CN116178681A - Polybutylene succinate resin and preparation method thereof - Google Patents
Polybutylene succinate resin and preparation method thereof Download PDFInfo
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- CN116178681A CN116178681A CN202310078772.6A CN202310078772A CN116178681A CN 116178681 A CN116178681 A CN 116178681A CN 202310078772 A CN202310078772 A CN 202310078772A CN 116178681 A CN116178681 A CN 116178681A
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- Prior art keywords
- inhibitor
- polybutylene succinate
- butanediol
- succinate resin
- chromatographic peak
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- 229920002961 polybutylene succinate Polymers 0.000 title claims abstract description 54
- 239000004631 polybutylene succinate Substances 0.000 title claims abstract description 54
- -1 Polybutylene succinate Polymers 0.000 title claims abstract description 49
- 239000011347 resin Substances 0.000 title claims abstract description 49
- 229920005989 resin Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000003112 inhibitor Substances 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000005886 esterification reaction Methods 0.000 claims abstract description 22
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 230000002829 reductive effect Effects 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- NMPJHMFXHISVBR-UHFFFAOYSA-N 4-(oxolan-2-yloxy)butan-1-ol Chemical group OCCCCOC1CCCO1 NMPJHMFXHISVBR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000010561 standard procedure Methods 0.000 claims description 13
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000001384 succinic acid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 100
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 49
- 229920000642 polymer Polymers 0.000 abstract description 11
- 238000007086 side reaction Methods 0.000 abstract description 10
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000032050 esterification Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000704 biodegradable plastic Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- GRWIABMEEKERFV-UHFFFAOYSA-N methanol;oxolane Chemical compound OC.C1CCOC1 GRWIABMEEKERFV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- SDLFRXZYUSIEBE-UHFFFAOYSA-N [Si][Ti][Co] Chemical compound [Si][Ti][Co] SDLFRXZYUSIEBE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a polybutylene succinate resin and a preparation method thereof, belonging to the technical field of high polymer materials. The preparation method of the polybutylene succinate resin comprises the following steps: s1, esterification reaction: mixing 1, 4-butanediol, succinic acid, a catalyst, a stabilizer and an inhibitor for esterification reaction to obtain an esterified substance; s2, polymerization reaction: carrying out polymerization reaction on the esterified substance of the S1 to obtain polybutylene succinate resin; wherein the inhibitor is 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol. According to the invention, the specific inhibitor is added, so that the side reaction of generating tetrahydrofuran from 1, 4-butanediol in the esterification reaction process is effectively inhibited, the yield of tetrahydrofuran is obviously reduced, and the yield of tetrahydrofuran can be reduced to below 25%. And the residual THF content in the polymer is less than or equal to 500ppm.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polybutylene succinate resin and a preparation method thereof.
Background
Degradable polyester materials have been widely used such as films, foams, injection molded articles, etc. Such materials have good physical properties and can be degraded into water and carbon dioxide in a composted or natural state without potential harm to the environment. Among them, polybutylene succinate resin is one of the degradation materials which are very active in the current biodegradable plastic research. The polybutylene succinate resin is prepared by condensation polymerization of succinic acid and butanediol, and has excellent mechanical property, good heat resistance, thermal deformation temperature and product use temperature of more than 100 ℃. The synthetic raw material source of the biodegradable plastic can be petroleum resources or biological resources, and the biodegradable plastic is one of the best degradable materials applied to the current biodegradable plastic market.
In the high-temperature esterification reaction process of the succinic acid in a strong acid environment, the polybutylene succinate (PBS) can strongly generate side reaction to BDO (1, 4-butanediol) to generate tetrahydrofuran THF and water; the side reaction not only can increase the unit consumption of BDO and the load of a vacuum system and increase the production cost, but also can reach the emission requirement after the excessive mixture of high-content THF, water and other gases is pumped out, condensed and collected by the vacuum system and is subjected to concentrated separation treatment by a THF recovery device; therefore, how to reduce the side reaction degree of BDO in the esterification process is one of the important points of research for preparing polybutylene succinate resin.
In addition, PBS resins are mainly processed into food-grade products such as straws, coffee capsules, knives, forks, spoons, and the like, and THF is a carcinogen, which greatly influences the application of the products because more tetrahydrofuran THF remains in the polymer.
The prior art discloses a method for inhibiting tetrahydrofuran side reaction in the polymerization process of poly (butylene succinate), which reduces the generation of tetrahydrofuran by adding a titanium-silicon-cobalt composite catalyst. However, the addition of a certain amount of polycarbonate diol prior to polycondensation does not reduce the production of THF during esterification.
Disclosure of Invention
The invention aims to overcome the defect and the defect of overlarge yield of tetrahydrofuran which is a side reaction product in the production process of the existing polybutylene succinate resin, and provides a preparation method of the polybutylene succinate resin, wherein a specific inhibitor is added to effectively inhibit side reaction of 1, 4-butanediol to generate tetrahydrofuran in the esterification reaction process, so that the yield of tetrahydrofuran is obviously reduced, and compared with the input amount of 1, 4-Butanediol (BDO), the yield of tetrahydrofuran can be reduced to below 25%. And the residual THF content in the polymer is less than or equal to 500ppm.
Another object of the present invention is to provide a polybutylene succinate resin.
The above object of the present invention is achieved by the following technical scheme:
a preparation method of polybutylene succinate resin comprises the following steps:
s1, esterification reaction: mixing 1, 4-butanediol, succinic acid, a catalyst, a stabilizer and an inhibitor for esterification reaction to obtain an esterified substance;
s2, polymerization reaction: carrying out polymerization reaction on the esterified substance of the S1 to obtain polybutylene succinate resin;
wherein the inhibitor is 4- [ (tetrahydro-2-furanyl) oxy ] -1-butanol;
the molar ratio of the 1, 4-butanediol to the succinic acid is (1.4-1.8): 1, a step of;
based on the national standard method GB/T24768-2009, the chromatographic peak area of the inhibitor is 0.03% -2.0% of the sum of the chromatographic peak areas of the inhibitor and the 1, 4-butanediol relative to the chromatographic purity of the 1, 4-butanediol.
The chromatographic peak area can be calculated by a chromatograph.
The specific test method of the chromatographic peak area comprises the following steps: before the S1 esterification reaction, the inhibitor raw material is dissolved in the 1, 4-butanediol raw material and mixed, and the integral area of the chromatographic peak is obtained by the test calculation of a chromatograph.
Wherein the ratio of the chromatographic peak area of the inhibitor to the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol may represent the content of the inhibitor raw material added to the sum of the inhibitor and 1, 4-butanediol raw material.
The chromatographic peak area of the inhibitor can be controlled to be the sum percentage of the chromatographic peak areas of the inhibitor and the 1, 4-butanediol by controlling the adding amount of the inhibitor.
According to the invention, by adding the specific inhibitor, the side reaction of generating tetrahydrofuran from 1, 4-butanediol in the esterification reaction process of the preparation method of the polybutylene succinate resin is effectively inhibited, the yield of tetrahydrofuran is obviously reduced, and the yield of tetrahydrofuran can be reduced to below 25%. And the residual THF content in the polymer is less than or equal to 500ppm.
Succinic acid may also be a succinate derivative or a succinic anhydride derivative.
Preferably, the chromatographic peak area of the inhibitor is 0.6% to 1.5% of the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol.
Preferably, the chromatographic peak area of the inhibitor is 0.8% to 1.2% of the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol.
Preferably, the chromatographic peak area of the inhibitor is 0.95% of the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol.
Preferably, the retention time of the inhibitor is 12.6-12.8 min and the retention time of the inhibitor is 17.9-18.1 min based on the national standard method GB/T24768-2009,1,4-butanediol.
Preferably, in the S1 esterification reaction, each component after being mixed is replaced by nitrogen, then the temperature is raised to 190 ℃ to 210 ℃, the vacuum degree is 40 KPa to 60KPa, and the esterification product is obtained after 3 hours to 5 hours of reaction.
Preferably, in the S2 polymerization reaction, the pressure of the esterified substance obtained in the S1 is reduced to below 50Pa within 25-30 min, the reaction is continued for 3.5-5 hours at 240-250 ℃ until the intrinsic viscosity reaches 1.4-1.6 dg/L, nitrogen is filled, and the polybutylene succinate resin is obtained by extrusion and granulation.
Preferably, in S1, tetrahydrofuran is also obtained, the weight ratio of tetrahydrofuran to 1, 4-butanediol in S1 being less than or equal to 0.25.
Preferably, in S1, tetrahydrofuran is also obtained, the weight ratio of tetrahydrofuran to 1, 4-butanediol in S1 being less than or equal to 0.2.
Preferably, the catalyst is tetrabutyl orthotitanate and/or tetraisopropyl orthotitanate.
In practical application, the catalyst can be used in an amount of 10-5000 ppm based on the theoretical yield weight of the polybutylene succinate resin.
Preferably, the stabilizer is one or more of phosphoric acid, phosphorous acid, triphenyl phosphite, triphenyl phosphate or sodium phosphite.
In practical application, the dosage of the stabilizer can be 10-1000 ppm of the theoretical yield weight of the polybutylene succinate resin.
The invention also protects the polybutylene succinate resin prepared by the preparation method of any one of the polybutylene succinate resins.
The invention also protects application of the polybutylene succinate resin in preparing films, foaming materials or injection molded parts.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a preparation method of polybutylene succinate resin, which effectively inhibits side reaction of 1, 4-butanediol to tetrahydrofuran in the esterification reaction process by adding a specific inhibitor, obviously reduces the yield of tetrahydrofuran, and reduces the yield of tetrahydrofuran to below 25 percent relative to the input amount of 1, 4-Butanediol (BDO). And the residual THF content in the polymer is less than or equal to 500ppm.
Drawings
FIG. 1 is a chromatogram of example 1.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
The catalyst is tetrabutyl orthotitanate catalyst;
the stabilizer is phosphoric acid;
the inhibitor is 4- [ (tetrahydro-2-furanyl) oxy ] -1-butanol.
Example 1
A preparation method of polybutylene succinate resin comprises the following steps:
s1, 883g of inhibitor raw material is dissolved in 135kg of 1, 4-butanediol to obtain 1, 4-butanediol solution in which the inhibitor is dissolved, and chromatographic peak area of the inhibitor and chromatographic peak area of the 1, 4-butanediol are obtained through a chromatograph. The method comprises the following steps: based on national standard method GB/T24768-2009, the chromatographic peak area of the inhibitor and the chromatographic peak area of the 1, 4-butanediol are calculated by a chromatograph.
Wherein, the chromatographic conditions are as follows: the sample to be tested is a mixed phase solution of 1, 4-Butanediol (BDO) and an inhibitor (namely 1, 4-butanediol solution in which the inhibitor is dissolved), the initial temperature of a chromatograph is 60 ℃, the chromatograph is heated up after being kept at 1-2 min, the temperature is raised to 260 ℃ according to 10 ℃/min, the flow rate of carrier gas is 5mL/min, a chromatographic column is Agilent 123-1334UL, the carrier gas is nitrogen, the sample injection amount is 0.2-0.5 mu L, the temperature of a gasification chamber is 300 ℃, the temperature of a detector is 300 ℃, and the retention time is 30min, so that the figure 1 is obtained.
As can be seen from FIG. 1, the larger chromatographic peak was the chromatographic peak area of 1, 4-butanediol, retention time was 12.653s, and peak area was 763365897. The smaller area chromatographic peak was the inhibitor chromatographic peak area with retention time 17.914s and peak area 4994341. The ratio of the chromatographic peak area of the inhibitor to the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol was 4994341/(763365897+499441) =0.65%, i.e., the chromatographic peak area percentage of 1, 4-butanediol was 99.35%, the chromatographic peak area percentage of the inhibitor was 0.65%, and the chromatographic peak area of the inhibitor was 0.65% of the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol.
The retention time of the 1, 4-butanediol is 12.65-12.7 min, and the retention time of the inhibitor is 17.9-18.0 min.
Mixing 1, 4-butanediol solution with inhibitor dissolved therein, 118kg of succinic acid, 70g of catalyst and 35g of stabilizer for esterification reaction, heating to 195-200 ℃ after nitrogen substitution, and reacting for 3.5 hours at a vacuum degree of 45-50 KPa to obtain esterified substance;
s2, reducing the pressure of the esterified substance obtained in the S1 to 30-40 Pa within 26-28 min, continuously reacting for 4-4.5 hours at 245 ℃, charging nitrogen when the intrinsic viscosity reaches 1.5dL/g, extruding and granulating to obtain the polybutylene succinate resin.
Wherein the inhibitor is 4- [ (tetrahydro-2-furyl) oxy ] -1-butanol;
the molar ratio of 1, 4-butanediol to succinic acid is 1.5:1.
example 2
A method for preparing polybutylene succinate resin, which is basically the same as in example 1,
the difference from example 1 is that the inhibitor is used in a different amount and the chromatographic peak area of the inhibitor is 1.32% of the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol, based on the national standard method GB/T24768-2009, relative to the chromatographic purity of 1, 4-butanediol.
The remainder is the same as in example 1 and will not be described again here.
Example 3
A method for preparing polybutylene succinate resin, which is basically the same as in example 1,
the difference from example 1 is that the inhibitor is used in a different amount and the chromatographic peak area of the inhibitor is 2.0% of the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol, based on the national standard method GB/T24768-2009, relative to the chromatographic purity of 1, 4-butanediol.
The remainder is the same as in example 1 and will not be described again here.
Example 4
A method for preparing polybutylene succinate resin, which is basically the same as in example 1,
the difference from example 1 is that the inhibitor is used in a different amount and the chromatographic peak area of the inhibitor is 0.03% of the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol, based on the national standard method GB/T24768-2009, relative to the chromatographic purity of 1, 4-butanediol.
The remainder is the same as in example 1 and will not be described again here.
Example 5
A method for preparing polybutylene succinate resin, which is basically the same as in example 1,
the difference from example 1 is that the inhibitor is used in a different amount and the chromatographic peak area of the inhibitor is 0.95% of the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol, based on the national standard method GB/T24768-2009, relative to the chromatographic purity of 1, 4-butanediol.
The remainder is the same as in example 1 and will not be described again here.
Comparative example 1
A method for preparing polybutylene succinate resin, which is basically the same as in example 1,
the difference from example 1 is that: the dosage of the inhibitor is different, and the chromatographic peak area of the inhibitor is 0.01 percent of the sum of the chromatographic peak areas of the inhibitor and the 1, 4-butanediol relative to the chromatographic purity of the 1, 4-butanediol based on the national standard method GB/T24768-2009.
The remainder is the same as in example 1 and will not be described again here.
Comparative example 2
A method for preparing polybutylene succinate resin, which is basically the same as in example 1,
the difference from example 1 is that: the dosage of the inhibitor is different, and the chromatographic peak area of the inhibitor is 2.3 percent of the sum of the chromatographic peak areas of the inhibitor and the 1, 4-butanediol relative to the chromatographic purity of the 1, 4-butanediol based on the national standard method GB/T24768-2009.
The remainder is the same as in example 1 and will not be described again here.
Comparative example 3
A method for preparing polybutylene succinate resin, which is basically the same as in example 1,
the difference from example 1 is that: the dosage of the inhibitor is different, and the chromatographic peak area of the inhibitor is 3.0 percent of the sum of the chromatographic peak areas of the inhibitor and the 1, 4-butanediol relative to the chromatographic purity of the 1, 4-butanediol based on the national standard method GB/T24768-2009.
The remainder is the same as in example 1 and will not be described again here.
Result detection
(1) The yield of the byproduct Tetrahydrofuran (THF) in the preparation method of the polybutylene succinate resin is as follows: tetrahydrofuran weight/1, 4-butanediol weight of 100%,
wherein the weight of the 1, 4-butanediol is the input weight of the 1, 4-butanediol before the reaction;
the weight calculation formula of tetrahydrofuran THF is the weight of the esterified water (100% -water mass fraction) and the weight fraction of tetrahydrofuran THF in the esterified water. Wherein the weight of the esterification water is the mass of the esterification water which is extracted by a vacuum system and is collected after cooling in the esterification process; the mass fraction of water and the mass fraction of THF are based on the national standard method GB/T24772-2009 test.
(2) The method for measuring the Tetrahydrofuran (THF) content in the polybutylene succinate resin polymer comprises the following steps:
preparation of THF standard curve:
preparing THF methanol solutions with the concentrations of 0.01g/L, 0.1g/L, 1.0g/L, 5.0g/L, 10.0g/L, 20.0g/L, 50.0g/L and 100.0g/L, respectively testing the peak areas of THF in the THF methanol solutions with different concentrations by a static headspace method, and preparing a THF standard curve by taking the peak areas of THF as an ordinate and the concentration of THF as an abscissa.
Determination of THF in polymer:
1.200+/-0.020 g of PBS polymer is accurately weighed and added into a static headspace test bottle, the peak area of THF in the PBS polymer is tested by a static headspace method, and the THF content in the polybutylene succinate resin can be calculated according to the peak area of THF in the PBS polymer and a THF standard curve, wherein the standard curve is calibrated by tetrahydrofuran/methanol solution.
The static headspace test conditions were as follows:
the headspace temperature was 105℃and the headspace time was 2 hours. Testing was performed using an Agilent 7697A-7890A apparatus.
Agilent 7697A-7890A test parameters and test methods are shown in tables 1 and 2:
TABLE 1 Aglient 7697A test parameters
TABLE 2 Aglient 7890A test parameters
GC temperature increase program:
initial value 50 ℃, holding time: 3 minutes;
heating to 200 ℃, heating rate of 12 ℃/min, and holding time: 4 minutes.
Intrinsic viscosity: using an Ubbelohde viscometer to test, wherein the solvent is phenol with the mass ratio: mixed solvent of o-dichlorobenzene=372 configuration.
Specific test results are shown in Table 3 below:
from the data, the preparation method of the polybutylene succinate resin effectively inhibits the side reaction of generating the tetrahydrofuran by the 1, 4-butanediol in the esterification reaction process by adding the specific inhibitor, obviously reduces the yield of the tetrahydrofuran, and can reduce the yield of the tetrahydrofuran to below 25 percent. And the residual THF content in the polymer is less than or equal to 500ppm.
As can be seen from comparative example 1, the ratio of the chromatographic peak area of the inhibitor to the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol was too small, and the yield of tetrahydrofuran was 35.3%.
As can be seen from comparative examples 2 and 3, the ratio of the chromatographic peak area of the inhibitor to the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol is too large, and the yield of tetrahydrofuran is also 25% or more, probably because the reaction of the inhibitor is a reversible process, and when the concentration of the inhibitor is too high, the inhibiting effect is lowered. Moreover, too much inhibitor increases the production cost.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The preparation method of the polybutylene succinate resin is characterized by comprising the following steps of:
s1, esterification reaction: mixing 1, 4-butanediol, succinic acid, a catalyst, a stabilizer and an inhibitor for esterification reaction to obtain an esterified substance;
s2, polymerization reaction: carrying out polymerization reaction on the esterified substance of the S1 to obtain polybutylene succinate resin;
wherein the inhibitor is 4- [ (tetrahydro-2-furanyl) oxy ] -1-butanol;
the molar ratio of the 1, 4-butanediol to the succinic acid is (1.4-1.8): 1, a step of;
based on the national standard method GB/T24768-2009, the chromatographic peak area of the inhibitor is 0.03% -2.0% of the sum of the chromatographic peak areas of the inhibitor and the 1, 4-butanediol relative to the chromatographic purity of the 1, 4-butanediol.
2. The method for preparing a polybutylene succinate resin according to claim 1, wherein the chromatographic peak area of the inhibitor is 0.6% to 1.5% of the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol.
3. The method for preparing a polybutylene succinate resin according to claim 2, wherein the chromatographic peak area of the inhibitor is 0.8% to 1.2% of the sum of the chromatographic peak areas of the inhibitor and 1, 4-butanediol.
4. The method for preparing a polybutylene succinate resin according to claim 1, wherein the retention time of the inhibitor is from 17.9 to 18.1min based on national standard method GB/T24768-2009,1,4-butanediol of 12.6 to 12.8 min.
5. The method for preparing a polybutylene succinate resin according to claim 1, wherein in the esterification reaction of S1, each component after mixing is replaced by nitrogen, and then heated to 190 ℃ to 210 ℃, the vacuum degree is 40 to 60KPa, and the reaction is carried out for 3 to 5 hours, thereby obtaining an esterified product.
6. The process for preparing a polybutylene succinate resin as claimed in claim 1, wherein in the polymerization reaction of S2, the pressure of the esterified product obtained in S1 is reduced to 50Pa or lower within 25 to 30 minutes, the reaction is continued at 240 to 250 ℃ for 3.5 to 5 hours until the intrinsic viscosity reaches 1.4 to 1.6dg/L, and the mixture is filled with nitrogen and extruded to pelletize to obtain the polybutylene succinate resin.
7. The method for preparing polybutylene succinate resin according to claim 1, wherein the catalyst is tetrabutyl orthotitanate and/or tetraisopropyl orthotitanate.
8. The method for preparing polybutylene succinate resin according to claim 1, wherein the stabilizer is one or more of phosphoric acid, phosphorous acid, triphenyl phosphite, triphenyl phosphate or sodium phosphite.
9. A polybutylene succinate resin prepared by the method for preparing a polybutylene succinate resin according to any one of claims 1 to 8.
10. Use of the polybutylene succinate resin of claim 9 for the preparation of films, foamed materials or injection molded articles.
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