CN115785424A - Hydrolysis-resistant composite titanium catalyst, preparation method and preparation method of high-molecular-weight oxalic acid-based polyester - Google Patents
Hydrolysis-resistant composite titanium catalyst, preparation method and preparation method of high-molecular-weight oxalic acid-based polyester Download PDFInfo
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000010936 titanium Substances 0.000 title claims abstract description 38
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 38
- 229920000728 polyester Polymers 0.000 title claims abstract description 34
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 26
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 235000006408 oxalic acid Nutrition 0.000 title claims abstract description 23
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 150000002148 esters Chemical group 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003085 diluting agent Substances 0.000 claims abstract description 13
- -1 sulfonic acid compound Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000032050 esterification Effects 0.000 claims abstract description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 14
- 238000010907 mechanical stirring Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
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- 239000007788 liquid Substances 0.000 claims description 7
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 7
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 2
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- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
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- 150000003384 small molecules Chemical class 0.000 abstract 1
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- ZYYKBUPALNSJSI-UHFFFAOYSA-N C(CCC)(O)O.[Sb] Chemical compound C(CCC)(O)O.[Sb] ZYYKBUPALNSJSI-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 229920000229 biodegradable polyester Polymers 0.000 description 1
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- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
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- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Abstract
In order to solve the problem that the common titanium catalyst in the prior art is easy to hydrolyze in water to generate white precipitate for inactivation, the invention provides a hydrolysis-resistant composite titanium catalyst for synthesizing polyester, high molecular weight oxalic acid based polyester and a preparation method thereof. Under the condition of low temperature, adding a titanium-containing compound and a sulfonic acid compound into the diluent, mechanically stirring, raising the temperature to be 20 ℃ above the boiling point of the diluent, evaporating redundant diluent, reacting to generate small molecules, and naturally cooling to room temperature to obtain the titanium-sulfonic acid composite catalyst. Oxalic acid/dimethyl oxalate/diethyl oxalate and aliphatic dihydric alcohol are taken as raw materials, and are sequentially subjected to esterification or ester exchange reaction, pre-polycondensation and final polycondensation under the action of the catalyst to obtain the polyoxalate. The composite titanium catalyst prepared by the invention has simple preparation process, can greatly inhibit the generation of byproducts in the reaction process, and can synthesize a degradable oxalate-based polyester product with excellent performance at a lower temperature.
Description
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and particularly relates to a hydrolysis-resistant composite titanium catalyst, a preparation method of the hydrolysis-resistant composite titanium catalyst and a preparation method of high-molecular-weight oxalic acid-based polyester.
Background
In recent years, the development of new bio-based monomers and polymers from natural renewable biomass resources has attracted great attention in all aspects of society, enabling significant reduction and improvement of fossil fuel consumption and environmental pollution problems. While synthetic biodegradable and bio-based polyester materials have become sustainable alternatives to traditional petroleum-based polymers and are being used in a wide variety of applications. With the rapid development of the degradable polyester material, the environmental pollution and the energy crisis are reduced to a certain extent. In recent years, the raw material cost of the degradable polyester material is continuously increased, and the overall popularization of the degradable polyester plastic is hindered by the excessively high production cost. Therefore, it is urgent to develop and prepare a new degradable polyester polymer material with low cost.
The oxalic acid based polyester material is a novel degradable material, has excellent mechanical property, biocompatibility and degradation property, is widely available as the simplest dicarboxylic acid which can be extracted from plants, is a component usually contained in herbaceous plants, has low price, is the most potential monomer as a biodegradable polyester material in the future, and has huge development market.
At present, in the synthesis process of general polyester, the adopted catalyst is mainly a compound of three elements of titanium, antimony or tin. Antimony catalysts such as antimony trioxide, antimony acetate, antimony butanediol, antimony glycol and the like have the advantages of low cost, less side reaction in the reaction process, lower activity, easy pollution of contained heavy metals to the environment and easy gray appearance of the obtained product; in recent years, titanium catalysts have been the focus of research in polyester synthesis catalysts because of their high activity and their products being environment-friendly compounds without heavy metals. However, the common titanium-based catalyst is easy to hydrolyze in water to generate white precipitate and is deactivated, which is a problem mainly solved by researchers at present.
Therefore, the main problem to be solved by the application is to develop a hydrolysis-resistant composite titanium-based polyester synthesis catalyst and use the catalyst in the preparation of a novel degradable oxalic acid-based polyester material.
Disclosure of Invention
In order to solve the problem that the common titanium catalyst in the prior art is easy to hydrolyze when meeting water to generate white precipitate for inactivation, the invention provides a hydrolysis-resistant composite titanium catalyst for synthesizing polyester, a high molecular weight oxalic acid based polyester and a preparation method thereof. The hydrolysis-resistant composite titanium catalyst for synthesizing the polyester has simple and convenient preparation process, overcomes the problem that the common titanium catalyst is easy to inactivate when meeting water, can greatly inhibit the generation of byproducts in the reaction process, and can synthesize a degradable oxalate-based polyester product with excellent performance at a lower temperature.
In order to achieve the above object, the present invention provides a method for preparing a hydrolysis-resistant composite titanium-based catalyst, comprising the following steps:
s1: adding a titanium-containing compound and a sulfonic acid compound into anhydrous diluent at low temperature (0-5 ℃), and mechanically stirring for more than 30min;
s2: the system is returned to the room temperature (20-30 ℃), and the stirring is continued for more than 20 min;
s3: and (3) raising the temperature to 20 ℃ above the boiling point of the diluent, evaporating redundant diluent and micromolecules generated by reaction, and naturally cooling to room temperature (20-30 ℃) to obtain light yellow liquid, namely the hydrolysis-resistant composite titanium catalyst, wherein the hydrolysis-resistant composite titanium catalyst is a titanium-sulfonic acid composite catalyst.
Further, in the step S1, mechanical stirring is carried out for 30-60min, and the stirring speed is 80r/min.
Further, the stirring time in the step S2 is 20-30min.
Further, the titanium-containing compound is selected from at least one of tetrabutyl titanate, tetraisopropyl titanate and tetra-tert-butyl titanate; the sulfonic acid compound is at least one selected from methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, ethylsulfonic acid, p-hydroxybenzenesulfonic acid, m-hydroxybenzenesulfonic acid, o-toluenesulfonic acid and sulfamic acid.
Further, the diluent is at least one selected from absolute methanol and absolute ethanol, and is preferably absolute ethanol.
Further, the molar ratio of the titanium-containing compound to the sulfonic acid compound is 0.5-2, preferably 1;
furthermore, the mass ratio of the diluent to the titanium-containing compound and the sulfonic acid compound is 1-2, preferably 1.5;
the titanium-sulfonic acid composite catalyst prepared by taking tetrabutyl titanate and methanesulfonic acid as raw materials has the following chemical reaction formula:
according to another aspect of the invention, oxalic acid-based polyester and aliphatic diol are used as raw materials, and esterification or ester exchange reaction, pre-polycondensation and final polycondensation are sequentially carried out under the action of the titanium-sulfonic acid composite catalyst to obtain the oxalic acid-based polyester which is polyoxalate.
Further, the aliphatic diol is aliphatic diol with different carbon chain lengths, and the structural formula is as follows:
wherein n is a natural number of 2 or more and 12 or less, such as 2, 3, 4, 5 … …, 12.
Further, the preparation method of the oxalate-based polyester comprises the following steps:
(1) Adding oxalic acid/dimethyl oxalate/diethyl oxalate and aliphatic dihydric alcohol into a reactor, heating the system to 80 ℃ at the heating rate of 10 ℃/min, and stirring for 60min; then putting the titanium-sulfonic acid composite catalyst into a reactor;
(2) Esterification or transesterification reaction: heating the system to 120-140 ℃ at a heating rate of 10 ℃/min, taking the first drop of micromolecule water/methanol/ethanol as a timing zero point, and reacting for 120-180min;
(3) Pre-polycondensation reaction: controlling the pre-polycondensation temperature to be 120-140 ℃, the pre-polycondensation pressure to be 2-3 KPa absolute pressure, and carrying out pre-polycondensation reaction for 30-60min;
(4) And (3) final polycondensation reaction: heating to 185-200 deg.C, and final polycondensation pressure of below 100Pa for 120-240min; thus obtaining the oxalic acid based polyester.
Further, the feeding molar ratio of the oxalic acid/dimethyl oxalate/diethyl oxalate to the aliphatic diol is 1:1.1-1.5; the adding amount of the hydrolysis-resistant composite titanium catalyst is 1-3 per mill of the total mass of the system.
Further, the weight average relative molecular mass of the prepared oxalate-based polyester is 40-80kDa.
Further, the ester exchange temperature is 140 ℃, and the esterification or exchange reaction time is 160min;
the pre-polycondensation temperature is 120 ℃, and the pre-polycondensation reaction time is 45min;
the final polycondensation temperature is 190 ℃, and the final polycondensation reaction time is 180min.
The invention has the beneficial effects that:
(1) According to the preparation method of the oxalate-based polyester, the titanium-sulfonic acid composite catalyst is used for solving the problem that the common titanium catalyst is easy to hydrolyze and deactivate, so that the consumption of the catalyst in the synthesis process is reduced, and the economic benefit is improved;
(2) The preparation method of the oxalate-based polyester can synthesize the oxalate-based polyester with high quality at lower temperature in shorter time, and the production energy consumption is reduced.
Drawings
FIG. 1 shows the reaction equation of the catalyst preparation process (taking tetrabutyl titanate and methanesulfonic acid as an example);
FIG. 2 is a hydrogen nuclear magnetic resonance spectrum of polyoxalate.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1 (preparation of titanium-sulfonic acid composite catalyst)
(1) At 0 ℃, adding 0.1mol (34 g) of tetrabutyl titanate and 0.1mol (9.6 g) of methylbenzenesulfonic acid into 65.4g of absolute ethyl alcohol, and mechanically stirring for 45min at the stirring speed of 80r/min;
(2) The system is returned to the room temperature of 25 ℃, and stirring is continued for 30min;
(3) Raising the temperature to be 20 ℃ above the boiling point of the absolute ethyl alcohol, evaporating the redundant absolute ethyl alcohol and micromolecule butanediol generated by reaction, and naturally cooling to the room temperature of 25 ℃ to obtain light yellow liquid, namely the hydrolysis-resistant titanium-sulfonic acid composite catalyst.
Example 2 (preparation of titanium-sulfonic acid composite catalyst)
(1) At the temperature of 5 ℃, adding 0.15mol (51 g) of tetrabutyl titanate and 0.1mol (9.6 g) of methanesulfonic acid into 66.1g of absolute ethyl alcohol, and mechanically stirring for 30min at the stirring speed of 80r/min;
(2) The system is recovered to the room temperature of 30 ℃, and the stirring is continued for 30min;
(3) Raising the temperature to 20 ℃ above the boiling point of the absolute ethyl alcohol, evaporating the redundant absolute ethyl alcohol and the micromolecule butanediol generated by the reaction, and naturally cooling to the room temperature of 30 ℃ to obtain light yellow liquid, namely the hydrolysis-resistant titanium-sulfonic acid composite catalyst.
Example 3 (preparation of titanium-sulfonic acid composite catalyst)
(1) Adding 0.1mol (28.4 g) of tetraisopropyl titanate and 0.1mol (17.2 g) of p-toluenesulfonic acid into 68.4g of absolute ethyl alcohol at 0 ℃, and mechanically stirring for 45min at the stirring speed of 80r/min;
(2) The system is returned to the room temperature of 25 ℃, and the stirring is continued for 30min;
(3) And (3) raising the temperature to 20 ℃ above the boiling point of the absolute ethyl alcohol, evaporating the redundant absolute ethyl alcohol and the micromolecule butanediol generated by the reaction, and naturally cooling to 25 ℃ at room temperature to obtain light yellow liquid, namely the hydrolysis-resistant titanium-sulfonic acid composite catalyst.
Example 4 (preparation of titanium-sulfonic acid composite catalyst)
(1) At the temperature of 2 ℃, 0.12mol (40.8 g) of tetrabutyl titanate and 0.08mol (13.8 g) of p-toluenesulfonic acid are added into 81.9g of anhydrous methanol, and the mixture is mechanically stirred for 35min at the stirring speed of 80r/min;
(2) The system is returned to the room temperature of 25 ℃, and the stirring is continued for 30min;
(3) Raising the temperature to 20 ℃ above the boiling point of the anhydrous methanol, evaporating the redundant anhydrous ethanol and the micromolecule butanediol generated by the reaction, and naturally cooling to 25 ℃ at room temperature to obtain light yellow liquid, namely the hydrolysis-resistant titanium-sulfonic acid composite catalyst.
Example 5 (preparation of titanium-sulfonic acid composite catalyst)
(1) Adding 0.1mol (28.4 g) of tetraisopropyl titanate and 0.1mol (15.8 g) of benzenesulfonic acid into 57.5g of absolute ethyl alcohol at 4 ℃, and mechanically stirring for 35min at the stirring speed of 80r/min;
(2) The system is returned to the room temperature of 25 ℃, and stirring is continued for 30min;
(3) And (3) raising the temperature to 20 ℃ above the boiling point of the absolute ethyl alcohol, evaporating the redundant absolute ethyl alcohol and the micromolecule butanediol generated by the reaction, and naturally cooling to 25 ℃ at room temperature to obtain light yellow liquid, namely the hydrolysis-resistant titanium-sulfonic acid composite catalyst.
Example 6 (oxalic acid based polyester preparation case)
1. The poly (penta (pentanediol) oxalate of the invention is prepared by the following steps:
(1) 354.3g dimethyl oxalate and 374.9g1, 5-pentanediol are added into a 1L glass flask with mechanical stirring, the system is stirred for 60min from room temperature to 80 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen; after mixing well, 1.3g of the titanium-sulfonic acid composite catalyst prepared in example 1 was added;
(2) Heating to 140 ℃ at a heating rate of 10 ℃/min to perform ester exchange reaction, taking the first drop of micromolecular water as a timing zero point, and reacting for 160min;
(3) After the ester exchange reaction is finished, carrying out a pre-polycondensation reaction, and keeping the absolute pressure at 2.5kPa for 45min;
(4) Heating to the final polycondensation reaction temperature of 190 ℃ at the heating rate of 10 ℃/min, controlling the pressure to be less than 100Pa absolute, and reacting for 180min.
2. Product detection and result analysis
The obtained oxalic acid based polyester was examined as follows:
1. the nuclear magnetic resonance hydrogen spectrum analysis is carried out by adopting equipment with the instrument model of DLG 400 of Vaian company in America, and the reagent is deuterated dimethyl sulfoxide.
2. The weight average relative molecular weight of the corresponding polymer was measured by Gel Permeation Chromatography (GPC) using a gel permeation chromatograph manufactured by Waters corporation, USA (equipped with a high performance liquid chromatography pump model 1515 and a differential refractive index detector model 2414). The sample was dissolved in chromatographically pure tetrahydrofuran at a sample concentration of 10mg/mL. When Polystyrene (PS) is used as a standard sample and chromatographic pure Tetrahydrofuran (THF) is used as a mobile phase (the mobile phase speed is 1.0mL/min; the column temperature is 30 ℃) and n =2 and 4, the prepared polymer is insoluble in the GPC mobile phase, so the weight average molecular weight cannot be characterized, but the rod climbing phenomenon which is peculiar to high molecular weight polymers occurs in the synthesis process.
The test results are as follows: the synthesized poly (penta) oxalate has a weight average molecular weight of 42kDa and a molecular weight distribution of 1.78.
Comparative example 1: the poly (pentylene oxalate) in this comparative example was prepared by the following steps:
(1) Adding 354.3g dimethyl oxalate and 374.9g1, 5-pentanediol into a 1L glass flask with mechanical stirring, uniformly mixing, adding 1.6g tetrabutyl titanate catalyst, heating the system from room temperature to 80 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, and stirring for 60min;
(2) Heating to 140 ℃ at a heating rate of 10 ℃/min to perform ester exchange reaction, taking the first drop of micromolecular water as a timing zero point, and reacting for 160min;
(3) After the ester exchange reaction is finished, carrying out pre-polycondensation reaction, and keeping the absolute pressure at 2kPa for 35min;
(4) Heating to the final polycondensation reaction temperature of 190 ℃ at the heating rate of 10 ℃/min, controlling the pressure to be less than 100Pa absolute, and reacting for 200min.
The test results are: the synthesized poly (penta-oxalate) has a weight average molecular weight of 17kDa and a molecular weight distribution of 1.89.
Comparative example 2: the poly (pentylene oxalate) in this comparative example was prepared by the following steps:
(1) Adding 354.3g dimethyl oxalate and 374.9g1, 5-pentanediol into a 1L glass flask with mechanical stirring, uniformly mixing, adding 0.5g methanesulfonic acid catalyst, heating the system from room temperature to 80 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen, and stirring for 60min;
(2) Heating to 140 ℃ at a heating rate of 10 ℃/min to perform ester exchange reaction, taking the first drop of micromolecule water as a timing zero point, and reacting for 160min;
(3) After the ester exchange reaction is finished, carrying out a pre-polycondensation reaction, and keeping the absolute pressure at 2kPa for 35min;
(4) Heating to the final polycondensation reaction temperature of 190 ℃ at the heating rate of 10 ℃/min, controlling the pressure to be less than 100Pa absolute, and reacting for 200min.
The test results are as follows: the synthesized poly (penta-oxalate) has a weight average molecular weight of 28kDa and a molecular weight distribution of 1.73.
Comparative example 3: the poly (pentylene oxalate) in this comparative example was prepared by the following steps:
(1) Adding 354.3g dimethyl oxalate and 374.9g1, 5-pentanediol into a 1L glass flask with mechanical stirring, uniformly mixing, adding 1.6g tetrabutyl titanate and 0.5g methanesulfonic acid catalyst, heating the system from room temperature to 80 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen, and stirring for 60min;
(2) Heating to 140 ℃ at a heating rate of 10 ℃/min to perform ester exchange reaction, taking the first drop of micromolecular water as a timing zero point, and reacting for 160min;
(3) After the ester exchange reaction is finished, carrying out a pre-polycondensation reaction, and keeping the absolute pressure at 2kPa for 35min;
(4) Heating to the final polycondensation reaction temperature of 190 ℃ at the heating rate of 10 ℃/min, controlling the pressure to be less than 100Pa absolute, and reacting for 200min.
The test results are: the synthesized poly (penta-oxalate) has a weight average molecular weight of 26kDa and a molecular weight distribution of 1.68.
Comparative example 4: the poly (pentylene oxalate) in this comparative example was prepared by the following steps:
(1) 354.3g dimethyl oxalate and 423.1g1, 5-pentanediol are added into a 1L glass flask with mechanical stirring, 1.1g of the titanium-sulfonic acid composite catalyst prepared in the example 1 is added after uniform mixing, and the system is stirred for 60min from room temperature to 80 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen;
(2) Heating to 120 ℃ at a heating rate of 10 ℃/min to perform ester exchange reaction, taking the first drop of micromolecular water as a timing zero point, and reacting for 140min;
(3) After the ester exchange reaction is finished, carrying out a pre-polycondensation reaction, and keeping the absolute pressure at 2kPa for 35min;
(4) Heating to the final polycondensation reaction temperature of 200 ℃ at the heating rate of 10 ℃/min, controlling the pressure to be less than 100Pa absolute, and reacting for 200min.
The test results are: the synthesized poly (penta-oxalate) has a weight average molecular weight of 31kDa and a molecular weight distribution of 1.62.
Comparative example 5: the poly (pentylene oxalate) in this comparative example was prepared by the following steps:
(1) 230g of dimethyl oxalate and 320g of 1, 5-pentanediol are added into a 1L glass flask with mechanical stirring, 1.1g of the titanium-sulfonic acid composite catalyst prepared in example 1 is added after uniform mixing, and the system is stirred for 60min from room temperature to 80 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen;
(2) Heating to 105 ℃ at a heating rate of 10 ℃/min to perform ester exchange reaction, taking the first drop of micromolecular water as a timing zero point, and reacting for 240min;
(3) After the ester exchange reaction is finished, carrying out a pre-polycondensation reaction, and keeping the absolute pressure at 1kPa for 60min;
(4) Heating to the final polycondensation reaction temperature of 220 ℃ at a heating rate of 10 ℃/min, controlling the pressure to be less than 100Pa absolute, and reacting for 270min.
The test results are: the synthesized poly (penta-oxalate) has a weight average molecular weight of 20kDa and a molecular weight distribution of 1.95.
Example 7: the poly (hexamethylene oxalate) of the invention is prepared by the following steps:
(1) 354.3g dimethyl oxalate and 425.4g 1, 6-hexanediol are added into a 1L glass flask with mechanical stirring, 1.4g titanium-sulfonic acid composite catalyst prepared in example 1 is added after uniform mixing, and the system is stirred for 60min from room temperature to 80 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen;
(2) Heating to 140 ℃ at a heating rate of 10 ℃/min to perform ester exchange reaction, taking the first drop of micromolecular water as a timing zero point, and reacting for 160min;
(3) After the ester exchange reaction is finished, carrying out pre-polycondensation reaction, and keeping the absolute pressure at 2.5kPa for 45min;
(4) Heating to the final polycondensation reaction temperature of 190 ℃ at the heating rate of 10 ℃/min, controlling the pressure to be less than 100Pa absolute, and reacting for 180min.
The test results are: the synthesized poly (hexamethylene oxalate) has the weight-average molecular weight of 79kDa and the molecular weight distribution of 1.74.
Example 8: the poly octyl diol oxalate is prepared by the following steps:
(1) 236.8g dimethyl oxalate and 263.2g 1, 8-octanediol are added into a 1L glass flask with mechanical stirring, 0.8g of the titanium-sulfonic acid composite catalyst prepared in example 3 is added after uniform mixing, and the system is stirred for 60min from room temperature to 80 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen;
(2) Heating to 140 ℃ at a heating rate of 10 ℃/min to perform ester exchange reaction, taking the first drop of micromolecular water as a timing zero point, and reacting for 160min;
(3) After the ester exchange reaction is finished, carrying out pre-polycondensation reaction, and keeping the absolute pressure at 2.5kPa for 45min;
(4) Heating to the final polycondensation reaction temperature of 190 ℃ at the heating rate of 10 ℃/min, controlling the pressure to be less than 100Pa absolute, and reacting for 180min.
The test results are: the weight average molecular weight of the synthesized poly (octanediol oxalate) was 51kDa, and the molecular weight distribution was 1.71.
Example 9: the poly (nonane oxalate) is prepared by the following steps:
(1) Adding 180g of oxalic acid and 263.2g of 1, 9-nonanediol into a 1L glass flask with mechanical stirring, uniformly mixing, adding 0.8g of the titanium-sulfonic acid composite catalyst prepared in example 3, heating the system from room temperature to 80 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, and stirring for 60min;
(2) Heating to 140 ℃ at a heating rate of 10 ℃/min to perform ester exchange reaction, taking the first drop of micromolecular water as a timing zero point, and reacting for 160min;
(3) After the ester exchange reaction is finished, carrying out a pre-polycondensation reaction, and keeping the absolute pressure at 2.5kPa for 45min;
(4) Heating to the final polycondensation reaction temperature of 190 ℃ at the heating rate of 10 ℃/min, controlling the pressure to be less than 100Pa absolute, and reacting for 180min.
The test results are: the weight average molecular weight of the synthesized poly (octanediol oxalate) was 50kDa, and the molecular weight distribution was 1.79.
Example 10: the poly (decanediol oxalate) is prepared by the following steps:
(1) 292.1g diethyl oxalate and 313.7g 1, 10-decanediol are added into a 1L glass flask with mechanical stirring, 0.9g titanium-sulfonic acid composite catalyst prepared in example 4 is added after uniform mixing, the system is stirred for 60min from room temperature to 80 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen;
(2) Heating to 140 ℃ at a heating rate of 10 ℃/min to perform ester exchange reaction, taking the first drop of micromolecular water as a timing zero point, and reacting for 160min;
(3) After the ester exchange reaction is finished, carrying out a pre-polycondensation reaction, and keeping the absolute pressure at 2.5kPa for 45min;
(4) Heating to the final polycondensation reaction temperature of 190 ℃ at the heating rate of 10 ℃/min, controlling the pressure to be less than 100Pa absolute, and reacting for 180min.
The test results are: the weight average molecular weight of the synthesized poly (sebacic acid glycol) is 57kDa, and the molecular weight distribution is 1.8.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a hydrolysis-resistant composite titanium catalyst is characterized by comprising the following steps:
s1: adding a titanium-containing compound and a sulfonic acid compound into anhydrous diluent at the temperature of 0-5 ℃, and mechanically stirring for more than 30min;
s2: heating the system to 20-30 deg.C, and stirring for more than 20 min;
s3: raising the temperature of the system to 20 ℃ above the boiling point of the diluent, evaporating redundant diluent and micromolecules generated by reaction, and naturally cooling to 20-30 ℃ to obtain light yellow liquid, namely the hydrolysis-resistant composite titanium catalyst, wherein the hydrolysis-resistant composite titanium catalyst is a titanium-sulfonic acid composite catalyst.
2. The method for preparing the hydrolysis-resistant composite titanium-based catalyst according to claim 1, wherein the titanium-containing compound is at least one selected from the group consisting of tetrabutyl titanate, tetraisopropyl titanate, and tetra-tert-butyl titanate; the sulfonic acid compound is at least one selected from methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, ethylsulfonic acid, p-hydroxybenzenesulfonic acid, m-hydroxybenzenesulfonic acid, o-toluenesulfonic acid and sulfamic acid.
3. The preparation method of the hydrolysis-resistant composite titanium-based catalyst according to claim 2, wherein the molar ratio of the titanium-containing compound to the sulfonic acid compound is 0.5 to 2; the mass ratio of the diluent to the titanium-containing compound and the sulfonic acid compound is 1-2.
4. The method for preparing the hydrolysis-resistant composite titanium-based catalyst according to claim 3, wherein the diluent is at least one selected from the group consisting of absolute methanol and absolute ethanol.
5. The preparation method of the hydrolysis-resistant composite titanium catalyst according to claim 1, wherein in the step S1, the mechanical stirring is performed for 30-60min, and the stirring speed is 80r/min; and the stirring time in the step S2 is 20-30min.
6. A hydrolysis-resistant composite titanium catalyst, which is characterized in that the titanium-sulfonic acid composite catalyst is a titanium-sulfonic acid composite catalyst and is prepared by the method of claims 1 to 5.
7. The method for preparing high molecular weight oxalic acid based polyester by using the titanium-sulfonic acid composite catalyst of claim 6, characterized in that oxalic acid/dimethyl oxalate/diethyl oxalate and aliphatic diol are used as raw materials, and the oxalic acid based polyester is obtained by esterification or ester exchange reaction, pre-polycondensation and final polycondensation stages in sequence under the action of the titanium-sulfonic acid composite catalyst.
8. The method of preparing a high molecular weight oxalic acid based polyester according to claim 7, characterized by comprising the following steps:
(1) Adding oxalic acid/dimethyl oxalate/diethyl oxalate and aliphatic diol into a reactor, heating the system to 80 ℃ at the heating rate of 10 ℃/min, and stirring for 60min; then putting the titanium-sulfonic acid composite catalyst into a reactor;
(2) Esterification or transesterification reaction: heating the system to 120-140 ℃, taking the first drop of micromolecular water/methanol/ethanol as a timing zero point, and reacting for 120-180min;
(3) Pre-polycondensation reaction: controlling the pre-polycondensation temperature to be 120-140 ℃, the pre-polycondensation pressure to be 2-3 KPa absolute pressure, and carrying out the pre-polycondensation reaction for 30-60min;
(4) And (3) final polycondensation reaction: heating to 185-200 deg.C, and final polycondensation pressure of below 100Pa for 120-240min; thus obtaining the oxalic acid based polyester.
9. The method of claim 8, wherein the molar ratio of oxalic acid/dimethyl oxalate/diethyl oxalate to the aliphatic diol is 1:1.1-1.5; the adding amount of the hydrolysis-resistant composite titanium catalyst is 1-3 per mill of the total mass of the system.
10. A method as claimed in any one of claims 7 to 9 wherein said aliphatic diols are aliphatic diols having different carbon chain lengths and having the following structural formula:
wherein n is a natural number of 2 or more and 12 or less.
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| CN101709110A (en) * | 2009-08-24 | 2010-05-19 | 吴江鹰翔万信化纤有限公司 | Novel polymerizing catalysis stable method of polyester |
| CN102219891A (en) * | 2011-05-13 | 2011-10-19 | 北京理工大学 | Method for preparing poly-oxalate-1,4-butylene |
| CN106366121A (en) * | 2015-12-18 | 2017-02-01 | 中国科学院深圳先进技术研究院 | Titanium ligand modified black phosphorus, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101709110A (en) * | 2009-08-24 | 2010-05-19 | 吴江鹰翔万信化纤有限公司 | Novel polymerizing catalysis stable method of polyester |
| CN102219891A (en) * | 2011-05-13 | 2011-10-19 | 北京理工大学 | Method for preparing poly-oxalate-1,4-butylene |
| CN106366121A (en) * | 2015-12-18 | 2017-02-01 | 中国科学院深圳先进技术研究院 | Titanium ligand modified black phosphorus, and preparation method and application thereof |
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