CN118292137A - PBAT fiber capable of crystallizing rapidly and preparation method thereof - Google Patents
PBAT fiber capable of crystallizing rapidly and preparation method thereof Download PDFInfo
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- CN118292137A CN118292137A CN202310001069.5A CN202310001069A CN118292137A CN 118292137 A CN118292137 A CN 118292137A CN 202310001069 A CN202310001069 A CN 202310001069A CN 118292137 A CN118292137 A CN 118292137A
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- Prior art keywords
- pbat
- butanediol
- adipic acid
- esterification
- acid
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- 239000000835 fiber Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920001896 polybutyrate Polymers 0.000 title claims description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 53
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 52
- -1 adipic acid butanediol ester Chemical class 0.000 claims abstract description 49
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002667 nucleating agent Substances 0.000 claims abstract description 39
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 35
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000008117 stearic acid Substances 0.000 claims abstract description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001361 adipic acid Substances 0.000 claims abstract description 24
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 24
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 14
- 238000002074 melt spinning Methods 0.000 claims abstract description 5
- 238000005886 esterification reaction Methods 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 45
- 230000032050 esterification Effects 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000009987 spinning Methods 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 25
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 20
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 20
- 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 20
- 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 20
- 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 20
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 16
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004246 zinc acetate Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000012760 heat stabilizer Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- KLLLJCACIRKBDT-UHFFFAOYSA-N 2-phenyl-1H-indole Chemical compound N1C2=CC=CC=C2C=C1C1=CC=CC=C1 KLLLJCACIRKBDT-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 4
- JYLRDAXYHVFRPW-UHFFFAOYSA-N butane-1,1-diol;terephthalic acid Chemical compound CCCC(O)O.OC(=O)C1=CC=C(C(O)=O)C=C1 JYLRDAXYHVFRPW-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 23
- 230000008025 crystallization Effects 0.000 abstract description 23
- 238000004804 winding Methods 0.000 abstract description 11
- 230000001105 regulatory effect Effects 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 abstract description 3
- 229920005586 poly(adipic acid) Polymers 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 34
- 238000010438 heat treatment Methods 0.000 description 32
- 238000007664 blowing Methods 0.000 description 16
- 238000001816 cooling Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 229920001634 Copolyester Polymers 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical group O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 4
- 239000011858 nanopowder Substances 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- 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
- C08G63/78—Preparation processes
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a biodegradable PBAT fiber capable of crystallizing rapidly and a preparation method thereof. The fiber comprises the following components in parts by weight: 100 parts of poly (adipic acid)/butylene terephthalate (PBAT) and 0.05-5% of nucleating agent. Wherein the molar content of the adipic acid butanediol ester (BA) chain segment is 80-150% relative to the terephthalic acid butanediol ester (BT) chain segment, and the nucleating agent is zinc oxide (SA-ZnO) modified by stearic acid. The preparation method of the invention comprises the following steps: the adipic acid is firstly esterified and prepolymerized to obtain PBA prepolymer, then terephthalic acid is esterified, and then the PBA prepolymer and PBA are directly subjected to final polycondensation, and a nucleating agent is added, and finally the PBAT fiber is prepared by a melt spinning mode. According to the invention, SA-ZnO is adopted as a nucleating agent for promoting the crystallization of PBAT through in-situ polymerization, and meanwhile, the relation between the crystallization capacity and the performance of PBAT is regulated and controlled through the chain segment length, so that the phenomenon that PBAT fibers are bonded in the winding process is effectively avoided, and the quality of the PBAT fibers is improved.
Description
Technical Field
The invention relates to a PBAT fiber capable of crystallizing rapidly and a preparation method thereof, belonging to the technical field of polymer fiber preparation.
Background
The poly (adipic acid)/butylene terephthalate (PBAT) is a terpolymer polymerized from terephthalic acid (PTA), succinic acid (AA) and 1, 4-Butanediol (BDO), and has the degradation performance of aliphatic polyester and the mechanical property of aromatic polyester. It is easy to be metabolized and decomposed by various microorganisms in nature or enzymes in animals and plants to produce carbon dioxide and water, and does not pollute the environment. Because the degradation properties of PBATs can alleviate the current environmental problems of white pollution, articles of PBAT are receiving great attention. The PBAT is widely applied to film materials such as plastic packaging films, agricultural mulching films and the like.
However, because the synthesis process of the PBAT adopts random copolymerization, the obtained high polymer is a ternary random copolymer, so that the crystallinity of the PBAT is lower, the fiber is bonded in the spinning process, the bonding phenomenon is generated due to the diffusion phenomenon among the fibers caused by the movement of molecular chain segments when the fibers are contacted with each other, the adhesion is generated in the subsequent drawing and winding processes, and the synthesis and application development of the PBAT in the fiber and the non-woven fabric are restricted. At present, aiming at the bonding phenomenon in the PBAT preparation process, the crystallization capacity and the crystallization speed of the PBAT are improved mainly by adding a nucleating agent in the melting process and regulating the length of a molecular chain segment, but the dispersibility of the nucleating agent in a polymer is not considered after the nucleating agent is added, and the degradation performance of the PBAT is seriously reduced after the molecular chain segment is regulated.
For example, patent documents CN113122952a and CN113201805A both disclose a preparation method of PBAT fiber, and the crystallization capability is improved by adjusting and controlling the lengths of the PBA chain segment and the PBT chain segment, but the degradation performance of the polymer is greatly reduced and even degradation cannot be realized; patent document CN108384200B discloses a rapidly crystallizing PBAT material and a preparation method thereof, which adopts melamine/cyanuric acid complex as a nucleating agent to promote crystallization of PBAT, but since the molecular structure of PBAT polymer itself is not changed, even if the effect of adding the nucleating agent to promote crystallization ability is not obvious, the dispersibility of the nucleating agent in the polymer is not considered.
Disclosure of Invention
Based on the problems of the PBAT fiber in the molding process, the invention combines the means of regulating and controlling the molecular chain segments and promoting crystallization by the nucleating agent, regulates and controls the length of the aliphatic PBA molecular chain segments, ensures that the copolymer has certain regularity, further improves the crystallization capability, and simultaneously, the biodegradability of the BT chain segments is not influenced because the BT chain segments are still in a random distribution state; in addition, the modified nucleating agent is introduced into the polymer system by a polymerization means of in-situ polymerization, so that the dispersibility of the nucleating agent is improved, and the crystallization performance and the thermal stability of the PBAT can be improved.
The technical difficulties of the invention are as follows: 1. controlling the degree of polymerization of the PBA prepolymer polymer, if the degree of polymerization of the PBA is too high, can result in a reduced service life of the article. If the polymerization degree is too low, the crystallization ability of the PBA segment is lowered; 2. inorganic nano powder is introduced by an in-situ polymerization mode to enhance the thermal stability of the matrix, and the surface modification is developed for preventing the problem of poor dispersion uniformity of inorganic split in the polymer.
Based on this, the invention provides a fast crystallizing PBAT fiber and a preparation method thereof, wherein the PBAT fiber comprises the stages of modification, esterification, pre-polycondensation, final polycondensation, spinning and the like of a nucleating agent. The invention improves the segment regularity by regulating and controlling the length of the molecular segment, thereby improving the crystallization capability; and then inorganic nano powder (namely a nucleating agent) is introduced in an in-situ polymerization mode to improve the crystallization performance of the inorganic nano powder, so that the stability in the spinning process is effectively improved, the dispersibility of the nucleating agent is improved, and the crystallization performance and the thermal stability of PBAT are improved.
The mode of regulating the length of the molecular chain segment is as follows: firstly, carrying out esterification reaction on adipic acid and butanediol to generate adipic acid butanediol esterified product, carrying out pre-polycondensation reaction to generate adipic acid butanediol (PBA) prepolymer, controlling the polymerization degree of the PBA prepolymer to be 30-40, carrying out esterification reaction on terephthalic acid and butanediol to generate terephthalic acid butanediol esterified product, and carrying out final polycondensation reaction on the terephthalic acid butanediol esterified product, the adipic acid butanediol (PBA) prepolymer and stearic acid modified zinc oxide to obtain the PBAT polyester.
The present invention provides a fast crystallizing PBAT fiber comprising the following components: 100 parts of polybutylene adipate/butylene terephthalate PBAT and 0.05-5% of nucleating agent (wherein, 0.05-5% of nucleating agent means that the nucleating agent accounts for 0.05-5% of the total mass of the polybutylene adipate/butylene terephthalate PBAT).
In the invention, the PBAT fiber molecular chain segment comprises a butylene terephthalate chain segment and a butylene adipate chain segment, wherein the molar content of the Butylene Adipate (BA) chain segment is 80-150% relative to the Butylene Terephthalate (BT) chain segment, and the degradation performance, the thermal stability, the strength and the like of the PBAT can be regulated by regulating the length of the molecular chain segment.
In the invention, the breaking strength of the PBAT fiber is 2.0-5.0cN/dtex, and the breaking elongation is 20-80%.
In the invention, the nucleating agent is zinc oxide modified by stearic acid.
Wherein, the preparation of the nucleating agent is as follows: dissolving stearic acid in sodium hydroxide aqueous solution under the water bath condition, dropwise adding zinc acetate aqueous solution into sodium hydroxide aqueous solution containing stearic acid under stirring, centrifuging, washing and drying a white precipitate generated by the reaction to obtain the stearic acid modified zinc oxide.
The water bath temperature is 80-95 ℃, the concentration of sodium hydroxide aqueous solution is 0.1mol/L, the amount of stearic acid is 6-10 mg, the concentration of zinc acetate aqueous solution is 0.1mol/L, and the reaction time is 1-2.5h; preferably, the water bath temperature is 90 ℃, the concentration of the sodium hydroxide aqueous solution is 0.1mol/L, the amount of stearic acid is 8mg, the concentration of the zinc acetate aqueous solution is 0.1mol/L, and the reaction time is 1.5h.
The invention adopts zinc oxide modified by stearic acid as a nucleating agent to promote the crystallization of PBAT, so that the crystallization speed and mechanical property of PBAT are greatly improved.
The invention also provides a preparation method of the PBAT fiber, which comprises the steps of respectively esterifying terephthalic acid and adipic acid with butanediol to obtain a terephthalic acid butanediol ester and an adipic acid butanediol ester, then pre-polycondensing the adipic acid butanediol ester to obtain an adipic acid butanediol prepolymer, then mixing the terephthalic acid butanediol ester and the adipic acid butanediol prepolymer, adding zinc oxide modified by a nucleating agent stearic acid for final polycondensation, and finally preparing the PBAT fiber by a melt spinning method.
As a preferred technical scheme, the preparation method of the PBAT fiber comprises the following specific steps:
(1) Esterification of terephthalic acid with butanediol: mixing terephthalic acid, butanediol, a catalyst I, a heat stabilizer I and an antioxidant I, and performing esterification reaction to obtain a butanediol terephthalate;
(2) Esterification of adipic acid with butanediol: mixing adipic acid, butanediol, a catalyst II, a heat stabilizer II and an antioxidant II, and performing esterification reaction to obtain adipic acid butanediol esterified product;
(3) Pre-polycondensation of adipic acid butanediol ester: carrying out pre-polycondensation reaction on the butanediol adipate obtained in the second step to obtain butanediol adipate (PBA) prepolymer;
(4) Preparation of stearic acid modified zinc oxide: dissolving stearic acid in sodium hydroxide aqueous solution under the water bath condition, dropwise adding zinc acetate aqueous solution into sodium hydroxide aqueous solution containing stearic acid under stirring, centrifuging, washing and drying a white precipitate generated by the reaction to obtain stearic acid modified zinc oxide;
(5) And (3) final polycondensation: carrying out final polycondensation reaction on butylene terephthalate, PBA prepolymer and stearic acid modified zinc oxide to obtain PBAT slices;
(6) And (3) carrying out melt spinning on the PBAT slice obtained in the fifth step to obtain the PBAT fiber.
In the step (1), the catalyst I is one or more of tetrabutyl titanate or ethylene glycol antimony.
In the step (1), the addition amount of the catalyst I is 50-200ppm of the addition amount of the terephthalic acid.
In the step (1), the heat stabilizer I is one or more of phosphorous acid or triphenyl phosphate.
In the step (1), the addition amount of the heat stabilizer I is 50-500ppm of the addition amount of the terephthalic acid.
In the step (1), the antioxidant I is one or more of an antioxidant 1010, an antioxidant 300 and an antioxidant 164.
In the step (1), the adding amount of the antioxidant I is 50-200ppm of the adding amount of the terephthalic acid.
In the step (1), the molar ratio of terephthalic acid to butanediol is 1:1.2-2.0; preferably, it is 1:1.2 to 1.5.
In the step (1), the esterification temperature is 180-230 ℃, the esterification pressure is 0.1-0.5 MPa, the esterification time is 90-300min, the water yield is more than or equal to 98% of the theoretical water yield, and the polymerization degree of the obtained butylene terephthalate is 2-8; preferably, the esterification temperature is 200 ℃, the esterification pressure is 0.3MPa, the esterification time is 150min, 98% or more of the theoretical water yield is taken as the end of esterification, and the polymerization degree of the obtained butylene terephthalate is 5.
In the step (2), the catalyst II is one or more of tetrabutyl titanate or ethylene glycol antimony;
in the step (2), the addition amount of the catalyst II is 50-200ppm of the addition amount of the adipic acid;
in the step (2), the heat stabilizer II is one or more of phosphorous acid or triphenyl phosphate;
In the step (2), the addition amount of the heat stabilizer II is 50-500ppm of the addition amount of the adipic acid;
In the step (2), the antioxidant II is one or more of an antioxidant 1010, an antioxidant 300 and an antioxidant 164;
in the step (2), the addition amount of the antioxidant II is 50-200ppm of the addition amount of the adipic acid.
In the step (2), the molar ratio of adipic acid to butanediol is 1:1.2-2.0; preferably, it is 1:1.2-1.5.
In the step (2), the esterification temperature is 160-200 ℃, the esterification pressure is 0.1-0.5 MPa, the esterification time is 90-300min, the water yield is more than or equal to 98% of the theoretical water yield and is regarded as the end of esterification, and the polymerization degree of the obtained adipic acid butanediol ester is 2-8; preferably, the esterification temperature is 180 ℃, the esterification pressure is 0.2MPa, the esterification time is 120min, 98% or more of the theoretical water yield is taken as the end of esterification, and the polymerization degree of the obtained butanediol adipate is 5.
In the step (3), the pre-polymerization reaction temperature is 210-240 ℃, the pre-polymerization pressure is 50-500Pa, the pre-polymerization time is 30-120min, and the polymerization degree of the obtained PBA prepolymer is 20-40; preferably, the pre-polycondensation reaction temperature is 220 ℃, the pre-polycondensation pressure is 200Pa, the pre-polycondensation time is 90min, and the polymerization degree of the obtained PBA prepolymer is 30-40.
Too high a polymerization degree of the PBA prepolymer may lead to a service life of the article (decrease in mechanical properties due to too fast degradation during use) and too low a polymerization degree may lead to a decrease in the crystallization ability of the PBA segment.
In the step (4), the water bath temperature is 80-95 ℃, the concentration of sodium hydroxide aqueous solution is 0.1mol/L, the amount of stearic acid is 6-10 mg, the concentration of zinc acetate aqueous solution is 0.1mol/L, and the reaction time is 1-2.5h; preferably, the water bath temperature is 90 ℃, the concentration of the sodium hydroxide aqueous solution is 0.1mol/L, the amount of stearic acid is 8mg, the concentration of the zinc acetate aqueous solution is 0.1mol/L, and the reaction time is 1.5h.
In the step (5), the final polycondensation reaction temperature is 240-260 ℃, the reaction pressure is 25-150Pa, the polycondensation time is 100-180min, and the content of stearic acid modified zinc oxide is 0.05-5wt%; preferably, the final polycondensation reaction temperature is 240 ℃, the reaction pressure is 50Pa, the polycondensation time is 150min, and the content of stearic acid modified zinc oxide is 0.25wt%.
In step (5), the intrinsic viscosity of the obtained PBAT slice is 0.8-1.2dL/g.
In the step (5), the molar content of the adipic acid butanediol ester (BA) chain segment relative to the terephthalic acid butanediol ester (BT) chain segment in the obtained PBAT slice is 80-150%.
In the step (6), the spinning temperature is 210-250 ℃, the spinning speed is 800-3000 m/min, and the draft ratio is 2-5 times; preferably, the spinning temperature is 220 ℃, the spinning speed is 2500m/min, and the draft ratio is 4 times.
The invention also provides the fast crystallizing PBAT fiber prepared by the method.
The invention also provides application of the fast crystallizing PBAT fiber in the textile field and the like.
Compared with the prior art, the invention has the remarkable advantages that:
(1) The segment regularity is improved by regulating and controlling the segment length, so that the crystallization performance of the PBAT is regulated, the stability of the PBAT is improved, and the biodegradability of the PBAT is not affected;
(2) Inorganic nano powder (namely zinc oxide modified by stearic acid) is introduced into the chain segment in an original polymerization mode, so that heterogeneous nucleation is achieved, PBAT is crystallized at high temperature, and meanwhile, the crystallization speed is increased, so that the phenomenon of sticking to rollers of the PBAT in the spinning process is avoided, and the quality of PBAT fibers is improved. Heterogeneous nucleation refers to the process in which molecules are adsorbed on the surface of solid impurities or the surface of undamaged seed crystals present in the melt to form nuclei. Heterogeneous nucleation is characterized by a variable crystallization rate and a relatively low supercooling (i.e., a temperature difference that is required for crystallization nucleation) due primarily to the presence of foreign impurities in the polymer melt, increasing the crystallization rate as heterogeneous nuclei and decreasing the free energy required for critical nuclei formation. These small additives are known as nucleating agents.
Detailed Description
The present invention will be further described in detail with reference to the following specific examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, and the present invention is not limited to the following examples. Variations and advantages that would occur to one skilled in the art are included in the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is defined by the appended claims. The procedures, conditions, reagents, experimental methods, etc. for carrying out the present invention are common knowledge and common knowledge in the art, except for those specifically mentioned below, and the present invention is not particularly limited.
Example 1a method for preparing a fast crystallizing PBAT fiber, comprising the following steps:
(1) Preparation and modification of nano ZnO particles: 8.1mg of stearic acid is dissolved in 110mL of 0.1mol/L aqueous sodium hydroxide solution at 90 ℃, stirred until the solution is completely dissolved to form solution 1, 50mL of 0.1mol/L aqueous zinc acetate solution is heated to 90 ℃ to form solution 2, then the solution 2 is slowly added dropwise to the solution 1 under the action of magnetic stirring at 90 ℃ for 2h of reaction. The white precipitate generated by the reaction is washed with distilled water after being centrifuged and washed with ethanol for three times. Finally, the product was dried in an oven at 105℃for 15h to give nucleating agent 1.
(2) Esterification reaction: 146.14g of adipic acid, 108.15g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 are added, the temperature is raised to 180 ℃, and when the water yield reaches 98% of the theoretical water yield, the esterification is considered to be finished, so that an adipic acid butanediol ester with the polymerization degree of 2 is obtained; 166.13g of terephthalic acid and 108.15g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 were added, the temperature was raised to 220 ℃, and when the water yield reached 98% of the theoretical water yield, the esterification was considered to be completed, and a terephthalic acid esterified product with a polymerization degree of 2 was obtained.
(3) Pre-polycondensation reaction: the butanediol adipate ester obtained in the second step is subjected to pre-polycondensation reaction at 220 ℃ under the pressure of 100pa for 90min to obtain the PBA prepolymer with the polymerization degree of 20.
(4) And (3) final polycondensation reaction: adding butylene terephthalate ester, PBA prepolymer and 2 wt% of nucleating agent 1 into a reaction bottle, heating to 240 ℃, starting a final polycondensation reaction, keeping the pressure below 50pa and the reaction time to 180min, and obtaining the PBAT copolyester.
(5) And (3) drying the PBAT slice in a blast oven at 80 ℃ for 48 hours, forming a primary fiber after melt extrusion, cooling by side blowing, stretching by high-power heat, and winding to prepare the non-bonded PBAT fiber. The spinning process parameters are as follows: the set temperatures of the first heating zone and the fourth heating zone are 225 ℃,230 ℃,220 ℃,220 ℃ and 225 ℃ respectively, and the heating temperature of the machine head is 225 ℃; spinning speed is 2500m/min; the cooling temperature of side air blowing is 0 ℃; the temperature of the hot stretching hot roller is 45 ℃,45 ℃,50 ℃ and 60 ℃. The prepared PBAT fiber has a breaking strength of 3.9cN/dtex and an elongation at break of 63.6%.
Example 2a method for preparing a fast crystallizing PBAT fiber, comprising the following steps:
(1) Preparation and modification of nano ZnO particles: 8.1mg of stearic acid is dissolved in 110mL of 0.1mol/L aqueous sodium hydroxide solution at 90 ℃, stirred until the solution is completely dissolved to form solution 1, 50mL of 0.1mol/L aqueous zinc acetate solution is heated to 90 ℃ to form solution 2, then the solution 2 is slowly added dropwise to the solution 1 under the action of magnetic stirring at 90 ℃ for 2h of reaction. The white precipitate generated by the reaction is washed with distilled water after being centrifuged and washed with ethanol for three times. Finally, the product was dried in an oven at 105℃for 15h to give nucleating agent 1.
(2) Esterification reaction: 146.14g of adipic acid, 108.15g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 are added, the temperature is raised to 170 ℃, and when the water yield reaches 98% of the theoretical water yield, the esterification is considered to be finished, so that an adipic acid butanediol ester with the polymerization degree of 2 is obtained; 166.13g of terephthalic acid and 108.15g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 were added, the temperature was raised to 210 ℃, and when the water yield reached 98% of the theoretical water yield, the esterification was considered to be completed, and a terephthalic acid esterified product with a polymerization degree of 2 was obtained.
(3) Pre-polycondensation reaction: the butanediol adipate ester obtained in the second step was pre-polymerized at 230℃under a pressure of 100pa for 120min to obtain a PBA prepolymer having a degree of polymerization of 30.
(4) And (3) final polycondensation reaction: adding butylene terephthalate ester, PBA prepolymer and 3 wt% of nucleating agent 1 into a reaction bottle, heating to 250 ℃, starting a final polycondensation reaction, keeping the pressure below 50pa and the reaction time to 150min, and obtaining the PBAT copolyester.
(5) And (3) drying the PBAT slice in a blast oven at 80 ℃ for 48 hours, forming a primary fiber after melt extrusion, cooling by side blowing, stretching by high-power heat, and winding to prepare the non-bonded PBAT fiber. The spinning process parameters are as follows: the set temperatures of the first heating zone and the fourth heating zone are 225 ℃,230 ℃,235 ℃,235 ℃ and 225 ℃ respectively, and the heating temperature of the machine head is 225 ℃; spinning speed is 2500m/min; the cooling temperature of side air blowing is 0 ℃; the temperature of the hot stretching hot roller is 45 ℃,45 ℃,50 ℃ and 60 ℃. The prepared PBAT fiber has a breaking strength of 4.0cN/dtex and an elongation at break of 65.4%.
Example 3 a method for preparing a fast crystallizing PBAT fiber, comprising the following steps:
(1) Preparation and modification of nano ZnO particles: 8.1mg of stearic acid is dissolved in 110mL of 0.1mol/L aqueous sodium hydroxide solution at 90 ℃, stirred until the solution is completely dissolved to form solution 1, 50mL of 0.1mol/L aqueous zinc acetate solution is heated to 90 ℃ to form solution 2, then the solution 2 is slowly added dropwise to the solution 1 under the action of magnetic stirring at 90 ℃ for 2h of reaction. The white precipitate generated by the reaction is washed with distilled water after being centrifuged and washed with ethanol for three times. Finally, the product was dried in an oven at 105℃for 15h to give nucleating agent 1.
(2) Esterification reaction: 146.14g of adipic acid, 117.16g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 are added, the temperature is raised to 180 ℃, and when the water yield reaches 98% of the theoretical water yield, the esterification is considered to be finished, so that an adipic acid butanediol esterified product with the polymerization degree of 2 is obtained; 166.13g of terephthalic acid and 117.16g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 were added, the temperature was raised to 220 ℃, and when the water yield reached 98% of the theoretical water yield, the esterification was considered to be completed, and a terephthalic acid esterified product with a polymerization degree of 2 was obtained.
(3) Pre-polycondensation reaction: the butanediol adipate ester obtained in the second step is subjected to pre-polycondensation reaction at 220 ℃ under the pressure of 100pa for 90min to obtain the PBA prepolymer with the polymerization degree of 40.
(4) And (3) final polycondensation reaction: adding butylene terephthalate ester, PBA prepolymer and 2 wt% of nucleating agent 1 into a reaction bottle, heating to 240 ℃, starting a final polycondensation reaction, keeping the pressure below 50pa and the reaction time to 180min, and obtaining the PBAT copolyester.
(5) And (3) drying the PBAT slice in a blast oven at 80 ℃ for 48 hours, forming a primary fiber after melt extrusion, cooling by side blowing, stretching by high-power heat, and winding to prepare the non-bonded PBAT fiber. The spinning process parameters are as follows: the set temperatures of the first heating zone and the fourth heating zone are 225 ℃,230 ℃,220 ℃,220 ℃ and 225 ℃ respectively, and the heating temperature of the machine head is 225 ℃; spinning speed is 2500m/min; the cooling temperature of side air blowing is 0 ℃; the temperature of the hot stretching hot roller is 45 ℃,45 ℃,50 ℃ and 60 ℃. The prepared PBAT fiber has a breaking strength of 3.7cN/dtex and an elongation at break of 72.9%.
Example 4a method for preparing a fast crystallizing PBAT fiber, comprising the following steps:
(1) Preparation and modification of nano ZnO particles: 8.1mg of stearic acid is dissolved in 110mL of 0.1mol/L aqueous sodium hydroxide solution at 90 ℃, stirred until the solution is completely dissolved to form solution 1, 50mL of 0.1mol/L aqueous zinc acetate solution is heated to 90 ℃ to form solution 2, then the solution 2 is slowly added dropwise to the solution 1 under the action of magnetic stirring at 90 ℃ for 2h of reaction. The white precipitate generated by the reaction is washed with distilled water after being centrifuged and washed with ethanol for three times. Finally, the product was dried in an oven at 105℃for 15h to give nucleating agent 1.
(2) Esterification reaction: 146.14g of adipic acid, 117.16g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 are added, the temperature is raised to 190 ℃, and when the water yield reaches 98% of the theoretical water yield, the esterification is considered to be finished, so that an adipic acid butanediol esterified product with the polymerization degree of 2 is obtained; 166.13g of terephthalic acid and 117.16g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 were added, the temperature was raised to 230 ℃, and when the water yield reached 98% of the theoretical water yield, the esterification was considered to be completed, and a terephthalic acid esterified product with a polymerization degree of 2 was obtained.
(3) Pre-polycondensation reaction: the butanediol adipate ester obtained in the second step is subjected to pre-polycondensation reaction at 220 ℃ under the pressure of 100pa for 90min to obtain the PBA prepolymer with the polymerization degree of 20.
(4) And (3) final polycondensation reaction: adding butylene terephthalate ester, PBA prepolymer and 4%wt of nucleating agent 1 into a reaction bottle, heating to 240 ℃, starting a final polycondensation reaction, keeping the pressure below 50pa and the reaction time to 180min, and obtaining the PBAT copolyester.
(5) And (3) drying the PBAT slice in a blast oven at 80 ℃ for 48 hours, forming a primary fiber after melt extrusion, cooling by side blowing, stretching by high-power heat, and winding to prepare the non-bonded PBAT fiber. The spinning process parameters are as follows: the set temperatures of the first heating zone and the fourth heating zone are 225 ℃,230 ℃,220 ℃,220 ℃ and 225 ℃ respectively, and the heating temperature of the machine head is 225 ℃; spinning speed is 2500m/min; the cooling temperature of side air blowing is 0 ℃; the temperature of the hot stretching hot roller is 45 ℃,45 ℃,50 ℃ and 60 ℃. The prepared PBAT fiber has a breaking strength of 4.0cN/dtex and an elongation at break of 52.3%.
Example 5a method for preparing a fast crystallizing PBAT fiber, comprising the following steps:
(1) Preparation and modification of nano ZnO particles: 8.1mg of stearic acid is dissolved in 110mL of 0.1mol/L aqueous sodium hydroxide solution at 90 ℃, stirred until the solution is completely dissolved to form solution 1, 50mL of 0.1mol/L aqueous zinc acetate solution is heated to 90 ℃ to form solution 2, then the solution 2 is slowly added dropwise to the solution 1 under the action of magnetic stirring at 90 ℃ for 2h of reaction. The white precipitate generated by the reaction is washed with distilled water after being centrifuged and washed with ethanol for three times. Finally, the product was dried in an oven at 105℃for 15h to give nucleating agent 1.
(2) Esterification reaction: 146.14g of adipic acid, 135.18g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 are added, the temperature is raised to 180 ℃, and when the water yield reaches 98% of the theoretical water yield, the esterification is considered to be finished, so that an adipic acid butanediol esterified product with the polymerization degree of 2 is obtained; 166.13g of terephthalic acid and 135.18g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 were added, the temperature was raised to 220 ℃, and when the water yield reached 98% of the theoretical water yield, the esterification was considered to be completed, and a terephthalic acid esterified product with a polymerization degree of 2 was obtained.
(3) Pre-polycondensation reaction: the butanediol adipate ester obtained in the second step is subjected to pre-polycondensation reaction at 220 ℃ under the pressure of 100pa for 90min to obtain the PBA prepolymer with the polymerization degree of 30.
(4) And (3) final polycondensation reaction: adding butylene terephthalate ester, PBA prepolymer and 2 wt% of nucleating agent 1 into a reaction bottle, heating to 230 ℃, starting a final polycondensation reaction, keeping the pressure below 50pa and the reaction time to 150min, and obtaining the PBAT copolyester.
(5) And (3) drying the PBAT slice in a blast oven at 80 ℃ for 48 hours, forming a primary fiber after melt extrusion, cooling by side blowing, stretching by high-power heat, and winding to prepare the non-bonded PBAT fiber. The spinning process parameters are as follows: the set temperatures of the first heating zone and the fourth heating zone are 225 ℃,230 ℃,225 ℃ and 225 ℃ respectively, and the heating temperature of the machine head is 225 ℃; spinning speed is 2500m/min; the cooling temperature of side air blowing is 0 ℃; the temperature of the hot stretching hot roller is 45 ℃,45 ℃,50 ℃ and 60 ℃. The prepared PBAT fiber has a breaking strength of 4.3cN/dtex and an elongation at break of 68.2%.
Example 6a method for preparing a fast crystallizing PBAT fiber, comprising the following steps:
(1) Preparation and modification of nano ZnO particles: 8.1mg of stearic acid is dissolved in 110mL of 0.1mol/L aqueous sodium hydroxide solution at 90 ℃, stirred until the solution is completely dissolved to form solution 1, 50mL of 0.1mol/L aqueous zinc acetate solution is heated to 90 ℃ to form solution 2, then the solution 2 is slowly added dropwise to the solution 1 under the action of magnetic stirring at 90 ℃ for 2h of reaction. The white precipitate generated by the reaction is washed with distilled water after being centrifuged and washed with ethanol for three times. Finally, the product was dried in an oven at 105℃for 15h to give nucleating agent 1.
(2) Esterification reaction: 146.14g of adipic acid, 135.18g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 are added, the temperature is raised to 170 ℃, and when the water yield reaches 98% of the theoretical water yield, the esterification is considered to be finished, so that an adipic acid butanediol esterified product with the polymerization degree of 2 is obtained; 166.13g of terephthalic acid and 135.18g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 were added, the temperature was raised to 210 ℃, and when the water yield reached 98% of the theoretical water yield, the esterification was considered to be completed, and a terephthalic acid esterified product with a polymerization degree of 2 was obtained.
(3) Pre-polycondensation reaction: the butanediol adipate ester obtained in the second step was pre-polymerized at 230℃under a pressure of 100pa for 120min to obtain a PBA prepolymer having a degree of polymerization of 40.
(4) And (3) final polycondensation reaction: adding butylene terephthalate ester, PBA prepolymer and 2%wt of nucleating agent 1 into a reaction bottle, heating to 250 ℃, starting a final polycondensation reaction, keeping the pressure below 50pa and the reaction time to 180min, and obtaining the PBAT copolyester.
(5) And (3) drying the PBAT slice in a blast oven at 80 ℃ for 48 hours, forming a primary fiber after melt extrusion, cooling by side blowing, stretching by high-power heat, and winding to prepare the non-bonded PBAT fiber. The spinning process parameters are as follows: the set temperatures of the first heating zone and the fourth heating zone are 225 ℃,230 ℃,235 ℃,235 ℃ and 225 ℃ respectively, and the heating temperature of the machine head is 225 ℃; spinning speed is 2500m/min; the cooling temperature of side air blowing is 0 ℃; the temperature of the hot stretching hot roller is 45 ℃,45 ℃,50 ℃ and 60 ℃. The prepared PBAT fiber has a breaking strength of 3.8cN/dtex and an elongation at break of 59.6%.
Comparative example 1
(1) Esterification reaction: 146.14g of adipic acid, 135.18g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 are added, the temperature is raised to 170 ℃, and when the water yield reaches 98% of the theoretical water yield, the esterification is considered to be finished, so that an adipic acid butanediol esterified product with the polymerization degree of 2 is obtained; 166.13g of terephthalic acid and 135.18g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 were added, the temperature was raised to 210 ℃, and when the water yield reached 98% of the theoretical water yield, the esterification was considered to be completed, and a terephthalic acid esterified product with a polymerization degree of 2 was obtained.
(2) Pre-polycondensation reaction: the butanediol adipate ester obtained in the second step was pre-polymerized at 230℃under a pressure of 100pa for 120min to obtain a PBA prepolymer having a degree of polymerization of 30.
(3) And (3) final polycondensation reaction: and (3) adding the butylene terephthalate ester and the PBA prepolymer into a reaction bottle, heating to 240 ℃, starting a final polycondensation reaction, keeping the pressure below 50pa and the reaction time to 180min, and obtaining the PBAT copolyester.
(4) And (3) drying the PBAT slice in a blast oven at 80 ℃ for 48 hours, forming a primary fiber after melt extrusion, cooling by side blowing, stretching by high-power heat, and winding to prepare the non-bonded PBAT fiber. The spinning process parameters are as follows: the set temperatures of the first heating zone and the fourth heating zone are 225 ℃,230 ℃,235 ℃,235 ℃ and 225 ℃ respectively, and the heating temperature of the machine head is 225 ℃; spinning speed is 2500m/min; the cooling temperature of side air blowing is 0 ℃; the temperature of the hot stretching hot roller is 45 ℃,45 ℃,50 ℃ and 60 ℃. The prepared PBAT fiber has a breaking strength of 2.3cN/dtex and an elongation at break of 37.6%.
Comparative example 2
(1) Esterification reaction: 146.14g of adipic acid, 135.18g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 are added, the temperature is raised to 170 ℃, and when the water yield reaches 98% of the theoretical water yield, the esterification is considered to be finished, so that an adipic acid butanediol esterified product with the polymerization degree of 2 is obtained; 166.13g of terephthalic acid and 135.18g of 1, 4-butanediol, 1.7g of tetrabutyl titanate, 1.6g of phosphorous acid, 0.098g of triphenyl phosphate and 0.03g of antioxidant 1010 were added, the temperature was raised to 210 ℃, and when the water yield reached 98% of the theoretical water yield, the esterification was considered to be completed, and a terephthalic acid esterified product with a polymerization degree of 2 was obtained.
(2) Pre-polycondensation reaction: the butanediol adipate ester obtained in the second step was pre-polymerized at 230℃under a pressure of 100pa for a pre-polymerization time of 100min to obtain a PBA prepolymer having a degree of polymerization of 30.
(3) And (3) final polycondensation reaction: and (3) adding the butylene terephthalate ester and the PBA prepolymer into a reaction bottle, heating to 250 ℃, starting a final polycondensation reaction, keeping the pressure below 100pa and the reaction time of 150min, and obtaining the PBAT copolyester.
(4) And (3) drying the PBAT slice in a blast oven at 80 ℃ for 48 hours, forming a primary fiber after melt extrusion, cooling by side blowing, stretching by high-power heat, and winding to prepare the non-bonded PBAT fiber. The spinning process parameters are as follows: the set temperatures of the first heating zone and the fourth heating zone are 225 ℃,230 ℃,230 ℃ and 230 ℃ respectively, and the heating temperature of the machine head is 225 ℃; spinning speed is 2500m/min; the cooling temperature of side air blowing is 0 ℃; the temperature of the hot stretching hot roller is 45 ℃,45 ℃,50 ℃ and 60 ℃. The prepared PBAT fiber has a breaking strength of 4.0cN/dtex and an elongation at break of 29.7%.
Therefore, the zinc oxide (SA-ZnO) modified by stearic acid can be used as a nucleating agent to improve the crystallization performance of the PBAT to a certain extent, effectively avoid the phenomenon that the PBAT fiber is bonded in the winding process, and improve the quality of the PBAT fiber.
The foregoing is merely illustrative of specific embodiments of the invention and is not intended to limit the invention so that modifications and advantages which will occur to those skilled in the art are included therein without departing from the spirit and principles of the invention, and the scope of the invention is defined by the appended claims.
Claims (12)
1. A fast crystallizing PBAT fiber, characterized in that said PBAT fiber comprises the following components: 100 parts of polybutylene adipate/butylene terephthalate PBAT and 0.05-5% of nucleating agent; wherein the molar content of the adipic acid butanediol ester chain segment is 80-150% relative to the terephthalic acid butanediol ester BT chain segment.
2. The fast crystallizing PBAT fiber of claim 1, wherein the PBAT fiber has a tenacity at break of 2.0 to 5.0cN/dtex and an elongation at break of 20 to 80%.
3. A preparation method of a PBAT fiber capable of crystallizing rapidly is characterized in that terephthalic acid and adipic acid are respectively esterified with butanediol to obtain a terephthalic acid butanediol ester and an adipic acid butanediol ester, the adipic acid butanediol ester is subjected to pre-polycondensation to obtain an adipic acid butanediol prepolymer, the terephthalic acid butanediol ester and the adipic acid butanediol prepolymer are mixed, zinc oxide modified by a nucleating agent stearic acid is added to carry out final polycondensation to obtain a polymer, and finally the PBAT fiber is prepared by a melt spinning method.
4. A method according to claim 3, characterized by the specific steps of:
(1) Esterification of terephthalic acid with butanediol: mixing terephthalic acid, butanediol, a catalyst I, a heat stabilizer I and an antioxidant I, and performing esterification reaction to obtain a butanediol terephthalate;
(2) Esterification of adipic acid with butanediol: mixing adipic acid, butanediol, a catalyst II, a heat stabilizer II and an antioxidant II, and performing esterification reaction to obtain adipic acid butanediol esterified product;
(3) Pre-polycondensation of adipic acid butanediol ester: carrying out pre-polycondensation reaction on the butanediol adipate obtained in the second step to obtain a PBA prepolymer;
(4) Preparation of stearic acid modified zinc oxide: dissolving stearic acid in sodium hydroxide aqueous solution under the water bath condition, dropwise adding zinc acetate aqueous solution into sodium hydroxide aqueous solution containing stearic acid under stirring, centrifuging, washing and drying a white precipitate generated by the reaction to obtain stearic acid modified zinc oxide;
(5) And (3) final polycondensation: carrying out a final polycondensation reaction on the butylene terephthalate, the PBA prepolymer and the stearic acid modified zinc oxide to obtain PBAT slices;
(6) And (3) carrying out melt spinning on the PBAT slice obtained in the fifth step to obtain the PBAT fiber.
5. The preparation method according to claim 4, wherein in the step (1), the catalyst I is one or more of tetrabutyl titanate or ethylene glycol antimony, and the addition amount of the catalyst I is 50-200ppm of the addition amount of terephthalic acid; the heat stabilizer I is one or more of phosphorous acid or triphenyl phosphate, and the addition amount of the heat stabilizer I is 50-500ppm of the addition amount of the terephthalic acid; the antioxidant I is one or more of an antioxidant 1010, an antioxidant 300 or an antioxidant 164, and the adding amount of the antioxidant I is 50-200ppm of the adding amount of the terephthalic acid;
in the step (2), the catalyst I is one or more of tetrabutyl titanate or ethylene glycol antimony, and the addition amount of the catalyst I is 50-200ppm of the addition amount of adipic acid; the heat stabilizer I is one or more than one of phosphorous acid or triphenyl phosphate, and the addition amount of the heat stabilizer I is 50-500ppm of the addition amount of adipic acid; the antioxidant I is one or more of an antioxidant 1010, an antioxidant 300 or an antioxidant 164, and the adding amount of the antioxidant I is 50-200ppm of the adding amount of the adipic acid.
6. The process of claim 4, wherein in step (1), the molar ratio of terephthalic acid to butanediol is 1:1.2-2.0; the esterification temperature is 180-230 ℃, the esterification pressure is 0.1-0.5MPa, the esterification time is 90-300min, the water yield is more than or equal to 98% of the theoretical water yield, the esterification is finished, and the polymerization degree of the obtained butylene terephthalate is 2-8; in the step (2), the molar ratio of adipic acid to butanediol is 1:1.2-2.0; the esterification temperature is 160-200 ℃, the esterification pressure is 0.1-0.5MPa, the esterification time is 90-300min, the water yield is more than or equal to 98% of the theoretical water yield, the esterification is finished, and the polymerization degree of the obtained adipic acid butanediol ester is 2-8.
7. The process according to claim 4, wherein in the step (3), the pre-polymerization reaction temperature is 210 to 240℃and the pre-polymerization pressure is 50 to 500Pa, the pre-polymerization time is 30 to 120 minutes, and the polymerization degree of the obtained PBA prepolymer is 20 to 40.
8. The process according to claim 4, wherein in the step (4), the water bath temperature is 80 to 95 ℃, the concentration of the aqueous sodium hydroxide solution is 0.1mol/L, the amount of stearic acid is 6 to 10mg, the concentration of the aqueous zinc acetate solution is 0.1mol/L, and the reaction time is 1 to 2.5 hours.
9. The process according to claim 4, wherein in the step (5), the final polycondensation reaction temperature is 240 to 260 ℃, the reaction pressure is 25 to 150Pa, the polycondensation time is 100 to 180min, and the content of the stearic acid modified zinc oxide is 0.05 to 5wt%; the intrinsic viscosity of the obtained PBAT sections was 0.8-1.2dL/g.
10. The process according to claim 4, wherein in the step (6), the spinning temperature is 210 to 250℃and the spinning speed is 800 to 3000m/min, and the draft ratio is 2 to 5 times.
11. A fast crystallizing PBAT fiber made by the method of any of claims 3-10.
12. Use of the fast crystallizing PBAT fiber of claim 1 or 11 in the textile field.
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| CN202310001069.5A CN118292137A (en) | 2023-01-03 | 2023-01-03 | PBAT fiber capable of crystallizing rapidly and preparation method thereof |
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| CN202310001069.5A CN118292137A (en) | 2023-01-03 | 2023-01-03 | PBAT fiber capable of crystallizing rapidly and preparation method thereof |
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