CN117736406A - Tank type container heat insulation structure and preparation method of heat insulation material thereof - Google Patents
Tank type container heat insulation structure and preparation method of heat insulation material thereof Download PDFInfo
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- CN117736406A CN117736406A CN202410191312.9A CN202410191312A CN117736406A CN 117736406 A CN117736406 A CN 117736406A CN 202410191312 A CN202410191312 A CN 202410191312A CN 117736406 A CN117736406 A CN 117736406A
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- 238000009413 insulation Methods 0.000 title claims abstract description 52
- 239000012774 insulation material Substances 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 98
- 150000003077 polyols Chemical class 0.000 claims abstract description 97
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 73
- 229920000570 polyether Polymers 0.000 claims abstract description 73
- 239000003063 flame retardant Substances 0.000 claims abstract description 43
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004814 polyurethane Substances 0.000 claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 16
- 239000000194 fatty acid Substances 0.000 claims abstract description 16
- 229930195729 fatty acid Natural products 0.000 claims abstract description 16
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 16
- 238000005187 foaming Methods 0.000 claims abstract description 16
- 239000004088 foaming agent Substances 0.000 claims abstract description 16
- 239000002114 nanocomposite Substances 0.000 claims abstract description 16
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- 238000004321 preservation Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 10
- 239000002121 nanofiber Substances 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000004872 foam stabilizing agent Substances 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 61
- 239000006260 foam Substances 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 16
- 239000003381 stabilizer Substances 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 13
- -1 pentamethylene diethylenetriamine Chemical compound 0.000 claims description 12
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003549 soybean oil Substances 0.000 claims description 9
- 235000012424 soybean oil Nutrition 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 8
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 7
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000000600 sorbitol Substances 0.000 claims description 6
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 claims description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 6
- 239000008158 vegetable oil Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- 239000005639 Lauric acid Substances 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000012802 nanoclay Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 229960002446 octanoic acid Drugs 0.000 claims description 4
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- FGNLEIGUMSBZQP-UHFFFAOYSA-N cadaverine dihydrochloride Chemical group Cl.Cl.NCCCCCN FGNLEIGUMSBZQP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011810 insulating material Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 5
- 239000011496 polyurethane foam Substances 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000011490 mineral wool Substances 0.000 description 3
- 239000011493 spray foam Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- 239000002385 cottonseed oil Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000011846 petroleum-based material Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000221089 Jatropha Species 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000021056 liquid food Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of heat preservation materials, and discloses a tank container heat preservation structure and a preparation method of the heat preservation material, wherein the heat preservation structure is formed by mixing, foaming and polymerizing a first component and a second component, and the first component is prepared from the following raw materials in parts by weight: 30-70 parts of polyether polyol, 10-30 parts of polyester polyol, 5-20 parts of flame-retardant polyether polyol, 10-30 parts of bio-based polyol, 1-3 parts of fatty acid, 1-3 parts of graphene, 1-3 parts of titanium dioxide, 1-5 parts of nano composite particles, 1-5 parts of nano fibers, 3-15 parts of catalysts, 1-5 parts of foam stabilizers, 25-45 parts of flame retardants, 10-30 parts of foaming agents and 1-3 parts of water; the second component is 100-267 parts of isocyanate. The properties of compressive strength, thermal stability, linear dimensional change rate, heat conductivity coefficient and the like of the polyurethane foam meet the technical requirements of low-temperature cold insulation and high-temperature heat insulation of polyurethane materials, and the prepared polyurethane foam also has higher flame retardant property, so that the heat insulation requirement of a tank container can be better met.
Description
Technical Field
The invention relates to the technical field of heat insulation materials, in particular to a tank container heat insulation structure and a preparation method of the heat insulation material.
Background
Under the background of the sustainable development of global trade, the tank container is increasingly popular in application and is widely applied to transporting various chemical raw materials, liquid foods and the like. In such transportation, insulation plays a vital role in maintaining cargo quality and improving transportation efficiency, and thus the market demand for tank container insulation is also continuously increasing. Currently, rock wool is the primary insulation material for tank containers. However, the production process of rock wool is relatively complex, and a series of complicated steps such as high-temperature melting, cotton blowing, blowing and the like are needed, and a large amount of energy is also needed to be consumed. In addition, rock wool can generate certain pollutants such as waste gas, waste water and the like in the production process, and corresponding treatment and emission control are required.
In contrast, the novel polyurethane thermal insulation material can be produced by different processes and formulations, and has relatively low production energy consumption and less pollutant. The material can better meet the environmental protection requirement while maintaining the quality of goods and improving the transportation efficiency, and accords with the development trend of the current market. Along with the continuous improvement of environmental awareness, the requirements of people on safety and environmental protection in the transportation process are also higher and higher. Therefore, the thermal insulation material of the tank container needs to have better thermal insulation performance and longer service life, and meanwhile has environmental protection performance, so that the influence on the environment is reduced.
The use requirement of the tank container heat insulation material needs to be determined according to specific application scenes and material types, but the requirements of temperature, strength, environmental protection, weather resistance and the like are generally met. Wherein the temperature requirement needs to be able to withstand cyclic changes from low to high temperatures (-40 ℃ to 150 ℃) or from high to low temperatures; the environmental requirements need to meet relevant environmental standards such as halogen-free, non-toxic, odorless, pollution-free, etc. to ensure that the equipment itself, the environment and the human health are not affected during use. Typically, the maximum use temperature of polyurethane rigid foams is from 100 ℃ to 120 ℃, and to increase the use temperature increases the proportion or index of polymeric MDI (second component) in the formulation, whereas the proportion of the two components is normally fixed for polyurethane spraying.
The tank polyurethane heat insulation material has certain fireproof performance, and is widely used for cold insulation of LNG transport ship tanks as a material with excellent heat insulation performance. The foaming molding of the polyurethane spray foam is to directly spray the double-component polyurethane foam composite material onto the surface of an object for foaming molding, and has the advantages that: the adhesive force with the base material is strong; the processing is simple, and the heat preservation and insulation layer can be formed by spraying on the surface of any shape, so that the labor productivity is greatly improved; meanwhile, the waterproof and sound-absorbing composite material has the functions of water resistance, sound absorption, sound insulation and the like. The main component of the polyhydroxy compound of the combined white material of the polyurethane rigid foam in the prior art is petroleum extraction products, which are non-renewable resources, the processing and production processes are complex, the cost is high, the environment is polluted, and the price also fluctuates along with the fluctuation of petroleum price. The bio-based polyether polyol is a polyol compound synthesized by taking soybean oil, rapeseed oil, cotton seed oil or palm oil as a starting raw material, is an environment-friendly and renewable resource, and has realized industrial production.
Due to the relatively high molecular weight of the bio-based polyether polyols, the hydroxyl number is relatively low, and the bio-based polyether polyols are mainly applied to the modification of flexible foams and polyisocyanate foams in the polyurethane field, and are relatively low in the application to rigid foams with low indexes and spray polyurethane, or the content of the introduced bio-based polyether polyols is extremely low, so that a large amount of petroleum-based polyesters and polyester polyols are still required. There remains a need for a polyurethane rigid foam in polyurethane spray foams that has both high levels of biobased materials and similar performance characteristics to foams made from existing petroleum-based materials. Therefore, the invention provides a tank container heat insulation structure and a preparation method of a heat insulation material thereof.
Disclosure of Invention
Aiming at the problems in the related art, the invention provides a tank type container heat insulation structure and a preparation method of a heat insulation material thereof, so as to overcome the technical problems in the prior art.
For this purpose, the invention adopts the following specific technical scheme:
according to one aspect of the invention, there is provided a tank container insulation structure, comprising a polyurethane rigid foam insulation layer adhered to the surface of a tank body of an LNG storage tank, wherein the polyurethane rigid foam insulation layer is formed by mixing, foaming and polymerizing a first component and a second component, and the weight ratio of the first component to the second component is 1:1, a step of;
the first component consists of the following raw materials in parts by weight:
30-70 parts of polyether polyol, 10-30 parts of polyester polyol, 5-20 parts of flame-retardant polyether polyol, 10-30 parts of bio-based polyol, 1-3 parts of fatty acid, 1-3 parts of graphene, 1-3 parts of titanium dioxide, 1-5 parts of nano composite particles, 1-5 parts of nano fibers, 3-15 parts of catalysts, 1-5 parts of foam stabilizers, 25-45 parts of flame retardants, 10-30 parts of foaming agents and 1-3 parts of water;
the second component consists of the following raw materials in parts by weight:
100-267 parts of isocyanate.
Further, the polyether polyol comprises the following raw materials in parts by weight:
20-40 parts of polyether polyol I and 10-30 parts of polyether polyol II.
Further, polyether polyol I is a sorbitol-initiated, refined polyether polyol having a hydroxyl value of 380mgKOH/g, a viscosity at 25℃of 10000 centipoise, and a hydroxyl functionality of 6;
polyether polyol II is an ethylenediamine-initiated polyether polyol having a hydroxyl value of 760mgKOH/g, a viscosity of 25000 centipoise at 25 ℃ and a hydroxyl functionality of 4;
the polyester polyol is an aromatic polyester polyol of phthalate, has a hydroxyl value of 310mgKOH/g, a viscosity of 3000 centipoise at 25 ℃, and a hydroxyl functionality of 2;
the flame-retardant polyether polyol is bromine-containing initial flame-retardant polyether polyol, has a hydroxyl value of 200mgKOH/g, has a viscosity of 15000 centipoise at 25 ℃ and has a hydroxyl functionality of 2;
the bio-based polyol is epoxidized soybean oil-based vegetable oil polyol, has a hydroxyl value of 380mgKOH/g, a viscosity of 5000 centipoise at 25 ℃, and a hydroxyl functionality of 4.5;
the isocyanate was polymeric diphenylmethane diisocyanate having an NCO group content of 32.4 and a viscosity of 25 centipoise at 25 ℃.
Further, the fatty acid is any one of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and arachidic acid.
Further, the nano composite particles are a mixture of any two or more of nano silicon, nano clay, nano oxide and nano ceramic particles.
Further, the catalyst comprises the following raw materials in parts by weight:
1-5 parts of pentamethylene diethylenetriamine, 1-5 parts of triethylene diamine and 1-5 parts of dibutyl tin dilaurate.
Further, the foam stabilizer is any one of a siloxane surfactant, an alcohol ether surfactant, an alcohol amine surfactant and a nonionic surfactant.
Further, the flame retardant is any one or a mixture of more of tri (2-chloroethyl) phosphate, tri (2-chloropropyl) phosphate, triethyl phosphate and dimethyl methylphosphonate.
Further, the foaming agent is any one or a mixture of more of pentane, 1, 3-pentafluoropropane and 1, 3-pentafluorobutane.
According to another aspect of the present invention, there is provided a method for preparing a thermal insulation material in a tank container thermal insulation structure, comprising the steps of:
s1, weighing raw materials of a first component and a second component according to preset weight parts;
s2, adding polyether polyol, polyester polyol, flame-retardant polyether polyol and bio-based polyol into a reaction kettle, uniformly stirring, sequentially adding fatty acid, graphene, titanium dioxide, nano composite particles and nano fibers into the reaction kettle, uniformly stirring, continuously adding a catalyst, a foam stabilizer, a flame retardant, a foaming agent and water into the reaction kettle, and uniformly stirring to obtain a first component;
s3, uniformly mixing the first component and the second component according to the weight ratio of 1:1, and performing foaming polymerization reaction to prepare the polyurethane rigid foam thermal insulation material.
The beneficial effects of the invention are as follows:
the tank container insulation structure has high content of biological base material, is applied to the insulation spraying foam spraying of tank, ensures that the foam material has similar performance to the foam produced by using all petroleum base materials, and has the performances of compressive strength, thermal stability, linear dimension change rate, heat conductivity coefficient and the like reaching the technical requirements of low-temperature insulation and high-temperature insulation of polyurethane materials, and meanwhile, the prepared polyurethane foam also has higher flame retardant property, and can better meet the insulation requirement of tank containers.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flowchart of a method for preparing a thermal insulation material in a tank container thermal insulation structure according to an embodiment of the present invention.
Detailed Description
For the purpose of further illustrating the various embodiments, the present invention provides the accompanying drawings, which are a part of the disclosure of the present invention, and which are mainly used to illustrate the embodiments and, together with the description, serve to explain the principles of the embodiments, and with reference to these descriptions, one skilled in the art will recognize other possible implementations and advantages of the present invention, wherein elements are not drawn to scale, and like reference numerals are generally used to designate like elements.
According to the embodiment of the invention, a tank container heat insulation structure and a preparation method of a heat insulation material thereof are provided.
The invention will be further described with reference to the accompanying drawings and the specific embodiments, according to one aspect of the invention, there is provided a tank container insulation structure, including a polyurethane rigid foam insulation layer bonded to the surface of a tank body of an LNG storage tank, the polyurethane rigid foam insulation layer is formed by mixing, foaming and polymerizing a first component and a second component, and the weight ratio of the first component to the second component is 1:1, a step of;
the first component consists of the following raw materials in parts by weight:
30-70 parts of polyether polyol, 10-30 parts of polyester polyol, 5-20 parts of flame-retardant polyether polyol, 10-30 parts of bio-based polyol, 1-3 parts of fatty acid, 1-3 parts of graphene, 1-3 parts of titanium dioxide, 1-5 parts of nano composite particles, 1-5 parts of nano fibers, 3-15 parts of catalysts, 1-5 parts of foam stabilizers, 25-45 parts of flame retardants, 10-30 parts of foaming agents and 1-3 parts of water;
the second component consists of the following raw materials in parts by weight:
100-267 parts of isocyanate.
Specifically, the polyether polyol consists of the following raw materials in parts by weight: 20-40 parts of polyether polyol I and 10-30 parts of polyether polyol II. The catalyst consists of the following raw materials in parts by weight: 1-5 parts of pentamethylene diethylenetriamine, 1-5 parts of triethylene diamine and 1-5 parts of dibutyl tin dilaurate.
Polyether polyol I is a sorbitol-initiated refined polyether polyol having a hydroxyl value of 380mgKOH/g, a viscosity at 25℃of 10000 centipoise, and a hydroxyl functionality of 6; polyether polyol II is an ethylenediamine-initiated polyether polyol having a hydroxyl value of 760mgKOH/g, a viscosity of 25000 centipoise at 25 ℃ and a hydroxyl functionality of 4; the polyester polyol is an aromatic polyester polyol of phthalate, has a hydroxyl value of 310mgKOH/g, a viscosity of 3000 centipoise at 25 ℃, and a hydroxyl functionality of 2; the flame-retardant polyether polyol is bromine-containing initial flame-retardant polyether polyol, has a hydroxyl value of 200mgKOH/g, has a viscosity of 15000 centipoise at 25 ℃ and has a hydroxyl functionality of 2; the bio-based polyol is epoxidized soybean oil-based vegetable oil polyol, has a hydroxyl value of 380mgKOH/g, a viscosity of 5000 centipoise at 25 ℃, and a hydroxyl functionality of 4.5; in addition, the bio-based polyols of the present invention may be produced from a variety of bio-based feedstocks, including, but not limited to: soybean oil, jatropha oil, palm oil, corn oil, peanut oil, cottonseed oil, rapeseed oil, olive oil, and mixtures thereof. A particularly preferred polyether polyol is derived from soybean oil polyol. The isocyanate was polymeric diphenylmethane diisocyanate having an NCO group content of 32.4 and a viscosity of 25 centipoise at 25 ℃.
The fatty acid is any one of octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid and arachidic acid. The nano composite particles are a mixture of any two or more of nano silicon, nano clay, nano oxide and nano ceramic particles. The foam stabilizer is any one of a siloxane surfactant, an alcohol ether surfactant, an alcohol amine surfactant and a nonionic surfactant. The flame retardant is any one or a mixture of more of tri (2-chloroethyl) phosphate, tri (2-chloropropyl) phosphate, triethyl phosphate and dimethyl methylphosphonate. The foaming agent is pentane 1, 3-pentafluoropropane 1, 3-pentafluorobutane any one or more of the following.
A small amount of foam stabilizer, which is advantageous for foaming, may be used in polyurethane spray foaming to stabilize the foaming reaction mixture at the initial stage of polymerization, helping to adjust the pore size, creating closed cells, and thus improving the thermal insulation properties. The foam stabilizer is one or two of non-hydrolytic silicon-carbon surfactant and non-silicone surfactant. The foam cells are relatively good due to the rapid rate of spray foaming, so the foam stabilizer used has a more favorable effect on the storage stability of the polyurethane spray composition white stock component prior to foaming.
Suitable flame retardants include phosphonates, phosphites and phosphates such as dimethyl methylphosphonate, ammonium polyphosphate, and various cyclic phosphates and phosphonates may be used in the bio-based polyurethane spray foam. Since polyurethane spray foam molding is foam molding by atomizing a foam gun head, materials such as one or more of tris (2-chloroethyl) phosphate (TCEP), tris (2-chloropropyl) phosphate (TCPP), triethyl phosphate (TEP) and dimethyl methylphosphonate (DMMP), of which tris (2-chloropropyl) phosphate (TCPP) and triethyl phosphate (TEP) are preferable, are more preferable to liquid and have relatively good storage stability when a flame retardant is selected.
In order to facilitate understanding of the above technical solutions of the present invention, specific embodiments of the present invention are described in detail below.
Example 1
The utility model provides a tank container insulation construction, includes the polyurethane rigid foam heat preservation of bonding at LNG storage tank jar body surface, polyurethane rigid foam heat preservation by first component and the mixed foaming polymerization of second component form, and the weight ratio of first component and second component is 1:1, a step of;
the first component consists of the following raw materials in parts by weight:
20g of polyether polyol I, 10g of polyether polyol II, 10g of polyester polyol, 5g of flame-retardant polyether polyol, 10g of bio-based polyol, 1g of fatty acid, 1g of graphene, 1g of titanium dioxide, 1g of nano composite particles, 1g of nano fibers, 1g of pentamethylene diethylenetriamine, 1g of triethylene diamine, 1g of dibutyl tin dilaurate, 1g of foam stabilizer, 25g of flame retardant, 10g of foaming agent and 1g of water;
the second component consists of the following raw materials in parts by weight:
100g of isocyanate.
Specifically, polyether polyol I is a sorbitol-initiated refined polyether polyol having a hydroxyl value of 380mgKOH/g, a viscosity at 25℃of 10000 centipoise, and a hydroxyl functionality of 6; polyether polyol II is an ethylenediamine-initiated polyether polyol having a hydroxyl value of 760mgKOH/g, a viscosity of 25000 centipoise at 25 ℃ and a hydroxyl functionality of 4; the polyester polyol is an aromatic polyester polyol of phthalate, has a hydroxyl value of 310mgKOH/g, a viscosity of 3000 centipoise at 25 ℃, and a hydroxyl functionality of 2; the flame-retardant polyether polyol is bromine-containing initial flame-retardant polyether polyol, has a hydroxyl value of 200mgKOH/g, has a viscosity of 15000 centipoise at 25 ℃ and has a hydroxyl functionality of 2; the bio-based polyol is epoxidized soybean oil-based vegetable oil polyol, has a hydroxyl value of 380mgKOH/g, a viscosity of 5000 centipoise at 25 ℃, and a hydroxyl functionality of 4.5; the isocyanate was polymeric diphenylmethane diisocyanate having an NCO group content of 32.4 and a viscosity of 25 centipoise at 25 ℃.
The fatty acid is octanoic acid, the nano composite particles are a mixture of nano silicon and nano ceramic particles, the foam stabilizer is a siloxane surfactant, the flame retardant is tris (2-chloroethyl) phosphate, and the foaming agent is pentane.
Example 2
The utility model provides a tank container insulation construction, includes the polyurethane rigid foam heat preservation of bonding at LNG storage tank jar body surface, polyurethane rigid foam heat preservation by first component and the mixed foaming polymerization of second component form, and the weight ratio of first component and second component is 1:1, a step of;
the first component consists of the following raw materials in parts by weight:
30g of polyether polyol I, 20g of polyether polyol II, 20g of polyester polyol, 15g of flame-retardant polyether polyol, 20g of bio-based polyol, 2g of fatty acid, 2g of graphene, 2g of titanium dioxide, 3g of nano composite particles, 3g of nano fibers, 3g of pentamethylene diethylenetriamine, 3g of triethylene diamine, 3g of dibutyl tin dilaurate, 3g of foam stabilizer, 35g of flame retardant, 20g of foaming agent and 2g of water;
the second component consists of the following raw materials in parts by weight:
150g of isocyanate.
Specifically, polyether polyol I is a sorbitol-initiated refined polyether polyol having a hydroxyl value of 380mgKOH/g, a viscosity at 25℃of 10000 centipoise, and a hydroxyl functionality of 6; polyether polyol II is an ethylenediamine-initiated polyether polyol having a hydroxyl value of 760mgKOH/g, a viscosity of 25000 centipoise at 25 ℃ and a hydroxyl functionality of 4; the polyester polyol is an aromatic polyester polyol of phthalate, has a hydroxyl value of 310mgKOH/g, a viscosity of 3000 centipoise at 25 ℃, and a hydroxyl functionality of 2; the flame-retardant polyether polyol is bromine-containing initial flame-retardant polyether polyol, has a hydroxyl value of 200mgKOH/g, has a viscosity of 15000 centipoise at 25 ℃ and has a hydroxyl functionality of 2; the bio-based polyol is epoxidized soybean oil-based vegetable oil polyol, has a hydroxyl value of 380mgKOH/g, a viscosity of 5000 centipoise at 25 ℃, and a hydroxyl functionality of 4.5; the isocyanate was polymeric diphenylmethane diisocyanate having an NCO group content of 32.4 and a viscosity of 25 centipoise at 25 ℃.
The fatty acid is capric acid, the nano composite particles are a mixture of nano oxide and nano ceramic particles, the foam stabilizer is a nonionic surfactant, and the flame retardant is a mixture of tri (2-chloroethyl) phosphate and dimethyl methylphosphonate. The foaming agent is a mixture of pentane and 1, 3-pentafluorobutane.
Example 3
The utility model provides a tank container insulation construction, includes the polyurethane rigid foam heat preservation of bonding at LNG storage tank jar body surface, polyurethane rigid foam heat preservation by first component and the mixed foaming polymerization of second component form, and the weight ratio of first component and second component is 1:1, a step of;
the first component consists of the following raw materials in parts by weight:
40g of polyether polyol I, 30g of polyether polyol II, 30g of polyester polyol, 20g of flame-retardant polyether polyol, 30g of bio-based polyol, 3g of fatty acid, 3g of graphene, 3g of titanium dioxide, 5g of nano composite particles, 5g of nano fibers, 5g of pentamethylene diethylenetriamine, 5g of triethylene diamine, 5g of dibutyl tin dilaurate, 5g of foam stabilizer, 45g of flame retardant, 30g of foaming agent and 3g of water;
the second component consists of the following raw materials in parts by weight:
267g of isocyanate.
Specifically, polyether polyol I is a sorbitol-initiated refined polyether polyol having a hydroxyl value of 380mgKOH/g, a viscosity at 25℃of 10000 centipoise, and a hydroxyl functionality of 6; polyether polyol II is an ethylenediamine-initiated polyether polyol having a hydroxyl value of 760mgKOH/g, a viscosity of 25000 centipoise at 25 ℃ and a hydroxyl functionality of 4; the polyester polyol is an aromatic polyester polyol of phthalate, has a hydroxyl value of 310mgKOH/g, a viscosity of 3000 centipoise at 25 ℃, and a hydroxyl functionality of 2; the flame-retardant polyether polyol is bromine-containing initial flame-retardant polyether polyol, has a hydroxyl value of 200mgKOH/g, has a viscosity of 15000 centipoise at 25 ℃ and has a hydroxyl functionality of 2; the bio-based polyol is epoxidized soybean oil-based vegetable oil polyol, has a hydroxyl value of 380mgKOH/g, a viscosity of 5000 centipoise at 25 ℃, and a hydroxyl functionality of 4.5; the isocyanate was polymeric diphenylmethane diisocyanate having an NCO group content of 32.4 and a viscosity of 25 centipoise at 25 ℃.
The fatty acid is lauric acid, the nano composite particles are a mixture of nano silicon and nano clay, the foam stabilizer is an alcohol amine surfactant, the flame retardant is tri (2-chloropropyl) phosphate, and the foaming agent is 1, 3-pentafluoropropane.
Experimental example
The properties of the insulation of the present invention are shown in table 1 below, compared to conventional container insulation systems (control).
Table 1 performance data table
According to another aspect of the present invention, as shown in fig. 1, there is provided a method for preparing a thermal insulation material in a thermal insulation structure of a tank container, comprising the steps of:
s1, weighing raw materials of a first component and a second component according to preset weight parts;
s2, adding polyether polyol, polyester polyol, flame-retardant polyether polyol and bio-based polyol into a reaction kettle, uniformly stirring, sequentially adding fatty acid, graphene, titanium dioxide, nano composite particles and nano fibers into the reaction kettle, uniformly stirring, continuously adding a catalyst, a foam stabilizer, a flame retardant, a foaming agent and water into the reaction kettle, and uniformly stirring to obtain a first component;
s3, uniformly mixing the first component and the second component according to the weight ratio of 1:1, and performing foaming polymerization reaction to prepare the polyurethane rigid foam thermal insulation material.
In summary, by means of the technical scheme, the tank container heat insulation structure provided by the invention has high-content bio-based material, and is applied to cold insulation spraying foam spraying of tanks, so that the foam material has similar performance to foam produced by using all petroleum-based materials, and the performances of compressive strength, thermal stability, linear dimensional change rate, heat conductivity coefficient and the like reach the technical requirements of low-temperature heat insulation and high-temperature heat insulation of polyurethane materials, and meanwhile, the prepared polyurethane foam also has higher flame retardant property, so that the heat insulation requirement of the tank container can be better met.
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. The utility model provides a tank container insulation structure, includes the polyurethane rigid foam heat preservation of bonding at LNG storage tank jar body surface, its characterized in that, polyurethane rigid foam heat preservation is mixed foaming polymerization by first component and second component and forms, and the weight ratio of first component and second component is 1:1, a step of;
the first component comprises the following raw materials in parts by weight:
30-70 parts of polyether polyol, 10-30 parts of polyester polyol, 5-20 parts of flame-retardant polyether polyol, 10-30 parts of bio-based polyol, 1-3 parts of fatty acid, 1-3 parts of graphene, 1-3 parts of titanium dioxide, 1-5 parts of nano composite particles, 1-5 parts of nano fibers, 3-15 parts of catalysts, 1-5 parts of foam stabilizers, 25-45 parts of flame retardants, 10-30 parts of foaming agents and 1-3 parts of water;
the second component consists of the following raw materials in parts by weight:
100-267 parts of isocyanate.
2. The tank container insulation structure according to claim 1, wherein the polyether polyol is composed of the following raw materials in parts by weight:
20-40 parts of polyether polyol I and 10-30 parts of polyether polyol II.
3. A tank container insulation structure according to claim 2, wherein the polyether polyol I is a sorbitol initiated refined polyether polyol having a hydroxyl value of 380mg koh/g, a viscosity of 10000 centipoise at 25 ℃, and a hydroxyl functionality of 6;
the polyether polyol II is an ethylenediamine-initiated polyether polyol, the hydroxyl value is 760mgKOH/g, the viscosity at 25 ℃ is 25000 centipoise, and the hydroxyl functionality is 4;
the polyester polyol is an aromatic polyester polyol of phthalate, has a hydroxyl value of 310mgKOH/g, a viscosity of 3000 centipoise at 25 ℃, and a hydroxyl functionality of 2;
the flame-retardant polyether polyol is a bromine-containing initial flame-retardant polyether polyol, the hydroxyl value is 200mgKOH/g, the viscosity at 25 ℃ is 15000 centipoise, and the hydroxyl functionality is 2;
the bio-based polyol is epoxidized soybean oil-based vegetable oil polyol, the hydroxyl value is 380mgKOH/g, the viscosity at 25 ℃ is 5000 centipoise, and the hydroxyl functionality is 4.5;
the isocyanate is polymeric diphenylmethane diisocyanate having an NCO group content of 32.4 and a viscosity of 25 centipoise at 25 ℃.
4. The insulated structure of claim 1, wherein the fatty acid is any one of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and arachidic acid.
5. The tank container insulation structure of claim 1, wherein the nanocomposite particles are a mixture of any two or more of nano-silicon, nano-clay, nano-oxide, and nano-ceramic particles.
6. The tank container insulation structure according to claim 1, wherein the catalyst is composed of the following raw materials in parts by weight:
1-5 parts of pentamethylene diethylenetriamine, 1-5 parts of triethylene diamine and 1-5 parts of dibutyl tin dilaurate.
7. The tank container insulation structure of claim 1, wherein the foam stabilizer is any one of a siloxane surfactant, an alcohol ether surfactant, an alcohol amine surfactant, and a nonionic surfactant.
8. The tank container insulation structure of claim 1, wherein the flame retardant is any one or more of tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, triethyl phosphate and dimethyl methylphosphonate.
9. A tank container insulation structure according to claim 1, wherein, the foaming agent is pentane 1, 3-pentafluoropropane and 1, 3-pentafluorobutane any one or more of the following.
10. A method for preparing a thermal insulation material in a tank container thermal insulation structure, which is used for preparing the tank container thermal insulation structure according to any one of claims 1 to 9, and is characterized in that the method for preparing the thermal insulation material in the tank container thermal insulation structure comprises the following steps:
s1, weighing raw materials of a first component and a second component according to preset weight parts;
s2, adding polyether polyol, polyester polyol, flame-retardant polyether polyol and bio-based polyol into a reaction kettle, uniformly stirring, sequentially adding fatty acid, graphene, titanium dioxide, nano composite particles and nano fibers into the reaction kettle, uniformly stirring, continuously adding a catalyst, a foam stabilizer, a flame retardant, a foaming agent and water into the reaction kettle, and uniformly stirring to obtain a first component;
and S3, uniformly mixing the first component and the second component according to the weight ratio of 1:1, and spraying the mixture on a box and tank heat-insulating foam mold through a high-pressure spraying machine to quickly react, solidify and form the polyurethane rigid foam heat-insulating material.
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