CN110041516B - The preparation method of permanent seal cooling poly butylene succinate - Google Patents
The preparation method of permanent seal cooling poly butylene succinate Download PDFInfo
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- CN110041516B CN110041516B CN201910388740.XA CN201910388740A CN110041516B CN 110041516 B CN110041516 B CN 110041516B CN 201910388740 A CN201910388740 A CN 201910388740A CN 110041516 B CN110041516 B CN 110041516B
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- China
- Prior art keywords
- butylene succinate
- poly butylene
- preparation
- permanent seal
- butanediol
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- -1 poly butylene succinate Polymers 0.000 title claims abstract description 63
- 239000004631 polybutylene succinate Substances 0.000 title claims abstract description 50
- 229920002961 polybutylene succinate Polymers 0.000 title claims abstract description 50
- 238000001816 cooling Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 86
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 69
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002815 homogeneous catalyst Substances 0.000 claims abstract description 27
- 239000001384 succinic acid Substances 0.000 claims abstract description 20
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 46
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 23
- 239000004408 titanium dioxide Substances 0.000 claims description 23
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002981 blocking agent Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 14
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- 150000002460 imidazoles Chemical class 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylaziridine Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 4
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 claims description 4
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 claims description 4
- VYDWQPKRHOGLPA-UHFFFAOYSA-N 5-nitroimidazole Chemical compound [O-][N+](=O)C1=CN=CN1 VYDWQPKRHOGLPA-UHFFFAOYSA-N 0.000 claims description 4
- 125000003386 piperidinyl group Chemical group 0.000 claims description 4
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical compound CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 claims description 2
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 claims description 2
- XHLKOHSAWQPOFO-UHFFFAOYSA-N 5-phenyl-1h-imidazole Chemical compound N1C=NC=C1C1=CC=CC=C1 XHLKOHSAWQPOFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000004842 1-phenylimidazoles Chemical class 0.000 claims 1
- SVNWKKJQEFIURY-UHFFFAOYSA-N 2-methyl-1-(2-methylpropyl)imidazole Chemical compound CC(C)CN1C=CN=C1C SVNWKKJQEFIURY-UHFFFAOYSA-N 0.000 claims 1
- 125000004069 aziridinyl group Chemical group 0.000 abstract description 4
- 230000000903 blocking effect Effects 0.000 abstract description 4
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 34
- 229920000642 polymer Polymers 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 238000006068 polycondensation reaction Methods 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 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 description 6
- 238000007172 homogeneous catalysis Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229960002479 isosorbide Drugs 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- BWCDLEQTELFBAW-UHFFFAOYSA-N 3h-dioxazole Chemical compound N1OOC=C1 BWCDLEQTELFBAW-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- KLPPPZWWHMSHBQ-UHFFFAOYSA-N C(C)(C)O[Nd] Chemical compound C(C)(C)O[Nd] KLPPPZWWHMSHBQ-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000004429 atom Chemical group 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
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- IZGCXMLPGPBWJN-UHFFFAOYSA-N lanthanum;pentane-2,4-dione Chemical compound [La].CC(=O)CC(C)=O IZGCXMLPGPBWJN-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007353 oxidative pyrolysis Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to technical field of macromolecules, and in particular to a kind of preparation method of permanent seal cooling poly butylene succinate.The preparation method is to be catalyzed 1,4-butanediol and succinic acid polymerization, then squeeze out to obtain permanent seal cooling poly butylene succinate first with compound homogeneous catalyst；When extrusion, the compound containing aziridine group is injected into poly butylene succinate melt for blocking.The content of carboxyl end group of permanent seal cooling poly butylene succinate produced by the present invention is reduced to≤15mmol/kg, substantially increases its durability and thermal stability.
Description
Technical field
The invention belongs to technical field of macromolecules, and in particular to a kind of preparation side of permanent seal cooling poly butylene succinate
Method.
Background technique
Plastics, with its superior service performance, have enriched rapidly people's lives since birth.However, due to people
Excessively using and relying on and processing method is improper to plastics, plastics also bring increasingly heavy burden to environment.
Aliphatic polyester has good biological degradability, advantageously accounts for caused by conventional plastic " white pollution " problem, increasingly
It is concerned by people and payes attention to.
It is well known that polyester can be obtained after over-churning, polycondensation reaction in binary acid and dihydric alcohol.For theoretically, polyester
End group should be hydroxyl, but in the course of the polymerization process, due to oxidative pyrolysis etc., so that the end of a part of polyester molecule chain
Base becomes carboxyl.The presence of carboxyl end group, can not only prevent the further growth of strand, but also can aggravate strand
Fracture.If the content of carboxyl end group of polyester material is high, either during storage, or it is thermally processed into subsequent
It during type, can all accelerate the degradation of polyester material, the performance of polyester material is caused to decline, durability is deteriorated.Therefore, for poly-
For ester material, the height of content of carboxyl end group is directly related to its durability, influences its service life.
As a kind of aliphatic poly ester material, poly butylene succinate (PBS) is obtained wide with its excellent comprehensive performance
General research and development.Since the melt viscosity of PBS is big, thermal stability is poor, and the phase is easier to be pyrolyzed after polymerisation, causes to hold
Carboxyl-content increases, so the content of carboxyl end group of control PBS is particularly critical and important.For PBS, general content of carboxyl end group
Control is controlled in 30mmol/kg or lower relatively difficult in 30-50mmol/kg.In the prior art, dioxazole can generally be used
Quinoline, carbodiimides etc. block carboxyl end group, but these end-capping reagents are all expensive, it is difficult to promote.
CN105566618A discloses a kind of preparation method of modified butanediol ester poly succinic acid, utilizes rare earth catalyst (chlorine
Change lanthanum, lanthanum acetylacetone and isopropoxy neodymium), it is catalyzed succinic acid, butanediol, and also introduce isobide and be copolymerized,
Obtain a kind of isosorbide modified PBS.The patent does not account for blocking PBS carboxyl end group, while rare earth catalyst cost
It is higher, it is unfavorable for promoting.
CN108047436A discloses a kind of chain extension method of poly butylene succinate, oligomeric with PBS using undecenoic acid
The hydroxyl of object carries out reaction sealing end, and chain extender and photoinitiator is recycled to carry out chain extension to it and obtain high molecular weight PBS.The patent
It is reacted, its carboxyl end group is not blocked, carboxyl end group contains with terminal hydroxy group just with the acid with unsaturated double-bond
Amount is unable to control, and undecenoic acid can not be reacted with carboxyl end group, thus the oligomer containing carboxyl end group affect it is next
Walk the efficiency of chain extending reaction.
To sum up, few documents are related to blocking PBS carboxyl end group in the prior art.Currently, reducing poly-succinic fourth
The aging speed of diol ester, improving its service life is urgent problem.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of permanent seal cooling poly butylene succinate, permanent seal cooling obtained is poly-
The content of carboxyl end group of succinic acid-butanediol ester is low, and aging speed is slow, long service life.
The preparation method of permanent seal cooling poly butylene succinate of the present invention, first with compound homogeneous catalyst,
It is catalyzed 1,4-butanediol and succinic acid polymerization, obtains poly butylene succinate melt；It squeezes out to obtain permanent seal cooling poly-succinic again
Butanediol ester；When extrusion, carboxy blocking agent is injected into poly butylene succinate melt；The carboxy blocking agent is to contain nitrogen
The compound of third piperidinyl group.
Wherein:
The carboxy blocking agent can be trifunctional aziridine group compound or two functional group's '-aziridino dough
Close object or simple function group aziridine group compound, preferably trifunctional aziridine group compound, most preferably trihydroxy methyl
Propane-three (3- '-aziridino) propionic ester, trimethylolpropane-three [3- (2- methylaziridine base)] propionic ester, pentaerythrite
One of three (3- '-aziridino) propionic esters are a variety of.
The carboxy blocking agent dosage is the 0.1-2% of poly butylene succinate gross mass.
The compound homogeneous catalyst is 1,4- butanediol, titanium dioxide, zirconium dioxide and glyoxaline compound
Mixture.
The 1,4- butanediol, titanium dioxide, zirconium dioxide, glyoxaline compound molar ratio be 10-30:3:2:3.
The mesh number of the titanium dioxide is 5000-10000 mesh, and the mesh number of zirconium dioxide is 5000-10000 mesh.
The glyoxaline compound be imidazoles, 4- nitroimidazole, 1- methylimidazole, 2-methylimidazole, 4-methylimidazole,
1- ethyl imidazol(e), 2- ethyl imidazol(e), 1- propyl imidazole, 2- propyl imidazole, 1- isopropylimdazole, 2 isopropyl imidazole, 1- butyl
Imidazoles, 2- butyl imidazole, 1- phenylimidazole, 2- phenylimidazole, 4- phenylimidazole, 2- 5-nitro imidazole, 1- isobutyl group-
One of 2-methylimidazole or 2- phenyl -4-methylimidazole are a variety of.
The compound homogeneous catalyst dosage is the 0.01-0.2% of poly butylene succinate gross mass.
The preparation method of the compound homogeneous catalyst is that titanium dioxide, zirconium dioxide are added sequentially to 1,4- fourth
In glycol, 15-30min is stirred at 40-60 DEG C, glyoxaline compound is added, is warming up to 100-150 DEG C, is stirred 30-60min, is obtained
It is the compound homogeneous catalyst of carrier to 1,4- butanediol.
The molar ratio of the 1,4- butanediol and succinic acid is 1.05-1.15:1.
The poly butylene succinate melt of the injection carboxy blocking agent is squeezed by double screw extruder continuous cooling
Out, double screw extruder draw ratio is 52-60:1.
In order to reduce the content of the carboxyl end group in polyester, the present invention is mainly controlled at two aspects:
First, compound homogeneous catalyst is selected, the content of carboxyl end group is advantageously reduced.Conventionally used for urging for PBS polymerization
Agent is generally titanate ester, and this kind of catalyst hydrolytic resistance is poor, it is easy to water decomposition is met, so that catalytic activity reduces,
And the high-temperature thermal stability of titanate esters is poor, is also unfavorable for catalytic polymerization.
It is catalyst that the present invention, which has selected excellent heat stability and the excellent composite type metallic oxide of hydrolytic resistance, is
Improve its catalytic activity, we have selected 1,4-butanediol for its carrier, with a large amount of 1,4-butanediol and titanium dioxide with
And zirconium dioxide powder forms the system of uniformly mixing dispersion.Meanwhile because selecting titanium dioxide and superfine zirconium dioxide powder,
Increase specific surface area.
In order to avoid titanium dioxide and zirconium dioxide precipitate in 1,4-butanediol, occur dispersing non-uniform situation,
Influence its catalytic effect.We joined glyoxaline compound into system again, and the hydrogen of 1 nitrogen-atoms of glyoxaline compound is easy
It is left away with hydrogen ion form, can be replaced by metal and generate salt, 3 nitrogen-atoms have coordination to metal ion, can be formed
Chelate, so that metallic atom can form stable chelate structure with the nitrogen-atoms on imidazoles, meanwhile, the nitrogen of imidazoles is former
Son can form stable hydrogen bond with the hydroxyl of 1,4-butanediol again, so that powdered titanium dioxide and zirconium dioxide can be
It is even to be dispersed stably in 1,4-butanediol, obtain evenly dispersed liquid-phase catalyst.Through a large number of experiments, it has been found that 1,
4- butanediol, titanium dioxide, zirconium dioxide, glyoxaline compound molar ratio be 10-30:3:2:3 when, effect is best.
The catalyst both may be used as esterification catalyst in the present invention, be also used as polycondensation catalyst, and be esterified
When, primary to add, subsequent to no longer need to add, additive amount is low, at low cost.Since the catalyst activity that we use is higher,
The feed ratio of 1,4-butanediol and succinic acid can control very low, and 1.05-1.15:1 can be further decreased into this way
This.
In addition, catalyst is using 1,4-butanediol as carrier, and 1,4-butanediol is also reactant, is increased and reactant
Compatibility, improve catalysis reaction effect.
Second, reaction sealing end is carried out to carboxyl end group using efficient end-capping reagent.We do not select the prior art to use
The carboxyl end groups end-capping reagent such as bisoxazoline or carbodiimides, but selected that price is lower, reactivity is higher containing nitrogen third
The compound of piperidinyl group.
The reactivity of aziridine group and carboxyl is higher, it can form stable ester bond and secondary amine after reacting with carboxyl
Structure, by taking simple function group aziridine group compound as an example, aziridine group and reacting for PBS carboxyl are as follows:
In order to make end-capping reagent and carboxyl end group quickly adequately react, we selected double screw extruder to melt into
Row reactive extrursion, and the major diameter of extruder is bigger, is 52-60:1.In order to reduce side reaction, in extrusion process, Wo Mentong
It crosses double screw extruder to cool down to high-temperature fusant, is stepped down to 180 DEG C from 240 DEG C, thus contain the generation of side reaction,
It also avoids high temperature pyrolysis simultaneously and leads to the generation of new carboxyl end group.
Beneficial effects of the present invention are as follows:
Permanent seal cooling poly butylene succinate is made using compound homogeneous catalyst in the present invention, and utilizes and contain aziridine
The compound of group carries out reaction sealing end as novel end-capping reagent, to its carboxyl end group, make its content of carboxyl end group be reduced to≤
15mmol/kg substantially increases its durability.Permanent seal cooling poly butylene succinate prepared by the present invention, feed intake alkyd mole
Than low, content of carboxyl end group is low, and thermal stability is good, and durability is good, and the invention is simple and feasible, is conducive to promote.
Specific embodiment
The invention will be further described with reference to embodiments.
Embodiment 1
9.9kg 1,4- butanediol, 11.8kg succinic acid and the compound homogeneous catalysis of 34.4g are sequentially added into reaction kettle
Agent, after the reaction of the esterifying polycondensation of 220-230 DEG C, 4h, double screw extruder continuous cooling is squeezed out, and when extrusion, passes through pump note
Enter carboxy blocking agent 344g pentaerythrite three (3- '-aziridino) propionic ester, obtain polymer A1, molecular weight is 11.5 ten thousand, holds carboxylic
Base content is 8mmol/kg.
Compound homogeneous catalyst preparation process is that titanium dioxide, zirconium dioxide are added sequentially in 1,4-butanediol,
It stirs 15min at 60 DEG C, 2-methylimidazole is added, be warming up to 120 DEG C, stir 50min, obtain compound homogeneous catalyst, 1,
4- butanediol, 5000 mesh titanium dioxide, 5000 mesh zirconium dioxides, 2-methylimidazole molar ratio be 30:3:2:3.
Comparative example 1
9.9kg 1,4-butanediol, 11.8kg succinic acid and 34.4g butyl titanate are sequentially added into reaction kettle, are passed through
220-230 DEG C, after the reaction of the esterifying polycondensation of 4h, double screw extruder continuous cooling squeezes out, and obtains polymer A2, molecular weight is
9.1 ten thousand, content of carboxyl end group 89mmol/kg.
Embodiment 2
9.45kg 1,4- butanediol, 11.8kg succinic acid and the compound homogeneous catalysis of 17.2g are sequentially added into reaction kettle
Agent, after the reaction of the esterifying polycondensation of 220-230 DEG C, 5h, double screw extruder continuous cooling is squeezed out, and when extrusion, passes through pump note
Enter carboxy blocking agent 86g trimethylolpropane-three [3- (2- methylaziridine base)] propionic ester, obtains polymer B 1, molecular weight
It is 10.3 ten thousand, content of carboxyl end group 10mmol/kg.
Compound homogeneous catalyst preparation process is that titanium dioxide, zirconium dioxide are added sequentially in 1,4-butanediol,
It stirs 30min at 40 DEG C, 1- ethyl imidazol(e) is added, be warming up to 140 DEG C, stir 40min, obtain compound homogeneous catalyst, 1,
4- butanediol, 8000 mesh titanium dioxide, 8000 mesh zirconium dioxides, 1- ethyl imidazol(e) molar ratio be 20:3:2:3.
Comparative example 2
9.45kg 1,4-butanediol, 11.8kg succinic acid and 17.2g tetraisopropyl titanate are sequentially added into reaction kettle,
After the reaction of the esterifying polycondensation of 220-230 DEG C, 5h, double screw extruder continuous cooling is squeezed out, and obtains polymer B 2, molecular weight
It is 8.9 ten thousand, content of carboxyl end group 62mmol/kg.
Embodiment 3
10.35kg 1,4- butanediol, 11.8kg succinic acid are sequentially added into reaction kettle and 1.72g is compound homogeneously urges
Agent, after the reaction of the esterifying polycondensation of 220-230 DEG C, 6h, double screw extruder continuous cooling is squeezed out, and when extrusion, passes through pump
Carboxy blocking agent 17.2g trimethylolpropane-three (3- '-aziridino) propionic ester is injected, obtains polymer C1, molecular weight is
10.1 ten thousand, content of carboxyl end group 15mmol/kg.
Compound homogeneous catalyst preparation process is that titanium dioxide, zirconium dioxide are added sequentially in 1,4-butanediol,
15min is stirred at 50 DEG C, 2- propyl imidazole, 4-methylimidazole is added, is warming up to 130 DEG C, stirs 50min, is obtained compound equal
Phase catalyst, 1,4-butanediol, 10000 mesh titanium dioxide, 10000 mesh zirconium dioxides, 2- propyl imidazole, 4-methylimidazole rub
You are than being 10:3:2:2:1.
Comparative example 3
10.35kg 1,4-butanediol, 11.8kg succinic acid and 1.72g tetraisopropyl titanate are sequentially added into reaction kettle,
After the reaction of the esterifying polycondensation of 220-230 DEG C, 6h, double screw extruder continuous cooling is squeezed out, and obtains polymer C2, molecular weight
It is 9.5 ten thousand, content of carboxyl end group 71mmol/kg.
Embodiment 4
10.08kg 1,4- butanediol, 11.8kg succinic acid are sequentially added into reaction kettle and 25.8g is compound homogeneously urges
Agent, after the reaction of the esterifying polycondensation of 220-230 DEG C, 4.5h, double screw extruder continuous cooling is squeezed out, and when extrusion, is passed through
Pump injection (3- '-aziridino) propionic ester of carboxy blocking agent 50g trimethylolpropane-three and (the 3- nitrogen third of 53.2g pentaerythrite three
Piperidinyl) propionic ester, polymer D1 is obtained, molecular weight is 120,000, content of carboxyl end group 6mmol/kg.
Compound homogeneous catalyst preparation process is that titanium dioxide, zirconium dioxide are added sequentially in 1,4-butanediol,
It stirs 20min at 60 DEG C, 4- nitroimidazole is added, be warming up to 100 DEG C, stir 60min, obtain compound homogeneous catalyst, 1,
4- butanediol, 7000 mesh titanium dioxide, 7000 mesh zirconium dioxides, 4- nitroimidazole molar ratio be 15:3:2:3.
Comparative example 4
10.08kg 1,4-butanediol, 11.8kg succinic acid and 25.8g butyl titanate are sequentially added into reaction kettle, are passed through
Cross 220-230 DEG C, after the reaction of the esterifying polycondensation of 4.5h, double screw extruder continuous cooling squeezes out, and obtains polymer D2, molecular weight
It is 10.5 ten thousand, content of carboxyl end group 58mmol/kg.
Embodiment 5
9.72kg 1,4- butanediol, 11.8kg succinic acid and the compound homogeneous catalysis of 13.8g are sequentially added into reaction kettle
Agent, after the reaction of the esterifying polycondensation of 220-230 DEG C, 5.5h, double screw extruder continuous cooling is squeezed out, and when extrusion, passes through pump
Inject carboxy blocking agent 100g trimethylolpropane-three [3- (2- methylaziridine base)] three (3- of propionic ester and 72g pentaerythrite
'-aziridino) propionic ester, polymer E1 is obtained, molecular weight is 100,000, content of carboxyl end group 9mmol/kg.
Compound homogeneous catalyst preparation process is that titanium dioxide, zirconium dioxide are added sequentially in 1,4-butanediol,
25min is stirred at 40 DEG C, 2 isopropyl imidazole, 2- phenylimidazole is added, is warming up to 150 DEG C, is stirred 30min, is obtained compound
Homogeneous catalyst, 1,4-butanediol, 6000 mesh titanium dioxide, 6000 mesh zirconium dioxides, 2 isopropyl imidazole, 2- phenylimidazole
Molar ratio is 25:3:2:1:2.
Comparative example 5
9.72kg1 is sequentially added into reaction kettle, 4- butanediol, 11.8kg succinic acid and 13.8g butyl titanate pass through
220-230 DEG C, after the reaction of the esterifying polycondensation of 5.5h, double screw extruder continuous cooling squeezes out, and obtains polymer E2, molecular weight is
9.7 ten thousand, content of carboxyl end group 65mmol/kg.
Comparative example 6
9.9kg 1,4- butanediol, 11.8kg succinic acid and the compound homogeneous catalysis of 34.4g are sequentially added into reaction kettle
Agent, after the reaction of the esterifying polycondensation of 220-230 DEG C, 4h, double screw extruder continuous cooling is squeezed out, and obtains polymer A3, point
Son amount is 11.2 ten thousand, content of carboxyl end group 51mmol/kg.
Compound homogeneous catalyst preparation process such as embodiment 1.
Comparative example 7
9.9kg 1,4-butanediol, 11.8kg succinic acid and 34.4g butyl titanate are sequentially added into reaction kettle, are passed through
220-230 DEG C, after the reaction of the esterifying polycondensation of 4h, double screw extruder continuous cooling squeezes out, and when extrusion, passes through pump injection carboxyl envelope
Agent 344g pentaerythrite three (3- '-aziridino) propionic ester is held, polymer A4 is obtained, molecular weight is 9.3 ten thousand, and content of carboxyl end group is
32mmol/kg。
Comparative example 8
9.45kg 1,4- butanediol, 11.8kg succinic acid and the compound homogeneous catalysis of 17.2g are sequentially added into reaction kettle
Agent, after the reaction of the esterifying polycondensation of 220-230 DEG C, 5h, double screw extruder continuous cooling is squeezed out, and obtains polymer B 3, point
Son amount is 10.1 ten thousand, content of carboxyl end group 48mmol/kg.
Compound homogeneous catalyst preparation process such as embodiment 2.
Comparative example 9
9.45kg 1,4-butanediol, 11.8kg succinic acid and 17.2g tetraisopropyl titanate are sequentially added into reaction kettle,
After the reaction of the esterifying polycondensation of 220-230 DEG C, 5h, double screw extruder continuous cooling is squeezed out, and when extrusion, passes through pump injection carboxylic
Base end-capping reagent 86g trimethylolpropane-three [3- (2- methylaziridine base)] propionic ester, obtains polymer B 4, molecular weight 9.0
Ten thousand, content of carboxyl end group 29mmol/kg.
For the ease of comparison, the polymer samples that embodiment and comparative example obtains all pass through double screw extruder extrusion, double
Screw extruder, screw diameter 35mm, draw ratio 56:1, temperature are arranged from front to back, by 240 DEG C, 230 DEG C, 220 DEG C, 210
DEG C, 200 DEG C be successively decremented to 180 DEG C.
In order to evaluate the durability of PBS after sealing end, the polymer samples that we prepare embodiment and comparative example are successively
Blown film under the same conditions, film thickness are unified for 0.02mm.We recycle constant temperature and humidity accelerated ageing case, in the same terms
Under, different thin polymer films are tested, the data of accelerated ageing situation see the table below 1, the survey of constant temperature and humidity accelerated ageing case
Strip part are as follows: 80 DEG C of temperature, relative humidity 90%.
The accelerated ageing tables of data of 1 difference PBS film of table
(1) it can be seen that in embodiment 1-5 from the data in table 1 by the accelerated ageing of the PBS polymer of carboxy blocking
Speed will be considerably slower than PBS polymer uncapped in comparative example 1-5.The present invention utilizes composite efficient catalyst preparation
PBS, and reaction sealing end is carried out to its carboxyl end group using the compound containing aziridine group, it is reduced to its content of carboxyl end group
15mmol/kg obtains permanent seal cooling PBS hereinafter, substantially increase durability.
(2) comparative example 6-9 illustrates, only with compound homogeneous catalyst or is only injected into carboxy blocking agent, cannot all reach
To effect of the invention.
(3) it can be seen that for compound homogeneous catalyst from comparative example 6-9, carboxy blocking agent is to polymer
Content of carboxyl end group influence it is bigger.
(4) molecular weight when 96h of comparative example 6-9 be higher than comparative example 1-5 96h when molecular weight.This absolutely proves, phase
Than in comparative example 1-5 neither use compound homogeneous catalyst, also not by the way of inject carboxy blocking agent for, compare
Example 6-9 only with compound homogeneous catalyst or be only injected into the mode of carboxy blocking agent and can also extend making for PBS polymer
Use the service life.
(5) content of carboxyl end group in comparative example 6-9 is followed successively by 51mmol/kg, 32mmol/kg, 48mmol/kg, 29mmol/
Kg, it is lower than the content of carboxyl end group in comparative example 1-5, it is higher than the content of carboxyl end group in embodiment 1-5.This is absolutely proved, right
In ratio 6-9 only with compound homogeneous catalyst or be only injected into control of the mode to content of carboxyl end group of carboxy blocking agent
Play certain effect, but effect it is best or embodiment 1-5.
Claims (9)
1. a kind of preparation method of permanent seal cooling poly butylene succinate, it is characterised in that: first with compound homogeneous catalyst,
It is catalyzed 1,4-butanediol and succinic acid polymerization, obtains poly butylene succinate melt；It squeezes out to obtain permanent seal cooling poly-succinic again
Butanediol ester；When extrusion, carboxy blocking agent is injected into poly butylene succinate melt；The carboxy blocking agent is to contain nitrogen
The compound of third piperidinyl group;
The compound homogeneous catalyst is the mixture of 1,4- butanediol, titanium dioxide, zirconium dioxide and glyoxaline compound；
Wherein, 1,4-butanediol, titanium dioxide, zirconium dioxide, glyoxaline compound molar ratio be 10-30:3:2:3.
2. the preparation method of permanent seal cooling poly butylene succinate according to claim 1, it is characterised in that: the carboxyl
End-capping reagent is trimethylolpropane-three (3- '-aziridino) propionic ester, trimethylolpropane-three [3- (2- methylaziridine base)]
One of propionic ester, pentaerythrite three (3- '-aziridino) propionic ester are a variety of.
3. the preparation method of permanent seal cooling poly butylene succinate according to claim 1, it is characterised in that: carboxy blocking
Agent dosage is the 0.1-2% of poly butylene succinate gross mass.
4. the preparation method of permanent seal cooling poly butylene succinate according to claim 1, it is characterised in that: titanium dioxide
Mesh number be 5000-10000 mesh, the mesh number of zirconium dioxide is 5000-10000 mesh.
5. the preparation method of permanent seal cooling poly butylene succinate according to claim 1, it is characterised in that: imidazoles
Conjunction object be imidazoles, 4- nitroimidazole, 1- methylimidazole, 2-methylimidazole, 4-methylimidazole, 1- ethyl imidazol(e), 2- ethyl imidazol(e),
1- propyl imidazole, 2- propyl imidazole, 1- isopropylimdazole, 2 isopropyl imidazole, 1- butyl imidazole, 2- butyl imidazole, 1- phenyl
Imidazoles, 2- phenylimidazole, 4- phenylimidazole, 2- 5-nitro imidazole, 1- isobutyl-2-methyl imidazole or 2- phenyl -4- first
One of base imidazoles is a variety of.
6. the preparation method of permanent seal cooling poly butylene succinate according to claim 1, it is characterised in that: compound equal
Phase catalyst dosage is the 0.01-0.2% of poly butylene succinate gross mass.
7. the preparation method of permanent seal cooling poly butylene succinate according to claim 1, it is characterised in that: compound equal
The preparation method of phase catalyst is that titanium dioxide, zirconium dioxide are added sequentially in 1,4-butanediol, is stirred at 40-60 DEG C
Glyoxaline compound is added in 15-30min, is warming up to 100-150 DEG C, stirs 30-60min, and obtaining 1,4-butanediol is carrier
Compound homogeneous catalyst.
8. the preparation method of permanent seal cooling poly butylene succinate according to claim 1, it is characterised in that: Isosorbide-5-Nitrae-fourth two
The molar ratio of pure and mild succinic acid is 1.05-1.15:1.
9. the preparation method of permanent seal cooling poly butylene succinate according to claim 1, it is characterised in that: injection carboxyl
The poly butylene succinate melt of end-capping reagent is squeezed out by double screw extruder continuous cooling, and double screw extruder draw ratio is
52-60:1。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161296A (en) * | 2007-11-20 | 2008-04-16 | 浙江大学 | Biological degradable elasticity anastomosis bracket and its preparing method |
| CN102443156A (en) * | 2010-09-30 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing polyester |
| CN102985449A (en) * | 2010-06-29 | 2013-03-20 | 3M创新有限公司 | Aziridinyl-containing compounds |
| CN103214659A (en) * | 2013-03-25 | 2013-07-24 | 山东汇盈新材料科技有限公司 | High molecular weight bio-based poly(butylene succinate) synthesis method |
| CN103435794A (en) * | 2013-07-26 | 2013-12-11 | 旭阳化学技术研究院有限公司 | Preparation method of polycondensation catalyst, polycondensation catalyst prepared by preparation method, and method used for preparing PBS and PBS copolymer by using catalyst |
| CN106046336A (en) * | 2016-07-15 | 2016-10-26 | 广州擎天材料科技有限公司 | A kind of water-soluble polyester resin with hydroxy acid end cap and preparation method thereof |
-
2019
- 2019-05-10 CN CN201910388740.XA patent/CN110041516B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161296A (en) * | 2007-11-20 | 2008-04-16 | 浙江大学 | Biological degradable elasticity anastomosis bracket and its preparing method |
| CN102985449A (en) * | 2010-06-29 | 2013-03-20 | 3M创新有限公司 | Aziridinyl-containing compounds |
| CN102443156A (en) * | 2010-09-30 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing polyester |
| CN103214659A (en) * | 2013-03-25 | 2013-07-24 | 山东汇盈新材料科技有限公司 | High molecular weight bio-based poly(butylene succinate) synthesis method |
| CN103435794A (en) * | 2013-07-26 | 2013-12-11 | 旭阳化学技术研究院有限公司 | Preparation method of polycondensation catalyst, polycondensation catalyst prepared by preparation method, and method used for preparing PBS and PBS copolymer by using catalyst |
| CN106046336A (en) * | 2016-07-15 | 2016-10-26 | 广州擎天材料科技有限公司 | A kind of water-soluble polyester resin with hydroxy acid end cap and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 不同端基PBS的合成与降解研究;张昌辉，翟文举，寇莹;《塑料工业》;20091031;第37卷(第10期);第13-15页 * |
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