CN118834461B - Polyethylene composite flame retardant waterproof material and preparation method thereof - Google Patents
Polyethylene composite flame retardant waterproof material and preparation method thereof Download PDFInfo
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- CN118834461B CN118834461B CN202411328837.9A CN202411328837A CN118834461B CN 118834461 B CN118834461 B CN 118834461B CN 202411328837 A CN202411328837 A CN 202411328837A CN 118834461 B CN118834461 B CN 118834461B
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- retardant
- flame
- flame retardant
- polyethylene composite
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- 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 182
- 239000003063 flame retardant Substances 0.000 title claims abstract description 182
- 239000000463 material Substances 0.000 title claims abstract description 156
- 239000002131 composite material Substances 0.000 title claims abstract description 94
- -1 Polyethylene Polymers 0.000 title claims abstract description 80
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 73
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 73
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 30
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- 229910052582 BN Inorganic materials 0.000 claims description 10
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- KKHAAAOUAMONAO-UHFFFAOYSA-N 1,4-diazabicyclo[2.2.2]octane;hexahydrate Chemical compound O.O.O.O.O.O.C1CN2CCN1CC2 KKHAAAOUAMONAO-UHFFFAOYSA-N 0.000 claims description 6
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 6
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 6
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
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- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 5
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 5
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- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 4
- DZSGDHNHQAJZCO-UHFFFAOYSA-N 1-isocyanato-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(N=C=O)=C1 DZSGDHNHQAJZCO-UHFFFAOYSA-N 0.000 claims description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 4
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- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 3
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
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- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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Abstract
The invention relates to the technical field of flame-retardant waterproof materials, in particular to a polyethylene composite flame-retardant waterproof material and a preparation method thereof. The invention solves the problems of poor flame retardant effect, low hydrophobicity and insufficient mechanical strength of polyethylene materials. The base layer is prepared by taking high-density polyethylene, a compatilizer and a silicon nitride loaded phosphorus-containing flame retardant as main raw materials, a composite polyimide foaming material, an intumescent flame retardant and modified mixed stone are added to obtain a protective layer, and finally the polyethylene composite flame-retardant waterproof material is prepared. The compatibility agent is obtained by modifying maleic anhydride grafted low-density polyethylene, the silicon nitride loaded phosphorus-containing flame retardant is prepared, the composite polyimide foaming material and the modified mixed stone are prepared, the preparation dosage of each component is changed, and the obtained polyethylene material has good flame retardant effect, large water contact angle, low water absorption rate and good tensile property and impact resistance.
Description
Technical Field
The invention relates to the technical field of flame-retardant waterproof materials, in particular to a polyethylene composite flame-retardant waterproof material and a preparation method thereof.
Background
There are many types of polyethylene, mainly including high density polyethylene, low density polyethylene and linear low density polyethylene. The high-density polyethylene has high crystallinity, few branched structures, excellent heat resistance and mechanical strength, good barrier property to water vapor, but insufficient toughness. The softness and elongation of the low-density polyethylene are better than those of the high-density polyethylene, but the low-density polyethylene is easy to crack. High-density polyethylene is widely used in the construction field and is often used as a raw material for waterproof rolls, but the use of one polyethylene alone produces a material having poor properties.
In order to improve the water blocking capability of a waterproof material, patent CN118219636B discloses a macromolecule self-adhesive pre-paved waterproof roll and a preparation method thereof, wherein a waterproof roll which is prepared from a high-density polyethylene serving as a main raw material, a compatilizer, an organic-inorganic composite flame retardant component, a polymerization function additive, an antioxidant, an ultraviolet absorbent, an elastomer and a powder additive, and a tire base layer and an asphalt layer is prepared, so that the problem of poor waterproof effect of the waterproof material is solved, but asphalt from petroleum sources serving as raw materials is not environment-friendly.
There are researches on taking high-density polyethylene as a main component of a waterproof material, and as patent CN111826102B discloses a modified HDPE waterproof roll and a preparation method thereof, the waterproof roll is structurally divided into an isolation layer, an adhesive layer, a protection layer and a carcass layer, and the obtained waterproof roll solves the problems of poor heat resistance, easy burning and poor flame retardant effect of the high-density polyethylene. However, the materials used are various, and the compatibility between the layers of the waterproof coiled material is reduced when the waterproof coiled material is used for a long time by physically mixing the materials, so that the mechanical properties of the material are deteriorated.
Patent CN112721339B discloses an environment-friendly polymer composite waterproof roll and a preparation method thereof, which are characterized in that linear low-density polyethylene resin, TPE thermoplastic elastomer, porous silicon nitride loaded butyl stearate composite material, flame retardant and various auxiliary materials are mixed and extruded to obtain an intermediate waterproof layer, an upper non-woven fabric layer, a lower non-woven fabric layer and the intermediate waterproof layer are hot pressed to obtain the polymer composite waterproof roll, the mechanical strength of the waterproof roll is high, but because the flame retardant is a halogen-containing organic compound, gas generated under the combustion condition can cause damage to human body.
The inorganic material is also used as a flame retardant of a waterproof material after modification, as disclosed in patent CN113969113B, a high-strength flame-retardant polymer self-adhesive film pre-laid anti-adhesive waterproof roll and a preparation method thereof are disclosed, sepiolite fibers are subjected to surface hydroxylation treatment, the surfaces of the sepiolite fibers are modified by using a silane coupling agent KH-560 to obtain flame retardant auxiliary materials, and the flame retardant auxiliary materials are further compounded with linear low-density polyethylene, metallocene polyethylene resin and the flame retardant to prepare the waterproof roll. The waterproof coiled material has good flame retardant effect and low mass abrasion loss, but the tensile strength of the waterproof coiled material is not high due to the addition of a large amount of modified sepiolite fibers.
In summary, the polyethylene waterproof coiled material in the prior art has the technical defects of poor flame retardant property and poor waterproof effect, and simultaneously has the problem that the tensile property and the impact strength cannot be simultaneously considered.
Therefore, a polyethylene composite flame-retardant waterproof material and a preparation method thereof are provided.
Disclosure of Invention
The invention aims to provide a polyethylene composite flame-retardant waterproof material and a preparation method thereof, wherein the type and the amount of a phosphorus-containing flame retardant in a compatilizer are changed, the use amount of the compatilizer and the part ratio of raw material silicon nitride and phosphorus-containing flame retardant in a silicon nitride loaded phosphorus-containing flame retardant are changed, the obtained polyethylene composite flame-retardant waterproof material has good stretching property, good flame-retardant effect and good flame-retardant stability, the part ratio of raw materials of a catalyst solution is changed to prepare a composite polyimide foam material, aerogel powder and the use amount of the powder are prepared, various isocyanates are selected as foaming black materials, the surface oxidation, reduction and grafting treatment are carried out on mixed stones, the notch impact strength of the prepared polyethylene composite flame-retardant waterproof material is high, the flame-retardant effect is good, the hydrophobicity of the obtained material is good, and the flame-retardant effect of the polyethylene composite flame-retardant waterproof material is further increased by changing the use amount and proportion of each component in a protective layer.
In order to achieve the above purpose, the present invention provides the following technical solutions:
In one aspect, the invention provides a preparation method of a polyethylene composite flame-retardant waterproof material, which comprises the following steps:
Putting high-density polyethylene, 0-2.2 parts of compatilizer, silicon nitride loaded phosphorus-containing flame retardant, antioxidant 1010 and vinyl acetate into an internal mixer, and banburying to obtain a mixed material I;
Mixing 5-18 parts of the high-density polyethylene, 13-16 parts of the composite polyimide foaming material, 5-7 parts of the intumescent flame retardant, 2-15 parts of the modified mixed stone, 4-12 parts of the silicon nitride loaded phosphorus flame retardant, the antioxidant 1010 and the vinyl acetate to obtain a mixed material II, transferring the mixed material II into a mould, and pressing to obtain a protective layer, wherein the part ratio of PAPP and MPP in the intumescent flame retardant is 1-7:1-3;
the protective layer, the base layer and the waterproof layer form the polyethylene composite flame-retardant waterproof material, wherein the part ratio of the polyurethane waterproof coating to the boron nitride and the lamellar graphene in the waterproof layer is 18-93:1-4:1-3;
The compatilizer is obtained by adding concentrated sulfuric acid and 0-4.5 parts of phosphorus-containing flame retardant into LDPE-g-MAH solution, reacting for 10 hours, filtering, washing and drying to constant weight;
The part ratio of the silicon nitride to the phosphorus-containing flame retardant in the silicon nitride-loaded phosphorus-containing flame retardant is 20-80:1-3;
the composite polyimide foaming material comprises triethylene diamine hexahydrate, melamine cyanurate, aerogel powder and foaming black material, wherein the modified mixed stone is prepared by treating mixed stone with an oxidation mixed liquid and a hydrogen peroxide aqueous solution, and then reacting the mixed stone with 1, 4-benzenediacetic acid and amino cage silane.
The structure of the amino cage silane is shown as a formula I:
I
Preferably, the dosage of the phosphorus-containing flame retardant in the compatilizer is 1.0-4.5 parts, and the phosphorus-containing flame retardant is one of diethyl phosphate, dibenzoxyphos, phytic acid and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
Under the high temperature condition, maleic anhydride in LDPE-g-MAH solution is hydrolyzed and broken, and the maleic anhydride and phosphoric acid groups in the phosphorus-containing flame retardant are subjected to condensation reaction under the action of a catalyst, so that the phosphorus-containing flame retardant is introduced into a compatilizer. The silicon nitride porous material is loaded with the phosphorus-containing flame retardant, so that the dispersibility of the phosphorus-containing flame retardant in the polyethylene composite flame-retardant waterproof material is improved, and the flame retardant property of the material is improved within a proper loading range.
The compatibility of the HDPE and the phosphorus-containing flame retardant loaded by the silicon nitride is improved by adding the compatilizer, so that the components of the polyethylene composite flame-retardant waterproof material are prevented from separating and separating out in the storage and use processes, and the stability of the material is improved. In addition, the compatilizer contains linear macromolecules with more branched chains, so that the flexibility is high, and the flexibility and the tensile property of the polyethylene composite flame-retardant waterproof material are improved after the compatilizer is blended with HDPE.
Preferably, the amount of the compatibilizing agent in the base layer is 1.5 to 2.2 parts.
The preparation method of the composite polyimide foam material comprises the steps of dissolving benzophenone tetracarboxylic dianhydride in methanol to obtain a ketone tetracarboxylic dianhydride solution, adding the ketone tetracarboxylic dianhydride solution into a three-neck flask containing DMF, heating to 60 ℃, refluxing for 10 hours under stirring to obtain a polymerization solution, mixing the triethylene diamine hexahydrate, dipropylene glycol and melamine cyanurate in a part ratio of 1-4:1-2:3-7, heating and stirring until the mixture is completely dissolved to obtain a catalyst solution, transferring the polymerization solution into a beaker, adding the catalyst solution, PEG-800, 5.5-7 parts of LDPE-g-MAH, dibutyltin dilaurate, deionized water and 0-37 parts of aerogel powder into the polymerization solution, stirring uniformly to obtain a foaming white material, rapidly pouring the foaming black material into the foaming white material, stirring at a high speed to obtain a material to be foamed, transferring the material to a mold, growing the foam, stopping growing the foam, shaping to obtain a foaming intermediate, and curing the foaming intermediate at 180 ℃ for 5-hour to obtain the polyimide foam material.
Preferably, the aerogel powder is used in an amount of 30 to 37 parts.
Preferably, the foaming black material is one of polymethylene polyphenyl polyisocyanate, 3, 5-dimethylphenyl isocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate and 3, 5-difluorophenylisoniazid, and the dosage of the foaming black material is 59.4-84.8 parts.
The preparation method of the aerogel powder comprises the steps of adding methyltrimethoxysilane, cetyltrimethylammonium chloride, 3 parts of DMF and deionized water into a three-neck flask, stirring and mixing for 15min to obtain a mixed solution, adding an oxalic acid solution into the mixed solution, heating to 50 ℃, stirring and reacting for 6h to obtain a sol, adding an ammonia water solution into the sol, heating to 80 ℃, adding 0-42 parts of 3-aminopropyl triethoxysilane, reacting for 10h to obtain a modified aerogel precursor, moving the modified aerogel precursor into a mold, aging at room temperature for 24h to obtain an aerogel precursor, drying the aerogel precursor at 85 ℃ for 3h to obtain aerogel, and grinding the aerogel to obtain the aerogel powder.
Preferably, the 3-aminopropyl triethoxysilane is used in an amount of 33-42 parts.
Preferably, the dosage of the modified mixed stone is 8-15 parts; the preparation method of the modified mixed stone comprises pulverizing mullite-cordierite to obtain mixed stone with average particle diameter of 120 μm; mixing the mixed stone, concentrated sulfuric acid and potassium permanganate at 50 ℃ for 2 hours to obtain an oxidation mixed liquid, adding deionized water into the oxidation mixed liquid for continuous heat preservation and stirring for 1 hour, adding 35% of aqueous hydrogen peroxide solution, stirring for 20 minutes to obtain an intermediate, adding 1:42-52% of aqueous hydrogen peroxide solution and the mixed stone, continuously adding 30% of aqueous potassium hydroxide solution into the intermediate, adjusting the pH value of the system to 10, reducing for 5 hours at 200 ℃, washing and drying by water to obtain a surface treatment mixed stone, mixing 3.4-4.8 parts of 1, 4-benzenediacetic acid with 400 parts of DMF, slowly adding concentrated sulfuric acid, raising the temperature to 80 ℃, stirring and reacting to obtain a grafting mixed stone, adding 8-14 g of amino silane into the intermediate, and washing and drying to obtain a cage-shaped modified MAH-modified stone, and carrying out continuous suction filtration and drying to obtain the MAH-modified mixed stone.
On the other hand, the invention provides a polyethylene composite flame-retardant waterproof material, which comprises a protective layer, a base layer and a waterproof layer, wherein the polyethylene composite flame-retardant waterproof material is prepared by the preparation method according to any one of the above steps, the preparation method of the base layer is changed, the tensile strength of the polyethylene composite flame-retardant waterproof material is 21.0-27.5MPa, the LOI is 17.7-33.8%, the LOI after 6 months is 17.5-31.3%, the preparation method of the composite polyimide foam material is changed, the LOI value of the polyethylene composite flame-retardant waterproof material is 18.5-34.9%, the flame-retardant grade is V-0, V-1 and V-2, the notch impact strength is 18.0-37.7KJ/m 2, the preparation method of the modified mixed stone is changed, the LOI value of the polyethylene composite flame-retardant waterproof material is 32.9-35.5%, the flame-retardant grade is V-0, the notch impact strength is 17.2-36.5KJ/m 2, the contact angle of the polyethylene composite flame-retardant waterproof material is 106.5-115%, and the water absorption rate of the flame-retardant composite material is 1.37% and the flame-retardant material is changed to the use level of the raw material.
Compared with the prior art, the invention has the beneficial effects that:
1. The maleic anhydride grafted low-density polyethylene is modified by using a phosphorus-containing flame retardant to obtain a compatilizer, and the compatilizer is matched with a silicon nitride loaded phosphorus-containing flame retardant to prepare the polyethylene composite flame-retardant waterproof material. The phosphorus-containing flame retardant forms a surface barrier of high-density polyethylene under the high-temperature condition, and the carbon-forming and carbon-forming layer has the functions of heat insulation and oxygen resistance, so that the flame retardant effect of the material is improved. The addition of the compatilizer improves the flexibility of the material and simultaneously improves the compatibility of the components and the flame-retardant stability.
2. By taking methyltrimethoxysilane as a raw material, further forming gel after hydrolysis, and finally curing to obtain the silica aerogel. The silica aerogel has flame retardance, but has low mechanical strength and poor brittleness, and the polyimide foam material has good heat insulation performance. The silica aerogel is used as a part of the composite polyimide foam material, the type and the dosage of the foaming black material are changed, the type of raw materials in the catalyst solution is changed, and the overall flame retardant property and mechanical property of the material are improved.
3. Mullite-cordierite is a composite crystalline phase material prepared by high-temperature calcination, and has the main chemical elements of aluminum, beryllium, silicon and oxygen, high-temperature resistance and fireproof performance. Through crushing mullite-cordierite, removing impurities on the surface of the mullite-cordierite through oxidation and reduction treatment, exciting the reactivity of hydroxyl groups on the surface of the mullite-cordierite, connecting the mullite-cordierite with 1, 4-benzenediacetic acid through chemical bonds, reacting unreacted carboxyl in benzeneethanedioic acid with a ring-opening product of LDPE-g-MAH, and realizing the surface modification of mixed stones. The compatibility of the modified mixed stone and organic components is improved, the flame retardant property is good, and the notch impact strength is high.
4. Through spraying polyurethane waterproof coating and waterproof coating of boron nitride and lamellar graphene outside the protective layer, carrying out hydrophobic modification carding on silicon dioxide aerogel, adding polystyrene-polysiloxane comb-shaped graft copolymer into the composite polyimide foaming material, carrying out oxidation, reduction and surface grafting modification treatment on mixed stones, and controlling the dosage of grafts, the obtained polyethylene composite flame-retardant waterproof material has good hydrophobic property.
5. The protective layer with the protection function on the base layer is obtained by reasonably using the compatilizer, the composite polyimide foaming material, the intumescent flame retardant, the modified mixed stone and the silicon nitride loaded phosphorus-containing flame retardant and changing the proportion of raw materials in the intumescent flame retardant. The production of the carbon layer is promoted, the density of the flammable gas is diluted, the heat transfer and incombustibility of the whole material are improved, and the finally obtained polyethylene composite flame-retardant waterproof material has high flame retardance.
Drawings
FIG. 1 is a schematic diagram of a structure of a polyethylene composite flame-retardant waterproof material of the invention;
FIG. 2 is a graph showing the results of the flame retardant property test of example 64 of the present invention.
In the figure, 1, a base layer, 2, a protective layer, 3 and a waterproof layer.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described 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.
Referring to fig. 1 to 2, the invention provides a polyethylene composite flame-retardant waterproof material and a preparation method thereof, and the technical scheme is as follows:
The substance information related to the present invention is as follows:
9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) CAS 35948-25-5, phytic acid CAS 83-86-3, diethyl phosphate CAS 598-02-7, dibenzooxyphosphorus CAS 55217-59-9, polymethylene polyphenyl polyisocyanate CAS 9016-87-9, 3, 5-dimethylphenyl isocyanate CAS 54132-75-1, isophthalate CAS 123-61-5, terephthalisocyanate CAS 104-49-4, naphthalene diisocyanate CAS 3173-72-6, 3, 5-difluorophenylisoniazid CAS 83594-83-6, benzophenone tetracarboxylic dianhydride CAS 2421-28-5, piperazine pyrophosphate (PAPP) CAS 66034-17-1, melamine polyphosphate (MPP) CAS 15541-60-3, 1, 4-benzenediacetic acid CAS 7325-46-4, 3-aminopropyl triethoxysilane (KH 550-919-30).
The polyurethane waterproof coating is purchased from Guangzhou Jiabaili waterproof engineering Co., ltd., the high-density polyethylene is purchased from Dushan petrochemical Co., the maleic anhydride grafted low-density polyethylene is purchased from Shanghai Michelson Biotechnology Co., ltd., and the polystyrene-polysiloxane comb-shaped graft copolymer is purchased from Sianziyue Biotechnology Co., ltd.
EXAMPLES 1 to 14 comparative examples 1 and 2
Adding 30 parts of maleic anhydride grafted low-density polyethylene into a three-necked flask, adding 300 parts of dimethylbenzene, heating to 120 ℃, dissolving to obtain LDPE-g-MAH solution, adding 0.2 part of concentrated sulfuric acid and a phosphorus-containing flame retardant into the LDPE-g-MAH solution, reacting for 10 hours, filtering, washing, and drying to constant weight to obtain the compatilizer.
The preparation method of the silicon nitride loaded phosphorus-containing flame retardant comprises the steps of dispersing 8 parts of silicon nitride in 100 parts of deionized water to obtain silicon nitride dispersion liquid, adding 0.5 part of fatty acid sorbitan into the silicon nitride dispersion liquid, adding the phosphorus-containing flame retardant, stirring for 6 hours at normal temperature, filtering and drying to obtain the silicon nitride loaded phosphorus-containing flame retardant. The part ratio of the silicon nitride to the phosphorus-containing flame retardant in the silicon nitride-loaded phosphorus-containing flame retardant is 80:1.
92 Parts of high-density polyethylene (HDPE), 1.5 parts of compatilizer, 1.5 parts of silicon nitride loaded phosphorus-containing flame retardant, 2 parts of antioxidant 1010 and 1 part of vinyl acetate plasticizer are put into an internal mixer, the temperatures of three areas are respectively set at 170 ℃, 180 ℃ and 185 ℃, the internal mixing time is 7min, a mixed material I is obtained, the mixed material I is transferred into a mould, and the mixed material I is pressed into a sheet with the thickness of 8mm by using a flat vulcanizing machine, so that a base layer is obtained.
Adding 10 parts of methyltrimethoxysilane, 32 parts of cetyl trimethyl ammonium chloride, 3 parts of DMF and 30 parts of water into a three-neck flask, stirring and mixing for 15min to obtain a mixed solution, adding an oxalic acid solution into the mixed solution, heating to 50 ℃, stirring and reacting for 6h to obtain a sol, adding an ammonia water solution into the sol, heating to 80 ℃, adding 33 parts of KH550, reacting for 10h to obtain a modified aerogel precursor, moving into a mould, ageing at room temperature for 24h to obtain the aerogel precursor, drying the aerogel precursor at 85 ℃ for 3h to obtain aerogel, and grinding the aerogel to obtain aerogel powder;
Dissolving 65 parts of benzophenone tetracarboxylic dianhydride in 120 parts of methanol to obtain a ketone tetracarboxylic dianhydride solution, adding the ketone tetracarboxylic dianhydride solution into a three-neck flask with 300 parts of DMF, heating to 60 ℃, refluxing for 10 hours under stirring to obtain a polymerization solution, mixing triethylene diamine hexahydrate, dipropylene glycol and melamine cyanurate in a part ratio of 1:1:3, heating and stirring to completely dissolve to obtain a catalyst solution, transferring the polymerization solution into the beaker, adding 1.2 parts of the catalyst solution, 5 parts of PEG-800, 5.5 parts of polystyrene-polysiloxane comb graft copolymer (PSt-g-PDMS), 0.8 part of dibutyltin dilaurate, 8 parts of deionized water and 30 parts of aerogel powder into the polymerization solution, stirring uniformly to obtain a foaming white material, rapidly pouring 60 parts of foaming black material polymethylene polyphenyl polyisocyanate into the foaming white material, transferring the foaming material into a mold, performing foam growth, stopping shaping to obtain a foaming intermediate, and curing the foaming intermediate at 180 ℃ for 5 hours to obtain a polyimide composite cured material;
Crushing mullite-cordierite to obtain mixed stone with an average particle size of 120 mu m, mixing the mixed stone with concentrated sulfuric acid and potassium permanganate, stirring at 50 ℃ for 2 hours to obtain an oxidized mixed liquid, adding deionized water into the oxidized mixed liquid, continuing to keep the temperature and stir for 1 hour, adding a 35% hydrogen peroxide aqueous solution, stirring for 20 minutes to obtain an intermediate, adding an amino cage-shaped silane, 55 parts of LDPE-g-MAH and 1.5 hours to the mixed stone, continuing to add a 30% potassium hydroxide aqueous solution to the intermediate, adjusting the pH of the system to be 10, then reducing at 200 ℃ for 5 hours, pickling, washing and drying to obtain a surface treated mixed stone, mixing 20 parts of the surface treated mixed stone, 3.4 parts of 1, 4-benzene diacetic acid with 400 parts of DMF, slowly adding 1 part of concentrated sulfuric acid, raising the temperature to 80 ℃, stirring and reacting to obtain a terephthalic acid grafting mixed stone, adding 8 parts of amino cage-shaped silane, 55 parts of LDPE-g-MAH and 1.5 hours to the terephthalic acid grafting mixed stone, and continuing to react with the mixed stone, and carrying out a washing and drying to obtain a modified mixed stone;
50 parts of HDPE, 10 parts of the compatilizer prepared in the example 10, 16 parts of the composite polyimide foaming material, 5 parts of the intumescent flame retardant, 8 parts of modified mixed stones, 6 parts of the silicon nitride loaded phosphorus flame retardant prepared in the example 10, 3 parts of antioxidant 1010 and 2 parts of vinyl acetate plasticizer are put into an internal mixer, and the part ratio of PAPP to MPP in the intumescent flame retardant is 2:3. Setting the temperature of the three areas of the internal mixer to 170 ℃, 180 ℃ and 185 ℃ respectively, mixing for 7min to obtain a mixed material II, transferring the mixed material II into a mould, and pressing the mixed material II into a sheet with the thickness of 2mm by using a flat vulcanizing machine to obtain the protective layer.
The method comprises the steps of superposing a protective layer, a base layer and the protective layer in sequence, continuously using a flat vulcanizing machine to carry out hot pressing, and then carrying out cold pressing to obtain a polyethylene composite flame-retardant waterproof material intermediate, spraying a layer of waterproof coating on the surface of the protective layer of the polyethylene composite flame-retardant waterproof material intermediate, and drying to form a waterproof layer, wherein the waterproof coating is formed by mixing polyurethane waterproof coating with boron nitride and lamellar graphene in a part ratio of 46:3:1.
Details of the preparation methods of the examples are shown in Table 1.
Table 1 preparation method of polyethylene composite flame-retardant waterproof material
Example 15
The polyethylene composite flame-retardant waterproof materials prepared in examples 1 to 14 and comparative examples 1 and 2 were subjected to flame-retardant performance and mechanical strength tests. The Limiting Oxygen Index (LOI) was measured according to GB/T2406.2-2009 Plastic oxygen index method for determination of Combustion behavior section 2, room temperature test, sample test size was 100X 6.5X 3.5mm 3. The initial flame retardant property and the flame retardant property of the polyethylene composite flame retardant waterproof material after being used for 6 months under natural conditions are tested. The polyethylene composite flame-retardant waterproof material is subjected to tensile test at room temperature by using a universal mechanical tester, the test method is carried out according to the ASTM-D638 standard, the test size of a sample is 165 multiplied by 6.5 multiplied by 3.5mm 3, and the tensile rate is 50mm/min. The final test results are shown in table 2. The structural schematic diagram of the polyethylene composite flame-retardant waterproof material prepared by the invention is shown in figure 1.
TABLE 2 mechanical Properties and flame retardant test results
As shown in fig. 1, the polyethylene composite flame-retardant waterproof material has the structure that a waterproof layer 3, a protective layer 2, a base layer 1, the protective layer 2 and the waterproof layer 3 are sequentially arranged from top to bottom. The results in Table 2 show that the tensile strength of the polyethylene composite flame-retardant waterproof material prepared by the invention is 21.0-27.5MPa, the LOI is 17.7-33.8%, and the LOI after 6 months of use is 17.5-31.3%. In examples 1-4, the tensile strength of the material is highest by changing the type of the phosphorus-containing flame retardant, wherein in example 1, diethyl phosphate is used as the phosphorus-containing flame retardant, and other flame retardants contain different amounts of rigid benzene ring structures, so that the tensile strength is reduced, in example 4, the compatibility agent is obtained by modifying LDPE-g-MAH by using phytic acid, the LOI value of the obtained material is highest, and in 6 months later, the material is subjected to flame retardant performance test, so that the LOI value is reduced to different degrees. The results of examples 4 and 5 show that the LOI value is increased by increasing the amount of the phosphorus-containing flame retardant. Since phytic acid has hydrophilicity, which is disadvantageous for improving the hydrophobic property of the material, DOPO is used as a flame retardant, and the results of examples 2, 6 and 7 show. As the amount of phosphorus-containing flame retardant increases, the LOI value tends to increase and then decrease. The results of examples 6 and 8 to 10 show that the LOI reduction value of the polyethylene composite flame-retardant and waterproof material after 6 months of use is 1.5% when the amount of the compatibilizer used in example 10 is 2.2 parts. When no compatibilizing agent was added, as shown in comparative example 2, the flame retardant effect was severely lowered after 6 months of use. The results of examples 10-14 show that by varying the ratio of parts of silicon nitride to parts of phosphorus-containing flame retardant, a silicon nitride-loaded phosphorus-containing flame retardant is obtained with an elevated, reduced, and thereafter maintained LOI value. Comparative example 1 was modified without using a phosphorus-containing flame retardant, and had the worst flame retardant effect.
EXAMPLES 16 to 29 COMPARATIVE EXAMPLE 3
Unlike example 1, the following preparation conditions were changed, as shown in Table 3.
TABLE 3 Condition changes in the preparation Process of composite polyimide foam Material
Example 30
The polyethylene composite flame-retardant waterproof materials prepared in examples 16 to 29 and comparative examples 3 and 4 were subjected to flame-retardant and impact-resistant tests. The LOI test method for flame retardant property was carried out with reference to example 15, and the vertical burning grade was measured with reference to ISO-9773 standard using a horizontal vertical burning tester of HT-00024 type. Impact strength was measured with reference to ASTM-D256, the dimensions of the waterproof material were 63.5X103X 3mm 3, the notched angle was 45℃and the impact energy was 2.8J. The final test results are shown in table 4.
Table 4 the flame retardant properties and impact strength test results for examples 16-29 and comparative examples 3,4
The LOI value of the polyethylene composite flame-retardant waterproof material prepared by the invention is 18.5-34.9%, the flame retardant grades are V-0, V-1 and V-2, and the notch impact strength is 18.0-37.7KJ/m 2. In examples 16-20, the impact strength was the lowest at the highest level as shown in example 20 by varying the ratio of amounts of triethylenediamine hexahydrate, dipropylene glycol and melamine cyanurate, wherein the LOI value tended to decrease and then increase with increasing amounts of melamine cyanurate. Melamine cyanurate is used as a foaming agent, wherein an amino group provides a gas source to promote the formation of foam bodies in the foaming process, the power of bubble formation is provided, the foaming is promoted under the action of triethylene diamine hexahydrate and dipropylene glycol, the polyimide foam material has the effects of protecting the internal base layer from constant temperature and promoting the diffusion and volatilization of combustible gas when a fire disaster occurs, the consumption is reasonable, the foaming effect is best, the flame retardant performance is best at the moment, and the foam holes of the embodiment 20 are oversized and even collapse holes occur, so that the final impact strength is reduced. The results of examples 16, 22-24 show that the flame retardant effect of example 23 is best, and the impact strength of the flame retardant and waterproof material is highest when the aerogel of example 24 is used in an amount of 37 parts. Comparative example 3 was free of aerogel powder, and both flame retardant effect and notched impact strength were reduced. The results of examples 16 and 25-29 show that the flame retardant grades are V-0 grade by changing the type and the amount of the foaming black material, the benzophenone tetracarboxylic dianhydride is ring-opened under the action of methanol, the hydroxyl groups at two ends are subsequently reacted with isocyanate structures in the foaming black material to form polyurethane structural compounds, and the polyurethane structural compounds are further condensed to obtain polyimide. After the isocyanate in the foaming black material is introduced into the system, the notch impact strength is changed, 84.8 parts of naphthalene diisocyanate is added in example 28, and the notch impact strength is maximum. Comparative example 4, in which isocyanate was not added, lacks a rigid structure as compared with the foamed black material added in the example, and the notched impact performance was lowered.
Examples 31 to 41
Unlike example 23, the following preparation conditions were changed, as shown in Table 5.
Table 5 preparation method and usage amount variation of modified mixed stone
Comparative example 5
Unlike example 31, the mixed stone was not subjected to surface treatment, and the other processes were kept unchanged.
Example 42
The polyethylene composite flame retardant and waterproof materials prepared in examples 31 to 41 and comparative example 5 were subjected to flame retardant property and impact strength test. Specific test methods were performed with reference to example 30 and the final test results are shown in table 6.
TABLE 6 flame retardant Properties and impact Strength results for polyethylene composite flame retardant waterproof materials of examples 31-41 and comparative example 5
The LOI value of the polyethylene composite flame-retardant waterproof material is 32.9-35.5%, the flame retardant grade is V-0 grade, and the notch impact strength is 17.2-36.5KJ/m 2. The mixed oxidation solution is formed by compounding concentrated sulfuric acid and potassium permanganate, so that impurities on the surface of the mixed stone can be removed, and the groups on the surface of the mixed stone are oxidized, and in examples 31-33, as the dosage of the concentrated sulfuric acid is increased, the LOI value is gradually increased, and the notch impact strength is not obviously changed. The results of examples 33-35 show that the flame retardant effect is best when the parts ratio of the mixed stone material, the concentrated sulfuric acid and the potassium permanganate of example 34 is 1:50:7. The results of examples 34, 36-38 show that the LOI value is highest when the part ratio of the aqueous hydrogen peroxide solution to the mixed stone is 1:47 in example 37, the notch impact strength of example 34 is the highest, the hydrogen peroxide oxidizes the groups on the surface of the mixed stone, the use amount of concentrated sulfuric acid, potassium permanganate and the aqueous hydrogen peroxide solution is reasonable, the aqueous hydrogen peroxide solution is reduced at high temperature after being oxidized, the number of reactive groups on the surface of the aqueous hydrogen peroxide solution reaches the highest, the compatibility is increased, and the mechanical strength is increased. Comparative example 5 did not have surface treatment of the mixed stone, and was good in flame retardant property, but the notched impact strength was lowered. Examples 37, 39-41 increase the amount of modified mix stone and the notched impact strength tended to increase and decrease.
Example 43
A base layer was obtained according to the preparation method of example 12;
A protective layer was prepared as in example 29.
Wherein the dosage of KH550 in the protective layer is 35 parts, and the dosage of 3, 5-difluorophenylisoniazid acid ester is 64.0 parts.
Examples 44 and 45
Unlike example 43, KH550 was used in an amount of 38 parts and 42 parts in this order.
Example 46
Unlike example 43, 3, 5-difluorophenylisoniazid acid ester was used in an amount of 65.5 parts.
Examples 47 and 48
Unlike example 43, the amount of the polystyrene-polysiloxane comb-shaped graft copolymer used in the composite polyimide foam was 6.5 parts and 7.0 parts in this order.
Example 49
Unlike example 43, 1, 4-benzenediacetic acid was used in an amount of 3.6 parts, and amino-cage silane was used in an amount of 10 parts.
Example 50
Unlike example 43, 1, 4-benzenediacetic acid was used in an amount of 4.8 parts, and the amino-cage silane was used in an amount of 14 parts.
Example 51
Unlike example 43, the waterproof coating was a polyurethane waterproof coating mixed with boron nitride and lamellar graphene in a part ratio of 18:1:1.
Example 52
Unlike example 43, the waterproof coating was a polyurethane waterproof coating mixed with boron nitride and lamellar graphene in a portion ratio of 93:4:3.
Comparative examples 6 to 9
Unlike example 43, KH550, polystyrene-polysiloxane comb graft copolymer, amino cage silane, and boron nitride were not added in this order.
Example 53
The polyethylene composite flame-retardant waterproof materials prepared in examples 43 to 52 and comparative examples 6 to 9 were subjected to a water resistance test, and their apparent water resistance and overall water resistance were respectively tested. The water contact angle of the sprayed waterproof layer was measured using a water contact angle meter to characterize apparent water resistance. The overall water resistance is measured according to GB/T1034-2008 'determination of Plastic Water absorption', firstly, a scratch knife is used for scraping the surface of a waterproof layer, then the scraped polyethylene composite flame-retardant waterproof material is soaked in water at 24 ℃ for 24 hours, taken out, dried and weighed, the water absorption is obtained according to a formula,Wherein m 1 is the mass after drying and m 0 is the mass before soaking. The final test structures are shown in table 7.
Table 7 results of water resistance test of polyethylene composite flame retardant waterproof material
The water contact angle of the polyethylene composite flame-retardant waterproof material prepared by the invention is 106-115 degrees, and the water absorption rate is 0.3-5.7%. The results of examples 43 to 45 show that the water contact angle did not change significantly with increasing amount of KH550, but the water absorption was gradually decreased, mainly because the amino groups of KH550 were bonded to the aerogel powder via chemical bonds to improve the hydrophobic property of the base layer, while the water contact angle was determined only by the hydrophobic property of the waterproof layer, the water absorption was decreased with increasing amount of KH550, the hydrophobic property of the base layer was improved, and comparative example 9 only added with the polyurethane waterproof coating layer, the hydrophobic angle was maximized. The results of examples 46 and 43 show that the increased fluorine element of 3, 5-difluorophenylisoniazid acid ester increases the water resistance of the polyethylene composite flame-retardant and waterproof material as the amount of 3, 5-difluorophenylisoniazid acid ester increases and the water absorption decreases. The results of examples 43, 47, 48 show that varying the amount of polystyrene-polysiloxane comb graft copolymer has little effect on the water resistance of the material. Examples 49 and 50 the amounts of 1, 4-benzenediacetic acid and amino-clathrating silane were varied to reduce the water absorption as compared to example 43. The results of examples 43, 51, 52 show that the water absorption is changed by changing the part ratio of the polyurethane waterproof coating to the boron nitride and the lamellar graphene, and the hydrophobicity of example 52 is the highest. Comparative example 9 does not add boron nitride and lamellar graphene, the water absorption rate is highest, and boron nitride and lamellar graphene have scratch resistance and have a protective effect on the protective layer and the base layer of the polyethylene composite flame-retardant waterproof material, so that only waterproof coating is added to obtain a waterproof layer, and the water absorption is improved. Comparative examples 6 to 8 were not added with KH550, polystyrene-polysiloxane comb graft copolymer, amino cage silane, respectively, resulting in a decrease in the hydrophobicity of the protective layer, and water gradually penetrated into the inside of the material after passing through the waterproof layer, so that the waterproof effect was decreased.
Examples 54 to 63
Unlike example 34, the raw material ratio of the protective layer was changed, as shown in table 8.
TABLE 8 amounts and proportions of protective layer raw materials
Example 64
The flame retardant property test was performed on the polyethylene composite flame retardant waterproof materials prepared in examples 54 to 63 and comparative example 10, wherein the test method of LOI was performed with reference to example 15, the vertical burning grade was performed with reference to example 30, and the final test results are shown in table 9 and fig. 2.
TABLE 9 flame retardant property test results for examples 54-63 and comparative example 10
FIG. 2 shows that the LOI value of the polyethylene composite flame-retardant waterproof material prepared by the invention is 32.1% -37.2%. Table 9 shows that the flame retardant rating of the material of comparative example 10 is V-1 and the flame retardant rating of the material obtained in the examples is V-0. In examples 54 to 56, the LOI value tended to increase and decrease with increasing amounts of the compatibilizing agent, and the compatibilizing agent contained a low-density polyethylene component in an excessive amount, and the proportion of the compatibilizing agent in the system increased, thereby decreasing the overall density of the material and the heat-resistant and flame-retardant properties. Example 57 reduced the amount of composite polyimide foam and reduced the LOI value compared to example 55. Example 58 further reduced the amount of composite polyimide foam but correspondingly increased the amount of modified mix stone, and thus increased the LOI. The results of examples 59 and 60 show that the amount of MPP is increased, the flame retardant performance is further improved, the polyethylene composite flame-retardant waterproof material prepared in example 60 achieves a high flame retardant level, PAPP and MPP serve as a carbon forming agent, an acid source and an air source, and the PAPP and MPP act synergistically with a compatilizer, a composite polyimide foam material and a silicon nitride loaded phosphorus-containing flame retardant when a fire disaster occurs to generate a compact carbon layer, so that the reduction of the density of combustible gas is promoted. The modified mixed stone is nonflammable, so that the fire resistance of the polyethylene composite flame-retardant waterproof material is improved. Examples 61-63 changed the amount of silicon nitride loaded phosphorus flame retardant and the overall LOI value reached 36.0% or more. The comparative example 10 has unsuitable usage amount of each component, the LOI value of the obtained polyethylene composite flame-retardant waterproof material is reduced, and the flame-retardant grade is V-1 grade.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The preparation method of the polyethylene composite flame-retardant waterproof material is characterized by comprising the following steps of:
putting 92 parts of high-density polyethylene, 1.2-2.2 parts of compatilizer, 1.5 parts of silicon nitride loaded phosphorus-containing flame retardant, 2 parts of antioxidant 1010 and 1 part of vinyl acetate into an internal mixer, and banburying to obtain a mixed material I;
Mixing 50 parts of high-density polyethylene, 5-18 parts of compatilizer, 13-16 parts of composite polyimide foaming material, 5-7 parts of intumescent flame retardant, 2-15 parts of modified mixed stone, 4-12 parts of silicon nitride loaded phosphorus flame retardant, 3 parts of antioxidant 1010 and 2 parts of vinyl acetate to obtain a mixed material II, transferring the mixed material II into a mould, and pressing to obtain a protective layer, wherein the part ratio of PAPP and MPP in the intumescent flame retardant is 1-7:1-3;
the protective layer, the base layer and the waterproof layer form the polyethylene composite flame-retardant waterproof material, wherein the part ratio of the polyurethane waterproof coating to the boron nitride and the lamellar graphene in the waterproof layer is 18-93:1-4:1-3;
the compatilizer is obtained by adding concentrated sulfuric acid and 1.0-4.5 parts of phosphorus-containing flame retardant into LDPE-g-MAH solution, reacting for 10 hours, filtering, washing and drying to constant weight;
The part ratio of the silicon nitride to the phosphorus-containing flame retardant in the silicon nitride-loaded phosphorus-containing flame retardant is 20-80:1-3;
The preparation method of the composite polyimide foam material comprises the steps of dissolving 65 parts of benzophenone tetracarboxylic dianhydride in 120 parts of methanol to obtain a ketone tetracarboxylic dianhydride solution, adding the ketone tetracarboxylic dianhydride solution into a three-neck flask containing DMF, heating to 60 ℃, refluxing for 10 hours under stirring to obtain a polymerization solution, mixing triethylene diamine hexahydrate, dipropylene glycol and melamine cyanurate in a part ratio of 1-4:1-2:3-7, heating and stirring until the mixture is completely dissolved to obtain a catalyst solution, transferring the polymerization solution into the beaker, adding 1.2 parts of the catalyst solution, 5 parts of PEG-800, 5.5-7 parts of LDPE-g-MAH, 0.8 part of dibutyltin dilaurate, 8 parts of deionized water and 25-37 parts of aerogel powder into the polymerization solution, stirring to obtain a foaming white material uniformly, rapidly pouring 60 parts of foaming black material into the foaming white material, stirring to obtain a to-be-foamed material, transferring the foaming material into a mold, stopping foam growth, setting the foaming intermediate to obtain the intermediate, and curing the polyimide foam material at 180 ℃ for 5 hours;
the preparation method of the modified mixed stone comprises pulverizing mullite-cordierite to obtain mixed stone with average particle diameter of 120 μm; mixing the mixed stone, concentrated sulfuric acid and potassium permanganate at 50 ℃ for 2 hours to obtain an oxidation mixed liquid, adding deionized water into the oxidation mixed liquid for continuous heat preservation and stirring for 1 hour, adding a 35% mass fraction hydrogen peroxide aqueous solution into the oxidation mixed liquid, stirring for 20 minutes to obtain an intermediate, the mass fraction of the deionized water and the mixed stone is 1:150, the mass fraction of the hydrogen peroxide aqueous solution and the mixed stone is 1:42-52, continuously adding a 30% mass fraction potassium hydroxide aqueous solution into the intermediate, adjusting the pH value of the system to be 10, reducing for 5 hours at 200 ℃, washing and drying by water to obtain a surface treatment mixed stone, mixing 20 parts of the surface treatment mixed stone, 3.4-4.8 parts of 1, 4-benzenediacetic acid with 400 parts of DMF, slowly adding 1 part of concentrated sulfuric acid, raising the temperature to 80 ℃, stirring to obtain a graft mixed stone, adding 1:42-52 parts of the aqueous solution of hydrogen peroxide and the mixed stone, continuously adding 1 g-14 parts of the aqueous solution of 30% mass fraction potassium hydroxide into the intermediate, washing and drying to obtain a cage-shaped mixed stone, and carrying out vacuum filtration reaction to obtain the modified MALDPE, and carrying out continuous filtration on the modified mixed stone for 1-55 g.
2. The method for preparing the polyethylene composite flame-retardant waterproof material according to claim 1, wherein the phosphorus-containing flame retardant is one of diethyl phosphate, dibenzoxyphos, phytic acid and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
3. The method for preparing a polyethylene composite flame-retardant and waterproof material according to claim 1, wherein the amount of the compatilizer in the base layer is 1.5-2.2 parts.
4. The method for preparing the polyethylene composite flame-retardant and waterproof material according to claim 1, wherein the aerogel powder is used in an amount of 30-37 parts.
5. The preparation method of the polyethylene composite flame-retardant waterproof material according to claim 1, wherein the foaming black material is one of polymethylene polyphenyl polyisocyanate, 3, 5-dimethylphenyl isocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate and 3, 5-difluorophenylisocyanate, and the amount of the foaming black material is 59.4-84.8 parts.
6. The preparation method of the polyethylene composite flame-retardant waterproof material is characterized by comprising the steps of adding methyltrimethoxysilane, cetyltrimethylammonium chloride, 3 parts of DMF and deionized water into a three-necked flask, stirring and mixing for 15min to obtain a mixed solution, adding an oxalic acid solution into the mixed solution, heating to 50 ℃, stirring and reacting for 6h to obtain a sol, adding an ammonia water solution into the sol, heating to 80 ℃, adding 33-42 parts of 3-aminopropyl triethoxysilane, reacting for 10h to obtain a modified aerogel precursor, moving the modified aerogel precursor into a mold, aging at room temperature for 24h to obtain an aerogel precursor, drying the aerogel precursor at 85 ℃ for 3h to obtain aerogel, and grinding the aerogel to obtain the aerogel powder.
7. The method for preparing the polyethylene composite flame-retardant and waterproof material according to claim 6, wherein the 3-aminopropyl triethoxysilane is used in an amount of 35-42 parts.
8. The method for preparing the polyethylene composite flame-retardant waterproof material according to claim 1, wherein the amount of the modified mixed stone is 8-15 parts.
9. A polyethylene composite flame-retardant waterproof material is characterized by comprising a protective layer, a base layer and a waterproof layer, wherein the polyethylene composite flame-retardant waterproof material is prepared by the preparation method of any one of claims 1-8, the preparation method of the base layer is changed, the tensile strength of the polyethylene composite flame-retardant waterproof material is 21.0-27.5MPa, the LOI is 17.7-33.8%, the LOI after 6 months is 17.5-31.3%, the preparation method of a composite polyimide foaming material is changed, the LOI value of the polyethylene composite flame-retardant waterproof material is 18.5-34.9%, the flame-retardant grades are V-0, V-1 and V-2, the notch impact strength is 18.0-37.7KJ/m 2%, the preparation method of a modified mixed stone is changed, the LOI value of the polyethylene composite flame-retardant waterproof material is 32.9-35.5%, the flame-retardant grade is V-0 grade, the notch impact strength is 17.2-36.5KJ/m 2, the contact angle of the polyethylene composite flame-retardant waterproof material is 106.5-3%, and the water absorption rate of the raw material is changed to be the flame-retardant grade of the polyethylene composite waterproof material is 1.37-32.37%.
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