CN111378289A - Chlorinated fatty acid ester environment-friendly plasticizer and preparation method thereof - Google Patents
Chlorinated fatty acid ester environment-friendly plasticizer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of plasticizers, and provides a chlorinated fatty acid ester environment-friendly plasticizer and a preparation method thereof. The palm oil is natural oil, resources are rich, components are stable, the cost is low, and the prepared plasticizer product is stable in quality and non-toxic; further, the invention can select the refined fatty acid methyl ester to be directly chlorinated or to be mixed with palm oil and then chlorinated, and the end point of the chlorination reaction is controlled according to the density requirement, thereby obtaining a series of chlorinated fatty acid ester environment-friendly plasticizers with different densities. The preparation method provided by the invention has the advantages that the whole reaction process is easy to control, the production process is environment-friendly and economical, the operation is simple, and the preparation method is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of plasticizers, and particularly relates to a chlorinated fatty acid ester environment-friendly plasticizer and a preparation method thereof.
Background
The plasticizer is the most important chemical auxiliary agent in the processing process of plastic, rubber and other products. Plasticizers are of a wide variety, with phthalate esters (butyl, octyl) being the most commonly used. Along with the enhancement of the environmental awareness of human beings, the toxicity of the plasticizer is more and more emphasized by people, and the traditional phthalate plasticizer is forbidden in many foreign fields due to the suspected carcinogenesis.
With the enhancement of environmental awareness of people, the application and processing of the vegetable oil-based plasticizer are more and more concerned. For a long time, the vegetable oil-based plasticizer mainly comprises epoxy products, and a large amount of three wastes are generated in the production and processing processes, so that the development of the industry is limited. The chlorinated fatty acid ester is an environment-friendly plasticizer developed by taking grease as a raw material, but the conventional chlorinated fatty acid ester product generally takes waste grease such as swill oil and acidified oil as raw materials, the preparation process is difficult to control, and the product quality is unstable.
Disclosure of Invention
In view of the above, the invention provides a chlorinated fatty acid ester environment-friendly plasticizer and a preparation method thereof. The preparation method provided by the invention uses palm oil as a raw material to prepare the chlorinated fatty acid ester environment-friendly plasticizer, the whole preparation process is easy to control, and the product quality is stable and nontoxic.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of chlorinated fatty acid ester environment-friendly plasticizer comprises the following steps:
(1) mixing palm oil, methanol and a sodium methoxide methanol solution for transesterification reaction to obtain crude fatty acid methyl ester;
(2) rectifying the crude fatty acid methyl ester to obtain refined fatty acid methyl ester;
(3) under the condition of chlorine, carrying out chlorination reaction on the refined fatty acid methyl ester to obtain a chlorinated material;
(4) and mixing the chlorinated material with a stabilizer to obtain the chlorinated fatty acid ester environment-friendly plasticizer.
Preferably, the temperature of the ester exchange reaction is 65-75 ℃, and the time is 0.5-1.5 h;
the acid value of the palm oil is less than or equal to 0.6mgKOH/g, the water content is less than or equal to 0.15 wt%, and the iodine value is 15-38; the mass percentage of sodium methoxide in the sodium methoxide methanol solution is 27.0-31.0%;
the palm oil, the methanol and the sodium methoxide methanol solution are counted by the total mass of 100%, the mass percentage of the palm oil is 85.0-86.4%, the mass percentage of the methanol is 12.9-14.2%, and the mass percentage of the sodium methoxide methanol solution is 0.6-0.9%.
Preferably, the vacuum degree of the rectification is-0.09-0.095 Mpa, the reflux ratio is 0-2, the temperature of the bottom of the tower is 220-240 ℃, the temperature of the top of the tower is 170-200 ℃, and the number of tower plates is 25-30.
Preferably, the temperature of the chlorination reaction is 85-115 ℃.
Preferably, in the step (3), before the chlorination reaction, refined fatty acid methyl ester and palm oil are mixed; the mass ratio of the refined fatty acid methyl ester to the palm oil is (1-9): 1.
Preferably, when no palm oil is added in the step (3), the density of the chlorinated material at the end point of the chlorination reaction is 1.06-1.25 g/m3。
Preferably, when the palm oil is added in the step (3), the density of the chlorinated material at the end point of the chlorination reaction is 1.06-1.18 g/m3。
Preferably, the chlorinated material further comprises, before being mixed with the stabilizer: and degassing the chlorinated material at the temperature of 60-90 ℃ until the acid value of the chlorinated material is less than or equal to 0.5 mgKOH/g.
Preferably, the stabilizer consists of glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent, and the mass ratio of the glycol glycidyl ether to the epoxy fatty acid methyl ester to the epoxy soybean oil to the anti-ultraviolet agent is 1 (0-20) to (0.05-0.1);
the addition amount of the stabilizer is 0.3-3% of the mass of the chlorinated material.
The invention also provides the chlorinated fatty acid ester environment-friendly plasticizer prepared by the preparation method in the scheme.
The invention provides a preparation method of a chlorinated fatty acid ester environment-friendly plasticizer. The palm oil is natural oil, resources are rich, components are stable, the cost is low, the quality of the prepared plasticizer product is stable and non-toxic, and the whole preparation process is easier to control due to the stable components of the palm oil; further, the invention can select the refined fatty acid methyl ester to be directly chlorinated or to be mixed with palm oil and then chlorinated, and the end point of the chlorination reaction is controlled according to the density requirement, thereby obtaining a series of chlorinated fatty acid ester environment-friendly plasticizers with different densities. The preparation method provided by the invention has the advantages that the whole reaction process is easy to control, the production process is environment-friendly and economical, the operation is simple, and the preparation method is suitable for large-scale industrial production.
The invention also provides the chlorinated fatty acid ester environment-friendly plasticizer prepared by the preparation method in the scheme. The chlorinated fatty acid ester environment-friendly plasticizer provided by the invention has stable product quality, does not contain heavy metal and o-benzene substances, has good compatibility with PVC, excellent flame retardance and environment-friendly performance, is low in price, can be widely applied to the PVC fields of films, artificial leather, plastic floors, wire and cable sheaths and the like, and can be applied to the polyurethane field instead of chlorinated paraffin. The results of the examples show that the performance of the PVC product prepared by using the chlorinated fatty acid ester environment-friendly plasticizer is similar to that of the PVC product prepared by using dioctyl terephthalate as the plasticizer, and the chlorinated fatty acid ester environment-friendly plasticizer can replace dioctyl terephthalate and is an ideal environment-friendly plasticizer.
Detailed Description
The invention provides a preparation method of chlorinated fatty acid ester environment-friendly plasticizer, which comprises the following steps:
(1) mixing palm oil, methanol and a sodium methoxide methanol solution for transesterification reaction to obtain crude fatty acid methyl ester;
(2) rectifying the crude fatty acid methyl ester to obtain refined fatty acid methyl ester;
(3) under the condition of chlorine, carrying out chlorination reaction on the refined fatty acid methyl ester to obtain a chlorinated material;
(4) and mixing the chlorinated material with a stabilizer to obtain the chlorinated fatty acid ester environment-friendly plasticizer.
The invention mixes palm oil, methanol and sodium methoxide methanol solution to carry out ester exchange reaction, and obtains crude fatty acid methyl ester. In the invention, the acid value of the palm oil is preferably less than or equal to 0.6mgKOH/g, more preferably 0.1 to 0.5mgKOH/g, the water content is preferably less than or equal to 0.15 wt%, more preferably 0.05 to 0.1 wt%, and the iodine value is preferably 15 to 38, more preferably 20 to 35; the purity of the methanol is preferably more than or equal to 99.0 percent; the mass percentage content of sodium methoxide in the sodium methoxide methanol solution is preferably 27.0-31.0%, and more preferably 28.0-30.0%. In the specific embodiment of the invention, the commercial sodium methoxide methanol solution is directly used for compounding.
In the invention, the mass percentage of the palm oil is preferably 85.0-86.4%, more preferably 85.5-86%, and the mass percentage of the methanol is preferably 12.9-14.2%, more preferably 13-14%, based on 100% of the total mass of the palm oil, the methanol and the sodium methoxide methanol solution, the mass percentage of the methanol does not include methanol introduced into the sodium methoxide methanol solution, and the mass percentage of the sodium methoxide methanol solution is preferably 0.6-0.9%, more preferably 0.7-0.8%.
In the invention, the temperature of the ester exchange reaction is preferably 65-75 ℃, more preferably 68-72 ℃, and the time of the ester exchange reaction is preferably 0.5-1.5 h, more preferably 1 h. In the present invention, the transesterification reaction is preferably performed in a transesterification reaction kettle, and in the present invention, it is preferred that the palm oil is preheated to 60 ℃ and then put into the transesterification reaction kettle, and then methanol and a methanol solution of sodium methoxide are sequentially added. In the transesterification process, palm oil and methanol are subjected to transesterification reaction under the catalytic action of sodium methoxide to generate fatty acid methyl ester and glycerol.
In the present invention, the product of the transesterification reaction is a mixture of fatty acid methyl esters and glycerin; the invention preferably separates crude fatty acid methyl ester from the transesterification reaction product by post-treatment; the post-treatment preferably comprises the steps of: and standing and layering the obtained transesterification reaction product, discharging crude glycerin at the lower layer, and carrying out reduced pressure distillation on the residual material to obtain crude fatty acid methyl ester. In the invention, the vacuum degree of the reduced pressure distillation is preferably-0.06 to-0.09 MPa, and the temperature of the reduced pressure distillation is preferably 60 to 90 ℃; the invention recovers the methanol by reduced pressure distillation and recycles the methanol.
After obtaining the crude fatty acid methyl ester, the invention rectifies the crude fatty acid methyl ester to obtain the refined fatty acid methyl ester. In the invention, the rectification is preferably carried out in a rectification tower, the vacuum degree of the rectification is preferably-0.09-0.095 Mpa, the reflux ratio is preferably 0-2, more preferably 1-2, the number of tower plates is preferably 25-30, the temperature at the bottom of the tower is preferably 220-240 ℃, more preferably 225-235 ℃, the temperature at the top of the tower is preferably 170-200 ℃, more preferably 180-190 ℃; in the invention, refined fatty acid methyl ester is obtained from the tower top by shunting in the rectifying tower, and incomplete reaction kettle residue is at the tower bottom; the yield of the refined fatty acid methyl ester is more than or equal to 96.5 percent. The refined fatty acid methyl ester can be obtained by rectification, so that the materials which are not completely reacted are prevented from participating in the subsequent chlorination reaction, methyl ester, monoglyceride, diglyceride, palm oil and the like exist in the materials which are not completely reacted, and the application performance of the product can be seriously influenced by hydroxyl in the materials.
After the refined fatty acid methyl ester is obtained, the invention performs chlorination reaction on the refined fatty acid methyl ester under the condition of chlorine gas to obtain a chlorinated material. In the invention, the temperature of the chlorination reaction is preferably 85-115 ℃, and more preferably 90-110 ℃; the chlorination reaction is preferably carried out in a chlorination reaction tower; according to the invention, refined fatty acid methyl ester is preferably fed into a chlorination reaction tower, a circulating pump is started, chlorine is introduced, the circulating water flow of a condenser is controlled, and the reaction temperature is maintained at 85-115 ℃.
In the invention, the step of mixing the refined fatty acid methyl ester with the palm oil before the chlorination reaction is preferably further included, namely the refined fatty acid methyl ester and the palm oil are mixed and then are fed into a chlorination reaction tower for chlorination reaction, and the specific chlorination reaction temperature is consistent with the scheme, so that details are not repeated. In the invention, the mass ratio of the refined fatty acid methyl ester to the palm oil is preferably (1-9): 1, and more preferably (3-8): 1. According to the invention, the average molecular weight of the finally obtained plasticizer finished product is increased by adding palm oil, the viscosity of the product is increased, and the prepared chlorinated fatty acid ester environment-friendly plasticizer can meet the requirements of different downstream customers.
The invention preferably controls the reaction end point by controlling the density of the product; in the invention, when the palm oil is not added, the density of the chlorinated material at the end point of the chlorination reaction is preferably 1.06-1.25 g/m3(ii) a When the palm oil is added, the density of the chlorinated material at the end point of the chlorination reaction is preferably 1.06-1.18 g/m3. In the invention, when no palm oil is added, the obtained chlorinated material is a mixture of chlorinated fatty acid methyl ester and chlorinated palm oil; the present invention preferably samples the density of the test product during production to determine the end point of the reaction.
In the invention, the density of the chlorinated material corresponds to the chlorine content, and when the chlorination reaction is carried out by adopting refined fatty acid methyl ester (without adding palm oil), the density is 1.06g/m3The chlorine content of the chlorinated mass of (a) is about 25%; the density was 1.25g/m3The chlorine content of the chlorinated mass of (a) is about 45%; when the chlorination reaction is carried out by mixing fatty acid methyl ester and palm oil, the density is 1.06g/m3The chlorine content of the chlorinated material is 23-25%, and the density is 1.25g/m3The chlorine content of the chlorinated material is 42-45%; under the condition of the same density, the viscosity of the chlorinated material obtained after the palm oil is added is increased, the chlorine content is reduced, and the average molecular weight is increased.
After the reaction reaches the set material density, preferably stopping introducing chlorine, and transferring the chloro-substituted material to a degassing tower for degassing while the chloro-substituted material is hot; in the present invention, the degassing is specifically: blowing compressed air or nitrogen into the degassing tower to remove chlorine and hydrogen chloride gas in the system, wherein the degassing temperature is preferably 60-90 ℃, more preferably 70-80 ℃, and stopping blowing when the acid value of the chlorinated material is less than or equal to 0.5 mgKOH/g.
After the degassing is finished, the invention preferably mixes the degassed chlorinated material with a stabilizer to obtain the chlorinated fatty acid ester environment-friendly plasticizer. In the invention, the stabilizer preferably comprises glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent, and the mass ratio of the glycol glycidyl ether, the epoxy fatty acid methyl ester, the epoxy soybean oil and the anti-ultraviolet agent is preferably 1 (0-20): 0.05-0.1; the addition amount of the stabilizer is preferably 0.3-3% of the mass of the chlorinated material; the present invention has no special requirement on the kind and source of the anti-ultraviolet agent, and can use the commercial anti-ultraviolet agent known to those skilled in the art, such as UV531, UV9000, UV326, etc. The invention avoids the decomposition of the chlorinated fatty acid ester by adding the stabilizer, improves the stability of the plasticizer and enables the plasticizer to be stored for a long time.
The invention also provides the chlorinated fatty acid ester environment-friendly plasticizer prepared by the preparation method in the scheme. The chlorinated fatty acid ester environment-friendly plasticizer provided by the invention has the advantages of stable product quality, no toxicity and excellent performance. And a series of products with different densities can be prepared by controlling the density, so that the requirements of different application fields are met.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Preheating 85 wt% of palm oil (the acid value is 0.58mgKOH/g, the water content is 0.15 wt%, and the iodine value is 38) to 60 ℃, putting the palm oil into a transesterification reaction kettle, sequentially adding 14.2 wt% of methanol (the purity is 99.2%) and 0.8 wt% of sodium methoxide methanol solution (the mass percentage of sodium methoxide is 27.1 wt%), heating to 70 +/-5 ℃ for reacting for 1 hour, standing for 1 hour to separate out lower-layer crude glycerol, distilling the upper-layer fatty acid methyl ester containing methanol under reduced pressure to remove the methanol, and distilling under reduced pressure at the vacuum degree of-0.06 to-0.09 MPa and the temperature of 60-90 ℃; feeding the crude fatty acid methyl ester without methanol into a rectifying tower for purification, wherein the vacuum degree is-0.09 to-0.095 Mpa, the reflux ratio is 0 to 2, the tower bottom temperature is 220 to 240 ℃, and the tower top temperature is 170 to 200 ℃; the refined fatty acid methyl ester is obtained from the top of the tower through the flow division of the rectifying tower, and the bottom of the tower is incomplete reaction kettle residue. The yield of refined fatty acid methyl ester is 96.5 percent by controlling the amount of crude fatty acid methyl ester entering the rectifying tower and the residual discharge amount of the bottom kettle.
The refined fatty acid methyl ester is used for preparing a subsequent plasticizer, and the method specifically comprises the following steps:
(1-1) putting refined fatty acid methyl ester into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and enabling the density to reach 1.06-1.09 g/cm3Stopping introducing chlorine gas, transferring the hot material into a degassing tower, blowing compressed air to maintain the temperature at 60-90 ℃, keeping the acid value at 0.5mgKOH/g, and stopping blowing gas to obtain a chlorinated material; adding a composite stabilizer accounting for 0.3 wt% of the chlorinated material, and uniformly mixing to obtain a mixture with the density of 1.06-1.09 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 0: 0: 0.05 and mixing.
Or:
(1-2) pouring the refined fatty acid methyl ester into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and enabling the density to reach 1.09-1.18 g/cm3Stopping introducing chlorine gas, transferring the hot material to a degassing tower, and blowing compressed air to maintain the temperatureThe temperature is 60-90 ℃, the acid value reaches 0.5mgKOH/g, and the air blowing is stopped to obtain a chlorinated material; adding a composite stabilizer accounting for 3 wt% of the chlorinated material, and uniformly mixing to obtain a mixture with the density of 1.09-1.18 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 20: 0: 0.06 of mixing.
Or:
(1-3) pouring the refined fatty acid methyl ester into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and enabling the density to reach 1.18-1.25 g/cm3Stopping introducing chlorine gas, transferring the hot material into a degassing tower, blowing compressed air to maintain the temperature at 60-90 ℃, keeping the acid value at 0.5mgKOH/g, and stopping blowing gas to obtain a chlorinated material; adding a composite stabilizer accounting for 3 wt% of the chlorinated material, and uniformly mixing to obtain a mixture with the density of 1.18-1.25 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 0: 20: 0.06 of mixing.
Or:
(1-4) mixing 9 parts by mass of refined fatty acid methyl ester and 1 part by mass of palm oil, uniformly pumping the mixture into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and controlling the density to reach 1.06-1.09 g/cm3Stopping introducing chlorine gas, transferring the hot material into a degassing tower, blowing compressed air to maintain the temperature at 60-90 ℃, keeping the acid value at 0.5mgKOH/g, and stopping blowing gas to obtain a chlorinated material; adding a composite stabilizer accounting for 0.3 wt% of the chlorinated material to obtain a mixture with a density of 1.06-1.09 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 0: 0: 0.05 and mixing.
Or:
(1-5) uniformly mixing 1 part by mass of refined fatty acid methyl ester and 1 part by mass of palm oil, pumping the mixture into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and enabling the density to reach 1.09-1.18 g/cm3Stopping introducing chlorine gas, transferring the hot material into a degassing tower, blowing compressed air to maintain the temperature at 60-90 ℃, keeping the acid value at 0.5mgKOH/g, and stopping blowing gas to obtain a chlorinated material; adding a composite stabilizer accounting for 3 wt% of the chlorinated material to obtain a mixture with a density of 1.09-1.18 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 10: 10: 0.06 of mixing.
Example 2
Preheating 86.4 wt% of palm oil (with an acid value of 0.28mgKOH/g, water content of 0.12% and an iodine value of 26) to 60 ℃, putting the palm oil into a transesterification reaction kettle, sequentially adding 13.0 wt% of methanol (with a purity of 99.0%) and 0.6 wt% of sodium methoxide methanol solution (with a sodium methoxide content of 31.0 wt%), heating to 70 +/-5 ℃ for reacting for 1 hour, standing for 1 hour to separate out crude glycerin at a lower layer, distilling the fatty acid methyl ester containing methanol at an upper layer under reduced pressure to remove the methanol, and distilling under reduced pressure at a vacuum degree of-0.06 to-0.09 MPa and a temperature of 60-90 ℃; the crude fatty acid methyl ester without methanol is sent into a rectifying tower for purification, the vacuum degree is-0.09 to-0.095 Mpa, the reflux ratio is 0 to 2, and the temperature at the bottom of the tower is
220-240 ℃ and the tower top temperature is 170-200 ℃; the refined fatty acid methyl ester is obtained from the rectifying tower through the flow division of the rectifying tower, and the bottom of the tower is incomplete reaction kettle residue. The yield of refined fatty acid methyl ester is 96.5 percent by controlling the amount of crude fatty acid methyl ester entering the rectifying tower and the residual discharge amount of the bottom kettle.
The refined fatty acid methyl ester is used for preparing a subsequent plasticizer, and the method specifically comprises the following steps:
(2-1) putting refined fatty acid methyl ester into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and enabling the density to reach 1.06-1.09 g/cm3Stopping introducing chlorine gas and transferring the hot material to a degassing towerBlowing compressed air to maintain the temperature of 60-90 ℃, stopping blowing air until the acid value reaches 0.5mgKOH/g, and obtaining a chlorinated material; adding a composite stabilizer accounting for 0.3 wt% of the chlorinated material, and uniformly mixing to obtain a mixture with the density of 1.06-1.09 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 0: 0: 0.06 of mixing.
Or:
(2-2) pouring the refined fatty acid methyl ester into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and enabling the density to reach 1.09-1.18 g/cm3Stopping introducing chlorine gas, transferring the hot material into a degassing tower, blowing compressed air to maintain the temperature at 60-90 ℃, keeping the acid value at 0.5mgKOH/g, and stopping blowing gas to obtain a chlorinated material; adding a composite stabilizer accounting for 3 wt% of the chlorinated material, and uniformly mixing to obtain a mixture with the density of 1.09-1.18 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 20: 0: 0.06 of mixing.
Or:
(2-3) pouring the refined fatty acid methyl ester into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and enabling the density to reach 1.18-1.25 g/cm3Stopping introducing chlorine gas, transferring the hot material into a degassing tower, blowing compressed air to maintain the temperature at 60-90 ℃, keeping the acid value at 0.5mgKOH/g, and stopping blowing gas to obtain a chlorinated material; adding a composite stabilizer accounting for 3 wt% of the chlorinated material, and uniformly mixing to obtain a mixture with the density of 1.18-1.25 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 0: 20: 0.06 of mixing.
Or:
(2-4) mixing 4 parts by mass of refined fatty acid methyl ester and 1 part by mass of palm oil uniformly, pumping the mixture into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and enabling the density to reach 1.06-1.09 g/cm3Stopping introducing chlorine gas, transferring the hot material into a degassing tower, blowing compressed air to maintain the temperature at 60-90 ℃, keeping the acid value at 0.5mgKOH/g, and stopping blowing gas to obtain a chlorinated material; adding a composite stabilizer accounting for 0.3 wt% of the chlorinated material to obtain a mixture with a density of 1.06-1.09 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 0: 0: 0.05 and mixing.
Or:
(2-5) mixing 2 parts by mass of refined fatty acid methyl ester and 1 part by mass of raw material palm oil uniformly, pumping the mixture into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and controlling the density to reach 1.09-1.18 g/cm3Stopping introducing chlorine gas, transferring the hot material into a degassing tower, blowing compressed air to maintain the temperature at 60-90 ℃, keeping the acid value at 0.5mgKOH/g, and stopping blowing gas to obtain a chlorinated material; adding a composite stabilizer accounting for 3 wt% of the chlorinated material to obtain a mixture with a density of 1.09-1.18 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 10: 10: 0.06 of mixing.
Example 3
Preheating 86.2 wt% of palm oil (with an acid value of 0.18mgKOH/g, water content of 0.09% and an iodine value of 15) to 60 ℃, putting the palm oil into an ester exchange reaction kettle, sequentially adding 12.9 wt% of methanol (with a purity of 99.5%) and 0.9 wt% of sodium methoxide methanol solution (with a sodium methoxide content of 28.5 wt%), heating to 70 +/-5 ℃ for reaction for 1 hour, standing for 1 hour to separate out crude glycerin at a lower layer, distilling the fatty acid methyl ester containing methanol at the upper layer under reduced pressure to remove the methanol, and distilling the fatty acid methyl ester containing the methanol at the lower layer under reduced pressure with a vacuum degree of-0.06 to-0.09 MPa at a temperature of 60-90; feeding the crude fatty acid methyl ester without methanol into a rectifying tower for purification, wherein the vacuum degree is-0.09 to-0.095 Mpa, the reflux ratio is 0 to 2, the tower bottom temperature is 220 to 240 ℃, and the tower top temperature is 170 to 200 ℃; the refined fatty acid methyl ester is obtained from the rectifying tower through the flow division of the rectifying tower, and the bottom of the tower is incomplete reaction kettle residue. The yield of refined fatty acid methyl ester is 96.5 percent by controlling the amount of crude fatty acid methyl ester entering the rectifying tower and the residual discharge amount of the bottom kettle.
The refined fatty acid methyl ester is used for preparing a subsequent plasticizer, and the method specifically comprises the following steps:
(3-1) putting refined fatty acid methyl ester into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and enabling the density to reach 1.06-1.09 g/cm3Stopping introducing chlorine gas, transferring the hot material into a degassing tower, blowing compressed air to maintain the temperature at 60-90 ℃, keeping the acid value at 0.5mgKOH/g, and stopping blowing gas to obtain a chlorinated material; adding a composite stabilizer accounting for 0.3 wt% of the chlorinated material, and uniformly mixing to obtain a mixture with the density of 1.06-1.09 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 0: 0: 0.06 of mixing.
Or:
(3-2) pouring the refined fatty acid methyl ester into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and enabling the density to reach 1.09-1.18 g/cm3Stopping introducing chlorine gas, transferring the hot material into a degassing tower, blowing compressed air to maintain the temperature at 60-90 ℃, keeping the acid value at 0.5mgKOH/g, and stopping blowing gas to obtain a chlorinated material; adding a composite stabilizer accounting for 3 wt% of the chlorinated material, and uniformly mixing to obtain a mixture with the density of 1.09-1.18 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 20: 0: 0.06 of mixing.
Or:
(3-3) pouring the refined fatty acid methyl ester into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and enabling the density to reach 1.18-1.25 g/cm3Stopping introducing chlorine gas, transferring the hot material into a degassing tower, blowing compressed air to maintain the temperature at 60-90 ℃, keeping the acid value at 0.5mgKOH/g, and stopping blowing gas to obtain a chlorinated material; adding a composite stabilizer accounting for 3 wt% of the chlorinated material, and uniformly mixing to obtain a mixture with the density of 1.18-1.25 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 0: 20: 0.06 of mixing.
Or:
(3-4)5 parts by mass of refined fatty acid methyl ester and 1 part by mass of palm oil are mixed uniformly and are put into a chlorination reaction tower, a circulating pump is started, chlorine is introduced, the circulating water flow of a condenser is controlled, the reaction temperature is maintained at 85-115 ℃, and the density reaches 1.06-1.09 g/cm3Stopping introducing chlorine gas, transferring the hot material into a degassing tower, blowing compressed air to maintain the temperature at 60-90 ℃, keeping the acid value at 0.5mgKOH/g, and stopping blowing gas to obtain a chlorinated material; adding a composite stabilizer accounting for 0.3 wt% of the chlorinated material to obtain a mixture with a density of 1.06-1.09 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 0: 0: 0.05 and mixing.
Or:
(3-5) mixing 3 parts by mass of refined fatty acid methyl ester and 1 part by mass of palm oil uniformly, pumping the mixture into a chlorination reaction tower, starting a circulating pump, introducing chlorine, controlling the circulating water flow of a condenser, maintaining the reaction temperature at 85-115 ℃, and enabling the density to reach 1.09-1.18 g/cm3Stopping introducing chlorine gas, transferring the hot material into a degassing tower, blowing compressed air to maintain the temperature at 60-90 ℃, keeping the acid value at 0.5mgKOH/g, and stopping blowing gas to obtain a chlorinated material; adding a composite stabilizer accounting for 3 wt% of the chlorinated material to obtainThe density is 1.09-1.18 g/cm3The chlorinated fatty acid ester environment-friendly plasticizer.
The composite stabilizer is prepared from ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent UV531 in a mass ratio of 1: 10: 10: 0.06 of mixing.
The obtained plasticizer was tested for stability, and was allowed to stand for 180 days under dry, sealed and normal temperature conditions, and the color, heating loss (2 hours at 125 ℃ C., and mass difference between after and before heating), acid value, density and thermal decomposition temperature of the plasticizer before and after standing were measured, wherein comparative test results of the plasticizer sample (sample 1-1) obtained in (1-1) in example 1 are shown in Table 1:
table 11-1 stability test results for samples
| In situ preparation of 1-1 sample | 1-1 sample after standing for 180 days | |
| Chroma (platinum cobalt color comparison) | 20 | 20 |
| Heating decrement/g (125 ℃, 2h) | 0.26 | 0.25 |
| Acid value/mgKOH/g | 0.5 | 0.48 |
| Density/g/mL (20 ℃ C.) | 1.075 | 1.075 |
| Thermal decomposition temperature/. degree.C | 175 | 174 |
The results in table 1 show that the obtained plasticizer is stored for 180 days under the conditions of drying, sealing and normal temperature, and the performance of the product is basically unchanged. The chlorinated fatty acid ester environment-friendly plasticizer prepared by the invention has higher quality stability.
The same stability test is carried out on other plasticizer samples obtained in examples 1-3, and the test results show that the obtained plasticizer is stored for 180 days under the conditions of drying, sealing and normal temperature, and the performances of the product are basically unchanged, which shows that the plasticizer prepared by the invention has higher quality stability.
Application example
Respectively adding 100 parts by mass of PVC resin powder, 2 parts by mass of calcium-zinc stabilizer and 0.5 part by mass of stearic acid into 50 parts by mass of the plasticizer sample obtained in the step (1-1) in the example 1 and 50 parts by mass of DOTP (dioctyl terephthalate), uniformly mixing, carrying out open milling on a double-roll open mill, and vulcanizing on a flat vulcanizing machine to prepare a PVC plastic product after the open milling is finished; the article was tested for properties and the results are shown in table 2:
table 21-1 results of performance tests on PVC Plastic articles prepared from samples
The results in Table 2 show that the difference between the physical properties of the PVC product processed by the plasticizer sample obtained in (1-1) in example 1 and the DOTP product is not large, which indicates that the chlorinated fatty acid ester plasticizer prepared by the invention is an ideal environment-friendly plasticizer.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the chlorinated fatty acid ester environment-friendly plasticizer is characterized by comprising the following steps of:
(1) mixing palm oil, methanol and a sodium methoxide methanol solution for transesterification reaction to obtain crude fatty acid methyl ester;
(2) rectifying the crude fatty acid methyl ester to obtain refined fatty acid methyl ester;
(3) under the condition of chlorine, carrying out chlorination reaction on the refined fatty acid methyl ester to obtain a chlorinated material;
(4) and mixing the chlorinated material with a stabilizer to obtain the chlorinated fatty acid ester environment-friendly plasticizer.
2. The preparation method according to claim 1, wherein the temperature of the ester exchange reaction is 65-75 ℃ and the time is 0.5-1.5 h;
the acid value of the palm oil is less than or equal to 0.6mgKOH/g, the water content is less than or equal to 0.15 wt%, and the iodine value is 15-38; the mass percentage of sodium methoxide in the sodium methoxide methanol solution is 27.0-31.0%;
the palm oil, the methanol and the sodium methoxide methanol solution are counted by the total mass of 100%, the mass percentage of the palm oil is 85.0-86.4%, the mass percentage of the methanol is 12.9-14.2%, and the mass percentage of the sodium methoxide methanol solution is 0.6-0.9%.
3. The preparation method according to claim 1, wherein the degree of vacuum of the rectification is-0.09 MPa to-0.095 MPa, the reflux ratio is 0 to 2, the temperature at the bottom of the column is 220 ℃ to 240 ℃, the temperature at the top of the column is 170 ℃ to 200 ℃, and the number of the plates is 25 to 30.
4. The method according to claim 1, wherein the chlorination reaction is carried out at a temperature of 85 to 115 ℃.
5. The method according to claim 1, wherein the step (3) further comprises mixing refined fatty acid methyl esters and palm oil before the chlorination reaction; the mass ratio of the refined fatty acid methyl ester to the palm oil is (1-9): 1.
6. The method according to claim 1, wherein when no palm oil is added in the step (3), the chlorinated material density at the end point of the chlorination reaction is 1.06-1.25 g/m3。
7. The method according to claim 5, wherein the chlorinated mass density at the end point of the chlorination reaction is 1.06-1.18 g/m when the palm oil is added in the step (3)3。
8. The method of claim 1, further comprising, prior to mixing the chlorinated mass with a stabilizer: and degassing the chlorinated material at the temperature of 60-90 ℃ until the acid value of the chlorinated material is less than or equal to 0.5 mgKOH/g.
9. The preparation method of claim 1 or 8, wherein the stabilizer consists of ethylene glycol glycidyl ether, epoxy fatty acid methyl ester, epoxy soybean oil and an anti-ultraviolet agent, and the mass ratio of the ethylene glycol glycidyl ether, the epoxy fatty acid methyl ester, the epoxy soybean oil and the anti-ultraviolet agent is 1 (0-20): 0.05-0.1;
the addition amount of the stabilizer is 0.3-3% of the mass of the chlorinated material.
10. The chlorinated fatty acid ester environment-friendly plasticizer prepared by the preparation method of any one of claims 1 to 9.
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| PCT/CN2020/109034 WO2021212703A1 (en) | 2020-04-20 | 2020-08-14 | Chlorinated fatty acid ester environment-friendly plasticizer and preparation method therefor |
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| CN111978180A (en) * | 2020-07-31 | 2020-11-24 | 南京信卓化工科技有限公司 | Method for tubular continuous production of chlorinated fatty acid ester |
| CN112592701A (en) * | 2020-12-22 | 2021-04-02 | 广州江盐化工有限公司 | Oil-based drilling fluid based on chlorinated fatty acid ester and preparation method and application thereof |
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| WO2021212703A1 (en) * | 2020-04-20 | 2021-10-28 | 山东岩海建设资源有限公司 | Chlorinated fatty acid ester environment-friendly plasticizer and preparation method therefor |
| CN115181328A (en) * | 2022-07-21 | 2022-10-14 | 浙江嘉澳环保科技股份有限公司 | Preparation method of chlorinated epoxy fatty acid methyl ester compound or main plasticizer and product |
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| DE1198549B (en) * | 1956-07-02 | 1965-08-12 | Dehydag Gmbh | Plasticizer mixtures for polyvinyl chloride and its copolymers |
| JPS4533294B1 (en) * | 1962-03-02 | 1970-10-26 | ||
| CN101704962B (en) * | 2009-11-13 | 2011-09-07 | 广州大学 | Method for preparing chlorinated alkoxy biomass plasticizer |
| CN103193637A (en) * | 2013-04-01 | 2013-07-10 | 福建致尚生物质材料发展有限公司 | Preparation method of bio-ester plasticizing agent |
| CN108849871B (en) * | 2018-08-22 | 2021-02-23 | 苏州丰倍生物科技有限公司 | Environment-friendly oil phase for dispersible oil suspending agent containing mesosulfuron-methyl and preparation method thereof |
| CN109651826A (en) * | 2018-12-19 | 2019-04-19 | 嘉兴若天新材料科技有限公司 | A kind of chlorinated fatty acid methyl esters Environment-friendlyheat heat stabilizer |
| CN109971551B (en) * | 2019-03-28 | 2022-09-20 | 福建省明洲环保发展有限公司 | Method for preparing environment-friendly chlorinated plasticizer from waste oil and fat and product |
| CN110317135A (en) * | 2019-07-08 | 2019-10-11 | 河北金谷再生资源开发有限公司 | Utilize production of biodiesel chlorinated fatty acid methyl esters technique |
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| CN111151199B (en) * | 2020-02-12 | 2024-10-18 | 浙江镇洋发展股份有限公司 | Continuous production device and process of methyl chloride fatty acid |
| CN111378289A (en) * | 2020-04-20 | 2020-07-07 | 山东岩海建设资源有限公司 | Chlorinated fatty acid ester environment-friendly plasticizer and preparation method thereof |
| CN111517951A (en) * | 2020-05-15 | 2020-08-11 | 福建致尚生物质材料发展有限公司 | Method for preparing methyl chloropalmitate plasticizer by using palmitic acid |
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| CN111978180A (en) * | 2020-07-31 | 2020-11-24 | 南京信卓化工科技有限公司 | Method for tubular continuous production of chlorinated fatty acid ester |
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