CN111808274A - Spinning filament type low-melting-point polyester chip and preparation method thereof - Google Patents
Spinning filament type low-melting-point polyester chip and preparation method thereof Download PDFInfo
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- 229920000728 polyester Polymers 0.000 title claims abstract description 36
- 238000009987 spinning Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 96
- 230000032050 esterification Effects 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 49
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000002844 melting Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 11
- 229920000180 alkyd Polymers 0.000 claims description 11
- 229940011182 cobalt acetate Drugs 0.000 claims description 9
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 9
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 9
- 239000012760 heat stabilizer Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000005690 diesters Chemical class 0.000 claims description 5
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 230000009477 glass transition Effects 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 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
- C08G63/78—Preparation processes
-
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—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
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
-
- 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
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
Landscapes
- 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 spinning filament type low-melting-point polyester chip and a preparation method thereof. According to the invention, through the implementation of processes such as process innovation, catalyst compounding, modified monomer stepwise esterification and the like, the precise regulation and control of the modified monomer in the product are realized, the key quality index of the prepared product is excellent, the glass transition temperature is higher than 66 ℃, the terminal carboxyl content is less than or equal to 25mol/T, the polycondensation reaction period is less than or equal to 200 min/batch, the comprehensive efficiency of the spinning filaments used in the downstream is high, the integral use effect is excellent, and the use requirements of high-grade special fields are met.
Description
Technical Field
The invention relates to a preparation method of spinning filament type low-melting-point polyester, belonging to the field of differential polyester manufacturing.
Background
The melting point of common PET polyester is 250-260 ℃, the melting point of low-melting-point polyester is 105-210 ℃, and the molecular structure of PET is changed by copolymerizing modified monomers, so that the effect of reducing the melting point is achieved. The main types of low-melting point products in the current market are 110 ℃, 180 ℃ and 210 ℃, wherein the 110 ℃ product can be spun into filaments or short fibers and is mainly used in the field of thermal bonding of non-woven fabrics and 3D fly-woven shoes, the 180 ℃ product is mainly used in the field of spinning skin-core composite filaments, and the 210 ℃ product is mainly used in the field of manufacturing polyester color master batches. According to the formula of Δ T ═ Δ H/. DELTA.s, it is necessary to reduce the melting enthalpy of the polymer structure or to increase the melting entropy in order to prepare low-melting polyesters by copolymerization, so that the chain segment regularity of the polyester itself can be destroyed in the block copolymerization process by adding some modifying monomers with asymmetric structures, and the effect of reducing intermolecular forces, i.e., the melting enthalpy is reduced. In addition, in order to keep the crystallization property of the polyester and further reduce the melting point, a modifying monomer containing a flexible long chain segment can be added in the copolymerization process, the distance between benzene rings is increased by a block polymerization mode, the content of the benzene rings in a system is reduced, and therefore the purpose that molecules have more possible conformations in a molten state, namely the purposes of entropy increase and crystallization promotion, is achieved. In the comprehensive view, the production of the domestic low-melting-point polyester chip mainly comprises two major types, wherein the first type is a modification system of isophthalic acid and long-chain dihydric alcohol, the second type is a modification system of adipic acid and long-chain dihydric alcohol, and modification monomers of the two systems are used for reducing the regularity of a high polymer chain segment so as to achieve the purpose of reducing the melting point.
Chinese patent CN111100278A "a manufacturing method of low melting point polyester chip", discloses a continuous production process of low melting point polyester chip, in the formula, titanium system and antimony system compound catalyst are adopted to play part of environmental protection effect, because of the defect of continuous production, modified monomer diethylene glycol is added in the diesterification reaction kettle, from the actual production, the reaction rate constant of diethylene glycol, PTA and IPA is small, the residence time in the diesterification reaction process is short, and the material is in the diesterification reaction kettle, the esterification rate is high, the difficulty of the diethylene glycol competing to the main chain is larger, finally the diethylene glycol exists in the product in free state, and the strength of the filament can be seriously influenced when spinning the filament. Chinese patent CN110938196A "a low-melting polyester and its preparation method", uses aromatic dibasic acid and 2-methyl-1, 3-propylene glycol to reduce the melting point of the product, adds infrared absorbent to increase the heat absorption rate of the product after processing, adds free radical scavenger to improve the thermal stability of the product, but the product uses 2-methyl-1, 3-propylene glycol, the polycondensation process is difficult to control, and the hot melt adhesive fluidity is inferior to that of diethylene glycol or triethylene glycol. Chinese patent CN110437430A 'A modified polyester and its preparation method', the esterification catalyst adopts tin compound, the glass transition temperature of the prepared low melting point polyester product can reach above 80 deg.C, the drying temperature can be increased during drying, thereby increasing the drying efficiency, and the slice is not easy to loop and slip in the screw during spinning. The improvement of the glass transition temperature is beneficial to the improvement of the spinning efficiency, but when the glass transition temperature is used for the hot melting bonding process, the hot melting speed can be influenced, particularly, the manufactured 3D vamp can have a prominent hard feeling, and the wearing comfort level is poor.
Disclosure of Invention
The invention aims to prepare the spun filament type low-melting-point polyester chip by innovating a formula and a process flow, the low-melting-point polyester chip has good copolymerization uniformity of modified monomers, high glass-transition temperature and good drying effect, and can realize high-efficiency filament spinning. The invention researches a multi-element modification polymerization mechanism, compounds a high-efficiency catalyst, improves the reaction rate, reduces the reaction final temperature, effectively reduces the thermal degradation of the product and greatly improves the fiber strength; meanwhile, the strength is guaranteed through optimization of the modified monomer, the flow performance of hot melt adhesion is met, the purposes in the fields of high-grade and special filaments are met, and the overall use performance is excellent.
The invention adopts the following technical scheme to achieve the aim of the invention
A spun filament type low-melting-point polyester chip comprises the following raw materials in parts by weight:
further, the mass ratio of the diethylene glycol to the triethylene glycol in the formula is controlled to be 2-5: 1, and preferably 3-5: 1.
Further, the heat stabilizer is TMP, TPP and H3PO4The heat stabilizer is preferably a compound heat stabilizer formed by mixing TMP and TPP according to the mass ratio of 2-3: 1.
Further, the catalyst is a complex catalyst and is formed by combining at least two of antimony trioxide, antimony acetate, ethylene glycol antimony and cobalt acetate. Preferably, the composite material is prepared by combining antimony trioxide, antimony acetate and cobalt acetate according to the mass ratio of 2-6: 2-4: 1-3.
The preparation method of the spun filament type low-melting-point polyester chip adopts a primary esterification, secondary esterification and final polycondensation intermittent three-kettle process flow, improves the copolymerization uniformity of products through step-by-step esterification, and prepares the spun filament type low-melting-point polyester chip. The method comprises the following specific steps:
step 1, esterification
Step 11, preparing a slurry from triethylene glycol (TEG) and isophthalic acid (IPA) with a proportion amount, controlling the molar ratio of alkyd to be 1.2-1.4, uniformly stirring, adding the mixture into an esterification kettle through a metering pump to perform esterification reaction, controlling the esterification temperature to be 255-260 ℃, controlling the esterification pressure to be normal pressure, and controlling the esterification rate to be 70-90%;
step 12, preparing a slurry from diethylene glycol (DEG) and isophthalic acid (IPA) with a proportion amount, controlling the molar ratio of alkyd to be 1.15-1.35, uniformly stirring, adding the mixture into an esterification kettle through a metering pump to perform esterification reaction, controlling the esterification temperature to be 250-255 ℃, controlling the esterification pressure to be normal pressure, and controlling the esterification rate to be 70-90%;
step 13, preparing a slurry from Ethylene Glycol (EG), terephthalic acid (PTA) and residual isophthalic acid (IPA) in proportion, controlling the molar ratio of alcohol acid to be 1.10-1.25, uniformly stirring, adding the mixture into an esterification kettle through a metering pump to perform esterification reaction, controlling the esterification temperature to be 245-250 ℃, controlling the esterification pressure to be normal pressure, and controlling the esterification rate to be 85-95%;
after the esterification reaction is finished, controlling the temperature in the first esterification kettle to be 255-260 ℃, controlling the total esterification rate to be 90-95% according to the receiving amount of esterification water, completing the first esterification reaction, and introducing the materials into the second esterification kettle through nitrogen pressurization;
step 2, diester formation
And (3) introducing the materials into a second esterification kettle, adding a heat stabilizer and a catalyst in proportion, slowly heating, controlling the temperature in the system to be 260-265 ℃, the esterification pressure to be normal pressure, and the total residence time of the second esterification to be 60-80 min, and introducing the materials into a final polycondensation kettle by nitrogen pressurization after the diester reaction is completed.
Step 3, final polycondensation
Introducing the materials into a final polycondensation kettle, firstly carrying out normal pressure reaction for 5-20 min, and controlling the internal temperature at 260-265 ℃ in the normal pressure reaction stage; after the normal pressure reaction is finished, carrying out negative pressure reaction, wherein the initial pressure is 101kpa (G), slowly reducing the pressure to 1.8kpa (G), and controlling the time to be 45-60 min; continuously reducing the pressure in the kettle to 50pa (G), and controlling the time to be 30-50 min; maintaining the pressure in the kettle at 50pa (G) for polycondensation reaction, raising the temperature, controlling the final temperature of the reaction to be 270-290 ℃, and pressurizing, casting strips and cutting into granules by using nitrogen after the reaction reaches the specified viscosity to obtain the finished product.
In order to improve the product quality, low-temperature polymerization is adopted, and the final temperature of the polycondensation reaction is controlled to be 270-290 ℃, preferably 270-285 ℃ and further preferably 275-280 ℃.
Through reaction process optimization and catalyst combination, the polymerization reaction period of the product is controlled to be 170-200 min/batch, and in order to improve the comprehensive use effect of the product, the reaction period is preferably controlled to be 180-190 min/batch through process and catalyst collaborative optimization.
The invention has the beneficial effects that:
1. the process flow of the invention adopts an intermittent three-kettle process flow of primary esterification, secondary esterification and final polycondensation, and improves the copolymerization uniformity of the product through stepwise esterification to prepare the spinning filament type low-melting-point polyester chip.
2. According to the invention, according to the characteristics of modified monomer competitive polymerization, the high-efficiency catalyst is compounded, low-temperature polymerization is realized, the high-temperature degradation of the product is inhibited, the final temperature of the polycondensation reaction is controlled to be 270-290 ℃ (preferably 270-285 ℃, and further preferably 275-280 ℃), the polycondensation period of the product is greatly reduced while the low-temperature reaction is carried out, 170-200 min/batch is realized, and the production efficiency is improved.
3. According to the invention, by optimizing a formula system and a process flow, the quality indexes of the finally prepared spinning filament type low-melting-point polyester chip product meet the following requirements: the intrinsic viscosity is 0.65-0.75 dl/g, the melting point is 105-115 ℃, the Tg is 66-70 ℃, the terminal carboxyl is 15-25 mol/T, and the downstream spinning filament has high efficiency, high fiber strength, excellent hot melt adhesive flow property and high adhesive fastness.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
The preparation method of the spun filament type low melting point polyester chip in this example is as follows:
step 1, esterification
Step 11, adding 255kg of IPA and 300kg of TEG (alcohol acid molar ratio is 1.3) into a slurry preparation kettle, uniformly stirring, adding into an esterification kettle through a metering pump to perform esterification reaction, controlling the esterification temperature to be 255-260 ℃, controlling the esterification pressure to be normal pressure, and completing the esterification reaction of the TEG when the esterification water is received to 44kg (esterification rate is 80%).
And step 12, adding 1625kg of IPA and 1300kg of DEG (alcohol acid molar ratio is 1.25) into the slurry preparation kettle, uniformly stirring, adding into the esterification kettle through a metering pump to perform esterification reaction, controlling the esterification temperature to be 250-255 ℃, controlling the esterification pressure to be normal pressure, and completing the esterification reaction of DEG when the esterification water is received to 299kg (esterification rate is 85%).
And step 13, adding 320kg of IPA, 5500kg of PTA and 2600kg of EG (the molar ratio of alcohol to acid is 1.19) into a slurry preparation kettle, uniformly stirring, adding into an esterification kettle through a metering pump for esterification reaction, controlling the esterification temperature to be 245-250 ℃, controlling the esterification pressure to be normal pressure, and finishing the esterification reaction of EG when esterification water is received to 1136kg (the esterification rate is 90%).
And continuously raising the temperature in the esterification kettle to 255-260 ℃, receiving the esterification water, completing the primary esterification reaction when the total amount of the esterification water reaches 1586kg (the esterification rate is 95%), and introducing the materials into the secondary esterification kettle by nitrogen pressurization.
Step 2, diester formation
After the materials are introduced into an esterification secondary kettle, 2kg of TMP and 1kg of TPP as compounded heat stabilizers and 2kg of antimony trioxide, 1.2kg of antimony acetate and 0.8kg of cobalt acetate as compounded catalysts are added, the temperature is slowly increased, the temperature in the system is controlled to be 263 ℃, the esterification pressure is controlled to be normal pressure, the total residence time of the two esterification is controlled to be 80min, and after the two esterification reactions are completed, the materials are introduced into a final polycondensation kettle through nitrogen pressurization.
Step 3, final polycondensation
Introducing the materials into a final polycondensation kettle, carrying out normal pressure reaction for 10min, controlling the internal temperature at a normal pressure reaction stage to be 264 ℃, carrying out negative pressure reaction after the normal pressure reaction is finished, and slowly reducing the pressure to 1.8kpa (G) at the initial pressure of 101kpa (G) for 50 min; continuously reducing the pressure in the kettle to 50pa (G), and controlling the time to be 40 min; maintaining the pressure in the kettle at 50pa (G) for polycondensation reaction, raising the temperature, controlling the final reaction temperature at 278 ℃, and pressurizing, casting strips and cutting into granules by using nitrogen after the reaction reaches the specified viscosity to obtain the finished product.
Example 2
The procedure of this example is the same as example 1 except that: the total amount of PTA in example 1 was 5500kg, the total amount of IPA was 2200kg, the total amount of PTA in this example was 5000kg, the total amount of IPA was 2700kg, and the rest of the distribution esterification process was performed according to the molar ratio of the alkyd in example 1.
Example 3
The procedure of this example is the same as example 1 except that: the total amount of PTA in example 1 is 5500kg, the total amount of IPA in example 1 is 2200kg, the total amount of PTA in this example is 4500kg, the total amount of IPA in this example is 3200kg, and the rest distribution esterification processes are carried out according to the molar ratio of the alkyd in example 1.
Example 4
The procedure of this example is the same as example 1 except that: the total amount of TEG was 300kg and the total amount of DEG was 1300kg in example 1, the total amount of TEG was 350kg and the total amount of DEG was 1300kg in this example, and the molar ratio of IPA to alkyd of TEG in step 11 was maintained at 1.3, the molar ratio of IPA to alkyd of DEG in step 12 was maintained at 1.25 and the total amount of IPA was maintained at 1.205, respectively, in step 13.
Example 5
The procedure of this example is the same as example 1 except that: the total amount of TEG was 300kg and the total amount of DEG was 1300kg in example 1, the total amount of TEG was 400kg and the total amount of DEG was 1300kg in this example, and the molar ratio of IPA to alkyd of TEG in step 11 was maintained at 1.3, the molar ratio of IPA to alkyd of DEG in step 12 was maintained at 1.25 and the total amount of IPA was maintained at 1.214, respectively, in step 13.
Example 6
The procedure of this example is the same as example 1 except that: the catalyst used in example 1 was 2kg of antimony trioxide, 1.2kg of antimony acetate and 0.8kg of cobalt acetate, and the catalyst used in this example was 1.5kg of antimony trioxide, 1.5kg of antimony acetate and 1kg of cobalt acetate, and the remainder of the process was carried out as in example 1.
Example 7
The procedure of this example is the same as example 1 except that: the catalyst used in example 1 was 2kg of antimony trioxide, 1.2kg of antimony acetate and 0.8kg of cobalt acetate, and the catalyst used in this example was 1kg of antimony trioxide, 2kg of antimony acetate and 1kg of cobalt acetate, and the rest of the process was carried out as in example 1.
The relevant indices of the spun filament type low melting point polyesters prepared in examples 1 to 7 are shown in Table 1.
TABLE 1
Remarking: the Tg detection method: the sample was tested using a differential scanning calorimeter of model DSC7010 manufactured by HITACHI corporation. Weighing about 5.0mg of sample, putting the sample into a crucible, heating the sample to 280 ℃ from room temperature at the speed of 10 ℃/min, and then cooling the sample to 0 ℃ at the speed of 20 ℃/min to carry out thermal history elimination operation; the secondary heating is carried out from 0 ℃ to 280 ℃ at the speed of 10 ℃/min. The whole process is protected by a nitrogen gas flow.
2. The detection methods of other quality indexes refer to GB/T14189-2015 detection method of fiber-grade polyester chips (PET).
The above description is only exemplary of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A spun filament type low-melting-point polyester chip is characterized by comprising the following raw materials in parts by weight:
2. a spun-filament type low-melting-point polyester chip as claimed in claim 1, wherein: the mass ratio of the diethylene glycol to the triethylene glycol in the formula is controlled to be 2-5: 1.
3. A spun-filament type low-melting-point polyester chip as claimed in claim 1, wherein: the heat stabilizer is TMP, TPP and H3PO4At least one of (1).
4. A spun-filament type low-melting-point polyester chip as claimed in claim 3, wherein: the heat stabilizer is a compound heat stabilizer formed by mixing TMP and TPP according to the mass ratio of 2-3: 1.
5. A spun-filament type low-melting-point polyester chip as claimed in claim 1, wherein: the catalyst is a complex catalyst and is formed by combining at least two of antimony trioxide, antimony acetate, ethylene glycol antimony and cobalt acetate.
6. A spun-filament type low-melting-point polyester chip as claimed in claim 5, wherein: the catalyst is formed by combining antimony trioxide, antimony acetate and cobalt acetate according to the mass ratio of 2-6: 2-4: 1-3.
7. A method for preparing a spun-filament type low-melting-point polyester chip according to any one of claims 1 to 6, characterized in that: the technological process adopts a primary esterification, secondary esterification and final polycondensation intermittent three-kettle process, and improves the copolymerization uniformity of the product through stepwise esterification to prepare the spinning filament type low-melting-point polyester slice.
8. The preparation method according to claim 7, comprising the following steps:
step 1, esterification
Step 11, preparing a slurry from triethylene glycol and isophthalic acid with a proportion amount, controlling the molar ratio of alkyd to be 1.2-1.4, uniformly stirring, adding the mixture into an esterification kettle through a metering pump to perform esterification reaction, controlling the esterification temperature to be 255-260 ℃, controlling the esterification pressure to be normal pressure, and controlling the esterification rate to be 70-90%;
step 12, preparing a slurry from diethylene glycol and isophthalic acid with a proportion amount, controlling the molar ratio of alkyd to be 1.15-1.35, uniformly stirring, adding the mixture into an esterification kettle through a metering pump to perform esterification reaction, controlling the esterification temperature to be 250-255 ℃, controlling the esterification pressure to be normal pressure, and controlling the esterification rate to be 70-90%;
step 13, preparing a slurry from ethylene glycol, terephthalic acid and the rest isophthalic acid in a proportion, controlling the molar ratio of alkyd to be 1.10-1.25, uniformly stirring, adding the mixture into an esterification kettle through a metering pump to perform esterification reaction, controlling the esterification temperature to be 245-250 ℃, controlling the esterification pressure to be normal pressure, and controlling the esterification rate to be 85-95%;
after the esterification reaction is finished, controlling the temperature in the first esterification kettle to be 255-260 ℃, controlling the total esterification rate to be 90-95% according to the receiving amount of esterification water, completing the first esterification reaction, and introducing the materials into the second esterification kettle through nitrogen pressurization;
step 2, diester formation
And (3) introducing the materials into a second esterification kettle, adding a heat stabilizer and a catalyst in proportion, slowly heating, controlling the temperature in the system to be 260-265 ℃, the esterification pressure to be normal pressure, and the total residence time of the second esterification to be 60-80 min, and introducing the materials into a final polycondensation kettle by nitrogen pressurization after the diester reaction is completed.
Step 3, final polycondensation
Introducing the materials into a final polycondensation kettle, firstly carrying out normal pressure reaction for 5-20 min, and controlling the internal temperature at 260-265 ℃ in the normal pressure reaction stage; after the normal pressure reaction is finished, carrying out negative pressure reaction, wherein the initial pressure is 101kpa (G), slowly reducing the pressure to 1.8kpa (G), and controlling the time to be 45-60 min; continuously reducing the pressure in the kettle to 50pa (G), and controlling the time to be 30-50 min; maintaining the pressure in the kettle at 50pa for polycondensation reaction, raising the temperature, controlling the final reaction temperature at 270-290 ℃, and pressurizing, strip casting and granulating by using nitrogen after the reaction reaches the specified viscosity to obtain the finished product.
9. The method of claim 8, wherein: the reaction period of the final polycondensation in the step 3 is controlled to be 170-200 min/batch.
10. The production method according to claim 7 or 8, characterized in that: the quality indexes of the obtained polyester chip products meet the following requirements: the intrinsic viscosity is 0.65-0.75 dl/g, the melting point is 105-115 ℃, the Tg is 66-70 ℃, and the terminal carboxyl is 15-25 mol/T.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112778509A (en) * | 2020-12-31 | 2021-05-11 | 安徽皖维高新材料股份有限公司 | Anti-attenuation low-melting-point polyester chip prepared by one-step spinning method and preparation method thereof |
| CN115109242A (en) * | 2022-07-14 | 2022-09-27 | 天津华新盈聚酯材料科技有限公司 | Low-melting-point polyester chip for producing antistatic milled hot melt adhesive and preparation method thereof |
| CN115449060A (en) * | 2022-10-28 | 2022-12-09 | 安徽皖维高新材料股份有限公司 | High-content high-compatibility SiO 2 Polyester chip for matte film and preparation method thereof |
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| CN102585185A (en) * | 2011-12-27 | 2012-07-18 | 厦门翔鹭化纤股份有限公司 | Manufacturing method of low-melting-point polyester granules |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112778509A (en) * | 2020-12-31 | 2021-05-11 | 安徽皖维高新材料股份有限公司 | Anti-attenuation low-melting-point polyester chip prepared by one-step spinning method and preparation method thereof |
| CN115109242A (en) * | 2022-07-14 | 2022-09-27 | 天津华新盈聚酯材料科技有限公司 | Low-melting-point polyester chip for producing antistatic milled hot melt adhesive and preparation method thereof |
| CN115109242B (en) * | 2022-07-14 | 2024-05-28 | 天津华新盈聚酯材料科技有限公司 | Low-melting-point polyester chip for producing antistatic type powder grinding hot melt adhesive and preparation method thereof |
| CN115449060A (en) * | 2022-10-28 | 2022-12-09 | 安徽皖维高新材料股份有限公司 | High-content high-compatibility SiO 2 Polyester chip for matte film and preparation method thereof |
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Application publication date: 20201023 |