CN116876212A - Preparation method of high-strength flame-retardant polyester fiber - Google Patents
Preparation method of high-strength flame-retardant polyester fiber Download PDFInfo
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- CN116876212A CN116876212A CN202310952464.1A CN202310952464A CN116876212A CN 116876212 A CN116876212 A CN 116876212A CN 202310952464 A CN202310952464 A CN 202310952464A CN 116876212 A CN116876212 A CN 116876212A
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- Prior art keywords
- polyester
- fiber
- retardant
- polyester fiber
- flame
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- 229920000728 polyester Polymers 0.000 title claims abstract description 127
- 239000000835 fiber Substances 0.000 title claims abstract description 117
- 239000003063 flame retardant Substances 0.000 title claims abstract description 74
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000009987 spinning Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- -1 polyethylene terephthalate Polymers 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 4
- GIGUCPHDHQUMII-UHFFFAOYSA-N P(O)(O)(O)=O.P(O)(O)(O)=O.P(O)(O)(O)=O.P(O)(O)(O)=O.P(O)(O)(O)=O.P(O)(O)(O)=O.C1CCCCC1 Chemical group P(O)(O)(O)=O.P(O)(O)(O)=O.P(O)(O)(O)=O.P(O)(O)(O)=O.P(O)(O)(O)=O.P(O)(O)(O)=O.C1CCCCC1 GIGUCPHDHQUMII-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 229920001634 Copolyester Polymers 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000002657 fibrous material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 5
- 238000001994 activation Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000002074 melt spinning Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- SFHBJXIEBWOOFA-UHFFFAOYSA-N 5-methyl-3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OC(C)COC(=O)C2=CC=C1C=C2 SFHBJXIEBWOOFA-UHFFFAOYSA-N 0.000 description 1
- LSYVCAOPFHHUHM-UHFFFAOYSA-N [hydroxy-[hydroxy-[hydroxy(phosphonooxy)phosphoryl]oxyphosphoryl]oxyphosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O LSYVCAOPFHHUHM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010035 extrusion spinning Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
-
- 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
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
- D06M13/148—Polyalcohols, e.g. glycerol or glucose
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Abstract
The invention discloses a preparation method of high-strength flame-retardant polyester fiber, which relates to the technical field of polyester and comprises the steps of pre-activating melt blending spinning high-viscosity polyester and high fluidity, and carrying out micro-alcoholysis on the fiber to form a reactive hydroxyl functional group so as to prepare the surface-activated polyester fiber. Dipping the activated polyester fiber in a solution containing a flame retardant to perform a chemical grafting reaction to prepare high-strength flame-retardant polyester fiber; the invention has the plasticizing effect by introducing the low-melting point copolyester into the high-viscosity polyester melt, weakens the interaction force of high-viscosity polyester molecular chains to a certain extent, reduces cohesive energy, further improves fluidity, reduces the viscosity drop of the high-viscosity polyester in spinning forming, and is beneficial to improving the strength of spun fibers.
Description
Technical Field
The invention relates to the technical field of polyester, in particular to a preparation method of high-strength flame-retardant polyester fiber.
Background
Polyester fiber is a basic raw material for textile, and is widely applied to the fields of clothing, home furnishings, industrial textiles and the like by virtue of the comprehensive cost performance. The global polyester fiber yield reaches 6000 ten thousand tons in 2021, and the yield is the first of all fiber varieties. With the continuous upgrading of the end consumption demands, the performance requirements of polyester fiber products are higher and higher, and the improvement of the functionalization of the polyester fibers is more and more urgent. The conventional polyester fiber has the characteristics of good mechanical property, wear resistance and the like, but has poor hygroscopicity when being used as a fiber material for administration, and the moisture regain under a standard environment is only 0.4%; when reinforcing industrial uses such as paper, it is often difficult to uniformly disperse the reinforcing effect is poor. In order to improve these disadvantages of polyester fibers, modification is necessary. In view of the above drawbacks, it is essentially polyester fibers that lack reactive functional groups, especially the surface chemistry of the fibers, is inert, resulting in low moisture absorption and difficult modification of the fiber surface. How to realize the surface activation of the polyester fiber material and improve the capability of further application or reaction of the polyester fiber material are important directions for improving the functionalization of the polyester fiber.
The invention patent CN110528109B discloses a high-strength flame-retardant polyester industrial yarn and a preparation method thereof, wherein phosphorus-containing tackifying polyester chips are prepared by utilizing low-temperature vacuum tackifying, high-temperature vacuum tackifying and high-temperature solid-phase tackifying processes, and the high-strength flame-retardant polyester industrial yarn is prepared by utilizing a flame-retardant tackifying polyester chip melt spinning process. The core is to improve the order of amorphous areas in the terylene industrial yarn so as to improve the flame-retardant durability of the flame-retardant terylene industrial yarn. However, in order to achieve an improvement in flame retardant properties, a large amount of flame retardant is introduced, and the original ordered structure of the polyester is destroyed. Meanwhile, the flame retardant can be uniformly distributed in the fiber material only when the using amount is large, and the phosphorus content in the fiber is 0.3-1.0%.
The Chinese patent No. 102102241A discloses a method for directly producing flame-retardant polyester staple fibers from recycled polyester bottle flakes, which comprises the step of mixing and spinning the dried polyester bottle flakes and flame-retardant polyester master batches to obtain the flame-retardant polyester staple fibers. However, no proposal is given for the strength and flame retardant property change of the flame retardant polyester staple fiber in post-processing, such as high-temperature dyeing and post-finishing.
The Chinese patent No. 112195532A discloses a flame-retardant polyester mother yarn and a preparation process thereof, wherein after melt blending of a blending inhibitor and polyester fiber master batch, a primary fiber is prepared by extrusion spinning, and then the primary fiber is subjected to after-treatment by using phosphate and a penetrating agent to prepare the flame-retardant polyester mother yarn. The polyester melt is extruded to form a primary filament which is a solid filament with a smooth surface and a chemically inert surface, and the phosphate and penetrant are difficult to form a strong bond on the surface of the fiber, although the orientation crystallinity of the primary filament is low.
From the prior art, the flame retardant performance of the polyester fiber is mainly realized by introducing a flame retardant to carry out copolymerization in the polyester synthesis stage, introducing a master batch containing the flame retardant in the polyester melt spinning forming stage or carrying out flame retardant treatment on the fiber. The copolymerization or blending method has great influence on the mechanical properties of the prepared flame-retardant polyester fiber, and especially the copolymerization method damages the original molecular chain regularity of the polyester. Meanwhile, the flame retardant component fiber introduced by the copolymerization or blending method has chemical bond breakage on linear molecular chains in a hot and humid environment such as dyeing or after-treatment, so that the loss of the flame retardant is caused, and the strength of the fiber is reduced. The post-treatment method of the fiber material has high efficiency, but the surface of the polyester fiber presents chemical inertia, so that chemical grafting is difficult to realize, the fiber material is attached to the surface of the fiber by physical bonding force, the fiber material is not wash-resistant, and the flame retardant property is obviously reduced in the use process. How to realize the flame retardant property of the polyester fiber in realizing durability and simultaneously has excellent mechanical strength becomes an important direction of the research of the polyester fiber.
In order to solve the problems, we provide a method for preparing a high-strength flame-retardant polyester fiber, so as to solve the problems.
Disclosure of Invention
The invention aims to provide a preparation method of high-strength flame-retardant polyester fiber, which aims to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a preparation method of high-strength flame-retardant polyester fiber comprises the following steps:
step one: melt blending and spinning the high-viscosity polyester and the high-fluidity pre-activated polyester;
step two: performing micro-alcoholysis on the fiber in the first step to form a reactive hydroxyl functional group, so as to obtain a surface-activated polyester fiber;
step three: and immersing the activated polyester fiber in a solution containing a flame retardant for chemical grafting reaction to obtain the high-strength flame-retardant polyester fiber.
As a further scheme of the invention: the high-viscosity polyester is one or a combination of more of fiber-grade polyethylene terephthalate, fiber-grade poly-1, 3-propylene terephthalate or fiber-grade polybutylene terephthalate, the intrinsic viscosity is 0.80-1.25 dL/g, and the melt index under the conditions of 280 ℃ and 2.16kg load is 10-30 g/10min.
As still further aspects of the invention: the high-fluidity preactivated polyester is low-melting-point polyester; the melting point is 120-200 ℃, and the melt index is 30-100 g/10min under the conditions of the temperature of 280 ℃ and the load of 2.16 kg.
As still further aspects of the invention: the mixing mass ratio of the activated polyester to the high-viscosity polyester is 99:1-90:10.
As still further aspects of the invention: the technological parameters of melt blending spinning in the first step comprise: the spinning temperature is 260-295 ℃, the intrinsic viscosity of the melt after extrusion is reduced by 0.01-0.05 dL/g, and the fiber stretching multiplying power is 3.0-5.0.
As still further aspects of the invention: the micro-alcoholysis in the second step specifically comprises the following steps: the fiber is soaked in dihydric alcohol with the temperature of 150-200 ℃ and the activated catalyst of 50-500 ppm for 10-100 s, wherein the mass ratio of the fiber to the dihydric alcohol is 1:10-40.
As still further aspects of the invention: in the third step, the mass ratio of the polyester fiber to the flame retardant solution is 1:10-30, the flame retardant is cyclohexane hexaphosphoric acid, and the mass fraction of the flame retardant in the water solution is 20-60%.
As still further aspects of the invention: the activation catalyst is one or more of sodium acetate, zinc acetate, manganese acetate, sodium sulfate, potassium sulfate, zinc chloride or magnesium chloride, the dihydric alcohol is one or more of ethylene glycol, propylene glycol, butanediol or pentanediol, and the content of the reactive hydroxyl functional group of the surface-activated polyester fiber is 100-1000 mol/t.
As still further aspects of the invention: the chemical grafting reaction process parameters comprise: the reaction temperature is 150-220 ℃, the reaction time is 30-300 s, the catalyst for the chemical grafting reaction is methanesulfonic acid, and the mass fraction of the catalyst is 100-1000 ppm relative to the flame retardant.
As still further aspects of the invention: the tensile breaking strength of the high-strength flame-retardant polyester fiber prepared in the step three is 4.5-8.0 cN/dtex, the elongation at break is 15-30%, the phosphorus content is 6000-10000 ppm, the limiting oxygen index is 30-35, the breaking strength of the fiber is reduced by less than 5% after 30 times of water washing, and the limiting oxygen index is reduced by less than 10%.
Compared with the prior art, the invention has the beneficial effects that:
1. the preactivator is low-melting-point copolyester, is introduced into a high-viscosity polyester melt to play a role of plasticization, weakens the interaction force of high-viscosity polyester molecular chains to a certain extent, reduces cohesive energy, further improves fluidity, reduces viscosity reduction of the high-viscosity polyester in spinning forming, and is beneficial to improvement of spun fiber strength.
2. Compared with the high-viscosity polyester, the preactivation agent has remarkable shear thinning behavior, is easier to migrate and distribute on the surface of the fiber under the same shearing acting force, and the depolymerization agent dihydric alcohol is diffused into the surface structure of the fiber to be activated in the activation process, so that the high-viscosity polyester part playing a role of a mechanical strength skeleton is not influenced, and the fiber strength is not reduced when the surface of the fiber is fully activated.
3. The activated fiber surface is rich in reactive hydroxyl functional groups, can carry out chemical reaction in a crosslinking mode with high-activity cyclohexanethol hexaphosphoric acid, improves the bonding acting force of the fiber, and the grafted flame retardant is not easy to fall off.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
In the embodiment of the invention, the preparation method of the high-strength flame-retardant polyester fiber is characterized in that the high-viscosity polyester and the high-fluidity pre-activated melt are blended and spun, and the fiber is subjected to micro-alcoholysis to form the reactive hydroxyl functional group, so that the surface-activated polyester fiber is prepared. And immersing the activated polyester fiber in a solution containing a flame retardant for chemical grafting reaction to obtain the high-strength flame-retardant polyester fiber.
Example 2
The difference from example 1 is that:
wherein the high-viscosity polyester is one or a combination of more of fiber-grade polyethylene terephthalate, fiber-grade poly-1, 3-propanediol terephthalate or fiber-grade polybutylene terephthalate; wherein the intrinsic viscosity is 0.80-1.25 dL/g, and the melt index is 10-30 g/10min under the conditions of 280 ℃ and 2.16kg load.
Still further aspects, wherein the high flow pre-activated polyester is a low melting polyester; wherein the melting point of the preactivated polyester is 120-200 ℃, and the melt index under the conditions of 280 ℃ and 2.16kg load is 30-100 g/10min.
In a further embodiment, the mass ratio of the preactivation of the high flowability to the mixing of the high-viscosity polyester is from 99:1 to 90:10.
Still further aspects, wherein the process parameters of melt blending spinning include: the spinning temperature is 260-295 ℃, the intrinsic viscosity of the melt after extrusion is reduced by 0.01-0.05 dL/g, and the fiber stretching multiplying power is 3.0-5.0.
In a further embodiment, the fiber is subjected to micro-alcoholysis by immersing the fiber in a glycol having a temperature of 150 to 200 ℃ and containing 50 to 500ppm of an activating catalyst for 10 to 100 seconds.
In a further scheme, the mass ratio of the fiber to the dihydric alcohol is 1:10-40.
Wherein the activating catalyst is one or a combination of more of sodium acetate, zinc acetate, manganese acetate, sodium sulfate, potassium sulfate, zinc chloride or magnesium chloride; the dihydric alcohol is one or a combination of more than one of ethylene glycol, propylene glycol, butanediol or pentanediol, and the content of the reactive hydroxyl functional group of the surface activated polyester fiber is 100-1000 mol/t.
In a further scheme, the activated polyester fiber is immersed in a solution containing a flame retardant for chemical grafting reaction to prepare the high-strength flame-retardant polyester fiber.
In a further scheme, the mass ratio of the fiber to the flame retardant solution is 1:10-30, and the flame retardant is cyclohexane hexaphosphoric acid.
Still further, wherein the mass fraction of the flame retardant in the aqueous solution is 20-60%.
Still further aspects, wherein the fibers are chemically grafted in a solution of the flame retardant; wherein the reaction temperature is 150-220 ℃ and the reaction time is 30-300 s; wherein the catalyst for the chemical grafting reaction is methanesulfonic acid, and the mass fraction of the catalyst is 100-1000 ppm relative to the mass fraction of the flame retardant.
The tensile breaking strength of the high-strength flame-retardant polyester fiber is 4.5-8.0 cN/dtex, the elongation at break is 15-30%, the phosphorus content is 6000-10000 ppm, and the limiting oxygen index is 30-35. After 30 times of water washing, the breaking strength of the fiber is reduced by less than 5 percent, and the limiting oxygen index is reduced by less than 10 percent.
The principle of the invention is as follows: the invention firstly introduces a preactivator with high flow characteristic in the preparation process of the polyester fiber, leads the preactivator to migrate to the surface of the fiber by controlling the preactivator to generate microphase separation, and then carries out micro-alcoholysis on the preactivator on the surface of the fiber to form a reactive hydroxyl functional group, thus preparing the surface-activated polyester fiber.
The mechanical strength of polyester fibers is affected by a number of factors, including the molecular weight of the fiber matrix, the degree of fiber stretch orientation, and the like. In theory, the higher the molecular weight of the spinning melt of the general fiber is, the higher the mechanical strength is, and the higher the orientation degree of the fiber in spinning and forming is, the higher the mechanical strength is. However, the melt flowability of the high molecular weight tends to be poor because the high molecular weight polyester molecules are entangled to a high degree, the cohesive energy is high, and the poor flowability leads to an increase in residence time at high temperature in spinning formation. In order to ensure flowability of the high viscosity melt, it is generally chosen to raise the forming temperature, but the degree of thermal oxygen degradation of the polymer at high temperatures is exacerbated, resulting in a decrease in molecular weight, and hence an unexpected high strength of the spun fibers. Thus, high viscosity polyesters are important methods for achieving high strength of fibers by promoting their flowability in spin forming. The spinning melt of the present invention is a high viscosity polyester, and in order to promote the fluidity of the high viscosity polyester, a preactivator having a high flow characteristic is introduced. The preactivator is low-melting-point copolyester, is introduced into a high-viscosity polyester melt to play a role of plasticization, weakens the interaction force of high-viscosity polyester molecular chains to a certain extent, reduces cohesive energy, further improves fluidity, reduces viscosity reduction of the high-viscosity polyester in spinning forming, and is beneficial to improvement of spun fiber strength.
Compared with the conventional polyester, the preactivated material has high fluidity, and phase separation can be formed between components in the blending melt spinning to a certain extent. According to the blending theory known in the art, the components with high flow characteristics are more easily distributed on the surface of the material by shearing, stretching and other acting forces in the mixing process, so that the introduced preactivator gradually migrates to the surface of the fiber and diffuses into the surface layer structure of the fiber in the blending melt spinning process. At the same time, the high viscosity polyesters are different from the preactivators due to their thermodynamic properties, and although they are compatible to some extent, they are not compatible at the molecular level. The preactivator is a macromolecular polymer, and is blended and introduced into polyester to form an alloy, so that the mechanical properties of the formed fiber are not reduced, and the introduction of the preactivator is ensured, and meanwhile, the spinnability of the polyester and the basic mechanical properties of the fiber are not adversely affected.
The preactivator with high flow characteristic is low-melting point polyester, on one hand, the polymers have high flow characteristic and can be distributed on the surface layer of the fiber, and on the other hand, the polymers have better compatibility with a polyester matrix, and macroscopic phase separation can not occur, so that the spinnability is ensured. If other types of polymers are used, the poor compatibility with polyester results in a significant decrease in the spinnability of the fiber, which results in the fiber being unusable. The preactivator distributed on the surface layer of the fiber is low-melting-point polyester which is prepared by copolymerizing polybasic acid and polyalcohol, and compared with high-viscosity polyester, the low-melting-point polyester has lower chemical stability except that the high-viscosity polyester has more obvious shear thinning under the same shearing force. The low-melting polyester of the surface layer is activated in a micro-alcoholysis mode under the activation condition, and the micro-alcoholysis reaction is essentially that ester bonds in the low-melting polyester are broken under the attack of a depolymerizing agent dihydric alcohol to form a chain segment with rich functional group end caps. And then the flame retardant is chemically reacted with the flame retardant, namely the cyclohexane hexaol hexaphosphoric acid containing multi-carboxyl functional groups, wherein the flame retardant, namely the cyclohexane hexaol hexaphosphoric acid is grafted on the surface of the fiber, and the cyclohexane hexaol hexaphosphoric acid has multi-chemical sites and high carboxyl activity, can generate cross-linking type multi-functional group reaction on the surface of the fiber, and has high flame retardant bonding fastness. The flame retardant can not fall off under the action of external heat, humidity and the like, and the durability is strong.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. Although the present disclosure describes embodiments in terms of one embodiment, not every embodiment is provided with only one embodiment, and the description is for clarity only, and those skilled in the art should recognize that the embodiments described in the disclosure may be combined appropriately to form other embodiments that will be understood by those skilled in the art.
Claims (10)
1. The preparation method of the high-strength flame-retardant polyester fiber is characterized by comprising the following steps of:
step one: melt blending and spinning the high-viscosity polyester and the high-fluidity pre-activated polyester;
step two: performing micro-alcoholysis on the fiber in the first step to form a reactive hydroxyl functional group, so as to obtain a surface-activated polyester fiber;
step three: and immersing the activated polyester fiber in a solution containing a flame retardant for chemical grafting reaction to obtain the high-strength flame-retardant polyester fiber.
2. The method for preparing high-strength flame-retardant polyester fiber according to claim 1, wherein the high-viscosity polyester is one or more of fiber-grade polyethylene terephthalate, fiber-grade poly-1, 3-propanediol terephthalate or fiber-grade polybutylene terephthalate, and has an intrinsic viscosity of 0.80-1.25 dL/g and a melt index of 10-30 g/10min at a temperature of 280 ℃ and a load of 2.16 kg.
3. The method for preparing a high-strength flame-retardant polyester fiber according to claim 1, wherein the high-fluidity pre-activated polyester is a low-melting polyester; the melting point is 120-200 ℃, and the melt index is 30-100 g/10min under the conditions of the temperature of 280 ℃ and the load of 2.16 kg.
4. The method for preparing the high-strength flame-retardant polyester fiber according to claim 1, wherein the mixing mass ratio of the activated polyester to the high-viscosity polyester is 99:1-90:10.
5. The method for preparing high-strength flame-retardant polyester fiber according to claim 1, wherein the process parameters of melt blending spinning in the first step comprise: the spinning temperature is 260-295 ℃, the intrinsic viscosity of the melt after extrusion is reduced by 0.01-0.05 dL/g, and the fiber stretching multiplying power is 3.0-5.0.
6. The method for preparing high-strength flame-retardant polyester fiber according to claim 1, wherein the micro-alcoholysis in the second step specifically comprises: the fiber is soaked in dihydric alcohol with the temperature of 150-200 ℃ and the activated catalyst of 50-500 ppm for 10-100 s, wherein the mass ratio of the fiber to the dihydric alcohol is 1:10-40.
7. The method for preparing the high-strength flame-retardant polyester fiber according to claim 6, wherein the mass ratio of the polyester fiber to the flame retardant solution in the third step is 1:10-30, the flame retardant is cyclohexane hexaphosphoric acid, and the mass fraction of the flame retardant in the aqueous solution is 20-60%.
8. The method for preparing the high-strength flame-retardant polyester fiber according to claim 7, wherein the activating catalyst is one or more of sodium acetate, zinc acetate, manganese acetate, sodium sulfate, potassium sulfate, zinc chloride or magnesium chloride, the dihydric alcohol is one or more of ethylene glycol, propylene glycol, butanediol or pentanediol, and the content of the reactive hydroxyl functional groups of the surface-activated polyester fiber is 100-1000 mol/t.
9. The method for preparing the high-strength flame-retardant polyester fiber according to claim 1, wherein the chemical grafting reaction process parameters comprise: the reaction temperature is 150-220 ℃, the reaction time is 30-300 s, the catalyst for the chemical grafting reaction is methanesulfonic acid, and the mass fraction of the catalyst is 100-1000 ppm relative to the flame retardant.
10. The method for preparing the high-strength flame-retardant polyester fiber according to claim 1, wherein the tensile breaking strength of the high-strength flame-retardant polyester fiber prepared in the step three is 4.5-8.0 cN/dtex, the elongation at break is 15-30%, the phosphorus content is 6000-10000 ppm, the limiting oxygen index is 30-35, the breaking strength of the fiber after washing for 30 times is reduced by less than 5%, and the limiting oxygen index is reduced by less than 10%.
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