CN117777703A - Suspension type water-cured elastomer prefabricated runway and preparation method thereof - Google Patents
Suspension type water-cured elastomer prefabricated runway and preparation method thereof Download PDFInfo
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- CN117777703A CN117777703A CN202311592645.4A CN202311592645A CN117777703A CN 117777703 A CN117777703 A CN 117777703A CN 202311592645 A CN202311592645 A CN 202311592645A CN 117777703 A CN117777703 A CN 117777703A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 82
- 229920001971 elastomer Polymers 0.000 title claims abstract description 53
- 239000000806 elastomer Substances 0.000 title claims abstract description 50
- 239000000725 suspension Substances 0.000 title claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 56
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000010438 heat treatment Methods 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010703 silicon Substances 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 35
- 239000000654 additive Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 25
- 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 abstract description 24
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 21
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 101
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 61
- 239000000920 calcium hydroxide Substances 0.000 claims description 61
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 61
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 51
- 239000000377 silicon dioxide Substances 0.000 claims description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 47
- 229910021389 graphene Inorganic materials 0.000 claims description 47
- 150000004692 metal hydroxides Chemical class 0.000 claims description 41
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 238000001723 curing Methods 0.000 claims description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 14
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 7
- 239000012346 acetyl chloride Substances 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 159000000003 magnesium salts Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000008157 edible vegetable oil Substances 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- -1 tween-40 Polymers 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 claims description 3
- 229960000228 cetalkonium chloride Drugs 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 16
- 239000004814 polyurethane Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229920002635 polyurethane Polymers 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 229920003225 polyurethane elastomer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000013008 moisture curing Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 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 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 150000002009 diols Chemical group 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
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- 230000035699 permeability Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000715 Mucilage Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 238000010292 electrical insulation Methods 0.000 description 1
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- 229920003052 natural elastomer Polymers 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 150000003672 ureas Chemical class 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a suspension type water-cured elastomer prefabricated runway and a preparation method thereof, and belongs to the technical field of high polymer materials. The organic silicon ether monomer reacts with the diphenylmethane diisocyanate to prepare the organic silicon resin modified polyurethane prepolymer, the organic silicon resin modified polyurethane prepolymer reacts with the diphenylmethane diisocyanate, isophorone diamine and 1, 4-butanediol by mixing, heating and stirring, the additive is added, the mixture is uniformly mixed, cooled, and poured into a mould after being uniformly mixed with water, and the elastomer coiled material is solidified to prepare the suspension type water-solidified elastomer prefabricated runway.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a suspension type water-cured elastomer prefabricated runway and a preparation method thereof.
Background
The traditional runway often has the conditions of cracking, foaming, aging, cracking and the like, and meanwhile, the traditional runway cannot be regenerated, so that resources are wasted. There is a strong need in the market today for a material that saves resources and has a longer service life as runway material. Polyurethane (PU) material is short for polyurethane, which is a high molecular material. Polyurethane is an emerging organic polymer material, and is widely applied to various fields of national economy due to the excellent performance, and the product application fields relate to light industry, chemical industry, electronics, textile, medical treatment, building materials, automobiles, national defense, aerospace, aviation and the like. Polyurethane materials are widely applied in the sports industry nowadays, in particular to the laying of plastic sports fields including basketball, volleyball, badminton, tennis court and runway.
The Chinese patent No. 104831600B discloses a non-water seepage self-texture plastic track, wherein a main part of a base layer is formed by mixing mixed polyurethane glue, a catalyst and black particles, solidifying and defoaming, and a self-texture clear pulp layer and a self-texture flower pulp layer are arranged on the base layer, and the main components of the two layers are polyurethane mucilage. The runway has uniform lines, good wear resistance, no threshing condition and long service life, but has large polyurethane consumption and higher cost.
The Chinese patent No. 101698988B discloses a plastic runway and a preparation method thereof, and the plastic runway is prepared by banburying, open milling, extrusion, vulcanization and the like of natural rubber, styrene-butadiene rubber, white carbon black and the like. The runway has good elasticity, but the rubber consumption is large, and the cost selling price is high.
The Chinese patent No. 104523109B discloses an elastic safety floor mat and a preparation method thereof, wherein the elastic safety floor mat is divided into a surface layer and a bottom layer, rubber is adopted as a main raw material, the surface layer is tough, wear-resistant and weather-resistant, the floor mat is suitable for long-time outdoor use, the bottom layer is prepared from a highly closed-cell foaming formula, the surface layer and the bottom layer are respectively prepared, and finally, the floor mat is formed by compounding and forming, and then, the floor mat is subjected to vulcanization chemical reaction. The runway has good cushioning and protecting performance, but has complex processing, low production efficiency and high energy consumption.
Chinese patent application CN107698923a discloses a recyclable plastic track, and the preparation process cancels the vulcanizing process, so that the method is environment-friendly and pollution-free; meanwhile, the intermolecular force is weaker than the covalent bond force after vulcanization, so that the plastic track can be recycled. The runway is simple to manufacture, but the TPU is large in dosage, the TPU is expensive in the market, the runway cost and the selling price are high, in addition, the talcum powder is flaky, and the talcum powder is selected as a filling material to have negative influence on the impact toughness of the runway.
In general, prefabricated runways in the market are manufactured by bonding various particles, such as EPDM particles, with more expensive polyurethane glue, and are manufactured into coiled materials, and the runways are manufactured by vulcanizing various rubbers, so that the runways are complex in processing, low in production efficiency and high in production energy consumption. And both runways use thermosetting materials, which are difficult to recycle after the service life is reached.
The moisture curing polyurethane does not use toxic friction cards suspected to be carcinogenic as curing agents, but reacts with water in the air through-NCO groups contained in the prepolymer after construction to generate urea bonds for curing, so that the high-elasticity, firm and durable seamless waterproof film is formed, and the moisture curing polyurethane is convenient to construct, excellent in performance and popular. But it also finds its shortcomings during application: 1) The curing time is long and uncertain. The paint is solidified by slowly performing chain extension reaction by absorbing moisture in the air, so that the paint is greatly influenced by the humidity of the air. 2) The coating on the wet substrate will foam.
Disclosure of Invention
The invention aims to provide a suspension type water-cured elastomer prefabricated runway and a preparation method thereof, wherein a catalyst is not added, a curing agent is water, the advantages of environmental protection, low cost and the like are achieved, meanwhile, compared with moisture curing, the suspension type water-cured elastomer prefabricated runway has the advantages of fixed and adjustable curing time by adding water, the influence of the environment on construction is reduced, the prepared polyurethane elastomer has good physical properties, good flame retardance, flexibility, wear resistance and antistatic property, heat resistance, stability and hydrophobicity, a large number of bubbles are not generated, the requirement of the suspension type water-cured elastomer prefabricated runway can be met, and the suspension type water-cured elastomer prefabricated runway has wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a suspension type water-cured elastomer prefabricated runway, which comprises the steps of reacting an organic silicon ether monomer with diphenylmethane diisocyanate to prepare an organic silicon resin modified polyurethane prepolymer, mixing the organic silicon resin modified polyurethane prepolymer with the diphenylmethane diisocyanate, isophorone diamine and 1, 4-butanediol, heating and stirring the mixture for reaction, adding additives, uniformly mixing, cooling, uniformly mixing with water, pouring the mixture into a mould, curing to prepare an elastomer coiled material, and preparing the suspension type water-cured elastomer prefabricated runway;
the structural formula of the organic silicon ether monomer is shown as formula I:
wherein n=2-5.
As a further improvement of the invention, the method comprises the following steps:
s1, preparing an organic silicon ether monomer: reacting acetyl chloride with glycol ether to obtain an intermediate, and then reacting the intermediate with 1, 3-tetramethyl disiloxane to obtain an organosilicon ether monomer;
the intermediate has the following structure:
s2, preparing an organosilicon resin modified polyurethane prepolymer: dehydrating an organic silicon ether monomer, adding diphenylmethane diisocyanate under the protection of inert gas, and heating and stirring for reaction to obtain an organic silicon resin modified polyurethane prepolymer;
s3, mixing additives: uniformly mixing modified porous silica coated calcium hydroxide, wrinkled graphene coated magnesium-aluminum double metal hydroxide and plasticizer to prepare an additive;
s4, preparing a mixture: uniformly mixing the organosilicon resin modified polyurethane prepolymer prepared in the step S2, diphenylmethane diisocyanate, isophorone diamine and 1, 4-butanediol, heating and stirring for reaction, detecting the content of-NCO in a system, stopping the reaction, adding the additive prepared in the step S3, uniformly mixing, cooling and discharging;
s5, preparing a suspension type water-cured elastomer prefabricated runway: and (3) uniformly mixing the mixture prepared in the step (S4) with water, pouring the mixture into a mold, and curing to obtain an elastomer coiled material, thus obtaining the suspension type water-cured elastomer prefabricated runway.
As a further improvement of the invention, the molar ratio of the acetyl chloride to the glycol ether in the step S1 is 1:1-1.1, the molar ratio of the intermediate to the 1, 3-tetramethyl disiloxane is 2-2.1:1, and the glycol ether is at least one selected from diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol.
As a further improvement of the present invention, the molar ratio of the organosilicon ether monomer to the diphenylmethane diisocyanate in step S2 is 1:1.03-1.05, wherein the temperature of the heating and stirring reaction is 70-80 ℃ and the time is 2-3h.
As a further improvement of the invention, in the step S3, the mass ratio of the modified porous silica coated calcium hydroxide, the wrinkled graphene coated magnesium aluminum double metal hydroxide and the plasticizer is 5-7:3-5:1-2, and the plasticizer is at least one selected from dibutyl phthalate, dioctyl phthalate and diisononyl phthalate; in the step S4, the mass ratio of the organosilicon resin modified polyurethane prepolymer to the diphenylmethane diisocyanate to the isophorone diamine to the 1, 4-butanediol to the additive is 92-240:255-260:160-170:85-90:10-12, the temperature of the heating and stirring reaction is 75-80 ℃, and the reaction is stopped when the content of-NCO in the detection system is 3-5%; the mass ratio of the mixture to the water in the step S5 is 100:10-15, and the curing time is 10-12h.
The diisononyl phthalate has the characteristics of good heat resistance, cold resistance and weather resistance and extremely low volatility, and after the diisononyl phthalate is added, the polyurethane elastomer runway and court can be used for a long time within the range of-40-95 ℃, and the diisononyl phthalate has the characteristics of low volatility, sanitation, safety and environmental protection.
As a further improvement of the present invention, the preparation method of the modified porous silica coated calcium hydroxide in step S3 is as follows:
t1. preparation of porous silica coated calcium hydroxide: after ball milling, calcium hydroxide is uniformly dispersed in methylene dichloride, tetraethoxysilane is added, and the mixture is stirred and mixed uniformly to obtain an oil phase; dissolving an emulsifying agent and a pore-forming agent in water to obtain a water phase; dropwise adding the oil phase into the water phase, emulsifying, regulating the pH value of the solution, stirring for reaction, centrifuging, washing and drying to obtain porous silica coated calcium hydroxide;
t2. preparation of modified porous silica coated calcium hydroxide: and (3) adding the porous silica coated calcium hydroxide prepared in the step (T1) into ethanol, adding a silane coupling agent, heating, stirring, reacting, centrifuging, washing and drying to obtain the modified porous silica coated calcium hydroxide.
As a further improvement of the invention, the ball milling time in the step T1 is 2-3h, the mass ratio of the calcium hydroxide to the tetraethoxysilane to the emulsifier to the pore-forming agent is 10-12:17-22:0.5-1:0.7-1.2, the emulsifier is at least one of Tween-20, tween-40, tween-60 and Tween-80, the pore-forming agent is at least one of cetyltrimethylammonium bromide, cetyldimethylbenzyl ammonium chloride and cetyltrimethylsodium bromide, the pH value of the solution is adjusted to 9-10, the stability of the stirring reaction is 40-45 ℃ and the time is 5-7h; in the step T2, the mass ratio of the porous silica coated calcium hydroxide to the silane coupling agent is 15-20:2-3, the silane coupling agent is at least one selected from KH550, KH602 and KH792, the temperature of the heating and stirring reaction is 45-50 ℃, and the time is 0.5-1h.
As a further improvement of the present invention, the preparation method of the folded graphene coated magnesium aluminum double metal hydroxide in step S3 is as follows:
u1. preparation of magnesium aluminum double metal hydroxide: dissolving magnesium salt and aluminum salt in water, regulating the pH value of the solution, heating and stirring for reaction, filtering, washing and drying to obtain magnesium-aluminum double-metal hydroxide;
u2. preparation of a folded graphene coated magnesium aluminum double metal hydroxide: and (3) ball-milling the magnesium-aluminum double-metal hydroxide prepared in the step (U1), uniformly dispersing in graphene oxide dispersion liquid, uniformly spraying into heated edible oil, stirring for reaction, suction filtering, and reducing in hydrazine hydrate steam to obtain the wrinkled graphene-coated magnesium-aluminum double-metal hydroxide.
As a further improvement of the invention, the mass ratio of the magnesium salt to the aluminum salt in the step U1 is 10-12:7-10, the magnesium salt is at least one of magnesium chloride, magnesium sulfate and magnesium nitrate, the aluminum salt is at least one of aluminum chloride, aluminum nitrate and aluminum sulfate, the pH value of the solution is adjusted to 9-9.5, the temperature of the heating and stirring reaction is 70-80 ℃, and the time is 3-5 hours; the ball milling time in the step U2 is 2-4h, the mass ratio of the magnesium aluminum double metal hydroxide to the graphene oxide dispersion liquid is 2-4:150-200, the concentration of the graphene oxide dispersion liquid is 0.5-1mg/mL, the temperature of the heated edible oil is 180-220 ℃, the stirring reaction time is 1-2h, the reduction time is 5-7h, and the concentration of the hydrazine hydrate steam is 50-70wt%.
The invention further provides the suspension type water-cured elastomer prefabricated runway prepared by the preparation method.
The invention has the following beneficial effects:
polyurethane has excellent mechanical properties, high toughness, oil resistance and other properties, but has the defects of poor water resistance and poor air permeability. The organic silicon resin has the characteristics of ventilation, hydrophobicity, aging resistance, electrical insulation, ozone resistance, good biocompatibility and the like, but has poor mechanical properties. Therefore, the invention prepares an organic silicon ether monomer, and the prepared organic silicon ether monomer is of a diol structure by connecting polyether alcohol groups on 1, 3-tetramethyl disiloxane, and can form a prepolymer with diphenylmethane diisocyanate, so that silane is introduced into a polyurethane molecular chain structure, organic silicon and polyurethane are organically combined, and the problems of unsatisfactory mechanical properties and the like of a product caused by poor mixing compatibility of the organic silicon ether monomer and the polyurethane are avoided, thereby greatly improving the heat-resistant stability, hydrophobicity, air permeability and other properties of the prepared elastomer.
In addition, the invention prepares the modified porous silica coated calcium hydroxide, the particles are coated with porous silica, the surface of the particles is further modified by the silane coupling agent with amino, so that the particles can participate in the polyurethane chain reaction, the problems of poor compatibility of the particles in an elastomer, uneven dispersion, influence on mechanical properties and the like are effectively avoided, meanwhile, the porous structure of the particles enables sodium hydroxide in the core to play a role of a gas absorbent well, and CO generated in the process of reacting and solidifying the mixture and water can be effectively avoided 2 Adsorption, thus avoiding the dissipation of the particles to form a large amount of bubbles in the elastomer to influence the service performance of the material, and compared with the addition of the latent curing agent, the addition of the particles has the effects of no pungent smell, environmental protection, good absorption effect and certain enhancement on the mechanical property of the elastomer.
According to the preparation method, the graphene-coated magnesium aluminum double metal hydroxide is prepared, the graphene oxide is coated on the surface of the prepared magnesium aluminum double metal hydroxide, and in the process of rapid heating and evaporation, water in the graphene oxide dispersion liquid is rapidly evaporated, so that a graphene oxide fold structure is formed on the surface of the magnesium aluminum double metal hydroxide, the graphene oxide fold structure is further reduced into the folded graphene-coated magnesium aluminum double metal hydroxide in hydrazine hydrate vapor, the folded structure can generate enhanced mechanical interlocking with a polyurethane elastomer polymer and adhesion with a polymer chain, interaction between graphene and a matrix is enhanced, compatibility of the material and the matrix is improved, and the magnesium aluminum double metal hydroxide can obviously improve the flame retardance of the material and has the advantages of no halogen, no toxicity, no volatilization, small corrosiveness, good stability and the like.
In addition, the polyurethane elastomer prepared by the method is free of catalyst, the curing agent is water, isocyanate reacts with water, firstly unstable carbamic acid is generated, then the carbamic acid is decomposed into carbon dioxide and amine, the generated amine continuously reacts with isocyanate in the presence of excessive isocyanate to generate substituted urea, and the polyurethane elastomer has the advantages of environmental protection, low cost and the like.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation example 1 preparation of modified porous silica coated calcium hydroxide
The method comprises the following steps:
t1. preparation of porous silica coated calcium hydroxide: after ball milling 10 parts by weight of calcium hydroxide for 2 hours, uniformly dispersing the calcium hydroxide in 200 parts by weight of dichloromethane, adding 17 parts by weight of tetraethoxysilane, and stirring and mixing for 10 minutes to obtain an oil phase; dissolving 0.5 weight part of tween-40 and 0.7 weight part of cetyltrimethyl sodium bromide in 500 weight parts of water to obtain a water phase; dropwise adding the oil phase into the water phase, emulsifying for 15 minutes at 10000r/min, adjusting the pH value of the solution to 9, heating to 40 ℃, stirring and reacting for 5 hours, centrifuging, washing and drying to obtain porous silica coated calcium hydroxide;
t2. preparation of modified porous silica coated calcium hydroxide: adding 15 parts by weight of porous silica coated calcium hydroxide prepared in the step T1 into 200 parts by weight of ethanol, adding 2 parts by weight of silane coupling agent, heating to 45 ℃, stirring and reacting for 0.5h, centrifuging, washing and drying to prepare modified porous silica coated calcium hydroxide;
the silane coupling agent is a mixture of KH550 and KH602, and the mass ratio is 3:7.
Preparation example 2 preparation of modified porous silica coated calcium hydroxide
The method comprises the following steps:
t1. preparation of porous silica coated calcium hydroxide: after ball milling 12 parts by weight of calcium hydroxide for 3 hours, uniformly dispersing the calcium hydroxide in 200 parts by weight of dichloromethane, adding 22 parts by weight of tetraethoxysilane, and stirring and mixing for 10 minutes to obtain an oil phase; dissolving 1 part by weight of tween-60 and 1.2 parts by weight of cetyl dimethylbenzyl ammonium chloride in 500 parts by weight of water to obtain a water phase; dropwise adding the oil phase into the water phase, emulsifying for 15 minutes at 10000r/min, adjusting the pH value of the solution to 10, heating to 45 ℃, stirring for reaction for 7 hours, centrifuging, washing and drying to obtain porous silica coated calcium hydroxide;
t2. preparation of modified porous silica coated calcium hydroxide: adding 20 parts by weight of the porous silica coated calcium hydroxide prepared in the step T1 into 200 parts by weight of ethanol, adding 3 parts by weight of a silane coupling agent, heating to 50 ℃, stirring and reacting for 1h, centrifuging, washing and drying to prepare modified porous silica coated calcium hydroxide;
the silane coupling agent is a mixture of KH550 and KH602, and the mass ratio is 5:7.
Preparation example 3 preparation of modified porous silica coated calcium hydroxide
The method comprises the following steps:
t1. preparation of porous silica coated calcium hydroxide: after ball milling 11 parts by weight of calcium hydroxide for 2.5 hours, uniformly dispersing the calcium hydroxide in 200 parts by weight of dichloromethane, adding 20 parts by weight of tetraethoxysilane, and stirring and mixing for 10 minutes to obtain an oil phase; dissolving 0.7 weight part of Tween-80 and 1 weight part of cetyltrimethylammonium bromide in 500 weight parts of water to obtain a water phase; dropwise adding the oil phase into the water phase, emulsifying for 15 minutes at 10000r/min, adjusting the pH value of the solution to 9.5, heating to 42 ℃, stirring for reaction for 6 hours, centrifuging, washing, and drying to obtain porous silica coated calcium hydroxide;
t2. preparation of modified porous silica coated calcium hydroxide: adding 17 parts by weight of the porous silica coated calcium hydroxide prepared in the step T1 into 200 parts by weight of ethanol, adding 2.5 parts by weight of a silane coupling agent, heating to 47 ℃, stirring for reacting for 1h, centrifuging, washing and drying to prepare modified porous silica coated calcium hydroxide;
the silane coupling agent is a mixture of KH550 and KH602, and the mass ratio is 4:7.
Preparation example 4
The difference compared to preparation example 3 is that the silane coupling agent is a single KH550.
Preparation example 5
The difference compared to preparation example 3 is that the silane coupling agent is a single KH602.
Comparative example 1
In comparison with preparation example 3, the difference is that step T2 is not carried out.
Preparation example 6 preparation of pleated graphene coated magnesium aluminum double metal hydroxide
The method comprises the following steps:
u1. preparation of magnesium aluminum double metal hydroxide: dissolving 10 parts by weight of magnesium nitrate and 7 parts by weight of aluminum nitrate in 200 parts by weight of water, regulating the pH value of the solution to 9, heating to 70 ℃, stirring and reacting for 3 hours, filtering, washing and drying to obtain magnesium-aluminum double-metal hydroxide;
u2. preparation of a folded graphene coated magnesium aluminum double metal hydroxide: and (2) uniformly dispersing 2 parts by weight of the magnesium aluminum double metal hydroxide prepared in the step (U1) in 150 parts by weight of graphene oxide dispersion liquid with the concentration of 0.5mg/mL after ball milling for 2 hours, uniformly spraying the graphene oxide dispersion liquid into 180 ℃ rapeseed oil, stirring and reacting for 1 hour, carrying out suction filtration, and reducing the graphene oxide dispersion liquid in hydrazine hydrate steam with the concentration of 50wt% for 5 hours to prepare the wrinkled graphene-coated magnesium aluminum double metal hydroxide.
Preparation example 7 preparation of pleated graphene coated magnesium aluminum double metal hydroxide
The method comprises the following steps:
u1. preparation of magnesium aluminum double metal hydroxide: dissolving 12 parts by weight of magnesium sulfate and 10 parts by weight of aluminum sulfate in 200 parts by weight of water, regulating the pH value of the solution to 9.5, heating to 80 ℃, stirring and reacting for 5 hours, filtering, washing and drying to obtain magnesium-aluminum double metal hydroxide;
u2. preparation of a folded graphene coated magnesium aluminum double metal hydroxide: and (3) ball-milling 4 parts by weight of the magnesium aluminum double metal hydroxide prepared in the step (U1) for 4 hours, uniformly dispersing in 200 parts by weight of graphene oxide dispersion liquid with the concentration of 1mg/mL, uniformly spraying into corn oil with the temperature of 220 ℃, stirring for reaction for 2 hours, carrying out suction filtration, and reducing in hydrazine hydrate steam with the concentration of 70wt% for 7 hours to prepare the wrinkled graphene-coated magnesium aluminum double metal hydroxide.
Preparation example 8 preparation of pleated graphene coated magnesium aluminum double metal hydroxide
The method comprises the following steps:
u1. preparation of magnesium aluminum double metal hydroxide: dissolving 11 parts by weight of magnesium chloride and 8.5 parts by weight of aluminum chloride in 200 parts by weight of water, regulating the pH value of the solution to 9.2, heating to 75 ℃, stirring and reacting for 4 hours, filtering, washing and drying to obtain magnesium-aluminum double-metal hydroxide;
u2. preparation of a folded graphene coated magnesium aluminum double metal hydroxide: and (3) uniformly dispersing 3 parts by weight of the magnesium aluminum double metal hydroxide prepared in the step (U1) in 170 parts by weight of graphene oxide dispersion liquid with the concentration of 0.7mg/mL after ball milling for 3 hours, uniformly spraying the mixture into soybean oil with the temperature of 200 ℃, stirring and reacting for 1.5 hours, carrying out suction filtration, and reducing the mixture in hydrazine hydrate steam with the concentration of 60wt% for 6 hours to prepare the wrinkled graphene-coated magnesium aluminum double metal hydroxide.
Comparative example 2
In comparison with preparation example 8, the difference is that no magnesium chloride was added in step U1.
Comparative example 3
In comparison with preparation example 8, the difference is that no aluminum chloride was added in step U1.
Comparative example 4
In comparison with preparation 8, the difference is that step U2 is not carried out.
Example 1
The embodiment provides a preparation method of a suspension type water-cured elastomer prefabricated runway, which comprises the following steps:
s1, preparing an organic silicon ether monomer:
the synthetic route is as follows:
dissolving 0.1mol of acetyl chloride, 0.1mol of diethylene glycol and 0.3mol of triethylamine in 200mL of dichloromethane, heating and refluxing, stirring and reacting for 2h, filtering, washing and drying to obtain an intermediate; ESI-MS calculated: c (C) 7 H 13 O 4 (m+h) +161.07, found: 161.1, yield 92.7%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ6.42(d，1H)，6.05(m，1H)，5.8(m，1H)，4.30(t，2H)，3.56-3.72(m，6H)，2.0(br，1H)。
the synthetic route is as follows:
uniformly mixing 0.2mol of intermediate, 0.1mol of 1, 3-tetramethyl disiloxane and 200mL of isopropanol, introducing nitrogen, heating to 50 ℃, adding a chloroplatinic acid catalyst accounting for 0.2 weight percent of the total mass of the system, heating to 80 ℃, stirring for reaction for 3 hours, removing the solvent under reduced pressure, filtering, washing and drying to obtain an organic silicon ether monomer; ESI-MS calculated: c (C) 18 H 39 O 9 Si 2 (m+h) +455.21, found: 455.2, the yield was 88.6%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ4.25(t，4H)，3.55-3.70(m，12H)，2.31(t，4H)，2.0(br，2H)，1.72(t，4H)，0.07(s，12H)。
s2, preparing an organosilicon resin modified polyurethane prepolymer: dehydrating 0.1mol of organic silicon ether monomer, adding 0.103mol of diphenylmethane diisocyanate under the protection of nitrogen, heating to 70 ℃, and stirring for reacting for 2 hours to obtain an organic silicon resin modified polyurethane prepolymer;
s3, mixing additives: 5 parts by weight of modified porous silica coated calcium hydroxide prepared in preparation example 1,3 parts by weight of wrinkled graphene coated magnesium aluminum double metal hydroxide prepared in preparation example 6 and 1 part by weight of diisononyl phthalate are stirred and mixed for 15min to prepare an additive;
s4, preparing a mixture: uniformly mixing 92 parts by weight of the organic silicon resin modified polyurethane prepolymer prepared in the step S2, 255 parts by weight of diphenylmethane diisocyanate, 160 parts by weight of isophorone diamine and 85 parts by weight of 1, 4-butanediol, heating to 75 ℃, stirring for reaction, stopping the reaction when the content of-NCO in a detection system is 3%, stopping the reaction, adding 10 parts by weight of the additive prepared in the step S3, uniformly mixing, cooling, and discharging;
s5, preparing a suspension type water-cured elastomer prefabricated runway: and (3) uniformly mixing 100 parts by weight of the mixture prepared in the step (S4) with 10 parts by weight of water, pouring the mixture into a mold, and curing for 10 hours to prepare an elastomer coiled material, thus preparing the suspension type water-cured elastomer prefabricated runway.
Example 2
The embodiment provides a preparation method of a suspension type water-cured elastomer prefabricated runway, which comprises the following steps:
s1, preparing an organic silicon ether monomer:
dissolving 0.1mol of acetyl chloride, 0.11mol of tetraethylene glycol and 0.3mol of triethylamine in 200mL of dichloromethane, heating and refluxing, stirring and reacting for 2h, filtering, washing and drying to obtain an intermediate; ESI-MS calculated: c (C) 13 H 25 O 7 (m+h) +293.05, found: 293.1, the yield thereof was found to be 91.0%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ6.40(d，1H)，6.02(m，1H)，5.82(m，1H)，4.32(t，2H)，3.65-3.70(m，4H)，3.53-3.57(m，14H)，2.0(br，1H)。
uniformly mixing 0.21mol of intermediate, 0.1mol of 1, 3-tetramethyl disiloxane and 200mL of isopropanol, introducing nitrogen, heating to 50 ℃, adding a chloroplatinic acid catalyst accounting for 0.2 weight percent of the total mass of the system, heating to 80 ℃, stirring for reaction for 3 hours, removing the solvent under reduced pressure, filtering, washing and drying to obtain an organic silicon ether monomer; ESI-MS calculated: c (C) 30 H 63 O 15 Si 2 (m+h) +719.36, found: 719.4, the yield was 84.7%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ4.27(t，4H)，3.62-3.67(m，8H)，3.53-3.37(m，28H)，2.32(t，4H)，2.0(br，2H)，1.72(t，4H)，0.08(s，12H)。
s2, preparing an organosilicon resin modified polyurethane prepolymer: dehydrating 0.1mol of organic silicon ether monomer, adding 0.105mol of diphenylmethane diisocyanate under the protection of nitrogen, heating to 80 ℃, and stirring for reaction for 3 hours to obtain an organic silicon resin modified polyurethane prepolymer;
s3, mixing additives: 7 parts by weight of modified porous silica coated calcium hydroxide prepared in preparation example 2, 5 parts by weight of wrinkled graphene coated magnesium aluminum double metal hydroxide prepared in preparation example 7 and 2 parts by weight of diisononyl phthalate are stirred and mixed for 15min to prepare an additive;
s4, preparing a mixture: uniformly mixing 240 parts by weight of the organic silicon resin modified polyurethane prepolymer prepared in the step S2, 260 parts by weight of diphenylmethane diisocyanate, 170 parts by weight of isophorone diamine and 90 parts by weight of 1, 4-butanediol, heating to 80 ℃, stirring for reaction, stopping the reaction when the content of-NCO in a detection system is 5%, stopping the reaction, adding 12 parts by weight of the additive prepared in the step S3, uniformly mixing, cooling, and discharging;
s5, preparing a suspension type water-cured elastomer prefabricated runway: and (3) uniformly mixing 100 parts by weight of the mixture prepared in the step (S4) with 15 parts by weight of water, pouring the mixture into a mold, and curing for 12 hours to prepare an elastomer coiled material, thus preparing the suspension type water-cured elastomer prefabricated runway.
Example 3
The embodiment provides a preparation method of a suspension type water-cured elastomer prefabricated runway, which comprises the following steps:
s1, preparing an organic silicon ether monomer:
dissolving 0.1mol of acetyl chloride, 0.105mol of triethylene glycol and 0.3mol of triethylamine in 200mL of dichloromethane, heating and refluxing, stirring and reacting for 2 hours, filtering, washing and drying to obtain an intermediate; SI-MS calculation: c (C) 9 H 17 O 5 (m+h) +205.10, found: 205.1, yield 92.2%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ6.45(d，1H)，6.01(m，1H)，5.82(m，1H)，4.30(t，2H)，3.62-3.67(m，4H)，3.54-3.57(m，6H)，2.0(br，1H)。
uniformly mixing 0.205mol of intermediate, 0.1mol of 1, 3-tetramethyl disiloxane and 200mL of isopropanol, introducing nitrogen, heating to 50 ℃, adding a chloroplatinic acid catalyst accounting for 0.2 weight percent of the total mass of the system, heating to 80 ℃, stirring for reaction for 3 hours, removing the solvent under reduced pressure, filtering, washing and drying to obtain an organic silicon ether monomer; ESI-MS calculated: c (C) 22 H 47 O 11 Si 2 (m+h) +543.26, found: 543.3, the yield was 86.5%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ4.22(t，4H)，3.65-3.72(m，8H)，3.54-3.58(m，12H)，2.27(t，4H)，2.0(br，2H)，1.68(t，4H)，0.09(s，12H)。
s2, preparing an organosilicon resin modified polyurethane prepolymer: dehydrating 0.1mol of organic silicon ether monomer, adding 0.104mol of diphenylmethane diisocyanate under the protection of nitrogen, heating to 75 ℃, and stirring for reacting for 2.5 hours to obtain an organic silicon resin modified polyurethane prepolymer;
s3, mixing additives: 6 parts by weight of modified porous silica coated calcium hydroxide prepared in preparation example 3, 4 parts by weight of wrinkled graphene coated magnesium aluminum double metal hydroxide prepared in preparation example 8 and 1.5 parts by weight of diisononyl phthalate are stirred and mixed for 15min to prepare an additive;
s4, preparing a mixture: uniformly mixing 152 parts by weight of the organic silicon resin modified polyurethane prepolymer prepared in the step S2, 257 parts by weight of diphenylmethane diisocyanate, 166 parts by weight of isophorone diamine and 87 parts by weight of 1, 4-butanediol, heating to 77 ℃, stirring for reaction, stopping the reaction when the content of-NCO in a detection system is 4%, stopping the reaction, adding 11 parts by weight of the additive prepared in the step S3, uniformly mixing, cooling, and discharging;
s5, preparing a suspension type water-cured elastomer prefabricated runway: and (3) uniformly mixing 100 parts by weight of the mixture prepared in the step (S4) with 12 parts by weight of water, pouring the mixture into a mold, and curing for 11 hours to prepare an elastomer coiled material, thus preparing the suspension type water-cured elastomer prefabricated runway.
Example 4
The difference compared to example 3 is that modified porous silica coated calcium hydroxide is produced from preparation example 4.
Example 5
The difference compared to example 3 is that modified porous silica coated calcium hydroxide is produced from preparation 5.
Comparative example 1
The difference compared to example 3 is that modified porous silica coated calcium hydroxide was prepared from comparative preparation 1.
Comparative examples 2 to 4
The difference compared to example 3 is that the wrinkled graphene-coated magnesium aluminum duplex metal hydroxides are prepared from comparative preparation examples 2-4, respectively.
Comparative example 5
In comparison with example 3, the difference is that the organosilicon ether monomer is replaced by polyoxypropylene diol.
The method comprises the following steps:
s1, preparation of a polyurethane prepolymer: dehydrating 0.1mol of polyoxypropylene glycol, adding 0.104mol of diphenylmethane diisocyanate under the protection of nitrogen, heating to 75 ℃, and stirring for reacting for 2.5 hours to obtain a polyurethane prepolymer;
s2, mixing additives: 6 parts by weight of modified porous silica coated calcium hydroxide prepared in preparation example 3, 4 parts by weight of wrinkled graphene coated magnesium aluminum double metal hydroxide prepared in preparation example 8 and 1.5 parts by weight of diisononyl phthalate are stirred and mixed for 15min to prepare an additive;
s3, preparing a mixture: uniformly mixing 152 parts by weight of the polyurethane prepolymer prepared in the step S1, 257 parts by weight of diphenylmethane diisocyanate, 166 parts by weight of isophorone diamine and 87 parts by weight of 1, 4-butanediol, heating to 77 ℃, stirring for reaction, stopping the reaction when the content of-NCO in a detection system is 4%, stopping the reaction, adding 11 parts by weight of the additive prepared in the step S2, uniformly mixing, cooling, and discharging;
s4, preparing a suspension type water-cured elastomer prefabricated runway: and (3) uniformly mixing 100 parts by weight of the mixture prepared in the step (S3) with 12 parts by weight of water, pouring the mixture into a mold, and curing for 11 hours to prepare an elastomer coiled material, thus preparing the suspension type water-cured elastomer prefabricated runway.
Comparative example 6
The difference compared to example 3 is that the polymethylsilicone resin is directly added.
The method comprises the following steps:
s1, mixing additives: 6 parts by weight of modified porous silica coated calcium hydroxide prepared in preparation example 3, 4 parts by weight of wrinkled graphene coated magnesium aluminum double metal hydroxide prepared in preparation example 8 and 1.5 parts by weight of diisononyl phthalate are stirred and mixed for 15min to prepare an additive;
s2, preparing a mixture: uniformly mixing 152 parts by weight of polymethyl silicone resin, 257 parts by weight of diphenylmethane diisocyanate, 166 parts by weight of isophorone diamine and 87 parts by weight of 1, 4-butanediol, heating to 77 ℃, stirring for reaction, stopping the reaction when the content of-NCO in a detection system is 4%, stopping the reaction, adding 11 parts by weight of the additive prepared in the step S1, uniformly mixing, cooling, and discharging;
s3, preparing a suspension type water-cured elastomer prefabricated runway: and (2) uniformly mixing 100 parts by weight of the mixture prepared in the step (S2) with 12 parts by weight of water, pouring the mixture into a mold, and curing for 11 hours to prepare an elastomer coiled material, thereby preparing the suspension type water-cured elastomer prefabricated runway.
Comparative example 7
The difference compared to example 3 is that no modified porous silica coated calcium hydroxide was added.
The method comprises the following steps:
s3, mixing additives: 10 parts by weight of the wrinkled graphene-coated magnesium-aluminum double-metal hydroxide prepared in preparation example 8 and 1.5 parts by weight of diisononyl phthalate are stirred and mixed for 15min to prepare the additive.
Comparative example 8
The difference compared to example 3 is that the modified porous silica coated calcium hydroxide is replaced by calcium hydroxide.
The method comprises the following steps:
s3, mixing additives: 6 parts by weight of calcium hydroxide, 4 parts by weight of the wrinkled graphene-coated magnesium-aluminum double-metal hydroxide prepared in preparation example 8 and 1.5 parts by weight of diisononyl phthalate are stirred and mixed for 15min to prepare the additive.
Comparative example 9
The difference compared to example 3 is that no pleated graphene coated magnesium aluminum duplex metal hydroxide was added.
The method comprises the following steps:
s3, mixing additives: 10 parts by weight of the modified porous silica coated calcium hydroxide prepared in preparation example 3 and 1.5 parts by weight of diisononyl phthalate were stirred and mixed for 15 minutes to prepare an additive.
Comparative example 10
The difference compared to example 3 is that the wrinkled graphene-coated magnesium aluminum double metal hydroxide and the modified porous silica-coated calcium hydroxide are not added.
The method comprises the following steps:
s3, mixing additives: 11.5 parts by weight of diisononyl phthalate as additive.
Test example 1
The suspension type water-curable elastomer prefabricated runways prepared in examples 1 to 5 and comparative examples 1 to 10 of the present invention were tested according to the method in GB/T14833 2020.
The results are shown in tables 1 and 2.
TABLE 1 basic physical Properties
TABLE 2 content of harmful substances
As can be seen from the above table, the suspension type water-cured elastomer prefabricated runway prepared in the embodiments 1-3 has good mechanical property and flame retardant property, extremely low content of harmful substances and high environmental protection.
Test example 2
The performance test was performed on the suspension type water-cured elastomer prefabricated runways prepared in examples 1 to 5 and comparative examples 1 to 10 according to the present invention.
LOI test: the minimum oxygen volume percent concentration required to allow the sample to remain burned for a length of 50mm or for a burn time of 3 minutes was measured. The test was performed according to GB/T2406.2-2009 with spline dimensions of 130mm by 6.5mm by 3mm.
Water contact angle test: distilled water was used as a reference solution at room temperature, and each sample was tested 5 times and averaged.
The results are shown in Table 2.
TABLE 2
As can be seen from the above table, the suspension type water-cured elastomer prefabricated runway prepared in the embodiments 1-3 has good hydrophobic and flame-retardant effects.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A preparation method of a suspension type water-cured elastomer prefabricated runway is characterized in that an organosilicon resin modified polyurethane prepolymer is prepared by reacting an organosilicon ether monomer with diphenylmethane diisocyanate, and is mixed with diphenylmethane diisocyanate, isophorone diamine and 1, 4-butanediol, heated and stirred for reaction, additives are added, uniformly mixed, cooled, uniformly mixed with water, poured into a mold, cured to prepare an elastomer coiled material, and the suspension type water-cured elastomer prefabricated runway is prepared;
the structural formula of the organic silicon ether monomer is shown as formula I:
wherein n=2-5.
2. The method of manufacturing according to claim 1, comprising the steps of:
s1, preparing an organic silicon ether monomer: reacting acetyl chloride with glycol ether to obtain an intermediate, and then reacting the intermediate with 1, 3-tetramethyl disiloxane to obtain an organosilicon ether monomer;
the intermediate has the following structure:
s2, preparing an organosilicon resin modified polyurethane prepolymer: dehydrating an organic silicon ether monomer, adding diphenylmethane diisocyanate under the protection of inert gas, and heating and stirring for reaction to obtain an organic silicon resin modified polyurethane prepolymer;
s3, mixing additives: uniformly mixing modified porous silica coated calcium hydroxide, wrinkled graphene coated magnesium-aluminum double metal hydroxide and plasticizer to prepare an additive;
s4, preparing a mixture: uniformly mixing the organosilicon resin modified polyurethane prepolymer prepared in the step S2, diphenylmethane diisocyanate, isophorone diamine and 1, 4-butanediol, heating and stirring for reaction, detecting the content of-NCO in a system, stopping the reaction, adding the additive prepared in the step S3, uniformly mixing, cooling and discharging;
s5, preparing a suspension type water-cured elastomer prefabricated runway: and (3) uniformly mixing the mixture prepared in the step (S4) with water, pouring the mixture into a mold, and curing to obtain an elastomer coiled material, thus obtaining the suspension type water-cured elastomer prefabricated runway.
3. The process according to claim 2, wherein the molar ratio of acetyl chloride to glycol ether selected from at least one of diethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol in step S1 is 1:1 to 1.1, and the molar ratio of the intermediate to 1, 3-tetramethyldisiloxane is 2 to 2.1:1.
4. The method according to claim 2, wherein the molar ratio of the organic silicon ether monomer to the diphenylmethane diisocyanate in step S2 is 1:1.03-1.05, wherein the temperature of the heating and stirring reaction is 70-80 ℃ and the time is 2-3h.
5. The preparation method according to claim 2, wherein in the step S3, the mass ratio of the modified porous silica coated calcium hydroxide, the wrinkled graphene coated magnesium aluminum double metal hydroxide and the plasticizer is 5-7:3-5:1-2, and the plasticizer is at least one selected from dibutyl phthalate, dioctyl phthalate and diisononyl phthalate; in the step S4, the mass ratio of the organosilicon resin modified polyurethane prepolymer to the diphenylmethane diisocyanate to the isophorone diamine to the 1, 4-butanediol to the additive is 92-240:255-260:160-170:85-90:10-12, the temperature of the heating and stirring reaction is 75-80 ℃, and the reaction is stopped when the content of-NCO in the detection system is 3-5%; the mass ratio of the mixture to the water in the step S5 is 100:10-15, and the curing time is 10-12h.
6. The preparation method according to claim 2, wherein the preparation method of the modified porous silica coated calcium hydroxide in step S3 is as follows:
t1. preparation of porous silica coated calcium hydroxide: after ball milling, calcium hydroxide is uniformly dispersed in methylene dichloride, tetraethoxysilane is added, and the mixture is stirred and mixed uniformly to obtain an oil phase; dissolving an emulsifying agent and a pore-forming agent in water to obtain a water phase; dropwise adding the oil phase into the water phase, emulsifying, regulating the pH value of the solution, stirring for reaction, centrifuging, washing and drying to obtain porous silica coated calcium hydroxide;
t2. preparation of modified porous silica coated calcium hydroxide: and (3) adding the porous silica coated calcium hydroxide prepared in the step (T1) into ethanol, adding a silane coupling agent, heating, stirring, reacting, centrifuging, washing and drying to obtain the modified porous silica coated calcium hydroxide.
7. The preparation method according to claim 6, wherein the ball milling time in the step T1 is 2-3 hours, the mass ratio of the calcium hydroxide to the tetraethoxysilane to the emulsifier to the pore-forming agent is 10-12:17-22:0.5-1:0.7-1.2, the emulsifier is at least one of tween-20, tween-40, tween-60 and tween-80, the pore-forming agent is at least one of cetyltrimethylammonium bromide, cetyldimethylbenzyl ammonium chloride and cetyltrimethylsodium bromide, the pH value of the solution is adjusted to 9-10, the stability of the stirring reaction is 40-45 ℃ and the time is 5-7 hours; in the step T2, the mass ratio of the porous silica coated calcium hydroxide to the silane coupling agent is 15-20:2-3, the silane coupling agent is at least one selected from KH550, KH602 and KH792, the temperature of the heating and stirring reaction is 45-50 ℃, and the time is 0.5-1h.
8. The preparation method according to claim 2, wherein the preparation method of the wrinkled graphene-coated magnesium aluminum duplex metal hydroxide in the step S3 comprises the following steps:
u1. preparation of magnesium aluminum double metal hydroxide: dissolving magnesium salt and aluminum salt in water, regulating the pH value of the solution, heating and stirring for reaction, filtering, washing and drying to obtain magnesium-aluminum double-metal hydroxide;
u2. preparation of a folded graphene coated magnesium aluminum double metal hydroxide: and (3) ball-milling the magnesium-aluminum double-metal hydroxide prepared in the step (U1), uniformly dispersing in graphene oxide dispersion liquid, uniformly spraying into heated edible oil, stirring for reaction, suction filtering, and reducing in hydrazine hydrate steam to obtain the wrinkled graphene-coated magnesium-aluminum double-metal hydroxide.
9. The preparation method according to claim 8, wherein in the step U1, the mass ratio of the magnesium salt to the aluminum salt is 10-12:7-10, the magnesium salt is at least one of magnesium chloride, magnesium sulfate and magnesium nitrate, the aluminum salt is at least one of aluminum chloride, aluminum nitrate and aluminum sulfate, the pH value of the solution is adjusted to 9-9.5, the temperature of the heating and stirring reaction is 70-80 ℃ and the time is 3-5h; the ball milling time in the step U2 is 2-4h, the mass ratio of the magnesium aluminum double metal hydroxide to the graphene oxide dispersion liquid is 2-4:150-200, the concentration of the graphene oxide dispersion liquid is 0.5-1mg/mL, the temperature of the heated edible oil is 180-220 ℃, the stirring reaction time is 1-2h, the reduction time is 5-7h, and the concentration of the hydrazine hydrate steam is 50-70wt%.
10. A prefabricated runway of suspended water-curable elastomer produced by the production method according to any one of claims 1 to 9.
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