CN117946376A - Preparation method of bio-based polyester polyol - Google Patents

Preparation method of bio-based polyester polyol Download PDF

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Publication number
CN117946376A
CN117946376A CN202211288283.5A CN202211288283A CN117946376A CN 117946376 A CN117946376 A CN 117946376A CN 202211288283 A CN202211288283 A CN 202211288283A CN 117946376 A CN117946376 A CN 117946376A
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bio
polyol
polyester polyol
borate
catalyst
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邢嘉成
徐云鹏
刘中民
王磊
产文涛
王艳涛
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Zhongke Guosheng Hangzhou Technology Co ltd
Dalian Institute of Chemical Physics of CAS
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Zhongke Guosheng Hangzhou Technology Co ltd
Dalian Institute of Chemical Physics of CAS
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Abstract

The application discloses a preparation method of bio-based polyester polyol, and belongs to the field of polymer synthesis. A method for preparing a bio-based polyester polyol, comprising the steps of: the mixture containing inorganic oxygen acid ester and bio-based polyol is subjected to transesterification reaction under the action of a catalyst to obtain the bio-based polyester polyol. The method adopts inorganic oxo acid ester and bio-based polyol as raw materials to carry out transesterification reaction to obtain the bio-based polyester polyol polymer, which replaces the traditional petroleum-based raw materials and is environment-friendly. The product obtained by the preparation method has better heat resistance, the initial decomposition temperature can reach 500 ℃, and the method can be applied to the field with higher heat resistance requirement.

Description

Preparation method of bio-based polyester polyol
Technical Field
The application relates to a preparation method of bio-based polyester polyol, belonging to the field of polymer synthesis.
Background
The research and development production of bio-based materials and bio-based platform compounds capable of replacing petroleum-based materials is a main direction of development in the field of material science and technology. The serious situation that fossil resources are continuously exhausted and environmental pollution is increasingly serious is faced, and the environment-friendly and process-efficient renewable biological resources are taken as raw materials, so that the trend is necessarily towards. The biobased material industry has undergone a subversion. The traditional large-scale petrochemical giant-scale Chemical large-scale raceways comprise large-scale transnational petrochemical industry such as British Petroleum company (BP), shell, basf, duPont (Dupont), dow Chemical, evonik, dissman (DSM) and the like, which are widely put into the biochemical industry to lay out the biobased industry chain.
The bio-based polyester polyol is prepared by polycondensation of dibasic organic carboxylic acid, carboxylic anhydride and bio-based polyol, and the relative molecular mass is generally less than 4500. The dibasic acid is phthalic acid or phthalic anhydride or ester thereof, adipic acid, halogenated phthalic acid and the like, and the bio-based polyol is polyol prepared from biomass materials and comprises at least one of 2, 5-tetrahydrofuran dimethanol, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polytrimethylene ether glycol, pentaerythritol, xylitol and sorbitol. The application of the bio-based material has higher value and is a process for changing waste into valuables. Among them, 2, 5-tetrahydrofuran dimethanol is a bio-based product having great application significance, which is derived from biomass such as sugar, starch or cellulose, etc. The 2, 5-tetrahydrofuran dimethyl has both an oxygen-containing rigid cyclic structure and a symmetrical diol functional group, can be widely applied to the fields of solvents, surfactants, polyesters and the like, and is expected to show unique advantages in the aspects of barrier property, dyeing property, degradability and the like. The class of bio-based polyester polyols is generally classified by carboxylic acid, and there are generally the following: adipic acid-based polyester polyol, alkyd-based polyester polyol, caprolactone-based polyester polyol, and acrylic-based polyester polyol. The polyester polyol is produced by vacuum dehydration and high temperature nitrogen dehydration. The vacuum dewatering process is to use acetate as catalyst to make binary acid and binary alcohol undergo the process of polycondensation reaction under the condition of vacuum so as to synthesize polyester polyol with a certain molecular weight. The high-temperature nitrogen dehydration method is to synthesize polyester polyol at high temperature under the protection of nitrogen. The high temperature dehydration method requires higher temperature, which is easy to cause yellowing of products and performance degradation of the products for many polymers.
Disclosure of Invention
According to a first aspect of the present application, there is provided a process for producing a bio-based polyester polyol, wherein the bio-based polyester polyol polymer of the present application is a novel bio-based polyester polyol polymer obtained by transesterification of an inorganic oxy acid ester with a bio-based polyol as a raw material, and the conventional polyester polyol is obtained by dehydration esterification of an organic acid with a polyol as a raw material, and the polyol used therein is mostly of petroleum-based origin. The bio-based polyester polyol prepared by the method replaces the traditional petroleum-based raw material, adopts the bio-based raw material with wide sources, has higher environmental protection and economic value, and has higher heat resistance.
A method for preparing a bio-based polyester polyol, comprising the steps of:
and (3) performing transesterification on the mixture containing the inorganic oxo acid ester and the bio-based polyol under the action of a catalyst to obtain the bio-based polyester polyol.
Optionally, the inorganic oxoacid ester is selected from at least one of a compound shown in a formula I and a compound shown in a formula II:
M (OR 1)n 1 formula I)
O=p (OR 2)n 2 formula II
Wherein M is not a P element;
R 1、R2 is independently selected from alkyl of C 1～C8;
n1＝2～8,n2＝2～8。
alternatively, n 1 = 2,3, 4,5, 6,7 or 8.
Alternatively, n 2 = 3.
Optionally, M is selected from one of B, si, ge, al, ti, fe, sn, V, ga, zr, cr, sb, W.
Optionally, the inorganic oxoacid ester is selected from at least one of trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, tri-n-hexyl borate, triisooctyl borate, trioctyl borate, methyl orthosilicate, tetraethyl silicate, tetrapropyl silicate, tetrabutyl silicate, ethyl orthogermanate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tri-n-pentyl phosphate, trihexyl phosphate, aluminum triethanolate, aluminum isopropoxide, aluminum n-butoxide, aluminum tert-butoxide, tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetrahexyl titanate, tetraisooctyl titanate, tetrabutyl ferrite, tetrabutyl stannate, butyl orthovanadate, gallium ethoxide, tetra-n-propyl zirconate, tetrabutyl zirconate, t-butyl chromate, ethyl antimonate, butyl antimonite, tungsten ethoxide, and tungsten isopropoxide.
Alternatively, the bio-based polyol refers to a polyol prepared from biomass material.
Optionally, the bio-based polyol is selected from at least one of 2, 5-tetrahydrofuran dimethanol, polytrimethylene ether glycol.
Optionally, the catalyst is at least one selected from an acidic catalyst and a basic catalyst.
Optionally, the acidic catalyst is selected from at least one of an alcohol-soluble acid, a solid acid, an aluminum alkoxide, an aluminum phenoxy, a tetrabutyl stannate, a titanium alkoxide, a zirconium alkoxide, an ethyl antimonite, a butyl antimonite;
The basic catalyst is at least one selected from alkali dissolved in alcohol and solid alkali.
Alternatively, the molar ratio of the inorganic oxoacid ester and the bio-based polyol satisfies:
inorganic oxy acid esters: bio-based polyol= (0.8-1.2) n 3/x;
Wherein x is the number of moles of alkoxy groups contained in each mole of the inorganic oxy acid ester;
n 3 is the number of moles of hydroxyl groups per mole of the bio-based polyol.
Alternatively, the molar ratio of the inorganic oxoacid ester and the bio-based polyol is independently selected from any value or range of values between any two of 0.8n3/x、0.85n3/x、0.9n3/x、0.95n3/x、1n3/x、1.05n3/x、1.1n3/x、1.2n3/x .
Optionally, the catalyst is added in an amount of 0.1wt% to 5wt% of the inorganic oxy acid ester.
Alternatively, the catalyst is added in an amount independently selected from any value or range of values between any two of 0.1wt％、0.3wt％、0.5wt％、 0.7wt％、0.9wt％、1wt％、1.1wt％、1.3wt％、1.5wt％、1.7wt％、1.9wt％、 1wt％、2wt％、2.3wt％、2.5wt％、2.7wt％、2.9wt％、3wt％、3.3wt％、3.5wt％、 3.7wt％、3.9wt％、4wt％、4.3wt％、4.5wt％、4.7wt％、4.9wt％、5wt％.
Alternatively, the transesterification conditions are as follows:
The temperature is 80-180 ℃;
The time is 2-10 h.
Alternatively, the time is independently selected from any value or range of values between any two of 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10 h.
Alternatively, the temperature is independently selected from any value or range of values between any two of 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃.
Alternatively, the transesterification reaction is carried out under an inert atmosphere;
the inactive gas is at least one selected from nitrogen, argon and neon.
Alternatively, the transesterification reaction is followed by distillation under reduced pressure.
Alternatively, the conditions of reduced pressure distillation are as follows:
the temperature is 170-230 ℃;
the time is 0.5 to 5 hours.
Alternatively, the temperature is independently selected from any value or range of values between any two of 170 ℃, 175 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 225 ℃, 230 ℃.
Alternatively, the time is independently selected from any value or range of values between any two of 0.5h, 0.8h, 1h, 2h, 3h, 4h, 4.5h, 5 h.
Alternatively, the vacuum degree is 0.01KPa to 5KPa.
Alternatively, the vacuum is independently selected from any value or range of values between any two of 0.01KPa, 0.02KPa, 0.05KPa, 1KPa, 2KPa, 3KPa, 4KPa, 4.5KPa, 5 KPa.
According to a second aspect of the present application there is provided a product of a process for the preparation of bio-based polyester polyols.
The bio-based polyester polyol polymer obtained by the preparation method has an initial decomposition temperature of 300-500 ℃.
Optionally, the method comprises:
a) Mixing inorganic oxygen acid ester, bio-based polyol and an ester exchange reaction catalyst, carrying out ester exchange reaction in a stirring state, and introducing an inactive atmosphere for protection, wherein the reaction temperature is 80-180 ℃ and the reaction time is 2-10 hours;
b) And c), carrying out reduced pressure distillation after the reaction in the step a), controlling the vacuum degree of the system at 0.01-5 KPa, the reaction temperature at 170-230 ℃ and the reaction time at 0.5-5 hours.
As a specific embodiment, the method comprises:
1) Uniformly mixing inorganic oxygen acid ester, bio-based polyol and an ester exchange reaction catalyst in a three-neck flask, carrying out ester exchange reaction under the stirring state, connecting a distillation device, introducing nitrogen for protection, wherein the reaction temperature is 80-180 ℃, the reaction time is 2-10 hours, and the conversion rate of the ester exchange reaction is 60-80%;
2) The device after the reaction in the step 1) is connected with a water pump or an oil pump to carry out reduced pressure distillation so that the transesterification reaction is carried out more completely, the vacuum degree of the system is controlled to be 0.01-5 KPa, the reaction temperature is between 170 and 230 ℃, the reaction time is between 0.5 and 5 hours, and the conversion rate of the transesterification reaction is more than 90 percent.
Optionally, the bio-based polyester polyol has an initial decomposition temperature of greater than 300 ℃.
Alternatively, the bio-based polyester polyol has an initial decomposition temperature of up to 500 ℃.
In the present application, "C1 to C8" and the like refer to the number of carbon atoms contained in the group.
In the present application, an "alkyl group" is a group formed by losing any one of hydrogen atoms on an alkane compound molecule.
In the present application, "initial decomposition temperature" means a temperature at which a significant weight loss peak of the polyester polyol occurs by thermogravimetric analysis.
The application has the beneficial effects that:
1) The preparation method of the bio-based polyester polyol provided by the application adopts inorganic oxo-acid ester and bio-based polyol as raw materials to carry out transesterification reaction to obtain the bio-based polyester polyol polymer, which replaces the traditional petroleum-based raw materials and is environment-friendly.
2) The bio-based polyester polyol polymer provided by the application has better heat resistance, the initial decomposition temperature can reach 500 ℃, and the bio-based polyester polyol polymer can be applied to the field with higher heat resistance requirements.
Drawings
FIG. 1 is a thermal analysis of the product synthesized in example 1 of the present application.
FIG. 2 is a thermal analysis of the synthesized product of example 2 of the present application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
The starting materials and catalysts in the examples of the present application were purchased commercially, unless otherwise specified.
The analysis method in the embodiment of the application is as follows:
Thermogravimetric analysis was performed using a thermogravimetric analyzer model TA Q-600, manufactured by TA Instruments Inc. The nitrogen flow rate was 100ml/min and the temperature was raised to 700℃at a heating rate of 10℃per minute.
In the examples of the present application, the conversion of the transesterification reaction was calculated by:
according to the molar number n of byproduct alcohols distilled in the reaction process, determining the number n of groups participating in the reaction in the transesterification reaction, wherein the sum of the molar numbers of esters in the reaction raw materials is m, and the conversion rate of the transesterification reaction is as follows: n/xm. x depends on the number of alkoxy groups attached to the central atom in the ester.
According to an embodiment of the present application, the bio-based polyester polyol polymer and the synthesis method thereof are characterized in that the method comprises the steps of:
a) Inorganic oxygen acid ester, bio-based polyol and an ester exchange reaction catalyst are uniformly mixed in a three-neck flask, the ester exchange reaction is carried out under the stirring state, a distillation device is connected, nitrogen is introduced for protection, the reaction temperature is 80-180 ℃, the reaction time is 2-10 hours, and the conversion rate of the ester exchange reaction is 60-80%.
B) The device after the reaction in the step a) is connected with a water pump or an oil pump to carry out reduced pressure distillation so that the transesterification reaction is carried out more completely, the vacuum degree of the system is controlled to be 0.01-5 KPa, the reaction temperature is between 170 and 230 ℃, the reaction time is between 0.5 and 5 hours, and the conversion rate of the transesterification reaction is more than 90 percent.
Alternatively, the inorganic oxoacid ester in step a) has the general formula M (OR) n, wherein M is B, si, ge, P, al, ti, fe, sn, V, ga, zr, cr, sb, W, etc.; r is an alkyl group of 1 to 8 carbon atoms; including trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, tri-n-hexyl borate, triisooctyl borate, trioctyl borate, methyl orthosilicate, tetraethyl silicate, tetrapropyl silicate, tetrabutyl silicate, ethyl orthogermanate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tri-n-pentyl phosphate, trihexyl phosphate, aluminum triethanolate, aluminum isopropoxide, aluminum n-butoxide, aluminum tert-butoxide, tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetrahexyl titanate, tetraisooctyl titanate, tetrabutyl ferrite, tetrabutyl stannate, butyl orthovanadate, gallium ethoxide, tetra-n-propyl zirconate, tetrabutyl zirconate, t-butyl chromate, ethyl antimonite, butyl antimonite, tungsten ethoxide, tungsten isopropoxide, and the like.
Alternatively, the bio-based polyol in step a) is mainly a polyol derived from biomass-based synthesis, including one or a mixture of any of 2, 5-tetrahydrofuran dimethanol and polytrimethylene ether glycol.
Optionally, the inorganic oxoacid ester in step a) is in the following molar ratio with respect to the bio-based polyol:
M(OR)n/R-(OH)x＝(0.8～1.2)x/n
alternatively, the transesterification catalyst used in step a) is: the basic catalyst comprises alkali (such as NaOH, KOH, naOCH 3, organic alkali and the like) which is easy to dissolve in alcohol and various solid alkali catalysts, the acid catalyst comprises acid (such as sulfuric acid, sulfonic acid and the like) which is easy to dissolve in alcohol and various solid acid catalysts, aluminum alkoxide, aluminum phenoxy, tetrabutyl stannate, titanium alkoxide, zirconium alkoxide, ethyl antimonate, butyl antimonate and the like, and the catalyst dosage is 0.1 to 5 weight percent of inorganic oxygen acid ester.
Optionally, the reaction in the step a) is carried out under the protection of nitrogen, the reaction temperature is 80-180 ℃, and the reaction time is 2-10 hours.
Optionally, the conversion rate of the transesterification reaction in the step a) is between 60% and 80%.
Optionally, the step b) is carried out under reduced pressure distillation, and the vacuum degree of the system is controlled to be 0.01-5 KPa.
Optionally, the reaction temperature in the step b) is 170-230 ℃ and the reaction time is 0.5-5 hours.
Optionally, the conversion of the transesterification reaction in step b) is greater than 90%.
Example 1
10G of bio-based 2, 5-tetrahydrofuran dimethanol, 6.84g of ethyl orthosilicate and 5g of methyl orthosilicate are added into a three-neck flask, a distillation device is connected, 0.12g of concentrated sulfuric acid is added dropwise as a catalyst in a stirring state, the temperature is raised to 100 ℃ under the protection of nitrogen, the reaction time is 6 hours, a large amount of methanol and ethanol are distilled out in the process, and the conversion rate of transesterification reaction is 75%; then connecting a vacuumizing device, carrying out reaction under the condition of reduced pressure distillation, controlling the vacuum degree of the system at 1KPa, heating to 170 ℃, stopping the reaction after reacting for one hour, naturally cooling to room temperature, and taking out a sample, wherein the conversion rate of the transesterification reaction is 93%.
Example 2
Adding 5g of bio-based 2, 5-tetrahydrofuran dimethanol and 8.7g of aluminum triethoxide into a three-neck flask, wherein the aluminum triethoxide is used as an inorganic oxysalt raw material and is also used as an ester exchange catalyst, connecting a distillation device, heating to 175 ℃ under the condition of stirring and nitrogen protection, reacting for 5 hours, distilling out a large amount of ethanol in the process, and the conversion rate of the ester exchange reaction is 73%; then connecting a vacuumizing device, carrying out reaction under the condition of reduced pressure distillation, controlling the vacuum degree of the system to be 0.1 KPa, heating to 210 ℃, stopping the reaction after reacting for one hour, naturally cooling to room temperature, and taking out a sample, wherein the conversion rate of the transesterification reaction is 92%.
Example 3
10G of bio-based 2, 5-tetrahydrofuran dimethanol and 9.07g of tripropyl borate are added into a three-neck flask, a distillation device is connected, 0.05g of tetrabutyl titanate is dropwise added as a catalyst under the stirring state, the temperature is raised to 180 ℃ under the protection of nitrogen, the reaction time is 6 hours, a large amount of propanol is distilled out in the process, and the conversion rate of the transesterification reaction is 75%; then connecting a vacuumizing device, carrying out reaction under the condition of reduced pressure distillation, controlling the vacuum degree of the system at 1KPa, heating to 230 ℃, stopping the reaction after reacting for one hour, naturally cooling to room temperature, and taking out a sample, wherein the conversion rate of the transesterification reaction is 93%.
Examples 4 to 13 the specific ingredients, materials and reaction conditions are shown in Table 1 below, and the other procedures in the synthesis were the same as in example 1.
Table 1 raw material compositions, ratios, and crystallization conditions of examples 4 to 13
Thermal analysis
Thermal analysis was performed on the bio-based polyester polyols prepared in examples 1 to 13, typically as shown in fig. 1 and 2. FIG. 1 is a graph showing the thermal analysis of the bio-based polyester polyol prepared in example 1, wherein the initial decomposition temperature of the bio-based polyester polyol prepared in example 1 is 500 ℃.
FIG. 2 is a graph showing the thermal analysis of the bio-based polyester polyol prepared in example 2, and it can be seen from the graph that the bio-based polyester polyol prepared in example 2 has an initial decomposition temperature of 500 ℃.
The results of the tests on the bio-based polyester polyols in other examples are similar to those described above, with the initial decomposition temperature of the bio-based polyester polyol being higher than 300 ℃.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims (10)

1. A process for the preparation of a bio-based polyester polyol comprising the steps of:
and (3) performing transesterification on the mixture containing the inorganic oxo acid ester and the bio-based polyol under the action of a catalyst to obtain the bio-based polyester polyol.
2. The method according to claim 1, wherein the bio-based polyol is a polyol obtained from biomass material;
preferably, the bio-based polyol is selected from at least one of 2, 5-tetrahydrofuran dimethanol, polytrimethylene ether glycol.
3. The method according to claim 1, wherein the inorganic oxoacid ester is at least one selected from the group consisting of a compound having the formula I and a compound having the formula II:
M (OR 1)n 1 formula I)
O=p (OR 2)n 2 formula II
Wherein M is not a P element;
R 1、R2 is independently selected from alkyl of C 1～C8;
n1＝2～8,n2＝2～8。
4. A method of preparation according to claim 3 wherein M is selected from one of B, si, ge, al, ti, fe, sn, V, ga, zr, cr, sb, W.
5. The method according to claim 1, wherein the inorganic oxoacid ester is at least one selected from the group consisting of trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, tri-n-hexyl borate, triisooctyl borate, trioctyl borate, methyl orthosilicate, tetraethyl silicate, tetrapropyl silicate, tetrabutyl silicate, ethyl orthogermanate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tri-n-pentyl phosphate, trihexyl phosphate, aluminum triethanolate, aluminum isopropoxide, aluminum n-butoxide, aluminum tert-butoxide, tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetrahexyl titanate, tetraisooctyl titanate, tetrabutyl ferrite, tetrabutyl stannate, butyl orthovanadate, gallium ethoxide, tetra-n-propyl zirconate, tetrabutyl zirconate, t-butyl chromate, ethyl antimonite, butyl antimonite, tungsten ethoxide, and tungsten isopropoxide.
6. The method according to claim 1, wherein the catalyst is at least one selected from an acidic catalyst and a basic catalyst;
preferably, the acidic catalyst is selected from at least one of an alcohol-soluble acid, a solid acid, an aluminum alkoxide, an aluminum phenoxy, a tetrabutyl stannate, a titanium alkoxide, a zirconium alkoxide, an ethyl antimonite, a butyl antimonite;
The basic catalyst is at least one selected from alkali dissolved in alcohol and solid alkali.
7. The method of claim 1, wherein the molar ratio of the inorganic oxoacid ester to the bio-based polyol is such that:
inorganic oxy acid esters: bio-based polyol= (0.8-1.2) n 3/x;
Wherein x is the number of moles of alkoxy groups contained in each mole of the inorganic oxy acid ester;
n 3 is the number of moles of hydroxyl groups per mole of the bio-based polyol.
8. The method according to claim 1, wherein the catalyst is added in an amount of 0.1 to 5wt% of the inorganic oxy acid ester.
9. The process according to claim 1, wherein the transesterification reaction conditions are as follows:
The temperature is 80-180 ℃;
The time is 2-10 hours;
preferably, the transesterification reaction is carried out under an inert atmosphere;
The inactive gas is at least one selected from nitrogen, argon and neon;
Preferably, the transesterification is followed by distillation under reduced pressure;
preferably, the conditions of the reduced pressure distillation are as follows:
the temperature is 170-230 ℃;
The time is 0.5 to 5 hours;
Preferably, the vacuum degree is 0.01KPa to 5KPa.
10. The bio-based polyester polyol polymer obtained by the production process according to any one of claims 1 to 9, wherein the initial decomposition temperature of the bio-based polyester polyol polymer is 300 ℃ to 500 ℃.
CN202211288283.5A 2022-10-20 2022-10-20 Preparation method of bio-based polyester polyol Pending CN117946376A (en)

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