CN117645714A - High-viscosity SiO 2 DDP flame-retardant copolyester slice, and preparation method and application thereof - Google Patents
High-viscosity SiO 2 DDP flame-retardant copolyester slice, and preparation method and application thereof Download PDFInfo
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- CN117645714A CN117645714A CN202410105301.4A CN202410105301A CN117645714A CN 117645714 A CN117645714 A CN 117645714A CN 202410105301 A CN202410105301 A CN 202410105301A CN 117645714 A CN117645714 A CN 117645714A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 153
- 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 151
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 89
- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 97
- 229920000728 polyester Polymers 0.000 claims abstract description 54
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 23
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000005886 esterification reaction Methods 0.000 claims abstract description 22
- 238000009987 spinning Methods 0.000 claims abstract description 22
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 20
- 239000007791 liquid phase Substances 0.000 claims abstract description 19
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000012792 core layer Substances 0.000 claims abstract description 12
- 239000000306 component Substances 0.000 claims description 24
- 230000009477 glass transition Effects 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000002485 combustion reaction Methods 0.000 claims description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000008358 core component Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 15
- 239000000377 silicon dioxide Substances 0.000 abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 13
- 230000000052 comparative effect Effects 0.000 description 22
- 230000000694 effects Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical group [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- XXDAXUSYDPWTPK-UHFFFAOYSA-N 2-(oxo-lambda5-phosphanylidyne)acetic acid Chemical compound P(=O)#CC(=O)O XXDAXUSYDPWTPK-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 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 description 2
- 238000005303 weighing Methods 0.000 description 2
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 description 1
- -1 Polyethylene terephthalate Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—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
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- 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
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the field of polyester industrial yarns, and relates to a high-viscosity SiO (silicon dioxide) 2 The method is that PTA, EG, DDP, TEOS, antimony catalyst and heat stabilizer are added into a reaction kettle together and then esterification reaction and sol-gel reaction are carried out simultaneously, after the esterification reaction and the sol-gel reaction are finished, polycondensation reaction and liquid phase tackifying reaction are carried out sequentially, thus obtaining the high-viscosity SiO 2 -DDP flame retardant copolyester chips; high viscosity SiO 2 DDP flame-retardant copolyester slice is prepared from modified polyester and two-dimensional S dispersed thereiniO 2 The modified polyester molecular chain consists of a PTA chain segment, an EG chain segment and a DDP chain segment; the application is that the high-viscosity PET is used as the component of the core layer, and the high-viscosity SiO is used at the same time 2 And (3) taking the DDP flame-retardant copolyester as a sheath component to carry out sheath-core composite spinning to obtain the high-strength flame-retardant industrial yarn. The high-strength flame-retardant industrial yarn has the advantages of good flame retardance, good molten drop resistance and the like.
Description
Technical Field
The invention belongs to the field of polyester industrial yarns, and relates to a high-viscosity SiO (silicon dioxide) 2 DDP flame-retardant copolyester slice, and preparation method and application thereof.
Background
Polyethylene terephthalate (PET) is widely used in the fields of clothing fabric, aerospace, electronic devices, buildings and the like due to its excellent physical and mechanical properties and chemical stability. However, the polyester material is composed of carbon and hydrogen combustible elements, is easy to decompose and burn at high temperature, and the burning process is accompanied by molten drops and toxic smog, so that the life and property safety of individuals and society is endangered, and the application scene of the polyester material is limited. Therefore, the research on how to improve the flame retardant property of the polyester material has great economic and social benefits.
The phosphorus-containing organic flame retardant has good compatibility with a polyester matrix and gives flame retardant effect to flame-retardant polyester, so researchers synthesize a series of organic phosphorus flame retardants, introduce silicon element into the flame retardants to form synergistic flame retardant effect, and obtain flame-retardant polyester with excellent flame retardant property through a blending and copolymerization method. However, the flame retardant polyester prepared by the prior art has lower viscosity, and industrial yarns with excellent mechanical properties are difficult to further prepare. For example, patent CN105908284a discloses an environment-friendly flame-retardant polyester fiber, which is prepared by melt spinning a phosphorus flame retardant, an inorganic substance (comprising silicon dioxide, aluminum hydroxide and magnesium hydroxide) and a polyester main body, wherein the inorganic substance can play a role in synergetic flame retardance in a system, and can obviously improve the LOI value of the fiber, but the spinning temperature of the flame-retardant polyester obtained by the method is only 240-245 ℃ and is completely lower than the spinning temperature (269-285 ℃) of a low-viscosity polyester slice, which shows that the obtained polyester fiber has low melting point and viscosity and cannot be used for preparing industrial yarns, and for example, patent CN101139435A discloses a polyester with excellent flame retardance and a preparation method thereof.
Therefore, research on a high-viscosity copolyester slice with excellent flame retardant property and preparation of high-strength flame-retardant polyester industrial yarn from the slice are of great significance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a high-viscosity SiO 2 DDP flame-retardant copolyester slice, and preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
high-viscosity SiO 2 Preparation of flame-retardant copolyester chips of (E) -DDP PTA, EG, DDP ([ (6-oxo-6H-dibenzo- (C, E) (1, 2) -oxaphosphorin-6-one) -methyl)]Succinic acid), TEOS (tetraethoxysilane), antimony-based catalysts and heatAdding a stabilizer into a reaction kettle together, then simultaneously carrying out esterification reaction and sol-gel reaction, steaming out excessive glycol in the reaction kettle under normal pressure after the esterification reaction and the sol-gel reaction are finished, carrying out polycondensation reaction, carrying out liquid-phase tackifying reaction after the polycondensation reaction is finished, extruding polyester after nitrogen is introduced into the reaction kettle after the liquid-phase tackifying is finished, and carrying out water cooling and slicing to obtain the high-viscosity SiO with the intrinsic viscosity of 0.93-1.12 dL/g 2 -DDP flame retardant copolyester chips, wherein the molar amount of TEOS is greater than the molar amount of water theoretically produced by the esterification reaction;
in the prior art, after esterification is finished, cooling, adding TEOS and water, performing sol-gel reaction to form three-dimensional silicon dioxide, and continuing polymerization reaction, wherein the three-dimensional silicon dioxide causes that polyester is difficult to realize high-power drafting in the spinning process, which is not beneficial to the preparation of polyester industrial yarns;
the invention adopts a one-step method to lead the esterification reaction and the sol-gel reaction to simultaneously occur, PTA and EG are subjected to the esterification reaction to generate water, DDP and EG are subjected to the esterification reaction to generate water, and the water and TEOS are subjected to the sol-gel reaction to obtain the two-dimensional silicon dioxide, and the DDP has a benzoxepin-hexamethylene ring structure, so that the steric effect is large, and the activity of the antimony catalyst used by the invention is low, so that the silicon dioxide is difficult to be subjected to the polycondensation reaction with the esterification reaction product in the polycondensation reaction process, and can only be uniformly dispersed in the polycondensation reaction product, and the reaction equation is as follows:
；
；
；
on one hand, the water generated in the esterification reaction process can regulate and control the sol-gel reaction degree, and on the other hand, the sol-gel reaction consumes water, so that the esterification reaction is carried out in the forward direction, and the esterification reaction rate is accelerated;
the polycondensation process takes place as follows:
；
in the prior art, after the flame-retardant monomer is introduced into the polyester, the difficulty of polymerization is increased in the later stage of polymerization, so that the high-viscosity flame-retardant copolyester slice is difficult to obtain by a liquid-phase tackifying method, and the problem can be solved by the method, because: the molar quantity of TEOS is larger than that of water generated by an esterification reaction theory, and excessive TEOS can still be hydrolyzed during polycondensation reaction, so that the polycondensation reaction is promoted to proceed forward, and the molecular weight is increased; the two-dimensional silicon dioxide is dispersed in a matrix and can be used as a carrier to transfer small molecules so as to promote the diffusion of small molecules such as glycol, water and acetaldehyde, and the liquid phase tackifying reaction is an equilibrium reaction, so that the small molecules such as glycol, water and acetaldehyde generated in the reaction process are continuously excluded to enable the polycondensation reaction to proceed forward.
As a preferable technical scheme:
a high viscosity SiO as described above 2 The preparation method of the DDP flame-retardant copolyester slice comprises the steps of (1) preparing a flame-retardant copolyester slice, wherein the molar ratio of PTA, EG, TEOS, DDP is 1:1.2-1.5:2.1-4.2:0.05-1.05, the mass addition amount of the antimony catalyst is 300-400 ppm of the mass addition amount of PTA, and the mass addition amount of the heat stabilizer is 300-600 ppm of the mass addition amount of PTA.
A high viscosity SiO as described above 2 The preparation method of the DDP flame-retardant copolyester slice comprises the steps that the antimony catalyst is ethylene glycol antimony, the antimony catalyst plays a role in the polycondensation process, and the heat stabilizer is more than one of trimethyl phosphate, phosphoric acid, triphenyl phosphate and triethyl phosphorylacetate.
A high viscosity SiO as described above 2 The preparation method of the DDP flame-retardant copolyester slice comprises the steps of carrying out esterification reaction and sol-gel reaction at 180-240 ℃ for 2-3 hours under nitrogen or inert gas, and stirring at a speed of 85-90 r/min.
A high viscosity SiO as described above 2 Preparation method of DDP flame-retardant copolyester slice, and polycondensation reaction temperatureThe reaction pressure is 30-60 Pa at 250-280 ℃ for 2-3.5 h.
A high viscosity SiO as described above 2 The preparation method of the DDP flame-retardant copolyester slice comprises two stages, wherein the liquid-phase tackifying reaction is carried out at the temperature of 285-290 ℃ and the reaction pressure of 30-70 Pa for 15-30 min, ethylene glycol micromolecules are removed as soon as possible under the conditions of high temperature and low viscosity, the transesterification rate is improved, and the second stage is carried out at the temperature of 270-285 ℃ and the reaction pressure of 30-70 Pa for 30-50 min, so that the molecular chain is continuously increased and the molecular weight is increased.
The invention also provides a high-viscosity SiO composition 2 High-viscosity SiO (SiO) prepared by preparation method of DDP (polyethylene glycol) flame-retardant copolyester chips 2 DDP flame-retardant copolyester slice made of modified polyester and two-dimensional SiO dispersed therein 2 The molecular chain of the modified polyester consists of a PTA chain segment, an EG chain segment and a DDP chain segment.
As a preferable technical scheme:
a high viscosity SiO as described above 2 DDP flame-retardant copolyester slice, high-viscosity SiO 2 The number average molecular weight of the DDP flame-retardant copolyester slice is 28,000-45,000 g/mol, the molecular weight distribution index is 2.35-2.75, and the glass transition temperature is 83.5-85.5 ℃.
The invention also provides the high-viscosity SiO 2 Application of DDP flame-retardant copolyester slice takes high-viscosity PET (intrinsic viscosity is 1.05-1.2 dL/g) as core layer component, and simultaneously takes high-viscosity SiO 2 And (3) taking the DDP flame-retardant copolyester as a sheath component, and carrying out sheath-core composite spinning to obtain the high-strength flame-retardant industrial yarn.
As a preferable technical scheme:
by the application, the mass ratio of the core component to the skin component is 25-35:75-65; the technological parameters of the sheath-core composite spinning comprise: the temperature of the screw is 270-305 ℃; the temperature of a back draft roller is 60-70 ℃ and the speed is 500-650 m/min; the temperature of the back drafting two rollers is 90-100 ℃, and the speed is 520-680 m/min; the temperature of the back drafting three rollers is 125-135 ℃, and the speed is 1900-2500 m/min; the temperature of the back drafting four rollers is 210-220 ℃, and the speed is 2850-3200 m/min; the temperature of the rear drafting five rollers is 140-155 ℃, and the speed is 2825-3175 m/min; the winding speed is 2750-3095 m/min.
By the application, the fineness of the high-strength flame-retardant industrial yarn is 1130-1160 dtex/192f, the breaking strength is more than or equal to 7.81cN/dtex, the elongation at break is 15-20%, the LOI value is more than or equal to 35%, the vertical combustion grade reaches V-0, and the flame-retardant industrial yarn is applicable to industrial mass production;
the invention can make up the deficiency of the prior art, the cortex of the high-strength flame-retardant industrial yarn plays a role in flame retardance, the core layer plays a role in improving strength, the adhesion and compatibility of the cortex core layer are good, the phenomena of phase separation and the like can not occur, the cortex core layers are all high in adhesion, the unstable melt pressure in the assembly can not be caused by the difference of the viscosity of the cortex core, and the fiber spinning molding is more stable; the cortex contains DDP and two-dimensional SiO 2 Two-dimensional SiO 2 Can obviously improve the glass transition temperature of the modified polyester, increase the thermal stability of the modified polyester, and can effectively restrict the migration phenomenon of DDP to a certain extent by utilizing the characteristics of a network structure of the modified polyester, in addition, in the combustion process of the high-strength flame-retardant industrial yarn, siO 2 The heat stability, the high temperature resistance and the compactness of the carbon layer can be improved by accumulating in the modified polyester, so that the transmission of heat inside and outside the modified polyester is blocked, and the release of pyrolysis products is slowed down.
The beneficial effects are that:
(1) The high-viscosity SiO prepared by the invention 2 Uniformly dispersed two-dimensional SiO in DDP flame-retardant copolyester chips 2 And the molecular weight is high, so that the problems of difficult polymerization and adhesion after the flame retardant monomer is introduced into the polyester are solved.
(2) The high-viscosity flame-retardant copolyester chips and the high-viscosity PET prepared by the method are used for sheath-core composite spinning, so that the high-strength flame-retardant industrial yarn with excellent flame retardant property and breaking strength can be prepared.
Drawings
FIG. 1 is a high viscosity SiO of the present invention 2 Nuclear magnetic hydrogen spectrogram of modified polyester in DDP flame-retardant copolyester chip (by dissolving high viscosity SiO 2 DDP flame-retardant copolyester slice and SiO removal 2 Post test).
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The test methods for the relevant performance indexes in the following examples and comparative examples are as follows:
glass transition temperature: the flame-retardant copolyester slice is fully dried, the weight of a sample is 5mg, after DSC sample preparation is completed, a sample preparation heat table is heated, heated and melted for 4min at 270 ℃, and immediately placed in liquid nitrogen for quenching after the sample preparation is completed, and then a differential scanning calorimeter (manufacturer is American TA, model is Q20) is used for thermal performance test, and the test conditions are as follows: heating from room temperature to 280 ℃ at a speed of 10 ℃/min, maintaining for 1min, and cooling to room temperature after finishing.
Intrinsic viscosity: the intrinsic viscosity ([ eta ] dL/g) of the fiber-grade polyester chip (PET) test method is tested by referring to the standard GB/T14190-2017, fully dried flame-retardant copolyester chip is dissolved in a mixed solvent of phenol and 1, 2-tetrachloroethane (50/50, wt/wt) to form a solution with the concentration of 0.50g/dL, and the solution is subjected to intrinsic viscosity measurement in a constant-temperature water bath at 25 ℃ by using an Ubbelohde viscometer with the capillary diameter of 0.88mm, wherein the calculation formula of the intrinsic viscosity is as follows:
；
；
wherein: []Is of intrinsic viscosity->To increase specific viscosity, < >>For the solution outflow time(s), +.>For the solvent run-off time(s), +.>Is the solution concentration (g/dL).
Number average molecular weight, molecular weight distribution index: the flame-retardant copolyester slice is dissolved in Hexafluoroisopropanol (HFIP), the concentration of the solution is 1.0mg/mL, polymethyl methacrylate (PMMA) with the average molecular weight of 1.0-30.0 kg/mol is used as a standard sample in a test to obtain a standard curve, the HFIP is a mobile phase (1.0 mL/min), the column temperature is 40 ℃, and the sample injection volume is 0.5mL.
Fineness: the flame-retardant industrial yarn was subjected to fineness test by using YG086 type yarn length measuring machine and FA2004 type electronic scale (Max: 200g, d:0.0001 g), each flame-retardant industrial yarn was wound 5 times, each time was wound 100m, each time was weighed, the weight was recorded and the average value was found, the result was expanded 100 times, and the 10000m long flame-retardant industrial yarn weight was obtained and recorded as the fineness of the flame-retardant industrial yarn.
Breaking strength and elongation at break: according to the method for testing the tensile property of the chemical fiber filaments (GB/T14344-2008), the mechanical property of the flame-retardant industrial filaments is tested by adopting an 3356 type Instron tester, and the testing conditions are as follows: the temperature (20+ -5) deg.C, relative humidity (65+ -5)%, clamping distance 500mm, stretching rate 500mm/min, and test 5 times for each group of samples in the experiment, average value was taken, and breaking strength and breaking elongation were calculated.
LOI value: LOI testing of flame retardant industrial filaments was performed using a PX-01-005 type oxygen index analyzer according to ASTM D2863-2017 Standard test method (oxygen index) for measuring minimum oxygen concentration to support plastics candle burning.
Vertical combustion test: the flame retardant polyester industrial yarn was woven into a plain weave fabric having a warp density of 20/10 cm and a weft density of 6.3/10 cm. Fabrics were tested with reference to GB/T5455-2014 determination of the vertical damage Length, smoldering and sustained Combustion time of the Combustion Performance of textiles.
Flame-retardant copolyester slice SiO 2 Content testing: accurately weighing 5g of flame-retardant copolyester slice to 0.1mg, adding 200mL of mixed solvent of phenol and 1, 2-tetrachloroethane (50/50, wt/wt), dissolving at 100 ℃ for 2h, filtering, drying the obtained residue, and weighing to obtain the silicon dioxide content.
Example 1
High-viscosity SiO 2 The preparation method of the DDP flame-retardant copolyester slice comprises the following specific steps:
(1) Preparing raw materials;
PTA；
EG；
DDP；
TEOS；
protective gas: nitrogen or inert gas;
antimony-based catalyst: ethylene glycol antimony;
heat stabilizer: trimethyl phosphate;
(2) PTA, EG, DDP, TEOS, an antimony catalyst and a heat stabilizer are added into a reaction kettle together, and then the first-stage reaction is carried out under the protection of protective gas; wherein, the mol ratio of PTA, EG, TEOS, DDP is 1:1.2:2.1:0.05, the mass adding amount of the antimony catalyst is 300ppm of the mass adding amount of the PTA, the mass adding amount of the heat stabilizer is 300ppm of the mass adding amount of the PTA, the temperature of the reaction in the first stage is 180 ℃, the time is 3h, and the stirring speed is 90r/min;
(3) After the first-stage reaction is finished, carrying out a second-stage reaction; wherein the temperature of the second stage reaction is 250 ℃, the reaction pressure is 60Pa, and the time is 3.5 hours;
(4) After the second stage reaction is finished, performing liquid phase tackifying reaction for 30min at the temperature of 285 ℃ and the reaction pressure of 70Pa, and performing liquid phase tackifying reaction for 50min at the temperature of 270 ℃ and the reaction pressure of 70Pa to obtain the high-viscosity SiO 2 -DDP flame retardant copolyester chips.
Finally prepared high-viscosity SiO 2 The DDP flame-retardant copolyester slice is formed by modified polyester and dispersed thereinTwo-dimensional SiO of (2) 2 The molecular chain of the modified polyester consists of a PTA chain segment, an EG chain segment and a DDP chain segment (the nuclear magnetic hydrogen spectrogram of the modified polyester is shown in figure 1), and the high-viscosity SiO is formed 2 The intrinsic viscosity of the DDP flame-retardant copolyester chip is 0.93dL/g, the number average molecular weight is 28,000g/mol, the molecular weight distribution index is 2.35, the glass transition temperature is 83.5 ℃, and the SiO is 2 The content of (C) was 7.4% by weight.
High-viscosity SiO 2 Application of DDP flame-retardant copolyester slice, high-viscosity PET (intrinsic viscosity is 1.05 dL/g) is used as core layer component, and high-viscosity SiO prepared by the embodiment 2 The DDP flame-retardant copolyester slice is taken as a skin component, and skin-core composite spinning is carried out to prepare the high-strength flame-retardant industrial yarn; wherein the mass ratio of the core component to the skin component is 30:70;
the technological parameters of the sheath-core composite spinning comprise: the first zone temperature of the screw is 285 ℃, the second zone temperature is 290 ℃, the third zone temperature is 285 ℃, the fourth zone temperature is 285 ℃, the fifth zone temperature is 280 ℃, and the sixth zone temperature is 270 ℃; the temperature of the back drafting roller is 60 ℃ and the speed is 500m/min; the temperature of the back drafting two rollers is 90 ℃ and the speed is 520m/min; the temperature of the back drafting three rollers is 125 ℃, and the speed is 1900m/min; the temperature of the back drafting four rollers is 210 ℃, and the speed is 2850m/min; the temperature of the rear drafting five rollers is 140 ℃ and the speed is 2825m/min; the winding speed was 2750m/min.
The fineness of the finally prepared high-strength flame-retardant industrial yarn is 1130dtex/192f, the breaking strength is 7.81cN/dtex, the elongation at break is 20%, the LOI value is 36%, the flame-retardant industrial yarn is difficult to ignite when ignited, and is extinguished immediately after being ignited, almost no molten drops fall, and the vertical combustion grade reaches V-0 grade.
Comparative example 1
A method for preparing a flame retardant copolyester chip, which is basically the same as in example 1, and only differs in that: step (1) does not prepare TEOS, and TEOS is not added in step (2).
The intrinsic viscosity of the finally prepared flame-retardant copolyester slice is 0.9dL/g, the number average molecular weight is 27,500g/mol, the molecular weight distribution index is 2.38, and the glass transition temperature is 80.5 ℃.
The use of flame retardant copolyester chips was substantially the same as in example 1, except that: the skin layer component adopts the flame-retardant copolyester slice prepared by the comparative example.
The LOI value of the finally produced flame retardant industrial yarn was 28%, and the vertical burning test found that the sample bars produced from the flame retardant industrial yarn of comparative example 1 were burned to produce more droplets accompanied by dripping of inflammable defatted cotton, and the vertical burning grade was V-2.
As can be seen from comparison of comparative example 1 and example 1, siO of example 1 2 The intrinsic viscosity, the number average molecular weight and the glass transition temperature of the DDP flame-retardant copolyester chips are higher, and the molecular weight distribution index is lower, because the TEOS added in the embodiment 1 can promote the esterification and the polycondensation of the polyester to be carried out in the positive reaction direction, so that the embodiment 1 has faster reaction rate and better liquid-phase tackifying effect under the same polycondensation temperature and pressure condition, and meanwhile, the hydrolysis reaction of the TEOS leads to the introduction of SiO into the system 2 Can obviously improve the glass transition temperature of the modified polyester and increase the thermal stability of the modified polyester. The LOI value and the anti-dripping property of the high strength flame retardant industrial yarn of example 1 are both higher than those of the flame retardant industrial yarn of comparative example 1 because of the SiO employed in example 1 2 Has synergistic flame retardant effect with DDP, and during combustion, siO 2 On one hand, the modified polyester can be accumulated, and the thermal stability, the high temperature resistance and the compactness of the carbon layer can be improved, so that the transmission of heat inside and outside the modified polyester is blocked, the release of pyrolysis products is slowed down, the anti-dripping effect is achieved, and on the other hand, the SiO is prepared 2 The two-dimensional network structure can effectively restrict the migration of DDP to a certain extent, and the flame retardant effect is improved.
Comparative example 2
SiO (silicon dioxide) 2 The process for preparing the DDP flame retardant copolyester chips is substantially the same as in example 1, except that: the adding time of TEOS in the step (2) is after the first stage reaction and before the second stage reaction.
Finally prepared SiO 2 The intrinsic viscosity of the DDP flame-retardant copolyester chip is 0.91dL/g, the number average molecular weight is 27,850g/mol, the molecular weight distribution index is 2.45, the glass transition temperature is 81.4 ℃, and the SiO is 2 The content of (C) was 0.1wt%.
SiO (silicon dioxide) 2 The application of DDP flame retardant copolyester chips is basically the same as in example 1, except that: the cortex component was SiO prepared in this comparative example 2 -DDP flame retardant copolyester chips.
The ultimate breaking strength of the flame-retardant industrial yarn is 7.10cN/dtex, the LOI value is 30%, and the vertical burning experiment shows that the sample bar made of the flame-retardant industrial yarn of comparative example 2 burns to generate more molten drops, but the molten drops cannot ignite absorbent cotton, and the vertical burning grade is V-1.
As can be seen from comparison of comparative example 2 and example 1, siO was obtained in comparative example 2 2 The intrinsic viscosity, number average molecular weight and glass transition temperature of the DDP flame retardant copolyester chips are lower, and the molecular weight distribution is larger, because the hydrolysis reaction of TEOS mainly occurs in the first stage esterification reaction, and in comparative example 2, TEOS is added after the esterification reaction is finished, and only a very small amount of TEOS is hydrolyzed to generate SiO 2 A large amount of TEOS needs to be pumped away in the vacuumizing process, so that the polycondensation reaction time is prolonged, the side reaction is increased, the molecular weight distribution of the finally thickened slice is widened, and the viscosity is lower. The flame retardant industrial yarn of comparative example 2 has extremely reduced breaking strength, and has poor LOI value and anti-dripping effect because of SiO in the chips obtained in comparative example 2 2 The content of the polymer is less, the molecular weight distribution of the slice is wider, the slice contains more small molecular impurities, the compatibility with the core layer is poor in the spinning process, the melt pressure in the spinning process is unstable, the strength of the obtained flame-retardant industrial yarn is lower, and the SiO which plays a role in synergic flame retardance and molten drop resistance in the system is also realized 2 The content of (C) is low, and the flame retardant and anti-dripping effects are poor.
Comparative example 3
SiO (silicon dioxide) 2 The process for preparing the DDP flame retardant copolyester chips is substantially the same as in example 1, except that: in step (2), the molar amount of TEOS is reduced, and the molar ratio of PTA to TEOS is 1:1.6.
SiO produced in step (4) 2 The glass transition temperature of the DDP flame-retardant copolyester chips was 82.5 ℃.
SiO (silicon dioxide) 2 The application of DDP flame retardant copolyester chips is basically the same as in example 1, except that:the cortex component was SiO prepared in this comparative example 2 -DDP flame retardant copolyester chips.
The LOI value of the finally prepared flame-retardant industrial yarn is 31%, and the vertical burning experiment shows that the sample bar prepared from the flame-retardant industrial yarn of the comparative example 3 burns to generate more molten drops, but the molten drops cannot ignite absorbent cotton, and the vertical burning grade is V-1 grade.
Comparative example 3 and example 1 it can be seen that SiO was obtained in comparative example 3 2 The glass transition temperature of the DDP flame retardant copolyester chips was lower because of the lower TEOS content of comparative example 3, resulting in polyester chips with SiO 2 The content of (2) was less than that of example 1, and the glass transition temperature of the modified polyester was less elevated. The flame retardant industrial yarn of comparative example 3 has a lower LOI value and a lower anti-dripping effect because of the SiO in the chips obtained in comparative example 3 2 The content is small, and after the flame-retardant industrial yarn is prepared, the SiO which plays a role in synergistic flame retardance and anti-molten drop in the system 2 The content is less, and the flame retardance and the anti-dripping effect are poor.
Example 2
High-viscosity SiO 2 The preparation method of the DDP flame-retardant copolyester slice comprises the following specific steps:
(1) Preparing raw materials;
PTA；
EG；
DDP；
TEOS；
protective gas: nitrogen or inert gas;
antimony-based catalyst: ethylene glycol antimony;
heat stabilizer: phosphoric acid;
(2) PTA, EG, DDP, TEOS, an antimony catalyst and a heat stabilizer are added into a reaction kettle together, and then the first-stage reaction is carried out under the protection of protective gas; wherein, the molar ratio of PTA, EG, TEOS, DDP is 1:1.3:3.1:0.09, the mass addition amount of the antimony catalyst is 320ppm of the mass addition amount of the PTA, the mass addition amount of the heat stabilizer is 450ppm of the mass addition amount of the PTA, the reaction temperature in the first stage is 185 ℃, the time is 2.5h, and the stirring speed is 90r/min;
(3) After the first-stage reaction is finished, carrying out a second-stage reaction; wherein the temperature of the second stage reaction is 265 ℃, the reaction pressure is 35Pa, and the time is 3 hours;
(4) After the second stage reaction is finished, carrying out liquid phase tackifying reaction for 30min at the temperature of 287 ℃ and the reaction pressure of 60Pa, and carrying out liquid phase tackifying reaction for 45min at the temperature of 275 ℃ and the reaction pressure of 30Pa to obtain the high-viscosity SiO 2 -DDP flame retardant copolyester chips.
Finally prepared high-viscosity SiO 2 DDP flame-retardant copolyester slice is prepared from modified polyester and two-dimensional SiO dispersed therein 2 The molecular chain of the modified polyester consists of a PTA chain segment, an EG chain segment and a DDP chain segment, and is high in viscosity SiO 2 The intrinsic viscosity of the DDP flame-retardant copolyester slice is 1.08dL/g, the number average molecular weight is 37,500g/mol, the molecular weight distribution index is 2.6, the glass transition temperature is 85 ℃, and the SiO is 2 The content of (2) was 9.3% by weight.
High-viscosity SiO 2 Application of DDP flame-retardant copolyester slice, high-viscosity PET (intrinsic viscosity is 1.12 dL/g) is used as core layer component, and high-viscosity SiO prepared by the embodiment 2 The DDP flame-retardant copolyester slice is taken as a skin component, and skin-core composite spinning is carried out to prepare the high-strength flame-retardant industrial yarn; wherein the mass ratio of the core component to the skin component is 25:75;
the technological parameters of the sheath-core composite spinning comprise: the first zone temperature of the screw is 285 ℃, the second zone temperature is 290 ℃, the third zone temperature is 295 ℃, the fourth zone temperature is 295 ℃, the fifth zone temperature is 285 ℃, and the sixth zone temperature is 280 ℃; the temperature of the back drafting roller is 65 ℃ and the speed is 530m/min; the temperature of the back drafting two rollers is 95 ℃ and the speed is 580m/min; the temperature of the back drafting three rollers is 132 ℃ and the speed is 2125m/min; the temperature of the back drafting four rollers is 217 ℃ and the speed is 3180m/min; the temperature of the rear drafting five rollers is 150 ℃ and the speed is 3160m/min; the winding speed was 3080m/min.
The fineness of the finally prepared high-strength flame-retardant industrial yarn is 1147dtex/192f, the breaking strength is 8.7cN/dtex, the elongation at break is 15%, the LOI value is 35%, the flame-retardant industrial yarn is difficult to ignite when ignited, the flame is extinguished immediately after being ignited, almost no molten drops are dropped, and the vertical combustion grade reaches V-0 grade.
Example 3
High-viscosity SiO 2 The preparation method of the DDP flame-retardant copolyester slice comprises the following specific steps:
(1) Preparing raw materials;
PTA；
EG；
DDP；
TEOS；
protective gas: nitrogen or inert gas;
antimony-based catalyst: ethylene glycol antimony;
heat stabilizer: triphenyl phosphate;
(2) PTA, EG, DDP, TEOS, an antimony catalyst and a heat stabilizer are added into a reaction kettle together, and then the first-stage reaction is carried out under the protection of protective gas; wherein, the molar ratio of PTA, EG, TEOS, DDP is 1:1.5:3.5:1, the mass addition amount of the antimony catalyst is 360ppm of the mass addition amount of the PTA, the mass addition amount of the heat stabilizer is 550ppm of the mass addition amount of the PTA, the temperature of the first-stage reaction is 210 ℃, the time is 2h, and the stirring rate is 85r/min;
(3) After the first-stage reaction is finished, carrying out a second-stage reaction; wherein the temperature of the second stage reaction is 275 ℃, the reaction pressure is 30Pa, and the time is 2 hours;
(4) After the second stage reaction is finished, carrying out liquid phase tackifying reaction for 20min at the temperature of 290 ℃ and the reaction pressure of 35Pa, and then carrying out liquid phase tackifying reaction for 40min at the temperature of 280 ℃ and the reaction pressure of 30Pa to obtain the high-viscosity SiO 2 -DDP flame retardant copolyester chips.
Finally prepared high-viscosity SiO 2 DDP flame-retardant copolyester slice is prepared from modified polyester and two-dimensional SiO dispersed therein 2 The molecular chain of the modified polyester consists of a PTA chain segment, an EG chain segment and a DDP chain segment, and is high in viscosity SiO 2 The intrinsic viscosity of the DDP flame-retardant copolyester slice is 1.1dL/g, the number average molecular weight is 39,400g/mol, the molecular weight distribution index is 2.63, the glass transition temperature is 84 ℃, and the SiO is 2 The content of (C) was 12.5% by weight.
High-viscosity SiO 2 Use of DDP flame retardant copolyester chips in high viscosity PET (intrinsic viscosity1.15 dL/g) as core layer component, and high viscosity SiO prepared in this example 2 The DDP flame-retardant copolyester slice is taken as a skin component, and skin-core composite spinning is carried out to prepare the high-strength flame-retardant industrial yarn; wherein the mass ratio of the core component to the skin component is 30:70;
the technological parameters of the sheath-core composite spinning comprise: the first temperature of the screw is 285 ℃, the second temperature of the screw is 290 ℃, the third temperature of the screw is 295 ℃, the fourth temperature of the screw is 295 ℃, the fifth temperature of the screw is 290 ℃, and the sixth temperature of the screw is 280 ℃; the temperature of the back drafting roller is 65 ℃ and the speed is 550m/min; the temperature of the back drafting two rollers is 98 ℃, and the speed is 600m/min; the temperature of the back drafting three rollers is 133 ℃, and the speed is 2130m/min; the temperature of the back drafting four rollers is 215 ℃ and the speed is 3185m/min; the temperature of the rear drafting five rollers is 153 ℃ and the speed is 3165m/min; the winding speed was 3085m/min.
The fineness of the finally prepared high-strength flame-retardant industrial yarn is 1145dtex/192f, the breaking strength is 8.52cN/dtex, the elongation at break is 16.5%, the LOI value is 38%, the flame-retardant industrial yarn is difficult to ignite when ignited, the flame is extinguished immediately after being ignited, almost no molten drops are dropped, and the vertical combustion grade reaches V-0 grade.
Example 4
High-viscosity SiO 2 The preparation method of the DDP flame-retardant copolyester slice comprises the following specific steps:
(1) Preparing raw materials;
PTA；
EG；
DDP；
TEOS；
protective gas: nitrogen or inert gas;
antimony-based catalyst: ethylene glycol antimony;
heat stabilizer: triethyl phosphorylacetate;
(2) PTA, EG, DDP, TEOS, an antimony catalyst and a heat stabilizer are added into a reaction kettle together, and then the first-stage reaction is carried out under the protection of protective gas; wherein, the mol ratio of PTA, EG, TEOS, DDP is 1:1.4:4:1.05, the mass addition amount of the antimony catalyst is 350ppm of the mass addition amount of the PTA, the mass addition amount of the heat stabilizer is 500ppm of the mass addition amount of the PTA, the temperature of the first-stage reaction is 190 ℃, the time is 2.5h, and the stirring rate is 85r/min;
(3) After the first-stage reaction is finished, carrying out a second-stage reaction; wherein the temperature of the second stage reaction is 275 ℃, the reaction pressure is 40Pa, and the time is 2.5 hours;
(4) After the second stage reaction is finished, performing liquid phase tackifying reaction for 15min at the temperature of 290 ℃ and the reaction pressure of 30Pa, and performing liquid phase tackifying reaction for 30min at the temperature of 285 ℃ and the reaction pressure of 50Pa to obtain the high-viscosity SiO 2 -DDP flame retardant copolyester chips.
Finally prepared high-viscosity SiO 2 DDP flame-retardant copolyester slice is prepared from modified polyester and two-dimensional SiO dispersed therein 2 The molecular chain of the modified polyester consists of a PTA chain segment, an EG chain segment and a DDP chain segment, and is high in viscosity SiO 2 The intrinsic viscosity of the DDP flame-retardant copolyester slice is 1.09dL/g, the number average molecular weight is 38,900g/mol, the molecular weight distribution index is 2.62, the glass transition temperature is 84.5 ℃, and the SiO is 2 The content of (C) was 15.6% by weight.
High-viscosity SiO 2 Application of DDP flame-retardant copolyester slice, high-viscosity PET (intrinsic viscosity is 1.15 dL/g) is used as core layer component, and high-viscosity SiO prepared by the embodiment 2 The DDP flame-retardant copolyester slice is taken as a skin component, and skin-core composite spinning is carried out to prepare the high-strength flame-retardant industrial yarn; wherein the mass ratio of the core component to the skin component is 35:65;
the technological parameters of the sheath-core composite spinning comprise: the first temperature of the screw is 285 ℃, the second temperature of the screw is 295 ℃, the third temperature of the screw is 295 ℃, the fourth temperature of the screw is 295 ℃, the fifth temperature of the screw is 290 ℃, and the sixth temperature of the screw is 280 ℃; the temperature of the back drafting roller is 65 ℃ and the speed is 550m/min; the temperature of the back drafting two rollers is 95 ℃ and the speed is 580m/min; the temperature of the back drafting three rollers is 132 ℃ and the speed is 2128m/min; the temperature of the back drafting four rollers is 218 ℃, and the speed is 3180m/min; the temperature of the rear drafting five rollers is 152 ℃ and the speed is 3163m/min; the winding speed was 3080m/min.
The fineness of the finally prepared high-strength flame-retardant industrial yarn is 1149dtex/192f, the breaking strength is 8.13cN/dtex, the elongation at break is 15.8%, the LOI value is 39%, the flame-retardant industrial yarn is difficult to ignite when ignited, the flame is extinguished immediately after being ignited, almost no molten drops are dropped, and the vertical combustion grade reaches V-0 grade.
Example 5
High-viscosity SiO 2 The preparation method of the DDP flame-retardant copolyester slice comprises the following specific steps:
(1) Preparing raw materials;
PTA；
EG；
DDP；
TEOS；
protective gas: nitrogen or inert gas;
antimony-based catalyst: ethylene glycol antimony;
heat stabilizer: a mixture of trimethyl phosphate and phosphoric acid in a mass ratio of 1:1;
(2) PTA, EG, DDP, TEOS, an antimony catalyst and a heat stabilizer are added into a reaction kettle together, and then the first-stage reaction is carried out under the protection of protective gas; wherein, the mol ratio of PTA, EG, TEOS, DDP is 1:1.5:4.2:1.05, the mass adding amount of the antimony catalyst is 400ppm of the mass adding amount of the PTA, the mass adding amount of the heat stabilizer is 600ppm of the mass adding amount of the PTA, the temperature of the reaction in the first stage is 240 ℃, the time is 2h, and the stirring speed is 85r/min;
(3) After the first-stage reaction is finished, carrying out a second-stage reaction; wherein the temperature of the second stage reaction is 280 ℃, the reaction pressure is 30Pa, and the time is 2 hours;
(4) After the second stage reaction is finished, performing liquid phase tackifying reaction for 30min at the temperature of 285 ℃ and the reaction pressure of 30Pa, and performing liquid phase tackifying reaction for 50min at the temperature of 285 ℃ and the reaction pressure of 30Pa to obtain the high-viscosity SiO 2 -DDP flame retardant copolyester chips.
Finally prepared high-viscosity SiO 2 DDP flame-retardant copolyester slice is prepared from modified polyester and two-dimensional SiO dispersed therein 2 The molecular chain of the modified polyester consists of a PTA chain segment, an EG chain segment and a DDP chain segment, and is high in viscosity SiO 2 The intrinsic viscosity of the DDP flame-retardant copolyester chip is 1.12dL/g, the number average molecular weight is 45,000g/mol, the molecular weight distribution index is 2.75, the glass transition temperature is 85.5 ℃, and the SiO is 2 Contains (1)The amount was 15.6wt%.
High-viscosity SiO 2 Application of DDP flame-retardant copolyester slice, high-viscosity PET (intrinsic viscosity is 1.2 dL/g) is used as core layer component, and high-viscosity SiO prepared by the embodiment 2 The DDP flame-retardant copolyester slice is taken as a skin component, and skin-core composite spinning is carried out to prepare the high-strength flame-retardant industrial yarn; wherein the mass ratio of the core component to the skin component is 30:70;
the technological parameters of the sheath-core composite spinning comprise: the first zone temperature of the screw is 285 ℃, the second zone temperature is 295 ℃, the third zone temperature is 305 ℃, the fourth zone temperature is 305 ℃, the fifth zone temperature is 300 ℃, and the sixth zone temperature is 290 ℃; the temperature of the back drafting roller is 70 ℃ and the speed is 650m/min; the temperature of the back drafting two rollers is 100 ℃ and the speed is 680m/min; the temperature of the back drafting three rollers is 135 ℃ and the speed is 2500m/min; the temperature of the back drafting four rollers is 220 ℃, and the speed is 3200m/min; the temperature of the rear drafting five rollers is 155 ℃ and the speed is 3175m/min; the winding speed was 3095m/min.
The fineness of the finally prepared high-strength flame-retardant industrial yarn is 1160dtex/192f, the breaking strength is 8.05cN/dtex, the elongation at break is 18%, the LOI value is 36%, the flame-retardant industrial yarn is difficult to ignite when ignited, and is extinguished immediately after being ignited, almost no molten drops fall, and the vertical combustion grade reaches V-0 grade.
Claims (10)
1. High-viscosity SiO 2 The preparation method of the DDP flame-retardant copolyester slice is characterized in that PTA, EG, DDP, TEOS, an antimony catalyst and a heat stabilizer are added into a reaction kettle together and then subjected to esterification reaction and sol-gel reaction simultaneously, after the esterification reaction and the sol-gel reaction are finished, polycondensation reaction is carried out, after the polycondensation reaction is finished, liquid phase tackifying reaction is carried out, and then high-viscosity SiO with the intrinsic viscosity of 0.93-1.12 dL/g is obtained 2 DDP flame retardant copolyester chips, wherein the molar amount of TEOS is greater than the molar amount of water theoretically produced by the esterification reaction.
2. A high viscosity SiO according to claim 1 2 The preparation method of the DDP flame-retardant copolyester slice is characterized in that the molar ratio of PTA, EG, TEOS, DDP is 1:1.2-1.5:2.1-4.2:0.05-1.05,the mass addition amount of the antimony catalyst is 300-400 ppm of the mass addition amount of the PTA, and the mass addition amount of the heat stabilizer is 300-600 ppm of the mass addition amount of the PTA.
3. A high viscosity SiO according to claim 1 2 The preparation method of the DDP flame-retardant copolyester slice is characterized in that the temperature of the esterification reaction and the sol-gel reaction is 180-240 ℃, the time is 2-3 h, the atmosphere is nitrogen or inert gas, and the stirring speed is 85-90 r/min.
4. A high viscosity SiO according to claim 1 2 The preparation method of the DDP flame-retardant copolyester slice is characterized in that the temperature of the polycondensation reaction is 250-280 ℃, the reaction pressure is 30-60 Pa, and the time is 2-3.5 h.
5. A high viscosity SiO according to claim 1 2 The preparation method of the DDP flame-retardant copolyester slice is characterized in that the liquid-phase tackifying reaction is carried out in two stages, wherein the first stage is carried out at the temperature of 285-290 ℃ and the reaction pressure of 30-70 Pa for 15-30 min, and the second stage is carried out at the temperature of 270-285 ℃ and the reaction pressure of 30-70 Pa for 30-50 min.
6. A high-viscosity SiO as claimed in claim 1 to 5 2 High-viscosity SiO (SiO) prepared by preparation method of DDP (polyethylene glycol) flame-retardant copolyester chips 2 DDP flame-retardant copolyester chip, characterized by that it is made up by using modified polyester and two-dimensional SiO dispersed in the modified polyester 2 The molecular chain of the modified polyester consists of a PTA chain segment, an EG chain segment and a DDP chain segment.
7. A high adhesion SiO according to claim 6 2 DDP flame-retardant copolyester chip is characterized by high-viscosity SiO 2 The number average molecular weight of the DDP flame-retardant copolyester slice is 28,000-45,000 g/mol, the molecular weight distribution index is 2.35-2.75, and the glass transition temperature is 83.5-85.5 ℃.
8. A high viscosity adhesive according to claim 6 or 7SiO 2 The application of the DDP flame-retardant copolyester slice is characterized in that the high-viscosity PET is used as a core layer component, and meanwhile, the high-viscosity SiO is used 2 And (3) taking the DDP flame-retardant copolyester as a sheath component, and carrying out sheath-core composite spinning to obtain the high-strength flame-retardant industrial yarn.
9. The use according to claim 8, wherein the mass ratio of core component to skin component is 25-35:75-65; the technological parameters of the sheath-core composite spinning comprise: the temperature of the screw is 270-305 ℃; the temperature of a back draft roller is 60-70 ℃ and the speed is 500-650 m/min; the temperature of the back drafting two rollers is 90-100 ℃, and the speed is 520-680 m/min; the temperature of the back drafting three rollers is 125-135 ℃, and the speed is 1900-2500 m/min; the temperature of the back drafting four rollers is 210-220 ℃, and the speed is 2850-3200 m/min; the temperature of the rear drafting five rollers is 140-155 ℃, and the speed is 2825-3175 m/min; the winding speed is 2750-3095 m/min.
10. The use according to claim 8, wherein the high-strength flame-retardant industrial yarn has a fineness of 1130-1160 dtex/192f, a breaking strength of not less than 7.81cN/dtex, an elongation at break of 15-20%, an LOI value of not less than 35% and a vertical combustion grade of V-0.
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