CN117736495A - Flame-retardant high-temperature-resistant polyurethane foam material and preparation method thereof - Google Patents
Flame-retardant high-temperature-resistant polyurethane foam material and preparation method thereof Download PDFInfo
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- CN117736495A CN117736495A CN202311740611.5A CN202311740611A CN117736495A CN 117736495 A CN117736495 A CN 117736495A CN 202311740611 A CN202311740611 A CN 202311740611A CN 117736495 A CN117736495 A CN 117736495A
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- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 69
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 69
- 239000003063 flame retardant Substances 0.000 title claims abstract description 49
- 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 46
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920002472 Starch Polymers 0.000 claims abstract description 37
- 239000008107 starch Substances 0.000 claims abstract description 37
- 235000019698 starch Nutrition 0.000 claims abstract description 37
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 25
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 25
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 25
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 21
- 239000010452 phosphate Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 15
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 15
- -1 silicon-boron modified hydroxyapatite Chemical class 0.000 claims abstract description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 37
- 229920001451 polypropylene glycol Polymers 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- 239000000945 filler Substances 0.000 claims description 19
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229920005862 polyol Polymers 0.000 claims description 14
- 150000003077 polyols Chemical class 0.000 claims description 14
- 230000001965 increasing effect Effects 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000004088 foaming agent Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000012974 tin catalyst Substances 0.000 claims description 5
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000006261 foam material Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 238000002156 mixing Methods 0.000 claims 2
- 238000007598 dipping method Methods 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 37
- 238000002791 soaking Methods 0.000 abstract description 17
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 3
- 229910000077 silane Inorganic materials 0.000 abstract description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052796 boron Inorganic materials 0.000 abstract description 2
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000006260 foam Substances 0.000 description 45
- 239000000243 solution Substances 0.000 description 22
- 238000005303 weighing Methods 0.000 description 18
- 229920002635 polyurethane Polymers 0.000 description 11
- 239000004814 polyurethane Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 210000000497 foam cell Anatomy 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910014472 Ca—O Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910003873 O—P—O Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- MXSJNBRAMXILSE-UHFFFAOYSA-N [Si].[P].[B] Chemical compound [Si].[P].[B] MXSJNBRAMXILSE-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000005620 boronic acid group Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 239000012466 permeate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical group [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant high-temperature-resistant polyurethane foam material and a preparation method thereof, belonging to the technical field of organic polymer synthesis. Firstly, carrying out surface modification on hydroxyapatite to obtain silane grafted hydroxyapatite, and then adding flame-retardant and high-temperature-resistant element boron into the silane grafted hydroxyapatite by boric acid to obtain silicon-boron modified hydroxyapatite, so as to obtain high-temperature-resistant Wen Chuji; then carrying out phosphate modification on starch to obtain phosphate starch, and preparing into an aqueous solution; oxidizing expandable graphite to obtain expanded graphite oxide EGO, and modifying the EGO with cetyltrimethylammonium bromide to prepare an aqueous solution; and preparing an ammonium polyphosphate aqueous solution, and respectively soaking and drying the polyurethane foam added with the high-temperature-resistant auxiliary agent in the three aqueous solutions in sequence to obtain the flame-retardant high-temperature-resistant polyurethane foam material. The invention greatly enhances the physical property stability at high temperature on the basis of not changing the original polyurethane foam structure and mechanical property, and the flame retardance can achieve self-extinguishing after leaving fire.
Description
Technical Field
The invention belongs to the technical field of organic polymer synthesis, and particularly relates to a flame-retardant high-temperature-resistant polyurethane foam material and a preparation method thereof.
Background
Polyurethane foam is a multifunctional material with light weight, high strength, heat insulation, sound insulation and weather resistance. It was traced back to the 40 s of the 20 th century when the German scientist invented this material and was originally applied in the aerospace field. The polyurethane foam has excellent heat insulation performance, can reduce energy loss and improve the energy efficiency of a building; it also effectively blocks the transmission of noise and has excellent properties in many respects, but also suffers from some drawbacks in terms of heat resistance and flame retardance. The following are some common disadvantages: the heat resistance of polyurethane foams is limited by temperature. Under high temperature conditions, polyurethane foam may melt, char or produce toxic fumes. Easy combustion: although polyurethane foams may have flame retardants added to improve their flame retardant properties, there is still a risk of combustion. In the event of a fire, the polyurethane foam may burn, producing flames and toxic gases. In view of the above, polyurethane foams have some disadvantages in terms of heat and flame resistance, and care must be taken during use and handling. Other alternative materials may need to be considered where higher heat and flame resistance properties are desired.
Conventionally, a method of improving the high temperature resistance of polyurethane foam mainly includes adding a flame retardant and an inorganic filler. Flame retardants such as melamine and DOPO can effectively inhibit the burning of foam at high temperatures, but these flame retardants tend to have certain toxicity and environmental concerns. Another approach is to add inorganic fillers such as white carbon black and expandable graphite. These fillers can increase the thermal stability and thermal expansion resistance of the foam. However, the main disadvantage of this method is that the combination of the inorganic filler and the polyurethane matrix is weak, resulting in marks left on the foam surface by the filler, affecting the appearance and properties of the foam. In addition, the conventional methods have other problems such as increasing the density of the material, decreasing the mechanical properties of the foam, and limiting the application temperature range of the foam.
Disclosure of Invention
The invention aims to provide a flame-retardant high-temperature-resistant polyurethane foam material and a preparation method thereof. On the basis of not changing the original polyurethane foam structure and mechanical property, the physical property stability of the polyurethane foam is greatly enhanced at high temperature, the flame retardance can achieve self-extinguishing after leaving fire, and the preparation process uses environment-friendly diphenylmethane diisocyanate, water and the like as raw materials for foaming, so that the polyurethane foam is suitable for practical production and application.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a high-temperature-resistant hydrolysis-resistant polyurethane foam material is composed of the following raw materials in parts by weight: 40-60 parts of polyether polyol, 40-60 parts of polypropylene glycol and 0-20 parts of polymer polyol (wherein the sum of the parts by weight of the polyether polyol, the polypropylene glycol and the polymer polyol is 100 parts), 0.4-1.0 part of amine catalyst, 0.8-1.4 parts of tin catalyst, 0.8-1.2 parts of surfactant, 2.8-3.6 parts of foaming agent, 1-5 parts of high-temperature resistant filler and 60-90 parts of diphenylmethane diisocyanate MDI, and soaking the prepared polyurethane foam in an aqueous solution containing a flame retardant auxiliary agent to obtain the flame-retardant high-temperature resistant polyurethane foam material.
The high-temperature-resistant filler is silicon-boron modified hydroxyapatite BSHA. The preparation process is as follows:
(1) 5g of nano-hydroxyapatite is weighed, added into a beaker filled with 100mL of deionized water and stirred for 0.5h to form an aqueous solution, then another beaker is taken to add 100mL of 90 wt% ethanol solution, 2mL of KH550 is added to hydrolyze the aqueous solution for 0.5h, and then the two solutions are mixed and reacted at 40 ℃ for 4h to obtain KH550 modified hydroxyapatite.
(2) And (3) carrying out suction filtration and washing on the NHA obtained after the reaction in the step (1), and adding the NHA into 100mL of deionized water again to obtain an aqueous solution of NHA, weighing 1g of boric acid, adding the aqueous solution of NHA into the aqueous solution of NHA, reacting for 3 hours at 40 ℃, carrying out vacuum filtration and drying to obtain the silicon-boron modified hydroxyapatite BSHA.
The preparation process of the flame-retardant impregnating solution comprises the following steps:
(1) Preparation of aqueous solution of phosphated starch: preparing phosphate starch P-CS through a wet method, weighing 3g of sodium dihydrogen phosphate into a 250mL three-necked flask, adding 50mL of deionized water, dispersing for 0.5h by ultrasound, adding 20g of starch into the mixed solution, fully stirring, adjusting the pH value of the mixture to be 6.5 by adopting dilute hydrochloric acid, transferring the three-necked flask into a water bath kettle, refluxing and cooling, reacting for 0.5h at 65 ℃, cooling, neutralizing to be neutral by adopting 1mol/LNaOH, washing with absolute ethyl alcohol and deionized water, carrying out suction filtration, and drying for 24h at 50 ℃ to obtain the P-CS. 10g P-CS was weighed into a beaker containing 200mL of deionized water to give a 5% wt aqueous P-CS solution.
(2) Expandable graphene oxide EGO was prepared by the modified Hummers method, 0.5g EGO was weighed and added to a beaker containing 100mL deionized water for ultrasonic dispersion for 1h, after which 2% wt 100mL cetyltrimethylammonium bromide aqueous solution was formulated and added to the ultrasonic dispersed EGO aqueous solution and stirred for 2h to obtain a modified EGO aqueous solution.
(3) 1g-5g of ammonium polyphosphate was added to a beaker containing 100mL of deionized water to prepare an aqueous ammonium polyphosphate solution.
The preparation of the high-temperature-resistant polyurethane foam material comprises the following steps:
(1) Adding polyether polyol, polypropylene glycol and polymer polyol into a container according to a proportion, adding high-temperature resistant filler, amine catalyst, tin catalyst, surfactant and foaming agent according to a formula, stirring for 2-3min under a stirring machine with the rotating speed of 1500r/min, and marking as a component A;
(2) Adding diphenylmethane diisocyanate MDI into another container according to a certain proportion, stirring for 10-30s under a stirrer with the rotating speed of 1000r/min, and marking as a component B;
(3) And (3) increasing the rotating speed of the component A to 2500-3000r/min, pouring the component B into a container filled with the component A, stirring for 10-15s under a high-speed stirrer, pouring the system into a mould when the system turns white, controlling the temperature of the mould to 25+/-0.5 ℃, and cutting after 24-72h to obtain the high-temperature-resistant polyurethane foam material.
The soaking method of the flame-retardant high-temperature-resistant polyurethane foam material comprises the following steps:
(1) Firstly, soaking the foam in a phosphate starch aqueous solution, carrying out repeated pinching and squeezing, then soaking for 0.5h, and then drying the soaked foam at 60 ℃ for 2h;
(2) Immersing the dried foam into the modified expandable graphene oxide aqueous solution, repeatedly pinching and extruding, immersing for 0.5h, and drying at 60 ℃ for 2h;
(3) And immersing the dried foam into an ammonium polyphosphate aqueous solution, repeatedly pinching and extruding, immersing for 0.5h, and drying at 60 ℃ for 2h to obtain the flame-retardant high-temperature-resistant polyurethane foam material.
The polyether polyol is produced by U.S. Henschel group
The polypropylene glycol is a polypropylene glycol PPG with Mn=3000 produced by Jiangsu sea-safe petrochemical plant;
the polymer polyol is POP-2045 produced by Ningbo macrosense chemical industry Co.
The amine catalyst is triethylene diamine A-33 produced by new material groups of Michaelis-A;
the tin catalyst is stannous octoate T-9 produced by Shanghai A Ding Shenghua technology Co., ltd;
the surfactant is silicone oil 6008 produced by the new material group of michaux in the united states;
the foaming agent is deionized water;
the diphenylmethane diisocyanate is MDI-8002 produced by the U.S. hounsfield group.
The invention has the beneficial effects that:
through reasonable design of production formula and process, nontoxic water is adopted as foaming agent, and the polyurethane sponge prepared from safer diphenylmethane diisocyanate has the advantages of health and environmental protection, has the characteristics of the traditional polyurethane sponge, and has the characteristics of high strength, high temperature resistance and good flame retardant effect, namely, the polyurethane sponge still maintains excellent thermal stability at 170 ℃, and the phenomenon of high-temperature cracking and the like in the insole molding process can not occur.
When nano hydroxyapatite is singly added, compared with a part of small molecular polyalcohol, foam is softened, and foam collapse is easy to occur due to the fact that the nano hydroxyapatite exists, the surface of the nano hydroxyapatite is modified to obtain silane grafted hydroxyapatite, and then boric acid is used for adding flame-retardant and high-temperature-resistant element boron to obtain silicon-boron modified hydroxyapatite which is added as nano filler, occupies most of the hydroxyl groups of the nano-hydroxyapatite and is better combined with a matrix after being modified by KH550, so that the strength can be increased, and the temperature resistance of the nano-hydroxyapatite can be improved due to the existence of silicon-boron-phosphorus element.
When the flame-retardant filler is added by using the addition method, the specific surface area of EGO is large, so that the EGO is difficult to disperse in a foam system, ammonium polyphosphate and phosphate starch are aggregated, nucleation points are formed in the foam, foam collapse or shrinkage is caused by uneven foaming, the flame-retardant filler is covered on the foam by using the soaking method, and particularly, the high viscosity and biocompatibility of the starch are used, so that the coating effect of the first layer with low base is good. According to the invention, firstly, the starch is subjected to phosphate modification to obtain phosphate starch, the phosphate starch is used as a carbon source, a layer of compact carbon layer is formed when a high molecular compound is combusted, expandable graphite is oxidized to obtain expanded graphite oxide EGO, hexadecyl trimethyl ammonium bromide is used for modifying the EGO to enable the EGO to be positively charged, and the phosphate starch can be self-assembled with the phosphate starch to be better combined due to negative charge in water, and the EGO is used as an air source, and simultaneously, the EGO expands to achieve the flame retardant purpose when being combusted; the method uses hydroxyapatite with better biocompatibility as high-temperature-resistant filler, is nontoxic and harmless, has high foam strength, and greatly enhances the physical property stability at high temperature on the basis of not changing the original polyurethane foam structure and mechanical property by using an impregnation method, and can achieve self-extinguishing of flame retardance.
Drawings
FIG. 1 is an infrared spectrum of a silicon-boron modified hydroxyapatite;
FIG. 2 is an infrared spectrum of a phosphate starch;
FIG. 3 is a scanning electron microscope image of a flame retardant, high temperature resistant polyurethane foam.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1 (1 g ammonium polyphosphate 1% solution concentration)
The high-temperature resistant filler is silicon-boron modified hydroxyapatite BSHA. The preparation process is as follows:
(1) 5g of nano-hydroxyapatite is weighed, added into a beaker filled with 100mL of deionized water and stirred for 0.5h to form an aqueous solution, then another beaker is taken to add 100mL of 90 wt% ethanol solution, 2mL of KH550 is added to hydrolyze the aqueous solution for 0.5h, and then the two solutions are mixed and reacted at 40 ℃ for 4h to obtain KH550 modified hydroxyapatite.
(2) And (3) carrying out suction filtration and washing on the NHA obtained after the reaction in the step (1), and adding the NHA into 100mL of deionized water again to obtain an aqueous solution of NHA, weighing 1g of boric acid, adding the aqueous solution of NHA, reacting for 3 hours at 40 ℃, carrying out vacuum filtration and drying to obtain the silicon-boron modified hydroxyapatite BSHA.
The preparation process of the flame-retardant impregnating solution is as follows:
(1) Preparation of aqueous solution of phosphated starch: preparing phosphate starch P-CS through a wet method, weighing 3g of sodium dihydrogen phosphate into a 250mL three-necked flask, adding 50mL of deionized water, dispersing for 0.5h by ultrasound, adding 20g of starch into the mixed solution, fully stirring, adjusting the pH value of the mixture to be 6.5 by adopting dilute hydrochloric acid, transferring the three-necked flask into a water bath kettle, refluxing and cooling, reacting for 0.5h at 65 ℃, cooling, neutralizing to be neutral by adopting 1mol/LNaOH, washing with absolute ethyl alcohol and deionized water, carrying out suction filtration, and drying for 24h at 50 ℃ to obtain the P-CS.
10g P-CS was weighed into a beaker containing 200mL of deionized water to give a 5% wt aqueous P-CS solution.
(2) Expandable graphene oxide EGO was prepared by the modified Hummers method, 0.5g EGO was weighed and added to a beaker containing 100mL deionized water for ultrasonic dispersion for 1h, after which 2% wt 100mL cetyltrimethylammonium bromide aqueous solution was formulated and added to the ultrasonic dispersed EGO aqueous solution and stirred for 2h to obtain a modified EGO aqueous solution.
(3) 1g of ammonium polyphosphate was added to a beaker containing 100mL of deionized water to prepare an aqueous ammonium polyphosphate solution.
The preparation of the high temperature resistant polyurethane foam material comprises the following steps:
(1) Weighing and weighingAQUAPER 40 parts, PPG 40 parts, POP20 parts, A-330.4 parts, T-90.8 parts, L-60020.8 parts, deionized water 3.2 parts, BSHA 3 parts, MDI 70 parts
(2) Will beAQUAPUR, PPG, PPG adding into a container according to a certain proportion, adding BSHA, A-33, T-9, L-6002 and deionized water according to a formula, stirring for 2-3min under a stirring machine with the rotating speed of 1500r/min, and marking as a component A;
(3) Adding MDI into another container according to a certain proportion, stirring for 10-30s under a stirrer with the rotating speed of 1000r/min, and marking as a component B;
(4) And (3) increasing the rotating speed of the component A to 2500-3000r/min, pouring the component B into a container filled with the component A, stirring for 10-15s under a high-speed stirrer, pouring the system into a mould when the system turns white, controlling the temperature of the mould to 25+/-0.5 ℃, and cutting after 24-72h to obtain the high-temperature-resistant polyurethane foam material.
The soaking method of the flame-retardant high-temperature-resistant polyurethane foam material comprises the following steps:
(1) Firstly, soaking the foam in a phosphate starch aqueous solution, carrying out repeated pinching and squeezing, then soaking for 0.5h, and then drying the soaked foam at 60 ℃ for 2h;
(2) Immersing the dried foam into the modified expandable graphene oxide aqueous solution, repeatedly pinching and extruding, immersing for 0.5h, and drying at 60 ℃ for 2h;
(3) And immersing the dried foam into an ammonium polyphosphate aqueous solution, repeatedly pinching and extruding, immersing for 0.5h, and drying at 60 ℃ for 2h to obtain the flame-retardant high-temperature-resistant polyurethane foam material.
Example 2 (3 g ammonium polyphosphate, 3% strength solution)
(1) The high-temperature resistant filler is silicon-boron modified hydroxyapatite BSHA: while example 1.
(2) Preparing a flame-retardant impregnating solution: while example 1, and wherein the ammonium polyphosphate was increased to 3g, the solution concentration was 3%.
(3) Preparation of high temperature resistant polyurethane foam material: while example 1.
(4) Preparing a flame-retardant high-temperature-resistant polyurethane foam material: while example 1.
Example 3 (5 g ammonium polyphosphate, 5% strength solution)
(1) The high-temperature resistant filler is silicon-boron modified hydroxyapatite BSHA: while example 1.
(2) Preparing a flame-retardant impregnating solution: while example 1, and wherein the ammonium polyphosphate was increased to 5g, the solution concentration was 5%.
(3) Preparation of high temperature resistant polyurethane foam material: while example 1.
(4) Preparing a flame-retardant high-temperature-resistant polyurethane foam material: while example 1.
Comparative example 1 (blank, no high temperature resistant filler added and no soak flame retardant solution)
Preparation of polyurethane foam:
(1) Weighing and weighing40 parts of AQUAPER, 40 parts of PPG, 20 parts of POP, 20 parts of A-330.4 parts of T-90.8 parts of L-60020.8 parts of deionized water, 3.2 parts of MDI and 70 parts of MDI.
(2) Will beAQUAPUR, PPG, PPG are added to the container in proportion,adding BSHA, A-33, T-9, L-6002 and deionized water according to the formula, stirring for 2-3min under a stirring machine with the rotating speed of 1500r/min, and marking as a component A;
(3) Adding MDI into another container according to a certain proportion, stirring for 10-30s under a stirrer with the rotating speed of 1000r/min, and marking as a component B;
(4) And (3) increasing the rotating speed of the component A to 2500-3000r/min, pouring the component B into a container filled with the component A, stirring for 10-15s under a high-speed stirrer, pouring the system into a mould, controlling the temperature of the mould to be 25+/-0.5 ℃, and cutting after 24-72h to obtain the polyurethane foam material.
Comparative example 2 (P-CS soaking alone)
Preparation of polyurethane foam:
(1) Weighing and weighing40 parts of AQUAPER, 40 parts of PPG, 20 parts of POP, A-330.4 parts, T-90.8 parts, L-60020.8 parts, 3.2 parts of deionized water, 3 parts of BSHA and 70 parts of MDI.
(2) Will beAQUAPUR, PPG, PPG adding into a container according to a certain proportion, adding BSHA, A-33, T-9, L-6002 and deionized water according to a formula, stirring for 2-3min under a stirring machine with the rotating speed of 1500r/min, and marking as a component A;
(3) Adding MDI into another container according to a certain proportion, stirring for 10-30s under a stirrer with the rotating speed of 1000r/min, and marking as a component B;
(4) And (3) increasing the rotating speed of the component A to 2500-3000r/min, pouring the component B into a container filled with the component A, stirring for 10-15s under a high-speed stirrer, pouring the system into a mould when the system turns white, controlling the temperature of the mould to 25+/-0.5 ℃, and cutting after 24-72h to obtain the high-temperature-resistant polyurethane foam material.
Preparation of flame-retardant high-temperature-resistant polyurethane foam materials:
(1) Preparation of aqueous solution of phosphated starch: preparing phosphate starch P-CS through a wet method, weighing 3g of sodium dihydrogen phosphate into a 250mL three-necked flask, adding 50mL of deionized water, dispersing for 0.5h by ultrasound, adding 20g of starch into the mixed solution, fully stirring, adjusting the pH value of the mixture to be 6.5 by adopting dilute hydrochloric acid, transferring the three-necked flask into a water bath kettle, refluxing and cooling, reacting for 0.5h at 65 ℃, cooling, neutralizing to be neutral by adopting 1mol/LNaOH, washing with absolute ethyl alcohol and deionized water, carrying out suction filtration, and drying for 24h at 50 ℃ to obtain the P-CS.
10g P-CS was weighed into a beaker containing 200mL of deionized water to give a 5% wt aqueous P-CS solution.
(2) Soaking the foam in a phosphate starch aqueous solution, kneading and extruding for many times, soaking for 0.5h, and drying the soaked foam at 60 ℃ for 2h to obtain the flame-retardant polyurethane foam.
Comparative example 3 (P-CS alone and modified EGO soaking)
Preparation of polyurethane foam:
(1) Weighing and weighing40 parts of AQUAPER, 40 parts of PPG, 20 parts of POP, A-330.4 parts, T-90.8 parts, L-60020.8 parts, 3.2 parts of deionized water, 3 parts of BSHA and 70 parts of MDI.
(2) Will beAQUAPUR, PPG, PPG adding into a container according to a certain proportion, adding BSHA, A-33, T-9, L-6002 and deionized water according to a formula, stirring for 2-3min under a stirring machine with the rotating speed of 1500r/min, and marking as a component A;
(3) Adding MDI into another container according to a certain proportion, stirring for 10-30s under a stirrer with the rotating speed of 1000r/min, and marking as a component B;
(4) And (3) increasing the rotating speed of the component A to 2500-3000r/min, pouring the component B into a container filled with the component A, stirring for 10-15s under a high-speed stirrer, pouring the system into a mould when the system turns white, controlling the temperature of the mould to 25+/-0.5 ℃, and cutting after 24-72h to obtain the high-temperature-resistant polyurethane foam material.
Preparation of flame-retardant high-temperature-resistant polyurethane foam materials:
(1) Preparation of aqueous solution of phosphated starch: preparing phosphate starch P-CS through a wet method, weighing 3g of sodium dihydrogen phosphate into a 250mL three-necked flask, adding 50mL of deionized water, dispersing for 0.5h by ultrasound, adding 20g of starch into the mixed solution, fully stirring, adjusting the pH value of the mixture to be 6.5 by adopting dilute hydrochloric acid, transferring the three-necked flask into a water bath kettle, refluxing and cooling, reacting for 0.5h at 65 ℃, cooling, neutralizing to be neutral by adopting 1mol/LNaOH, washing with absolute ethyl alcohol and deionized water, carrying out suction filtration, and drying for 24h at 50 ℃ to obtain the P-CS.
10g P-CS was weighed into a beaker containing 200mL of deionized water to give a 5% wt aqueous P-CS solution.
(2) Expandable graphene oxide EGO was prepared by the modified Hummers method, 0.5g EGO was weighed and added to a beaker containing 100mL deionized water for ultrasonic dispersion for 1h, after which 2% wt 100mL cetyltrimethylammonium bromide aqueous solution was formulated and added to the ultrasonic dispersed EGO aqueous solution and stirred for 2h to obtain a modified EGO aqueous solution.
(3) Soaking the foam in a phosphate starch aqueous solution, kneading and extruding for many times, soaking for 0.5h, and drying the soaked foam at 60 ℃ for 2h; and immersing the dried foam into an ammonium polyphosphate aqueous solution, repeatedly pinching and extruding, immersing for 0.5h, and drying at 60 ℃ for 2h to obtain the flame-retardant high-temperature-resistant polyurethane foam material.
Comparative example 4 (addition of 1 part of refractory filler)
Preparation of polyurethane foam:
(1) Weighing and weighing40 parts of AQUAPER, 40 parts of PPG, 20 parts of POP, A-330.4 parts, T-90.8 parts, L-60020.8 parts, 3.2 parts of deionized water, 1 part of BSHA and 70 parts of MDI.
(2) Will beAQUAPUR, PPG, PPG adding into a container according to a certain proportion, adding BSHA, A-33, T-9, L-6002 and deionized water according to a formula, stirring for 2-3min under a stirring machine with the rotating speed of 1500r/min, and marking as a component A;
(3) Adding MDI into another container according to a certain proportion, stirring for 10-30s under a stirrer with the rotating speed of 1000r/min, and marking as a component B;
(4) And (3) increasing the rotating speed of the component A to 2500-3000r/min, pouring the component B into a container filled with the component A, stirring for 10-15s under a high-speed stirrer, pouring the system into a mould when the system turns white, controlling the temperature of the mould to 25+/-0.5 ℃, and cutting after 24-72h to obtain the high-temperature-resistant polyurethane foam material.
Comparative example 5 (addition of 5 parts of refractory filler)
Preparation of polyurethane foam:
(1) Weighing and weighing40 parts of AQUAPER, 40 parts of PPG, 20 parts of POP, A-330.4 parts, T-90.8 parts, L-60020.8 parts, 3.2 parts of deionized water, 5 parts of BSHA and 70 parts of MDI.
(2) Will beAQUAPUR, PPG, PPG adding into a container according to a certain proportion, adding BSHA, A-33, T-9, L-6002 and deionized water according to a formula, stirring for 2-3min under a stirring machine with the rotating speed of 1500r/min, and marking as a component A;
(3) Adding MDI into another container according to a certain proportion, stirring for 10-30s under a stirrer with the rotating speed of 1000r/min, and marking as a component B;
(4) And (3) increasing the rotating speed of the component A to 2500-3000r/min, pouring the component B into a container filled with the component A, stirring for 10-15s under a high-speed stirrer, pouring the system into a mould when the system turns white, controlling the temperature of the mould to 25+/-0.5 ℃, and cutting after 24-72h to obtain the high-temperature-resistant polyurethane foam material.
Performance testing
The sponges obtained in examples 1 to 3 and comparative examples 1 to 5 were cut into different sizes, and foam density and tear strength were tested according to the requirements of national standards GB/T24451-2020 for soft polyurethane foam with slow rebound, GBT 6344-2008 for determination of tensile Strength and elongation at break of soft foam polymer, GBT 10807-2006 for determination of hardness of soft foam polymer (collapse method) GB/T9640-2008 for accelerated aging test method of soft and hard foam polymer, and the rates of change after thermal storage (170 ℃ C., 140h treatment) of the sponge, elongation at break, compression set and the three were tested. The detection results of the obtained sponge are shown in Table 1.
TABLE 1 polyurethane foam finished product Performance detection
The data in table 1 shows that: the flame-retardant high-temperature-resistant polyurethane foam material (examples 1-3) disclosed by the invention HAs the advantages that after being treated in a hot environment at 170 ℃, the change rate of physical and mechanical properties is not more than 5%, and compared with the foams of No. 1, no. 4 and No. 5 in comparative examples, the high-temperature resistance is greatly improved, and the strength is gradually improved, but the elongation at break is gradually reduced as the modified HA addition amount is increased from 1 part to 5 parts, because the HA particles are added into a polyurethane foam system as a filler, the additional strength and support can be provided, the foam material HAs good affinity, and good interface adhesion with polyurethane molecules can be formed. The adhesion can strengthen the combination between the hydroxyapatite and the polyurethane foam, and improve the comprehensive mechanical property of the material. HA HAs a chemical composition mainly comprising calcium, phosphorus, oxygen, hydroxyl groups, and the like, wherein the combination of phosphate groups and hydroxyl groups forms a stable calcium phosphate structure. The structure has better chemical stability under the high temperature condition, and is not easy to generate decomposition, dissolution or oxidation reaction. The crystal structure of the hydroxyapatite is stable, shows a hexagonal system and has higher crystallinity. The crystal structure of the composite material contains a large amount of Ca-O bonds and P-O bonds, and the bonds have high strength and can keep stability at high temperature. The surface energy of the modified HA is improved, the compatibility with polyurethane foam is better, and the addition of boric acid can react with nitrogen in the polyurethane foam to form amine borate, so that the heat resistance and the flame retardance are further improved.
As can be seen from examples 1-3, the flame retardant property of the soaked foam is related to the concentration of the ammonium polyphosphate impregnating solution, the effect is best when the concentration of the ammonium polyphosphate reaches 5%, the ammonium polyphosphate is matched with phosphate starch and EGO to achieve the flame retardant effect, and a carbon layer can be formed on the surface of the foam rapidly when the foam is burnt, so that oxygen is isolated, and flame is extinguished. Compared with the comparative example, when the polyurethane sponge is used alone or in combination, the polyurethane sponge has only the effect of delaying the burning time and is poor in self-extinguishing effect, and in conclusion, the BSHA has the high-temperature reinforcing effect on the polyurethane sponge, so that the polyurethane sponge is basically unchanged at high temperature, a compact carbon layer can be formed rapidly when the soaked sponge is burnt, the flame is quickly retarded, and the polyurethane sponge have better synergistic effect.
In FIG. 1, HA HAs a characteristic vibration peak of phosphate group, including 1099cm -1 And 1041cm -1 P-O antisymmetric telescopic vibration peak at position 962cm -1 P-O stretching vibration peak at position 603cm -1 And 566cm -1 An O-P-O bending vibration peak at the position. 3569cm -1 、1637cm -1 The peak at the position is the characteristic vibration peak of the hydroxyl group, 3450cm -1 The broad peak at this point represents a certain amount of water of crystallization present in the product. At 1340cm -1 The new peak formed is due to the successful grafting of KH550 at 750cm, due to the Si-O-C bond formed by KH550 with hydroxyl groups via silanol bonds -1 The left and right peaks strengthen the presence of surface B-N bonds, surface boronic acids react with amino groups above KH 550. In conclusion, the successful synthesis of the surface silicon-boron modified hydroxyapatite is described.
In FIG. 2, the successful synthesis of P-CS is at 933cm -1 Absorption peak at 1400cm -1 To 1150cm -1 Is 933cm -1 The absorption peak at the position is the characteristic peak of P-O-C, so that the successful esterification reaction of sodium dihydrogen phosphate and the hydroxyl group on the starch can be judged, and the reaction time is 1400cm -1 To 1150cm -1 A plurality of small peaks appear between the two, which belong to the characteristic peaks of P=N, can prove that P=N double bonds and P-O-C, ester are introduced into the starchThe chemical reaction is to add phosphate groups on the original structure so as to achieve the effect of phosphorylation.
In fig. 3, (a) shows the foam cell morphology after BSHA addition, and it can be seen that the foam cell morphology is good, the pore size is between 100 and 200 microns, the cell membrane wall is thin, and the cell gaps are small. (b) In the figure, the foam is dried by soaking the aqueous solution of the phosphate starch, and the adhesion amount of the starch is more and can permeate into the foam. (c) The graph shows that obvious folds exist on the surface of the foam after the foam is soaked by EGO, the foam is better in adsorption, the foam surface can be basically covered, the foam can be rapidly expanded during combustion, and the gas is released to achieve the flame-retardant effect. (d) The figure shows the foam after soaking three flame-retardant solutions, the phosphate starch is distributed on the foam, the EGO is attached to the foam to a high degree, the figure shows that the P element is distributed on the whole foam, and the surface ammonium polyphosphate can form electrostatic self-assembly with the modified EGO, so that the combination of the surface ammonium polyphosphate and the modified EGO is tighter.
From the test of Table 1, the macroscopic performance shows that BSHA tightly combined with the polyurethane matrix at high temperature can play a role in enhancing structural stability, and P-CS, EGO and ammonium polyphosphate cooperate with each other to play a role in synergistic flame retardance.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (5)
1. A flame retardant, high temperature resistant polyurethane foam material, characterized in that: dipping the high-temperature-resistant polyurethane foam material into a solution containing a flame retardant auxiliary agent to obtain the flame retardant high-temperature-resistant polyurethane foam material; the high-temperature-resistant polyurethane foam material comprises the following raw materials in parts by weight: 40-60 parts of polyether polyol, 40-60 parts of polypropylene glycol, 0-20 parts of polymer polyol, 0.4-1.0 part of amine catalyst, 0.8-1.4 parts of tin catalyst, 0.8-1.2 parts of surfactant, 2.8-3.6 parts of foaming agent, 1-5 parts of high temperature resistant filler and 60-90 parts of diphenylmethane diisocyanate; wherein the sum of the parts by weight of the polyether polyol, the polypropylene glycol and the polymer polyol is 100 parts.
2. The flame retardant, high temperature resistant polyurethane foam of claim 1, wherein: the high-temperature resistant filler is silicon-boron modified hydroxyapatite, and the preparation method comprises the following steps:
(1) Adding 5g of nano hydroxyapatite into 100mL of deionized water, and stirring for 0.5h to obtain a solution A; adding 2mL KH550 into 100mL ethanol solution with concentration of 90wt.% and hydrolyzing for 0.5h to obtain solution B; mixing the solution A and the solution B, and reacting for 4 hours at 40 ℃ to obtain KH550 modified hydroxyapatite;
(2) Dissolving KH550 modified hydroxyapatite in deionized water, adding boric acid, and reacting at 40 ℃ for 3 hours to obtain silicon-boron modified hydroxyapatite.
3. The flame retardant, high temperature resistant polyurethane foam of claim 1, wherein: the solution containing the flame retardant auxiliary is a phosphate starch solution, a modified EGO solution and an ammonium polyphosphate solution; the preparation method comprises the following steps:
preparation of a phosphated starch solution: dissolving 3g of sodium dihydrogen phosphate in 50mL of deionized water, carrying out ultrasonic treatment for 0.5h, adding 20g of starch, fully stirring, adjusting pH=6.5 by using dilute hydrochloric acid, reacting for 0.5h at 65 ℃, cooling, neutralizing to neutrality by using 1mol/L NaOH solution, washing by using absolute ethyl alcohol and deionized water, carrying out suction filtration, drying at 50 ℃ for 24h to obtain phosphorylated starch, and preparing 5wt.% of phosphorylated starch solution by using deionized water;
preparation of modified EGO solution: preparing expandable graphene oxide EGO by a modified Hummers method; adding 0.5g of EGO into 100mL of deionized water, performing ultrasonic dispersion for 1h, adding 100mL of 2wt.% cetyltrimethylammonium bromide solution, and stirring for 2h to obtain a modified EGO solution;
preparation of ammonium polyphosphate solution: 1-5g of ammonium polyphosphate was dissolved in 100mL of deionized water to obtain an ammonium polyphosphate solution.
4. The flame retardant, high temperature resistant polyurethane foam of claim 1, wherein: the preparation of the high temperature resistant polyurethane foam material comprises the following steps:
(1) Mixing polyether polyol, polypropylene glycol, polymer polyol, high-temperature-resistant filler, amine catalyst, tin catalyst, surfactant and foaming agent, stirring at 1500r/min for 2-3min, and marking as component A;
(2) Diphenylmethane diisocyanate was stirred 1030 s at a speed of 1000r/min, noted as component B;
(3) And (3) increasing the rotating speed of the component A to 2500-3000r/min, adding the component B, stirring for 10-15s, pouring into a mould, controlling the temperature of the mould to be 25+/-0.5 ℃, and cutting after 24-72h to obtain the high-temperature-resistant polyurethane foam material.
5. A method of making the flame retardant, high temperature resistant polyurethane foam of any one of claims 1-4, wherein: the method comprises the following steps:
(1) Immersing the high-temperature-resistant polyurethane foam material in a phosphate starch solution for 0.5h, and drying at 60 ℃ for 2h;
(2) Immersing the foam material dried in the step (1) in a modified EGO solution for 0.5h, and drying at 60 ℃ for 2h;
(3) And (3) immersing the foam material dried in the step (2) in an ammonium polyphosphate solution for 0.5h and drying at 60 ℃ for 2h to obtain the flame-retardant high-temperature-resistant polyurethane foam material.
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