Preparation method of textile polyether polyol derivative

Abstract

The invention belongs to the technical field of polyether polyol derivatives, and particularly relates to a preparation method of a polyether polyol derivative for spinning, which comprises the following steps: a, feeding and pretreatment: adding an initiator into a reaction kettle A, adding an alkali metal catalyst, carrying out nitrogen replacement, and heating; b, polymerization reaction: when the temperature in the reaction kettle A reaches the polymerization temperature, dropwise adding an epoxy compound, controlling the pressure in the reaction kettle A until all epoxide is dropwise added, preserving heat, curing, and vacuumizing to obtain polyether polyol crude ether; c, post-treatment: transferring the polyether polyol crude ether to a post-treatment kettle, adding distilled water and phosphoric acid, stirring, heating, crystallizing, dehydrating, and carrying out filter pressing to obtain polyether polyol; and d, end capping: vacuumizing, stirring and heating the polyether polyol to a reaction temperature, stopping vacuumizing, adding an end capping agent, carrying out heat preservation reaction, and vacuumizing to obtain the polyether polyol derivative. The polyether polyol derivative obtained by the invention can be used as a wetting agent for spinning, and is good in wetting effect and low in foam in a high-temperature state.

Description

Technical Field

[0001] The invention belongs to the technical field of polyether polyol derivatives, and in particular relates to a method for preparing a polyether polyol derivative for textile use. Background Art

[0002] Polyether polyols are referred to as polyethers, also called polyalkylene ethers or polyoxyolefins. They are prepared by ring-opening polymerization of epoxy compounds in the presence of active hydrogen compounds as initiators and catalysts. Polyether polyols are capped to obtain polyether polyol derivatives. Polyether polyol derivatives can be used for pretreatment of textiles and dyeing, and are effective wetting agents and penetrants. Different textile products have different requirements for the initiator type, molecular weight and capping agent of polyether polyol derivatives.

[0003] In the prior art, most textile and printing and dyeing pre-treatment auxiliaries use polyether polyols as wetting and penetrating agents. In alkaline and high temperature environments, the wetting and penetrating effects of polyether polyol wetting and penetrating agents deteriorate. In addition, in a high temperature water environment, the use of polyether polyol wetting agents and antistatic agents will cause multiple foaming. Polyether polyol wetting and penetrating agents are mostly concentrated on the foam surface, which reduces the use effect of polyether polyol wetting and penetrating agents. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a method for preparing a polyether polyol derivative for textile use. The obtained polyether polyol derivative can be used as a wetting agent for textile use, has good wetting effect and low foaming under high temperature conditions.

[0005] The method for preparing the polyether polyol derivative for textile use of the present invention comprises the following steps:

[0006] a. Feeding and pretreatment: Add the initiator into reactor A, add the alkali metal catalyst, replace with nitrogen 3 to 5 times, each time the nitrogen pressure in the reactor is increased to 0.15MPa, then vented, start stirring until all materials are evenly distributed, and start heating at the same time;

[0007] b. Polymerization reaction: Control the reactor A to the polymerization temperature, add the epoxy compound dropwise, control the pressure in the reactor A to be less than 0.35MPa, until all the epoxide is added dropwise, heat and mature to obtain a crude polyether polyol ether;

[0008] c. Post-treatment: transfer the crude polyether polyol to a post-treatment kettle, add distilled water and phosphoric acid, stir and heat to 75-85°C for crystallization, then dehydrate and filter press to obtain polyether polyol;

[0009] d. End-capping: Put the polyether polyol into reactor B, evacuate and stir to raise the temperature to the reaction temperature, stop the vacuum, slowly add the end-capping agent, keep the reaction at the reaction temperature, evacuate to below -0.095 MPa for 1 hour to obtain a polyether polyol derivative. If the polyether polyol derivative contains solids, centrifuge the polyether polyol derivative to remove the solids.

[0010] Preferably, the initiator is one or more of methanol, ethanol, isopropanol, n-butanol and isooctyl alcohol. The mass of the initiator accounts for 1% to 10% of the mass of the crude polyether polyol, more preferably 1% to 3% or 7% to 10%.

[0011] Preferably, the alkali metal catalyst is one or both of potassium hydroxide and sodium hydroxide, more preferably potassium hydroxide; the mass of the alkali metal catalyst accounts for 0.1‰ to 2‰ of the mass of the crude polyether polyol.

[0012] Preferably, in the post-treatment, the amount of distilled water added is 4% to 5% of the mass of the crude polyether polyol ether, and the molar amount of phosphoric acid added is twice the molar amount of the alkali metal.

[0013] Preferably, the epoxy compound is ethylene oxide or a mixture of ethylene oxide and propylene oxide. The mass of ethylene oxide is 40% to 100%, more preferably 80% to 100%, of the total mass of the epoxy compound, and the mass of propylene oxide is 0 to 60% of the total mass of the epoxy compound.

[0014] Preferably, in step b, the pressure of the reactor is controlled to be less than 0.35 MPa, and more preferably, the pressure of the reactor is controlled to be less than 0.3 MPa.

[0015] Preferably, in step b, the polymerization temperature and the aging temperature are 80 to 130°C, more preferably 90 to 115°C;

[0016] Preferably, in step d, the number average molecular weight of the polyether polyol is 200 to 2000, preferably 300 to 1400.

[0017] Preferably, the end-capping agent is one of methyl chloride and acetic anhydride.

[0018] Preferably, when methyl chloride is used as the end-capping agent, step d is specifically as follows: putting the polyether polyol into a reaction kettle B, adding sodium hydroxide, replacing with nitrogen until the oxygen content is less than 100 ppm, evacuating, stirring and heating to the reaction temperature, stopping the vacuum, slowly introducing methyl chloride, controlling the pressure to be less than 0.35 MPa, keeping the reaction at the reaction temperature for 2 to 4 hours, evacuating to below -0.095 MPa for 1 hour, and centrifuging to obtain a polyether polyol derivative; the molar amounts of sodium hydroxide and methyl chloride are equal; the amount of methyl chloride added is 1.05 to 1.13 times the molar amount of the polyether polyol, more preferably 1.05 to 1.1 times; when methyl chloride is used as the end-capping agent, the reaction temperature is 70 to 100° C., more preferably 85 to 95° C.

[0019] Preferably, when acetic anhydride is used as the end-capping agent, step c is specifically as follows: a polyether polyol is put into a reaction kettle B, and after nitrogen replacement until the oxygen content is less than 100 ppm, the polyether polyol is vacuumed and stirred and heated to reaction temperature 2, the vacuum is stopped, and acetic anhydride is slowly added dropwise, and the reaction is kept at the reaction temperature for 2 to 4 hours, the temperature is raised to 110 to 120° C., and the temperature is vacuumed to below -0.095 MPa for 1 hour to obtain a polyether polyol derivative; the amount of acetic anhydride added is 1.05 to 1.3 times, preferably 1.05 to 1.1 times, of the molar amount of the polyether polyol in step b; when acetic anhydride is used as the end-capping agent, the reaction temperature is 70 to 100° C., and more preferably 80 to 90° C.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] Polyether polyol derivatives can be used for pretreatment of textile weaving and dyeing, and are effective wetting agents and penetrants. As wetting and penetrants, polyether polyol derivatives will not react with alkali to form ions in alkaline and high temperature environments, and have high stability, and can continue to play a wetting and penetrant role. In addition, in a high temperature water environment, the blocked polyether polyol derivatives do not contain a large number of hydroxyl groups, which can avoid the multi-foaming phenomenon of the aqueous solution, so that the blocked polyether polyol derivative wetting and penetrants continue to dissolve in the aqueous solution and can continue to play a wetting and penetrant role. DETAILED DESCRIPTION

[0022] The technical solution of the present invention will be clearly and completely described below in conjunction with embodiments.

[0023] Unless otherwise specified, all raw materials used in the examples are commercially available.

[0024] Example 1

[0025] The preparation method of the polyether polyol derivative for textile use comprises the following steps:

[0026] a. Feeding and pretreatment: In a 3L high-pressure reactor A equipped with a stirrer, a meter, a heating and temperature control device, a cooling device (including an outer jacket and an inner coil) and a pressure sensor, add 160g of methanol and 2.6g of potassium hydroxide, and replace with nitrogen three times. Each time, the nitrogen pressure in the reactor A is raised to 0.15MPa, and then vented, stirring is started until all materials are evenly distributed, and heating is started;

[0027] b. Polymerization reaction: When the temperature was raised to 80°C, 140g of propylene oxide and 1300g of ethylene oxide mixture were continuously added dropwise, the temperature was maintained at 85-95°C, and the pressure in the reactor was controlled to be less than 0.35MPa. After the addition was completed, the reaction was aged at a temperature of 100-110°C. When the pressure in the reactor did not drop for 1h, the reaction was evacuated to -0.095MPa or less for 1h to obtain a crude polyether polyol ether;

[0028] c. Post-treatment: The crude polyether polyol ether is transferred to a post-treatment kettle, distilled water accounting for 4% of the mass of the crude polyether polyol ether and phosphoric acid (the amount of phosphoric acid added is 2 times the molar amount of potassium hydroxide) are added, and the mixture is stirred and heated to 75°C for crystallization, and then dehydrated and filtered to obtain a polyether polyol;

[0029] d. End-capping: Put the polyether polyol into reactor B, add 210g of sodium hydroxide, replace with nitrogen until the oxygen content is less than 100ppm, evacuate and stir, heat to 105℃, dehydrate for 5h, cool to 95℃ and stop vacuum, slowly add 265.5methylene chloride, control the pressure to be less than 0.35MPa, keep the reaction at 85-95℃ for 3h, evacuate to below -0.095MPa for 1h to obtain a polyether polyol derivative, and centrifuge to remove the solid.

[0030] Example 2

[0031] The preparation method of the polyether polyol derivative for textile use comprises the following steps:

[0032] a. Feeding and pretreatment: In a 3L high-pressure reactor A equipped with a stirrer, a meter, a heating and temperature control device, a cooling device (including an outer jacket and an inner coil) and a pressure sensor, add 92g of ethanol and 2.6g of potassium hydroxide, and replace with nitrogen three times. Each time, the nitrogen pressure in the reactor A is raised to 0.15MPa, and then vented, stirring is started until all materials are evenly distributed, and heating is started;

[0033] b. Polymerization reaction: When the temperature rises to 80°C, start to continuously add a mixture of 520g propylene oxide and 1616g ethylene oxide, control the feeding rate and the temperature control device to maintain the temperature at 105-115°C, control the pressure in the reactor to be less than 0.35MPa, after the addition is complete, 105-115°C aging reaction for 1h, turn on the vacuum pump, remove the single for 30min, turn off the vacuum, add 100g ethylene oxide, control the feeding rate and the temperature control device to maintain the reaction temperature at 110-120°C, control the pressure to be less than 0.25MPa, after the addition is complete, 110-120°C aging for 1h, wait for the pressure in the reactor to not drop for 1h, vacuumize and remove the single for 30min to obtain a crude polyether polyol ether;

[0034] c. Post-treatment: The crude polyether polyol ether is transferred to a post-treatment kettle, distilled water accounting for 4% of the mass of the crude polyether polyol ether and phosphoric acid (the amount of phosphoric acid added is 2 times the molar amount of potassium hydroxide) are added, and the mixture is stirred and heated to 85°C for crystallization, and then dehydrated and filtered to obtain a polyether polyol;

[0035] d. End-capping: Put the polyether polyol into reactor B, evacuate and stir, heat to 85°C, stop the vacuum, slowly add 218g of acetic anhydride, keep the temperature at 85-95°C for 3h, evacuate to below -0.095MPa for 1h to obtain a polyether polyol derivative.

[0036] Example 3

[0037] The preparation method of the polyether polyol derivative for textile use comprises the following steps:

[0038] a. Feeding and pretreatment: In a 3L high-pressure reactor A equipped with a stirrer, a meter, a heating and temperature control device, a cooling device (including an outer jacket and an inner coil) and a pressure sensor, add 120g of isopropanol and 2g of potassium hydroxide, and replace with nitrogen three times. Each time, the nitrogen pressure in the reactor is brought to 0.15MPa, and then vented, stirring is started until all materials are evenly distributed, and heating is started;

[0039] b. Polymerization reaction: After heating to 80°C, continue heating to 105°C, start to continuously drop 250g of propylene oxide and 950g of ethylene oxide mixture, control the reaction temperature to maintain at 105-115°C, control the pressure in the reactor to be less than 0.35MPa, after the addition is complete, mature the reaction at 105-115°C for 1h, vacuum stripping for 30min, to obtain a crude polyether polyol ether;

[0040] c. Post-treatment: The crude polyether polyol ether is transferred to a post-treatment kettle, distilled water accounting for 4% of the mass of the polyether polyol and phosphoric acid (the amount of phosphoric acid added is 2 times the molar amount of potassium hydroxide) are added, and the temperature is raised to 85°C for crystallization under stirring, and then dehydrated and filtered to obtain a polyether polyol;

[0041] d. End-capping: Put the polyether polyol into reactor B, evacuate and stir, heat to 85°C, stop the vacuum, slowly add 218g of acetic anhydride, keep the temperature at 85-95°C for 3h, evacuate to below -0.095MPa for 1h to obtain a polyether polyol derivative.

[0042] Example 4

[0043] The preparation method of the polyether polyol derivative for textile use comprises the following steps:

[0044] a. Feeding and pretreatment: In a 3L high-pressure reactor A equipped with a stirrer, a meter, a heating and temperature control device, a cooling device (including an outer jacket and an inner coil) and a pressure sensor, add 148.2g of n-butanol and 3.8g of potassium hydroxide, replace with nitrogen three times, each time the nitrogen pressure in the reactor is brought to 0.15MPa, then vented, start stirring until all materials are evenly distributed, and start heating;

[0045] b. Polymerization reaction: When the temperature was raised to 80 ° C, 540 g of propylene oxide and 1330 g of ethylene oxide mixture were continuously added dropwise, the reaction temperature was maintained at 105 to 115 ° C, and the pressure in the reactor was controlled to be less than 0.35 MPa. After the addition was completed, the reaction was aged at a temperature of 100 to 110 ° C. The pressure in the reactor did not decrease for 1 hour, and the crude polyether polyol was obtained after vacuum dehydration and degassing;

[0046] c. Post-treatment: The polyether polyol is transferred to a post-treatment kettle, distilled water accounting for 4% of the mass of the polyether polyol and phosphoric acid (the amount of phosphoric acid added is 2 times the molar amount of potassium hydroxide) are added, and the temperature is raised to 75°C for crystallization under stirring, and then dehydrated and filtered to obtain a polyether polyol;

[0047] d. End-capping: put the polyether polyol into reactor B, add 86g of sodium hydroxide, replace with nitrogen until the oxygen content is less than 100ppm, evacuate and stir, heat to 100℃, dehydrate for 5h, cool to 95℃ and stop vacuum, slowly add 108g of methyl chloride, control the pressure to be less than 0.35MPa, keep the reaction at 85-95℃ for 3h, evacuate to below -0.095MPa for 1h to obtain a polyether polyol derivative, and centrifuge to remove the solid.

[0048] Comparative Example 1

[0049] This comparative example 1 is a polyether polyol for textile use in the prior art, and its preparation method comprises the following steps:

[0050] a. Feeding and pretreatment: In a 3L autoclave equipped with a stirrer, a meter, a heating and temperature control device, a cooling device (including an outer jacket and an inner coil) and a pressure sensor, add 520g of isooctyl alcohol and 3.67g of potassium hydroxide, replace with nitrogen three times, each time the nitrogen pressure in the reactor is reduced to 0.15MPa, turn on the heating, turn on the vacuum pump, and when the temperature rises to 70°C, turn off the vacuum pump, and isolate the environment in the autoclave from the external environment, and continue to heat to 105°C;

[0051] b. Polymerization reaction: Start to add ethylene oxide continuously, maintain the reaction temperature in the autoclave at 105-115°C by controlling the feeding rate of ethylene oxide and the temperature control device, and control the pressure to be less than 0.25MPa until ethylene oxide is added to 704g. After the feeding is completed, ripen and react for 1h, start the vacuum pump, maintain the pressure less than -0.095MPa, and remove the monomer for 30min to obtain a crude polyether polyol ether;

[0052] c. Post-treatment: Transfer the crude polyether polyol to a post-treatment kettle, add 4% of the mass of the polyether polyol distilled water and phosphoric acid (the amount of phosphoric acid added is twice the molar amount of potassium hydroxide), stir and heat to 75°C for crystallization, then dehydrate and filter press to obtain.

[0053] Performance Testing

[0054] Determination of penetration time 1:

[0055] Weigh 8g (accurate to 0.0001g) of the sample into a 1000mL beaker, add 800mL of distilled water, stir, dissolve, and set aside. Adjust the sample solution temperature to 25℃±1℃, hook the tip of a fishhook (weight 20mg~40mg) to a canvas disc (21 3-strand × 21 4-strand fine canvas made into a 35mm diameter disc), about 2mm~3mm from the edge, tie the other end of the fishhook with a silk thread, and connect the end of the silk thread to a small iron wire hook. Move the above-made wire rack (made of galvanized iron wire with a diameter of 2mm) into the beaker containing the sample solution, and place it on the side of the beaker (1000mL), so that the canvas disc is immersed in the solution, and its apex should be 10mm below the liquid. Immediately start the stopwatch. When the lower end of the fishhook with the canvas piece touches the bottom of the beaker, it is the end point, and record the time required for sedimentation. Repeat the test 10 times, take the average value, eliminate the data that are more than 10 seconds away from the average value, and then calculate the average value, which is the penetration time 1 of the sample.

[0056] Determination of penetration time 2:

[0057] Weigh 8g (accurate to 0.0001g) of the sample into a 1000mL beaker, add 800mL of 10% sodium hydroxide aqueous solution, stir, dissolve, and set aside. Adjust the sample solution temperature to 55℃±1℃, hook the tip of a fishhook (weight 20mg~40mg) to a canvas disc (21 3-strand × 21 4-strand fine canvas made into a 35mm diameter disc), about 2mm~3mm away from the edge, tie the other end of the fishhook with a silk thread, and connect the end of the silk thread to a small iron wire hook. Move the above-made wire rack (made of galvanized iron wire with a diameter of 2mm) into the beaker containing the sample solution, and place it on the side of the beaker (1000mL), so that the canvas disc is immersed in the solution, and its top should be 10mm below the liquid. Immediately start the stopwatch. When the lower end of the fishhook with the canvas piece touches the bottom of the beaker, it is the end point, and record the time required for sedimentation. Repeat the test 10 times, take the average value, eliminate the data that are more than 10 seconds away from the average value, and then calculate the average value, which is the penetration time 2 of the sample.

[0058] The penetration time 1 and penetration time 2 of the polyether polyol derivatives of Examples 1 to 4 and the polyether polyol of Comparative Example 1 were tested. The results are shown in Table 1:

[0059] Table 1 Test table of penetration time 1 and penetration time 2 of Examples 1 to 4 and Comparative Example 1

[0060] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Penetration time 1 6.1s 7.4s 7.8s 8.8s 8.3s Penetration Time 2 8.2s 8.8s 9.2s 9.6s 106s

[0061] It can be seen from Table 1 that the polyether polyol of Comparative Example 1 has a short penetration time in a room temperature distilled water environment and has a good wetting and penetration effect, but in a high temperature and alkaline environment, the penetration time of Comparative Example 1 is long and the wetting and penetration effect is poor. The polyether polyol derivatives of the embodiment use a capping process in the synthesis process, which increases the alkali resistance of the polyether polyol derivatives, so that the polyether polyol derivatives can still maintain a good wetting and penetration effect under high temperature and alkaline conditions.

Claims

1. A method for preparing a polyether polyol derivative for textile use, characterized in that: The following steps are involved: a. Feeding and pretreatment: Add the initiator to the reactor A, add the alkali metal catalyst, replace with nitrogen, then vent, start stirring, and start heating at the same time; b. Polymerization reaction: controlling the temperature in the reactor A to the polymerization temperature, adding the epoxy compound dropwise, controlling the pressure in the reactor A until all the epoxy compound is added dropwise, and heat-aging to obtain a crude polyether polyol ether; c. Post-treatment: transfer the crude polyether polyol to a post-treatment kettle, add distilled water and phosphoric acid, stir and heat to 75-85°C for crystallization, then dehydrate and filter press to obtain polyether polyol; d. End-capping: Put the polyether polyol into the reaction kettle B, evacuate and stir, heat to the reaction temperature, stop the vacuum, add the end-capping agent, keep the reaction at the reaction temperature, evacuate to obtain the polyether polyol derivative.

2. The method for preparing a polyether polyol derivative for textile use according to claim 1, characterized in that: The initiator is one or more of methanol, ethanol, isopropanol, n-butanol and isooctyl alcohol.

3. The method for preparing a polyether polyol derivative for textile use according to claim 1, characterized in that: The alkali metal catalyst is one or both of potassium hydroxide and sodium hydroxide.

4. The method for preparing a polyether polyol derivative for textile use according to claim 1, characterized in that: In the post-treatment, the amount of distilled water added is 4% to 5% of the mass of the crude polyether polyol ether, and the molar amount of phosphoric acid added is twice the molar amount of the alkali metal.

5. The method for preparing a polyether polyol derivative for textile use according to claim 1, characterized in that: The epoxy compound is ethylene oxide or a mixture of ethylene oxide and propylene oxide.

6. The method for preparing a polyether polyol derivative for textile use according to claim 1, characterized in that: The end-capping agent is one of methyl chloride and acetic anhydride.

7. The method for preparing a polyether polyol derivative for textile use according to claim 6, characterized in that: When methyl chloride is used as the end-capping agent, step d is specifically as follows: the polyether polyol is put into a reaction kettle B, sodium hydroxide is added, nitrogen is replaced until the oxygen content is less than 100 ppm, vacuum is drawn, the temperature is raised to the reaction temperature with stirring, the vacuum is stopped, and after methyl chloride is introduced, the pressure is controlled to be less than 0.35 MPa, the reaction is kept at the reaction temperature for 2 to 4 hours, the vacuum is drawn to below -0.095 MPa for 1 hour, and the polyether polyol derivative is obtained by centrifugation.

8. The method for preparing a polyether polyol derivative for textile use according to claim 6, characterized in that: When acetic anhydride is used as the end-capping agent, step d is specifically as follows: the polyether polyol is put into a reaction kettle B, nitrogen is replaced until the oxygen content is less than 100 ppm, vacuum is applied, stirring is performed, and the temperature is raised to the reaction temperature, the vacuum is stopped, and after acetic anhydride is added dropwise, the reaction temperature is kept warm for 2 to 4 hours, the temperature is raised to 110 to 120° C., and vacuum is applied to below -0.095 MPa for 1 hour to obtain a polyether polyol derivative.

9. The method for preparing a polyether polyol derivative for textile use according to claim 7 or 8, characterized in that: The reaction temperature is 70-100°C.