CN116082822B - Preparation method of high-temperature-resistant halogen-free flame-retardant polyurethane elastomer - Google Patents
Preparation method of high-temperature-resistant halogen-free flame-retardant polyurethane elastomer Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 161
- 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 154
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 105
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 56
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- 239000000314 lubricant Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 13
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 13
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 13
- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 11
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 17
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003508 Dilauryl thiodipropionate Substances 0.000 claims description 14
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 14
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 claims description 14
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 14
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 14
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 14
- 150000001718 carbodiimides Chemical class 0.000 claims description 12
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- IINACGXCEZNYTF-UHFFFAOYSA-K trichloroyttrium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Y+3] IINACGXCEZNYTF-UHFFFAOYSA-K 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical compound CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 abstract description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract description 6
- 229940112669 cuprous oxide Drugs 0.000 abstract description 6
- 229960001545 hydrotalcite Drugs 0.000 description 9
- 229910001701 hydrotalcite Inorganic materials 0.000 description 9
- 239000005909 Kieselgur Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 239000000779 smoke Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of polyurethane elastomers, in particular to a preparation method of a high-temperature-resistant halogen-free flame-retardant polyurethane elastomer. The invention adds lubricant, antioxidant, anti-hydrolysis agent, modified diatomite flame retardant and modified hydrotalcite flame retardant into polyurethane elastomer to prepare the high temperature-resistant halogen-free flame retardant polyurethane elastomer. The modified diatomite flame retardant is added with ammonium polyphosphate, and cuprous oxide is loaded on the modified hydrotalcite flame retardant, so that the mechanical property of the polyurethane elastomer is ensured, and the flame retardance of the polyurethane elastomer is enhanced.
Description
Technical Field
The invention relates to the technical field of polyurethane elastomers, in particular to a preparation method of a high-temperature-resistant halogen-free flame-retardant polyurethane elastomer.
Background
The polyurethane elastomer has the advantages of high strength, good wear resistance, high toughness and good processability, has smooth surface and good biocompatibility, is acid and alkali resistant, and can be widely applied to the fields of wires and cables, foods, medical equipment, film sheets and the like. However, the polyurethane elastomer has the defects of flame retardance, is easy to burn in air, and can be accompanied by a large amount of smoke and molten drops during combustion, so that the polyurethane elastomer has fire risks and potential safety hazards, and the application of the polyurethane elastomer in the fields of wires, cables, film sheets, automobile parts and the like is greatly limited.
For this purpose, a flame retardant may be added to the polyurethane elastomer to enhance the flame retardancy of the polyurethane elastomer, and the polyurethane elastomer may be flame-retardant-modified. Most of the flame retardant of polyurethane elastomer uses halogen flame retardant, but when the flame retardant material containing chlorine and bromine burns, a large amount of smoke, a hydrogen halide gas with irritation and corrosiveness and the like are easily emitted, and secondary hazard is caused. At present, environmental protection regulations have limited the use of halogen flame retardants, and the use of halogen-free flame retardants is advocated, wherein the halogen-free flame retardants have small smoke amount generated during combustion, do not generate corrosive toxic gas, and greatly improve the safety factor during use. With the development of society and the continuous improvement of green industry requirements, the demand of halogen-free flame-retardant polyurethane elastomer is also increasing.
In order to solve the problems, the invention provides a preparation method of a high-temperature-resistant halogen-free flame-retardant polyurethane elastomer.
Disclosure of Invention
The invention aims to provide a preparation method of a high-temperature-resistant halogen-free flame-retardant polyurethane elastomer, which aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a high-temperature-resistant halogen-free flame-retardant polyurethane elastomer comprises the following steps:
step one: taking aluminum chloride, magnesium chloride, yttrium chloride hexahydrate and deionized water, and uniformly stirring to obtain a mixed solution; taking copper sulfate pentahydrate and deionized water, uniformly stirring, adding polyvinylpyrrolidone, carrying out ultrasonic dispersion for 10-20min, dropwise adding a mixed solution, stirring for 20-30min, dropwise adding a sodium hydroxide solution, adjusting the pH value to 9.5-10, transferring to a hydrothermal kettle, carrying out hydrothermal reaction for 22-26h at 95-105 ℃, washing, drying for 10-14h at 75-80 ℃, and grinding to obtain the modified hydrotalcite flame retardant;
step two: mixing polyurethane elastomer at 133-136 deg.c for 10-15min, adding lubricant, antioxidant, hydrolysis resisting agent, modified diatomite fire retardant and modified hydrotalcite fire retardant, mixing at 155-160 deg.c for 15-20min to obtain polyurethane elastomer composite, and pressing to obtain high temperature resistant halogen-free fire retarding polyurethane elastomer.
More optimally, the preparation method of the modified diatomite flame retardant comprises the following steps: taking modified diatomite and deionized water, and uniformly stirring to obtain a modified diatomite solution; and (3) taking sodium carboxymethylcellulose and deionized water, stirring for 4-6 hours, adding ammonium polyphosphate, continuously stirring for 1-2 hours to obtain a mixed solution, adding the mixed solution into a modified diatomite solution, heating to 40-45 ℃, and stirring for 1-2 hours to obtain the modified diatomite flame retardant.
More optimally, the preparation method of the modified diatomite comprises the following steps: calcining diatomite at 430-450 ℃ for 2-3h, adding sulfuric acid solution, performing ultrasonic treatment for 30-40min, drying, and grinding to obtain modified diatomite.
More optimally, the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer comprises the following components: 80-90% of polyurethane elastomer, 2-10% of modified diatomite flame retardant, 5-10% of modified hydrotalcite flame retardant, 0.5-1% of lubricant, 0.2-0.5% of antioxidant and 0.2-0.3% of anti-hydrolysis agent.
More optimally, the mass ratio of the modified diatomite flame retardant to the modified hydrotalcite flame retardant is (0.6-0.8): 1.
more preferably, the lubricant is any one or more of zinc stearate and hydroxyl silicone oil.
More preferably, the antioxidant is any one or more of dilauryl thiodipropionate and pentaerythritol tetra (3-laurylthiopropionate).
More preferably, the hydrolysis inhibitor is any one or more of carbodiimide and polycarbodiimide.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the diatomite of the biomass material is modified by using calcined sulfuric acid, so that the specific surface area of the diatomite is increased, and the loading amount of ammonium polyphosphate on the diatomite is greatly increased when the ammonium polyphosphate is added subsequently, thereby enhancing the high-temperature-resistant flame-retardant performance of the polyurethane elastomer. Sodium carboxymethyl cellulose is added into diatomite, and a large amount of carboxymethyl and hydroxyl groups are arranged on the sodium carboxymethyl cellulose, so that chelation is generated between the sodium carboxymethyl cellulose and cuprous oxide in the modified hydrotalcite flame retardant, and the mass ratio of the modified diatomite flame retardant to the modified hydrotalcite flame retardant is controlled to be (0.6-0.8): 1, the flame retardant effect is optimal at this time.
(2) Hydrotalcite is a green environment-friendly material with a good lamellar structure. The hydrotalcite has good thermal stability, can catalyze and promote the formation of a carbon layer, and is a flame retardant with excellent flame retardant effect. According to the invention, the copper sulfate pentahydrate is added, so that the cuprous oxide with the smoke suppression effect is loaded on the hydrotalcite, and the flame retardant property of the hydrotalcite is greatly enhanced. The polyurethane elastomer prepared by the method provided by the invention has good flame retardance and high temperature resistance, does not contain chlorine and bromine flame retardant elements, does not generate toxic gas when in use, and is environment-friendly.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The chemical reagents used in the present invention are purchased as follows:
polyvinylpyrrolidone K-30, purchased from national pharmaceutical group chemical reagent Co., ltd;
polyurethane elastomer WHT-1185, available from Wanhua chemical group Co., ltd.
Example 1
Step one: preparation of modified diatomite flame retardant:
7g of diatomite is taken, calcined for 2.5 hours at 440 ℃, 100mL of sulfuric acid solution with the concentration of 37% is added, ultrasonic treatment is carried out for 35 minutes, drying and grinding are carried out, and modified diatomite is obtained;
taking 5g of modified diatomite and 100mL of deionized water, and uniformly stirring to obtain a modified diatomite solution; taking 1.5g of sodium carboxymethyl cellulose and 100mL of deionized water, stirring for 5 hours, adding 5g of ammonium polyphosphate, continuously stirring for 1.5 hours to obtain a mixed solution, adding the mixed solution into the modified diatomite solution, heating to 43 ℃, and stirring for 1.5 hours to obtain the modified diatomite flame retardant.
Step two: preparation of modified hydrotalcite flame retardant:
taking 10mM aluminum chloride, 20mM magnesium chloride, 1mM yttrium chloride hexahydrate and 100mL deionized water, and uniformly stirring to obtain a mixed solution; taking 1g of copper sulfate pentahydrate and 150mL of deionized water, uniformly stirring, adding 0.8g of polyvinylpyrrolidone, performing ultrasonic dispersion for 15min, dropwise adding the mixed solution, stirring for 25min, dropwise adding a sodium hydroxide solution, adjusting the pH value to 9.5, transferring to a hydrothermal kettle, performing hydrothermal reaction at 102 ℃ for 24h, washing, drying at 77 ℃ for 12h, and grinding to obtain the modified hydrotalcite flame retardant.
Step three: preparation of high-temperature-resistant halogen-free flame-retardant polyurethane elastomer:
mixing polyurethane elastomer at 135 ℃ for 12min, adding lubricant zinc stearate, antioxidant dilauryl thiodipropionate, anti-hydrolysis agent carbodiimide, modified diatomite flame retardant and modified hydrotalcite flame retardant, mixing at 157 ℃ for 18min to obtain polyurethane elastomer composite material, placing the polyurethane elastomer composite material into a mould, and pressing to obtain the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer, wherein the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer is a sheet with the thickness of 100mm multiplied by 3 mm.
The high-temperature-resistant halogen-free flame-retardant polyurethane elastomer comprises the following components: 85% of polyurethane elastomer, 5.6% of modified diatomite flame retardant, 8% of modified hydrotalcite flame retardant, 0.7% of lubricant zinc stearate, 0.3% of antioxidant dilauryl thiodipropionate and 0.2% of hydrolytic agent carbodiimide.
The mass ratio of the modified diatomite flame retardant to the modified hydrotalcite flame retardant is 0.7:1.
example 2
Step one: preparation of modified diatomite flame retardant:
7g of diatomite is taken, calcined for 2 hours at 430 ℃, 100mL of sulfuric acid solution with the concentration of 37% is added, ultrasonic treatment is carried out for 30 minutes, drying and grinding are carried out, and modified diatomite is obtained;
taking 5g of modified diatomite and 100mL of deionized water, and uniformly stirring to obtain a modified diatomite solution; taking 1.5g of sodium carboxymethyl cellulose and 100mL of deionized water, stirring for 4 hours, adding 5g of ammonium polyphosphate, continuously stirring for 1 hour to obtain a mixed solution, adding the mixed solution into the modified diatomite solution, heating to 40 ℃, and stirring for 1 hour to obtain the modified diatomite flame retardant.
Step two: preparation of modified hydrotalcite flame retardant:
taking 10mM aluminum chloride, 20mM magnesium chloride, 1mM yttrium chloride hexahydrate and 100mL deionized water, and uniformly stirring to obtain a mixed solution; taking 1g of copper sulfate pentahydrate and 150mL of deionized water, uniformly stirring, adding 0.8g of polyvinylpyrrolidone, performing ultrasonic dispersion for 10min, dropwise adding the mixed solution, stirring for 20min, dropwise adding a sodium hydroxide solution, adjusting the pH value to 9.5, transferring to a hydrothermal kettle, performing hydrothermal reaction at 95 ℃ for 22h, washing, drying at 75 ℃ for 14h, and grinding to obtain the modified hydrotalcite flame retardant.
Step three: preparation of high-temperature-resistant halogen-free flame-retardant polyurethane elastomer:
mixing polyurethane elastomer at 133 ℃ for 10min, adding lubricant hydroxyl silicone oil, antioxidant pentaerythritol tetra (3-laurylthiopropionate), anti-hydrolysis agent polycarbodiimide, modified diatomite flame retardant and modified hydrotalcite flame retardant, mixing at 155 ℃ for 15min to obtain polyurethane elastomer composite material, placing the polyurethane elastomer composite material in a mould, and pressing to obtain the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer, wherein the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer is a sheet with the thickness of 100mm multiplied by 3 mm.
The high-temperature-resistant halogen-free flame-retardant polyurethane elastomer comprises the following components: 80% of polyurethane elastomer, 3% of modified diatomite flame retardant, 5% of modified hydrotalcite flame retardant, 0.5% of lubricant hydroxyl silicone oil, 0.2% of antioxidant pentaerythritol tetra (3-laurylthiopropionate) and 0.2% of hydrolysis inhibitor polycarbodiimide by weight.
The mass ratio of the modified diatomite flame retardant to the modified hydrotalcite flame retardant is 0.6:1.
example 3
Step one: preparation of modified diatomite flame retardant:
7g of kieselguhr is taken and calcined for 3 hours at 450 ℃, 100mL of sulfuric acid solution with the concentration of 37 percent is added, ultrasonic treatment is carried out for 40 minutes, drying and grinding are carried out, and modified kieselguhr is obtained;
taking 5g of modified diatomite and 100mL of deionized water, and uniformly stirring to obtain a modified diatomite solution; taking 1.5g of sodium carboxymethyl cellulose and 100mL of deionized water, stirring for 6 hours, adding 5g of ammonium polyphosphate, continuously stirring for 2 hours to obtain a mixed solution, adding the mixed solution into the modified diatomite solution, heating to 45 ℃, and stirring for 2 hours to obtain the modified diatomite flame retardant.
Step two: preparation of modified hydrotalcite flame retardant:
taking 10mM aluminum chloride, 20mM magnesium chloride, 1mM yttrium chloride hexahydrate and 100mL deionized water, and uniformly stirring to obtain a mixed solution; taking 1g of copper sulfate pentahydrate and 150mL of deionized water, uniformly stirring, adding 0.8g of polyvinylpyrrolidone, performing ultrasonic dispersion for 20min, dropwise adding the mixed solution, stirring for 30min, dropwise adding a sodium hydroxide solution, adjusting the pH value to 10, transferring to a hydrothermal kettle, performing hydrothermal reaction at 105 ℃ for 26h, washing, drying at 80 ℃ for 14h, and grinding to obtain the modified hydrotalcite flame retardant.
Step three: preparation of high-temperature-resistant halogen-free flame-retardant polyurethane elastomer:
mixing polyurethane elastomer at 136 ℃ for 15min, adding lubricant zinc stearate, antioxidant dilauryl thiodipropionate, hydrolysis-resistant agent polycarbodiimide, modified diatomite flame retardant and modified hydrotalcite flame retardant, mixing at 160 ℃ for 20min to obtain polyurethane elastomer composite material, placing the polyurethane elastomer composite material into a mould, and pressing to obtain the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer, wherein the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer is a sheet with the thickness of 100mm multiplied by 3 mm.
The high-temperature-resistant halogen-free flame-retardant polyurethane elastomer comprises the following components: 90% of polyurethane elastomer, 8% of modified diatomite flame retardant, 10% of modified hydrotalcite flame retardant, 1% of lubricant zinc stearate, 0.5% of antioxidant dilauryl thiodipropionate and 0.3% of hydrolysis inhibitor polycarbodiimide.
The mass ratio of the modified diatomite flame retardant to the modified hydrotalcite flame retardant is 0.8:1.
example 4: the diatomaceous earth was not modified, and the rest was the same as in example 1.
Step one: preparation of modified diatomite flame retardant:
taking 5g of diatomite and 100mL of deionized water, and uniformly stirring to obtain a diatomite solution; taking 1.5g of sodium carboxymethyl cellulose and 100mL of deionized water, stirring for 5 hours, adding 5g of ammonium polyphosphate, continuously stirring for 1.5 hours to obtain a mixed solution, adding the mixed solution into a diatomite solution, heating to 43 ℃, and stirring for 1.5 hours to obtain the modified diatomite flame retardant.
Step two: preparation of modified hydrotalcite flame retardant:
taking 10mM aluminum chloride, 20mM magnesium chloride, 1mM yttrium chloride hexahydrate and 100mL deionized water, and uniformly stirring to obtain a mixed solution; taking 1g of copper sulfate pentahydrate and 150mL of deionized water, uniformly stirring, adding 0.8g of polyvinylpyrrolidone, performing ultrasonic dispersion for 15min, dropwise adding the mixed solution, stirring for 25min, dropwise adding a sodium hydroxide solution, adjusting the pH value to 9.5, transferring to a hydrothermal kettle, performing hydrothermal reaction at 102 ℃ for 24h, washing, drying at 77 ℃ for 12h, and grinding to obtain the modified hydrotalcite flame retardant.
Step three: preparation of high-temperature-resistant halogen-free flame-retardant polyurethane elastomer:
mixing polyurethane elastomer at 135 ℃ for 12min, adding lubricant zinc stearate, antioxidant dilauryl thiodipropionate, anti-hydrolysis agent carbodiimide, modified diatomite flame retardant and modified hydrotalcite flame retardant, mixing at 157 ℃ for 18min to obtain polyurethane elastomer composite material, placing the polyurethane elastomer composite material into a mould, and pressing to obtain the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer, wherein the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer is a sheet with the thickness of 100mm multiplied by 3 mm.
The high-temperature-resistant halogen-free flame-retardant polyurethane elastomer comprises the following components: 85% of polyurethane elastomer, 5.6% of modified diatomite flame retardant, 8% of modified hydrotalcite flame retardant, 0.7% of lubricant zinc stearate, 0.3% of antioxidant dilauryl thiodipropionate and 0.2% of hydrolytic agent carbodiimide.
The mass ratio of the modified diatomite flame retardant to the modified hydrotalcite flame retardant is 0.7:1.
example 5: sodium carboxymethyl cellulose was not added to diatomaceous earth, and the rest was the same as in example 1.
Step one: preparation of modified diatomite flame retardant:
7g of diatomite is taken, calcined for 2.5 hours at 440 ℃, 100mL of sulfuric acid solution with the concentration of 37% is added, ultrasonic treatment is carried out for 35 minutes, drying and grinding are carried out, and modified diatomite is obtained;
taking 5g of modified diatomite and 100mL of deionized water, and uniformly stirring to obtain a modified diatomite solution; taking 5g of ammonium polyphosphate and 100mL of deionized water, stirring for 2h to obtain a mixed solution, adding the mixed solution into the modified diatomite solution, heating to 43 ℃, and stirring for 1.5h to obtain the modified diatomite flame retardant.
Step two: preparation of modified hydrotalcite flame retardant:
taking 10mM aluminum chloride, 20mM magnesium chloride, 1mM yttrium chloride hexahydrate and 100mL deionized water, and uniformly stirring to obtain a mixed solution; taking 1g of copper sulfate pentahydrate and 150mL of deionized water, uniformly stirring, adding 0.8g of polyvinylpyrrolidone, performing ultrasonic dispersion for 15min, dropwise adding the mixed solution, stirring for 25min, dropwise adding a sodium hydroxide solution, adjusting the pH value to 9.5, transferring to a hydrothermal kettle, performing hydrothermal reaction at 102 ℃ for 24h, washing, drying at 77 ℃ for 12h, and grinding to obtain the modified hydrotalcite flame retardant.
Step three: preparation of high-temperature-resistant halogen-free flame-retardant polyurethane elastomer:
mixing polyurethane elastomer at 135 ℃ for 12min, adding lubricant zinc stearate, antioxidant dilauryl thiodipropionate, anti-hydrolysis agent carbodiimide, modified diatomite flame retardant and modified hydrotalcite flame retardant, mixing at 157 ℃ for 18min to obtain polyurethane elastomer composite material, placing the polyurethane elastomer composite material into a mould, and pressing to obtain the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer, wherein the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer is a sheet with the thickness of 100mm multiplied by 3 mm.
The high-temperature-resistant halogen-free flame-retardant polyurethane elastomer comprises the following components: 85% of polyurethane elastomer, 5.6% of modified diatomite flame retardant, 8% of modified hydrotalcite flame retardant, 0.7% of lubricant zinc stearate, 0.3% of antioxidant dilauryl thiodipropionate and 0.2% of hydrolytic agent carbodiimide.
The mass ratio of the modified diatomite flame retardant to the modified hydrotalcite flame retardant is 0.7:1.
example 6: the hydrotalcite was not loaded with cuprous oxide, and the rest was the same as in example 1.
Step one: preparation of modified diatomite flame retardant:
7g of diatomite is taken, calcined for 2.5 hours at 440 ℃, 100mL of sulfuric acid solution with the concentration of 37% is added, ultrasonic treatment is carried out for 35 minutes, drying and grinding are carried out, and modified diatomite is obtained;
taking 5g of modified diatomite and 100mL of deionized water, and uniformly stirring to obtain a modified diatomite solution; taking 1.5g of sodium carboxymethyl cellulose and 100mL of deionized water, stirring for 5 hours, adding 5g of ammonium polyphosphate, continuously stirring for 1.5 hours to obtain a mixed solution, adding the mixed solution into the modified diatomite solution, heating to 43 ℃, and stirring for 1.5 hours to obtain the modified diatomite flame retardant.
Step two: preparation of hydrotalcite flame retardant:
taking 10mM aluminum chloride, 20mM magnesium chloride, 1mM yttrium chloride hexahydrate and 100mL deionized water, and uniformly stirring to obtain a mixed solution; dropwise adding sodium hydroxide solution, regulating the pH value to 9.5, transferring to a hydrothermal kettle, performing hydrothermal reaction at 102 ℃ for 24 hours, washing, drying at 77 ℃ for 12 hours, and grinding to obtain the hydrotalcite flame retardant.
Step three: preparation of high-temperature-resistant halogen-free flame-retardant polyurethane elastomer:
mixing polyurethane elastomer at 135 ℃ for 12min, adding lubricant zinc stearate, antioxidant dilauryl thiodipropionate, anti-hydrolysis agent carbodiimide, modified diatomite flame retardant and modified hydrotalcite flame retardant, mixing at 157 ℃ for 18min to obtain polyurethane elastomer composite material, placing the polyurethane elastomer composite material into a mould, and pressing to obtain the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer, wherein the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer is a sheet with the thickness of 100mm multiplied by 3 mm.
The high-temperature-resistant halogen-free flame-retardant polyurethane elastomer comprises the following components: 85% of polyurethane elastomer, 5.6% of modified diatomite flame retardant, 8% of hydrotalcite flame retardant, 0.7% of lubricant zinc stearate, 0.3% of antioxidant dilauryl thiodipropionate and 0.2% of hydrolytic agent carbodiimide.
The mass ratio of the modified diatomite flame retardant to the modified hydrotalcite flame retardant is 0.7:1.
example 7: the mass ratio of the modified diatomite flame retardant to the modified hydrotalcite flame retardant is controlled to be 0.4:1, the remainder being the same as in example 1.
Step one: preparation of modified diatomite flame retardant:
7g of diatomite is taken, calcined for 2.5 hours at 440 ℃, 100mL of sulfuric acid solution with the concentration of 37% is added, ultrasonic treatment is carried out for 35 minutes, drying and grinding are carried out, and modified diatomite is obtained;
taking 5g of modified diatomite and 100mL of deionized water, and uniformly stirring to obtain a modified diatomite solution; taking 1.5g of sodium carboxymethyl cellulose and 100mL of deionized water, stirring for 5 hours, adding 5g of ammonium polyphosphate, continuously stirring for 1.5 hours to obtain a mixed solution, adding the mixed solution into the modified diatomite solution, heating to 43 ℃, and stirring for 1.5 hours to obtain the modified diatomite flame retardant.
Step two: preparation of modified hydrotalcite flame retardant:
taking 10mM aluminum chloride, 20mM magnesium chloride, 1mM yttrium chloride hexahydrate and 100mL deionized water, and uniformly stirring to obtain a mixed solution; taking 1g of copper sulfate pentahydrate and 150mL of deionized water, uniformly stirring, adding 0.8g of polyvinylpyrrolidone, performing ultrasonic dispersion for 15min, dropwise adding the mixed solution, stirring for 25min, dropwise adding a sodium hydroxide solution, adjusting the pH value to 9.5, transferring to a hydrothermal kettle, performing hydrothermal reaction at 102 ℃ for 24h, washing, drying at 77 ℃ for 12h, and grinding to obtain the modified hydrotalcite flame retardant.
Step three: preparation of high-temperature-resistant halogen-free flame-retardant polyurethane elastomer:
mixing polyurethane elastomer at 135 ℃ for 12min, adding lubricant zinc stearate, antioxidant dilauryl thiodipropionate, anti-hydrolysis agent carbodiimide, modified diatomite flame retardant and modified hydrotalcite flame retardant, mixing at 157 ℃ for 18min to obtain polyurethane elastomer composite material, placing the polyurethane elastomer composite material into a mould, and pressing to obtain the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer, wherein the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer is a sheet with the thickness of 100mm multiplied by 3 mm.
The high-temperature-resistant halogen-free flame-retardant polyurethane elastomer comprises the following components: 85% of polyurethane elastomer, 3.2% of modified diatomite flame retardant, 8% of modified hydrotalcite flame retardant, 0.7% of lubricant zinc stearate, 0.3% of antioxidant dilauryl thiodipropionate and 0.2% of hydrolytic agent carbodiimide.
The mass ratio of the modified diatomite flame retardant to the modified hydrotalcite flame retardant is 0.4:1.
experiment:
the polyurethane elastomers prepared in examples 1 to 7 were subjected to performance test, the polyurethane elastomers were cut into sheets of 100mm×6.5mm×3mm, and the limiting oxygen index of the polyurethane elastomers was tested using a digital oxygen display index meter model 5801. Polyurethane elastomer was prepared as a 50mm dumbbell-shaped standard sample and subjected to mechanical testing at a speed of 200mm/min using an electronic universal tester model E44, and the data obtained are shown in the following table:
| LOI/% | tensile Strength/MPa | |
| Example 1 | 30.8 | 21.36 |
| Example 2 | 30.5 | 22.49 |
| Example 3 | 31.1 | 21.03 |
| Example 4 | 30.2 | 21.27 |
| Example 5 | 29.7 | 21.16 |
| Example 6 | 28.9 | 21.22 |
| Example 7 | 29.4 | 21.46 |
Conclusion: as can be seen from the comparison of the data on the table, the polyurethane elastomer prepared by the invention has good mechanical properties. In example 4, diatomaceous earth was not modified, the specific surface area of diatomaceous earth was small, and the amount of ammonium polyphosphate supported was small, and the flame retardancy was deteriorated. In example 5, sodium carboxymethylcellulose was not added to diatomaceous earth, but the sodium carboxymethylcellulose did not chelate with cuprous oxide in the modified hydrotalcite flame retardant, and the flame retardancy was deteriorated. In example 6, cuprous oxide was not supported on hydrotalcite, and flame retardancy was deteriorated. Example 7 control the mass ratio of the modified diatomite flame retardant and the modified hydrotalcite flame retardant to be 0.4:1, the addition amount of the modified diatomite flame retardant becomes smaller, the limiting oxygen index of the polyurethane elastomer becomes lower, and the flame retardance becomes worse.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of a high-temperature-resistant halogen-free flame-retardant polyurethane elastomer is characterized by comprising the following steps of: the method comprises the following steps:
step one: taking aluminum chloride, magnesium chloride, yttrium chloride hexahydrate and deionized water, and uniformly stirring to obtain a mixed solution; taking copper sulfate pentahydrate and deionized water, uniformly stirring, adding polyvinylpyrrolidone, carrying out ultrasonic dispersion for 10-20min, dropwise adding a mixed solution, stirring for 20-30min, dropwise adding a sodium hydroxide solution, adjusting the pH value to 9.5-10, transferring to a hydrothermal kettle, carrying out hydrothermal reaction for 22-26h at 95-105 ℃, washing, drying for 10-14h at 75-80 ℃, and grinding to obtain the modified hydrotalcite flame retardant;
step two: mixing polyurethane elastomer at 133-136 ℃ for 10-15min, adding lubricant, antioxidant, anti-hydrolysis agent, modified diatomite flame retardant and modified hydrotalcite flame retardant, mixing at 155-160 ℃ for 15-20min to obtain polyurethane elastomer composite material, placing the polyurethane elastomer composite material in a mould, and pressing to obtain high-temperature-resistant halogen-free flame retardant polyurethane elastomer;
the preparation method of the modified diatomite flame retardant comprises the following steps: taking modified diatomite and deionized water, and uniformly stirring to obtain a modified diatomite solution; and (3) taking sodium carboxymethylcellulose and deionized water, stirring for 4-6 hours, adding ammonium polyphosphate, continuously stirring for 1-2 hours to obtain a mixed solution, adding the mixed solution into a modified diatomite solution, heating to 40-45 ℃, and stirring for 1-2 hours to obtain the modified diatomite flame retardant.
2. The method for preparing the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer according to claim 1, which is characterized in that: the preparation method of the modified diatomite comprises the following steps: calcining diatomite at 430-450 ℃ for 2-3h, adding sulfuric acid solution, performing ultrasonic treatment for 30-40min, drying, and grinding to obtain modified diatomite.
3. The method for preparing the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer according to claim 1, which is characterized in that: the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer comprises the following components: 80-90% of polyurethane elastomer, 2-10% of modified diatomite flame retardant, 5-10% of modified hydrotalcite flame retardant, 0.5-1% of lubricant, 0.2-0.5% of antioxidant and 0.2-0.3% of anti-hydrolysis agent.
4. The method for preparing the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer according to claim 3, which is characterized in that: the mass ratio of the modified diatomite flame retardant to the modified hydrotalcite flame retardant is (0.6-0.8): 1.
5. the method for preparing the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer according to claim 1, which is characterized in that: the lubricant is any one or more of zinc stearate and hydroxyl silicone oil.
6. The method for preparing the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer according to claim 1, which is characterized in that: the antioxidant is any one or more of dilauryl thiodipropionate and pentaerythritol tetra (3-laurylthiopropionate).
7. The method for preparing the high-temperature-resistant halogen-free flame-retardant polyurethane elastomer according to claim 1, which is characterized in that: the anti-hydrolysis agent is any one or more of carbodiimide and polycarbodiimide.
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