CN115725066A - Preparation method of bio-based polytetrahydrofuran - Google Patents
Preparation method of bio-based polytetrahydrofuran Download PDFInfo
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- CN115725066A CN115725066A CN202211423411.2A CN202211423411A CN115725066A CN 115725066 A CN115725066 A CN 115725066A CN 202211423411 A CN202211423411 A CN 202211423411A CN 115725066 A CN115725066 A CN 115725066A
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- 229920000909 polytetrahydrofuran Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 239000011973 solid acid Substances 0.000 claims abstract description 9
- 239000012530 fluid Substances 0.000 claims abstract description 7
- 239000011949 solid catalyst Substances 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- -1 oxides Chemical class 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 3
- 229940023913 cation exchange resins Drugs 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000002184 metal Chemical class 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000005086 pumping Methods 0.000 abstract 1
- 229920000570 polyether Polymers 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- BLBBMBKUUHYSMI-UHFFFAOYSA-N furan-2,3,4,5-tetrol Chemical class OC=1OC(O)=C(O)C=1O BLBBMBKUUHYSMI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 125000005517 carbenium group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
The invention relates to a preparation method of bio-based polytetrahydrofuran, which comprises monomer raw materials and monomer raw materials in CO 2 The concentration in the fluid, the ratio of the catalyst to the regulator, the reaction time, the reaction pressure and the reaction temperature. The invention adds a given amount of bio-based tetrahydrofuran and solid catalyst into a reaction kettle, and then uses CO 2 Replacing air in the kettle, pumping CO by a high-pressure pump 2 The reaction kettle is heated to a specified temperature to start reaction when the pressure in the reaction kettle reaches a specified pressure, a regulator is injected into the kettle after the reaction time is reached, and CO in the kettle is slowly discharged 2 Cooling and filtering solid acid, and evaporating redundant regulator and tetrahydrofuran to obtain pure bio-based polytetrahydrofuran. The method utilizes fluid CO under the condition of using solid acid 2 The catalytic efficiency of the solid catalyst is greatly improved due to the characteristics (such as low viscosity, low surface tension, diffusion coefficient of 10 to 100 times of that of liquid, and the like), and the defects of environmental pollution, difficult separation and the like of the homogeneous catalyst are avoided.
Description
Technical Field
The invention belongs to the technical field of polymer preparation, and particularly relates to a preparation method of bio-based polytetrahydrofuran.
Background
The bio-based polytetrahydrofuran is also called polytetramethylene ether glycol, and is called PTMEG for short. The chemical structure is as follows:
the bio-based polytetrahydrofuran is also called polytetramethylene ether glycol, PTMEG for short, polytetramethylene ether glycol and tetrahydrofuran polyether, is a linear polyether diol with different molecular weights prepared by cationic initiated ring opening polymerization of monomer tetrahydrobrane, has main chain comprising carbon-carbon bond and ether bond and high flexibility, and is used as soft segment material for block copolymerization with polyurethane or polyvinyl acetate to prepare elastomer. The soft segment does not contain unsaturated bonds, so that the soft segment has better aging resistance; and because the polyether does not contain a cool bond, the polyether has better hydrolysis resistance, and the block product prepared from various aliphatic polyethers has the best mechanical property, so that the polyether is widely applied to industrial production of petrochemical industry, machinery, military industry, shipbuilding, automobiles, synthetic leather and the like.
Currently, the focus of research is mainly on the selection and utilization of catalysts. The catalytic reaction system is divided into a homogeneous catalytic system and a heterogeneous catalytic system. Homogeneous catalyst: essentially comprising, ionic catalysts, e.g. [ EtO ] 3 ]BF 4 It has the characteristics of high initiation efficiency, high reaction rate and the like; however, the obtained polymer has alkoxy at the end and is not easy to be converted into light end groups, so the application value in industrial production is not great. Carbenium catalysts, triphenylcarbenium ionsThe catalyst has the characteristics of very high reaction rate and narrow molecular weight distribution under the condition of low conversion rate, but has the defects of large molecular weight change and difficult control; the catalyst system is also the most widely researched and most productive catalyst. The use of superacids to initiate tetrahydroxyfurans is the simplest and most straightforward method for the preparation of double-ended light-based tetrahydroxyfurans. Fuming sulfuric acid, fluorosulfonic acid, acetic acid complex perchloric acid, etc. are used more frequently in homogeneous systems. Heterogeneous catalytic system: essentially comprising, immobilizing a liquid acid, e.g. HF/Al 2 O 3 (ii) a Oxides, e.g. Al 2 O 3 ，SiO 2 Etc.; sulfides, znS, and the like; metal salt of Fe 2 (SO 4 ) 3 、CuSO 4 Etc.; molecular sieves, ZSM-5, zeolite, etc.; heteropoly acids; cation exchange resins; natural clays; solid super acids, and the like.
In the homogeneous catalytic system, the acid is fully contacted with the raw material, and participates in chemical reaction in a molecular form, so that the catalytic activity is higher at lower temperature. However, the catalyst has many problems in the actual chemical production, such as generation of a large amount of waste liquid, pollution to the environment, severe corrosion to production equipment, frequent maintenance of the equipment, great increase of production cost, formation of a homogeneous body of the catalyst, raw materials and products, complex post-treatment, and difficulty in realizing continuous production in industry. Compared with liquid acid catalysts, solid acid catalysts have the following advantages: the catalyst has the advantages of no corrosion to equipment, easy treatment and storage, easy separation after reaction, realization of industrial continuous production, easy regeneration, high stability and elimination of pollution caused by waste liquid, but the catalyst is often low in catalytic efficiency. Limiting the development of the use thereof.
Disclosure of Invention
In view of the problems of the prior art, the present invention is directed to a novel method for preparing bio-based polytetrahydrofuran using fluid CO using solid acid 2 The solid catalyst is greatly increased due to the characteristics (such as low viscosity, low surface tension, diffusion coefficient of 10 to 100 times of liquid and the like)The catalytic efficiency of the catalyst and the disadvantages of environmental pollution, difficult separation and the like of the homogeneous catalyst are avoided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for preparing bio-polytetrahydrofuran from the monomer raw material chosen from CO 2 The concentration in the fluid, the ratio of the catalyst to the regulator, the reaction time, the reaction pressure and the reaction temperature;
the monomer raw material is tetrahydrofuran, and the monomer raw material is in CO 2 The concentration range of medium is 1 to 50 percent;
the catalyst accounts for 0.1 to 2 percent of the mass of the monomer raw material tetrahydrofuran;
the regulator accounts for 1 to 30 percent of the mass of the tetrahydrofuran;
the reaction time range is 1 to 12h;
the reaction pressure range is 7.0 to 8.5MPa;
the reaction temperature is 40 to 80 ℃.
Specifically, the catalyst includes, but is not limited to, immobilized liquid acids such as HF/Al 2 O 3 Etc.; oxides, e.g. Al 2 O 3 ，SiO 2 Etc.; sulfides such as ZnS and the like; metal salts, e.g. Fe 2 (SO 4 ) 3 CuSO 4 Etc.; molecular sieves such as ZSM-5, zeolite, etc.; heteropoly acids, cation exchange resins, natural clays such as diatomaceous earth, etc.; or solid super-strong acids such as HND-31, HNF-5W, etc.
Further, the modifier includes, but is not limited to, dihydric alcohols (e.g., 1, 4-butanediol, 1, 4-cyclohexanedimethanol, ethylene glycol, hexylene glycol, etc.) or water.
Specifically, the preparation method of the bio-based polytetrahydrofuran comprises the following steps:
(1) Adding a proper amount of bio-based Tetrahydrofuran (THF) and a catalyst into a stainless steel reaction kettle, and sealing to ensure no air leakage;
(2) With CO 2 Replacing the air in the reaction kettle for at least three times to ensure that all the air in the kettle is replaced;
(3) Is pressed into the reaction kettle by a high-pressure pumpAdding high purity CO 2 The pressure in the kettle is controlled to be 7.0 to 8.5MPa;
(4) The temperature in the reaction kettle is raised to 40 to 80 ℃;
(5) Reacting for 2 to 10h at the reaction temperature;
(6) Adding a regulator into the reaction kettle; cooling to 35-38 ℃, and discharging CO through an exhaust valve 2 Opening the reaction kettle, filtering out the solid catalyst, and evaporating out tetrahydrofuran and the regulator to obtain the bio-based polytetrahydrofuran.
In the step (1), the addition amount of tetrahydrofuran in the 1L reaction kettle is 20 to 500g, preferably 100 to 450g, and most preferably 200 to 400g.
Further, in the step (2), the adding amount of the solid catalyst in the 1L reaction kettle is 0.1 to 2 percent of the mass of the tetrahydrofuran, preferably 0.2 to 1.5 percent, and most preferably 0.5 to 1 percent.
Further, in the step (4), the temperature in the reaction vessel is preferably from 45 to 80 ℃, and most preferably from 50 to 60 ℃.
Further, in the step (5), the reaction time is preferably 3 to 8 hours, and more preferably 4 to 7 hours.
Further, in the step (6), the addition amount of the regulator is preferably 8 to 25% of the mass of tetrahydrofuran, and most preferably 10 to 20%.
Compared with the prior art, the method for preparing the polytetrahydrofuran by adopting the supercritical fluid to replace the conventional liquid dissolution mainly has the following characteristics:
(1) No waste liquid is generated, and carbon dioxide gas can be repeatedly used;
(2) The catalytic efficiency of the conventional solid acid catalyst is increased, and the liquid catalyst is prevented from corroding a reaction container;
(3) The post-treatment is simple, and hydrogenation is not needed.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1
Step (1), 50g of tetrahydrofuran and a catalyst are added into a 1.0L stainless steel high-pressure reaction kettle, the mass of the solid acid catalyst of the Nanda synthetic brand HND-31 is 1 percent of that of the tetrahydrofuran, and sealing is carried out to ensure no gas leakage;
replacing air in the reaction kettle with carbon dioxide for three to five times to ensure that all the air in the kettle is replaced;
step (3) introducing CO into the reaction kettle through a high-pressure pump 2 The pressure in the kettle reaches 7.2MPa (CO) 2 Weight about 134.4g, monomeric tetrahydrofuran in CO 2 About 37% w/w);
heating for reaction, wherein the temperature in the reaction kettle is increased to 45 ℃;
the reaction time is 5 hours at the reaction temperature in the step (5);
step (6), adding a regulator ethylene glycol into the reaction kettle, wherein the feeding amount of the ethylene glycol is 10% of the mass of the tetrahydrofuran;
after the temperature in the step (7) is reduced to 35 to 38 ℃, CO is discharged through an exhaust valve 2 Discharging the mixture out of the reaction kettle;
and (8) opening the reaction kettle, filtering out the solid catalyst, and evaporating out tetrahydrofuran and the regulator to obtain the bio-based polytetrahydrofuran.
Example 2
The procedure was identical to the conditions of example 1, with only the amount of tetrahydrofuran being varied and increased to 100g.
Example 3
The procedure was identical to the conditions of example 1, with only the amount of tetrahydrofuran being changed and increased to 200g.
Example 4
The procedure was identical to the conditions of example 1, with only the amount of tetrahydrofuran being changed and increased to 400g.
Example 5
The procedure was in accordance with the conditions of example 1, with only the reaction temperature being varied to 55 ℃.
Example 6
The process was identical to the conditions of example 1, only the amount of regulator was changed and the ethylene glycol feed increased from 10% to 15% by mass of tetrahydrofuran.
Example 7
The procedure was in accordance with the conditions of example 1, with only the reaction temperature being changed to 65 ℃.
The products prepared in examples 1 to 7 under different conditions were tested as follows:
TABLE 1 product test results under different conditions
And (4) conclusion: from a comparison of the results of examples 1, 5 and 7, it can be seen that: the molecular weight and the conversion rate of the polymer can be increased by properly increasing the reaction temperature, and the molecular weight of the product is reduced on the contrary though the conversion rate of tetrahydrofuran can be increased if the reaction temperature is too high; from a comparison of the results of examples 1 to 4, it can be seen that: the molecular weight of the polymerization product increased with increasing amount of tetrahydrofuran, but the conversion rate gradually became lower; from a comparison of the results of examples 1 and 6, it can be seen that: the proper increase of the feeding amount of the regulator can increase the conversion rate of tetrahydrofuran and the molecular weight of the polymer.
In the following, we carried out experiments with a reaction temperature of 55 ℃ and a regulator dosage of 15% of the mass of tetrahydrofuran.
Example 8
The reaction temperature was 55 ℃ and the amount of the modifier was 15%, and the other conditions were the same as in example 1.
Example 9
The process is consistent with the conditions of the example 8, and the catalyst is changed into a fluorine-containing solid acid Nada synthetic brand HNF-5W solid acid catalyst for experiment.
Example 10
The procedure was in accordance with the conditions of example 8, the catalyst was instead tested using a ZSM-5 molecular sieve.
Example 11
The procedure was in accordance with the conditions of example 8, the catalyst was changed to a kieselguhr experiment.
Example 12
The procedure was in accordance with example 8, the catalyst was changed to gamma-Al 2 O 3 Experiments were performed.
The detection results of the products of examples 8 to 12 are compared as follows:
TABLE 2 product testing results for different catalysts
And (4) conclusion: the results in Table 2 show that the reaction proceeds more advantageously due to the stronger acidity, and we prefer HND-31 as the catalyst.
The following examine different CO 2 Reaction conditions under fluid concentration conditions.
Example 13
The procedure was as in example 8, CO being introduced by means of a high-pressure pump 2 And cutting off the valve after the pressure in the kettle reaches 5.0MPa, and continuously punching to 7.2MPa by using nitrogen.
Example 14
The procedure was as in example 8, with continued flushing to 7.2MPa by means of a high-pressure pump using nitrogen.
Example 15
The procedure was as in example 8, CO being introduced by means of a high-pressure pump 2 So that the pressure in the kettle reaches 9.0MPa.
The results of the product tests of examples 13 to 17 were compared with those of example 8 as follows:
TABLE 3 different CO 2 Product test results under partial pressure conditions
And (4) conclusion: as can be seen from comparison of the results of the tests of the products in examples 8 and 13 to 15, with CO 2 The partial pressure decreases, i.e. with tetrahydrofuran in CO 2 The concentration ratio in the product is increased, the conversion rate of tetrahydrofuran and the molecular weight of the product are obviously reduced, if CO is not used 2 When used as a solvent, the tetrahydrofuran conversion was very low, and a comparison of the results of examples 8 and 15 shows that the increase in CO continues 2 Partial pressure, tetrahydrofuran conversion and product molecular weight increase were insignificant, and we prefer to use the process of example 8 to ensure safe operation and improve production efficiency.
From the above results, it can be seen that: increasing the amount of biobased tetrahydrofuran in CO 2 In the middle, can reduce the raw materialMolecular weight of the glycosyl polytetrahydrofuran; the reaction temperature is properly increased, so that the molecular weight can be increased, and the conversion rate can be increased; the molecular weight and conversion are slightly increased by increasing the amount of the regulator.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all alternative means and applications having the same functionality.
Claims (9)
1. The preparation method of the bio-based polytetrahydrofuran is characterized by comprising the steps of preparing a monomer raw material and adding the monomer raw material in CO 2 The concentration in the fluid, the ratio of the catalyst to the regulator, the reaction time, the reaction pressure and the reaction temperature;
the monomer raw material is tetrahydrofuran, and the monomer raw material is in CO 2 The concentration range of the intermediate is 1 to 50 percent;
the catalyst accounts for 0.1 to 2 percent of the mass of the monomer raw material tetrahydrofuran;
the regulator accounts for 1 to 30 percent of the mass of the tetrahydrofuran;
the reaction time range is 1 to 12h;
the reaction pressure range is 7.0 to 8.5MPa;
the reaction temperature range is 40 to 80 ℃.
2. The method according to claim 1, wherein the catalyst comprises immobilized liquid acids, oxides, sulfides, metal salts, molecular sieves, heteropoly acids, cation exchange resins, natural clays, or solid acids.
3. The method of claim 1, wherein the modifier comprises 1, 4-butanediol, 1, 4-cyclohexanedimethanol, ethylene glycol, hexanediol, or water.
4. The method for preparing bio-based polytetrahydrofuran according to any one of claims 1 to 3, characterized by comprising the steps of:
(1) Adding tetrahydrofuran and a catalyst into a reaction kettle, and sealing to ensure no air leakage;
(2) With CO 2 Replacing air in the reaction kettle;
(3) Injecting CO into the reaction kettle 2 Keeping the pressure in the kettle at 7.0 to 8.5MPa;
(4) The temperature in the reaction kettle is raised to 40 to 80 ℃;
(5) Reacting for 2 to 10h at the reaction temperature;
(6) Adding a regulator into the reaction kettle; cooling to 35 to 38 ℃, and discharging CO 2 Filtering out the solid catalyst, and evaporating out tetrahydrofuran and the regulator to obtain the bio-based polytetrahydrofuran.
5. The method for preparing biobased polytetrahydrofuran according to claim 4, wherein the tetrahydrofuran is added in an amount of 20 to 500g in the reaction kettle of 1L in the step (1).
6. The method for preparing bio-based polytetrahydrofuran according to claim 4, wherein in the step (2), the amount of the catalyst added in the 1L reaction kettle is 0.2 to 1.5 percent of the mass of the tetrahydrofuran.
7. The method for producing biobased polytetrahydrofuran according to claim 4, wherein the temperature in the reaction vessel in the step (4) is 50 to 60 ℃.
8. The method for preparing biobased polytetrahydrofuran according to claim 4, characterized in that the reaction time in step (5) is 3 to 8 hours.
9. The method for preparing bio-based polytetrahydrofuran according to claim 4, wherein in the step (6), the regulator is added in an amount of 8 to 25% by mass of the tetrahydrofuran.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108553A (en) * | 1985-11-27 | 1987-06-03 | 北京大学 | The method for preparing polytetramethylene glycol |
| CN1226570A (en) * | 1998-11-26 | 1999-08-25 | 北京大学 | Preparation of polyether by polymerization of tetramethylene oxide |
| CN1440437A (en) * | 2000-07-03 | 2003-09-03 | 巴斯福股份公司 | Improved method for single-step production of polytetrahydrofuran and tetrahydrofuran compolymers |
| CN115322357A (en) * | 2022-09-02 | 2022-11-11 | 浙江皇马科技股份有限公司 | Method for preparing tetrahydrofuran homopolyether by using supercritical carbon dioxide |
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2022
- 2022-11-15 CN CN202211423411.2A patent/CN115725066A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108553A (en) * | 1985-11-27 | 1987-06-03 | 北京大学 | The method for preparing polytetramethylene glycol |
| CN1226570A (en) * | 1998-11-26 | 1999-08-25 | 北京大学 | Preparation of polyether by polymerization of tetramethylene oxide |
| CN1440437A (en) * | 2000-07-03 | 2003-09-03 | 巴斯福股份公司 | Improved method for single-step production of polytetrahydrofuran and tetrahydrofuran compolymers |
| US20030176630A1 (en) * | 2000-07-03 | 2003-09-18 | Gerd Bohner | Method for the single-step production of polytetrahydrofuran and tetrahydrofuran copolymers |
| CN115322357A (en) * | 2022-09-02 | 2022-11-11 | 浙江皇马科技股份有限公司 | Method for preparing tetrahydrofuran homopolyether by using supercritical carbon dioxide |
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