CN109734888B - Method for synthesizing phosphorus-containing polyester polyol by using PTA residues - Google Patents
Method for synthesizing phosphorus-containing polyester polyol by using PTA residues Download PDFInfo
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- CN109734888B CN109734888B CN201910077496.5A CN201910077496A CN109734888B CN 109734888 B CN109734888 B CN 109734888B CN 201910077496 A CN201910077496 A CN 201910077496A CN 109734888 B CN109734888 B CN 109734888B
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Abstract
The application relates to a method for synthesizing phosphorus-containing polyester polyol by using PTA residues, which comprises the following steps: s1: reacting the PTA residue, unsaturated monobasic fatty acid, phosphorus-containing inorganic acid, catalyst and polyol at a first temperature for a first predetermined period of time to obtain a first reaction mixture; s2: and (3) keeping the temperature of the first reaction mixture at a second temperature for a second preset time period, and obtaining the phosphorus-containing polyester polyol after the reaction is finished. The method has the advantages that the phosphorus-containing inorganic acid is added as the additive in the process of synthesizing the polyester polyol by using the PTA residues for the first time, so that the filtering time in the subsequent process is obviously shortened, the precious heavy metal catalyst can be recycled, and the cost for preparing the polyester polyol is indirectly reduced.
Description
Technical Field
The application relates to the technical field of organic synthesis and chemical waste recycling. In particular, the present application relates to a process for synthesizing phosphorus-containing polyester polyols using PTA residues.
Background
As specified in the group Standard "T/SPUIA 000001-2018" issued by the polyurethane industry Association in Shanghai, Purified Terephthalic Acid (PTA) residue (residual quenching in pure terephthalic acid contamination) refers to a residue produced in both oxidation and purification processes for producing Purified Terephthalic Acid (PTA), and has terephthalic acid, p-toluic acid, isophthalic acid, benzoic acid, and the like as main components. 90% of these components in the PTA residue have recycling value.
China is a large country for PTA production, producing at least 4000 million tons of PTA per year, producing about 5 kilograms of PTA residue per ton of PTA produced, and producing at least 20 million tons of PTA residue per year. Therefore, the task of recycling the PTA residues is very difficult. The chemical method for recycling PTA residues at present mainly comprises the steps of preparing a plasticizer by an esterification method, synthesizing a methyl ester compound by esterification of methanol, preparing unsaturated resin by esterification of the methyl ester compound and ethylene glycol, preparing activated carbon by utilizing the PTA residues and the like.
In addition, the synthesis of polyester polyol using PTA residues as raw materials of polybasic acids is another important direction for recycling PTA residues. The aromatic polyester polyol synthesized from PTA residues can be used as a raw material for preparing polyurethane, and has wide application prospect and considerable economic benefit. However, in the PTA production process, heavy metals such as cobalt and manganese are used as catalysts, and these heavy metal catalysts also remain in the PTA residues, which poses certain obstacles to recycling of the PTA residues.
For this reason, there is a continuing need in the art to develop a method for synthesizing phosphorus-containing polyester polyols using PTA residues that can reduce or even eliminate the effect of heavy metal catalysts.
Disclosure of Invention
The PTA residue contains residual heavy metal catalyst such as cobalt or manganese, etc. On the one hand, these heavy metal catalysts are expensive but cannot be effectively recovered because they are contained in the PTA residue, resulting in a waste of valuable resources. On the other hand, these heavy metal catalysts or their ions easily form metal soaps with organic acids, which are not easily water-soluble, and this brings great difficulty to the subsequent filtration process, resulting in excessively long filtration time and significantly shortened service life of the filtration equipment. Furthermore, in the process of producing PTA, it is often necessary to wash the piping with a strong base such as sodium hydroxide in order to descale the piping. When polymers are synthesized using PTA residues, cations in the strong base also form metal soaps, increasing filtration difficulty.
The present application aims to provide a method for synthesizing phosphorus-containing polyester polyol by using PTA residues, which can reduce or even eliminate the effect of heavy metal catalysts, thereby solving the above technical problems in the prior art. Specifically, the process of the present application pioneers the addition of phosphorus-containing inorganic acids as additives during the synthesis of polyester polyols using PTA residues. The phosphorus-containing inorganic acid can convert various water-insoluble metal soaps in the PTA residue into inorganic acid salts which are easily soluble in water or a reaction system, which surprisingly shortens the time consumed by the synthesized polyester polyol in subsequent filtration and can simultaneously recover the precious heavy metals.
In order to achieve the above object, the present application provides the following technical solutions.
In a first aspect, the present application provides a process for synthesizing phosphorus-containing polyester polyols using PTA residues, characterized in that said process comprises the steps of:
s1: reacting the PTA residue, unsaturated monobasic fatty acid, phosphorus-containing inorganic acid, catalyst and polyol at a first temperature for a first predetermined period of time to obtain a first reaction mixture;
s2: and (3) keeping the temperature of the first reaction mixture at a second temperature for a second preset time period, and obtaining the phosphorus-containing polyester polyol after the reaction is finished.
In one embodiment of the first aspect, the method further comprises dehydrating the starting materials forming the first reaction mixture at 170 ℃ prior to step S1.
In one embodiment of the first aspect, the method further comprises maintaining the phosphorus-containing polyester polyol under vacuum for a third predetermined period of time after step S2.
In one embodiment of the first aspect, the unsaturated monobasic fatty acid is oleic acid.
In one embodiment of the first aspect, the phosphorus-containing inorganic acid is one or more of phosphoric acid, phosphorous acid, or hypophosphorous acid.
In one embodiment of the first aspect, the polyol is a mixture of glycerol and diethylene glycol.
In one embodiment of the first aspect, at least a portion of the diethylene glycol is by-product diethylene glycol.
In one embodiment of the first aspect, the catalyst comprises one or more of tetrabutyl titanate, zinc acetate, or dibutyltin dilaurate.
In one embodiment of the first aspect, the first predetermined period of time is 4-6 hours.
In one embodiment of the first aspect, the second predetermined period of time is 5-8 hours.
In one embodiment of the first aspect, the first temperature is 190-220 ℃.
In one embodiment of the first aspect, the second temperature is 220-230 ℃.
Compared with the prior art, the method has the advantages that the phosphorus-containing inorganic acid is added as the additive in the process of synthesizing the polyester polyol by using the PTA residues for the first time, so that the filtering time in the subsequent process is obviously shortened, the precious heavy metal catalyst can be recycled, and the cost for preparing the polyester polyol is indirectly reduced.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical, or other property (e.g., molecular weight, melt index, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. these are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. The numerical ranges within this application provide, among other things, the amount of each comonomer in the acrylate copolymer, the amount of each component in the photoresist composition, the temperature at which the acrylate is synthesized, and the various characteristics and properties of these components.
When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
In a first aspect, the present application provides a process for synthesizing phosphorus-containing polyester polyols using PTA residues, characterized in that said process comprises the steps of:
s1: reacting the PTA residue, unsaturated monobasic fatty acid, phosphorus-containing inorganic acid and polyol at a first temperature for a first predetermined period of time to obtain a first reaction mixture;
s2: and keeping the first reaction mixture and the catalyst at a second temperature for a second preset time period, and obtaining the phosphorus-containing polyester polyol after the reaction is finished.
In one embodiment, when the catalyst is unstable under the reaction conditions of step S1, the catalyst may be added in step S2.
In one embodiment, the first predetermined period of time is 4-6 hours. The length of the first predetermined time period can be adjusted by a person skilled in the art according to actual needs.
In one embodiment, the second predetermined period of time is 5-8 hours. Similarly, the person skilled in the art can adjust the length of the second predetermined period of time according to the actually required index, such as acid value. In one embodiment, the acid number index at this stage is less than or equal to 10 mgKOH/g.
In one embodiment, the first temperature is 190-220 ℃. In a specific embodiment, the first temperature is 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃ or 220 ℃. In one embodiment, the ramp rate for this stage is preferably 10-20 deg.C/hr, and can be, for example, 10 deg.C/hr, 11 deg.C/hr, 12 deg.C/hr, 13 deg.C/hr, 14 deg.C/hr, 15 deg.C/hr, 16 deg.C/hr, 17 deg.C/hr, 18 deg.C/hr, 19 deg.C/hr, or 20 deg.C/hr.
In one embodiment, the second temperature is 220-230 ℃. In one embodiment, the second temperature is 220 ℃, 221 ℃, 222 ℃, 223 ℃, 224 ℃, 225 ℃, 226 ℃, 227 ℃, 228 ℃, 229 ℃ or 230 ℃. In one embodiment, the ramp rate for this stage is preferably 10-20 deg.C/hr, and can be, for example, 10 deg.C/hr, 11 deg.C/hr, 12 deg.C/hr, 13 deg.C/hr, 14 deg.C/hr, 15 deg.C/hr, 16 deg.C/hr, 17 deg.C/hr, 18 deg.C/hr, 19 deg.C/hr, or 20 deg.C/hr.
In one embodiment, the method further comprises dehydrating the starting materials forming the first reaction mixture at 170 ℃ prior to step S1.
Dehydrating the feedstock may include removing water from the components of the feedstock by applying a vacuum to the reaction apparatus.
In a specific embodiment, the method further comprises maintaining the phosphorus-containing polyester polyol in a vacuum state for a third predetermined period of time after step S2.
In one embodiment, the vacuum dewatering is performed at a vacuum level of 0 to-0.09 MPa. As will be understood by those skilled in the art, the term "vacuum degree of 0 to 0.09 MPa" means a vacuum degree of-0.02 MPa, -0.03MPa … … to 0.09MPa, etc. of the reaction vessel during vacuum dehydration.
In one embodiment, the third predetermined period of time may be 1-2 hours, for example, may be 1 hour, 1.5 hours, or 2 hours. The length of the period of time for which the vacuum state is maintained can be used to adjust and optimize the indices of the reaction product polyester polyol, such as acid value, viscosity, and hydroxyl value, to the desired value range. And when the indexes reach the standard, cooling the polyester polyol serving as a reaction product, filtering, discharging and packaging.
In one embodiment, the purified terephthalic acid residue is a PTA residue from ashore petrochemical. Although the main concepts and spirit of the present application are described in the following examples by way of examples of PTA residues from ashore petrochemical, it will be understood by those skilled in the art that the process of the present application is equally applicable to other PTA residues of different compositions.
In one embodiment, the unsaturated monobasic fatty acid is oleic acid.
The addition of phosphorus-containing inorganic acid in the process of synthesizing polyester polyol is the initiative of the inventor in the industry. In one embodiment, the type of phosphorus-containing inorganic acid used is not particularly limited herein, so long as it can convert the organic metal soap into an inorganic salt that is readily soluble in water. In a particularly preferred embodiment, the phosphorus-containing inorganic acid is one or more of phosphoric acid, phosphorous acid or hypophosphorous acid. The phosphoric acid can convert a metal soap, which is hardly soluble in water, in the PTA residue into an inorganic salt, which is easily soluble in water, in the synthesis of polyester polyol using the PTA residue. In addition, the organic carboxylic acid and the excessive phosphoric acid generated by the method can react with the polyhydric alcohol to generate corresponding carboxylic ester and phosphate ester, and the phosphorus-containing polyester polyol is obtained without generating additional waste acid wastewater.
In one embodiment, the amount of the phosphorus-containing inorganic acid is not particularly limited. In one embodiment, the phosphorus-containing inorganic acid is in excess, on a molar basis, relative to the total amount of heavy metal catalyst, metal soap, etc. in the PTA residue. In one embodiment, the phosphorus-containing inorganic acid is present in an amount less than or equal to 5% by weight based on the total weight of all the raw material components. For example, in one embodiment, the phosphorus-containing inorganic acid is used in an amount of 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.5%, 4.0%, 4.5%, or 5.0% by weight based on the total weight of all the raw material components.
In one embodiment, the polyol is a mixture of glycerol and diethylene glycol.
In one embodiment, at least a portion of the diethylene glycol is by-product diethylene glycol.
As used herein, the term "by-product diethylene glycol" is a mixture of diethylene glycol, triethylene glycol and water. The by-product diethylene glycol comprises 70-80% of diethylene glycol, 15-20% of triethylene glycol and 5-10% of water by weight.
In one embodiment, the catalyst used is not particularly limited. In a preferred embodiment, the catalyst comprises one or more of tetrabutyl titanate, zinc acetate, or dibutyltin dilaurate. In one embodiment, the amount of the catalyst is not particularly limited. In a preferred embodiment, the catalyst is used in an amount less than or equal to 5% by weight based on the total weight of all feed components. For example, in one embodiment, the catalyst is used in an amount of 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.5%, 4.0%, 4.5%, or 5.0% by weight based on the total weight of all feed components.
Any combination of the above preferred conditions, while meeting the general knowledge in the art, will result in a preferred embodiment of the invention.
Examples
The technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present application. The reagents and raw materials used are commercially available unless otherwise specified.
In the following examples, the PTA residue used was PTA residue from Shanghai petrochemical.
Viscosity according to the national standard GB/T12008.7 Plastic polyether polyol part 7: measurement of viscosity "was carried out as defined in the above section.
The hydroxyl number is determined according to the provisions of the industry Standard HG/T2709-1995-determination of the hydroxyl number in the polyester polyol.
The acid number is determined according to the provisions of the industry Standard "determination of acid number in polyester polyols HG/T2708-1995".
The color is determined according to the regulations of the national standard GB/T1722-1992 iron-cobalt colorimetric method.
The water content is measured according to the regulations of the national standard GB/T22313-2008 'determination of the water content of the polyol of the plastic for polyurethane production'.
Example 1
This example relates to a method for the synthesis of the phosphorus-containing polyester polyol LPS-360.
First, 5 tons of PTA residue (Kaishiki), 3 tons of diethylene glycol, 2 tons of a byproduct of diethylene glycol, 1.3 tons of glycerin, 1 ton of oleic acid, and 5kg of phosphoric acid were charged into a reaction vessel. The reaction mass was dehydrated at 170 ℃ for 2 hours under atmospheric pressure. After completion of the dehydration, the temperature of the reaction system was raised to 190 ℃ at a temperature rising rate of 20 ℃/hr, and the temperature was maintained at that temperature for 6 hours to obtain a first reaction mixture.
Then, 5kg of catalyst tetrabutyl titanate is added into the reaction kettle, the temperature of the reaction system is increased to 230 ℃ at the heating rate of 10 ℃/hour, the temperature is maintained for 5 hours, and when the acid value of the reaction product is detected to be less than 10mgKOH/g, the next reaction stage is carried out.
Next, the reaction system was maintained under a vacuum of-0.09 MPa for 2 hours. And when the acid value of the reaction product is detected to be less than 2.5mgKOH/g, cooling to below 150 ℃, filtering for 2 hours by using a CT-10 type filter with the filtering area of 10 square meters at the flux of 6000 kg/hour, discharging the filtrate with the flow rate of a discharge pump of 12 cubic meters per hour, and packaging the discharged filtrate to obtain the finished product of the phosphorus-containing polyester polyol.
The phosphorus-containing polyester polyol of this example was tested according to the various national, industrial or corporate standards as described above, and found to have a viscosity of 3000 mPa.s at 25 ℃, a hydroxyl value of 390mgKOH/g, an acid value of 1.5mgKOH/g, a color (Fe-Co) of No. 12, and a water content of 0.1% by weight.
The phosphorus-containing polyester polyol of this example has an acid value, viscosity, hydroxyl value and color that meet the requirements for the type I polyester polyol physical properties in the group Standard T/SPUIA000001-2018 issued by the polyurethane industry Association of Shanghai.
Example 2
This example relates to a method for the synthesis of the phosphorus-containing polyester polyol LPS-360.
First, 5 tons of PTA residue (Kaishiki), 3 tons of diethylene glycol, 2 tons of a byproduct of diethylene glycol, 1.3 tons of glycerin, 1 ton of oleic acid, 15kg of catalytic zinc acetate, and 15kg of phosphoric acid were charged into a reaction vessel. The reaction mass was dehydrated at 170 ℃ for 2 hours under atmospheric pressure. After completion of the dehydration, the temperature of the reaction system was raised to 200 ℃ at a temperature rising rate of 20 ℃/hr and kept at that temperature for 5 hours to obtain a first reaction mixture.
Then, the temperature of the reaction system was raised to 230 ℃ at a temperature rising rate of 10 ℃/hr, and the temperature was maintained for 7 hours, and when the acid value of the reaction product was detected to be less than 10mgKOH/g, the reaction was carried out in the next reaction stage.
Next, the reaction system was maintained under a vacuum of-0.09 MPa for 2 hours. When the acid value of the reaction product is detected to be less than 2.5mgKOH/g, the temperature is reduced to be below 150 ℃, the reaction product is filtered for 2 hours by a CT-10 type filter with the filtering area of 10 square meters at the flux of 5000 kg/hour, the flow of a filtrate discharging pump is 12 cubic meters per hour, and the filtrate is discharged and packaged to obtain the finished product of the phosphorus-containing polyester polyol.
The phosphorus-containing polyester polyol of this example was tested according to the various national, industrial or corporate standards as described above, and found to have a viscosity of 3900 mPas at 25 ℃, a hydroxyl value of 360mgKOH/g, an acid value of 1.5mgKOH/g, a color (Fe-Co) of No. 13, and a water content of 0.1% by weight.
The phosphorus-containing polyester polyol of this example has an acid value, viscosity, hydroxyl value and color that meet the requirements for the type I polyester polyol physical properties in the group Standard T/SPUIA000001-2018 issued by the polyurethane industry Association of Shanghai.
Example 3
This example relates to a method for the synthesis of the phosphorus-containing polyester polyol LPS-360.
First, 5 tons of PTA residue (Kashihikari), 3 tons of diethylene glycol, 2 tons of a byproduct of diethylene glycol, 1.3 tons of glycerin, 1 ton of oleic acid, 5kg of dibutyltin dilaurate as a catalyst, and 35kg of phosphoric acid were charged into a reaction vessel. The reaction mass was dehydrated at 170 ℃ for 2 hours under atmospheric pressure. After completion of the dehydration, the temperature of the reaction system was raised to 210 ℃ at a temperature rising rate of 20 ℃/hr and kept at that temperature for 5 hours to obtain a first reaction mixture.
Then, the temperature of the reaction system is increased to 220 ℃ at a heating rate of 10 ℃/hour, the temperature is maintained for 8 hours, and when the acid value of the reaction product is detected to be less than 10mgKOH/g, the next reaction stage is carried out.
Next, the reaction system was maintained under a vacuum of-0.09 MPa for 2 hours. And when the acid value of the reaction product is detected to be less than 2.5mgKOH/g, cooling to below 150 ℃, filtering for 2 hours by using a CT-10 type filter with the filtering area of 10 square meters at the flux of 7000 kg/hour, discharging the filtrate with the flow rate of a discharge pump of 12 cubic meters per hour, and packaging to obtain the finished product of the phosphorus-containing polyester polyol.
The phosphorus-containing polyester polyol of this example was tested according to the various national, industrial or corporate standards as described above, and found to have a viscosity of 4000 mPa.s at 25 ℃, a hydroxyl value of 360mgKOH/g, an acid value of 1.2mgKOH/g, a color (Fe-Co) of No. 12, and a water content of 0.1% by weight.
The phosphorus-containing polyester polyol of this example has an acid value, viscosity, hydroxyl value and color that meet the requirements for the type I polyester polyol physical properties in the group Standard T/SPUIA000001-2018 issued by the polyurethane industry Association of Shanghai.
Example 4
This example relates to a method for the synthesis of the phosphorus-containing polyester polyol LPS-410.
First, 5 tons of PTA residue (Kaishiki), 5 tons of diethylene glycol, 1.3 tons of glycerol, 1 ton of oleic acid and 45kg of phosphoric acid were charged into a reaction vessel. The reaction mass was dehydrated at 170 ℃ for 2 hours under atmospheric pressure. After completion of the dehydration, the temperature of the reaction system was raised to 210 ℃ at a temperature rising rate of 20 ℃/hr and kept at that temperature for 5 hours to obtain a first reaction mixture.
Then, 5kg of catalyst tetrabutyl titanate is added into the reaction kettle, the temperature of the reaction system is increased to 220 ℃ at the heating rate of 10 ℃/hour, the temperature is maintained for 8 hours, and when the acid value of the reaction product is detected to be less than 10mgKOH/g, the next reaction stage is carried out.
Next, the reaction system was maintained under a vacuum of-0.09 MPa for 2 hours. And when the acid value of the reaction product is detected to be less than 2.5mgKOH/g, cooling to below 150 ℃, filtering for 2 hours by using a CT-10 type filter with the filtering area of 10 square meters at the flux of 6000 kg/hour, discharging the filtrate with the flow rate of a discharge pump of 12 cubic meters per hour, and packaging the discharged filtrate to obtain the finished product of the phosphorus-containing polyester polyol.
The phosphorus-containing polyester polyol of this example was tested according to the various national, industrial or corporate standards as described above, and found to have a viscosity of 3900 mPa.s at 25 ℃, a hydroxyl value of 450mgKOH/g, an acid value of 1.0mgKOH/g, a color (Fe-Co) of No. 9, and a water content of 0.1% by weight.
The phosphorus-containing polyester polyol of this example has an acid value, viscosity, hydroxyl value and color that meet the requirements for the type II polyester polyol physical properties in the group Standard T/SPUIA000001-2018 issued by the polyurethane industry Association of Shanghai.
Example 5
This example relates to a method for the synthesis of the phosphorus-containing polyester polyol LPS-410.
First, 5 tons of PTA residue (Shanghai petrochemical), 5 tons of diethylene glycol, 1.3 tons of glycerol, 1 ton of oleic acid, 25kg of catalytic zinc acetate, and 5kg of phosphoric acid were charged into a reaction vessel. The reaction mass was dehydrated at 170 ℃ for 2 hours under atmospheric pressure. After completion of the dehydration, the temperature of the reaction system was raised to 190 ℃ at a temperature rising rate of 10 ℃/hr, and the temperature was maintained at that temperature for 6 hours to obtain a first reaction mixture.
Then, the temperature of the reaction system was raised to 220 ℃ at a temperature rising rate of 10 ℃/hr, and the temperature was maintained for 8 hours, and when the acid value of the reaction product was detected to be less than 10mgKOH/g, the reaction was carried out in the next reaction stage.
Next, the reaction system was maintained under a vacuum of-0.09 MPa for 2 hours. When the acid value of the reaction product is detected to be less than 2.5mgKOH/g, the temperature is reduced to be below 150 ℃, the reaction product is filtered for 2 hours by a CT-10 type filter with the filtering area of 10 square meters at the flux of 5000 kg/hour, the flow of a filtrate discharging pump is 12 cubic meters per hour, and the filtrate is discharged and packaged to obtain the finished product of the phosphorus-containing polyester polyol.
The phosphorus-containing polyester polyol of this example was tested according to the various national, industrial, or corporate standards as described above, and found to have a viscosity of 3600mPa · s at 25 ℃, a hydroxyl value of 410mgKOH/g, an acid value of 1.0mgKOH/g, a color (Fe-Co) of No. 8, and a water content of 0.1% by weight.
The phosphorus-containing polyester polyol of this example has an acid value, viscosity, hydroxyl value and color that meet the requirements for the type II polyester polyol physical properties in the group Standard T/SPUIA000001-2018 issued by the polyurethane industry Association of Shanghai.
Example 6
This example relates to a method for the synthesis of the phosphorus-containing polyester polyol LPS-410.
First, 5 tons of PTA residue (Kashikoku), 5 tons of diethylene glycol, 1.3 tons of glycerol, 1 ton of oleic acid, 4kg of dibutyltin dilaurate as a catalyst, and 25kg of phosphoric acid were charged into a reaction vessel. The reaction mass was dehydrated at 170 ℃ for 2 hours under atmospheric pressure. After completion of the dehydration, the temperature of the reaction system was raised to 190 ℃ at a temperature rising rate of 15 ℃/hr, and the temperature was maintained at that temperature for 6 hours to obtain a first reaction mixture.
Then, the temperature of the reaction system was raised to 220 ℃ at a temperature rising rate of 10 ℃/hr, and the temperature was maintained for 8 hours, and when the acid value of the reaction product was detected to be less than 10mgKOH/g, the reaction was carried out in the next reaction stage.
Next, the reaction system was maintained under a vacuum of-0.09 MPa for 2 hours. And when the acid value of the reaction product is detected to be less than 2.5mgKOH/g, cooling to below 150 ℃, filtering for 2 hours by using a CT-10 type filter with the filtering area of 10 square meters at the flux of 6000 kg/hour, discharging the filtrate with the flow rate of a discharge pump of 12 cubic meters per hour, and packaging the discharged filtrate to obtain the finished product of the phosphorus-containing polyester polyol.
The phosphorus-containing polyester polyol of this example was tested according to the various national, industrial or corporate standards as described above, and found to have a viscosity of 3700mPa · s at 25 ℃, a hydroxyl value of 390mgKOH/g, an acid value of 1.0mgKOH/g, a color (Fe-Co) of 9 # and a water content of 0.1% by weight.
The phosphorus-containing polyester polyol of this example has an acid value, viscosity, hydroxyl value and color that meet the requirements for the type II polyester polyol physical properties in the group Standard T/SPUIA000001-2018 issued by the polyurethane industry Association of Shanghai.
In the examples described above, heavy metals can be recovered from the phosphorus-containing polyester polyol product by conventional means. For example, sodium carbonate is added to the phosphorus-containing polyester polyol, followed by separation.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (9)
1. A method for synthesizing phosphorus-containing polyester polyol using PTA residues, comprising the steps of:
s1: reacting the PTA residue, unsaturated monobasic fatty acid, phosphorus-containing inorganic acid, catalyst and polyol at a first temperature for a first predetermined period of time to obtain a first reaction mixture;
s2: keeping the first reaction mixture at a second temperature for a second preset time period, and obtaining the phosphorus-containing polyester polyol after the reaction is finished;
wherein the inorganic acid containing phosphorus is phosphoric acid.
2. The process for synthesizing phosphorus-containing polyester polyol using PTA residues as in claim 1, further comprising dehydrating the raw materials forming the first reaction mixture at 170 ℃ before step S1.
3. The method for synthesizing phosphorus-containing polyester polyol using PTA residues of claim 1, wherein the method further comprises maintaining the phosphorus-containing polyester polyol in a vacuum state for a third predetermined period of time after step S2.
4. The method for synthesizing phosphorus-containing polyester polyol using PTA residues as in any one of claims 1-3, wherein the unsaturated monobasic fatty acid is oleic acid.
5. The process for synthesizing phosphorus-containing polyester polyol using PTA residues as in any one of claims 1-3, wherein the polyol is a mixture of glycerol and diethylene glycol.
6. The method for synthesizing phosphorus-containing polyester polyol using PTA residues as in claim 5, wherein at least a portion of the diethylene glycol is a by-product diethylene glycol.
7. The method for synthesizing phosphorus-containing polyester polyol using PTA residues as in any one of claims 1-3, wherein the catalyst comprises one or more of tetrabutyl titanate, zinc acetate or dibutyltin dilaurate.
8. The method for synthesizing phosphorus-containing polyester polyol using PTA residues as in any one of claims 1-3, wherein the first predetermined period of time is 4-6 hours;
and/or the second predetermined period of time is 5-8 hours.
9. The method for synthesizing phosphorus-containing polyester polyol using PTA residues as in any one of claims 1-3, wherein the first temperature is 190-220 ℃;
and/or the second temperature is 220-230 ℃.
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