CN117484901A - Preparation method of phosphorus-modified carbon nitride flame-retardant modified BOPET film - Google Patents
Preparation method of phosphorus-modified carbon nitride flame-retardant modified BOPET film Download PDFInfo
- Publication number
- CN117484901A CN117484901A CN202410004116.6A CN202410004116A CN117484901A CN 117484901 A CN117484901 A CN 117484901A CN 202410004116 A CN202410004116 A CN 202410004116A CN 117484901 A CN117484901 A CN 117484901A
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- phosphorus
- flame
- modified
- retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 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 116
- 239000003063 flame retardant Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 68
- 239000002344 surface layer Substances 0.000 claims abstract description 58
- 238000001125 extrusion Methods 0.000 claims abstract description 50
- 239000010410 layer Substances 0.000 claims abstract description 49
- 239000000155 melt Substances 0.000 claims abstract description 49
- 239000000779 smoke Substances 0.000 claims abstract description 34
- 239000012792 core layer Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 26
- 239000002105 nanoparticle Substances 0.000 claims abstract description 26
- 239000010452 phosphate Substances 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 25
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 238000010345 tape casting Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims description 68
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000011574 phosphorus Substances 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 14
- -1 phosphorus modified carbon nitride Chemical class 0.000 claims description 14
- 238000000354 decomposition reaction Methods 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 238000009998 heat setting Methods 0.000 claims description 11
- 125000003003 spiro group Chemical group 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 230000001629 suppression Effects 0.000 abstract description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 42
- 239000005020 polyethylene terephthalate Substances 0.000 description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 34
- 239000010439 graphite Substances 0.000 description 27
- 229910002804 graphite Inorganic materials 0.000 description 27
- 238000002485 combustion reaction Methods 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229920002292 Nylon 6 Polymers 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- MORLYCDUFHDZKO-UHFFFAOYSA-N 3-[hydroxy(phenyl)phosphoryl]propanoic acid Chemical compound OC(=O)CCP(O)(=O)C1=CC=CC=C1 MORLYCDUFHDZKO-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000467 phytic acid Substances 0.000 description 2
- 229940068041 phytic acid Drugs 0.000 description 2
- 235000002949 phytic acid Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical class OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000137 polyphosphoric acid Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/32—Making multilayered or multicoloured articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of a phosphorus-modified carbon nitride flame-retardant modified BOPET film, wherein the phosphorus-modified carbon nitride flame-retardant modified BOPET film is of a three-layer composite structure and consists of a core layer, an upper surface layer and a lower surface layer; respectively and uniformly mixing the core layer master batch with the upper surface layer master batch and the lower surface layer master batch, then carrying out melt extrusion, carrying out tape casting and casting on the melt after the melt is extruded by a three-layer co-extrusion die head, and preparing the phosphorus-modified carbon nitride flame-retardant modified BOPET film by biaxial stretching; the core layer master batch is PET flame-retardant master batch, and is obtained by melting, blending, extruding and granulating phosphorus-modified carbon nitride nano particles and PET; the phosphorus-modified carbon nitride nano-particles are obtained by ball milling after reacting graphite-phase carbon nitride with spiro-phosphate diacid chloride. The preparation method of the phosphorus-modified carbon nitride flame-retardant modified BOPET film is simple and easy to implement, and the prepared phosphorus-modified carbon nitride flame-retardant modified BOPET film has good flame retardant effect, smoke suppression performance and thermal stability.
Description
Technical Field
The invention belongs to the technical field of flame-retardant modified BOPET films, and relates to a preparation method of a phosphorus-modified carbon nitride flame-retardant modified BOPET film.
Background
BOPET biaxially oriented polyester film has the characteristics of excellent optical performance, chemical performance, weather resistance and recycling. However, BOPET has a Limiting Oxygen Index (LOI) of only 18-20%, belongs to inflammable materials, and generates a large amount of smoke and molten drops in the burning process, so that serious damage is caused to life health and property safety. Therefore, flame retardant modification of BOPET is necessary.
Carbon nitride has shown great potential in enhancing the flame retardancy of high molecular materials in recent years due to its high thermal stability, excellent chemical stability and excellent barrier effect.
The modification of carbon nitride generally includes the following methods:
firstly, doping elements, namely introducing other elements into a carbon nitride structure; for example, document 1 (research on the use of flame-retardant functionalized polyaniline-modified carbon nitride in epoxy coating materials [ D ]]Phosphoric acid doped carbon nitride nanoplatelets (cp@ppa) prepared by in situ chemical oxidation method for flame retarding EP, result shows that when 0.25 wt% cp@ppa is added, the total smoke release (TSP) of EP material is instead increased, from 22.6m 2 Lifting to 24.1 and 24.1 m 2 Reduced smoke suppression performance, maximum mass loss temperature (T max ) The thermal stability of the composite material is reduced from 439.3 ℃ to 392.5 ℃.
Secondly, heterogeneous compounding is carried out; for example, document 2 (preparation of graphite-phase carbon nitride hybrid phosphide flame retardant and flame-retarding application thereof in epoxy resin [ D ]]University of Hebei 2020.) core-shell structure g-C containing N, P and Zn flame retardant elements was synthesized by calcination and chemical precipitation 3 N 4 PAZn hybrid material for flame retardant modified epoxy resin (EP), the result shows that when 5 wt% g-C is added 3 N 4 at/PAZn, the total smoke emission (TSP) of the EP composite material is reduced by only 0.3% compared to the pure EP material.
Thirdly, grafting some organic compounds capable of reacting with amino groups on the surface of carbon nitride through chemical reaction; for example: literature 3 (preparation of graphite-like carbon nitride and its synergistic system and flame retardant polyamide 6 research [ D ]. University of east China, 2023.). Reacting carbon nitride with 2-carboxyethyl phenyl phosphinic acid under acidic condition, combining the two by hydrogen bond, preparing phosphorus-modified Carbon Nitride (CNALCPA) for flame retardant nylon 6 (PA 6); when 10-12 wt% of CNALCPA is added, the peak heat release rate (phr) of the composite is reduced by about 30.0% compared to the pure polyamide 6 material, but a large amount of droplets are generated during combustion and the absorbent cotton is ignited.
In summary, the prior art adopts phosphorus-containing substances to modify carbon nitride, and the flame retardant effect is not good enough.
Therefore, the preparation method of the phosphorus-modified carbon nitride flame-retardant modified BOPET film is researched to further improve the flame retardant property, and has very important significance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of a phosphorus-modified carbon nitride flame-retardant modified BOPET film.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the phosphorus-modified carbon nitride flame-retardant modified BOPET film comprises the steps that the phosphorus-modified carbon nitride flame-retardant modified BOPET film is of a three-layer composite structure and consists of a core layer, an upper surface layer and a lower surface layer; respectively and uniformly mixing the core layer master batch with the upper surface layer master batch and the lower surface layer master batch, then carrying out melt extrusion, carrying out tape casting and casting on the melt after the melt is extruded by a three-layer co-extrusion die head, and preparing the phosphorus-modified carbon nitride flame-retardant modified BOPET film by biaxial stretching; the core layer master batch is PET flame-retardant master batch, and is obtained by melting, blending, extruding and granulating phosphorus-modified carbon nitride nano particles and PET;
phosphorus modified nitrogenThe carbon-converted nano particles are prepared by mixing graphite phase carbon nitride (g-C 3 N 4 ) Reacting with spiro phosphate diacid chloride (SPDPC) and then ball-milling to obtain the product;
the PET, the graphite-phase carbon nitride and the spiro-phosphate diacid chloride are directly mixed without adopting a physical blending means, because the preparation of the graphite-phase carbon nitride needs to be carried out at a high temperature of more than 500 ℃, the number of amino groups at the edge or the end part of the graphite-phase carbon nitride is reduced, the number and the probability of hydrogen bonds formed with the PET are low when the graphite-phase carbon nitride is blended with the PET, the compatibility of the graphite-phase carbon nitride and the PET is poor, the mechanical property is reduced, and the graphite-phase carbon nitride and the PET are not directly physically blended; the invention adopts spiro phosphate diacid chloride to modify graphite phase carbon nitride, and then blends phosphorus modified carbon nitride with PET, which has the following advantages: the end amino hydrogen of unmodified graphite phase carbon nitride and PET carbon-based oxygen, N atoms of carbon nitride and the hydrogen of PET main chain can form hydrogen bonds, after spiro phosphate diacyl chloride is used for modifying graphite phase carbon nitride, phosphorus modification carbon nitride contains more O atoms besides the hydrogen bonds which can be formed, and a large number of hydrogen bonds can be formed with H on PET molecular chain, so that the compatibility between graphite phase carbon nitride and PET is enhanced, and the mechanical property of PET composite material is improved.
As a preferable technical proposal
According to the preparation method of the phosphorus-modified carbon nitride flame-retardant modified BOPET film, the mass ratio of the core layer master batch in the phosphorus-modified carbon nitride flame-retardant modified BOPET film is 80-90%, and the ratio of the upper surface layer master batch to the lower surface layer master batch is the same;
the mass ratio of the phosphorus modified carbon nitride nano particles to PET in the core layer master batch is 0.5-10:90-99.5.
The preparation method of the phosphorus-modified carbon nitride flame-retardant modified BOPET film has the advantages that the master batches on the upper surface layer and the lower surface layer are anti-adhesion master batches, and SiO is used for preparing the flame-retardant modified BOPET film 2 And (3) carrying out melt blending extrusion and granulation on the PET and the PET according to a mass ratio of 5:95.
According to the preparation method of the phosphorus-modified carbon nitride flame-retardant modified BOPET film, the Limiting Oxygen Index (LOI) of the phosphorus-modified carbon nitride flame-retardant modified BOPET film is not lower than 24.1%, and the initial oxygen index (LOI) is not lower than 24.1%Decomposition temperature (T) i ) At a maximum mass loss temperature (T) of not lower than 358 DEG C max ) Not lower than 433 ℃, and the Peak Heat Release Rate (PHRR) is lower than 796kW/m 2 Total Heat Release (THR) of less than 128MJ/m 2 Peak smoke release rate (PSPR) is less than 0.226. 0.226m 2 Per s, total smoke emission (TSP) below 37.6m 2 。
The preparation method of the phosphorus-modified carbon nitride flame-retardant modified BOPET film comprises the following specific steps:
(1) Taking urea in a crucible, heating to 350-420 ℃ in a muffle furnace at a heating rate of 5 ℃/min, heating to 500-550 ℃ after 2h of reaction, continuing the reaction for 2h, and cooling to room temperature after the reaction is completed to obtain graphite-phase carbon nitride;
the method adopts a gradient heating mode to fully calcine, urea can generate intermediates such as cyanuric acid, cyanuramide, melamine, cyanuramide, biuret and the like in the calcination process, and if insufficient calcination is carried out, the prepared graphite phase carbon nitride has too many impurities, so that the performance is affected; if the calcination time is too long, a part of graphite phase carbon nitride is decomposed, so that the yield is reduced; the temperature is increased at a heating rate of 5 ℃/min, the temperature of the first section is controlled to be 350-420 ℃, and an intermediate is fully generated at the first section; the temperature of the second section is controlled at 500-550 ℃, so that the intermediate is fully reacted to produce high-purity graphite-phase carbon nitride;
(2) Adding graphite-phase carbon nitride into toluene, performing ultrasonic dispersion, adding spiro phosphate diacyl chloride under the protection of nitrogen, reacting for 3-6 hours at 50-70 ℃, adding triethylamine, stirring and refluxing, and finally sequentially washing with acetone, performing suction filtration, performing vacuum drying at 80-100 ℃ for 8-12 hours, and performing ball milling to obtain phosphorus modified carbon nitride nano particles;
(3) Mixing the phosphorus-modified carbon nitride nano particles with PET, and carrying out melt blending extrusion and granulation by a double-screw extruder to obtain PET flame-retardant master batch;
(4) SiO is made of 2 Melt blending with PET, extruding, granulating to obtain anti-blocking master batch;
(5) Feeding the PET flame-retardant master batch into a main extruder for melt extrusion, feeding the anti-blocking master batch into an auxiliary extruder for melt extrusion, respectively feeding the melt into the same distribution block after passing through respective prefilters, metering pumps and fine filters of the main extruder and the auxiliary extruder, distributing the melt of the main extruder on a core layer, and distributing the melt of the auxiliary extruder on an upper surface layer and a lower surface layer;
(6) The distributed melt enters a three-layer co-extrusion die head, the melt of the core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and casting sheets are carried out after the extruded melt is cooled to obtain BOPET film sheets;
(7) Preheating a BOPET film sheet to above the glass transition temperature, carrying out longitudinal stretching, then carrying out transverse stretching, and cooling to room temperature after heat setting to obtain the phosphorus-modified carbon nitride flame-retardant modified BOPET film.
According to the preparation method of the phosphorus-modified carbon nitride flame-retardant modified BOPET film, in the step (2), the mass volume ratio of graphite-phase carbon nitride to toluene is 10g to 80-100 ml, the mass ratio of graphite-phase carbon nitride to spiro-phosphate diacid chloride is 10:50-80, the mass ratio of graphite-phase carbon nitride to triethylamine is 10:3-5, the ultrasonic dispersion time is 15min, and the reflux time is 1-2 h.
According to the preparation method of the phosphorus-modified carbon nitride flame-retardant modified BOPET film, the grinding balls are added according to the mass ratio of the materials to the grinding balls of 1:100 in the step (2), the grinding balls comprise three types of large, medium and small grinding balls with diameters of 5mm, 3mm and 2mm, the weight ratio of the large, medium and small grinding balls is 2:2:5, the grinding balls are stopped for 5min after rotating forward for 30min, and then rotated reversely for 30min to be a cycle, and the total cycle is 3 times; according to the invention, the mass ratio of the material to the grinding ball is respectively tried to be 1:50, 1:80 and 1:100, the mass ratio of the grinding ball to the grinding ball is 2:2:3, 2:2:5, 2:2:7, 3:2:3, 3:2:5, 3:2:7 and the like, and finally, the mass ratio of the material to the grinding ball is 1:100, and the mass ratio of the grinding ball to the grinding ball is 2:2:5, so that phosphorus-modified carbon nitride nano particles with high consistent particle size can be prepared; the ball milling time is too short to achieve good ball milling effect, but too long time can cost too much time, the ball mill can excessively generate heat to influence the service life of the machine, so that the positive rotation and the negative rotation are respectively determined to be 30 minutes, one positive rotation and one negative rotation are respectively determined to be one cycle, and one sample is subjected to 3 cycles, and the obtained effect is good.
According to the preparation method of the phosphorus-modified carbon nitride flame-retardant modified BOPET film, the stretching temperature of longitudinal stretching in the step (7) is 67-95 ℃, and the stretching multiplying power is 3-3.2 times; the stretching temperature of transverse stretching is 110-120 ℃, and the stretching multiplying power is 3-4 times; the heat setting temperature is 190-230 ℃ and the heat setting time is 10-20 s.
The mechanism of the invention is as follows:
the graphite-phase carbon nitride (g-C) 3 N 4 ) Synergistic effects with spiro-phosphate diacid chloride (SPDPC) exist in flame retardance, and specific flame retarding mechanisms involve condensed phase flame retardance and gas phase flame retardance.
(1) Condensed phase flame retardant mechanisms;
in the combustion process, SPDPC can generate compounds such as metaphosphoric acid, phosphoric acid and the like, so that dehydration and carbonization of a matrix (BOPET) can be promoted, and the carbon residue after combustion is increased; at the same time, graphite-phase carbon nitride and SiO as an opening agent 2 Can be separated out, and forms a continuous and compact protective layer together with carbon residue generated by BOPET combustion, and covers the surface of the matrix to play a role in isolating oxygen and heat, thereby preventing combustion.
(2) A gas phase flame retardant mechanism;
SPDPC generates active free radicals such as PO and Cl during combustion, and in air, the active free radicals can capture OH and H free radicals required by combustion, and the combustion is prevented or interrupted; meanwhile, the phosphorus-modified carbon nitride nano particles can generate non-combustible gases such as ammonia gas and the like in the combustion process, so that air and oxygen are diluted, the combustion trend is slowed down, and the effect of active free radicals and ammonia gas in the air is further improved, so that the flame retardant property of BOPET is further improved.
In document 1, phosphoric acid doped carbon nitride nano-sheets (cp@ppa) promote cp@ppa decomposition when heated due to the existence of a phosphoric acid group, and severe degradation occurs at about 390 ℃, so that the maximum thermal weightlessness temperature of the composite material is reduced; the cone calorimetric test result shows that the sample is continuously subjected to the action of the catalyst because the carbonization capability of a small amount of CP@PPA is weaker than that of the catalytic decompositionThe thermal decomposition and the carbon residue rate are reduced, so that the release of smoke cannot be effectively inhibited, and the smoke inhibition performance is reduced. In the invention, the maximum thermal weight loss temperature of the phosphorus modified carbon nitride modified BOPET film is not lower than 433 ℃, and the thermal stability is higher, because active free radicals such as PO, cl, and the like generated in the combustion process of the spirocyclic phosphate diacyl chloride can capture OH and H free radicals required by combustion, inhibit the progress of combustion reaction, and the spirocyclic phosphate diacyl chloride has the effect of catalyzing and carbonizing, the formed carbon layer can be used as a protective barrier for heat and mass transfer, and graphite phase carbon nitride and SiO as an opening agent 2 Can outwards separate out when burning, form continuous and compact protective layer with the carbon residue that BOPET burns and cover on the base member surface, play thermal-insulated effect of oxygen insulation to prevent the progression of burning, hinder the release of flue gas, improve composite's smoke suppression performance.
In document 2, the total smoke emission (TSP) of pure EP is 35.2. 35.2 m 2 When 5 wt% g-C was added 3 N 4 with/PAZn flame retardant, the TSP of the composite material was 35.1. 35.1 m 2 The TSP reduction rate is low. g-C 3 N 4 The two-dimensional nano lamellar structure has physical barrier and labyrinth effect on the release of smoke, can slow down the release rate of the smoke, but can lead g-C at higher temperature due to lower thermal stability of Phytic Acid (PA) component in the flame retardant 3 N 4 The nitrogen-containing nonflammable small molecule gas released by the decomposition in advance, resulting in low TSP reduction rate of the EP composite material. In the invention, the phosphorus-modified carbon nitride has higher thermal stability and does not decompose in advance, so the total smoke release (TSP) is low.
In document 3, carbon nitride is reacted with 2-carboxyethyl phenyl phosphinic acid to prepare phosphorus modified Carbon Nitride (CNALCPA) for flame retardant nylon 6 (PA 6); when 10-12 wt% of CNALCAPA is added, a large amount of molten drops are generated in the combustion process of the composite material and absorbent cotton is ignited, because the grafted phosphorus source chain length in the document 3 is relatively long, the content of rigid components in the modified PA6 molecular chain is seriously reduced, the flexibility of the molecular chain is greatly increased, the melt viscosity is reduced, and the serious molten drop phenomenon is generated in the combustion process of the composite material, so that the flame retardance is not facilitated; the phosphorus source in the invention is of a ring structure, so that the rigidity of BOPET can be enhanced to a certain extent, the melt viscosity is increased, and the molten drop phenomenon in the combustion process of the composite material is reduced.
The beneficial effects are that:
(1) The invention relates to a preparation method of a phosphorus-modified carbon nitride flame-retardant modified BOPET film, which takes urea as a raw material and prepares graphite-phase carbon nitride (g-C) by high-temperature calcination 3 N 4 ) The method comprises the steps of carrying out a first treatment on the surface of the Then in g-C 3 N 4 The novel phosphorus-modified carbon nitride flame retardant is synthesized by reacting a nitrogen source (nitrogen flame retardant) and spiro-phosphate diacyl chloride (SPDPC) serving as a phosphorus source (phosphorus flame retardant) under the protection of nitrogen for the first time; the phosphorus-modified carbon nitride flame retardant integrates N, P flame retardant elements, so that the synergistic effect of the nitrogen flame retardant and the phosphorus flame retardant can be exerted, and the flame retardant effect is enhanced; and because of the increase of organic components and reaction points in the flame retardant, the flame retardant has good compatibility with high polymer materials, and can improve the mechanical properties of the composite material.
(2) The flame retardant property, the smoke suppression property and the thermal stability of the phosphorus-modified carbon nitride flame retardant modified BOPET film prepared by the preparation method of the phosphorus-modified carbon nitride flame retardant modified BOPET film are all improved.
Drawings
FIG. 1 is a schematic diagram of a synthetic route of phosphorus-modified carbon nitride nanoparticles.
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 involved in the examples are as follows:
(1) Limiting Oxygen Index (LOI): adopting a JF-3 type oxygen index instrument of Nanjing Bright Lei Yiqi equipment limited company, testing conditions are implemented according to GB/T2406.2-2009, and the size of a sample (namely the phosphorus modified carbon nitride flame retardant modified BOPET film) is 125 mm multiplied by 10 mm multiplied by 4 mm;
(2) Thermogravimetric analysis: firstly, a sample to be tested (namely a phosphorus modified carbon nitride flame-retardant modified BOPET film) is subjected to drying pretreatment, 5mg of the sample is respectively taken and placed in a dry and clean crucible, and a TGA-601 type thermal analyzer of Nanjing Hui Chengjingjinginstrument and meter Co., ltd is used for measuring the temperature of the sample in nitrogen (N) 2 ) Heating from 30 ℃ to 800 ℃ at a heating rate of 10 ℃/min under the atmosphere, testing, and recording a TG curve and a DTG curve;
(3) Peak heat release rate (phr), total Heat Release (THR), peak smoke release rate (PSPR), and total smoke release (TSP): drying and pre-treating a sample to be tested (namely a phosphorus modified carbon nitride flame retardant modified BOPET film), and testing by using a ZY-6243 type cone calorimeter of a middle-Nox quality inspection instrument and equipment company, wherein the size of the sample is 100mm multiplied by 100mm multiplied by 3 mm; during testing, the sample is wrapped by aluminum foil and horizontally placed in a cone calorimeter, and the heat flux is set at 35kW/m 2 ；
(4) UL-94 rating by vertical burn method: the test is carried out by adopting a 5402 type horizontal vertical combustor of Suzhou Yang Yiwo Moire detection technology Co., ltd, the test conditions are implemented according to GB/T2408-2008, and the sizes of the samples are 125 mm multiplied by 13mm multiplied by 3.2mm;
(5) Tensile strength MD, tensile strength TD, elongation at break MD and elongation at break TD: the test was performed using an AG-IS universal tester from Michaelis electronic devices Co., ltd, with a sample length of 230 mm, a width of 15mm, and a stretching rate of 100mm/min; wherein MD and TD refer to machine direction and transverse direction stretching, respectively.
The manufacturer information of part of raw material components used in the embodiment of the invention is shown in table 1:
TABLE 1
| Name of the name | Abbreviation name and specification | Manufacturing factories |
| Polyethylene terephthalate | PET（FG720) | China petrochemical industry and chemical fiber Limited |
| Urea | H 2 NCONH 2 (analytical grade) | Shanghai Aba Ding Shenghua technologies Co.Ltd |
| Spirocyclic phosphate diacid chlorides | SPDPC (analytically pure) | Shanghai chemical reagent Co Ltd |
| Sulfuric acid | H 2 SO 4 (analytical grade) | Shanghai chemical reagent Co Ltd |
| Silica dioxide | SiO 2 (nanoscale) | Bowis nanotechnology Co Ltd |
Example 1
A preparation method of a phosphorus-modified carbon nitride flame-retardant modified BOPET film comprises the following specific steps:
(1) As shown in fig. 1, taking urea, placing the urea in a crucible, heating to 420 ℃ in a muffle furnace at a heating rate of 5 ℃/min, heating to 540 ℃ after 2 hours of reaction, continuing the reaction for 2 hours, and cooling to room temperature after the reaction is completed to obtain graphite-phase carbon nitride;
(2) Adding graphite phase carbon nitride into toluene, performing ultrasonic dispersion for 15min, adding spiro phosphate diacid chloride under the protection of nitrogen, reacting for 3h at 50 ℃, then adding triethylamine, stirring and refluxing for 1h, and finally sequentially washing with acetone, performing suction filtration, performing vacuum drying at 80 ℃ for 8h and performing ball milling to obtain phosphorus modified carbon nitride nano particles;
wherein, the mass volume ratio of the graphite phase carbon nitride to the toluene is 10g to 80ml, the mass ratio of the graphite phase carbon nitride to the spiro-phosphate diacid chloride is 1 to 5, and the mass ratio of the graphite phase carbon nitride to the triethylamine is 10 to 3; ball milling is to add grinding balls according to the mass ratio of the materials to the grinding balls of 1:100, wherein the grinding balls comprise a large grinding ball, a medium grinding ball and a small grinding ball with the diameters of 5mm, 3mm and 2mm, the weight ratio of the large grinding ball to the medium grinding ball to the small grinding ball is 2:2:5, the grinding balls stop for 5min after rotating forward for 30min, and then rotate reversely for 30min to form a cycle for 3 times;
(3) Mixing phosphorus-modified carbon nitride nano particles with PET according to the mass ratio of 0.5:99.5, carrying out melt blending extrusion by a double-screw extruder, and granulating by a SY-6217-ZBQ-20 type granulator to obtain PET flame-retardant master batch;
wherein the three-stage temperature of the extruder is respectively set at 260 ℃, 270 ℃, 280 ℃ and the rotating speed of the granulator is 50r/min;
(4) SiO is made of 2 Melt blending and extruding with PET according to the mass ratio of 5:95, and granulating by using a SY-6217-ZBQ-20 granulator to obtain anti-blocking master batch;
wherein the three-stage temperature of the extruder is respectively set at 260 ℃, 270 ℃, 280 ℃ and the rotating speed of the extruder is 50r/min, and the rotating speed of the granulator is set at 50r/min;
(5) Feeding the PET flame-retardant master batch into a main extruder for melt extrusion, feeding the anti-blocking master batch into an auxiliary extruder for melt extrusion, respectively feeding the melt into the same distribution block after passing through respective prefilters, metering pumps and fine filters of the main extruder and the auxiliary extruder, distributing the melt of the main extruder on a core layer, and distributing the melt of the auxiliary extruder on an upper surface layer and a lower surface layer;
the main extruder is mainly divided into 4 temperature sections, namely 284, 278, 280 and 283 ℃, the pressure of a vacuum system is 5mbar, and the rotating speed of a screw is 109rpm; the auxiliary extruder is mainly divided into 3 temperature sections, namely 285 ℃, 278 and 280 ℃, the pressure of a vacuum system is 8mbar, and the rotating speed of a screw is 150rpm;
(6) The distributed melt enters a three-layer co-extrusion die head, the melt of the core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and casting sheets are carried out after the extruded melt is cooled to obtain BOPET film sheets;
wherein, in the BOPET film sheet, the mass ratio of the core layer master batch is 90%, and the ratio of the upper surface layer master batch to the lower surface layer master batch is the same;
(7) Preheating a BOPET film sheet to above the glass transition temperature, longitudinally stretching at 67 ℃ and 3 times of stretching multiplying power, transversely stretching at 110 ℃ and 3 times of stretching multiplying power, heat-setting at 190 ℃ for 10 seconds, and cooling to room temperature to obtain the phosphorus-modified carbon nitride flame-retardant modified BOPET film.
The ultimate oxygen index of the finally prepared phosphorus-modified carbon nitride flame-retardant modified BOPET film is 24.1%, the initial decomposition temperature is 358 ℃, the maximum mass loss temperature is 433 ℃, the average mass loss rate is 0.060g/s, and the peak value of the heat release rate is 796kW/m 2 The total heat release amount was 128MJ/m 2 The peak smoke release rate was 0.226m 2 Per second, the total smoke release is 37.6m 2 UL-94 rating is V-2, tensile strength MD is 222MPa, tensile strength TD is 221MPa, elongation at break MD is 115%, and elongation at break TD is 118%.
Comparative example 1
A preparation method of a flame-retardant modified BOPET film is basically the same as that in example 1, except that 2-carboxyethyl phenyl phosphinic acid with the same mass is used for replacing spiro phosphate diacid chloride in the step (2).
The ultimate oxygen index of the finally prepared flame-retardant modified BOPET film is 21.1%, the initial decomposition temperature is 341 ℃, the maximum mass loss temperature is 404 ℃, and the peak value of the heat release rate is 1512.37kW/m 2 The total heat release amount was 249.45MJ/m 2 Peak smoke release rate of 0.295m 2 Per second, the total smoke release amount is45.3m 2 UL-94 rating is V-2, tensile strength MD is 193MPa, tensile strength TD is 190MPa, elongation at break MD is 95%, and elongation at break TD is 86%.
Comparing comparative example 1 with example 1, it can be found that the flame retardant modified BOPET film in comparative example 1 has lower initial decomposition temperature and maximum mass loss temperature than those in example 1, and lower thermal stability; the peak heat release rate and total heat release amount of the flame-retardant modified BOPET film in comparative example 1 are far greater than those of example 1, and the flame-retardant effect is poor; and the tensile strength and elongation at break of the flame retardant modified BOPET film in comparative example 1 are reduced, and the mechanical properties are lowered. This is because the phosphorus source in comparative example 1 is decomposed in advance when the temperature is raised, resulting in a decrease in the thermal stability of the flame retardant modified BOPET film, thereby affecting the flame retardant effect of the material; the decrease in mechanical properties of comparative example 1 was due to poor compatibility between the phosphorus-modified carbon nitride and the matrix.
Comparative example 2
A method for preparing a flame-retardant modified BOPET film, which is basically the same as example 1, and is different in that: the operations of the steps (1) and (2) are not carried out, and the g-C with equal mass is used in the step (3) 3 N 4 PAZn (prepared according to the method of document 2) is substituted for phosphorus-modified carbon nitride nanoparticles.
The ultimate oxygen index of the finally prepared flame-retardant modified BOPET film is 22.0%, the initial decomposition temperature is 346.7 ℃, the maximum mass loss temperature is 361.2 ℃, and the peak value of the heat release rate is 1054.3kW/m 2 The total heat release amount was 214MJ/m 2 Peak smoke release rate of 0.36 m 2 Per s, total smoke release of 39.1m 2 UL-94 rating is V-1, tensile strength MD is 190MPa, tensile strength TD is 196MPa, elongation at break MD is 92%, and elongation at break TD is 89%.
Comparing comparative example 2 with example 1, it can be found that the limiting oxygen index, initial decomposition temperature and maximum mass loss temperature of the flame retardant modified BOPET film in comparative example 2 are all lower than those in example 1; when the flame retardant of equal quality is added, the flame-retardant modified BOPET film has lower smoke suppression effect and also has reduced mechanical property. This is because of g-C 3 N 4 The PAZn mainly undergoes a two-step degradation process when heated: dehydrating and condensing corresponding phosphate groups at the temperature of 250-350 ℃ into pyrophosphoric acid and polyphosphoric acid compounds; further pyrolysis of corresponding phosphoric acid compound at 550-650 ℃ and g-C 3 N 4 The first degradation results in a decrease in the thermal stability of the composite material, while the decrease in the mechanical properties is due to g-C 3 N 4 The addition of/PAZn causes concentration of internal stress in the matrix molecule and hinders the movement of the molecular chain.
Example 2
A preparation method of a phosphorus-modified carbon nitride flame-retardant modified BOPET film comprises the following specific steps:
(1) Taking urea in a crucible, heating to 420 ℃ in a muffle furnace at a heating rate of 5 ℃/min, heating to 540 ℃ after 2h of reaction, continuing the reaction for 2h, and cooling to room temperature after the reaction is completed to obtain graphite-phase carbon nitride;
(2) Adding graphite phase carbon nitride into toluene, performing ultrasonic dispersion for 15min, adding spiro phosphate diacid chloride under the protection of nitrogen, reacting for 3.5h at 55 ℃, then adding triethylamine, stirring and refluxing for 1.2h, and finally sequentially washing with acetone, performing suction filtration, performing vacuum drying at 90 ℃ for 9h and performing ball milling to obtain phosphorus modified carbon nitride nano particles;
wherein the mass volume ratio of the graphite phase carbon nitride to toluene is 10g:90ml, the mass ratio of the graphite phase carbon nitride to spiro-phosphate diacid chloride is 1:6, and the mass ratio of the graphite phase carbon nitride to triethylamine is 10:4; ball milling is to add grinding balls according to the mass ratio of the materials to the grinding balls of 1:100, wherein the grinding balls comprise a large grinding ball, a medium grinding ball and a small grinding ball with the diameters of 5mm, 3mm and 2mm, the weight ratio of the large grinding ball to the medium grinding ball to the small grinding ball is 2:2:5, the grinding balls stop for 5min after rotating forward for 30min, and then rotate reversely for 30min to form a cycle for 3 times;
(3) Mixing phosphorus-modified carbon nitride nano particles with PET according to the mass ratio of 1:99, carrying out melt blending extrusion by a double-screw extruder, and granulating by a SY-6217-ZBQ-20 type granulator to obtain PET flame-retardant master batch;
wherein the three-stage temperature of the extruder is respectively set at 260 ℃, 270 ℃, 280 ℃ and the rotating speed of the granulator is 50r/min;
(4) SiO is made of 2 Melt blending and extruding with PET according to the mass ratio of 5:95, and granulating by using a SY-6217-ZBQ-20 granulator to obtain anti-blocking master batch;
wherein the three-stage temperature of the extruder is respectively set at 260 ℃, 270 ℃, 280 ℃ and the rotating speed of the extruder is 50r/min, and the rotating speed of the granulator is set at 50r/min;
(5) Feeding the PET flame-retardant master batch into a main extruder for melt extrusion, feeding the anti-blocking master batch into an auxiliary extruder for melt extrusion, respectively feeding the melt into the same distribution block after passing through respective prefilters, metering pumps and fine filters of the main extruder and the auxiliary extruder, distributing the melt of the main extruder on a core layer, and distributing the melt of the auxiliary extruder on an upper surface layer and a lower surface layer;
the main extruder is mainly divided into 4 temperature sections, namely 284, 278, 280 and 283 ℃, the pressure of a vacuum system is 5mbar, and the rotating speed of a screw is 109rpm; the auxiliary extruder is mainly divided into 3 temperature sections, namely 285 ℃, 278 and 280 ℃, the pressure of a vacuum system is 8mbar, and the rotating speed of a screw is 150rpm;
(6) The distributed melt enters a three-layer co-extrusion die head, the melt of the core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and casting sheets are carried out after the extruded melt is cooled to obtain BOPET film sheets;
wherein, in the BOPET film sheet, the mass ratio of the core layer master batch is 88%, and the ratio of the upper surface layer master batch to the lower surface layer master batch is the same;
(7) Preheating a BOPET film sheet to above the glass transition temperature, longitudinally stretching at the temperature of 70 ℃ and stretching multiplying power of 3.2 times, transversely stretching at the temperature of 112 ℃ and stretching multiplying power of 3.2 times, heat-setting for 13s at the temperature of 200 ℃, and cooling to room temperature to obtain the phosphorus-modified carbon nitride flame-retardant modified BOPET film.
The ultimate oxygen index of the finally prepared phosphorus-modified carbon nitride flame-retardant modified BOPET film is 25.8%, the initial decomposition temperature is 364 ℃, the maximum mass loss temperature is 437 ℃, the average mass loss rate is 0.052g/s, and the peak value of the heat release rate is 785kW/m 2 The total heat release amount was 117MJ/m 2 The peak smoke release rate was 0.205m 2 Per second, the total smoke release is 33.2m 2 UL-94 rating is V-1, tensile strength MD is 227MPa, tensile strength TD is 226MPa, elongation at break MD is 117%, and elongation at break TD is 123%.
Example 3
A preparation method of a phosphorus-modified carbon nitride flame-retardant modified BOPET film comprises the following specific steps:
(1) Taking urea in a crucible, heating to 420 ℃ in a muffle furnace at a heating rate of 5 ℃/min, heating to 540 ℃ after 2h of reaction, continuing the reaction for 2h, and cooling to room temperature after the reaction is completed to obtain graphite-phase carbon nitride;
(2) Adding graphite phase carbon nitride into toluene, performing ultrasonic dispersion for 15min, adding spiro phosphate diacid chloride under the protection of nitrogen, reacting for 4h at 60 ℃, then adding triethylamine, stirring and refluxing for 1.6h, and finally sequentially washing with acetone, performing suction filtration, performing vacuum drying at 85 ℃ for 8.5h and performing ball milling to obtain phosphorus modified carbon nitride nano particles;
wherein the mass volume ratio of the graphite phase carbon nitride to toluene is 10g to 95ml, the mass ratio of the graphite phase carbon nitride to spiro-phosphate diacid chloride is 1 to 5.5, and the mass ratio of the graphite phase carbon nitride to triethylamine is 10 to 5; ball milling is to add grinding balls according to the mass ratio of the materials to the grinding balls of 1:100, wherein the grinding balls comprise a large grinding ball, a medium grinding ball and a small grinding ball with the diameters of 5mm, 3mm and 2mm, the weight ratio of the large grinding ball to the medium grinding ball to the small grinding ball is 2:2:5, the grinding balls stop for 5min after rotating forward for 30min, and then rotate reversely for 30min to form a cycle for 3 times;
(3) Mixing phosphorus-modified carbon nitride nano particles with PET according to the mass ratio of 2:98, carrying out melt blending extrusion by a double-screw extruder, and granulating by a SY-6217-ZBQ-20 type granulator to obtain PET flame-retardant master batch;
wherein the three-stage temperature of the extruder is respectively set at 260 ℃, 270 ℃, 280 ℃ and the rotating speed of the granulator is 50r/min;
(4) SiO is made of 2 Melt blending and extruding with PET according to the mass ratio of 5:95, and granulating by using a SY-6217-ZBQ-20 granulator to obtain anti-blocking master batch;
wherein the three-stage temperature of the extruder is respectively set at 260 ℃, 270 ℃, 280 ℃ and the rotating speed of the extruder is 50r/min, and the rotating speed of the granulator is set at 50r/min;
(5) Feeding the PET flame-retardant master batch into a main extruder for melt extrusion, feeding the anti-blocking master batch into an auxiliary extruder for melt extrusion, respectively feeding the melt into the same distribution block after passing through respective prefilters, metering pumps and fine filters of the main extruder and the auxiliary extruder, distributing the melt of the main extruder on a core layer, and distributing the melt of the auxiliary extruder on an upper surface layer and a lower surface layer;
the main extruder is mainly divided into 4 temperature sections, namely 284, 278, 280 and 283 ℃, the pressure of a vacuum system is 5mbar, and the rotating speed of a screw is 109rpm; the auxiliary extruder is mainly divided into 3 temperature sections, namely 285 ℃, 278 and 280 ℃, the pressure of a vacuum system is 8mbar, and the rotating speed of a screw is 150rpm;
(6) The distributed melt enters a three-layer co-extrusion die head, the melt of the core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and casting sheets are carried out after the extruded melt is cooled to obtain BOPET film sheets;
wherein, in the BOPET film sheet, the mass ratio of the core layer master batch is 86%, and the ratio of the upper surface layer master batch to the lower surface layer master batch is the same;
(7) Preheating a BOPET film sheet to above the glass transition temperature, longitudinally stretching at the temperature of 80 ℃ and stretching multiplying power of 3.1 times, transversely stretching at the temperature of 115 ℃ and stretching multiplying power of 3.5 times, heat-setting for 12 seconds at the temperature of 210 ℃, and cooling to room temperature to obtain the phosphorus-modified carbon nitride flame-retardant modified BOPET film.
The ultimate oxygen index of the finally prepared phosphorus-modified carbon nitride flame-retardant modified BOPET film is 26.6%, the initial decomposition temperature is 369 ℃, the maximum mass loss temperature is 441 ℃, the average mass loss rate is 0.050g/s, and the peak value of the heat release rate is 768kW/m 2 The total heat release amount was 103MJ/m 2 Peak smoke release rate of 0.182m 2 Per second, the total smoke release amount was 31.9m 2 UL-94 rating of V-1, tensile strength MD of 228MPa, tensile strengthThe tensile strength TD was 227MPa, the elongation at break MD was 120%, and the elongation at break TD was 127%.
Example 4
A preparation method of a phosphorus-modified carbon nitride flame-retardant modified BOPET film comprises the following specific steps:
(1) Taking urea in a crucible, heating to 420 ℃ in a muffle furnace at a heating rate of 5 ℃/min, heating to 540 ℃ after 2h of reaction, continuing the reaction for 2h, and cooling to room temperature after the reaction is completed to obtain graphite-phase carbon nitride;
(2) Adding graphite phase carbon nitride into toluene, performing ultrasonic dispersion for 15min, adding spiro phosphate diacid chloride under the protection of nitrogen, reacting for 4.5h at 55 ℃, then adding triethylamine, stirring and refluxing for 2h, and finally sequentially washing with acetone, performing suction filtration, performing vacuum drying at 87 ℃ for 10h and performing ball milling to obtain phosphorus modified carbon nitride nano particles;
wherein the mass volume ratio of the graphite phase carbon nitride to toluene is 10g to 85ml, the mass ratio of the graphite phase carbon nitride to spiro-phosphate diacid chloride is 1 to 7, and the mass ratio of the graphite phase carbon nitride to triethylamine is 10 to 3.5; ball milling is to add grinding balls according to the mass ratio of the materials to the grinding balls of 1:100, wherein the grinding balls comprise a large grinding ball, a medium grinding ball and a small grinding ball with the diameters of 5mm, 3mm and 2mm, the weight ratio of the large grinding ball to the medium grinding ball to the small grinding ball is 2:2:5, the grinding balls stop for 5min after rotating forward for 30min, and then rotate reversely for 30min to form a cycle for 3 times;
(3) Mixing phosphorus-modified carbon nitride nano particles with PET according to a mass ratio of 5:95, carrying out melt blending extrusion by a double-screw extruder, and granulating by a SY-6217-ZBQ-20 type granulator to obtain PET flame-retardant master batch;
wherein the three-stage temperature of the extruder is respectively set at 260 ℃, 270 ℃, 280 ℃ and the rotating speed of the granulator is 50r/min;
(4) SiO is made of 2 Melt blending and extruding with PET according to the mass ratio of 5:95, and granulating by using a SY-6217-ZBQ-20 granulator to obtain anti-blocking master batch;
wherein the three-stage temperature of the extruder is respectively set at 260 ℃, 270 ℃, 280 ℃ and the rotating speed of the extruder is 50r/min, and the rotating speed of the granulator is set at 50r/min;
(5) Feeding the PET flame-retardant master batch into a main extruder for melt extrusion, feeding the anti-blocking master batch into an auxiliary extruder for melt extrusion, respectively feeding the melt into the same distribution block after passing through respective prefilters, metering pumps and fine filters of the main extruder and the auxiliary extruder, distributing the melt of the main extruder on a core layer, and distributing the melt of the auxiliary extruder on an upper surface layer and a lower surface layer;
the main extruder is mainly divided into 4 temperature sections, namely 284, 278, 280 and 283 ℃, the pressure of a vacuum system is 5mbar, and the rotating speed of a screw is 109rpm; the auxiliary extruder is mainly divided into 3 temperature sections, namely 285 ℃, 278 and 280 ℃, the pressure of a vacuum system is 8mbar, and the rotating speed of a screw is 150rpm;
(6) The distributed melt enters a three-layer co-extrusion die head, the melt of the core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and casting sheets are carried out after the extruded melt is cooled to obtain BOPET film sheets;
wherein, in the BOPET film sheet, the mass ratio of the core layer master batch is 84%, and the ratio of the upper surface layer master batch to the lower surface layer master batch is the same;
(7) Preheating a BOPET film sheet to above the glass transition temperature, longitudinally stretching at the temperature of 90 ℃ and stretching multiplying power of 3.5 times, transversely stretching at the temperature of 118 ℃ and stretching multiplying power of 3.8 times, heat-setting for 16s at the temperature of 220 ℃, and cooling to room temperature to obtain the phosphorus-modified carbon nitride flame-retardant modified BOPET film.
The ultimate oxygen index of the finally prepared phosphorus-modified carbon nitride flame-retardant modified BOPET film is 27.1%, the initial decomposition temperature is 382 ℃, the maximum mass loss temperature is 449 ℃, the average mass loss rate is 0.048g/s, and the peak value of the heat release rate is 631kW/m 2 The total heat release amount was 92MJ/m 2 The peak smoke release rate was 0.168m 2 Per second, the total smoke release is 28.8m 2 UL-94 rating is V-1, tensile strength MD is 231MPa, tensile strength TD is 229MPa, elongation at break MD is 124%, and elongation at break TD is 129%.
Example 5
A preparation method of a phosphorus-modified carbon nitride flame-retardant modified BOPET film comprises the following specific steps:
(1) Taking urea in a crucible, heating to 420 ℃ in a muffle furnace at a heating rate of 5 ℃/min, heating to 540 ℃ after 2h of reaction, continuing the reaction for 2h, and cooling to room temperature after the reaction is completed to obtain graphite-phase carbon nitride;
(2) Adding graphite phase carbon nitride into toluene, performing ultrasonic dispersion for 15min, adding spiro phosphate diacid chloride under the protection of nitrogen, reacting for 6h at 59 ℃, then adding triethylamine, stirring and refluxing for 1.5h, and finally sequentially washing with acetone, performing suction filtration, performing vacuum drying at 100 ℃ for 11h and performing ball milling to obtain phosphorus modified carbon nitride nano particles;
wherein the mass volume ratio of the graphite phase carbon nitride to toluene is 10g to 89ml, the mass ratio of the graphite phase carbon nitride to spiro-phosphate diacid chloride is 1 to 5.7, and the mass ratio of the graphite phase carbon nitride to triethylamine is 10 to 4.5; ball milling is to add grinding balls according to the mass ratio of the materials to the grinding balls of 1:100, wherein the grinding balls comprise a large grinding ball, a medium grinding ball and a small grinding ball with the diameters of 5mm, 3mm and 2mm, the weight ratio of the large grinding ball to the medium grinding ball to the small grinding ball is 2:2:5, the grinding balls stop for 5min after rotating forward for 30min, and then rotate reversely for 30min to form a cycle for 3 times;
(3) Mixing phosphorus-modified carbon nitride nano particles with PET according to the mass ratio of 10:90, carrying out melt blending extrusion by a double-screw extruder, and granulating by a SY-6217-ZBQ-20 type granulator to obtain PET flame-retardant master batch;
wherein the three-stage temperature of the extruder is respectively set at 260 ℃, 270 ℃, 280 ℃ and the rotating speed of the granulator is 50r/min;
(4) SiO is made of 2 Melt blending and extruding with PET according to the mass ratio of 5:95, and granulating by using a SY-6217-ZBQ-20 granulator to obtain anti-blocking master batch;
wherein the three-stage temperature of the extruder is respectively set at 260 ℃, 270 ℃, 280 ℃ and the rotating speed of the extruder is 50r/min, and the rotating speed of the granulator is set at 50r/min;
(5) Feeding the PET flame-retardant master batch into a main extruder for melt extrusion, feeding the anti-blocking master batch into an auxiliary extruder for melt extrusion, respectively feeding the melt into the same distribution block after passing through respective prefilters, metering pumps and fine filters of the main extruder and the auxiliary extruder, distributing the melt of the main extruder on a core layer, and distributing the melt of the auxiliary extruder on an upper surface layer and a lower surface layer;
the main extruder is mainly divided into 4 temperature sections, namely 284, 278, 280 and 283 ℃, the pressure of a vacuum system is 5mbar, and the rotating speed of a screw is 109rpm; the auxiliary extruder is mainly divided into 3 temperature sections, namely 285 ℃, 278 and 280 ℃, the pressure of a vacuum system is 8mbar, and the rotating speed of a screw is 150rpm;
(6) The distributed melt enters a three-layer co-extrusion die head, the melt of the core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and casting sheets are carried out after the extruded melt is cooled to obtain BOPET film sheets;
wherein, in the BOPET film sheet, the mass ratio of the core layer master batch is 80%, and the ratio of the upper surface layer master batch to the lower surface layer master batch is the same;
(7) Preheating a BOPET film sheet to above the glass transition temperature, longitudinally stretching at the temperature of 95 ℃ and the stretching multiplying power of 3.7 times, transversely stretching at the temperature of 120 ℃ and the stretching multiplying power of 4 times, heat-setting for 20s at the temperature of 230 ℃, and cooling to room temperature to obtain the phosphorus-modified carbon nitride flame-retardant modified BOPET film.
The ultimate oxygen index of the finally prepared phosphorus-modified carbon nitride flame-retardant modified BOPET film is 29.5%, the initial decomposition temperature is 397 ℃, the maximum mass loss temperature is 455 ℃, the average mass loss rate is 0.041g/s, and the peak value of the heat release rate is 564kW/m 2 The total heat release amount was 85MJ/m 2 The peak smoke release rate was 0.140m 2 Per second, the total smoke release is 25.3m 2 UL-94 rating is V-0, tensile strength MD is 234MPa, tensile strength TD is 231MPa, elongation at break MD is 131%, and elongation at break TD is 133%.
Claims (8)
1. The preparation method of the phosphorus-modified carbon nitride flame-retardant modified BOPET film comprises the steps that the phosphorus-modified carbon nitride flame-retardant modified BOPET film is of a three-layer composite structure and consists of a core layer, an upper surface layer and a lower surface layer; the core layer master batch, the upper surface layer master batch and the lower surface layer master batch are evenly mixed and then are subjected to melt extrusion, the melt is extruded by a three-layer co-extrusion die head and then is subjected to tape casting, and the phosphorus-modified carbon nitride flame-retardant modified BOPET film is prepared by biaxial stretching, and is characterized in that: the core layer master batch is PET flame-retardant master batch, and is obtained by melting, blending, extruding and granulating phosphorus-modified carbon nitride nano particles and PET;
the phosphorus-modified carbon nitride nano-particles are obtained by ball milling after reacting graphite-phase carbon nitride with spiro-phosphate diacid chloride.
2. The preparation method of the phosphorus-modified carbon nitride flame-retardant modified BOPET film according to claim 1, wherein the mass ratio of the core layer master batch in the phosphorus-modified carbon nitride flame-retardant modified BOPET film is 80-90%, and the ratio of the upper surface layer master batch to the lower surface layer master batch is the same;
the mass ratio of the phosphorus modified carbon nitride nano particles to PET in the core layer master batch is 0.5-10:90-99.5.
3. The method for preparing the phosphorus-modified carbon nitride flame-retardant modified BOPET film according to claim 2, wherein the upper surface layer master batch and the lower surface layer master batch are anti-adhesion master batches, and SiO 2 And (3) carrying out melt blending extrusion and granulation on the PET and the PET according to a mass ratio of 5:95.
4. The method for preparing a phosphorus-modified carbon nitride flame-retardant modified BOPET film according to claim 3, wherein the limiting oxygen index of the phosphorus-modified carbon nitride flame-retardant modified BOPET film is not lower than 24.1%, the initial decomposition temperature is not lower than 358 ℃, the maximum mass loss temperature is not lower than 433 ℃, and the peak value of the heat release rate is lower than 796kW/m 2 The total heat release is less than 128MJ/m 2 Peak smoke release rate of less than 0.226. 0.226m 2 Per second, the total smoke release is lower than 37.6 and 37.6m 2 。
5. The method for preparing the phosphorus-modified carbon nitride flame-retardant modified BOPET film according to claim 4, which is characterized by comprising the following specific steps:
(1) Taking urea in a crucible, heating to 350-420 ℃ in a muffle furnace at a heating rate of 5 ℃/min, heating to 500-550 ℃ after 2h of reaction, continuing the reaction for 2h, and cooling to room temperature after the reaction is completed to obtain graphite-phase carbon nitride;
(2) Adding graphite-phase carbon nitride into toluene, performing ultrasonic dispersion, adding spiro phosphate diacyl chloride under the protection of nitrogen, reacting for 3-6 hours at 50-70 ℃, then adding triethylamine, stirring and refluxing, and finally sequentially cleaning, suction filtering, vacuum drying and ball milling to obtain phosphorus-modified carbon nitride nano particles;
(3) Mixing the phosphorus-modified carbon nitride nano particles with PET, and carrying out melt blending extrusion and granulation by a double-screw extruder to obtain PET flame-retardant master batch;
(4) SiO is made of 2 Melt blending with PET, extruding, granulating to obtain anti-blocking master batch;
(5) Feeding the PET flame-retardant master batch into a main extruder for melt extrusion, feeding the anti-blocking master batch into an auxiliary extruder for melt extrusion, respectively feeding the melt into the same distribution block after passing through respective prefilters, metering pumps and fine filters of the main extruder and the auxiliary extruder, distributing the melt of the main extruder on a core layer, and distributing the melt of the auxiliary extruder on an upper surface layer and a lower surface layer;
(6) The distributed melt enters a three-layer co-extrusion die head, the melt of the core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and casting sheets are carried out after the extruded melt is cooled to obtain BOPET film sheets;
(7) Preheating a BOPET film sheet to above the glass transition temperature, carrying out longitudinal stretching, then carrying out transverse stretching, and cooling to room temperature after heat setting to obtain the phosphorus-modified carbon nitride flame-retardant modified BOPET film.
6. The preparation method of the phosphorus-modified carbon nitride flame-retardant modified BOPET film according to claim 5, wherein in the step (2), the mass volume ratio of graphite-phase carbon nitride to toluene is 10 g:80-100 ml, the mass ratio of graphite-phase carbon nitride to spiro-phosphate diacid chloride is 10:50-80, the mass ratio of graphite-phase carbon nitride to triethylamine is 10:3-5, the ultrasonic dispersion time is 15min, and the reflux time is 1-2 h.
7. The method for preparing the phosphorus-modified carbon nitride flame-retardant modified BOPET film according to claim 5, wherein in the step (2), grinding balls are added according to the mass ratio of the material to the grinding balls of 1:100, the grinding balls comprise three types of large, medium and small grinding balls with diameters of 5mm, 3mm and 2mm, the weight ratio of the large, medium and small grinding balls is 2:2:5, the grinding balls stop for 5min after rotating forward for 30min, and rotate reversely for 30min to form a cycle, and the total cycle is 3 times.
8. The method for preparing a phosphorus-modified carbon nitride flame-retardant modified BOPET film according to claim 5, wherein the stretching temperature of the longitudinal stretching in the step (7) is 67-95 ℃, and the stretching multiplying power is 3-3.2 times; the stretching temperature of transverse stretching is 110-120 ℃, and the stretching multiplying power is 3-4 times; the heat setting temperature is 190-230 ℃ and the heat setting time is 10-20 s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410004116.6A CN117484901B (en) | 2024-01-03 | 2024-01-03 | Preparation method of phosphorus-modified carbon nitride flame-retardant modified BOPET film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410004116.6A CN117484901B (en) | 2024-01-03 | 2024-01-03 | Preparation method of phosphorus-modified carbon nitride flame-retardant modified BOPET film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117484901A true CN117484901A (en) | 2024-02-02 |
| CN117484901B CN117484901B (en) | 2024-03-22 |
Family
ID=89680488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410004116.6A Active CN117484901B (en) | 2024-01-03 | 2024-01-03 | Preparation method of phosphorus-modified carbon nitride flame-retardant modified BOPET film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117484901B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990081266A (en) * | 1998-04-28 | 1999-11-15 | 장용균 | Flame retardant polyester film and manufacturing method thereof |
| CN103627150A (en) * | 2013-11-21 | 2014-03-12 | 浙江南洋科技股份有限公司 | Preparation method of polyether material, polyether film and preparation method thereof |
| CN113354868A (en) * | 2021-06-17 | 2021-09-07 | 中山大学 | Phosphorus-doped polypyrrole-loaded carbon nitride nanocomposite and preparation method and application thereof |
| CN116178795A (en) * | 2022-08-19 | 2023-05-30 | 台州学院 | Multifunctional phosphorus-nickel doped graphite-like carbon nitride nano sheet, preparation method thereof and ABS material |
| CN116874944A (en) * | 2023-05-31 | 2023-10-13 | 江苏立晟德新材料有限公司 | Preparation process of hyperbranched polymer modified polyvinyl chloride cable material |
-
2024
- 2024-01-03 CN CN202410004116.6A patent/CN117484901B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990081266A (en) * | 1998-04-28 | 1999-11-15 | 장용균 | Flame retardant polyester film and manufacturing method thereof |
| CN103627150A (en) * | 2013-11-21 | 2014-03-12 | 浙江南洋科技股份有限公司 | Preparation method of polyether material, polyether film and preparation method thereof |
| CN113354868A (en) * | 2021-06-17 | 2021-09-07 | 中山大学 | Phosphorus-doped polypyrrole-loaded carbon nitride nanocomposite and preparation method and application thereof |
| CN116178795A (en) * | 2022-08-19 | 2023-05-30 | 台州学院 | Multifunctional phosphorus-nickel doped graphite-like carbon nitride nano sheet, preparation method thereof and ABS material |
| CN116874944A (en) * | 2023-05-31 | 2023-10-13 | 江苏立晟德新材料有限公司 | Preparation process of hyperbranched polymer modified polyvinyl chloride cable material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117484901B (en) | 2024-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| He et al. | P, N-decorated halloysite nanotubes for flame retardancy enhancement of polyamide 6/aluminum diethylphosphinate | |
| Ren et al. | Construction of few-layered black phosphorus/graphite-like carbon nitride binary hybrid nanostructure for reducing the fire hazards of epoxy resin | |
| Cai et al. | Halogen and halogen-free flame retarded biologically-based polyamide with markedly suppressed smoke and toxic gases releases | |
| CN111040293B (en) | Intumescent flame-retardant polypropylene and preparation method thereof | |
| Xu et al. | Functionalization of α-zirconium phosphate by polyphosphazene and its effect on the flame retardance of an intumescent flame retardant polypropylene system | |
| Feng et al. | A cross-linked charring strategy for mitigating the hazards of smoke and heat of aluminum diethylphosphonate/polyamide 6 by caged octaphenyl polyhedral oligomeric silsesquioxanes | |
| Wang et al. | Enhanced flame retardancy of natural rubber composite with addition of microencapsulated ammonium polyphosphate and MCM-41 fillers | |
| CN110591157A (en) | Preparation method and application of polyphosphazene polymer modified halloysite nanotube composite material with different coating thicknesses | |
| CN112321895A (en) | Nano-silica-modified macromolecular flame-retardant char-forming agent and preparation method thereof | |
| Khanal et al. | Effects of α-zirconium phosphate and zirconium organophosphonate on the thermal, mechanical and flame retardant properties of intumescent flame retardant high density polyethylene composites | |
| CN117484901B (en) | Preparation method of phosphorus-modified carbon nitride flame-retardant modified BOPET film | |
| Zhu et al. | Preparation and thermal cross-linking mechanism of co-polyester fiber with flame retardancy and anti-dripping by in situ polymerization | |
| CN114507380B (en) | MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant and preparation method and application thereof | |
| CN108250646B (en) | Halogen-free flame retardant composition | |
| CN108624027B (en) | High-efficiency halogen-free flame-retardant PC/ABS mixture for catalytic carbonization and preparation method thereof | |
| CN110564114B (en) | Preparation method of flame-retardant material | |
| Zhan et al. | A novel strategy to improve the flame retardancy and electrical conductivity of polymethyl methacrylate by controlling the configuration of phosphorus-containing polyaniline@ needle coke with magnetic field | |
| CN114133734B (en) | Low-filling efficient synergistic flame-retardant nylon 66 and preparation method thereof | |
| CN111334009B (en) | Flame-retardant master batch for low-toxicity low-smoke polyester fiber and preparation method thereof | |
| Wu et al. | Synergistic effect of lanthanum oxide on intumescent flame-retardant polypropylene-based formulations | |
| CN114479385B (en) | Conductive flame-retardant biodegradable PBAT composite material and preparation method and application thereof | |
| CN112608485B (en) | Organic-inorganic hybrid efficient synergistic flame-retardant char-forming agent and preparation method thereof | |
| CN114773871A (en) | High-stability and high-flame-retardancy composite elastomer material and preparation method thereof | |
| Zhang et al. | The synergistic effect of inorganic hybrid nanofibers and phytic acid-based nanosheets towards improving the fire retardancy and comprehensive performance of epoxy resin. | |
| Li et al. | Intumescent flame retardancy and smoke suppression of Eucommia ulmoides gum/natural rubber blends based on synergistic gC 3 N 4@ Fe 3 O 4 nanocomposites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |