CN115045001A - High-melting-point PBAT copolyester fiber and preparation method thereof - Google Patents
High-melting-point PBAT copolyester fiber and preparation method thereof Download PDFInfo
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- CN115045001A CN115045001A CN202210690342.5A CN202210690342A CN115045001A CN 115045001 A CN115045001 A CN 115045001A CN 202210690342 A CN202210690342 A CN 202210690342A CN 115045001 A CN115045001 A CN 115045001A
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- pbat
- oligomer
- copolyester fiber
- acid
- amino acid
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- 239000000835 fiber Substances 0.000 title claims abstract description 120
- 229920001896 polybutyrate Polymers 0.000 title claims abstract description 112
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 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 60
- 238000009987 spinning Methods 0.000 claims abstract description 38
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 36
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 33
- 238000002844 melting Methods 0.000 claims abstract description 29
- 230000008018 melting Effects 0.000 claims abstract description 29
- 150000001413 amino acids Chemical class 0.000 claims abstract description 27
- 239000001361 adipic acid Substances 0.000 claims abstract description 18
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 18
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 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 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 4
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002074 melt spinning Methods 0.000 claims abstract description 3
- 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 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 229920002643 polyglutamic acid Polymers 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 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 13
- 238000000034 method Methods 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 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 10
- 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 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 108010020346 Polyglutamic Acid Proteins 0.000 claims description 8
- 239000012760 heat stabilizer Substances 0.000 claims description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 5
- 108010039918 Polylysine Proteins 0.000 claims description 5
- -1 amino acid butylene glycol ester Chemical class 0.000 claims description 5
- 108010064470 polyaspartate Proteins 0.000 claims description 5
- 229920000656 polylysine Polymers 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- AIABEETXTKSDLE-UHFFFAOYSA-J 2,3-dihydroxybutanedioate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O AIABEETXTKSDLE-UHFFFAOYSA-J 0.000 claims description 2
- MSYNCHLYGJCFFY-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;titanium(4+) Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O MSYNCHLYGJCFFY-UHFFFAOYSA-B 0.000 claims description 2
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 claims description 2
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- ZTNIBBZMDWOVCJ-UHFFFAOYSA-N butane-1,4-diol;titanium Chemical compound [Ti].OCCCCO ZTNIBBZMDWOVCJ-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 2
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- CTSAXXHOGZNKJR-UHFFFAOYSA-N methyl 2-diethoxyphosphorylacetate Chemical compound CCOP(=O)(OCC)CC(=O)OC CTSAXXHOGZNKJR-UHFFFAOYSA-N 0.000 claims description 2
- SIGOIUCRXKUEIG-UHFFFAOYSA-N methyl 2-dimethoxyphosphorylacetate Chemical compound COC(=O)CP(=O)(OC)OC SIGOIUCRXKUEIG-UHFFFAOYSA-N 0.000 claims description 2
- 108010054442 polyalanine Proteins 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- ZPCURARBHFHEFQ-UHFFFAOYSA-N propane-1,2-diol;titanium Chemical compound [Ti].CC(O)CO ZPCURARBHFHEFQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 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
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 claims description 2
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 claims description 2
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 claims description 2
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005453 pelletization Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000376 reactant Substances 0.000 description 13
- 238000005886 esterification reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000004804 winding Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 241000662429 Fenerbahce Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003275 alpha amino acid group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a high melting point PBAT copolyester fiber and a preparation method thereof, wherein the PBAT copolyester fiber comprises mother particles as follows: a butylene terephthalate segment, a butylene adipate segment, and an amino acid butylene glycol segment. The preparation method comprises the following steps: (1) reacting adipic acid, terephthalic acid and 1, 4-Butanediol (BDO) to obtain an oligomer A; (2) reacting the oligomer A with an amino acid oligomer to obtain PBAT copolyester fiber master batch; (3) drying the PBAT copolyester fiber master batch, and then carrying out melt spinning to obtain the high-melting-point PBAT copolyester fiber. The PBAT copolyester fiber has higher melting point and melt strength by introducing amino acid oligomer with a linear chain fiber framework for copolymerization, reduces the yarn breakage of PBAT at high spinning temperature, realizes continuous and stable high-speed spinning, and has performance quality meeting the requirements of downstream products.
Description
Technical Field
The invention belongs to the field of synthesis of high polymer materials, and particularly relates to a high-melting-point PBAT copolyester fiber and a preparation method thereof.
Background
As a biodegradable copolyester, the PBAT not only has good thermal stability and mechanical property of PBT, but also has good stretchability and ductility of aliphatic polyester, and can be degraded into water and carbon dioxide under natural conditions. Therefore, the film can be widely applied to the fields of packaging, medical treatment, agricultural films and the like.
As a degradable plastic with excellent performance, PBAT can be used in the field of textile and clothing as well. However, there are few reports on PBAT fiber spinning, and most of them are spun after blending with other polymer materials. Mainly because the PBAT has low melting point, low melt strength and low crystallization speed in the high-temperature spinning process, the PBAT fiber can be broken at high spinning temperature, so that the fiber can not be continuously and stably formed, and the application and popularization of the PBAT fiber are seriously restricted.
Therefore, the preparation of PBAT fibers with good performance has important practical significance. The cooling distance is lengthened in patent 201210349313.9, so that the problems that the spinning process is not easy to cool and easy to bond are solved, but the performance of the polymer is not improved, and the investment of post processing equipment and site cost is increased. In patent 202110337999.9, adipic acid and terephthalic acid are esterified and pre-condensed respectively, and then mixed to perform final condensation, so as to adjust the chain length between the components, thereby improving the crystallization performance of PBAT and improving the spinning stability of PBAT fibers. However, because the final condensation is a transesterification process, the obtained PBAT is still a random copolymer and has no obvious influence on the crystallization performance, and meanwhile, the introduced third component can also influence the molecular chain regularity and destroy the crystallization of the PBAT.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a PBAT copolyester fiber and a preparation method thereof, wherein a third component amino acid oligomer with a linear chain fiber skeleton is introduced for copolymerization, so that the PBAT copolyester fiber has higher melting point and melt strength on the premise of keeping good mechanical comprehensive performance, avoids the phenomenon of yarn breakage in high-temperature spinning, and greatly widens the application of PBAT in the field of fiber spinning. The introduced amino acid oligomer is non-toxic, easy to disperse and biodegradable, and the degradability and biocompatibility of the copolyester are not influenced.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a high melting PBAT copolyester fiber, the PBAT copolyester fiber having a matrix comprising: a butylene terephthalate chain segment, a butylene adipate chain segment and an amino acid butylene glycol ester chain segment;
wherein the molar content of the butanediol adipate segment is 50-150%, preferably 80-120%, and more preferably 100-120% with respect to the butanediol terephthalate segment.
The molar content of the amino acid butylene glycol segment is 1.0 to 4.0%, preferably 2.0 to 3.0%, and more preferably 2.5% with respect to the butylene terephthalate segment.
In the invention, the amino acid butanediol ester segment, wherein the amino acid chain segment is derived from amino acid oligomer, and the number average molecular weight of the amino acid oligomer is 0.1-0.5 × 10 5 g/mol;
preferably, the amino acid oligomer is selected from any one of or a combination of at least two of polyglutamic acid, polyaspartic acid, polylysine and polyalanine, preferably polyglutamic acid.
In the high-melting-point PBAT copolyester fiber, the melting point of the PBAT copolyester is increased and then slightly reduced along with the increase of the proportion of the amino acid butanediol ester chain segment. When the molar content of the amino acid butanediol ester chain segment is lower than 1.0 percent relative to the butanediol terephthalate chain segment, the content of the amino acid oligomer is too small, so that the PBAT performance is not obviously improved, and the melting point, the melt strength and the fiber mechanical property are not obviously improved; with the further increase of the chain segment of the amino acid butanediol ester chain segment, the melting point of the copolyester is gradually increased, and the melt strength and the fiber tensile strength of the copolyester are obviously improved; when the content of the amino acid butanediol ester chain segment is higher than 4.0%, the irregularity of the copolyester chain segment is intensified, and the crystallinity is reduced, so that the melting point of the copolyester is reduced. Therefore, the molar content of the amino acid butylene glycol segment is 1.0 to 4.0%, preferably 2.0 to 3.0%, more preferably 2.5% with respect to the butylene terephthalate segment.
In a second aspect, the invention also provides a preparation method of the high-melting-point PBAT copolyester fiber, which comprises the following steps:
(1) reacting adipic acid, terephthalic acid and 1, 4-Butanediol (BDO) to obtain an oligomer A;
(2) reacting the oligomer A with an amino acid oligomer to obtain PBAT copolyester fiber master batch;
(3) drying the PBAT copolyester fiber master batch, and then carrying out melt spinning to obtain the high-melting-point PBAT copolyester fiber.
In the invention, step (1) is specifically to uniformly mix adipic acid, terephthalic acid, 1, 4-butanediol and a titanium catalyst, perform esterification reaction for 2-3h, preferably 2-2.5h, at 190-220 ℃, preferably 200-210 ℃, then perform prepolymerization reaction for 1-1.5h, raising the temperature to 230-240 ℃, preferably 240 ℃, and gradually reducing the pressure to 500-1000PaA, preferably 600-800PaA during the prepolymerization reaction to obtain the oligomer A.
In the step (1), the molar ratio of the addition amount of the 1, 4-butanediol to the sum of the addition amounts of the adipic acid and the terephthalic acid is 1.1-2.0:1, preferably 1.4-1.6: 1;
the molar ratio of the addition of adipic acid to the addition of terephthalic acid is from 0.5 to 1.5:1, preferably from 1 to 1.2: 1.
In the step (1), the dosage of the titanium catalyst is 60-160ppm, preferably 90-130ppm of the total mass of the succinic acid, the terephthalic acid and the 1, 4-butanediol based on the mass of titanium element therein;
preferably, the titanium-based catalyst is selected from any one or a combination of at least two of titanium dioxide, n-butyl titanate, isopropyl titanate, tetraisopropyl titanate, tetraisobutyl titanate, tetraisooctyl titanate, titanium acetate, titanium lactate, titanium tartrate, titanium citrate, titanium glycol, titanium propylene glycol and titanium butylene glycol, and is preferably n-butyl titanate.
In the step (1), after the oligomer A is dissolved in chloroform, the number average molecular weight of the oligomer A is measured to be 0.5 to 2.0 x 10 by a gel chromatograph 5 g/mol.
The oligomer A takes a solution of phenol-tetrachloroethane (volume ratio is 1:1) as a solvent, and the intrinsic viscosity is between 0.1 and 0.6dL/g measured by an Ubbelohde viscometer.
In the invention, the step (2) is specifically to mix the oligomer A, the amino acid oligomer and the heat stabilizer, perform copolymerization reaction for 3-4h, preferably 3-3.5h at the temperature of 230-250 ℃, preferably 235-245 ℃ and the vacuum degree of 10-200Pa, preferably 10-100Pa, extrude under the protection of nitrogen, cool to room temperature and cut into particles to obtain the PBAT copolyester fiber master batch.
In the step (2), the molar ratio of the amino acid oligomer to the terephthalic acid in the step (1) is 0.01-0.04:1, preferably 0.02-0.03: 1;
in the step (2), the heat stabilizer is a phosphorus compound, and the addition amount of the heat stabilizer in the system is 20-70ppm, preferably 30-60ppm based on the mass of phosphorus element;
preferably, the heat stabilizer is selected from any one of phosphoric acid, phosphorous acid, triphenyl phosphite, triphenyl phosphate, sodium hypophosphite, sodium phosphite, disodium hydrogen phosphate, calcium hypophosphite, calcium phosphite, triphenyl phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triethyl phosphonoacetate, trimethyl phosphonoacetate, diethyl methylphosphonoacetate, polyphosphoric acid or a combination of at least two thereof, preferably triethyl phosphate.
In the step (2), the moisture content of the PBAT copolyester fiber master batch is 0-50ppm, preferably 0-20 ppm.
In the step (2), the PBAT copolyester fiber master batch is dissolved in chloroform, and the number average molecular weight is measured to be 2.5-3.5 multiplied by 10 by a gel chromatograph 5 g/mol.
In the step (2), the PBAT copolyester fiber master batch takes a solution of phenol-tetrachloroethane (volume ratio of 1:1) as a solvent, and the intrinsic viscosity is measured by a Ubbelohde viscometer to be between 1.2 and 1.8 dL/g.
In the invention, the step (3) is to dry the PBAT copolyester fiber master batch at 80-100 ℃, preferably 80 ℃, for 20-24 hours, preferably 24 hours, and then to perform fiber spinning, wherein the spinning temperature is 170-.
In the invention, the high-melting-point PBAT copolyester fiber has a water content of 0-50ppm measured by a Karl Fischer moisture titrator.
In the invention, the melting point of the high-melting-point PBAT copolyester fiber is measured by a differential scanning calorimeter to be between 125 ℃ and 140 ℃.
In the invention, the melt strength of the high-melting-point PBAT copolyester fiber is measured by a melt extensional rheometer to be between 60 and 80F/mN.
In the invention, the tensile strength of the high-melting-point PBAT copolyester fiber is measured by a universal material testing machine to be between 3.0 and 5.0cN/dtex, and the elongation at break is between 40 and 70 percent.
In the invention, the high-melting-point PBAT copolyester fiber is measured for fiber diameter by adopting a three-dimensional microscopic system, and the fiber fineness is calculated to be between 10 and 20 dtex.
According to research, the amino acid oligomer with a linear chain fiber skeleton is introduced in a certain proportion in the preparation process of the PBAT fiber, so that the melting point and the melt strength of the PBAT copolyester can be effectively improved, the yarn breakage phenomenon under high-temperature spinning is avoided, and the PBAT fiber also has good mechanical properties. Firstly, the amino acid oligomer contains a large number of amido bonds, so that the melting point of PBAT copolyester can be effectively improved, and the thermal stability of PBAT at high spinning temperature is improved; secondly, the amino acid oligomer has a fiber skeleton structure, so that the copolyester can be endowed with better melt strength, and the phenomenon of yarn breakage in the spinning process is avoided; and finally, the amino acid oligomer is non-toxic and degradable, and the degradable performance of the PBAT can not be influenced while the thermodynamic performance of the copolyester is improved. Therefore, the application prospect of the PBAT copolyester in the field of degradable fibers is greatly expanded through copolymerization modification with amino acid oligomer.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the invention introduces amino acid oligomer for copolymerization in the PBAT synthesis process, the melting point can be increased by 5-20 ℃, the melt strength can be increased by 10-30F/mN, so that the PBAT copolyester is not easy to break in the fiber spinning process, the tensile strength of the prepared PBAT copolyester fiber is 3.0-5.0cN/dtex, the elongation at break is 40-70%, the performance requirement of the PBAT copolyester in the fiber spinning field is met, the competitiveness of the PBAT in the biodegradable fiber field is greatly improved, and better technical effect is obtained.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
The examples of the present invention employ, but are not limited to, the following raw materials:
gamma-polyglutamic acid: laddin, M n ＝0.1-2.0×10 5 g/mol；
Polyaspartic acid: ron, M n ＝0.1×10 5 g/mol；
Polylysine: adamas, M n ＝0.2×10 5 g/mol；
1, 4-butanediol, adipic acid, terephthalic acid, tetrabutyl titanate and triethyl phosphate are all commercially available, and all of the other raw materials are common commercially available raw materials unless otherwise specified.
The main properties of the PBAT copolyester fibers in the examples of the invention were tested by the following methods:
a) relative molecular mass: the relative molecular mass of the polymer was tested by Waters gel chromatography with chloroform as the mobile phase, an outflow rate of 1mL/min, a temperature of 40 ℃ and a standard of narrow-distribution polystyrene.
b) Intrinsic viscosity: according to the national standard GB/T1632.5-2008, the intrinsic viscosity is measured by using a phenol-tetrachloroethane (1:1) solution as a solvent and adopting an Ubbelohde viscometer.
c) Melting point: the melting point of the copolyester was measured using a Pris 1 model differential scanning calorimeter from Perkins Elmer, by first heating the sample to 180 ℃ at 20 ℃/min, eliminating the thermal history, then cooling to-30 ℃ at 20 ℃/min, and then increasing the temperature at 10 ℃/min to obtain the DSC curve of the sample.
d) Melt strength: testing the strength of the copolyester melt by using a Rheotens melt tensile rheometer of Gottfert company, and starting up to correct the maximum force value of Rheotens to be 2N and the zero point to be 0N; putting a sample into a Lebtech extruder (length-diameter ratio 30/1, neck ring diameter 2mm), extruding melt lines at 180 ℃, sampling and weighing in unit time to calculate the melt extrusion rate to be synchronous with the initial rotation speed of Rheotens, inserting the melt lines into Rheotens test rollers, finely adjusting the relative force value to be 0, performing accelerated test on the test rollers by 6mm/s2, recording the force value change in the accelerated stretching process until the melt lines break, taking the maximum value of the break as the melt strength value, and performing repeated test for 5 times to obtain the average value.
e) The mechanical properties of the fiber are as follows: cutting off the middle part of the collected copolyester nascent fiber, wherein the length is 20mm, testing by adopting a universal material testing machine at a tensile rate of 20mm/min and a clamping spacing of 10mm, and performing at least 10 repeated experiments on each group.
Examples 1 to 7 and comparative examples 1 to 4:
[ example 1 ]
Preparation of high melting point PBAT copolyester fiber:
(1) reacting 1, 4-butanediol, adipic acid and terephthalic acid in a molar ratio of 1.6: 0.53: 0.47, adding tetrabutyl titanate (calculated by the mass of titanium element) with the total mass of reactants of 86ppm, uniformly mixing, carrying out esterification reaction for 2 hours at 200 ℃, then heating to 240 ℃, carrying out prepolymerization reaction for 1 hour, and gradually reducing the pressure to 600PaA during the reaction to obtain an oligomer A;
the number average molecular weight of oligomer A was 1.0X 10 5 g/mol, and the intrinsic viscosity is 0.2 dL/g.
(2) Reacting the oligomer A of the step (1) with gamma-polyglutamic acid (M) n ＝0.1×10 5 g/mol), triethyl phosphate, the molar ratio of gamma-polyglutamic acid to the terephthalic acid of the step (1) is 0.01: 1, the triethyl phosphate accounts for 30ppm of the mass of the phosphorus element in the system, the copolymerization reaction is carried out for 3.2h at 235 ℃ and under the pressure of 80PaA, the extrusion is carried out under the protection of nitrogen after the reaction is finished, the cooling is carried out to room temperature, and the granules are cut to obtain the triethyl phosphateTo PBAT copolyester fiber master batch; wherein the molar content of the butanediol adipate chain segment is 112.8 percent relative to the butanediol terephthalate chain segment, and the molar content of the amino acid butanediol ester chain segment is 1.0 percent relative to the butanediol terephthalate chain segment;
PBAT copolyester fiber master batch has number average molecular weight of 3.0 multiplied by 10 5 g/mol, intrinsic viscosity 1.68dL/g, water content 35 ppm.
(3) Drying the PBAT copolyester fiber master batch at 80 ℃ for 24 hours, and then carrying out fiber spinning at the spinning temperature of 190 ℃, the spinning winding speed of 1400m/min, the hot drawing temperature of 100 ℃ and the drawing multiple of 3.0 times to obtain the high-melting-point PBAT copolyester fiber.
[ example 2 ]
Preparation of high melting point PBAT copolyester fiber:
(1) reacting 1, 4-butanediol, adipic acid and terephthalic acid in a molar ratio of 1.5: 0.52: 0.48, adding 96ppm by mass of isopropyl titanate (calculated by the mass of titanium element in the isopropyl titanate) of the total mass of reactants, uniformly mixing, carrying out esterification reaction for 2.0h at 205 ℃, then heating to 240 ℃, carrying out prepolymerization reaction for 1h, and gradually reducing the pressure to 600PaA during the reaction to obtain an oligomer A;
the number average molecular weight of oligomer A was 1.2X 10 5 g/mol, and the intrinsic viscosity is 0.23 dL/g.
(2) Reacting the oligomer A of the step (1) with gamma-polyglutamic acid (M) n ＝0.1×10 5 g/mol), triphenyl phosphate, and the molar ratio of gamma-polyglutamic acid to the terephthalic acid of the step (1) is 0.02: 1, triphenyl phosphate accounts for 35ppm in the system by mass of phosphorus element, and is subjected to copolymerization reaction for 3.0 hours at the temperature of 240 ℃ and under the pressure of 60PaA, and after the reaction is finished, the triphenyl phosphate is extruded under the protection of nitrogen, cooled to room temperature and then cut into particles to obtain PBAT copolyester fiber master batches; wherein the molar content of the butanediol adipate chain segment is 108.3 percent relative to the butanediol terephthalate chain segment, and the molar content of the amino acid butanediol ester chain segment is 2.0 percent relative to the butanediol terephthalate chain segment;
PBAT copolyester fiber master batch has number average molecular weight of 2.8 multiplied by 10 5 g/mol, intrinsic viscosity 1.53dL/g, water content 33 ppm.
(3) Drying the PBAT copolyester fiber master batch at 80 ℃ for 24h, and then carrying out fiber spinning at the spinning temperature of 190 ℃, the spinning winding speed of 1350m/min, the hot traction temperature of 95 ℃ and the traction multiple of 3.0 times to obtain the high-melting-point PBAT copolyester fiber.
[ example 3 ]
Preparation of high melting point PBAT copolyester fiber:
(1) reacting 1, 4-butanediol, adipic acid and terephthalic acid serving as reactants according to a mol ratio of 1.4: 0.54: 0.46, adding titanium dioxide (calculated by the mass of titanium element) with the total mass of reactants of 120ppm, uniformly mixing, carrying out esterification reaction for 2.0h at 205 ℃, then raising the temperature to 240 ℃, carrying out prepolymerization reaction for 1h, and gradually reducing the pressure to 600PaA during the reaction to obtain oligomer A;
the number average molecular weight of oligomer A was 1.2X 10 5 g/mol, and the intrinsic viscosity is 0.23 dL/g.
(2) Reacting the oligomer A of the step (1) with gamma-polyglutamic acid (M) n ＝0.1×10 5 g/mol), triphenyl phosphate, and the molar ratio of gamma-polyglutamic acid to the terephthalic acid of the step (1) is 0.03:1, triphenyl phosphate accounts for 35ppm in the system by mass of phosphorus element, and is subjected to copolymerization reaction for 3.0 hours at the temperature of 240 ℃ and under the pressure of 60PaA, and after the reaction is finished, the triphenyl phosphate is extruded under the protection of nitrogen, cooled to room temperature and then cut into particles to obtain PBAT copolyester fiber master batches; wherein the molar content of the butanediol adipate segment is 117.4 percent relative to the butanediol terephthalate segment, and the molar content of the amino acid butanediol ester segment is 3.0 percent relative to the butanediol terephthalate segment;
PBAT copolyester fiber master batch has number average molecular weight of 2.7 multiplied by 10 5 g/mol, intrinsic viscosity 1.48dL/g, water content 20 ppm.
(3) Drying the PBAT copolyester fiber master batch at 80 ℃ for 24h, and then carrying out fiber spinning at the spinning temperature of 190 ℃, the spinning winding speed of 1350m/min, the hot traction temperature of 95 ℃ and the traction multiple of 3.0 times to obtain the high-melting-point PBAT copolyester fiber.
[ example 4 ]
Preparation of high melting point PBAT copolyester fiber:
(1) reacting 1, 4-butanediol, adipic acid and terephthalic acid serving as reactants according to a mol ratio of 1.4: 0.55: 0.45, adding 124ppm by mass of tetraisooctyl titanate (based on the mass of titanium element in the tetraisooctyl titanate) of the total mass of reactants, uniformly mixing, carrying out esterification reaction at 210 ℃ for 2.5h, then heating to 240 ℃, carrying out prepolymerization reaction for 1.5h, and gradually reducing the pressure to 700PaA during the reaction to obtain an oligomer A;
the number-average molecular weight of oligomer A was 1.1X 10 5 g/mol, and the intrinsic viscosity is 0.22 dL/g.
(2) Reacting the oligomer A of the step (1) with gamma-polyglutamic acid (M) n ＝0.1×10 5 g/mol), triphenyl phosphite, and the molar ratio of gamma-polyglutamic acid to terephthalic acid of step (1) is 0.035: 1, triphenyl phosphite with the content of 55ppm in the system by mass of phosphorus element, carrying out copolymerization reaction for 3.2h at 245 ℃ and under the pressure of 80PaA, extruding under the protection of nitrogen after the reaction is finished, cooling to room temperature, and then cutting into particles to obtain PBAT copolyester fiber master batches; wherein the molar content of the butanediol adipate chain segment is 122.2 percent relative to the butanediol terephthalate chain segment, and the molar content of the amino acid butanediol chain segment is 3.5 percent relative to the butanediol terephthalate chain segment;
PBAT copolyester fiber master batch has number average molecular weight of 2.8 multiplied by 10 5 g/mol, intrinsic viscosity 1.56dL/g, water content 45 ppm.
(3) Drying the PBAT copolyester fiber master batch at 80 ℃ for 24h, and then carrying out fiber spinning at the spinning temperature of 190 ℃, the spinning winding speed of 1350m/min, the hot traction temperature of 95 ℃ and the traction multiple of 3.0 times to obtain the high-melting-point PBAT copolyester fiber.
[ example 5 ]
Preparation of high melting point PBAT copolyester fiber:
(1) reacting 1, 4-butanediol, adipic acid and terephthalic acid serving as reactants according to a mol ratio of 1.4: 0.53: 0.47, adding 128ppm by mass of tetraisopropyl titanate (based on the mass of titanium element) of the total mass of reactants, uniformly mixing, carrying out esterification reaction at 210 ℃ for 2.0h, then heating to 240 ℃, carrying out prepolymerization reaction for 1.0h, and gradually reducing the pressure to 900PaA during the reaction to obtain an oligomer A;
the number average molecular weight of oligomer A was 0.9X 10 5 g/mol, and the intrinsic viscosity is 0.18 dL/g.
(2) Reacting the oligomer A of the step (1) with gamma-polyglutamic acid (M) n ＝0.1×10 5 g/mol), trimethyl phosphate, and the molar ratio of the gamma-polyglutamic acid to the terephthalic acid in the step (1) is 0.04:1, taking the content of trimethyl phosphate in a system by mass of phosphorus element as 65ppm, carrying out copolymerization reaction for 3.8h at 250 ℃ and under the pressure of 150PaA, extruding under the protection of nitrogen after the reaction is finished, cooling to room temperature, and then cutting into particles to obtain PBAT copolyester fiber master batch; wherein the molar content of the butanediol adipate chain segment is 112.8 percent relative to the butanediol terephthalate chain segment, and the molar content of the amino acid butanediol ester chain segment is 4.0 percent relative to the butanediol terephthalate chain segment;
PBAT copolyester fiber master batch has number average molecular weight of 2.5 multiplied by 10 5 g/mol, intrinsic viscosity 1.43dL/g, water content 47 ppm.
(3) Drying the PBAT copolyester fiber master batch at 80 ℃ for 24 hours, and then carrying out fiber spinning at the spinning temperature of 180 ℃, the spinning winding speed of 1400m/min, the hot drawing temperature of 100 ℃ and the drawing multiple of 3.5 times to obtain the high-melting-point PBAT copolyester fiber.
[ example 6 ]
Preparation of high melting point PBAT copolyester fiber:
(1) reacting 1, 4-butanediol, adipic acid and terephthalic acid serving as reactants according to a mol ratio of 1.4: 0.50: 0.50, adding 88ppm of n-butyl titanate (based on the mass of titanium element) of the total mass of reactants, uniformly mixing, carrying out esterification reaction for 3.0h at 200 ℃, then heating to 240 ℃, carrying out prepolymerization reaction for 1.5h, and gradually reducing the pressure to 500PaA during the reaction to obtain an oligomer A;
oligomer A number average molecular weight of 1.4X 10 5 g/mol, and the intrinsic viscosity is 0.30 dL/g.
(2) Reacting the oligomer A of step (1) with polyaspartic acid (M) n ＝0.1×10 5 g/mol), triethyl phosphate, the molar ratio of polyaspartic acid to terephthalic acid of step (1) being 0.03:1, the triethyl phosphate accounts for 45ppm of the mass of the phosphorus in the system at 245℃,Carrying out copolymerization reaction for 3.6h under the pressure of 80PaA, extruding under the protection of nitrogen after the reaction is finished, cooling to room temperature, and then cutting into particles to obtain PBAT copolyester fiber master batches; wherein the molar content of the butanediol adipate chain segment is 100.0 percent relative to the butanediol terephthalate chain segment, and the molar content of the amino acid butanediol ester chain segment is 3.0 percent relative to the butanediol terephthalate chain segment;
PBAT copolyester fiber master batch has number average molecular weight of 2.6 multiplied by 10 5 g/mol, intrinsic viscosity 1.51dL/g, water content 38 ppm.
(3) Drying the PBAT copolyester fiber master batch at 80 ℃ for 24h, and then carrying out fiber spinning at the spinning temperature of 180 ℃, the spinning winding speed of 1250m/min, the hot drawing temperature of 100 ℃ and the drawing multiple of 3.0 times to obtain the high-melting-point PBAT copolyester fiber.
[ example 7 ]
Preparation of high melting point PBAT copolyester fiber:
(1) reacting 1, 4-butanediol, adipic acid and terephthalic acid serving as reactants according to a mol ratio of 1.4: 0.53: 0.47, adding 110ppm by mass of the total mass of reactants of n-butyl titanate (based on the mass of titanium element in the reactant) and uniformly mixing, carrying out esterification reaction for 2.0h at 200 ℃, then raising the temperature to 240 ℃, carrying out prepolymerization reaction for 1.0h, and gradually reducing the pressure to 800PaA during the reaction to obtain an oligomer A;
the number average molecular weight of oligomer A was 1.5X 10 5 g/mol, and the intrinsic viscosity is 0.32 dL/g.
(2) Reacting the oligomer A of step (1) with polylysine (M) n ＝0.2×10 5 g/mol), triethyl phosphate, the molar ratio of polylysine to terephthalic acid of step (1) being 0.03:1, triethyl phosphate accounts for 55ppm of the mass of phosphorus in the system, the copolymerization reaction is carried out for 3.5h at 245 ℃ and under the pressure of 40PaA, the extrusion is carried out under the protection of nitrogen after the reaction is finished, and the extrusion is carried out after the reaction is cooled to room temperature and then the extrusion is carried out, so as to obtain PBAT copolyester fiber master batches; wherein the molar content of the butanediol adipate chain segment is 112.8 percent relative to the butanediol terephthalate chain segment, and the molar content of the amino acid butanediol ester chain segment is 3.0 percent relative to the butanediol terephthalate chain segment;
PBAT copolyester fiber motherThe particle number average molecular weight is 2.9X 10 5 g/mol, intrinsic viscosity 1.63dL/g, water content 32 ppm.
(3) Drying the PBAT copolyester fiber master batch at 80 ℃ for 24 hours, and then carrying out fiber spinning at the spinning temperature of 180 ℃, the spinning winding speed of 1350m/min, the hot traction temperature of 90 ℃ and the traction multiple of 3.5 times to obtain the high-melting-point PBAT copolyester fiber.
Comparative example 1
PBAT copolyester fibers were prepared by referring to the method of example 1, except that polyglutamic acid was not added in step (2), and the other operations were not changed.
In the obtained PBAT copolyester fiber master batch, the molar content of the butanediol adipate chain segment is 112.8 percent relative to the butanediol terephthalate chain segment, and the molar content of the amino acid butanediol ester chain segment is 0 percent relative to the butanediol terephthalate chain segment.
Comparative example 2
PBAT copolyester fibers were prepared with reference to the procedure of example 1, except that the amount of polyglutamic acid added in step (2) was 0.05 in terms of the molar ratio of terephthalic acid in step (1): 1, the other operations were not changed.
In the obtained PBAT copolyester fiber master batch, the molar content of the butanediol adipate chain segment is 112.8 percent relative to the butanediol terephthalate chain segment, and the molar content of the amino acid butanediol ester chain segment is 5.0 percent relative to the butanediol terephthalate chain segment.
Comparative example 3
PBAT copolyester fiber was prepared by referring to the method of example 1, except that gamma-polyglutamic acid (M) was used in step (2) n ＝0.1×10 5 g/mol) is replaced by high polymer polyglutamic acid M n ＝2.0×10 5 g/mol, all other operations were unchanged.
In the obtained PBAT copolyester fiber master batch, the molar content of the butanediol adipate chain segment is 112.8 percent relative to the butanediol terephthalate chain segment, and the molar content of the amino acid butanediol ester chain segment is 3.0 percent relative to the butanediol terephthalate chain segment.
Comparative example 4
The PBAT copolyester fiber was prepared by referring to the method of example 1, except that polyglutamic acid in step (2) was added in step (1) instead, and the other operations were not changed.
In the obtained PBAT copolyester fiber master batch, the molar content of the butanediol adipate chain segment is 112.8 percent relative to the butanediol terephthalate chain segment, and the molar content of the amino acid butanediol ester chain segment is 3.0 percent relative to the butanediol terephthalate chain segment.
The molecular weight, intrinsic viscosity, melting point, water content, fineness, melt strength and fiber mechanical properties of the PBAT copolyester fibers provided in examples 1 to 7 and comparative examples 1 to 4 were tested by the aforementioned methods, and the test results are shown in table 1:
TABLE 1
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A high melting PBAT copolyester fiber, wherein the PBAT copolyester fiber has a matrix comprising: a butylene terephthalate chain segment, a butylene adipate chain segment and an amino acid butylene glycol ester chain segment;
wherein the molar content of the butanediol adipate segment is 50-150%, preferably 80-120%, and more preferably 100-120% with respect to the butanediol terephthalate segment.
The molar content of the amino acid butylene glycol segment is 1.0 to 4.0%, preferably 2.0 to 3.0%, and more preferably 2.5% with respect to the butylene terephthalate segment.
2. The high melting point PBAT copolyester fiber of claim 1, wherein the amino acid butylene glycol ester segment, in which the amino acid segment is derived from an amino acid oligomer having a number average molecular weight of 0.1-0.5 x 10 5 g/mol;
preferably, the amino acid oligomer is selected from any one of or a combination of at least two of polyglutamic acid, polyaspartic acid, polylysine and polyalanine, preferably polyglutamic acid.
3. The high melting PBAT copolyester fiber of claim 1 or 2, wherein the high melting PBAT copolyester fiber has a water content of 0-50ppm, a melting point of 125-140 ℃, a melt strength of 60-80F/mN, a tensile strength of 3.0-5.0cN/dtex, an elongation at break of 40-70%, and a fiber fineness of 10-20 dtex.
4. A method of preparing the high melting PBAT copolyester fiber of any of claims 1-3, comprising the steps of:
(1) reacting adipic acid, terephthalic acid and 1, 4-butanediol to obtain an oligomer A;
(2) reacting the oligomer A with an amino acid oligomer to obtain PBAT copolyester fiber master batch;
(3) drying the PBAT copolyester fiber master batch, and then carrying out melt spinning to obtain the high-melting-point PBAT copolyester fiber.
5. The preparation method according to claim 4, wherein the step (1) comprises mixing adipic acid, terephthalic acid, 1, 4-butanediol and titanium catalyst uniformly, esterifying at 220 ℃, 200 ℃ and 210 ℃ for 2-3h, preferably 2-2.5h, heating to 230 ℃ and 240 ℃ for prepolymerization for 1-1.5h, and gradually reducing the pressure during the prepolymerization to 500 ℃ and 1000Pa, preferably 600Pa, to obtain the oligomer A.
6. The production method according to claim 4 or 5, wherein in the step (1), the molar ratio of the added amount of the 1, 4-butanediol to the sum of the added amounts of the adipic acid and the terephthalic acid is 1.1-2.0:1, preferably 1.4-1.6: 1;
the molar ratio of the addition amount of the adipic acid to the addition amount of the terephthalic acid is 0.5-1.5:1, preferably 1-1.2: 1; and/or
In the step (1), the dosage of the titanium catalyst is 60-160ppm, preferably 90-130ppm of the total mass of the succinic acid, the terephthalic acid and the 1, 4-butanediol based on the mass of titanium element in the titanium catalyst;
preferably, the titanium-based catalyst is selected from any one or a combination of at least two of titanium dioxide, n-butyl titanate, isopropyl titanate, tetraisopropyl titanate, tetraisobutyl titanate, tetraisooctyl titanate, titanium acetate, titanium lactate, titanium tartrate, titanium citrate, titanium glycol, titanium propylene glycol and titanium butylene glycol, and is preferably n-butyl titanate.
7. The preparation method according to any one of claims 4-6, characterized in that step (2) is mixing the oligomer A, the amino acid oligomer and the heat stabilizer, carrying out copolymerization reaction at 230-250 ℃, preferably 235-245 ℃ and 10-200Pa, preferably 10-100Pa vacuum degree for 3-4h, preferably 3-3.5h, then extruding under the protection of nitrogen, cooling to room temperature, and then pelletizing to obtain the PBAT copolyester fiber master batch.
8. The process according to any one of claims 4 to 7, wherein in step (2), the molar ratio of the amino acid oligomer to the terephthalic acid in step (1) is from 0.01 to 0.04:1, preferably from 0.02 to 0.03: 1; and/or
In the step (2), the heat stabilizer is a phosphorus compound, and the addition amount of the heat stabilizer in the system is 20-70ppm, preferably 30-60ppm based on the mass of phosphorus element;
preferably, the heat stabilizer is selected from any one of phosphoric acid, phosphorous acid, triphenyl phosphite, triphenyl phosphate, sodium hypophosphite, sodium phosphite, disodium hydrogen phosphate, calcium hypophosphite, calcium phosphite, triphenyl phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triethyl phosphonoacetate, trimethyl phosphonoacetate, diethyl methylphosphonoacetate, polyphosphoric acid or a combination of at least two thereof, preferably triethyl phosphate.
9. The process according to any one of claims 4 to 8, wherein in the step (1), the oligomer A has a number average molecular weight of 0.5 to 2.0X 10 5 g/mol, and the intrinsic viscosity is between 0.1 and 0.6 dL/g; and/or
In the step (2), the moisture content of the PBAT copolyester fiber master batch is 0-50ppm, preferably 0-20 ppm; the number average molecular weight is 2.5-3.5 × 10 5 g/mol, and the intrinsic viscosity is between 1.2 and 1.8 dL/g.
10. The preparation method according to any of claims 4-9, characterized in that step (3) is drying the PBAT copolyester fiber masterbatch at 80-100 ℃ for 20-24h, and then fiber spinning at 190 ℃ at 170-.
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