A modified polyether fatty acid ester and its continuous production method, system and application

Abstract

The invention belongs to the technical field of polyether type compositions, and relates to a modified polyether fatty acid ester and a continuous production method, system and application thereof, and the production method includes: 1) polyether polyol, fatty acid, catalyst and color retainer are uniformly mixed to obtain a mixture; 2) the mixture continuously enters a polyether ester reactor, and a crude product is obtained at a temperature of 70°C to 180°C, a vacuum degree of ‑0.08Mpa to ‑0.1Mpa, and a reaction time of 10min to 30min; 3) the crude product is decolorized and filtered to obtain a final product. The present invention realizes continuous production, the product has a light chromaticity, qualified and stable quality, and the prepared modified polyether fatty acid ester has good defoaming performance.

Description

Technical Field

[0001] The invention belongs to the technical field of polyether type compositions and relates to a modified polyether fatty acid ester and a continuous production method, system and application thereof. Background Art

[0002] Polyether type composition is a copolymer of ethylene oxide and propylene oxide. This type of composition can be used as a defoamer. The main principle is to use the different characteristics of its solubility at different temperatures to achieve the defoaming effect. Polyether type defoamers are non-toxic, odorless, low taste, non-irritating and well dispersible in water. They have strong antifoaming ability, high temperature resistance, acid and alkali resistance, and a wide range of applications. However, due to selectivity, some fields still cannot be used. This requires improvements on this type of defoamer to further enhance its performance and expand its scope of application. Polyether ester defoamer is a polyether derivative with end esterification. It inherits the advantages of polyether defoamers such as easy dispersion, high temperature resistance, acid and alkali resistance, and strong antifoaming ability. Moreover, after esterification, the hydrophilicity is further reduced and the lipophilicity is increased, which weakens the hydrogen bonds between the original polyoxyethylene chain and the water molecules and is conducive to the reduction of surface tension. It is often flat on the gas-liquid interface in a folded structure, so it is more active, less in dosage, and has stronger defoaming power. For example, polyether fatty acid esters with excellent performance were synthesized using p-toluenesulfonic acid as a catalyst and petroleum ether as a water-carrying agent. The esters can be used as one of the monomers in high-speed spinning chemical fiber oils and have good heat resistance, smoothness, bundling and drawing properties. Another example is the synthesis of polyether fatty acid esters (Wei Yuyun and Liang Dejun (Dalian Lushun Chemical Plant 116041)), which is a non-ionic surfactant synthesized by esterification of polyoxyethylene-polyoxypropylene block copolymers and fatty acids. The esters are suitable for cleaning large molecular weight natural oils and fats and have the characteristics of low foaming. However, the current polyether fatty acid esters have the problems of dark color and poor defoaming performance.

[0003] At present, the production method of polyether fatty acid esters generally adopts the intermittent method. The intermittent production method makes the differences between each batch of products, and the product quality is unstable, resulting in unqualified product quality and poor performance. Although the patent document with the announcement number CN208933254U discloses a continuous esterification production equipment for allyl polyether, including a main line and a first feed line and a second feed line connected to the inlet end of the main line; the main line is provided with a static mixer, a fixed bed reactor, an evaporator and a finished product tank from upstream to downstream, and the number of evaporators is at least two. The evaporator is also provided with a purification and separation device, and the purification and separation device includes a separation storage tank connected to the evaporator, and a condenser is provided between the separation storage tank and the evaporator. A vacuum pump is connected to the fixed bed reactor; a heat exchanger is respectively arranged on the first feed pipeline and the second feed pipeline; the allyl alcohol polyether raw material and the acetic anhydride raw material can continuously enter the fixed bed reactor for reaction; the product after the reaction leaves the fixed bed reactor and continues the deacidification process, thereby realizing the continuous esterification production of allyl polyether; however, this production system is suitable for the esterification and deacidification reaction of small molecular acetic anhydride raw materials, and is not suitable for the dehydration esterification reaction of macromolecular polyether fatty acid esters, and therefore it is necessary to develop a production method that ensures the stable performance of macromolecular (polymer) polyether fatty acid esters. Summary of the invention

[0004] In view of the technical problems that existing polyether fatty acid esters have dark chroma, poor performance and unstable product quality, the present invention provides a modified polyether fatty acid ester and a continuous production method, system and application thereof, which can realize continuous production, and the product has light chroma, qualified and stable quality. The prepared modified polyether fatty acid ester has good defoaming performance.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] A method for continuously producing a modified polyether fatty acid ester comprises the following steps:

[0007] 1) stirring and mixing polyether polyol, fatty acid, catalyst and color preservative to obtain a mixture; the molar ratio of the polyether polyol to the fatty acid is 1:(0.6-1), the amount of the catalyst is 0.1%-1% of the total mass of the polyether polyol and the fatty acid, and the amount of the color preservative is 0.1%-1% of the total mass of the polyether polyol and the fatty acid; the catalyst is concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid or phosphoric acid;

[0008] 2) The mixed material continuously enters the polyetherester reactor, at a temperature of 70°C to 180°C, a vacuum degree of -0.08Mpa to -0.1Mpa, and a reaction time of 10min to 30min to obtain a crude product;

[0009] 3) The crude product is decolorized and filtered to obtain the final product.

[0010] It is further defined that the molecular weight of the polyether polyol is 2000, and the hydroxyl value of the polyether polyol is 50mKOH / g to 60mKOH / g; the structure of the polyether polyol is XPEP type, wherein: X is an initiator, P is a propylene oxide segment, and E is an ethylene oxide segment; the fatty acid is a straight-chain acid having a carbon number greater than 10; and the color preservative is oxalic acid, antioxidant 1010, antioxidant 1076, tea polyphenols or ascorbic acid.

[0011] It is further defined that the initiator is propylene glycol, glycerol, pentaerythritol, hexadecanol, octadecyl alcohol, behenyl alcohol or isomeric 12-20 alcohol; and the fatty acid is lauric acid, palmitic acid or stearic acid.

[0012] A continuous production system for realizing the modified polyether fatty acid ester continuous production method, the continuous production system comprises a raw material mixing tank, a polyether ester reactor, a crude product buffer tank and a decolorization filter which are connected in sequence; a packing layer is arranged in the decolorization filter; the packing layer is composed of an activated white carbon black filler and / or a diatomaceous earth filler; the particle size of the activated white carbon black filler and the particle size of the diatomaceous earth filler are both 100 mesh to 300 mesh.

[0013] It is further defined that the filler layer is composed of activated white carbon black filler and diatomaceous earth filler in a mass ratio of 4:1 to 1:1.

[0014] It is further defined that the polyetherester reactor includes a shell, an agitator, a scraper and a dispersion disk; one end of the agitator is located in the shell, and the other end of the agitator is located outside the shell, the scraper is placed in the shell, the scraper is connected to one end of the agitator located in the shell, and a distance is left between the scraper and the inner wall; the distance is less than 3 mm; the dispersion disk is arranged on the cross section of the shell and is located above the scraper.

[0015] It is further defined that a plurality of liquid flow holes are provided on the dispersion disk near the edge of the dispersion disk, the plurality of liquid flow holes are distributed in a ring shape along the center point of the dispersion disk, and the aperture of the liquid flow holes is 10 mm.

[0016] It is further defined that the modified polyether fatty acid ester continuous production system also includes a vacuum device and a condenser, a condenser interface is opened on the shell of the polyether ester reactor, the condenser interface is located between the scraper and the dispersion disk, and the vacuum device is connected to the inside of the shell through the condenser and the condenser interface.

[0017] The modified polyether fatty acid ester is prepared by the modified polyether fatty acid ester continuous production method.

[0018] The application of modified polyether fatty acid ester in improving defoaming performance and antifoaming performance.

[0019] The beneficial effects of the present invention are:

[0020] 1. The production method of the present invention realizes the continuous production of polymer modified polyether ester by sequentially carrying out material mixing, esterification reaction and decolorization filtration. The obtained modified polyether ester product has stable indicators, which overcomes the problem of batch differences in existing intermittent production. At the same time, the continuous production can prevent the unsaturated bonds in fatty acids from being easily oxidized and discolored by high temperature, which causes the problem of easy discoloration of the catalyst. The produced product has light chromaticity and a wide range of applications.

[0021] 2. The modified polyether fatty acid ester of the present invention comprises polyether polyol, fatty acid, catalyst and color preservative. The color preservative is added and a continuous production process is adopted, so that the material stays at high temperature for a short time, further ensuring that the final product produced by the processing has a light color, a Gardner chroma of 1GU to 2GU, and has good defoaming performance.

[0022] 3. The present invention utilizes polyether polyol, fatty acid, catalyst and color preservative to prepare a polymer composition modified polyether fatty acid ester, and its defoaming time and antifoaming time are greatly improved, which has a good market prospect, especially in the application of white water in mineral wool board production line.

[0023] 4. After the raw materials react, the present invention also sets a decolorization filter to filter out the catalyst, color retainer and other components in the raw materials, so that the pH value of the product is neutral, which increases the scope of application; the filler in the decolorization filter is activated white carbon black, diatomaceous earth, etc., the filler particles are 100 mesh to 300 mesh, and the filtering effect is good.

[0024] 5. In the present invention, a scraper is arranged on the inner wall of the polyetherester reactor, so that the polyetherester reactor has a full-wall scraping structure. In this way, when the mixed material continuously flows into the polyetherester reactor, it can be quickly forced to form a film, which is convenient for the rapid removal of the reacted water and improves the esterification reaction rate of the polyetherester; further, the distance between the scraper and the inner wall is less than 3mm, which enhances the forced film-forming effect of the mixed raw materials, and the esterification reaction time is 10min to 30min, which shortens the reaction time. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 A diagram of a continuous production system for modified polyether fatty acid esters provided by the present invention;

[0026] Figure 2 A schematic diagram of the structure of a modified polyether fatty acid ester reactor provided by the present invention;

[0027] in:

[0028] 1—raw material mixing tank; 2—polyether ester reactor; 201—mixed material inlet; 202—dispersion plate; 203—heating jacket; 204—scraper; 205—crude product outlet; 206—condenser interface; 3—crude product buffer tank; 4—decolorization filter; 5—vacuum device; 6—condenser. DETAILED DESCRIPTION

[0029] The present invention is described in detail below in conjunction with the accompanying drawings and embodiments so that those skilled in the art can have a clear and complete understanding of the present invention.

[0030] See also Figure 1 A modified polyether fatty acid ester continuous production system comprises a raw material mixing tank 1, a polyether ester reactor 2, a crude product buffer tank 3 and a decolorization filter 4 which are connected in sequence; a packing layer is arranged in the decolorization filter 4.

[0031] In the present invention, the filler layer is composed of activated white carbon filler and / or diatomaceous earth filler. There are three ways to form the filler layer: all activated white carbon filler, all diatomaceous earth filler; or a mixture of activated white carbon filler and diatomaceous earth filler, wherein the mixture is composed in a mass ratio of 4:1 to 1:1, and preferably, the mass ratio of the two fillers is 3:1 or 2:1.

[0032] Specifically, the particle size of the activated white carbon filler and the particle size of the diatomaceous earth filler are both 100 mesh to 300 mesh, preferably, the particle size is 150 mesh, 200 mesh or 250 mesh.

[0033] In the present invention, the structure of the raw material mixing tank 1 is a cylindrical closed tank body with a sealing cover on the top. The raw material mixing tank 1 is mainly used to melt and mix all the raw materials. Therefore, the raw material mixing tank 1 has heating and stirring functions.

[0034] In order to ensure the mixing temperature, the raw material mixing tank 1 is provided with a heating component to heat the raw material mixing tank 1 . The heating component can be a heating jacket or connected to a heating device, thereby realizing the heating function of the raw material mixing tank 1 .

[0035] In order to improve the raw material mixing effect, a raw material agitator is also provided inside the raw material mixing tank 1. Figure 1 One end of the raw material agitator is placed outside the raw material mixing tank 1, and the other end of the raw material agitator is placed inside the raw material mixing tank 1. The end placed outside is connected to the motor to provide power to the raw material agitator, and the end placed inside is provided with stirring blades to improve the stirring effect.

[0036] Preferably, there are two raw material mixing tanks 1, one for backup and one for use, to ensure that the mixed material continuously enters the polyetherester reactor 2.

[0037] See also Figure 2The polyetherester reactor 2 includes a shell, an agitator and a scraper 204; the agitator ( Figure 1 The agitator (denoted by M in the figure) has one end located in the shell, and the other end of the agitator is located outside the shell, and the agitator and the shell are coaxial; the scraper 204 is placed in the shell and located around the outside of the agitator, the scraper 204 is close to the inner wall of the shell, and a distance is left between the scraper 204 and the inner wall of the shell. The scraper 204 is also connected to one end of the agitator located in the shell, so that the scraper 204 rotates along the axial direction of the shell with the agitator.

[0038] Preferably, the distance between the scraper 204 and the inner wall of the shell is less than 3 mm, and the scraper 204 is a polytetrafluoroethylene scraper. In this way, when the material flows down from the dispersion disk 202, since the scraper 204 is connected to the agitator, the scraper 204 rotates with the agitator. The scraper 204 is used to force the inflowing mixture to form a film, so that the water formed by the reaction can be quickly removed, thereby accelerating the reaction process.

[0039] In the present invention, the agitator is provided to accelerate the reaction speed of the esterification reaction in the polyetherester reactor 2. Specifically, the agitator includes a stirring shaft and a blade disposed on the stirring shaft, one end of the stirring shaft is disposed outside the shell, and the other end of the stirring shaft is disposed inside the shell, the end disposed outside the shell is connected to a motor to provide power to the agitator, and the end disposed inside the shell is provided with a stirring blade to improve the stirring effect; the scraper 204 is connected to the stirring shaft and does not rotate synchronously with the stirring shaft, so that the material is forced to form a film.

[0040] In the present invention, the polyetherester reactor 2 further comprises a dispersion plate 202 disposed in the shell and located above the scraper 204; the dispersion plate 202 is arranged on the cross section of the shell.

[0041] Specifically, a plurality of liquid flow holes are provided on the dispersion disk 202 , and the plurality of liquid flow holes are distributed in a ring shape along the center point of the dispersion disk 202 , and the diameter of the liquid flow holes is 10 mm. The liquid flow holes are close to the edge of the dispersion disk 202 .

[0042] That is, a circle of liquid flow holes is provided near the edge of the dispersion plate 202, so that the mixed material entering the polyetherester reactor 2 can flow evenly through the liquid flow holes on the dispersion plate 202 downward from the kettle wall of the polyetherester reactor 2 to the scraper 204. Preferably, the liquid flow holes are distributed in two circles.

[0043] See also Figure 2The shell of the polyetherester reactor 2 is also provided with a mixture inlet 201 and a crude product outlet 205, respectively. The mixture inlet 201 is located above the dispersion disk 202, and the crude product outlet 205 is located at the bottom of the shell of the polyetherester reactor 2. The shell is a closed reactor with a round upper part and a conical lower part. The side of the cone bottom of the shell is the crude product outlet 205. A scraper 204 is also provided at the cone bottom of the shell. The scraper forces film formation to facilitate the rapid removal of water formed by the reaction and accelerate the reaction process. When the upper material in the shell flows to the cone bottom of the shell by gravity, the crude product obtained by the esterification reaction is scraped out and enters the crude product buffer tank 3.

[0044] In order to ensure the temperature of the esterification reaction in the polyetherester reactor 2 , the polyetherester reactor 2 further comprises a heating jacket 203 arranged outside the shell, and the heating jacket 203 is used to heat the polyetherester reactor 2 .

[0045] The modified polyether fatty acid ester continuous production system provided by the present invention also includes a vacuum device 5 and a condenser 6. A condenser interface 206 is opened on the shell of the polyether ester reactor 2. The condenser interface 206 is located between the scraper 204 and the dispersion disk 202. The vacuum device 5 is connected to the inside of the shell through the condenser 6 and the condenser interface 206.

[0046] In the present invention, the function of the vacuum device 5 is to provide vacuum to the esterification reaction in the polyetherester reactor 2, so that the interior of the reactor is in a negative pressure state, which is convenient for moisture to escape; the vacuum device 5 uses a vacuum pump or other vacuum equipment, which is a vacuum device.

[0047] In the present invention, the function of the condenser 6 is to condense the escaped water to avoid pumping high-temperature gas or water into the vacuum device to affect the operation of the equipment.

[0048] The invention also provides a modified polyether fatty acid ester comprising polyether polyol, fatty acid, catalyst and color preserving agent, and the polymer composition modified polyether fatty acid ester is formed by polyether polyol, fatty acid, catalyst and color preserving agent.

[0049] In the present invention, the molar ratio of polyether polyol to fatty acid is 1:(0.6-1), the amount of catalyst is 0.1%-1% of the total mass of polyether polyol and fatty acid, and the amount of color preservative is 0.1%-1% of the total mass of polyether polyol and fatty acid.

[0050] The reaction principle of the modified polyether fatty acid ester of the present invention is:

[0051] R-OH+R-COOH→R-COO-R+H2O

[0052] The structure of the polyether polyol is XPEP; X is an initiator, P is a propylene oxide segment, and E is an ethylene oxide segment. The initiator is propylene glycol, glycerol, pentaerythritol, hexadecanol, octadecyl alcohol, docosanol, or isomeric 12-20 alcohols. The isomeric 12-20 alcohols specifically refer to isomeric dodecanol, isomeric tridecanol, isomeric tetradecanol, isomeric pentadecanol, isomeric hexadecanol, isomeric heptadecanol, isomeric octadecyl alcohol, isomeric nonadecanol, and isomeric eicosanol.

[0053] In the present invention, the polyether polyol structure is of "XPEP" type, that is, the structure is X:PO:EO:PO. The molecular weight of the polyether polyol is 2000, EO accounts for 15%, and the tail PO accounts for 5%. The hydroxyl value of the polyether polyol is required to be 50mgKOH / g to 60mgKOH / g.

[0054] In the present invention, the fatty acid is a straight chain acid having a carbon number greater than 10. Preferably, the fatty acid is lauric acid, palmitic acid or stearic acid.

[0055] In the present invention, the catalyst is a strong acid, and the catalyst is concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid or phosphoric acid. Preferably, the catalyst is p-toluenesulfonic acid.

[0056] In the present invention, the color preservative is oxalic acid, antioxidant 1010, antioxidant 1076, tea polyphenols or ascorbic acid. The color preservative is used to prevent the unsaturated bonds in fatty acids from being oxidized at high temperatures so that the product has color. Generally, a reducing substance is used as the color preservative.

[0057] In order to improve the stability of the modified polyether fatty acid ester, the modified polyether fatty acid ester continuous production system provided above is used to prepare the modified polyether fatty acid ester.

[0058] The modified polyether fatty acid ester production method provided by the present invention comprises the following steps:

[0059] 1) Add polyether polyol, fatty acid, catalyst and color preservative into a raw material mixing tank 1 and stir and mix them evenly to obtain a mixture.

[0060] The molar ratio of polyether polyol to fatty acid is 1:0.6-1, the amount of catalyst is 0.1%-1% of the total mass of polyether polyol and fatty acid, and the amount of color preservative is 0.1%-1% of the total mass of polyether polyol and fatty acid.

[0061] Specifically, polyether polyol, fatty acid, catalyst and color preservative in the above mass ratio are added to the raw material mixing tank 1 in sequence; after the addition is completed, the stirrer on the raw material mixing tank 1 is turned on, and the temperature is raised to 80° C. to melt and stir evenly to obtain a mixture.

[0062] 2) The mixed material continuously enters the polyetherester reactor 2 from the raw material mixing tank 1, at a temperature of 70°C to 180°C, a vacuum degree of -0.08Mpa to -0.1Mpa, and a reaction time of 10min to 30min, and the obtained crude product enters the crude product buffer tank 3.

[0063] In this step, preferably, the reaction temperature in the polyetherester reactor 2 is 70°C, 80°C, 90°C, 100°C, 120°C, 150°C, 160°C or 180°C; the vacuum degree is -0.08Mpa, -0.09Mpa or -0.1Mpa; and the reaction time is 10min, 15min, 20min, 25min or 30min.

[0064] Specifically, the vacuum device 5 and the heating jacket 203 on the polyetherester reactor 2 are started, the temperature in the polyetherester reactor 2 is raised to 120°C, the vacuum degree is reduced to -0.1Mpa, and then the agitator on the polyetherester reactor 2 is turned on, the mixture in the raw material mixing tank 1 flows into the polyetherester reactor 2 from the mixture inlet 201 at a uniform speed, and after being evenly dispersed through the liquid flow holes on the dispersion plate 202, the mixture flows downward from the kettle wall of the polyetherester reactor 2 to the scraper 204, and the scraper forces the mixture to form a film, so that the moisture of the esterification reaction of the mixture can be quickly removed, the esterification reaction is completed quickly, and the reaction time is shortened. The esterification reaction of the mixture takes 10 minutes. After the reaction is completed, the obtained crude product flows into the crude product buffer tank 3 from the crude product outlet 205, and the crude product is kept warm at 80°C; then it flows into the decolorization filter 4, and the filler layer filters out the catalyst and the color retaining agent in the crude product to obtain the final product. After testing, the pH value of the product is neutral, and the product is colorless or light yellow and transparent.

[0065] 3) The crude product is passed through the crude product buffer tank 3 into the decolorization filter 4, and after decolorization and filtration through the packing layer, the final product is obtained.

[0066] Taking several groups of different material ratios as examples, products are prepared using the continuous production system and method of the present invention, and the performance advantages of the products prepared by the present invention are verified through experiments.

[0067] It should be noted that in the following performance tests, the foaming liquid is white water from the mineral wool board production line, the product defoaming time and foam suppression time are determined by the bubbling method, and the air flow rate is 3L / min.

[0068] Experimental Groups 1 to 8 are material ratios of the modified polyether fatty acid ester provided by the present invention, see Table 1 for details.

[0069] Comparative groups 1 to 8 are comparative examples of the present invention. Compared with the experimental group, no color preservative is added. The materials and proportions thereof are shown in Table 2.

[0070] Comparative groups 9 to 16 are comparative examples of the present invention. Compared with the experimental group, different polyether polyols are selected. The materials and proportions thereof are shown in Table 3.

[0071] Table 1 Material ratio of experimental group 1 to experimental group 8

[0072]

[0073] Table 2 Material ratios of comparison groups 1 to 8

[0074] Group Polyether polyols fatty acid catalyst Comparison group 1 Propylene glycol polyether 920g Lauric acid 80g p-Toluenesulfonic acid 5g Comparison group 2 Propylene glycol polyether 920g Lauric acid 80g Concentrated sulfuric acid 5g Comparison group 3 Propylene glycol polyether 900g Stearic acid 100g p-Toluenesulfonic acid 5g Comparison group 4 Propylene glycol polyether 900g Stearic acid 100g Concentrated sulfuric acid 5g Comparison group 5 Propylene glycol polyether 500g, hexadecanol polyether 420g Lauric acid 80g p-Toluenesulfonic acid 5g Comparison group 6 Propylene glycol polyether 500g, hexadecanol polyether 420g Lauric acid 80g Concentrated sulfuric acid 5g Comparison group 7 Propylene glycol polyether 500g, hexadecanol polyether 400g Lauric acid 40g, stearic acid 60g p-Toluenesulfonic acid 5g Comparison group 8 Propylene glycol polyether 500g, hexadecanol polyether 400g Lauric acid 40g, stearic acid 60g Concentrated sulfuric acid 5g

[0075] Table 3 Material ratios of comparison groups 9 to 16

[0076] Group Polyether polyols fatty acid catalyst Color Preservative Comparison group 9 Polyether GPE2000 / 920g Lauric acid 80g p-Toluenesulfonic acid 5g Oxalic acid 5g Comparison group 10 Polyether GPE2000 / 920g Lauric acid 80g Concentrated sulfuric acid 5g Antioxidant 1010 5g Comparison group 11 Polyether GPE2000 / 920g Stearic acid 100g p-Toluenesulfonic acid 5g Oxalic acid 5g Comparison group 12 Polyether GPE2000 / 920g Stearic acid 100g Concentrated sulfuric acid 5g Antioxidant 1010 5g Comparison group 13 Polyether GP2000 / 920g Lauric acid 80g p-Toluenesulfonic acid 5g Oxalic acid 5g Comparison group 14 Polyether GP2000 / 920g Lauric acid 80g Concentrated sulfuric acid 5g Antioxidant 1010 5g Comparison group 15 Polyether GP2000 / 920g Lauric acid 40g, stearic acid 60g p-Toluenesulfonic acid 5g Oxalic acid 5g Comparison group 16 Polyether GP2000 / 920g Lauric acid 40g, stearic acid 60g Concentrated sulfuric acid 5g Antioxidant 1010 5g

[0077] Test 1: Continuous production stability

[0078] The materials and proportions of experimental group 1, experimental group 7 and experimental group 8 were used to prepare modified polyether fatty acid esters according to the continuous production method provided by the present invention.

[0079] It should be noted that in continuous production, the residence time of the materials in the polyetherester reactor 2 is 10 minutes, the vacuum degree in the polyetherester reactor 2 is -0.08 MPa, the reaction temperature is 160°C, the continuous production time of each group of raw materials is 72 hours, and samples are taken from the polyetherester reactor 2 at the continuous production time of 12 hours, 24 hours, 36 hours, 48 ​​hours, 60 hours and 72 hours to detect the conversion rate, chromaticity, defoaming time and anti-foaming time. The test results are shown in Table 4.

[0080] Table 4 Performance test results of the experimental group in continuous production for 72 hours

[0081] Group Sampling time / h Conversion rate / % Chroma / GU Defoaming time / s Anti-foam time / min Experimental Group 1 12 82 1 6 ＞10 Experimental Group 1 24 83 1 6 ＞10 Experimental Group 1 36 83 1 5 ＞10 Experimental Group 1 48 82 1 6 ＞10 Experimental Group 1 60 81 1 5 ＞10 Experimental Group 1 72 83 1 6 ＞10 Experimental Group 7 12 81 1 6 ＞10 Experimental Group 7 24 82 1 5 ＞10 Experimental Group 7 36 83 1 5 ＞10 Experimental Group 7 48 82 1 5 ＞10 Experimental Group 7 60 81 1 6 ＞10 Experimental Group 7 72 82 1 5 ＞10 Experimental Group 8 12 84 2 5 ＞10 Experimental Group 8 24 82 2 4 ＞10 Experimental Group 8 36 83 2 5 ＞10 Experimental Group 8 48 82 2 5 ＞10 Experimental Group 8 60 81 2 5 ＞10 Experimental Group 8 72 83 2 4 ＞10

[0082] As can be seen from Table 4, when the modified polyether fatty acid ester is prepared by the continuous production method, the product chromaticity is stable, and the defoaming time and the foam suppression time are stable, indicating that the product stability of the continuous production process is very good; from the defoaming time and the foam suppression time, it is also shown that the modified polyether fatty acid ester prepared by the present invention has good defoaming and foam suppression performance, and can be used as a defoaming agent, especially in the white water of the mineral wool board production line.

[0083] Test 2: Chroma Detection

[0084] Using experimental groups 1 to 8 and comparative groups 1 to 8, modified polyether fatty acid esters were prepared according to the continuous production method provided by the present invention.

[0085] It should be noted that in the continuous production, the residence time of the material in the polyetherester reactor 2 is 10 minutes, the vacuum degree in the polyetherester reactor 2 is -0.08 MPa, the reaction temperature is 160°C, and under the same continuous production time of 24 hours, samples are taken from the polyetherester reactor 2 to test the color. The test results are shown in Table 5.

[0086] Table 5 Chromaticity results of products obtained with different raw materials

[0087] Comparison Group Chroma GU Experimental groups Chroma GU Comparison group 1 9 Experimental Group 1 1 Comparison group 2 11 Experimental Group 2 2 Comparison group 3 9 Experimental Group 3 1 Comparison group 4 11 Experimental Group 4 2 Comparison group 5 9 Experimental Group 5 1 Comparison group 6 11 Experimental Group 6 2 Comparison group 7 9 Experimental Group 7 1 Comparison group 8 11 Experimental Group 8 2

[0088] It can be seen from the data in Table 5 that, compared with the control group, the Gardner chromaticity of the product of the present invention is between 1GU and 2GU. It can be seen that when a color preservative is added and under continuous production, the chromaticity value of the sample can be significantly reduced, and the product produced is light in color, basically colorless or light yellow transparent, thereby solving the technical problems that the catalyst is easy to change color and the unsaturated bonds in fatty acids are easily oxidized and discolored by high temperature.

[0089] Test 3

[0090] Experimental groups 1 to 8 and comparative groups 9 to 16 were selected to prepare modified polyether fatty acid esters according to the continuous production method provided by the present invention.

[0091] It should be noted that in continuous production, the residence time of the material in the polyetherester reactor 2 is 10 minutes, the vacuum degree in the polyetherester reactor 2 is -0.08 MPa, and the reaction temperature is 160°C. Under the same continuous production time, samples are taken from the polyetherester reactor 2 to test the defoaming time and the anti-foaming time. The test results are shown in Table 6.

[0092] Table 6 Comparison of defoaming and antifoaming performance of experimental groups 1 to 8 and comparison groups 9 to 16

[0093] Comparison group Defoaming time / s Anti-foam time / min Experimental Group Defoaming time / s Anti-foam time / min Comparison group 9 24 4 Experimental Group 1 5 ＞10 Comparison group 10 31 4.5 Experimental Group 2 4 ＞10 Comparison group 11 28 5 Experimental Group 3 4 ＞10 Comparison group 12 29 4 Experimental Group 4 5 ＞10 Comparison group 13 10 15 Experimental Group 5 6 ＞10 Comparison group 14 12 1 Experimental Group 6 5 ＞10 Comparison group 15 14 1 Experimental Group 7 4 ＞10 Comparison group 16 11 1.5 Experimental Group 8 6 ＞10

[0094] As can be seen from Table 6, compared with the polyether esters prepared by using the polyethers of GPE and GP structures sold on the market, the defoaming performance and antifoaming performance of the polymer modified polyether fatty acid esters obtained by continuous production using the special structure polyether polyols of the present invention are greatly improved.

[0095] In addition, the pH value of the polymer modified polyether fatty acid ester obtained by the continuous production method of the present invention from polyether polyols, fatty acids, catalysts and color preservatives was also tested. The results showed that the pH value of the product was 6 to 8 and the pH value was in the neutral range, indicating that the modified polyether fatty acid ester product can be used in many fields and has a wide range.

[0096] The above-mentioned embodiments illustrate the continuous production method of the modified polyether fatty acid ester provided by the present invention, which sequentially carries out material mixing, esterification reaction and decolorization and filtration, which can not only realize continuous production and eliminate the problem of batch differences in quality of intermittent reaction products, but also obtain stable defoaming agent product indicators. In addition, a polymer modified polyether fatty acid ester is formed by using a polyether polyol with a special structure, and its defoaming performance and antifoaming performance are much higher than those of the existing polyether ester products of the same type on the market. At the same time, the reaction time is short during production, which can prevent the defects of unsaturated bonds in fatty acids in existing production that are easily oxidized and discolored by high temperature and catalysts that are easily discolored, and effectively filter out components such as catalysts and color preservatives in the raw materials. The pH value of the obtained product is 6-8, which belongs to the neutral range, the chromaticity value is small, and the product has a wider range of use.

[0097] The above are several specific implementations of the technical solution of the present invention, but they cannot be used as limitations on the protection scope of the present invention. Any equivalent replacements and modifications made on the basis of the present invention will fall within the protection scope of the present invention.

Claims

1. A method for continuously producing modified polyether fatty acid esters, characterized in that: The following steps are involved: 1) Stirring and mixing polyether polyol, fatty acid, catalyst and color preservative to obtain a mixture; the molar ratio of the polyether polyol to the fatty acid is 1: (0.6-1), the amount of the catalyst is 0.5% of the total mass of the polyether polyol and the fatty acid, and the amount of the color preservative is 0.5% of the total mass of the polyether polyol and the fatty acid; the catalyst is p-toluenesulfonic acid; the structure of the polyether polyol is XPEP type, wherein: X is an initiator, P is a propylene oxide segment, and E is an ethylene oxide segment; the polyether polyol is a propylene glycol polyether; the fatty acid is lauric acid or stearic acid; the color preservative is oxalic acid; 2) The mixed material continuously enters the polyetherester reactor (2) at a temperature of 70°C to 180°C and a vacuum degree of -0.08Mpa to -0.1Mpa for a reaction time of 10min to 30min to obtain a crude product; 3) The crude product is decolorized and filtered to obtain the final product.

2. The modified polyether fatty acid ester prepared by the modified polyether fatty acid ester continuous production method according to claim 1.

3. Use of the modified polyether fatty acid ester as claimed in claim 2 in improving defoaming performance and foam suppression performance.

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