CN115045001B - 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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- CN115045001B CN115045001B CN202210690342.5A CN202210690342A CN115045001B CN 115045001 B CN115045001 B CN 115045001B CN 202210690342 A CN202210690342 A CN 202210690342A CN 115045001 B CN115045001 B CN 115045001B
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- pbat
- copolyester fiber
- oligomer
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- 239000000835 fiber Substances 0.000 title claims abstract description 131
- 229920001896 polybutyrate Polymers 0.000 title claims abstract description 120
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 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 70
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 44
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 42
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000009987 spinning Methods 0.000 claims abstract description 38
- 150000001413 amino acids Chemical class 0.000 claims abstract description 28
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 23
- 239000001361 adipic acid Substances 0.000 claims abstract description 21
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 21
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 14
- 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
- 238000002074 melt spinning Methods 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
- -1 adipic acid butanediol ester Chemical class 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 229920002643 polyglutamic acid Polymers 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 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 18
- 238000002156 mixing Methods 0.000 claims description 15
- 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 14
- 239000000155 melt Substances 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 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 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 10
- 238000004804 winding Methods 0.000 claims description 10
- 239000012760 heat stabilizer Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 108010020346 Polyglutamic Acid Proteins 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 5
- 108010039918 Polylysine Proteins 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 108010064470 polyaspartate Proteins 0.000 claims description 5
- 229920000656 polylysine Polymers 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- JYLRDAXYHVFRPW-UHFFFAOYSA-N butane-1,1-diol;terephthalic acid Chemical group CCCC(O)O.OC(=O)C1=CC=C(C(O)=O)C=C1 JYLRDAXYHVFRPW-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 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
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-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
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 2
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 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
- KRXBVZUTZPDWQI-UHFFFAOYSA-N ethane-1,2-diol;titanium Chemical compound [Ti].OCCO KRXBVZUTZPDWQI-UHFFFAOYSA-N 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
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 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
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 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
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000376 reactant Substances 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 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
- 230000001133 acceleration Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000000463 material Substances 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
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction 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
- 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
- 230000015556 catabolic process Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000004090 dissolution 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
- 238000001125 extrusion Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004448 titration Methods 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 the following master batches: a butylene terephthalate segment, a butylene adipate segment, and an amino acid butylene segment. The preparation method comprises the following steps: (1) Adipic acid and terephthalic acid are reacted with 1, 4-Butanediol (BDO) to obtain an oligomer A; (2) Reacting the oligomer A with an amino acid oligomer to obtain a PBAT copolyester fiber master batch; (3) And 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 the amino acid oligomer with the linear fiber skeleton for copolymerization, reduces the condition that the PBAT breaks at high spinning temperature, realizes continuous and stable high-speed spinning, and achieves the requirements of downstream products in performance and quality.
Description
Technical Field
The invention belongs to the field of high polymer material synthesis, and particularly relates to a high-melting-point PBAT copolyester fiber and a preparation method thereof.
Background
The PBAT serving as the biodegradable copolyester has good thermal stability and mechanical property of PBT, 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 textile and clothing field as well. However, there are few reports about PBAT fiber spinning at present, and many of them are spun after being blended with other polymer materials. The PBAT fiber has low melting point, low melt strength and low crystallization speed in the high-temperature spinning process, so that the PBAT fiber is broken at high spinning temperature, the fiber cannot 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 properties is of great practical significance. In the 201210349313.9 patent, the problems of difficult cooling and easy bonding in the spinning process are improved by lengthening the cooling distance, 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 respectively esterified and preshrinked, and then are mixed for final shrinkage, so that the segment length between the components is regulated, the crystallization performance of PBAT is improved, and the spinning stability of PBAT fiber is improved. However, since the final shrinkage is a transesterification process, the obtained PBAT is still a random copolymer, the influence on the crystallization performance is not obvious, and meanwhile, the introduced third component also can 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 the PBAT copolyester fiber and the preparation method thereof, and the third component amino acid oligomer with a straight-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, the yarn breakage phenomenon under high-temperature spinning is avoided, and the application of the PBAT in the field of fiber spinning is greatly widened. The introduced amino acid oligomer is nontoxic, easy to disperse and biodegradable, and the degradability and biocompatibility of the copolyester are not affected.
In order to achieve the aim of the invention, the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a high melting point PBAT copolyester fiber, the PBAT copolyester fiber comprising a masterbatch comprising: a butylene terephthalate segment, a butylene adipate segment, and an amino acid butylene segment;
wherein the molar content of the adipic acid butanediol ester segment is 50-150%, preferably 80-120%, and more preferably 100-120% relative to the terephthalic acid butanediol ester segment.
The molar content of the amino acid butanediol ester segment is 1.0 to 4.0%, preferably 2.0 to 3.0%, and more preferably 2.5% relative to the butanediol terephthalate segment.
In the invention, the amino acid butanediol ester chain segment, wherein the amino acid chain segment is derived from an amino acid oligomer, and the number average molecular weight of the amino acid oligomer is between 0.1 and 0.5 multiplied by 10 5 g/mol;
Preferably, the amino acid oligomer is selected from any one or a combination of at least two of polyglutamic acid, polyaspartic acid, polylysine and phenylalanine, preferably polyglutamic acid.
In the high-melting-point PBAT copolyester fiber, as the proportion of the amino acid butanediol ester chain segments increases, the melting point of the PBAT copolyester is slightly reduced after the rising. 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 performance of the PBAT is not obviously improved, and the melting point, the melt strength and the mechanical properties of the fiber are not obviously improved; with the further increase of the amino acid butanediol chain segment, the melting point of the copolyester is gradually increased, and the melt strength of the copolyester and the tensile strength of the fiber are obviously improved; when the amino acid butanediol ester chain segment is higher than 4.0%, the irregularity of the copolyester chain segment is aggravated, and the crystallinity is lowered, thereby resulting in a decrease in the melting point of the copolyester. Thus, the molar content of the amino acid butylene ester segment is preferably 2.0 to 3.0%, more preferably 2.5% with respect to the butylene terephthalate segment.
In a second aspect, the present invention also provides a method for preparing the high melting point PBAT copolyester fiber, which comprises the steps of:
(1) Adipic acid and terephthalic acid are reacted with 1, 4-Butanediol (BDO) to obtain an oligomer A;
(2) Reacting the oligomer A with an amino acid oligomer to obtain a PBAT copolyester fiber master batch;
(3) And 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 2-3 hours, preferably 2-2.5 hours, at 190-220 ℃ and preferably 200-210 ℃, then perform prepolymerization reaction for 1-1.5 hours at 230-240 ℃ and preferably 240 ℃ for example, and gradually reduce the pressure to 500-1000PaA, preferably 600-800PaA, during the prepolymerization reaction, so as to obtain an 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 amount of adipic acid to the addition amount of terephthalic acid is 0.5-1.5:1, preferably 1-1.2:1.
In the step (1), the amount 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 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, ethylene glycol titanium, propylene glycol titanium and butylene glycol titanium, preferably n-butyl titanate.
In step (1), the oligomer A, after dissolution in chloroform, has a number average molecular weight of between 0.5 and 2.0X10 5 g/mol as determined by gel chromatography.
The oligomer A takes a phenol-tetrachloroethane (volume ratio is 1:1) solution as a solvent, and the intrinsic viscosity is between 0.1 and 0.6dL/g measured by using a Ubbelohde viscometer.
In the invention, the step (2) is specifically to mix the oligomer A, the amino acid oligomer and the heat stabilizer, carry out copolymerization reaction for 3-4 hours, preferably 3-3.5 hours at 230-250 ℃, preferably 235-245 ℃ and 10-200Pa, preferably 10-100Pa vacuum degree, extrude under the protection of nitrogen, cool to room temperature and cut into granules, thus obtaining the PBAT copolyester fiber master batch.
In step (2), the molar ratio of the amino acid oligomer to terephthalic acid in step (1) is from 0.01 to 0.04:1, preferably from 0.02 to 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 or a combination of at least two of phosphoric acid, phosphorous acid, triphenyl phosphite, triphenyl phosphate, sodium hypophosphite, sodium phosphite, disodium hydrogen phosphate, calcium hypophosphite, calcium phosphite, calcium phosphate, triphenyl phosphite, triphenyl phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triethyl phosphonoacetate, trimethyl phosphonoacetate, diethyl methylphosphonoacetate, polyphosphoric acid, preferably triethyl phosphate.
In the step (2), the PBAT copolyester fiber master batch has a moisture content of 0-50ppm, preferably 0-20ppm.
In the step (2), after the PBAT copolyester fiber master batch is dissolved in chloroform, the number average molecular weight is measured to be between 2.5 and 3.5X10 5 g/mol by a gel chromatograph.
In the step (2), the PBAT copolyester fiber master batch uses a phenol-tetrachloroethane (volume ratio is 1:1) solution as a solvent, and the intrinsic viscosity is between 1.2 and 1.8dL/g measured by using a Ubbelohde viscometer.
In the invention, the step (3) is specifically to dry the PBAT copolyester fiber master batch at 80-100 ℃, preferably 80 ℃ for 20-24 hours, preferably 24 hours, and then spin the fiber, wherein the spinning temperature is 170-190 ℃, preferably 180-190 ℃, the winding speed is 1000-1500m/min, preferably 1200-1400m/min, the hot drawing temperature is 85-110 ℃, preferably 90-100 ℃, and the drawing multiple is 2.5-4 times, preferably 3-3.5 times, so as to obtain the high-melting-point PBAT copolyester fiber.
In the invention, the high-melting-point PBAT copolyester fiber has the water content of 0-50ppm measured by a Karl Fischer water titration apparatus.
In the invention, the high-melting-point PBAT copolyester fiber is measured by a differential scanning calorimeter to have a melting point of 125-140 ℃.
In the invention, the high-melting-point PBAT copolyester fiber adopts a melt tensile rheometer to measure the melt strength between 60F/mN and 80F/mN.
In the invention, the high-melting-point PBAT copolyester fiber has tensile strength of 3.0-5.0cN/dtex and elongation at break of 40-70% measured by a universal material testing machine.
In the invention, the high-melting-point PBAT copolyester fiber is obtained by measuring the fiber diameter by a three-dimensional microscopic system and calculating the fiber fineness of 10-20 dtex.
According to the invention, the research shows that in the preparation process of the PBAT fiber, a certain proportion of amino acid oligomer with a linear fiber skeleton is introduced, so that the melting point and the melt strength of the PBAT copolyester can be effectively improved, the filament breakage phenomenon under high-temperature spinning is avoided, and meanwhile, the fiber has good mechanical properties. Firstly, the amino acid oligomer contains a large number of amide bonds, so that the melting point of the PBAT copolyester can be effectively improved, and the thermal stability of the 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 good melt strength, and the phenomenon of yarn breakage in the spinning process is avoided; finally, the amino acid oligomer is nontoxic and degradable, and the degradation performance of the PBAT is not affected while the thermodynamic performance of the copolyester is improved. Therefore, through copolymerization modification with amino acid oligomer, the application prospect of the PBAT copolyester in the field of degradable fibers is greatly expanded.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
According to the invention, the amino acid oligomer is introduced in the PBAT synthesis process for copolymerization, the melting point can be raised 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 prepared PBAT copolyester fiber has the tensile strength of 3.0-5.0cN/dtex and the elongation at break of 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 a better technical effect is achieved.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention as claimed.
Examples of the present invention employ the following materials, but are not limited to these:
gamma-polyglutamic acid: aladdin, M n＝0.1-2.0×105 g/mol;
Polyaspartic acid: ron, M n＝0.1×105 g/mol;
polylysine: adamas, M n＝0.2×105 g/mol;
1, 4-butanediol, adipic acid, terephthalic acid, tetrabutyl titanate and triethyl phosphate are all commercially available, and all the raw materials are common commercial raw materials unless otherwise specified.
The main properties of the PBAT copolyester fiber in the embodiment of the invention are tested by the following method:
a) Relative molecular mass: the polymer was tested for relative molecular mass using Waters gel chromatography with chloroform as the mobile phase and at an outflow rate of 1mL/min at 40℃and a narrow distribution of polystyrene as the standard.
B) Intrinsic viscosity: with reference to national standard GB/T1632.5-2008, the intrinsic viscosity is measured by using a Ubbelohde viscometer by taking a phenol-tetrachloroethane (1:1) solution as a solvent.
C) Melting point: the melting point of the copolyester is tested by using a type-Pyris 1 differential scanning calorimeter of PERKINS ELMER company, the sample is heated to 180 ℃ at 20 ℃/min, the heat history is eliminated, then the sample is cooled to-30 ℃ at the rate of 20 ℃/min, and then the temperature is increased at the rate of 10 ℃/min, so that the DSC curve of the sample is obtained.
D) Melt strength: testing the melt strength of the copolyester by using a Rheotens melt tensile rheometer of Gottfert company, and starting up to correct the maximum force value of the Rheotens to be 2N and the zero point to be 0N; and (3) putting the sample into a Lebtech extruder (length-diameter ratio is 30/1, die diameter is 2 mm), extruding melt lines at 180 ℃, sampling and weighing in unit time, calculating the melt extrusion rate and the initial rotating speed of Rheotens, synchronizing the melt lines between Rheotens test rollers, finely adjusting the relative force value to be 0, testing the test rollers at an acceleration speed of 6mm/s2, recording the force value change in the acceleration stretching process until the melt lines are broken, wherein the maximum value of the breaking is the melt strength value, and repeating the measurement for 5 times to obtain the average value.
E) Mechanical properties of the fiber: the middle part of the collected copolyester nascent fiber is cut off, the length is 20mm, a universal material tester is adopted to test the copolyester nascent fiber at a 20mm/min stretching rate and a 10mm clamping gauge, and at least 10 repeated experiments are carried out on each group.
Examples 1-7 and comparative examples 1-4:
[ example 1]
Preparing high-melting-point PBAT copolyester fiber:
(1) Reactant 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a mole ratio of 1.6:0.53:0.47, adding tetrabutyl titanate (based on the mass of titanium element in the tetrabutyl titanate) with the total mass of 86ppm of reactants, uniformly mixing, esterifying at 200 ℃ for 2 hours, heating to 240 ℃ for prepolymerization for 1 hour, and gradually reducing the pressure to 600PaA during the reaction to obtain an oligomer A;
the number average molecular weight of the oligomer A was 1.0X10 5 g/mol and the intrinsic viscosity was 0.2dL/g.
(2) Mixing the oligomer A in the step (1) with gamma-polyglutamic acid (M n＝0.1×105 g/mol) and triethyl phosphate, wherein the molar ratio of the gamma-polyglutamic acid to terephthalic acid in the step (1) is 0.01:1, carrying out copolymerization reaction on triethyl phosphate with the content of phosphorus element in a system of 30ppm for 3.2 hours at 235 ℃ under the pressure of 80PaA, extruding under the protection of nitrogen after the reaction is finished, cooling to room temperature, and granulating to obtain PBAT copolyester fiber master batch; wherein the molar content of the adipic acid butanediol ester segment is 112.8 percent relative to the terephthalic acid butanediol ester segment, and the molar content of the amino acid butanediol ester segment is 1.0 percent relative to the terephthalic acid butanediol ester segment;
The PBAT copolyester fiber masterbatch had a number average molecular weight of 3.0X10 5 g/mol, an intrinsic viscosity of 1.68dL/g and a moisture content of 35ppm.
(3) And (3) drying the PBAT copolyester fiber master batch for 24 hours at 80 ℃, and then carrying out fiber spinning, wherein the spinning temperature is 190 ℃, the spinning winding speed is 1400m/min, the thermal traction temperature is 100 ℃, and the traction multiple is 3.0 times, so as to obtain the high-melting-point PBAT copolyester fiber.
[ Example 2]
Preparing high-melting-point PBAT copolyester fiber:
(1) Reactant 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a mole ratio of 1.5:0.52:0.48, adding isopropyl titanate (based on the mass of titanium element in the isopropyl titanate) with the total mass of 96ppm of reactants, uniformly mixing, carrying out esterification reaction for 2.0h at 205 ℃, then heating to 240 ℃ for prepolymerization 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 1.2X10 5 g/mol and the intrinsic viscosity was 0.23dL/g.
(2) Mixing the oligomer A in the step (1) with gamma-polyglutamic acid (M n＝0.1×105 g/mol) and triphenyl phosphate, wherein the molar ratio of the gamma-polyglutamic acid to terephthalic acid in the step (1) is 0.02:1, the content of triphenyl phosphate in a system is 35ppm by the mass of phosphorus element, the triphenyl phosphate is subjected to copolymerization reaction for 3.0h at 240 ℃ under the pressure of 60PaA, the triphenyl phosphate is extruded under the protection of nitrogen after the reaction is finished, and the PBAT copolyester fiber master batch is obtained after the triphenyl phosphate is cooled to room temperature and then is pelletized; wherein the molar content of the adipic acid butanediol ester segment is 108.3 percent relative to the terephthalic acid butanediol ester segment, and the molar content of the amino acid butanediol ester segment is 2.0 percent relative to the terephthalic acid butanediol ester segment;
The PBAT copolyester fiber masterbatch had a number average molecular weight of 2.8X10 5 g/mol, an intrinsic viscosity of 1.53dL/g, and a moisture content of 33ppm.
(3) And (3) drying the PBAT copolyester fiber master batch for 24 hours at 80 ℃, and then carrying out fiber spinning, wherein the spinning temperature is 190 ℃, the spinning winding speed is 1350m/min, the thermal traction temperature is 95 ℃, and the traction multiple is 3.0 times, so as to obtain the high-melting-point PBAT copolyester fiber.
[ Example 3]
Preparing high-melting-point PBAT copolyester fiber:
(1) Reactant 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a mole ratio of 1.4:0.54:0.46, adding titanium dioxide (based on the mass of titanium element in the titanium dioxide) with the total mass of 120ppm of reactants, uniformly mixing, carrying out esterification reaction for 2.0h at 205 ℃, then heating to 240 ℃ for prepolymerization 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 1.2X10 5 g/mol and the intrinsic viscosity was 0.23dL/g.
(2) Mixing the oligomer A in the step (1) with gamma-polyglutamic acid (M n＝0.1×105 g/mol) and triphenyl phosphate, wherein the molar ratio of the gamma-polyglutamic acid to terephthalic acid in the step (1) is 0.03:1, the content of triphenyl phosphate in a system is 35ppm by the mass of phosphorus element, the triphenyl phosphate is subjected to copolymerization reaction for 3.0h at 240 ℃ under the pressure of 60PaA, the triphenyl phosphate is extruded under the protection of nitrogen after the reaction is finished, and the PBAT copolyester fiber master batch is obtained after the triphenyl phosphate is cooled to room temperature and then is pelletized; wherein the molar content of the adipic acid butanediol ester segment is 117.4 percent relative to the terephthalic acid butanediol ester segment, and the molar content of the amino acid butanediol ester segment is 3.0 percent relative to the terephthalic acid butanediol ester segment;
The PBAT copolyester fiber masterbatch had a number average molecular weight of 2.7X10 5 g/mol, an intrinsic viscosity of 1.48dL/g, and a moisture content of 20ppm.
(3) And (3) drying the PBAT copolyester fiber master batch for 24 hours at 80 ℃, and then carrying out fiber spinning, wherein the spinning temperature is 190 ℃, the spinning winding speed is 1350m/min, the thermal traction temperature is 95 ℃, and the traction multiple is 3.0 times, so as to obtain the high-melting-point PBAT copolyester fiber.
[ Example 4]
Preparing high-melting-point PBAT copolyester fiber:
(1) Reactant 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a mole ratio of 1.4:0.55:0.45, adding tetraisooctyl titanate (based on the mass of titanium element in the tetraisooctyl titanate) with the total mass of 124ppm of reactants, uniformly mixing, carrying out esterification reaction at 210 ℃ for 2.5 hours, then heating to 240 ℃ for prepolymerization reaction for 1.5 hours, and gradually reducing the pressure to 700PaA during the reaction to obtain an oligomer A;
The number average molecular weight of oligomer A was 1.1X10 5 g/mol and the intrinsic viscosity was 0.22dL/g.
(2) Mixing the oligomer A in the step (1) with gamma-polyglutamic acid (M n＝0.1×105 g/mol) and triphenyl phosphite, wherein the molar ratio of the gamma-polyglutamic acid to terephthalic acid in the step (1) is 0.035:1, the content of triphenyl phosphite in a system is 55ppm by the mass of phosphorus element, the triphenyl phosphite is subjected to copolymerization reaction for 3.2 hours at 245 ℃ under the pressure of 80PaA, the triphenyl phosphite is extruded under the protection of nitrogen after the reaction is finished, and the triphenyl phosphite is cooled to room temperature and then pelletized, so that PBAT copolyester fiber master batch is obtained; wherein the molar content of the adipic acid butanediol ester segment is 122.2 percent relative to the terephthalic acid butanediol ester segment, and the molar content of the amino acid butanediol ester segment is 3.5 percent relative to the terephthalic acid butanediol ester segment;
The PBAT copolyester fiber masterbatch had a number average molecular weight of 2.8X10 5 g/mol, an intrinsic viscosity of 1.56dL/g and a moisture content of 45ppm.
(3) And (3) drying the PBAT copolyester fiber master batch for 24 hours at 80 ℃, and then carrying out fiber spinning, wherein the spinning temperature is 190 ℃, the spinning winding speed is 1350m/min, the thermal traction temperature is 95 ℃, and the traction multiple is 3.0 times, so as to obtain the high-melting-point PBAT copolyester fiber.
[ Example 5]
Preparing high-melting-point PBAT copolyester fiber:
(1) Reactant 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a mole ratio of 1.4:0.53:0.47, adding tetraisopropyl titanate (based on the mass of titanium element in the tetraisopropyl titanate) with the total mass of 128ppm of reactants, uniformly mixing, carrying out esterification reaction at 210 ℃ for 2.0h, then heating to 240 ℃ for prepolymerization 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 0.9X10 5 g/mol and the intrinsic viscosity was 0.18dL/g.
(2) Mixing the oligomer A in the step (1) with gamma-polyglutamic acid (M n＝0.1×105 g/mol) and trimethyl phosphate, wherein the molar ratio of the gamma-polyglutamic acid to terephthalic acid in the step (1) is 0.04:1, carrying out copolymerization reaction on trimethyl phosphate with the content of 65ppm in a system according to the mass of phosphorus element at 250 ℃ and under the pressure of 150PaA for 3.8 hours, extruding under the protection of nitrogen after the reaction is finished, cooling to room temperature, and granulating to obtain PBAT copolyester fiber master batch; wherein the molar content of the adipic acid butanediol ester segment is 112.8% relative to the terephthalic acid butanediol ester segment, and the molar content of the amino acid butanediol ester segment is 4.0% relative to the terephthalic acid butanediol ester segment;
The PBAT copolyester fiber masterbatch had a number average molecular weight of 2.5X10 5 g/mol, an intrinsic viscosity of 1.43dL/g, and a moisture content of 47ppm.
(3) And (3) drying the PBAT copolyester fiber master batch for 24 hours at 80 ℃, and then carrying out fiber spinning, wherein the spinning temperature is 180 ℃, the spinning winding speed is 1400m/min, the thermal traction temperature is 100 ℃, and the traction multiple is 3.5 times, so as to obtain the high-melting-point PBAT copolyester fiber.
[ Example 6]
Preparing high-melting-point PBAT copolyester fiber:
(1) Reactant 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a mole ratio of 1.4:0.50:0.50, adding n-butyl titanate (based on the mass of titanium element in the mixture) with the total mass of 88ppm of reactants, uniformly mixing, esterifying at 200 ℃ for 3.0h, heating to 240 ℃ for prepolymerization for 1.5h, and gradually reducing the pressure to 500PaA during the reaction to obtain an oligomer A;
The number average molecular weight of oligomer A was 1.4X10 5 g/mol and the intrinsic viscosity was 0.30dL/g.
(2) Mixing the oligomer A in the step (1) with polyaspartic acid (M n＝0.1×105 g/mol) and triethyl phosphate, wherein the molar ratio of polyaspartic acid to terephthalic acid in the step (1) is 0.03:1, carrying out copolymerization reaction on triethyl phosphate with the content of 45ppm in a system according to the mass of phosphorus element at 245 ℃ and under the pressure of 80PaA for 3.6 hours, extruding under the protection of nitrogen after the reaction is finished, cooling to room temperature, and granulating to obtain PBAT copolyester fiber master batch; wherein the molar content of the adipic acid butanediol ester segment is 100.0 percent relative to the terephthalic acid butanediol ester segment, and the molar content of the amino acid butanediol ester segment is 3.0 percent relative to the terephthalic acid butanediol ester segment;
The PBAT copolyester fiber masterbatch had a number average molecular weight of 2.6X10 5 g/mol, an intrinsic viscosity of 1.51dL/g, and a moisture content of 38ppm.
(3) And (3) drying the PBAT copolyester fiber master batch for 24 hours at 80 ℃, and then carrying out fiber spinning, wherein the spinning temperature is 180 ℃, the spinning winding speed is 1250m/min, the thermal traction temperature is 100 ℃, and the traction multiple is 3.0 times, so as to obtain the high-melting-point PBAT copolyester fiber.
[ Example 7]
Preparing high-melting-point PBAT copolyester fiber:
(1) Reactant 1, 4-butanediol, adipic acid and terephthalic acid are mixed according to a mole ratio of 1.4:0.53:0.47, adding n-butyl titanate (based on the mass of titanium element in the mixture) with the total mass of the reactants being 110ppm, uniformly mixing, esterifying at 200 ℃ for 2.0h, heating to 240 ℃ for prepolymerization 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 1.5X10 5 g/mol and the intrinsic viscosity was 0.32dL/g.
(2) Mixing the oligomer A in the step (1) with polylysine (M n＝0.2×105 g/mol) and triethyl phosphate, wherein the molar ratio of polylysine to terephthalic acid in the step (1) is 0.03:1, carrying out copolymerization reaction on triethyl phosphate with the content of 55ppm in a system according to the mass of phosphorus element at 245 ℃ under the pressure of 40PaA for 3.5 hours, extruding under the protection of nitrogen after the reaction is finished, cooling to room temperature, and granulating to obtain PBAT copolyester fiber master batch; wherein the molar content of the adipic acid butanediol ester segment is 112.8 percent relative to the terephthalic acid butanediol ester segment, and the molar content of the amino acid butanediol ester segment is 3.0 percent relative to the terephthalic acid butanediol ester segment;
the PBAT copolyester fiber masterbatch had a number average molecular weight of 2.9X10 5 g/mol, an intrinsic viscosity of 1.63dL/g, and a moisture content of 32ppm.
(3) And (3) drying the PBAT copolyester fiber master batch for 24 hours at 80 ℃, and then carrying out fiber spinning, wherein the spinning temperature is 180 ℃, the spinning winding speed is 1350m/min, the thermal traction temperature is 90 ℃, and the traction multiple is 3.5 times, so as to obtain the high-melting-point PBAT copolyester fiber.
Comparative example 1
The PBAT copolyester fiber was prepared according to the method of example 1, except that the polyglutamic acid was not added in step (2), and the other operations were unchanged.
The obtained PBAT copolyester fiber master batch has the molar content of the adipic acid butanediol ester chain segment relative to the terephthalic acid butanediol ester chain segment of 112.8 percent and the molar content of the amino acid butanediol ester chain segment relative to the terephthalic acid butanediol ester chain segment of 0 percent.
Comparative example 2
The PBAT copolyester fiber was prepared according to the method of example 1, except that the polyglutamic acid was added in the step (2) in a molar ratio to terephthalic acid in the step (1) of 0.05:1, the other operations are unchanged.
The obtained PBAT copolyester fiber master batch has the molar content of the adipic acid butanediol ester chain segment relative to the terephthalic acid butanediol ester chain segment of 112.8 percent and the molar content of the amino acid butanediol ester chain segment relative to the terephthalic acid butanediol ester chain segment of 5.0 percent.
[ Comparative example 3]
The PBAT copolyester fiber was prepared by the method of example 1, except that gamma-polyglutamic acid (M n＝0.1×105 g/mol) was replaced with high polymer polyglutamic acid M n＝2.0×105 g/mol in the step (2), and the other operations were unchanged.
The obtained PBAT copolyester fiber master batch has the molar content of the adipic acid butanediol ester chain segment relative to the terephthalic acid butanediol ester chain segment of 112.8 percent and the molar content of the amino acid butanediol ester chain segment relative to the terephthalic acid butanediol ester chain segment of 3.0 percent.
[ Comparative example 4]
The PBAT copolyester fiber was prepared according to the method of example 1, except that the polyglutamic acid was added in step (1) instead in step (2), and the other operations were unchanged.
The obtained PBAT copolyester fiber master batch has the molar content of the adipic acid butanediol ester chain segment relative to the terephthalic acid butanediol ester chain segment of 112.8 percent and the molar content of the amino acid butanediol ester chain segment relative to the terephthalic acid butanediol ester chain segment of 3.0 percent.
The PBAT copolyester fibers provided in examples 1-7 and comparative examples 1-4 were tested for molecular weight, intrinsic viscosity, melting point, moisture content, fineness, melt strength and fiber mechanical properties using the methods described above, and the test results are shown in table 1:
TABLE 1
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention.
Claims (24)
1. A high melting point PBAT copolyester fiber, characterized in that the PBAT copolyester fiber comprises a masterbatch comprising: a butylene terephthalate segment, a butylene adipate segment, and an amino acid butylene segment;
Wherein the molar content of the adipic acid butanediol ester chain segment is 50-150% relative to the terephthalic acid butanediol ester chain segment;
The molar content of the amino acid butanediol ester chain segment is 1.0-4.0% relative to the butanediol terephthalate chain segment;
the amino acid butanediol ester chain segment, wherein the amino acid chain segment is derived from an amino acid oligomer, and the number average molecular weight of the amino acid oligomer is between 0.1 and 0.5 multiplied by 10 5 g/mol; the amino acid oligomer is selected from any one or a combination of at least two of polyglutamic acid, polyaspartic acid, polylysine and phenylalanine;
The high-melting-point PBAT copolyester fiber has the water content of 0-50ppm, the melting point of 125-140 ℃, the melt strength of 60-80F/mN, the tensile strength of 3.0-5.0cN/dtex, the elongation at break of 40-70% and the fiber fineness of 10-20 dtex;
the preparation method of the high-melting-point PBAT copolyester fiber comprises the following steps:
(1) Adipic acid and terephthalic acid react with 1, 4-butanediol to obtain an oligomer A;
(2) Reacting the oligomer A with an amino acid oligomer to obtain a PBAT copolyester fiber master batch;
(3) And drying the PBAT copolyester fiber master batch, and then carrying out melt spinning to obtain the high-melting-point PBAT copolyester fiber.
2. The high melting point PBAT copolyester fiber according to claim 1, wherein the molar content of the adipic acid butanediol ester segment is 80-120% relative to the terephthalic acid butanediol ester segment.
3. The high melting point PBAT copolyester fiber according to claim 2, wherein the molar content of the adipic acid butanediol ester segment is 100-120% with respect to the terephthalic acid butanediol ester segment.
4. The high melting point PBAT copolyester fiber according to claim 1, characterized in that the molar content of the amino acid butylene glycol segment is 2.0-3.0% relative to the butylene terephthalate segment.
5. The high melting point PBAT copolyester fiber according to claim 4, wherein the molar content of the amino acid butylene segments relative to the butylene terephthalate segments is 2.5%.
6. A method of making the high melting point PBAT copolyester fiber of any one of claims 1 to 5, comprising the steps of:
(1) Adipic acid and terephthalic acid react with 1, 4-butanediol to obtain an oligomer A;
(2) Reacting the oligomer A with an amino acid oligomer to obtain a PBAT copolyester fiber master batch;
(3) And drying the PBAT copolyester fiber master batch, and then carrying out melt spinning to obtain the high-melting-point PBAT copolyester fiber.
7. The process according to claim 6, wherein the step (1) comprises uniformly mixing adipic acid, terephthalic acid, 1, 4-butanediol and a titanium catalyst, esterifying at 190-220 ℃ for 2-3 hours, and then heating to 230-240 ℃ for prepolymerization for 1-1.5 hours, wherein the pressure is gradually reduced to 500-1000PaA during the prepolymerization to obtain the oligomer A.
8. The process of claim 7, wherein the esterification reaction is carried out at a temperature of 190 to 220 ℃ for a period of 2 to 2.5 hours.
9. The process of claim 7, wherein the pressure is gradually reduced to 600-800PaA during the prepolymerization.
10. The method according to claim 7, wherein the molar ratio of the addition amount of 1, 4-butanediol to the sum of the addition amounts of adipic acid and terephthalic acid is 1.1-2.0:1;
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; and/or
The dosage of the titanium catalyst is 60-160ppm of the total mass of succinic acid, terephthalic acid and 1, 4-butanediol based on the mass of titanium element.
11. The method according to claim 10, wherein the molar ratio of the amount of 1, 4-butanediol added to the sum of the amounts of adipic acid and terephthalic acid added is 1.4-1.6:1.
12. The process according to claim 10, wherein the molar ratio of the amount of adipic acid added to the amount of terephthalic acid added is 1-1.2:1.
13. The method according to claim 10, wherein the amount of the titanium-based catalyst is 90 to 130ppm based on the total mass of succinic acid, terephthalic acid, 1, 4-butanediol, based on the mass of titanium element therein.
14. The method according to claim 7, wherein 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 ethylene glycol, titanium propylene glycol, and titanium butylene glycol.
15. The preparation method of claim 6, wherein the step (2) is to mix the oligomer A, the amino acid oligomer and the heat stabilizer, carry out copolymerization reaction for 3-4 hours at 230-250 ℃ and 10-200Pa vacuum degree, extrude under nitrogen protection, cool to room temperature and cut into particles to obtain the PBAT copolyester fiber master batch.
16. The process of claim 15, wherein the copolymerization is carried out at a temperature of 235-245 ℃ and a pressure of 10-100Pa for a period of 3-3.5 hours.
17. The process of claim 15, wherein in step (2), the molar ratio of the amino acid oligomer to terephthalic acid in step (1) is from 0.01 to 0.04:1; and/or
In the step (2), the heat stabilizer is a phosphorus compound, and the adding amount of the heat stabilizer in the system is 20-70ppm based on the mass of phosphorus element.
18. The process of claim 17 wherein the molar ratio of the amino acid oligomer to terephthalic acid in step (1) is from 0.02 to 0.03:1.
19. The process according to claim 17, wherein the heat stabilizer is added to the system in an amount of 30 to 60ppm based on the mass of phosphorus.
20. The method of producing according to claim 15, wherein 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, calcium phosphate, triphenyl 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.
21. The process according to claim 6, wherein in step (1), the oligomer A has a number average molecular weight of between 0.5 and 2.0X10 5 g/mol and an intrinsic viscosity of between 0.1 and 0.6 dL/g; and/or
In the step (2), the PBAT copolyester fiber master batch has the moisture content of 0-50ppm; the number average molecular weight is between 2.5 and 3.5X10 5 g/mol, and the intrinsic viscosity is between 1.2 and 1.8 dL/g.
22. The method of claim 21 wherein the PBAT copolyester fiber masterbatch has a moisture content of 0 to 20ppm.
23. The preparation method according to claim 6, wherein the step (3) is to dry the PBAT copolyester fiber master batch at 80-100 ℃ for 20-24 hours, then to spin the fiber, wherein the spinning temperature is 170-190 ℃, the winding speed is 1000-1500m/min, the hot drawing temperature is 85-110 ℃, and the drawing multiple is 2.5-4 times, so as to obtain the high-melting-point PBAT copolyester fiber.
24. The process according to claim 23, wherein the spinning temperature is 180-190 ℃, the winding speed is 1200-1400m/min, the hot drawing temperature is 90-100 ℃, and the drawing multiple is 3-3.5 times.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474490A (en) * | 2017-07-27 | 2017-12-15 | 青岛金典生化器材有限公司 | Heparin tube environment-friendly type polyester master batch and preparation method thereof |
| JP2019147322A (en) * | 2018-02-28 | 2019-09-05 | シンワ株式会社 | Nanofiber composite sheet comprising polyglutamic acid |
| CN110257945A (en) * | 2019-05-10 | 2019-09-20 | 海盐县硕创服装研究所 | Biodegradable copolyesters monofilament |
| CN110467726A (en) * | 2018-05-07 | 2019-11-19 | 上海凯赛生物技术股份有限公司 | A kind of high-melting-point biological poly esteramides and preparation method thereof |
| CN111850735A (en) * | 2020-06-10 | 2020-10-30 | 安徽东锦资源再生科技有限公司 | Preparation method of anti-fracture sea-island composite fiber |
| CN113667103A (en) * | 2021-08-30 | 2021-11-19 | 万华化学集团股份有限公司 | Preparation method of PBAT resin |
| WO2022060942A1 (en) * | 2020-09-16 | 2022-03-24 | Danisco Us Inc | Esterase and methods of use, thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8895660B2 (en) * | 2012-03-01 | 2014-11-25 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture, and uses thereof |
-
2022
- 2022-06-17 CN CN202210690342.5A patent/CN115045001B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474490A (en) * | 2017-07-27 | 2017-12-15 | 青岛金典生化器材有限公司 | Heparin tube environment-friendly type polyester master batch and preparation method thereof |
| JP2019147322A (en) * | 2018-02-28 | 2019-09-05 | シンワ株式会社 | Nanofiber composite sheet comprising polyglutamic acid |
| CN110467726A (en) * | 2018-05-07 | 2019-11-19 | 上海凯赛生物技术股份有限公司 | A kind of high-melting-point biological poly esteramides and preparation method thereof |
| CN110257945A (en) * | 2019-05-10 | 2019-09-20 | 海盐县硕创服装研究所 | Biodegradable copolyesters monofilament |
| CN111850735A (en) * | 2020-06-10 | 2020-10-30 | 安徽东锦资源再生科技有限公司 | Preparation method of anti-fracture sea-island composite fiber |
| WO2022060942A1 (en) * | 2020-09-16 | 2022-03-24 | Danisco Us Inc | Esterase and methods of use, thereof |
| CN113667103A (en) * | 2021-08-30 | 2021-11-19 | 万华化学集团股份有限公司 | Preparation method of PBAT resin |
Non-Patent Citations (3)
| Title |
|---|
| An investigation of the impact of an amino-ended hyperbranched polymer as a new type of modifier on the compatibility of PLA/PBAT blends;Jin, Yujuan et al.;《JOURNAL OF POLYMER ENGINEERING》;20180531;第38卷(第3期);第223-229页 * |
| 乙二醇-1,6-己二酸-1,6-己二胺型聚酯酰胺的合成及表征;缪永建 等;《化工技术与开发》(06);第28-30、45页 * |
| 李良训.《高分子物理学》.中国石化出版社,1995,第183页. * |
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