CN115677988A - In-situ preparation method of polybutylene oxalate - Google Patents
In-situ preparation method of polybutylene oxalate Download PDFInfo
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- -1 polybutylene oxalate Polymers 0.000 title claims abstract description 41
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 150000002148 esters Chemical group 0.000 claims abstract description 26
- 238000002425 crystallisation Methods 0.000 claims abstract description 22
- 230000008025 crystallization Effects 0.000 claims abstract description 22
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZRGYUQUHZCEOFH-UHFFFAOYSA-N 1,4-dioxocane-2,3-dione Chemical compound O=C1OCCCCOC1=O ZRGYUQUHZCEOFH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002667 nucleating agent Substances 0.000 claims abstract description 16
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 35
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 34
- 238000001816 cooling Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- 230000008018 melting Effects 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 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 12
- 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 10
- 239000003085 diluting agent Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 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
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- ZCLXQTGLKVQKFD-UHFFFAOYSA-N 3-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC(S(O)(=O)=O)=C1 ZCLXQTGLKVQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 241001085205 Prenanthella exigua Species 0.000 claims description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 2
- 238000010907 mechanical stirring Methods 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
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000686 lactone group Chemical group 0.000 claims 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 abstract description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 11
- 150000003016 phosphoric acids Chemical class 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 34
- 229920000728 polyester Polymers 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 238000004537 pulping Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000004581 coalescence Methods 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 101001098482 Homo sapiens Peroxisomal N(1)-acetyl-spermine/spermidine oxidase Proteins 0.000 description 1
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 102100037209 Peroxisomal N(1)-acetyl-spermine/spermidine oxidase Human genes 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- VIMBFJSTKMOQLU-UHFFFAOYSA-N butane-1,1-diol oxalic acid Chemical compound C(C(=O)O)(=O)O.C(CCC)(O)O VIMBFJSTKMOQLU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 230000006837 decompression Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229960002479 isosorbide Drugs 0.000 description 1
- RPONRISSUINNRF-UHFFFAOYSA-L magnesium;2-hydroxy-2-phenylacetate Chemical compound [Mg+2].[O-]C(=O)C(O)C1=CC=CC=C1.[O-]C(=O)C(O)C1=CC=CC=C1 RPONRISSUINNRF-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
In order to solve the problems of slow crystallization rate, low intrinsic viscosity, poor chromaticity and the like of the polybutylene oxalate in the prior art, the invention provides an in-situ preparation method of the polybutylene oxalate, which takes dimethyl oxalate/diethyl oxalate and butanediol as raw materials and sequentially carries out ester exchange reaction, pre-polycondensation and final polycondensation stages under the action of a titanium-sulfonic acid composite catalyst and a second metal oxide to obtain the polybutylene oxalate. Wherein, the high-efficiency catalyst in the ester exchange stage is compounded by titanate compounds and phosphoric acid compounds, and the in-situ nucleating agent in the polycondensation stage is selected from titanium dioxide, antimony trioxide and antimony acetate. The polybutanediol oxalate synthesized by the synthesis method has high molecular weight, high intrinsic viscosity, white color, high crystallinity and high crystallization rate. Improves the performance of the poly (butylene oxalate) and enlarges the application market range.
Description
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and particularly relates to an in-situ preparation method capable of simultaneously improving the crystallization temperature, the crystallization rate and the intrinsic viscosity of polybutylene oxalate and reducing the chroma of polybutylene oxalate.
Background
PAOX is a generic name of a class of oxalate-based polyester materials, and is generally prepared by taking dimethyl oxalate/diethyl oxalate monomers as raw materials and different diols through condensation polymerization, wherein common alcohol monomers used for polymerization reaction are aliphatic diols such as ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and the like, and cyclic diols such as 1, 4-cyclohexanedimethanol, isosorbide and the like. Currently, among the numerous oxalate-based aliphatic polyester materials, polyethylene oxalate (PEOX), polybutylene oxalate (PBOX) have gained widespread attention due to their high melting points and good degradability.
Compared with polyethylene oxalate (PEOX), although the melting point of PBOX is slightly lower, about 100 ℃, PBOX has unique properties as aliphatic polyester material with a few melting points reaching above 100 ℃, such as good ductility, higher elongation at break and breaking strength, and heat resistance and degradation performance, and can relieve the vacancy of degradable material in the market to a certain extent.
Patent CN102219891B relates to a preparation method of poly (oxalic acid) -1, 4-butanediol ester, which comprises the following steps: stirring diethyl oxalate and butanediol at constant temperature of 80-170 ℃ for 0.5-5h under the condition of controlling nitrogen flow rate to obtain an esterification product, wherein the alcohol ester ratio is 1-3, the catalyst is preferably oxalic acid, and then carrying out constant-temperature and constant-pressure reaction at high temperature of 110-180 ℃ and under vacuum of 200-500Pa for 3-8h to obtain a target product. Its intrinsic viscosity is only 0.05-0.45dL/g, its melting point and crystallization temperature are only 104.8 deg.C and 55.9 deg.C, and its product is a dark white solid.
U.S. Pat. No. 4,186,189a discloses that diethyl oxalate and 1,4-butanediol are used as raw materials, and that an ester exchange reaction is carried out under normal pressure, and then a polycondensation reaction is carried out under reduced pressure. The mass ratio of substances is 1:1.15 of diethyl oxalate and 1, 4-butanediol, adding 1 percent of tetra (2-ethylhexanol) titanate as a catalyst, reacting for 2 hours at the constant temperature of 140 ℃ and 160 ℃ respectively under the protection of nitrogen, and reacting for 20 hours and 2 hours at the constant temperature and the constant pressure of 2-3mm Hg at the pressure of 160 ℃ and 180 ℃ respectively in a decompression stage. The product had an intrinsic viscosity of 0.95 dl/g and a Tm of 105 ℃. The method has harsh reaction conditions, very high cost and long reaction time of 26 hours, and is not suitable for industrial production.
In the synthesis process of the polyester, most commercial polyester is synthesized by a melt condensation polymerization mode of dicarboxylic acid and dihydric alcohol, and the polyester has the advantages of low cost, abundant monomer sources, complete conversion, no need of using an organic solvent and the like. The melt polycondensation of dicarboxylic acids and diols is based on a reversible acid-alcohol esterification reaction, the molecular weight control of which is influenced both thermodynamically and kinetically. Thermodynamically, small molecules such as water or methanol, which are byproducts generated in the esterification reaction, are discharged from the system by means of high temperature, high vacuum and the like, so that they can be converted into irreversible reactions. Another factor that limits the molecular weight of polyesters is their kinetic behavior, i.e., the requirement to precisely control the equimolar ratio of functional groups to react. In the actual operation process, the precise group equimolar ratio is difficult to realize, and even if the purity of the monomer at the beginning of the reaction is high and the weighing is accurate, the monomer may deviate from the equimolar ratio in the reaction process due to the different evaporation or sublimation rates of the monomer and the consumption of carboxyl or hydroxyl groups caused by various side reactions. Therefore, the molecular weight of the polyester product obtained by the traditional esterification method is not high, and the dynamic equimolar ratio of the functional groups in the reaction process must be realized to realize the synthesis of the high molecular weight polyester. Basically, the monomers are prepared according to the stoichiometric ratio, and a trace amount of monofunctional substance is added or a certain bifunctional raw material monomer is excessive to control the molecular weight, but the method can cause the waste of raw materials and increase the production cost on one hand, and can cause adverse effects on the product performance because the excessive monomer can increase the degree of side reaction on the other hand.
Although researchers pay attention to the field of polybutylene oxalate currently, all the methods are only in the experimental stage of a small laboratory experimental container, and the researchers do not successfully amplify the method, namely, the existing method has a certain difference from industrial production. The realization of industrial amplification has close relation to polyester synthesis formula, synthesis route, experimental operation and steps, and in the case of poly (butylene oxalate), when oxalic acid is used as a raw material, the reaction is difficult to carry out due to the easy decomposition property of the oxalic acid at low temperature; when oxalic diester is used as a raw material, the alcohol ester ratio can be changed in the reaction process due to the sublimability of the oxalic diester, and the dynamic balance of the alcohol ester ratio cannot be well controlled. In addition, in the process of polymerizing the poly (butylene oxalate), the side reaction of butanediol etherification to generate tetrahydrofuran is easy to occur to the raw material butanediol, and the side reaction degree is aggravated by the large increase of the butanediol in the amplification process, which seriously influences the progress of the polymerization reaction. In the latter stage of the polymerization reaction, the temperature of the system is continuously increased due to the huge exothermic effect caused by the rapid increase of the viscosity of the system, so that the degree of side reaction is further deepened and the product is also easily thermally decomposed at high temperature. The process from the laboratory vial experiment stage to the gradual scale-up is extremely difficult.
Aiming at the defects of long reaction time, low intrinsic viscosity and color difference of the poly (butylene oxalate) in the prior art, the method for preparing the poly (butylene oxalate) which can obtain low color and high intrinsic viscosity and can improve the crystallization rate is particularly urgent, the application range of the poly (butylene oxalate) is improved, and the dilemma of shortage of degradable materials can be relieved to a certain extent.
Disclosure of Invention
Aiming at the defects of long reaction time, low intrinsic viscosity, low crystallization temperature and poor color in the preparation of the poly (butylene oxalate) in the prior art, the in-situ preparation method of the poly (butylene oxalate) is developed, the obtained poly (butylene oxalate) has the properties of low chroma and high intrinsic viscosity, the crystallization temperature and the melting point are also obviously improved, the application range of the poly (butylene oxalate) is improved, and the dilemma of shortage of degradable materials can be relieved to a certain extent.
According to the first aspect, the invention provides an in-situ preparation method of poly (butylene oxalate), which is characterized in that dimethyl oxalate/diethyl oxalate and 1, 4-butanediol are used as raw materials, and under the action of a titanium-sulfonic acid composite catalyst and a second metal oxide, the poly (butylene oxalate) is obtained through ester exchange reaction, pre-polycondensation and final polycondensation stages in sequence, and the prepared poly (butylene oxalate) is bright white and has the characteristics of high crystallinity and high intrinsic viscosity; the titanium-sulfonic acid composite catalyst is added before the ester exchange reaction; the second type of metal oxide is added after the transesterification reaction and before the precondensation reaction. The specific reaction equation is as follows:
wherein n is the number of the butanediol oxalate structural units, n is more than 100, n is an integer more than 100, such as 100, 101, 102, 103, 104, 105, 106, \8230 \ 8230;, 200, \8230; \8230300, and the like.
Before reaction, the mol ratio of dimethyl oxalate/diethyl oxalate to 1, 4-butanediol is strictly controlled to be 1:1 during feeding, so that the ratio of ester groups to hydroxyl groups in a system is ensured during feeding
The addition amount of the titanium-sulfonic acid composite catalyst is 0.5-1 per mill of the mass fraction of dimethyl oxalate/diethyl oxalate; the dosage of the second metal oxide is 1-3 per mill of the mass fraction of dimethyl oxalate/diethyl oxalate.
Further, as a key technical link:
before ester exchange reaction, adding reaction raw materials of dimethyl oxalate or diethyl oxalate, 1, 4-butanediol and a titanium-sulfonic acid composite catalyst into a reaction kettle, heating the system to 70-80 ℃ at a heating rate of 10 ℃/min, stirring and pulping for more than 60min; preferably 80 deg.c.
The transesterification temperature is 120-160 ℃, preferably 160 ℃, the first drop of the micromolecular methanol/ethanol is taken as a timing zero point, and the transesterification reaction time is 180-300min.
The pre-polycondensation temperature is 120-130 ℃, the pre-polycondensation reaction time is 30-60min, the pre-polycondensation reaction time is 45min, and the pre-polycondensation pressure is 2-3 kPa absolute pressure.
The final polycondensation temperature is 185-195 ℃, preferably 185 ℃, the final polycondensation time is 120-240 min, preferably 180min, and the final polycondensation pressure is less than 100Pa absolute.
Further, the second metal oxide is at least one of titanium dioxide, antimony trioxide and antimony acetate.
Further, the titanium-sulfonic acid composite catalyst is prepared by the following method, and the specific steps comprise:
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 recovered to the room temperature (20-30 ℃), and the stirring is continued for more than 20 min;
s3: and (3) raising the temperature to be 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 titanium-sulfonic acid composite catalyst.
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, ethanesulfonic acid, p-hydroxyphenylsulfonic acid, m-hydroxybenzenesulfonic acid, o-toluenesulfonic acid and sulfamic acid.
Further, the molar ratio of the titanium-containing compound to the sulfonic acid compound is 0.5 to 2, preferably 1.
Further, the diluent is at least one selected from absolute methanol and absolute ethanol, and is preferably absolute ethanol.
Furthermore, the mass ratio of the diluent to the titanium-containing compound and the sulfonic acid compound is 1-2, and preferably 1.5.
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.
The titanium-sulfonic acid composite catalyst prepared by taking tetrabutyl titanate and methanesulfonic acid as raw materials has the following chemical reaction formula:
the intrinsic viscosity of the polybutylene oxalate material is 1.4-1.8; the weight average molecular weight is 130-180kDa; the value of L is more than 80; the crystallization temperature is 61-73 ℃; the melting point is 105-110 ℃; the crystallinity is 30-60%.
Has the beneficial effects that:
(1) According to the in-situ preparation method of the poly (butylene oxalate), the adopted titanium-sulfonic acid composite catalyst solves the problem that the common titanium catalyst is easy to hydrolyze and deactivate, reduces the consumption of the catalyst in the synthesis process, and improves the economic benefit;
(2) According to the in-situ preparation method provided by the invention, the second metal oxide catalyst is added in the pre-polycondensation reaction stage, so that the catalytic effect is achieved, the nucleation sites can be provided for the crystallization of the polybutyleneoxalate, and the in-situ catalytic nucleation effect is achieved;
(3) The in-situ preparation method of the poly (butylene oxalate) can synthesize high-quality poly (butylene oxalate) at a lower temperature in a shorter time, and the production energy consumption is reduced.
Drawings
FIG. 1 is a DSC of polybutyleneoxalate synthesized using an in situ catalytic nucleating agent;
FIG. 2 is a DSC of a conventionally synthesized polybutylene oxalate;
FIG. 3 is a NMR chart of polybutyleneoxalate synthesized using an in situ nucleating agent;
FIG. 4 is a diagram showing the pelletized polybutylene oxalate polymer synthesized by using a 5L polymerization reaction kettle and an in-situ catalytic nucleating agent.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the drawings.
In the invention, the method for testing the intrinsic viscosity comprises the following steps: the method is carried out according to the regulation of 5.1.1 in GB/T14190-2008. The solvent is phenol/1, 2-tetrachloroethane (mass ratio is 50.
The method for testing the chroma L value comprises the following steps: the test was carried out as specified in GB/T14190-2008 at 5.5.2. The CIE1976L a b color series was used.
The crystallization temperature and the enthalpy of crystallization were measured by DSC25, an instrument model of TA of USA, and the crystallization temperature and the melting point of the polymer were calculated from the results. During testing, the adopted procedure is as follows: under the nitrogen atmosphere (the flow rate is 50 ml/min), the temperature rising and falling speed is 10 ℃/min.
The microscopic morphology of the catalytic nucleating agent is tested by adopting a JSM-7900 type field emission scanning electron microscope produced by FEI company of America to perform microscopic morphology test on magnesium mandelate, the working voltage and the current are respectively 230V and 8A, and a sample needs to be subjected to metal spraying and blowing treatment before the test.
The molecular weight and molecular weight distribution of the polymer were characterized by Waters-2414 gel permeation chromatograph with 1515HPLC type pump, waters corporation, USA, with Tetrahydrofuran (THF) as the mobile phase, 40 deg.C test temperature, to dissolve 10mg of the sample in 5ml of THF solvent, filter by syringe filter after complete dissolution, flow rate of 1.0ml/min, and using Polystyrene (PS) as the standard to calculate the molecular weight.
The crystallinity of the polybutylene oxalate material is measured by an X-ray diffractometer of RigakuD/Max-Ultima + type.
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.
Comparative example 1 (sulfonic acid out of limits in titanium-sulfonic acid composite catalyst)
(1) At 0 ℃, adding 0.1mol (34 g) of tetrabutyl titanate and 0.3mol (28.6 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 the 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.
Comparative example 2 (titanic acid substance out of limits in titanium-sulfonic acid composite catalyst)
(1) At the temperature of 0 ℃, adding 0.3mol (102 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) 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 2 (preparation of titanium-sulfonic acid composite catalyst)
(1) At 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 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 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 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 (preparation of polybutylene oxalate)
(1) Adding 17mol (2007 g) of dimethyl oxalate, 17mol (1532 g) of 1, 4-butanediol and 1g (0.5 per thousand wt) of the titanium-sulfonic acid composite catalyst prepared in the example 1 into a 5L steel reaction kettle, heating the system to 80 ℃ at a heating rate of 10 ℃/min, stirring and pulping for 60min;
(2) After the pulping is finished, heating the system to 160 ℃, starting ester exchange reaction, and taking the first drop of the micromolecule methanol/ethanol as a timing zero point, wherein the reaction time is 240min;
(3) After the ester exchange is finished, cooling the system to 130 ℃, adding 6g (3 per thousand wt) of a second type of in-situ catalytic nucleating agent antimony trioxide, and then starting the pre-polycondensation reaction, wherein the absolute pressure of the system is 2kPa, and the pre-polycondensation time is 45min;
(4) After the pre-condensation and coalescence, the system pressure is increased to be below 100Pa absolute, the reaction temperature is increased to 185 ℃, and the polycondensation reaction is started and stopped for 180min. And after the reaction is finished, extruding the material melt in the reaction kettle under the action of nitrogen, and granulating by using a water cooling and granulating machine to obtain the target polyester material.
Testing the obtained polybutylene oxalate polyester material to obtain the weight average molecular weight of 180kDa; the intrinsic viscosity is 1.8dL/g; the crystallization temperature is 73 ℃; the melting point is 110 ℃; a chroma L value of 87; the crystallinity was 60%.
Comparative example 3 (without in situ catalytic nucleating agent)
(1) Adding 17mol (2007 g) of dimethyl oxalate, 17mol (1532 g) of 1, 4-butanediol and 1g (0.5 per thousand wt%) of the titanium-sulfonic acid composite catalyst prepared in example 1 into a 5L steel reaction kettle, heating the system to 80 ℃ at a heating rate of 10 ℃/min, stirring and pulping for 60min;
(2) After the pulping is finished, heating the system to 160 ℃, starting ester exchange reaction, and taking the first drop of the micromolecule methanol/ethanol as a timing zero point, wherein the reaction time is 240min;
(3) After the ester exchange is finished, cooling the system to 130 ℃, and then starting a pre-polycondensation reaction, wherein the absolute pressure of the system is 2kPa, and the pre-polycondensation time is 45min;
(4) After the pre-condensation and coalescence, the system pressure is increased to be below 100Pa absolute, the reaction temperature is increased to 185 ℃, and the polycondensation reaction is started and stopped for 180min. And after the reaction is finished, extruding the material melt in the reaction kettle under the action of nitrogen, and granulating by using a water cooling and granulating machine to obtain the target polyester material.
Testing the obtained polybutylene oxalate polyester material to obtain the weight-average molecular weight of 164kDa; the intrinsic viscosity is 1.65dL/g; the crystallization temperature is 54 ℃; the melting point is 105 ℃; a chroma L value of 81; the crystallinity was 42%.
Comparative example 4 (sulfonic acid excess in titanium-sulfonic acid catalyst + No in situ catalytic nucleating agent)
(1) 2007g (17 mol) of dimethyl oxalate, 1532g (17 mol) of 1, 4-butanediol and 1g (0.5 per thousand wt%) of the titanium-sulfonic acid composite catalyst prepared in comparative example 1 are added into a 5L steel reaction kettle, and the system is heated to 80 ℃ at the heating rate of 10 ℃/min and stirred and pulped for 60min;
(2) After the pulping is finished, heating the system to 160 ℃, starting ester exchange reaction, taking the first drop of the micromolecular methanol/ethanol as a timing zero point, and reacting for 240min;
(3) After the ester exchange is finished, cooling the system to 130 ℃, and then starting a pre-polycondensation reaction, wherein the absolute pressure of the system is 2kPa, and the pre-polycondensation time is 45min;
(4) After the pre-shrinking and the coalescence, the system pressure is increased to be below 100Pa absolute, the reaction temperature is increased to 185 ℃, and the polycondensation reaction is started and stopped for 180min. After the reaction is finished, extruding the material melt in the reaction kettle under the action of nitrogen, and granulating by a water cooling and granulator to obtain the target polyester material.
Testing the obtained polybutylene oxalate polyester material to obtain the weight average molecular weight of 96kDa; the intrinsic viscosity is 0.87dL/g; the crystallization temperature is 47 ℃; the melting point is 103 ℃; a chroma L value of 68; the crystallinity was 36%.
Comparative example 5 (excess of titanic acid material in titanium-sulfonic acid catalyst + Insitu catalysis-free nucleating agent)
(1) Adding 17mol (2007 g) of dimethyl oxalate, 17mol (1532 g) of 1, 4-butanediol and 1g (0.5 per thousand wt%) of the titanium-sulfonic acid composite catalyst prepared in comparative example 2 into a 5L steel reaction kettle, heating the system to 80 ℃ at a heating rate of 10 ℃/min, stirring and pulping for 60min;
(2) After the pulping is finished, heating the system to 160 ℃, starting ester exchange reaction, and taking the first drop of the micromolecule methanol/ethanol as a timing zero point, wherein the reaction time is 240min;
(3) After the ester exchange is finished, cooling the system to 130 ℃, and then starting the pre-polycondensation reaction, wherein the absolute pressure of the system is 2kPa, and the pre-polycondensation time is 45min;
(4) After the pre-condensation and coalescence, the system pressure is increased to be below 100Pa absolute, the reaction temperature is increased to 185 ℃, and the polycondensation reaction is started and stopped for 180min. After the reaction is finished, extruding the material melt in the reaction kettle under the action of nitrogen, and granulating by a water cooling and granulator to obtain the target polyester material.
Testing the obtained polybutylene oxalate polyester material to obtain the weight-average molecular weight of 86kDa; the intrinsic viscosity is 0.84dL/g; the crystallization temperature is 46 ℃; the melting point is 103 ℃; the chroma L value is 67; the crystallinity was 36%.
Comparative example 6 (tetrabutyl titanate catalyst alone + Insitu catalysis-free nucleating agent)
(1) Adding 17mol (2007 g) of dimethyl oxalate, 17mol (1532 g) of 1, 4-butanediol and 1g (0.5 per thousand wt) of tetrabutyl titanate catalyst into a 5L steel reaction kettle, heating the system to 80 ℃ at the heating rate of 10 ℃/min, stirring and pulping for 60min;
(2) After the pulping is finished, heating the system to 160 ℃, starting ester exchange reaction, and taking the first drop of the micromolecule methanol/ethanol as a timing zero point, wherein the reaction time is 240min;
(3) After the ester exchange is finished, cooling the system to 130 ℃, and then starting the pre-polycondensation reaction, wherein the absolute pressure of the system is 2kPa, and the pre-polycondensation time is 45min;
(4) After the pre-shrinking and the coalescence, the system pressure is increased to be below 100Pa absolute, the reaction temperature is increased to 185 ℃, and the polycondensation reaction is started and stopped for 180min. And after the reaction is finished, extruding the material melt in the reaction kettle under the action of nitrogen, and granulating by using a water cooling and granulating machine to obtain the target polyester material.
Testing the obtained polybutylene oxalate polyester material to obtain the weight-average molecular weight of the polybutylene oxalate polyester material of 136kDa; the intrinsic viscosity is 1.25dL/g; the crystallization temperature is 53 ℃; the melting point is 103 ℃; a chroma L value of 73; the crystallinity was 38%.
Comparative example 7 (toluene sulfonic acid catalyst alone + Insitu catalysis-free nucleating agent)
(1) Adding 17mol (2007 g) of dimethyl oxalate, 17mol (1532 g) of 1, 4-butanediol and 1g (0.5 per thousand wt) of methyl benzene sulfonic acid catalyst into a 5L steel reaction kettle, heating the system to 80 ℃ at the heating rate of 10 ℃/min, stirring and pulping for 60min;
(2) After the pulping is finished, heating the system to 160 ℃, starting ester exchange reaction, and taking the first drop of the micromolecule methanol/ethanol as a timing zero point, wherein the reaction time is 240min;
(3) After the ester exchange is finished, cooling the system to 130 ℃, and then starting a pre-polycondensation reaction, wherein the absolute pressure of the system is 2kPa, and the pre-polycondensation time is 45min;
(4) After the pre-condensation and coalescence, the system pressure is increased to be below 100Pa absolute, the reaction temperature is increased to 185 ℃, and the polycondensation reaction is started and stopped for 180min. And after the reaction is finished, extruding the material melt in the reaction kettle under the action of nitrogen, and granulating by using a water cooling and granulating machine to obtain the target polyester material.
Testing the obtained polybutylene oxalate polyester material to obtain the weight average molecular weight of 141kDa; the intrinsic viscosity is 1.33dL/g; the crystallization temperature is 53 ℃; the melting point is 104 ℃; a chroma L value of 74; the crystallinity was 38%.
Example 7 (preparation of polybutylene oxalate)
(1) 2007g (17 mol) of dimethyl oxalate, 1532g (17 mol) of 1, 4-butanediol and 1g (0.5 per thousand wt) of the titanium-sulfonic acid composite catalyst prepared in the embodiment 3 are added into a 5L steel reaction kettle, and the system is heated to 80 ℃ at the heating rate of 10 ℃/min and stirred and pulped for 60min;
(2) After the pulping is finished, heating the system to 160 ℃, starting ester exchange reaction, and taking the first drop of the micromolecule methanol/ethanol as a timing zero point, wherein the reaction time is 240min;
(3) After the ester exchange is finished, cooling the system to 130 ℃, adding 6g (3 per thousand wt) of a second type in-situ catalytic nucleating agent antimony trioxide, and then starting a pre-polycondensation reaction, wherein the absolute pressure of the system is 2kPa, and the pre-polycondensation time is 45min;
(4) After the pre-condensation and coalescence, the system pressure is increased to be below 100Pa absolute, the reaction temperature is increased to 185 ℃, and the polycondensation reaction is started and stopped for 180min. And after the reaction is finished, extruding the material melt in the reaction kettle under the action of nitrogen, and granulating by using a water cooling and granulating machine to obtain the target polyester material.
Testing the obtained polybutylene oxalate polyester material to obtain the weight-average molecular weight of 177kDa; the intrinsic viscosity is 1.74dL/g; the crystallization temperature is 70 ℃; the melting point is 109 ℃; the chroma L value is 86; the crystallinity was 58%.
Example 8 preparation of polybutylene oxalate
(1) Adding 17mol (2007 g) of dimethyl oxalate, 17mol (1532 g) of 1, 4-butanediol and 1g (0.5 per thousand wt%) of the titanium-sulfonic acid composite catalyst prepared in example 1 into a 5L steel reaction kettle, heating the system to 80 ℃ at a heating rate of 10 ℃/min, stirring and pulping for 60min;
(2) After the pulping is finished, heating the system to 160 ℃, starting ester exchange reaction, and taking the first drop of the micromolecule methanol/ethanol as a timing zero point, wherein the reaction time is 240min;
(3) After the ester exchange is finished, cooling the system to 130 ℃, adding 6g (3 per thousand wt) of titanium dioxide serving as a second type in-situ catalytic nucleating agent, and then starting the pre-polycondensation reaction, wherein the absolute pressure of the system is 2kPa, and the pre-polycondensation time is 45min;
(4) After the pre-condensation and coalescence, the system pressure is increased to be below 100Pa absolute, the reaction temperature is increased to 185 ℃, and the polycondensation reaction is started and stopped for 180min. And after the reaction is finished, extruding the material melt in the reaction kettle under the action of nitrogen, and granulating by using a water cooling and granulating machine to obtain the target polyester material.
Testing the obtained polybutylene oxalate polyester material to obtain the weight average molecular weight of 165kDa; the intrinsic viscosity is 1.65dL/g; the crystallization temperature is 55 ℃; the melting point is 105 ℃; the chroma L value is 83; the crystallinity was 43%.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (10)
1. An in-situ preparation method of poly (butylene oxalate) is characterized in that dimethyl oxalate or diethyl oxalate and 1, 4-butanediol are taken as raw materials, and ester exchange reaction, pre-polycondensation reaction and final polycondensation reaction are sequentially carried out under the action of a titanium-sulfonic acid composite catalyst and an in-situ catalytic nucleating agent to prepare the poly (butylene oxalate);
the titanium-sulfonic acid composite catalyst is added into a reaction system before ester exchange reaction;
the in-situ catalytic nucleating agent is added into a reaction system after the ester exchange reaction and before the pre-polymerization reaction;
the in-situ catalytic nucleating agent is at least one of titanium dioxide, antimony trioxide and antimony acetate.
2. The in-situ preparation method according to claim 1, wherein the titanium-sulfonic acid composite catalyst is prepared by the following steps:
s1: adding a titanium-containing compound and a sulfonic acid compound into anhydrous diluent at 0-5 ℃, and mechanically stirring for more than 30min;
s2: the system is returned to the room temperature and is continuously stirred for more than 20 min;
s3: raising the temperature to 20 ℃ above the boiling point of the diluent, evaporating redundant diluent and small molecules generated by reaction, and naturally cooling to room temperature to obtain light yellow liquid, namely the titanium-sulfonic acid composite catalyst;
the titanium-containing compound is at least one selected from 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, ethanesulfonic acid, p-hydroxyphenylsulfonic acid, m-hydroxybenzenesulfonic acid, o-toluenesulfonic acid and sulfamic acid.
3. The in-situ preparation method according to claim 2, wherein the titanium-sulfonic acid composite catalyst is added in an amount of 0.5 to 1 per thousand of the mass fraction of dimethyl oxalate/diethyl oxalate; the dosage of the second metal oxide is 1-3 per mill of the mass fraction of dimethyl oxalate/diethyl oxalate.
4. The in-situ preparation method of claim 3, wherein the molar ratio of dimethyl oxalate/diethyl oxalate to 1, 4-butanediol is controlled to be 1:1 during feeding before the reaction, so as to ensure the feeding systemRatio of lactone groups to hydroxyl groups
5. The in-situ preparation method of claim 1, wherein before the ester exchange reaction, the reaction raw materials of dimethyl oxalate or diethyl oxalate, 1, 4-butanediol and titanium-sulfonic acid composite catalyst are added into a reaction kettle together, and the system is heated to 70-80 ℃ at a heating rate of 10 ℃/min and stirred and pulped for more than 60 min.
6. The in-situ preparation method of claim 1, wherein the transesterification temperature is 120 ℃ to 160 ℃, the first drop of the small molecule methanol/ethanol is taken as a timing zero point, and the transesterification reaction time is 180min to 300min;
the pre-polycondensation temperature is 120-130 ℃, the pre-polycondensation reaction time is 30-60min, and the pre-polycondensation pressure is 2-3 kPa under absolute pressure;
the final polycondensation temperature is 185-195 ℃, the final polycondensation time is 120-240 min, and the final polycondensation pressure is less than 100 Pa.
7. The in-situ preparation method according to claim 2, wherein the molar ratio of the titanium-containing compound to the sulfonic acid compound is 0.5-2;
the mass ratio of the diluent to the titanium-containing compound and the sulfonic acid compound is 1-2.
8. The in situ preparation method according to claim 2, wherein the diluent is at least one selected from the group consisting of absolute methanol and absolute ethanol.
9. The in-situ preparation method according to claim 2, wherein in the step S1, the mechanical stirring is carried out for 30-60min, and the stirring speed is 80r/min; and the stirring time in the step S2 is 20-30min.
10. The in-situ preparation method according to any one of claims 1 to 9, wherein the prepared polybutyleneoxalate is bright white and has an intrinsic viscosity of 1.4 to 1.8; the weight average molecular weight is 130-180kDa; the value of L is more than 80; the crystallization temperature is 61-73 ℃; the melting point is 105-110 ℃; the crystallinity is 30-60%.
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| KR19980082075A (en) * | 1998-08-20 | 1998-11-25 | 김석태 | Polyester resin composition and its manufacturing method |
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| CN114437321A (en) * | 2021-12-30 | 2022-05-06 | 康辉新材料科技有限公司 | Poly (butylene succinate) and preparation method thereof |
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| KR19980082075A (en) * | 1998-08-20 | 1998-11-25 | 김석태 | Polyester resin composition and its manufacturing method |
| 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 |
| CN102746493A (en) * | 2012-07-09 | 2012-10-24 | 北京旭阳化工技术研究院有限公司 | Preparation method of all-biological-base poly butylenes succinate (PBS) |
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