CN114685766B - Modified biodegradable polyester and preparation method thereof - Google Patents
Modified biodegradable polyester and preparation method thereof Download PDFInfo
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- CN114685766B CN114685766B CN202011633711.4A CN202011633711A CN114685766B CN 114685766 B CN114685766 B CN 114685766B CN 202011633711 A CN202011633711 A CN 202011633711A CN 114685766 B CN114685766 B CN 114685766B
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- biodegradable polyester
- modified biodegradable
- acid
- butanediol
- suspension
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- 229920000229 biodegradable polyester Polymers 0.000 title claims abstract description 27
- 239000004622 biodegradable polyester Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920000728 polyester Polymers 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 14
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 92
- 239000000725 suspension Substances 0.000 claims description 70
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 68
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 62
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 24
- 238000006068 polycondensation reaction Methods 0.000 claims description 15
- 238000005886 esterification reaction Methods 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 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 3
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 239000001384 succinic acid 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
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000010096 film blowing Methods 0.000 abstract description 4
- 239000002932 luster Substances 0.000 abstract description 2
- 229910052582 BN Inorganic materials 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 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 description 2
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 206010064571 Gene mutation Diseases 0.000 description 1
- 208000001953 Hypotension Diseases 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000036543 hypotension Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001896 polybutyrate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Abstract
The invention discloses a modified biodegradable polyester and a preparation method thereof, wherein the polyester comprises the following raw material components: the ratio of the sum of the aliphatic dibasic acid or the derivative thereof and the aromatic dibasic acid or the derivative thereof to the molar amount of the aliphatic dibasic alcohol is 1 (1.8-2.5), the catalyst is 50-1000ug/g of the modified biodegradable polyester, the stabilizer is 50-1000ug/g of the modified biodegradable polyester, and the additive is 30-300ug/g of the modified biodegradable polyester, and the preparation method of the polyester is provided. The polyester disclosed by the invention has good color and luster, and has good openness after being prepared into a film, an opening agent is not required to be added in the film blowing process, and the subsequent procedures are reduced.
Description
Technical Field
The invention relates to biodegradable polyester and a preparation method thereof, in particular to modified biodegradable polyester and a preparation method thereof.
Background
The aliphatic-aromatic polyester is a biodegradable high polymer material with good comprehensive performance, can be used for covering mulching films of crops, is used as a packaging bag for express packaging, is used as a food packaging bag for food packaging, and the like. But as packaging material, the color of the product is darker, and the customer experience is directly affected. For the phenomenon of poor color, color matching is generally performed using cobalt compounds (CN 100447177, CN 1412218), organic toners, and the like. The toner includes blue toner, red toner, violet toner, and the like. The organic toner is added in the polymerization process, so that the high temperature and high pressure can cause degradation, the thermal stability of the polyester is affected, and the transparency is reduced. Cobalt salts can improve color, but when the cobalt concentration exceeds the standard, the cobalt salts can cause a plurality of serious health problems, such as hypotension, paralysis, diarrhea, bone defect and the like, and can also cause gene mutation of living cells. Through cobalt salt modification, human exposure in excessive cobalt environment can not only poison, and plastic products can also pollute the atmosphere, water and soil, and especially degrade through microbial treatment in soil, when soil is seriously polluted by cobalt, crops can die when the cobalt concentration is 10 mg/L.
CN101050273 solid-phase tackifies PET low-viscosity slices, improves color, increases solid-phase tackification process, but PBAT cannot carry out solid-phase tackification due to lower melting point. Patent CN101104678A adds titanium catalyst, phosphorus heat stabilizer, toner to improve the hue of titanium polyester, but the addition of stabilizer can prolong the reaction time, and the addition of toner can affect the cleanliness of polyester.
Disclosure of Invention
The invention aims to: the first object of the present invention is to provide a biodegradable polyester having a good color and a good opening property after being formed into a film, and the second object of the present invention is to provide a method for producing a biodegradable polyester which does not require the addition of an opening agent during film blowing and which reduces the number of subsequent steps.
The technical scheme is as follows: the modified biodegradable polyester of the invention comprises the following raw material components: the molar ratio of the sum of the aliphatic dibasic acid or the derivative thereof and the aromatic dibasic acid or the derivative thereof to the aliphatic diol is 1: (1.8-2.5), the catalyst is 50-1000ug/g of modified biodegradable polyester, the stabilizer is 50-1000ug/g of modified biodegradable polyester, and the additive is 30-300ug/g of modified biodegradable polyester.
Further, the aromatic dibasic acid is one or more of refined terephthalic acid, isophthalic acid or phthalic acid. The aliphatic dibasic acid is one or more of adipic acid, succinic acid and sebacic acid. The aliphatic diol is butanediol or neopentyl glycol.
The catalyst is one or more of tetrabutyl titanate, tetraisopropyl titanate, potassium titanium oxalate or stannous octoate.
The stabilizer is one or more of phosphoric acid, triphenyl phosphate, trimethyl phosphate, phosphorous acid or triphenyl phosphite. The additive is a composition of nano barium sulfate, nano calcium carbonate and nano boron nitride with the mass ratio of (1-2) to (0.5-2).
The particle size of the nanometer barium sulfate is 10-1000nm, the particle size of the nanometer calcium carbonate is 10-1000nm, and the particle size of the nanometer boron nitride is 10-1000nm.
The preparation method of the modified biodegradable polyester comprises the following steps:
(1) Mixing aliphatic dibasic acid or derivative thereof, aromatic dibasic acid or derivative thereof, aliphatic dihydric alcohol, catalyst, stabilizer and additive into slurry, and carrying out esterification reaction under the conditions that the reaction temperature is 160-250 ℃ and the reaction pressure is 40-85 kPa;
(2) The preshrinking reaction is carried out at 235-245 ℃ and 3-4.5 kPa to obtain preshrinking material, and the polycondensation reaction is carried out at 235-260 ℃ and vacuum degree less than 100 Pa;
(3) Extruding, granulating and drying to obtain the modified biodegradable polyester.
In the step (1), the additive is pre-dispersed in aliphatic dihydric alcohol to prepare suspension, and then the suspension is added into a polyester synthesis system, wherein the mass concentration of the additive in the suspension is 10% -20%.
The combination of barium sulfate, calcium carbonate and boron nitride has synergistic effect in the product, and compared with the single additive or two additives, the prepared biodegradable polyester has obviously improved appearance, and meanwhile, the composition has better openness, does not need to add an opening agent in the film blowing process, and reduces subsequent procedures.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: the polyester disclosed by the invention has good color and luster, and has good openness after being prepared into a film, an opening agent is not required to be added in the film blowing process, and the subsequent procedures are reduced.
Detailed Description
The technical scheme of the invention is further described below by referring to examples.
Example 1
Grinding barium sulfate, calcium carbonate and boron nitride with butanediol to prepare 20% concentration barium sulfate/butanediol suspension, calcium carbonate/butanediol suspension and boron nitride/butanediol suspension, and adding the suspension into the polyester synthesis system to obtain barium sulfate with average particle size of 100nm, barium sulfate with average particle size of 80nm and boron nitride with average particle size of 100nm.
250g PTA,177g AA,540g BDO and 50ug/g tetrabutyl titanate are sequentially added into a PU2.5 reaction polymerization kettle, esterification reaction is carried out under the conditions that the reaction temperature is 160 ℃ and the reaction pressure is 40-85 kPa, when the esterification rate reaches more than 95 percent, 100ug/g barium sulfate/butanediol suspension, 100ug/g calcium carbonate/butanediol suspension and 100ug/g boron nitride/butanediol suspension are added, then the pressure is gradually reduced to 100Pa within 45min at the reaction temperature of 235 ℃, and polycondensation reaction is carried out under the conditions that the vacuum degree is less than 100Pa for 88min. And (5) after the reaction is finished, vacuum-eliminating by using nitrogen, discharging, granulating and drying to obtain the polyester chip.
Example 2
The barium sulfate, the calcium carbonate and the boron nitride are respectively ground with butanediol to prepare a suspension containing 20 percent of barium sulfate/butanediol, a suspension containing calcium carbonate/butanediol and a suspension containing boron nitride/butanediol, and then the suspension containing 20 percent of barium sulfate/butanediol and the suspension containing calcium carbonate/butanediol and the suspension containing boron nitride/butanediol are added into a polyester synthesis system. The average particle size of barium sulfate is 100nm, the average particle size of barium sulfate is 80nm, and the average particle size of boron nitride is 100nm.
250g PTA,219g SA,540g BDO and 1000ug/g tetraisopropyl titanate are sequentially added into a PU2.5 reaction polymerization kettle, esterification reaction is carried out under the conditions that the reaction temperature is 250 ℃ and the reaction pressure is 40-85 kPa, when the esterification rate reaches more than 95%, 30ug/g barium sulfate/butanediol suspension liquid of barium sulfate, 60ug/g calcium carbonate/butanediol suspension liquid of calcium carbonate and 60ug/g boron nitride/butanediol suspension liquid of boron nitride are added, then the temperature is 245 ℃ and the pressure is gradually reduced to 100Pa within 45min, and polycondensation reaction is carried out under the conditions that the temperature is 260 ℃ and the vacuum degree is less than 100Pa for 88min. And (5) after the reaction is finished, vacuum-eliminating by using nitrogen, discharging, granulating and drying to obtain the polyester chip.
Example 3
The barium sulfate, the calcium carbonate and the boron nitride are respectively ground with butanediol to prepare a suspension containing 20 percent of barium sulfate/butanediol, a suspension containing calcium carbonate/butanediol and a suspension containing boron nitride/butanediol, and then the suspension containing 20 percent of barium sulfate/butanediol and the suspension containing calcium carbonate/butanediol and the suspension containing boron nitride/butanediol are added into a polyester synthesis system. The average particle size of barium sulfate is 100nm, the average particle size of barium sulfate is 80nm, and the average particle size of boron nitride is 100nm.
250g PTA,303g sebacic acid, 540g BDO,500ug/g potassium titanate are sequentially added into a PU2.5 reaction polymerization kettle, esterification reaction is carried out under the conditions that the reaction temperature is 240 ℃ and the reaction pressure is 40-85 kPa, when the esterification rate reaches more than 95%, 8.5ug/g barium sulfate/butanediol suspension, 17ug/g calcium carbonate/butanediol suspension and 4.5ug/g boron nitride/butanediol suspension are added, then the temperature is 240 ℃ and the pressure is gradually reduced to 100Pa within 45min, and polycondensation reaction is carried out under the conditions that the temperature is 240 ℃ and the vacuum degree is less than 100Pa for 88min. And (5) after the reaction is finished, vacuum-eliminating by using nitrogen, discharging, granulating and drying to obtain the polyester chip.
Example 4
The barium sulfate, the calcium carbonate and the boron nitride are respectively ground with butanediol to prepare a suspension containing 20 percent of barium sulfate/butanediol, a suspension containing calcium carbonate/butanediol and a suspension containing boron nitride/butanediol, and then the suspension containing 20 percent of barium sulfate/butanediol and the suspension containing calcium carbonate/butanediol and the suspension containing boron nitride/butanediol are added into a polyester synthesis system. The average particle size of barium sulfate is 100nm, the average particle size of barium sulfate is 80nm, and the average particle size of boron nitride is 100nm. 250g ITA,177g AA,540g BDO,500ug/g tetrabutyl titanate are sequentially added into a PU2.5 reaction polymerization kettle, esterification reaction is carried out under the conditions that the reaction temperature is 235 ℃ and the reaction pressure is 40-85 kPa, when the esterification rate reaches more than 95%, a barium sulfate/butanediol suspension of 40ug/g barium sulfate, a calcium carbonate/butanediol suspension of 80ug/g calcium carbonate and a boron nitride/butanediol suspension of 80ug/g boron nitride are added, then the temperature is 240 ℃ and the pressure is gradually reduced to 100Pa within 45min, and polycondensation reaction is carried out under the conditions that the temperature is 240 ℃ and the vacuum degree is less than 100Pa for 88min. And (5) after the reaction is finished, vacuum-eliminating by using nitrogen, discharging, granulating and drying to obtain the polyester chip.
Example 5
The barium sulfate, the calcium carbonate and the boron nitride are respectively ground with butanediol to prepare a suspension containing 20 percent of barium sulfate/butanediol, a suspension containing calcium carbonate/butanediol and a suspension containing boron nitride/butanediol, and then the suspension containing 20 percent of barium sulfate/butanediol and the suspension containing calcium carbonate/butanediol and the suspension containing boron nitride/butanediol are added into a polyester synthesis system. The average particle size of barium sulfate is 100nm, the average particle size of barium sulfate is 80nm, and the average particle size of boron nitride is 100nm. 250g PTA,177g AA,540g BDO,500ug/g potassium titanate are sequentially added into a PU2.5 reaction polymerization kettle, esterification reaction is carried out under the conditions that the reaction temperature is 245 ℃ and the reaction pressure is 40-85 kPa, when the esterification rate reaches more than 95%, 1ug/g barium sulfate/butanediol suspension, 1ug/g calcium carbonate/butanediol suspension and 298ug/g boron nitride/butanediol suspension are added, then the reaction temperature is 240 ℃, the pressure is gradually reduced to 100Pa within 45min, and polycondensation reaction is carried out under the conditions that the temperature is 240 ℃ and the vacuum degree is less than 100Pa, and the reaction time is 88min. And (5) after the reaction is finished, vacuum-eliminating by using nitrogen, discharging, granulating and drying to obtain the polyester chip.
Example 6
The barium sulfate, the calcium carbonate and the boron nitride are respectively ground with butanediol to prepare a suspension containing 20 percent of barium sulfate/butanediol, a suspension containing calcium carbonate/butanediol and a suspension containing boron nitride/butanediol, and then the suspension containing 20 percent of barium sulfate/butanediol and the suspension containing calcium carbonate/butanediol and the suspension containing boron nitride/butanediol are added into a polyester synthesis system. The average particle size of barium sulfate is 100nm, the average particle size of barium sulfate is 80nm, and the average particle size of boron nitride is 100nm. 250g PTA,177g AA,540g BDO,500ug/g tetraisopropyl titanate are sequentially added into a PU2.5 reaction polymerization kettle, esterification reaction is carried out under the conditions that the reaction temperature is 240 ℃ and the reaction pressure is normal pressure and 40-85 kPa, when the esterification rate reaches more than 95%, 80ug/g barium sulfate/butanediol suspension, 80ug/g calcium carbonate/butanediol suspension and 40ug/g boron nitride/butanediol suspension are added, then the reaction temperature is 240 ℃ and the pressure is gradually reduced to 100Pa within 45min, and polycondensation reaction is carried out under the conditions that the temperature is 240 ℃ and the vacuum degree is less than 100Pa for 88min. And (5) after the reaction is finished, vacuum-eliminating by using nitrogen, discharging, granulating and drying to obtain the polyester chip.
Comparative example 1
A conventional polyester was produced in the same manner as in example 1 except that the barium sulfate/butanediol suspension, the calcium carbonate/butanediol suspension, and the boron nitride/butanediol suspension were not added, and the polycondensation reaction time was 88 minutes, to obtain a conventional polyester.
Comparative example 2
A conventional polyester was prepared in the same manner as in example 1, except that only the barium sulfate suspension was added, and the polycondensation time was 88 minutes.
Comparative example 3
A conventional polyester was prepared in the same manner as in example 1, except that only the calcium carbonate suspension was added, and the polycondensation time was 88 minutes.
Comparative example 4
A conventional polyester was prepared in the same manner as in example 1, except that only the boron nitride suspension was added, and the polycondensation time was 88 minutes.
Comparative example 5
A conventional polyester was prepared in the same manner as in example 1, except that only the barium sulfate suspension and the calcium carbonate suspension were added, and the polycondensation time was 88 minutes.
Comparative example 6
A conventional polyester was prepared in the same manner as in example 1, except that only the barium sulfate suspension and the boron nitride suspension were added, and the polycondensation reaction time was 88 minutes.
Comparative example 7
A conventional polyester was prepared in the same manner as in example 1, except that only a calcium carbonate suspension and a boron nitride suspension were added, and the polycondensation reaction time was 88 minutes.
Table 1 shows the performance parameters of the polyesters prepared in the examples and comparative examples.
TABLE 1
Claims (8)
1. The modified biodegradable polyester is characterized by comprising the following raw material components: the catalyst comprises (by weight) 1 (1.8-2.5) of aliphatic dibasic acid or derivative thereof, 50-1000ug/g of aromatic dibasic acid or derivative thereof, 50-1000ug/g of modified biodegradable polyester, and 30-300ug/g of stabilizer;
the additive is a composition of nano barium sulfate, nano calcium carbonate and nano boron nitride in a mass ratio of (1-2) to (0.5-2); the particle size of the nano barium sulfate is 10-1000nm, the particle size of the nano calcium carbonate is 10-1000nm, and the particle size of the nano boron nitride is 10-1000nm.
2. The modified biodegradable polyester according to claim 1, characterized in that: the aromatic dibasic acid is one or more of refined terephthalic acid, isophthalic acid or phthalic acid.
3. The modified biodegradable polyester according to claim 1, characterized in that: the aliphatic dibasic acid is one or more of adipic acid, succinic acid or sebacic acid.
4. The modified biodegradable polyester according to claim 1, characterized in that: the aliphatic dihydric alcohol is butanediol or neopentyl glycol.
5. The modified biodegradable polyester according to claim 1, characterized in that: the catalyst is one or more of tetrabutyl titanate, tetraisopropyl titanate, potassium titanium oxalate or stannous octoate.
6. The modified biodegradable polyester according to claim 1, characterized in that: the stabilizer is one or more of phosphoric acid, triphenyl phosphate, trimethyl phosphate, phosphorous acid or triphenyl phosphate.
7. A process for the preparation of the modified biodegradable polyester according to claim 1, comprising the steps of:
(1) Mixing aliphatic dibasic acid or derivative thereof, aromatic dibasic acid or derivative thereof, aliphatic dihydric alcohol, catalyst, stabilizer and additive into slurry, and carrying out esterification reaction under the conditions that the reaction temperature is 160-250 ℃ and the reaction pressure is 40-85 kPa;
(2) The preshrinking reaction is carried out under the conditions that the reaction temperature is 235-245 ℃ and the reaction pressure is 3-4.5 kPa to obtain preshrinking substances, and the polycondensation reaction is carried out under the conditions that the temperature is 235-260 ℃ and the vacuum degree is less than 100 Pa;
(3) Extruding, granulating and drying to obtain the modified biodegradable polyester.
8. The method for producing a modified biodegradable polyester according to claim 7, characterized in that: in the step (1), the additive is pre-dispersed in aliphatic dihydric alcohol to prepare suspension, and then the suspension is added into a polyester synthesis system, wherein the mass concentration of the additive in the suspension is 10% -20%.
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