and the metal halide is 80-120° C., and the reaction time is 6-13 hours.

9. The method for preparing the algicidal ionic liquid modified polyether polyol according to claim 2, characterized in that: In the step (4), the metal halide is one of potassium chloride, potassium bromide, sodium chloride, sodium bromide, zinc chloride and zinc bromide.

10. Use of the algicidal ionic liquid modified polyether polyol according to claim 1 in the preparation of filter cotton.

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