CN118271955A - Elastic bonding coating for preventing aluminum veneer from deforming of heat-insulating and decorative integrated plate and preparation method thereof - Google Patents
Elastic bonding coating for preventing aluminum veneer from deforming of heat-insulating and decorative integrated plate and preparation method thereof Download PDFInfo
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- CN118271955A CN118271955A CN202410509322.2A CN202410509322A CN118271955A CN 118271955 A CN118271955 A CN 118271955A CN 202410509322 A CN202410509322 A CN 202410509322A CN 118271955 A CN118271955 A CN 118271955A
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- 238000000576 coating method Methods 0.000 title claims abstract description 32
- 239000011248 coating agent Substances 0.000 title claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004952 Polyamide Substances 0.000 claims abstract description 40
- 229920001971 elastomer Polymers 0.000 claims abstract description 40
- 239000000806 elastomer Substances 0.000 claims abstract description 40
- 229920002647 polyamide Polymers 0.000 claims abstract description 40
- 239000006260 foam Substances 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 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 11
- 239000003063 flame retardant Substances 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 10
- 229920005862 polyol Polymers 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 50
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 35
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 30
- -1 polyoxytetramethylene Polymers 0.000 claims description 27
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 25
- 239000004677 Nylon Substances 0.000 claims description 19
- 229920001778 nylon Polymers 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
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- 238000006243 chemical reaction Methods 0.000 claims description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 230000008859 change Effects 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
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- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 4
- 229940009714 erythritol Drugs 0.000 claims description 4
- 235000019414 erythritol Nutrition 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
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- 229920001903 high density polyethylene Polymers 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 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 abstract description 11
- 230000032683 aging Effects 0.000 abstract description 2
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- 229920002635 polyurethane Polymers 0.000 description 16
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- 239000010410 layer Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 238000004321 preservation Methods 0.000 description 15
- 229920003225 polyurethane elastomer Polymers 0.000 description 14
- 238000005034 decoration Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000005187 foaming Methods 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
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- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 3
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- 229920006197 POE laurate Polymers 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 125000005442 diisocyanate group Chemical group 0.000 description 2
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- 239000011490 mineral wool Substances 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- NDKGUMMLYBINOC-UHFFFAOYSA-N 1,2-dichloro-1-fluoroethane Chemical compound FC(Cl)CCl NDKGUMMLYBINOC-UHFFFAOYSA-N 0.000 description 1
- ZRSCWSKNSQLFFI-UHFFFAOYSA-N Cl.C(=O)=CCOP(OCC=C=O)(OCC=C=O)=O Chemical compound Cl.C(=O)=CCOP(OCC=C=O)(OCC=C=O)=O ZRSCWSKNSQLFFI-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
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- 229920001400 block copolymer Polymers 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
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- 150000002009 diols Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
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- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
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- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000013514 silicone foam Substances 0.000 description 1
- 239000004590 silicone sealant Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
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- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an elastic bonding coating for preventing an aluminum veneer from deforming of a heat-insulating and decorating integrated plate and a preparation method thereof, wherein the elastic bonding coating consists of a component A and a component B, and the component A comprises the following raw materials in parts by weight: 75 parts of polyol, 5 parts of catalyst, 4 parts of surfactant, 2 parts of foaming agent, 15 parts of flame retardant and 1 to 20 parts of polyamide 1212 elastomer low-foam particles; wherein the component B comprises the following raw materials in parts by mass: 30-70 parts of crude MDI and 10 parts of phase-change composite material; the elastic coating is sprayed on the back of an aluminum veneer and has the advantages of good wear resistance, corrosion resistance, high toughness, high rebound resilience, aging resistance and the like.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to an elastic bonding coating for preventing an aluminum veneer of an integrated board for heat preservation and decoration from deforming and a preparation method thereof.
Background
The heat-insulating and decorating integrated plate has light weight, greatly reduces the weight load of a building body, has simple and convenient installation process, and is light in matched material system, so that the heat-insulating and decorating integrated plate is very suitable for decorating the outer wall of the building. The heat preservation and decoration integrated plate has simpler plate surface flatness, better heat preservation effect than the traditional heat preservation method, and is far superior to the common and traditional heat preservation method. In the practical application of the product, the heat-insulating core material is used as an intermediate of the heat-insulating and decorating integrated plate, so that the heat-insulating effect is achieved, and the heat-insulating core material and the decoration panel are bonded by the adhesive layer with high strength adhesive force or are riveted and fixed by the rivet so as to prevent peeling and falling.
The invention patent with the application number ZL201220001205.8 discloses a rock wool heat-insulating and decorating integrated plate, which comprises a bottom plate, a heat-insulating layer, a rigid carrier and a facing layer; the bottom plate is an inorganic composite plate; the heat preservation layer is a heat preservation material formed by self-adhesion of rock wool filling materials through brushing, one surface is fixedly bonded with the bottom plate through an adhesive layer, and the other surface is fixedly bonded with one surface of the rigid carrier through the adhesive layer; the facing layer is arranged on the other side of the rigid carrier.
The application is Ke Gaojie, and the invention patent of patent number ZL201921246830.7 discloses a heat preservation decoration integrative board system, includes interface power bridge layer, tie coat, sealing layer, heat preservation and finish coat at least, interface power bridge layer passes through the original veneer of bi-directional infiltration bonding wall body and tie coat, the tie coat is located between interface power bridge layer and the sealing layer, sealing layer is heat preservation and finish coat in proper order in back tie coat one side, sealing layer comprises silicone sealant and foam strip, through anchor assembly fixed connection between sealing layer and the heat preservation.
The heat-insulating and decorating integrated plate has high fireproof performance, the heat-insulating layer, the carrier layer and the structural adhesive part have incombustibility, and the product has the advantages of beautiful decoration, heat preservation, energy conservation, simple and convenient construction, long service life and the like, can realize industrial standard production, and has short production period. Not only has super-strong flexibility, but also increases the cleanliness of the surface, and effectively prevents the occurrence of chromatic aberration.
In the prior art, a decoration panel of an integrated plate is generally bonded with a heat-insulating core material and the decoration panel by adopting a viscose layer with high strength and adhesion; the operation easily leads to aluminium veneer panel and heat preservation core tie coat rigidity big and toughness is not enough thereby leads to aluminium veneer to warp seriously, seriously influences the outward appearance effect, and serious condition can panel and heat preservation core strip, even the board limit bursts apart, has influenced the factor of safety of this heat preservation decoration integration board.
Disclosure of Invention
At present, the microporous polyurethane elastomer is used as a special polyurethane foam material, and has the advantages of better wear resistance, corrosion resistance, high toughness, high rebound resilience, aging resistance and the like. Meanwhile, the material has the advantages of simple production process, high production efficiency, low production cost, flexible design of the formula, large adjustable space of product performance and great application prospect.
The microcellular polyurethane elastomer as a whole can be regarded as a block polymer consisting of hard segments and soft segments. Therefore, the microporous polyurethane elastomer has the characteristics of low-temperature flexibility and high rebound resilience, and also has certain rigidity and strength. The different polyols form the soft segment of the material, and the influence of the different polyols on the performance of the microcellular polyurethane elastomer is the effect of the soft segment part in the microphase structure on the performance of the material. The different polyols may also have different compositions, e.g., different molecular weights, different molecular structures, different functionalities, etc. The macromolecular chains generated after the reaction with isocyanate chain extension are different in molecular chain length, structure and the like, so that the overall performance of the microcellular polyurethane elastomer is affected. The polyamide 1212 elastomer low-foam particles and diisocyanate are utilized to carry out crosslinking reaction during foaming, and the polyamide 1212 elastomer low-foam particles form a support body in the polyurethane foam, so that the density of the polyurethane is reduced, and the bearing property and elasticity of the polyurethane are enhanced. By adjusting the components and the proportion of the reactive bi-component raw materials, the added polyamide 1212 elastomer low-foam particles and the phase change material absorb heat for the heat absorbing material to control the supercooling and overheating deformation of the elastic coating, thereby avoiding the larger fluctuation of the coating performance along with the temperature.
The elastic bonding coating for preventing the aluminum veneer from deforming of the heat-insulating and decorating integrated plate consists of a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 75 parts of polyol, 5 parts of catalyst, 4 parts of surfactant, 2 parts of foaming agent, 15 parts of flame retardant and 1 to 20 parts of polyamide 1212 elastomer low-foam particles; wherein the component B comprises the following raw materials in parts by mass: 30-70 parts of crude polymeric MDI and 10 parts of phase change composite material.
The preparation method of the elastic bonding coating for preventing the aluminum veneer of the heat-insulating and decorative integrated plate from deforming comprises the following steps:
S1, mixing polyalcohol, a catalyst, a surfactant, a foaming agent, a flame retardant and polyamide 1212 elastomer low-foam particles for 1-2 h to obtain a component A;
S2, mixing the polymeric MDI and the phase change composite material, and stirring for 1-1.5 h to obtain a component B;
and S3, mixing the component A and the component B, stirring at a high speed to uniformly mix the components A and the component B, spraying the components A and the component B on the back surface of the aluminum veneer, adhering the heat-insulating core material after reaching a specified thickness, and further assembling the heat-insulating and decorating integrated plate.
Preferably, the catalyst is one or a mixture of a bis (dimethylaminoethyl) ether catalyst and triethylenediamine.
Preferably, the polyol is one or more of polyoxytetramethylene ether glycol with molecular weight of 2000, polycaprolactone glycol with molecular weight of 2000 and polyoxypropylene ether glycol with molecular weight of 2000.
Preferably, the catalyst is one or a mixture of a bis (dimethylaminoethyl) ether catalyst and triethylenediamine.
Preferably, the surfactant is one or more of tween-80, sodium dodecyl benzene sulfonate, silicone oil 8860, polyoxyethylene laurate and polyoxyethylene laurate.
Preferably, the foaming agent is one or more of water, PU-88, pentane and HCFC-141 b.
Preferably, the flame retardant is one or more of aluminum hydroxide, magnesium hydroxide, zinc borate, antimony trioxide, colloidal antimony pentoxide, sodium antimonate, tris (2-carbonylethyl) phosphate hydrochloride, tris (1-chloro-2-propyl) phosphate, ammonium polyphosphate, silicone flame retardant, expandable graphite, and dihydroxymetal oxide.
Preferably, the crude MDI is a polyisocyanate.
Preferably, the phase-change composite material comprises the following raw materials in parts by mass: 80 parts of high-density polyethylene, 20 parts of maleic anhydride grafted polyethylene, 100 parts of polyethylene glycol with molecular weight 10000, 5 parts of RT110 paraffin, 10 parts of erythritol, 15 parts of graphite powder, 3 parts of polyvinylpyrrolidone and 0.5 part of antioxidant.
Preferably, the polyamide 1212 elastomer low-foam particles comprise the following raw materials in parts by mass: 100 parts of nylon 1212 salt, 5-10 parts of dodecanedioic acid and 30-90 parts of polytetramethylene glycol.
Preferably, the preparation method of the polyamide 1212 elastomer low-foam particles comprises the following steps:
Firstly, dodecanedioic acid and dodecanediamine are dissolved in ethanol at 55-65 ℃, the ethanol is filtered after being stirred for 1 hour to obtain nylon 1212 salt, and the nylon 1212 salt is put into a vacuum oven for drying for standby;
Adding the dried nylon 1212 salt and dodecanedioic acid into an autoclave, filling nitrogen into the autoclave, heating the autoclave to 120 ℃, continuously stirring, heating to 220 ℃ after 30min, preserving heat and pressure for 1.5h, releasing the pressure in the autoclave and increasing the temperature in the autoclave to 260 ℃; reacting for about 1h, adding polytetramethylene glycol with molecular weight of 2000 into an autoclave, adding 1-3 parts of tetrabutyl titanate to promote esterification reaction, and carrying out the reaction for 3h at 280 ℃ and 1000Pa pressure to obtain a polyamide 1212 elastomer;
Placing the polyamide 1212 elastomer in an autoclave equipped with a heating jacket and a temperature controller, replacing air in the autoclave with CO2 fluid, filling CO2 into the autoclave to reach 15MPa pressure, heating to 160-180 ℃, preserving heat and maintaining pressure for 2h, rapidly decompressing to the ambient pressure to obtain the polyamide 1212 elastomer low-foam material, and crushing to obtain the polyamide 1212 elastomer low-foam particles.
The invention discloses the following technical effects:
(1) Adjusting the influence of the type and the molecular weight of the polyol in the formula on the performance of the microporous polyurethane elastomer; when the cost of polyurethane foam is reduced, the defects that the bearing capacity of polyurethane is poor, the compression deformation is large, the polyurethane is easy to deform under long-time load and difficult to recover after the elastic coating is foamed are overcome by controlling low foaming.
(2) The surface of the polyamide 1212 elastomer low-foam particles is provided with hydroxyl groups, so that the polyamide 1212 elastomer low-foam particles are easy to disperse in polyurethane stock solution, and particularly the hydroxyl groups on the surfaces of the particles are subjected to expandable cross-linking reaction with diisocyanate, so that interface defects cannot be formed due to polyurethane foaming. The polyamide 1212 elastomer has low foam particles, high toughness, high rebound resilience and high strength, thereby increasing the high temperature rigidity and low temperature toughness of the polyurethane elastic coating.
(3) The invention provides a phase change composite material which is prepared by taking high-density polyethylene, maleic anhydride grafted polyethylene, polyethylene glycol with molecular weight 10000, RT110 paraffin, erythritol, graphite powder, polyvinylpyrrolidone and an antioxidant as raw materials, uniformly mixing, adding the raw materials into a double-screw extruder, and extruding and granulating. The phase-change composite material has very high mechanical strength and elastic modulus, simultaneously has two phase-change temperatures of 40 ℃ and high-temperature phase-change temperature of 120 ℃, and can better regulate adverse effects caused by overlarge temperature fluctuation of the coating in summer.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
The parts of the invention are calculated according to the parts by weight unless otherwise specified.
The preparation method of the polyamide 1212 elastomer low-foam particles comprises the following steps:
Firstly, dodecanedioic acid and dodecanediamine are dissolved in ethanol at 55-65 ℃, the ethanol is filtered after being stirred for 1 hour to obtain nylon 1212 salt, and the nylon 1212 salt is put into a vacuum oven for drying for standby;
Adding the dried nylon 1212 salt and dodecanedioic acid into an autoclave, filling nitrogen into the autoclave, heating the autoclave to 120 ℃, continuously stirring, heating to 220 ℃ after 30min, preserving heat and pressure for 1.5h, releasing the pressure in the autoclave and increasing the temperature in the autoclave to 260 ℃; reacting for about 1h, adding polytetramethylene glycol with molecular weight of 2000 into an autoclave, adding 1-3 parts of tetrabutyl titanate to promote esterification reaction, and carrying out the reaction for 3h at 280 ℃ and 1000Pa pressure to obtain a polyamide 1212 elastomer;
Placing the polyamide 1212 elastomer in an autoclave equipped with a heating jacket and a temperature controller, replacing air in the autoclave with CO2 fluid, filling CO2 into the autoclave to reach 15MPa pressure, heating to 160-180 ℃, preserving heat and maintaining pressure for 2h, rapidly decompressing to the ambient pressure to obtain the polyamide 1212 elastomer low-foam material, and crushing to obtain the polyamide 1212 elastomer low-foam particles.
The properties are shown in Table 1.
Table 1:
Polyamide 1212 elastomers are the mechanical properties of segmented block copolymers, which play a decisive role in the process conditions of extrusion and injection molding, and are generally influenced by the proportion of soft and hard segments in the polymer, the chemical composition, the relative molecular mass distribution, and the method of synthesis. When 5 parts of dodecanedioic acid is added by analysis of tensile strength and elongation at break, the content of terminal carboxylic acid is insufficient during polymerization of nylon salt, resulting in performance deviation from the insufficient polymerization degree of polytetramethylene glycol. When 7.5 parts of dodecanedioic acid is added, the content of terminal carboxylic acid is greatly increased during polymerization of nylon salt, so that the polymerization degree with polytetramethylene glycol is increased, and the performance is improved. When 10 parts of dodecanedioic acid content is added, the content of residual free carboxylic acid increases during polymerization of nylon salt, resulting in polymerization with polytetramethylene glycol to form a low molecular weight oligomer, and performance deviation. Comprehensive analysis 7.5 parts of dodecanedioic acid and 60 parts of butanediol are added into nylon salt for polymerization to obtain the product with optimal performance.
The experiment adopts full water foaming, selects polyols with the molecular weight of 2000 and the functionality of 2, namely polyoxytetramethylene ether glycol, polycaprolactone glycol and polyoxypropylene ether glycol, respectively reacts with polyisocyanate (MDI), and uses bis (dimethylaminoethyl) ether and triethylenediamine as catalysts, and prepares the polyurethane elastomer by adjusting the isocyanate index R of the two to be 1.1 and controlling the gel reaction, so as to study the influence of the three raw materials on the performances of the polyurethane elastomer, as shown in Table 2.
TABLE 2
It can be seen from table 2 that the physical and mechanical properties of polyurethane elastomer synthesized by four different polyols are different, and the polyoxytetramethylene ether glycol and the polyoxypropylene ether glycol have ether bonds with better flexibility in the molecular chains, so that chain segments in the molecular chains are easier to move, and the material has better flexibility, thus having better ball falling rebound resilience. And because the main chain of the molecular chain of the polyoxypropylene ether glycol contains side methyl groups, the arrangement among the molecular chains is not tight enough, and the molecular chain of the polyoxytetramethylene ether glycol contains more methylene with regular arrangement, so that the molecular chain arrangement is ordered, the crystallization is more favorable, and the crystallization degree is greater than that of the polyoxypropylene ether glycol type polyurethane elastomer. It is also because of the existence of the crystal area, the hardness, tensile strength and elongation at break of the material are improved, and the physical and mechanical properties of the polyoxytetramethylene ether glycol-type microporous polyurethane elastomer are better than those of the polyoxypropylene ether glycol-type microporous polyurethane elastomer.
Polycaprolactone diols are polyester polyols with more polar ester groups present between their molecular chains, thereby enhancing the inter-molecular attractive forces. And because the polyurethane elastomer is formed by soft segments and hard segments alternately, after the relative attractive force between molecular chains is strong, a large number of hydrogen bonds are formed between the soft segments and the hard segments, and further the intermolecular interaction is promoted, so that the material has higher tensile strength and tensile elongation. It can also be seen from the table that the tensile strength of the polyester type material is significantly better than that of the polyether type material. The drop rebound resilience performance of the polyester material is inferior to that of the polyether material, because the interaction force among molecular chains greatly limits the movement of the molecular chains, so that the flexibility of the material is reduced, and the impact rebound resilience performance is further reduced.
The product performance of the polyoxytetramethylene ether glycol-type polyurethane elastomer is best through comprehensive analysis.
The technical scheme of the invention is further described by the following examples.
Example 1
The elastic bonding coating for preventing the aluminum veneer from deforming of the heat-insulating and decorating integrated plate consists of a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 75 parts of molecular weight 2000 polyoxytetramethylene ether glycol, 3 parts of bis (dimethylaminoethyl) ether catalyst, 2 parts of triethylenediamine catalyst, 4 parts of silicone oil 8860 surfactant, 2 parts of water, 15 parts of aluminum hydroxide flame retardant and 5 parts of polyamide 1212 elastomer low foam particles; wherein the component B comprises the following raw materials in parts by mass: 50 parts of crude polymeric MDI and 10 parts of phase change composite material;
The phase-change composite material comprises the following raw materials in parts by mass: 80 parts of high-density polyethylene, 20 parts of maleic anhydride grafted polyethylene, 100 parts of polyethylene glycol with molecular weight 10000, 5 parts of RT110 paraffin, 10 parts of erythritol, 15 parts of graphite powder, 3 parts of polyvinylpyrrolidone and 0.5 part of antioxidant.
The preparation method of the elastic bonding coating for preventing the aluminum veneer of the heat-insulating and decorative integrated plate from deforming comprises the following steps:
S1, mixing polyalcohol, a catalyst, a surfactant, a foaming agent, a flame retardant and polyamide 1212 elastomer low-foam particles for 1-2 h to obtain a component A;
s2, mixing the crude polymeric MDI and the phase change composite material, and stirring for 1-1.5 h to obtain a component B;
and S3, mixing the component A and the component B, stirring at a high speed to uniformly mix the components A and the component B, spraying the components A and the component B on the back surface of the aluminum veneer, adhering the heat-insulating core material after reaching a specified thickness, and further assembling the heat-insulating and decorating integrated plate.
Preferably, the catalyst is one or a mixture of a bis (dimethylaminoethyl) ether catalyst and triethylenediamine.
The polyamide 1212 elastomer low foam particles comprise the following raw materials in parts by mass: 100 parts of nylon 1212 salt, 7.5 parts of dodecanedioic acid and 60 parts of polytetramethylene glycol;
Firstly, dodecanedioic acid and dodecanediamine are dissolved in ethanol at 55-65 ℃, the ethanol is filtered after being stirred for 1 hour, 100 parts of nylon 1212 salt is obtained, and the nylon 1212 salt is put into a vacuum oven for drying for standby;
Adding dried nylon 1212 salt and 7.5 parts of dodecanedioic acid into an autoclave, filling nitrogen into the autoclave, heating the autoclave to 120 ℃, continuously stirring, heating to 220 ℃ after 30min, preserving heat and pressure for 1.5h, releasing the pressure in the autoclave and increasing the temperature in the autoclave to 260 ℃; adding 80 parts of polytetramethylene glycol with the molecular weight of 2000 into an autoclave, and adding 1-3 parts of tetrabutyl titanate to promote esterification reaction, wherein the reaction is carried out for 3 hours at the temperature of 280 ℃ and the pressure of 1000Pa to obtain a polyamide 1212 elastomer;
Placing the polyamide 1212 elastomer in an autoclave equipped with a heating jacket and a temperature controller, replacing air in the autoclave with CO2 fluid, filling CO2 into the autoclave to reach 15MPa pressure, heating to 160-180 ℃, preserving heat and maintaining pressure for 2h, rapidly decompressing to the ambient pressure to obtain the polyamide 1212 elastomer low-foam material, and crushing to obtain the polyamide 1212 elastomer low-foam particles.
Example 2
The low-foam polyurethane elastic coating was prepared by replacing the addition amount of the polyamide 1212 elastomer low-foam particles in example 1 with 10 parts (5 parts in example 1) and the other technical indexes and the preparation method are the same as in example 1.
Example 3
The low-foam polyurethane elastic coating was prepared by replacing the addition amount of the polyamide 1212 elastomer low-foam particles in example 1 with 15 parts, and the other technical indexes and the preparation method were the same as those in example 1.
Example 4
The low-foam polyurethane elastic coating was prepared by replacing the addition amount of the polyamide 1212 elastomer low-foam particles in example 1 with 20 parts, and the other technical indexes and the preparation method were the same as those in example 1.
Example 5
The low-foam polyurethane elastic coating is prepared by replacing the crude MDI in example 3 with 30 parts, and the other technical indexes and the preparation method are the same as those of example 3.
Example 6
The low-foam polyurethane elastic coating is prepared by replacing the crude MDI in example 3 with 70 parts, and the other technical indexes and the preparation method are the same as those of example 3.
Performance testing
The polyurethane elastic coatings prepared in examples 1 to 6 were tested for properties such as hardness, tensile strength, elongation, tear strength, etc., and the test results are shown in table 3.
TABLE 3 Table 3
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Hardness, shore A | 65 | 69 | 71 | 74 | 63 | 81 |
| Tensile strength, MPa | 9.1 | 9.4 | 9.6 | 9.5 | 7.8 | 8.4 |
| Elongation at elongation% of | 384 | 401 | 425 | 412 | 364 | 285 |
| Tear Strength, kN/m | 9.1 | 9.7 | 10.6 | 10.2 | 7.5 | 10.5 |
As can be seen from Table 3, the polyurethane elastic coatings prepared in examples 1 to 6 were optimized in terms of hardness, tensile strength, elongation, tear strength, etc. as the content of the polyamide 1212 elastomer low-foam particles was increased, but at 20 parts, some decrease in performance occurred due to increased particle interface bonding defects; when the content of MDI is too low, internal reaction is incomplete, negative effects are caused, and the performance index is generally not high. When the MDI content is too high, the NCO group content is too high, so that brittleness is increased, the extensibility is reduced, and the performance index is generally not high. As a result of comparison, it was found that the polyurethane elastic coating prepared under the conditions of example 3 had the best performance.
Claims (9)
1. Elastic bonding coating for preventing aluminum veneer deformation of heat-insulating and decorating integrated plate, and is characterized in that: the composite material consists of a component A and a component B, wherein the component A comprises the following raw materials in parts by mass: 75 parts of polyol, 5 parts of catalyst, 4 parts of surfactant, 2 parts of foaming agent, 15 parts of flame retardant and 1 to 20 parts of polyamide 1212 elastomer low-foam particles; wherein the component B comprises the following raw materials in parts by mass: 30-70 parts of crude polymeric MDI and 10 parts of phase change composite material.
2. The preparation method of the elastic bonding coating for preventing the aluminum veneer from deforming of the heat-insulating and decorating integrated plate is characterized by comprising the following steps of: the method comprises the following steps:
S1, mixing polyalcohol, a catalyst, a surfactant, a foaming agent, a flame retardant and polyamide 1212 elastomer low-foam particles for 1-2 h to obtain a component A;
S2, mixing the polymeric MDI and the phase change composite material, and stirring for 1-1.5 h to obtain a component B;
and S3, mixing the component A and the component B, stirring at a high speed to uniformly mix the components A and the component B, spraying the components A and the component B on the back surface of the aluminum veneer, adhering the heat-insulating core material after reaching a specified thickness, and further assembling the heat-insulating and decorating integrated plate.
3. The method for preparing the elastic bonding coating for preventing the aluminum veneer from deforming of the heat-insulating and decorating integrated plate according to claim 2, which is characterized in that: the catalyst is one or a mixture of a double ether catalyst and triethylenediamine.
4. The method for preparing the elastic bonding coating for preventing the aluminum veneer from deforming of the heat-insulating and decorating integrated plate according to claim 2, which is characterized in that: the polyalcohol is one or more of polyoxytetramethylene ether glycol with molecular weight of 2000, polycaprolactone glycol with molecular weight of 2000 and polyoxypropylene ether glycol with molecular weight of 2000.
5. The method for preparing the elastic bonding coating for preventing the aluminum veneer from deforming of the heat-insulating and decorating integrated plate according to claim 2, which is characterized in that: the catalyst is one or a mixture of a double ether catalyst and triethylenediamine.
6. The method for preparing the elastic bonding coating for preventing the aluminum veneer from deforming of the heat-insulating and decorating integrated plate according to claim 2, which is characterized in that: the flame retardant is one or a mixture of more of aluminum hydroxide, magnesium hydroxide, zinc borate, antimony trioxide, colloidal antimony pentoxide, sodium antimonate, ammonium polyphosphate, organic silicon flame retardant, expandable graphite and dihydroxyl metal oxide.
7. The method for preparing the elastic bonding coating for preventing the aluminum veneer from deforming of the heat-insulating and decorating integrated plate according to claim 2, which is characterized in that: the phase-change composite material comprises the following raw materials in parts by mass: 80 parts of high-density polyethylene, 20 parts of maleic anhydride grafted polyethylene, 100 parts of polyethylene glycol with molecular weight 10000, 5 parts of RT110 paraffin, 10 parts of erythritol, 15 parts of graphite powder, 3 parts of polyvinylpyrrolidone and 0.5 part of antioxidant.
8. The method for preparing the elastic bonding coating for preventing the aluminum veneer from deforming of the heat-insulating and decorating integrated plate according to claim 2, which is characterized in that: the polyamide 1212 elastomer low-foam particles comprise the following raw materials in parts by mass: 100 parts of nylon 1212 salt, 5-10 parts of dodecanedioic acid and 30-90 parts of polytetramethylene glycol.
9. The method for preparing the elastic bonding coating for preventing the aluminum veneer from deforming of the heat-insulating and decorating integrated plate according to claim 8, which is characterized in that: the preparation method of the polyamide 1212 elastomer low-foam particles comprises the following steps:
Firstly, dodecanedioic acid and dodecanediamine are dissolved in ethanol at 55-65 ℃, the ethanol is filtered after being stirred for 1 hour to obtain nylon 1212 salt, and the nylon 1212 salt is put into a vacuum oven for drying for standby;
Adding the dried nylon 1212 salt and dodecanedioic acid into an autoclave, filling nitrogen into the autoclave, heating the autoclave to 120 ℃, continuously stirring, heating to 220 ℃ after 30min, preserving heat and pressure for 1.5h, releasing the pressure in the autoclave and increasing the temperature in the autoclave to 260 ℃; reacting for about 1h, adding polytetramethylene glycol with molecular weight of 2000 into an autoclave, adding 1-3 parts of tetrabutyl titanate to promote esterification reaction, and carrying out the reaction for 3h at 280 ℃ and 1000Pa pressure to obtain a polyamide 1212 elastomer;
Placing the polyamide 1212 elastomer in an autoclave equipped with a heating jacket and a temperature controller, replacing air in the autoclave with CO2 fluid, filling CO2 into the autoclave to reach 15MPa pressure, heating to 160-180 ℃, preserving heat and maintaining pressure for 2h, rapidly decompressing to the ambient pressure to obtain the polyamide 1212 elastomer low-foam material, and crushing to obtain the polyamide 1212 elastomer low-foam particles.
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