CN114058051A - Core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film and preparation method thereof - Google Patents
Core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film and preparation method thereof Download PDFInfo
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- CN114058051A CN114058051A CN202111503537.6A CN202111503537A CN114058051A CN 114058051 A CN114058051 A CN 114058051A CN 202111503537 A CN202111503537 A CN 202111503537A CN 114058051 A CN114058051 A CN 114058051A
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- ammonium polyphosphate
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 91
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 59
- 239000011258 core-shell material Substances 0.000 title claims abstract description 57
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title claims abstract description 42
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 126
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 126
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 126
- 229920000728 polyester Polymers 0.000 claims abstract description 63
- 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 claims abstract description 43
- 229920002635 polyurethane Polymers 0.000 claims abstract description 43
- 239000004814 polyurethane Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- 150000002009 diols Chemical class 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 25
- 150000003863 ammonium salts Chemical class 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 17
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- 239000002184 metal Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
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- 150000001412 amines Chemical class 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 12
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
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- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- DTCPBBPYYOBKGN-UHFFFAOYSA-N N,N-dihydroxy-2,3-di(propan-2-yl)aniline Chemical compound ON(C1=C(C(=CC=C1)C(C)C)C(C)C)O DTCPBBPYYOBKGN-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 150000003384 small molecules Chemical group 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
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- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000009775 high-speed stirring Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000010985 leather Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920006264 polyurethane film Polymers 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 108010020346 Polyglutamic Acid Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical group [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 229920000370 gamma-poly(glutamate) polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an in-situ modified solvent-free polyurethane resin film with a core-shell structure halogen-free flame retardant and a preparation method thereof. The core-shell flame retardant has good expansion flame retardant effect, and has good dispersibility and compatibility in the solvent-free polyurethane resin, in the synthesis process of the solvent-free polyurethane resin film, the polyester-coated ammonium polyphosphate can be used as a polyol component to participate in the reaction of the solvent-free polyurethane, so that the dispersibility and compatibility of the ammonium polyphosphate in the solvent-free polyurethane are improved, meanwhile, the ammonium polyphosphate generates phosphoric acid, metaphosphoric acid and the like in the thermal decomposition process to catalyze the solvent-free polyurethane to form carbon, the decomposition of the solvent-free polyurethane resin is inhibited along with the increase of the amount of residual carbon, and the flame retardant property is improved.
Description
Technical Field
The invention belongs to the technical field of industrial semi-finished products and polyurethane synthetic leather, and particularly relates to a core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film and a preparation method thereof.
Background
Solvent-free polyurethane (SFPU) resins are thermoplastic materials prepared based on solvent-free two-component in-situ polymerization. SFPU uses almost no organic solvent in the synthesis, so the method has the advantages of environmental protection, high reaction speed and low production energy consumption, and simultaneously has good mechanical property, bonding property and chemical stability, thereby being widely applied to the fields of sofa leather, automobile leather, shoe leather and the like. However, SFPU is very easily burned in air, and generates a large amount of harmful gas upon combustion, accompanied by a large amount of droplets, causing rapid spread of fire. In order to solve the problem, people develop the flame retardant technical research aiming at the solvent-free polyurethane, and the flame retardant research of the solvent-free polyurethane resin is mainly divided into three categories: the additive flame retardant flame-retardant solvent-free polyurethane resin, the reactive flame retardant flame-retardant solvent-free polyurethane resin and the synergistic flame retardant flame-retardant solvent-free polyurethane resin.
The flame retardant is a functional filler for improving the flame retardant property of a flammable polymer matrix and comprises halogen flame retardants, phosphorus flame retardants, silicon flame retardants, inorganic metal flame retardants, intumescent flame retardants and the like. The flame retardant mechanism of the flame retardant can be different when the flame retardant is applied to a polymer matrix. The flame retardant mechanism of flame retardants in polymer matrices can be broadly divided into three categories: gas phase flame retardance, condensed phase flame retardance-a covering effect and a heat absorption effect. The intumescent flame retardant is a flame retardant mainly composed of N, P elements, does not contain halogen, and is composed of a carbon source, an acid source and a gas source. When the high polymer is heated, the flame retardant can generate a layer of uniform carbon on the surface, and simultaneously generate non-combustible gas to expand and foam the system to form a porous carbon layer. The porous carbon layer can insulate heat, isolate oxygen and inhibit smoke, can prevent molten drops from being generated, and has good flame retardant property. The invention patent CN110951438A discloses a flame-retardant solvent-free two-component polyurethane structural adhesive, which is composed of a component A and a component B containing a ammonium polyphosphate flame retardant, and the structural adhesive with high bonding strength and flame retardance is prepared. Ammonium polyphosphate belongs to an inorganic polymer, has poor compatibility with an organic phase, and the physical properties of the obtained structural adhesive are poor. The invention patent CN112851899A discloses a high-flame-retardancy solvent-free polyurethane resin for automobile leather, which contains a micromolecular ammonia alcohol grafted ammonium polyphosphate flame retardant, wherein after the surface of ammonium polyphosphate is modified, the dispersibility of the ammonium polyphosphate and solvent-free polyurethane is improved, but the requirement on surface modification is higher, and the defects of compatibility, flame retardancy and the like are still remained. The invention patent CN113402919A discloses that the flame retardant epoxy resin of ammonium polyphosphate is copolymerized and coated by chitosan and polyglutamate, although the flame retardant property is greatly improved, the coating layer and the core material lack firm acting force to be combined, and the coating layer is easy to fall off, so that the durability of the material is poor.
Disclosure of Invention
Based on the situation, the problems can be effectively solved by the in-situ modified solvent-free polyurethane resin film with the halogen-free flame retardant with the core-shell structure and the preparation method thereof.
A preparation method of a core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film comprises the following steps:
s1, preparing ultra-fine ammonium polyphosphate: adding ammonium polyphosphate into a ball milling tank, adding zirconia balls and ethanol, grinding at a high speed, taking out a sample, drying, and sieving to obtain superfine ammonium polyphosphate;
s2, preparing an ammonium polyphosphate system solution: adding the superfine ammonium polyphosphate into an ethanol solution, and uniformly dispersing by ultrasonic;
s3, preparing a polyester glycol solution: adding polyester dihydric alcohol into an ethanol solution, and uniformly stirring and mixing to obtain a polyester dihydric alcohol solution;
s4, preparing an aminosilane surface modified ammonium polyphosphate solution: dropwise adding aminosilane into the ammonium polyphosphate system solution obtained in the step S2, mixing, stirring and reacting for 30-60min, heating to 80-90 ℃, and continuing to react for 1-2 h to obtain an aminosilane surface modified ammonium polyphosphate solution;
s5, preparing polyester diol-coated ammonium polyphosphate: dropwise adding the polyester diol solution obtained in the step S3 into the aminosilane surface modified ammonium polyphosphate solution prepared in the step S4 in a stirring state, heating to 85 ℃, treating for 4-5 hours through a condensation reflux device, cooling to room temperature, and removing the solvent by rotary evaporation to obtain polyester diol coated ammonium polyphosphate;
s6, preparing a core-shell structure halogen-free flame retardant modified solvent-free polyurethane component A and a component B: uniformly stirring and mixing polyester dihydric alcohol, polyester dihydric alcohol-coated ammonium polyphosphate, a micromolecular chain extender, DOPO, an amine catalyst, a metal catalyst and a flatting agent C-15 at a high speed to obtain a core-shell flame retardant modified solvent-free polyurethane A component, wherein the B component is composed of a polyurethane prepolymer with 15-28% of isocyanate content;
s7, preparing the core-shell structure halogen-free flame retardant modified solvent-free polyurethane resin film: and (4) stirring and mixing the component A and the component B prepared in the step S6 at a high speed by a low-pressure casting machine, coating the mixture on release paper, and drying the release paper at a high temperature of 110-130 ℃ to obtain the core-shell flame retardant modified solvent-free polyurethane resin film.
Preferably, in the step S1, the mass ratio of the ammonium polyphosphate to the zirconia is 10-20:1, and the ball milling time is 5-25 h.
Preferably, in the step S2, the mass ratio of the ammonium polyphosphate to the ethanol is 40-70: 100.
Preferably, in the step S3, the polyester diol is one or more of 1000, 1500, 2000 and 3000 polycarbonate diol, polycaprolactone diol, polybutylene adipate diol and neopentyl glycol adipate diol, and the mass ratio of the polyester diol to the ethanol is 8-18: 100.
Preferably, in step S4, the aminosilane is one or more of KH550, KH540, KH792 and KH602, and the mass ratio of the ammonium polyphosphate to the aminosilane is 100: 4-10.
Preferably, in the step S5, the mass ratio of the polyester diol to the ammonium polyphosphate is 16-40: 100.
Preferably, in the step S6, the mass ratio of the polyester diol, the polyester diol-coated ammonium polyphosphate, the small molecular chain extender, the DOPO, the amine catalyst, the metal catalyst, and the leveling agent C-15 is 100: 10-25: 5-15: 5-10: 0.1-2: 0.1-2: 3-10.
Preferably, in the step S7, the mass ratio of the component a to the component B is 2:3 to 3: 2.
Preferably, in step S2, the small molecule chain extender is one or more of 1, 4-Butanediol (BDO), 1, 6-hexanediol, glycerol, trimethylolpropane, diethylene glycol (DEG), triethylene glycol, neopentyl glycol (NPG), sorbitol, Diethylaminoethanol (DEAE), ethylenediamine (DA), and N, N-dihydroxy (diisopropyl) aniline (HPA).
A core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film is prepared by the preparation method of any one of the application rights.
Has the advantages that:
1. the invention provides a core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane film and a preparation method thereof. The thickness and the performance of the coating layer can be regulated and controlled by changing the molecular weight and the branched chain structure of the polyester diol, the polyester diol and the branched chain structure are introduced into the material A through high-speed shearing and blending, and further introduced into the polyurethane resin through double-component in-situ polymerization, so that the core-shell flame retardant in-situ modified solvent-free polyurethane resin is obtained.
2. The invention provides an in-situ modified solvent-free polyurethane film of a core-shell structure halogen-free flame retardant and a preparation method thereof, wherein a polyester diol coated ammonium polyphosphate core-shell flame retardant is synthesized by designing the surface molecular structure of ammonium polyphosphate and using 3-aminopropyltriethoxysilane and polyester diol as modification raw materials. The core-shell flame retardant contains N, P, Si and other elements, and the core-shell, the coupling agent and the ammonium polyphosphate have a synergistic flame retardant effect. In the thermal decomposition process, ammonium polyphosphate can be firstly decomposed to generate ammonia and water, flame retardance is carried out in a gas phase, meanwhile, polyphosphoric acid, metaphosphoric acid and the like are gradually used for promoting polyester and polyurethane to be dehydrated into carbon, and meanwhile, the ammonium polyphosphate can further react with a silane coupling agent to form a high-stability crosslinking structure, so that the flame retardant effect of the solvent-free polyurethane is remarkably improved.
3. The invention provides a core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane film and a preparation method thereof, wherein the surface of the core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane film is coated with ammonium polyphosphate by polyester diol to form active hydroxyl groups, so that the ammonium polyphosphate can be bonded to a polyurethane chain through covalent bonds after a material A is introduced, the dispersibility and compatibility of the ammonium polyphosphate in polyurethane resin are improved, and meanwhile, the polyester-coated ammonium polyphosphate can form a cross-linked network system in the polyurethane resin to further improve the strength and toughness of the solvent-free polyurethane resin.
Drawings
FIG. 1 is an SEM image of ammonium polyphosphate (APP) and polyester-coated modified ammonium polyphosphate (CAPP);
fig. 2 is a photograph showing the shapes of water drops on the surfaces of ammonium polyphosphate (a), polyester (b), and polyester-coated modified ammonium polyphosphate (c), and the corresponding contact angles are 10 °, 83.5 °, and 96.3 °, respectively.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. All other embodiments, which can be made by those skilled in the art without any inventive step, within the spirit and principle of the present invention, shall be included in the scope of the present invention.
Example 1
With the attached drawings 1-2, the preparation of the core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film comprises the following steps:
(1) preparing superfine ammonium polyphosphate: adding 500g of ammonium polyphosphate into a ball milling tank, adding 2g of zirconia balls and ethanol, grinding at a high speed for 12 hours, taking out a sample, drying, and sieving with a 300-mesh sieve to obtain the ultrafine ammonium polyphosphate.
(2) Preparing an ammonium polyphosphate system solution: 100g of ammonium polyphosphate is added into 110ml of ethanol solution and uniformly dispersed by ultrasound.
(3) Preparing a polyester diol solution: 26g of poly butylene adipate glycol with molecular weight of 2000 is added into 150ml of ethanol solution, and the mixture is stirred and mixed evenly to obtain the polyester glycol solution.
(4) Preparing a KH550 surface modified ammonium polyphosphate solution: dropwise adding 8g of 3-aminopropyltriethoxysilane into an ammonium polyphosphate system solution, mixing and stirring for reaction for 30min, heating to 85 ℃, and continuing to react for 1h to obtain the KH550 surface modified ammonium polyphosphate solution.
(5) Preparing polyester diol coated ammonium polyphosphate: and (2) dropwise adding 80ml of polybutylene adipate glycol solution into the KH550 surface modified ammonium polyphosphate solution in a stirring state, heating to 85 ℃, treating for 4 hours by using a condensation reflux device, cooling to room temperature, and removing the solvent by using rotary evaporation to obtain the polyester coated ammonium polyphosphate.
(6) Preparing a core-shell structure halogen-free flame retardant modified solvent-free polyurethane component A: uniformly stirring and mixing 33g of polycaprolactone diol, 25g of polyester-coated ammonium polyphosphate, 15g of micromolecular chain extender, 5g of DOPO, 0.1g of amine catalyst, 0.1g of metal catalyst and 1g of flatting agent C-15 at a high speed to obtain the core-shell flame retardant modified solvent-free polyurethane component A.
(7) Preparing the core-shell structure halogen-free flame retardant modified solvent-free polyurethane resin film: and coating 49g of the modified solvent-free polyurethane A component and 120g B component on release paper after high-speed stirring and mixing by a low-pressure casting machine, and drying at a high temperature of 110 ℃ to obtain the core-shell flame retardant modified solvent-free polyurethane resin film.
Example 2
A preparation method of a core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film comprises the following steps:
(1) preparing superfine ammonium polyphosphate: adding 500g of ammonium polyphosphate into a ball milling tank, adding 2g of zirconia balls and ethanol, grinding at a high speed for 12 hours, taking out a sample, drying, and sieving with a 300-mesh sieve to obtain the ultrafine ammonium polyphosphate.
(2) Preparing an ammonium polyphosphate system solution: 100g of ammonium polyphosphate is added into 110ml of ethanol solution and uniformly dispersed by ultrasound.
(3) Preparing a polyester diol solution: 26g of poly butylene adipate glycol with molecular weight of 2000 is added into 150ml of ethanol solution, and the mixture is stirred and mixed evenly to obtain the polyester glycol solution.
(4) Preparing a KH550 surface modified ammonium polyphosphate solution: dropwise adding 12g of 3-aminopropyltriethoxysilane into an ammonium polyphosphate system solution, mixing and stirring for reaction for 30min, heating to 85 ℃, and continuing to react for 1h to obtain the KH550 surface modified ammonium polyphosphate solution.
(5) Preparing polyester diol coated ammonium polyphosphate: and (2) dropwise adding 80ml of polybutylene adipate glycol solution into the KH550 surface modified ammonium polyphosphate solution in a stirring state, heating to 85 ℃, treating for 4 hours by using a condensation reflux device, cooling to room temperature, and removing the solvent by using rotary evaporation to obtain the polyester coated ammonium polyphosphate.
(6) Preparing a core-shell flame retardant modified solvent-free polyurethane component A: and uniformly stirring and mixing 33g of polyester diol, 25g of polyester-coated ammonium polyphosphate, 15g of micromolecular chain extender, 5g of DOPO, 0.1g of amine catalyst, 0.1g of metal catalyst and 1g of flatting agent C-15 at a high speed to obtain the core-shell structure halogen-free flame retardant modified solvent-free polyurethane A component.
(7) Preparing the core-shell structure halogen-free flame retardant modified solvent-free polyurethane resin film: and coating 49g of the modified solvent-free polyurethane A component and 120g B component on release paper after high-speed stirring and mixing by a low-pressure casting machine, and drying at a high temperature of 130 ℃ to obtain the core-shell structure halogen-free flame retardant modified solvent-free polyurethane resin film.
Example 3
A preparation method of a core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film comprises the following steps:
(1) preparing superfine ammonium polyphosphate: adding 500g of ammonium polyphosphate into a ball milling tank, adding 2g of zirconia balls and ethanol, grinding at a high speed for 12 hours, taking out a sample, drying, and sieving with a 300-mesh sieve to obtain the ultrafine ammonium polyphosphate.
(2) Preparing an ammonium polyphosphate system solution: 100g of ammonium polyphosphate is added into 110ml of ethanol solution and uniformly dispersed by ultrasound.
(3) Preparing a polyester diol solution: 52g of polybutylene adipate glycol with the molecular weight of 4000 is added into 150ml of ethanol solution, and the mixture is stirred and mixed uniformly to obtain the polyester glycol solution.
(4) Preparing a KH550 surface modified ammonium polyphosphate solution: dropwise adding 8g of 3-aminopropyltriethoxysilane into an ammonium polyphosphate system solution, mixing and stirring for reaction for 30min, heating to 85 ℃, and continuing to react for 1h to obtain the KH550 surface modified ammonium polyphosphate solution.
(5) Preparing polyester diol coated ammonium polyphosphate: and (2) dropwise adding 80ml of polybutylene adipate glycol solution into the KH550 surface modified ammonium polyphosphate solution in a stirring state, heating to 85 ℃, treating for 4 hours by using a condensation reflux device, cooling to room temperature, and removing the solvent by using rotary evaporation to obtain the polyester coated ammonium polyphosphate.
(6) Preparing a core-shell structure halogen-free flame retardant modified solvent-free polyurethane component A: and uniformly stirring and mixing 33g of polyester diol, 25g of polyester-coated ammonium polyphosphate, 15g of micromolecular chain extender, 5g of DOPO, 0.1g of amine catalyst, 0.1g of metal catalyst and 1g of flatting agent C-15 at a high speed to obtain the core-shell structure halogen-free flame retardant modified solvent-free polyurethane A component.
(7) Preparing the core-shell structure halogen-free flame retardant modified solvent-free polyurethane resin film: and coating 49g of the modified solvent-free polyurethane A component and 120g B component on release paper after high-speed stirring and mixing by a low-pressure casting machine, and drying at a high temperature of 110 ℃ to obtain the core-shell structure halogen-free flame retardant modified solvent-free polyurethane resin film.
Example 4
A preparation method of a core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film comprises the following steps:
(1) preparing superfine ammonium polyphosphate: adding 500g of ammonium polyphosphate into a ball milling tank, adding 2g of zirconia balls and ethanol, grinding at a high speed for 12 hours, taking out a sample, drying, and sieving with a 300-mesh sieve to obtain the ultrafine ammonium polyphosphate.
(2) Preparing an ammonium polyphosphate system solution: 100g of ammonium polyphosphate is added into 110ml of ethanol solution and uniformly dispersed by ultrasound.
(3) Preparing a polyester diol solution: 52g of polybutylene adipate glycol with the molecular weight of 4000 is added into 150ml of ethanol solution, and the mixture is stirred and mixed uniformly to obtain the polyester glycol solution.
(4) Preparing a KH550 surface modified ammonium polyphosphate solution: dropwise adding 12g of 3-aminopropyltriethoxysilane into an ammonium polyphosphate system solution, mixing and stirring for reaction for 30min, heating to 85 ℃, and continuing to react for 1h to obtain the KH550 surface modified ammonium polyphosphate solution.
(5) Preparing polyester diol coated ammonium polyphosphate: and (2) dropwise adding 80ml of polybutylene adipate glycol solution into the KH550 surface modified ammonium polyphosphate solution in a stirring state, heating to 85 ℃, treating for 4 hours by using a condensation reflux device, cooling to room temperature, and removing the solvent by using rotary evaporation to obtain the polyester coated ammonium polyphosphate.
(6) Preparing a core-shell structure halogen-free flame retardant modified solvent-free polyurethane component A: and uniformly stirring and mixing 33g of polyester diol, 25g of polyester-coated ammonium polyphosphate, 15g of micromolecular chain extender, 5g of DOPO, 0.1g of amine catalyst, 0.1g of metal catalyst and 1g of flatting agent C-15 at a high speed to obtain the core-shell structure halogen-free flame retardant modified solvent-free polyurethane A component.
(7) Preparing the core-shell structure halogen-free flame retardant modified solvent-free polyurethane resin film: and coating 49g of the modified solvent-free polyurethane A component and 120g B component on release paper after high-speed stirring and mixing by a low-pressure casting machine, and drying at a high temperature of 110 ℃ to obtain the core-shell structure halogen-free flame retardant modified solvent-free polyurethane resin film.
Comparative example 1
A preparation method of an ammonium polyphosphate modified solvent-free polyurethane resin film comprises the following steps:
(1) preparing an ammonium polyphosphate modified solvent-free polyurethane A component: and uniformly stirring and mixing 33g of polyester diol, 25g of ammonium polyphosphate, 15g of micromolecular chain extender, 5g of DOPO, 0.1g of amine catalyst, 0.1g of metal catalyst and 1g of flatting agent C-15 at a high speed to obtain the core-shell flame retardant modified solvent-free polyurethane A component.
(2) Preparing an ammonium polyphosphate modified solvent-free polyurethane resin film: and coating 49g of the modified solvent-free polyurethane A component and 120g B component on release paper after high-speed stirring and mixing by a low-pressure casting machine, and drying at a high temperature of 110 ℃ to obtain the core-shell flame retardant modified solvent-free polyurethane resin film.
Comparative example 2
A method for preparing a modified solvent-free polyurethane resin film, comprising the steps of:
(1) preparing an ammonium polyphosphate system solution: 100g of ammonium polyphosphate is added into 110ml of ethanol solution and uniformly dispersed by ultrasound.
(2) Preparation of A-171 hydrolysate: dispersing 12g of vinyl trimethoxy silane in 150ml of deionized water, adding hydrochloric acid to adjust the pH to 5-6, and stirring at 80 ℃ for 1 h.
(3) Preparation of A-171 surface-modified ammonium polyphosphate: and dropwise adding 70g of ammonium polyphosphate system solution into the A-171 hydrolysate in a stirring state, treating for 4 hours at 60 ℃, and after the reaction is finished, carrying out suction filtration, drying and crushing to obtain the A-171 surface modified ammonium polyphosphate.
(4) Preparing a modified solvent-free polyurethane component A: and uniformly stirring and mixing 33g of polyester diol, 25g of A-171 surface modified ammonium polyphosphate, 15g of micromolecule chain extender, 5g of DOPO, 0.1g of amine catalyst, 0.1g of metal catalyst and 1g of flatting agent C-15 at a high speed to obtain the modified solvent-free polyurethane A component.
(5) Preparation of modified solvent-free polyurethane resin film: and coating 49g of the modified solvent-free polyurethane A component and 120g B component on release paper after high-speed stirring and mixing by a low-pressure casting machine, and drying at a high temperature of 110 ℃ to obtain the modified solvent-free polyurethane resin film.
Comparative example 3
A method for preparing a modified solvent-free polyurethane resin film, comprising the steps of:
(1) preparing ammonium polyphosphate system raw materials: 100g of ammonium polyphosphate, 0.5g of OP-10 and 0.24g of dibutyltin dilaurate are mixed by high-speed shearing to obtain the ammonium polyphosphate system raw material.
(2) Preparing polyurethane-coated ammonium polyphosphate: stirring and mixing 2.7g of PER and 40ml of DMSO, then adding 7.28g of TDI and 40ml of 1, 4-dioxane, stirring for 30min at 40 ℃, continuously adding 150g of ammonium polyphosphate system solution, reacting for 6h at 85 ℃, filtering, washing, drying and crushing after the reaction is finished to obtain the polyurethane-coated ammonium polyphosphate.
(3) Preparing a modified solvent-free polyurethane component A: and uniformly stirring and mixing 33g of polyester diol, 25g of polyurethane-coated ammonium polyphosphate, 15g of micromolecular chain extender, 5g of DOPO, 0.1g of amine catalyst, 0.1g of metal catalyst and 1g of flatting agent C-15 at a high speed to obtain the modified solvent-free polyurethane A component.
(4) Preparation of modified solvent-free polyurethane resin film: and coating 49g of the modified solvent-free polyurethane A component and 120g B component on release paper after high-speed stirring and mixing by a low-pressure casting machine, and drying at a high temperature of 110 ℃ to obtain the modified solvent-free polyurethane resin film.
The component B in the examples and the comparative examples is a polyurethane prepolymer with 18 to 22 percent of isocyanate; the micromolecular chain extender is 1, 4-butanediol; the amine catalyst is triethylene diamine; the metal catalyst is cobalt nickel metal catalyst.
In order to better embody the benefits of the present invention, the following performance tests were performed on the core-shell flame retardant in-situ modified solvent-free polyurethane resin film obtained in examples 1 to 4 of the present invention and the solvent-free polyurethane resin film obtained in the comparative example, and the test results are described as follows:
note: the hand feeling hardness is detected by a hardness tester, and the higher the value is, the softer the hand feeling is; the tensile strength and the elongation at break are detected by a universal tester; the limit oxygen index is tested by an oxygen index tester, and the high oxygen index indicates that the material is not easy to burn; a low oxygen index indicates that the material is readily combustible. Generally, the oxygen index is less than 22% and belongs to flammable materials, the oxygen index is between 22% and 27% and belongs to flame-retardant materials, and the oxygen index is more than 27%.
The data in the table show that the modified solvent-free polyurethane resin film prepared by the invention has better surface flexibility, mechanical property and flame retardant property, and is greatly improved compared with comparative example 1 (ammonium polyphosphate is not modified); the flame retardance of the comparative example 2 (the silane coupling agent surface modified ammonium polyphosphate) and the comparative example 3 (the polyurethane coated ammonium polyphosphate) is obviously improved compared with that of the comparative example 1, but the mechanical property of the polyurethane coated ammonium polyphosphate is far not improved as compared with that of the examples. The technology is proved to be capable of greatly improving the mechanical property of the solvent-free polyurethane while improving the flame retardance of the solvent-free polyurethane, and the surface softness is also enhanced, so that the development of the solvent-free polyurethane resin in the fields of automobile leather and the like is facilitated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of the core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film is characterized by comprising the following steps:
s1, preparing ultra-fine ammonium polyphosphate: adding ammonium polyphosphate into a ball milling tank, adding zirconia balls and ethanol, grinding at a high speed, taking out a sample, drying, and sieving to obtain superfine ammonium polyphosphate;
s2, preparing an ammonium polyphosphate system solution: adding the superfine ammonium polyphosphate into an ethanol solution, and uniformly dispersing by ultrasonic;
s3, preparing a polyester glycol solution: adding polyester dihydric alcohol into an ethanol solution, and uniformly stirring and mixing to obtain a polyester dihydric alcohol solution;
s4, preparing an aminosilane surface modified ammonium polyphosphate solution: dropwise adding aminosilane into the ammonium polyphosphate system solution obtained in the step S2, mixing, stirring and reacting for 30-60min, heating to 80-90 ℃, and continuing to react for 1-2 h to obtain an aminosilane surface modified ammonium polyphosphate solution;
s5, preparing polyester diol-coated ammonium polyphosphate: dropwise adding the polyester diol solution obtained in the step S3 into the aminosilane surface modified ammonium polyphosphate solution prepared in the step S4 in a stirring state, heating to 85 ℃, treating for 4-5 hours through a condensation reflux device, cooling to room temperature, and removing the solvent by rotary evaporation to obtain polyester diol coated ammonium polyphosphate;
s6, preparing a core-shell structure halogen-free flame retardant modified solvent-free polyurethane component A and a component B: uniformly stirring and mixing polyester dihydric alcohol, polyester dihydric alcohol-coated ammonium polyphosphate, a micromolecular chain extender, DOPO, an amine catalyst, a metal catalyst and a flatting agent C-15 at a high speed to obtain a core-shell flame retardant modified solvent-free polyurethane A component, wherein the B component is composed of a polyurethane prepolymer with 15-28% of isocyanate content;
s7, preparing the core-shell structure halogen-free flame retardant modified solvent-free polyurethane resin film: and (4) stirring and mixing the component A and the component B prepared in the step S6 at a high speed by a low-pressure casting machine, coating the mixture on release paper, and drying the release paper at a high temperature of 110-130 ℃ to obtain the core-shell flame retardant modified solvent-free polyurethane resin film.
2. The method for preparing the core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film according to claim 1, wherein in the step S1, the mass ratio of ammonium polyphosphate to zirconium oxide is 10-20:1, and the ball milling time is 5 h-25 h.
3. The method for preparing the core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film according to claim 1, wherein in the step S2, the mass ratio of ammonium polyphosphate to ethanol is 40-70: 100.
4. The method for preparing the core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film according to any one of claims 1 to 3, wherein in the step S3, the polyester diol is one or more of 1000, 1500, 2000 and 3000 polycarbonate diol, polycaprolactone diol, polybutylene adipate diol and neopentyl glycol adipate diol, and the mass ratio of the polyester diol to the ethanol is 8-18: 100.
5. The method for preparing the in-situ modified solvent-free polyurethane resin film with the core-shell structure halogen-free flame retardant according to any one of claims 1 to 3, wherein in the step S4, the aminosilane is one or more of KH550, KH540, KH792 and KH602, and the mass ratio of the ammonium polyphosphate to the aminosilane is 100: 4-10.
6. The method for preparing the core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film according to claim 3, wherein in the step S5, the mass ratio of the polyester diol to the ammonium polyphosphate is 16-40: 100.
7. The preparation method of the core-shell structure halogen-free flame retardant in-situ modification solvent-free polyurethane resin film according to claim 5, wherein in the step S6, the mass ratio of the polyester diol, the polyester diol-coated ammonium polyphosphate, the small molecular chain extender, the DOPO, the amine catalyst, the metal catalyst and the leveling agent C-15 is 100: 10-25: 5-15: 5-10: 0.1-2: 0.1-2: 3-10.
8. The preparation method of the core-shell structure halogen-free flame retardant in-situ modified solvent-free polyurethane resin film according to claim 6 or 7, wherein in the step S7, the mass ratio of the component A to the component B is 2: 3-3: 2.
9. The method for preparing the core-shell halogen-free flame retardant in-situ modified solvent-free polyurethane resin film according to claim 8, wherein in the step S2, the small molecule chain extender is one or more of 1, 4-Butanediol (BDO), 1, 6-hexanediol, glycerol, trimethylolpropane, diethylene glycol (DEG), triethylene glycol, neopentyl glycol (NPG), sorbitol, Diethylaminoethanol (DEAE), ethylenediamine (DA), and N, N-dihydroxy (diisopropyl) aniline (HPA).
10. The in-situ modified solvent-free polyurethane resin film with the core-shell structure halogen-free flame retardant is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115716985A (en) * | 2022-11-24 | 2023-02-28 | 上海皆利新材料科技有限公司 | Halogen-free flame-retardant polyurethane elastomer and preparation method thereof |
| CN115975370A (en) * | 2022-12-26 | 2023-04-18 | 中天科盛科技股份有限公司 | Halogen-free flame retardant TPU and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115716985A (en) * | 2022-11-24 | 2023-02-28 | 上海皆利新材料科技有限公司 | Halogen-free flame-retardant polyurethane elastomer and preparation method thereof |
| CN115975370A (en) * | 2022-12-26 | 2023-04-18 | 中天科盛科技股份有限公司 | Halogen-free flame retardant TPU and preparation method thereof |
| CN115975370B (en) * | 2022-12-26 | 2024-04-09 | 中天科盛科技股份有限公司 | Halogen-free flame retardant TPU and preparation method thereof |
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Application publication date: 20220218 |