CN116004170A - Yellowing-resistant polyurethane film for laminated glass and preparation method thereof - Google Patents
Yellowing-resistant polyurethane film for laminated glass and preparation method thereof Download PDFInfo
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- CN116004170A CN116004170A CN202211507906.3A CN202211507906A CN116004170A CN 116004170 A CN116004170 A CN 116004170A CN 202211507906 A CN202211507906 A CN 202211507906A CN 116004170 A CN116004170 A CN 116004170A
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- polyurethane film
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- 229920006264 polyurethane film Polymers 0.000 title claims abstract description 44
- 238000004383 yellowing Methods 0.000 title claims abstract description 25
- 239000005340 laminated glass Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229920005862 polyol Polymers 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 150000003077 polyols Chemical class 0.000 claims abstract description 37
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 31
- 239000004417 polycarbonate Substances 0.000 claims abstract description 31
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 18
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 aliphatic diols Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 28
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 24
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 15
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 15
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 15
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- GAGSAAHZRBTRGD-UHFFFAOYSA-N oxirane;oxolane Chemical compound C1CO1.C1CCOC1 GAGSAAHZRBTRGD-UHFFFAOYSA-N 0.000 claims description 13
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 13
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 229940116335 lauramide Drugs 0.000 claims description 12
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000391 magnesium silicate Substances 0.000 claims description 12
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 12
- 235000019792 magnesium silicate Nutrition 0.000 claims description 12
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 10
- 238000009849 vacuum degassing Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000007670 refining Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 229910019089 Mg-Fe Inorganic materials 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004814 polyurethane Substances 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 238000012360 testing method Methods 0.000 description 25
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 1
- 238000012704 multi-component copolymerization Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the field of polyurethane films, and discloses a yellowing-resistant polyurethane film for laminated glass and a preparation method thereof; according to the invention, the dimethyl carbonate and various aliphatic diols are used as raw materials to synthesize the polycarbonate polyol, so that the light transmittance of the laminated glass is improved; meanwhile, the anti-yellowing agent has stronger anti-yellowing performance; 1, 4-cyclohexanedimethanol is used for replacing 1, 6-hexanediol in the synthesis process, so that the viscosity of the polyurethane film is improved. The prepared polyol product is further refined, so that the catalyst residues are effectively removed, and the catalyst residues are removed from the molecular chain segments, so that the storage stability and the light transmittance of the polyurethane film are improved. A small amount of silicon dioxide nano particles wrapped by cerium and titanium are added, so that the ultraviolet light is reflected, scattered, absorbed and blocked while the light transmittance is basically unchanged, the yellowing phenomenon of polyurethane is further reduced, and the yellowing resistance of the polyurethane film is improved.
Description
Technical Field
The invention relates to the field of polyurethane films, in particular to a yellowing-resistant polyurethane film for laminated glass and a preparation method thereof.
Background
Polyurethane film prepared from polyurethane as a main material is widely used as an important bonding material in the preparation process of laminated glass due to its unique flexibility and impact resistance.
Polyurethane is used as a material which is easy to age and degrade, and ultraviolet rays have a destructive effect on the polyurethane under the irradiation of sunlight. The polyurethane film material in the inorganic laminated glass is a natural aging sensitive material, and the problems of yellowing of the film, reduced adhesive property and the like can occur under solar radiation.
Therefore, the invention provides the yellowing-resistant polyurethane film for laminated glass.
Disclosure of Invention
The invention aims to provide a yellowing-resistant polyurethane film for laminated glass and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a yellowing-resistant polyurethane film for laminated glass comprises the following steps:
s1: adding acrylic polyol and lauramide into N, N-dimethylformamide, uniformly mixing, adding modified silicon dioxide nano particles, uniformly stirring, and sieving to obtain a nano particle mixture;
s2: and uniformly mixing polycarbonate polyol and tetrahydrofuran-ethylene oxide copolyether, adding isophorone diisocyanate, a nanoparticle mixture and triphenylbismuth, uniformly mixing, vacuum degassing, pouring into a tetrafluoroethylene mold, curing, and drying to obtain the polyurethane film.
Further, in the step S1, the modified silica nanoparticle is prepared as follows:
adding cerium nitrate and titanium sulfate into a polyvinyl alcohol solution, adding acetic acid and ammonium hydroxide to adjust the pH of the solution to 4, adding silicon dioxide nano particles, heating and stirring, drying, calcining and grinding to obtain modified silicon dioxide nano particles.
Further, the cerium nitrate: titanium sulfate: the mass ratio of the silicon dioxide is 1: (0.8-1): 7.5; the heating and stirring temperature is 75-80 ℃, the drying temperature is 100-105 ℃, and the calcining temperature is 540-550 ℃; the particle size of the modified nano-particles is 20-50nm.
Further, in the step S2, the polycarbonate polyol is prepared as follows:
uniformly mixing dimethyl carbonate, 1, 5-pentanediol and a catalyst, heating for reaction, filtering, and evaporating under reduced pressure to obtain a carbonate monomer; and uniformly mixing the carbonate monomer, 1, 4-cyclohexanedimethanol and a catalyst, heating for reaction, filtering, and refining to obtain the polycarbonate polyol.
Further, the reaction process is carried out under the atmosphere of nitrogen; the dimethyl carbonate: the mass ratio of the 1, 5-pentanediol is (6-10): 1, a step of; the carbonate monomer: the mass ratio of the 1, 4-cyclohexanedimethanol is (1-1.25): 1, a step of; the adding amount of the catalyst in the carbonic ester monomer is 1% of the total mass of the dimethyl carbonate and the 1, 5-pentanediol; the catalyst is added into the polycarbonate polyol, wherein the addition amount of the catalyst is 1% of the total mass of the carbonate monomer and the 1, 4-cyclohexanedimethanol.
Further, in the carbonate monomer, the heating reaction temperature is 90-100 ℃ and the time is 5 hours; the reduced pressure evaporating temperature is 100-110 deg.c and the pressure is-0.05-0.1 MPa.
Further, in the polycarbonate polyol, the heating reaction step is that the reaction is carried out for 1h at 100 ℃ and for 4h at 180 ℃.
Further, the catalyst is prepared by the following method:
and uniformly mixing the magnesium solution and the ferrotitanium solution, adding a precipitator, crystallizing, filtering, washing and drying to obtain the catalyst.
Further, the magnesium solution is magnesium nitrate solution with the concentration of 0.06mol/L; the iron-titanium solution is a mixed solution of ferric nitrate and titanium sulfate, and the concentration is 0.2mol/L; the precipitant is a mixed solution of 2mol/L sodium hydroxide and 1.5mol/L sodium carbonate.
Further, the refining process is to add phosphoric acid into the precipitate, mix evenly, add magnesium silicate, stir, suction filter, vacuum drying; the adding amount of the phosphoric acid is 0.7-0.8% of the mass of the precipitate; the adding amount of the magnesium silicate is 0.5-0.6% of the mass of the precipitate; the refining process is carried out at 85-90deg.C for 30-45min.
Further, the pH of the solution in the refining process is 7, and the pH solution is regulated to 0.5mol/L sodium hydroxide.
Further, in the step S1, the acrylic polyol: lauramide: the mass ratio of the modified silicon dioxide nano particles is 75:1: (100-125); in the step S2, 5-10 parts of polycarbonate polyol, 40-60 parts of tetrahydrofuran-ethylene oxide copolyether, 20-30 parts of isophorone diisocyanate, 1-2 parts of nanoparticle mixture and 0.1-0.5 part of triphenylbismuth in parts by weight.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, the dimethyl carbonate and various aliphatic diols are used as raw materials to synthesize the polycarbonate polyol through multi-component copolymerization by an ester exchange method, so that the internal regular and orderly structure of the polyol is effectively broken, the crystallinity of the polyurethane film prepared by the polyol is reduced, and the light transmittance of the polyurethane film is greatly improved; meanwhile, as the polycarbonate polyol and the isophorone diisocyanate belong to aliphatic groups, the polyol structure does not contain ether bonds, and the molecular structure of the isophorone diisocyanate does not contain benzene rings, the polycarbonate polyol and the isophorone diisocyanate have stronger yellowing resistance under illumination; 1, 4-cyclohexanedimethanol is used for replacing 1, 6-hexanediol in the synthesis process, and the self cyclic structure is utilized to improve the viscosity of the polyurethane film. The polyol product obtained by the preparation is further refined, catalyst residues are effectively removed, the catalyst residues are removed from the chain ends of molecules, the influence of the catalyst residues in the subsequent polymerization process is reduced, and the storage stability and the light transmittance of the polyurethane film are improved.
In the preparation process, a small amount of silicon dioxide nano particles wrapped by cerium and titanium are added, the nano particles are embedded in the polyurethane film, the light transmittance is basically unchanged, and the ultraviolet light is reflected, scattered, absorbed and blocked, so that the occurrence of yellowing of the polyurethane film is further reduced, and the yellowing resistance of the polyurethane film is improved.
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.
In the following examples, dimethyl carbonate is supplied by Shanghai Runner chemical Co., ltd, and tetrahydrofuran-ethylene oxide copolyether is supplied by dawn chemical industry institute with a relative molecular weight of 4100; the acrylic polyol is prepared by the method of literature (study on stability of acrylic polyol dispersion and preparation of fluorine-containing coating).
The catalyst is prepared by the following steps:
mixing 50mL of magnesium solution and 50mL of ferrotitanium solution uniformly, heating to 65 ℃, titrating the precipitant by using a basic burette, stopping titration when the pH value is 10, heating a sealed reaction container to 80 ℃ for crystallization 24 hours, filtering, washing 3 by deionized water, drying at 60 ℃ for 12 hours, grinding, and sieving by using a 200-mesh screen powder to obtain the catalyst.
Example 1
S1: adding 1g of cerium nitrate and 0.8g of titanium sulfate into 50mL of polyvinyl alcohol solution, adding 1M of acetic acid and ammonium hydroxide solution with the concentration of 25% to adjust the pH of the solution to 4, adding 7.5g of silica nanoparticles, heating to 75 ℃, stirring for 4 hours, drying at 100 ℃ for 8 hours, calcining at 550 ℃ for 2 hours, and grinding to obtain modified silica nanoparticles with the particle size of 30 nm;
s2: adding 75g of acrylic polyol and 1g of lauramide into 50mLN, N-dimethylformamide, uniformly mixing, adding 100g of modified silica nanoparticles, stirring for 4 hours, and passing through a sieve with a pore diameter of 37 mu m to obtain a nanoparticle mixture;
s3: uniformly mixing 60g of dimethyl carbonate, 10g of 1, 5-pentanediol and 0.7g of catalyst, heating to 90 ℃ under the nitrogen atmosphere for reaction for 5 hours, suction filtering, and evaporating under reduced pressure at 100 ℃ and minus 0.05MPa to obtain carbonate monomers; uniformly mixing 10g of carbonate monomer, 10g of 1, 4-cyclohexanedimethanol and 0.2g of catalyst, reacting for 1h at 100 ℃, reacting for 4h at 180 ℃, suction filtering, adding 0.15g of phosphoric acid into the precipitate, uniformly mixing, adding 0.5mol/L of sodium hydroxide to adjust the pH to 7, adding 0.08g of magnesium silicate to stir, adjusting the pH to 7, suction filtering, and vacuum drying for 30min at 85 ℃ to obtain polycarbonate polyol;
s4: 5g of polycarbonate polyol and 40g of tetrahydrofuran-ethylene oxide copolyether are uniformly mixed, 20g of isophorone diisocyanate, 1g of nanoparticle mixture and 0.2g of triphenylbismuth are added to be uniformly mixed, the mixture is placed in a vacuum oven at 60 ℃ for vacuum degassing for 1h, poured into a tetrafluoroethylene mold for curing for 7d at 60 ℃, and the mixture is dried for 7d at normal temperature, so as to obtain the polyurethane film.
And (3) testing: yellowness index test: the test piece was cut into a rectangle with a size of 30X 10mm according to HG/T3689-2014A, and measured by a 3nh spectrocolorimeter. The irradiation time was 300 hours, and the sample was tested for yellowness, as shown in the following table.
Example 2
S1: adding 1g of cerium nitrate and 0.8g of titanium sulfate into 50mL of polyvinyl alcohol solution, adding 1M of acetic acid and ammonium hydroxide solution with the concentration of 25% to adjust the pH of the solution to 4, adding 7.5g of silica nanoparticles, heating to 75 ℃, stirring for 4 hours, drying at 100 ℃ for 8 hours, calcining at 550 ℃ for 2 hours, and grinding to obtain modified silica nanoparticles with the particle size of 30 nm;
s2: adding 75g of acrylic polyol and 1g of lauramide into 50mLN, N-dimethylformamide, uniformly mixing, adding 100g of modified silica nanoparticles, stirring for 4 hours, and passing through a sieve with a pore diameter of 37 mu m to obtain a nanoparticle mixture;
s3: uniformly mixing 70g of dimethyl carbonate, 10g of 1, 5-pentanediol and 0.8g of catalyst, heating to 90 ℃ under the nitrogen atmosphere for reaction for 5 hours, suction filtering, and evaporating under reduced pressure at 100 ℃ and minus 0.05MPa to obtain carbonate monomers; uniformly mixing 10g of carbonate monomer, 10g of 1, 4-cyclohexanedimethanol and 0.2g of catalyst, reacting for 1h at 100 ℃, reacting for 4h at 180 ℃, suction filtering, adding 0.15g of phosphoric acid into the precipitate, uniformly mixing, adding 0.5mol/L of sodium hydroxide to adjust the pH to 7, adding 0.08g of magnesium silicate to stir, adjusting the pH to 7, suction filtering, and vacuum drying for 30min at 85 ℃ to obtain polycarbonate polyol;
s4: 5g of polycarbonate polyol and 40g of tetrahydrofuran-ethylene oxide copolyether are uniformly mixed, 20g of isophorone diisocyanate, 1g of nanoparticle mixture and 0.2g of triphenylbismuth are added to be uniformly mixed, the mixture is placed in a vacuum oven at 60 ℃ for vacuum degassing for 1h, poured into a tetrafluoroethylene mold for curing for 7d at 60 ℃, and the mixture is dried for 7d at normal temperature, so as to obtain the polyurethane film.
And (3) testing: yellowness index test: the test piece was cut into a rectangle with a size of 30X 10mm according to HG/T3689-2014A, and measured by a 3nh spectrocolorimeter. The irradiation time was 300 hours, and the sample was tested for yellowness, as shown in the following table.
Example 3
S1: adding 1g of cerium nitrate and 0.8g of titanium sulfate into 50mL of polyvinyl alcohol solution, adding 1M of acetic acid and ammonium hydroxide solution with the concentration of 25% to adjust the pH of the solution to 4, adding 7.5g of silica nanoparticles, heating to 75 ℃, stirring for 4 hours, drying at 100 ℃ for 8 hours, calcining at 550 ℃ for 2 hours, and grinding to obtain modified silica nanoparticles with the particle size of 30 nm;
s2: adding 75g of acrylic polyol and 1g of lauramide into 50mLN, N-dimethylformamide, uniformly mixing, adding 100g of modified silica nanoparticles, stirring for 4 hours, and passing through a sieve with a pore diameter of 37 mu m to obtain a nanoparticle mixture;
s3: uniformly mixing 80g of dimethyl carbonate, 10g of 1, 5-pentanediol and 0.9g of catalyst, heating to 90 ℃ under the nitrogen atmosphere for reaction for 5 hours, suction filtering, and evaporating under reduced pressure at 100 ℃ and minus 0.05MPa to obtain carbonate monomers; uniformly mixing 10g of carbonate monomer, 10g of 1, 4-cyclohexanedimethanol and 0.2g of catalyst, reacting for 1h at 100 ℃, reacting for 4h at 180 ℃, suction filtering, adding 0.15g of phosphoric acid into the precipitate, uniformly mixing, adding 0.5mol/L of sodium hydroxide to adjust the pH to 7, adding 0.08g of magnesium silicate to stir, adjusting the pH to 7, suction filtering, and vacuum drying for 30min at 85 ℃ to obtain polycarbonate polyol;
s4: 5g of polycarbonate polyol and 40g of tetrahydrofuran-ethylene oxide copolyether are uniformly mixed, 20g of isophorone diisocyanate, 1g of nanoparticle mixture and 0.2g of triphenylbismuth are added to be uniformly mixed, the mixture is placed in a vacuum oven at 60 ℃ for vacuum degassing for 1h, poured into a tetrafluoroethylene mold for curing for 7d at 60 ℃, and the mixture is dried for 7d at normal temperature, so as to obtain the polyurethane film.
And (3) testing: yellowness index test: the test piece was cut into a rectangle with a size of 30X 10mm according to HG/T3689-2014A, and measured by a 3nh spectrocolorimeter. The irradiation time was 300 hours, and the sample was tested for yellowness, as shown in the following table.
Example 4
S1: adding 1g of cerium nitrate and 0.8g of titanium sulfate into 50mL of polyvinyl alcohol solution, adding 1M of acetic acid and ammonium hydroxide solution with the concentration of 25% to adjust the pH of the solution to 4, adding 7.5g of silica nanoparticles, heating to 75 ℃, stirring for 4 hours, drying at 100 ℃ for 8 hours, calcining at 550 ℃ for 2 hours, and grinding to obtain modified silica nanoparticles with the particle size of 30 nm;
s2: adding 75g of acrylic polyol and 1g of lauramide into 50mLN, N-dimethylformamide, uniformly mixing, adding 100g of modified silica nanoparticles, stirring for 4 hours, and passing through a sieve with a pore diameter of 37 mu m to obtain a nanoparticle mixture;
s3: uniformly mixing 90g of dimethyl carbonate, 10g of 1, 5-pentanediol and 1.0g of catalyst, heating to 90 ℃ under the nitrogen atmosphere for reaction for 5 hours, suction filtering, and evaporating under reduced pressure at 100 ℃ and minus 0.05MPa to obtain carbonate monomers; uniformly mixing 10g of carbonate monomer, 10g of 1, 4-cyclohexanedimethanol and 0.2g of catalyst, reacting for 1h at 100 ℃, reacting for 4h at 180 ℃, suction filtering, adding 0.15g of phosphoric acid into the precipitate, uniformly mixing, adding 0.5mol/L of sodium hydroxide to adjust the pH to 7, adding 0.08g of magnesium silicate to stir, adjusting the pH to 7, suction filtering, and vacuum drying for 30min at 85 ℃ to obtain polycarbonate polyol;
s4: 5g of polycarbonate polyol and 40g of tetrahydrofuran-ethylene oxide copolyether are uniformly mixed, 20g of isophorone diisocyanate, 1g of nanoparticle mixture and 0.2g of triphenylbismuth are added to be uniformly mixed, the mixture is placed in a vacuum oven at 60 ℃ for vacuum degassing for 1h, poured into a tetrafluoroethylene mold for curing for 7d at 60 ℃, and the mixture is dried for 7d at normal temperature, so as to obtain the polyurethane film.
And (3) testing: yellowness index test: the test piece was cut into a rectangle with a size of 30X 10mm according to HG/T3689-2014A, and measured by a 3nh spectrocolorimeter. The irradiation time was 300 hours, and the sample was tested for yellowness, as shown in the following table.
Example 5
S1: adding 1g of cerium nitrate and 0.8g of titanium sulfate into 50mL of polyvinyl alcohol solution, adding 1M of acetic acid and ammonium hydroxide solution with the concentration of 25% to adjust the pH of the solution to 4, adding 7.5g of silica nanoparticles, heating to 75 ℃, stirring for 4 hours, drying at 100 ℃ for 8 hours, calcining at 550 ℃ for 2 hours, and grinding to obtain modified silica nanoparticles with the particle size of 30 nm;
s2: adding 75g of acrylic polyol and 1g of lauramide into 50mLN, N-dimethylformamide, uniformly mixing, adding 100g of modified silica nanoparticles, stirring for 4 hours, and passing through a sieve with a pore diameter of 37 mu m to obtain a nanoparticle mixture;
s3: uniformly mixing 100g of dimethyl carbonate, 10g of 1, 5-pentanediol and 1.1g of catalyst, heating to 90 ℃ under nitrogen atmosphere for reaction for 5 hours, suction filtering, and evaporating under reduced pressure at 100 ℃ and minus 0.05MPa to obtain carbonate monomers; uniformly mixing 10g of carbonate monomer, 10g of 1, 4-cyclohexanedimethanol and 0.2g of catalyst, reacting for 1h at 100 ℃, reacting for 4h at 180 ℃, suction filtering, adding 0.15g of phosphoric acid into the precipitate, uniformly mixing, adding 0.5mol/L of sodium hydroxide to adjust the pH to 7, adding 0.08g of magnesium silicate to stir, adjusting the pH to 7, suction filtering, and vacuum drying for 30min at 85 ℃ to obtain polycarbonate polyol;
s4: 5g of polycarbonate polyol and 40g of tetrahydrofuran-ethylene oxide copolyether are uniformly mixed, 20g of isophorone diisocyanate, 1g of nanoparticle mixture and 0.2g of triphenylbismuth are added to be uniformly mixed, the mixture is placed in a vacuum oven at 60 ℃ for vacuum degassing for 1h, poured into a tetrafluoroethylene mold for curing for 7d at 60 ℃, and the mixture is dried for 7d at normal temperature, so as to obtain the polyurethane film.
And (3) testing: yellowness index test: the test piece was cut into a rectangle with a size of 30X 10mm according to HG/T3689-2014A, and measured by a 3nh spectrocolorimeter. The irradiation time was 300 hours, and the sample was tested for yellowness, as shown in the following table.
Comparative example 1
S1: adding 1g of cerium nitrate and 0.8g of titanium sulfate into 50mL of polyvinyl alcohol solution, adding 1M of acetic acid and ammonium hydroxide solution with the concentration of 25% to adjust the pH of the solution to 4, adding 7.5g of silica nanoparticles, heating to 75 ℃, stirring for 4 hours, drying at 100 ℃ for 8 hours, calcining at 550 ℃ for 2 hours, and grinding to obtain modified silica nanoparticles with the particle size of 30 nm;
s2: adding 75g of acrylic polyol and 1g of lauramide into 50mLN, N-dimethylformamide, uniformly mixing, adding 100g of modified silica nanoparticles, stirring for 4 hours, and passing through a sieve with a pore diameter of 37 mu m to obtain a nanoparticle mixture;
s3: uniformly mixing 60g of dimethyl carbonate, 10g of 1, 5-pentanediol and 0.7g of catalyst, heating to 90 ℃ under the nitrogen atmosphere for reaction for 5 hours, suction filtering, and evaporating under reduced pressure at 100 ℃ and minus 0.05MPa to obtain carbonate monomers; uniformly mixing 10g of carbonate monomer, 10g of 1, 6-hexanediol and 0.2g of catalyst, reacting for 1h at 100 ℃, reacting for 4h at 180 ℃, suction filtering, adding 0.15g of phosphoric acid into the precipitate, uniformly mixing, adding 0.5mol/L of sodium hydroxide to adjust the pH to 7, adding 0.08g of magnesium silicate, stirring, adjusting the pH to 7, suction filtering, and vacuum drying for 30min at 85 ℃ to obtain polycarbonate polyol;
s4: 5g of polycarbonate polyol and 40g of tetrahydrofuran-ethylene oxide copolyether are uniformly mixed, 20g of isophorone diisocyanate, 1g of nanoparticle mixture and 0.2g of triphenylbismuth are added to be uniformly mixed, the mixture is placed in a vacuum oven at 60 ℃ for vacuum degassing for 1h, poured into a tetrafluoroethylene mold for curing for 7d at 60 ℃, and the mixture is dried for 7d at normal temperature, so as to obtain the polyurethane film.
And (3) testing: yellowness index test: the test piece was cut into a rectangle with a size of 30X 10mm according to HG/T3689-2014A, and measured by a 3nh spectrocolorimeter. The irradiation time was 300 hours, and the sample was tested for yellowness, as shown in the following table.
Comparative example 2
S1: adding 1g of cerium nitrate and 0.8g of titanium sulfate into 50mL of polyvinyl alcohol solution, adding 1M of acetic acid and ammonium hydroxide solution with the concentration of 25% to adjust the pH of the solution to 4, adding 7.5g of silica nanoparticles, heating to 75 ℃, stirring for 4 hours, drying at 100 ℃ for 8 hours, calcining at 550 ℃ for 2 hours, and grinding to obtain modified silica nanoparticles with the particle size of 30 nm;
s2: adding 75g of acrylic polyol and 1g of lauramide into 50mLN, N-dimethylformamide, uniformly mixing, adding 100g of modified silica nanoparticles, stirring for 4 hours, and passing through a sieve with a pore diameter of 37 mu m to obtain a nanoparticle mixture;
s3: uniformly mixing 60g of dimethyl carbonate, 10g of 1, 5-pentanediol and 0.2g of catalyst, heating to 90 ℃ under the nitrogen atmosphere for reaction for 5 hours, suction filtering, and evaporating under reduced pressure at 100 ℃ and minus 0.05MPa to obtain carbonate monomers; uniformly mixing 10g of carbonate monomer, 10g of 1, 4-cyclohexanedimethanol and 0.2g of catalyst, reacting for 1h at 100 ℃, reacting for 4h at 180 ℃, suction filtering, adding 0.15g of phosphoric acid into the precipitate, uniformly mixing, adding 0.5mol/L of sodium hydroxide to adjust the pH to 7, adding 0.08g of magnesium silicate to stir, adjusting the pH to 7, suction filtering, and vacuum drying for 30min at 85 ℃ to obtain polycarbonate polyol;
s4: 5g of polycarbonate polyol and 40g of tetrahydrofuran-ethylene oxide copolyether are uniformly mixed, 20g of isophorone diisocyanate, 1g of nanoparticle mixture and 0.2g of triphenylbismuth are added to be uniformly mixed, the mixture is placed in a vacuum oven at 60 ℃ for vacuum degassing for 1h, poured into a tetrafluoroethylene mold for curing for 7d at 60 ℃, and the mixture is dried for 7d at normal temperature, so as to obtain the polyurethane film.
And (3) testing: yellowness index test: the test piece was cut into a rectangle with a size of 30X 10mm according to HG/T3689-2014A, and measured by a 3nh spectrocolorimeter. The irradiation time was 300 hours, and the sample was tested for yellowness, as shown in the following table.
Comparative example 3
S1: adding 1g of cerium nitrate and 0.8g of titanium sulfate into 50mL of polyvinyl alcohol solution, adding 1M of acetic acid and ammonium hydroxide solution with the concentration of 25% to adjust the pH of the solution to 4, adding 7.5g of silica nanoparticles, heating to 75 ℃, stirring for 4 hours, drying at 100 ℃ for 8 hours, calcining at 550 ℃ for 2 hours, and grinding to obtain modified silica nanoparticles with the particle size of 30 nm;
s2: adding 75g of acrylic polyol and 1g of lauramide into 50mLN, N-dimethylformamide, uniformly mixing, adding 100g of modified silica nanoparticles, stirring for 4 hours, and passing through a sieve with a pore diameter of 37 mu m to obtain a nanoparticle mixture;
s3: uniformly mixing 60g of dimethyl carbonate, 10g of 1, 5-pentanediol and 0.7g of catalyst, heating to 90 ℃ under the nitrogen atmosphere for reaction for 5 hours, suction filtering, and evaporating under reduced pressure at 100 ℃ and minus 0.05MPa to obtain carbonate monomers; uniformly mixing 10g of carbonate monomer, 10g of 1, 4-cyclohexanedimethanol and 0.2g of catalyst, reacting for 1h at 100 ℃, reacting for 4h at 180 ℃, suction filtering, adding 0.3g of phosphoric acid into the precipitate, uniformly mixing, adding 0.5mol/L of sodium hydroxide to adjust the pH to 7, adding 0.08g of magnesium silicate to stir, adjusting the pH to 7, suction filtering, and vacuum drying for 30min at 85 ℃ to obtain polycarbonate polyol;
s4: 5g of polycarbonate polyol and 40g of tetrahydrofuran-ethylene oxide copolyether are uniformly mixed, 20g of isophorone diisocyanate, 1g of nanoparticle mixture and 0.2g of triphenylbismuth are added to be uniformly mixed, the mixture is placed in a vacuum oven at 60 ℃ for vacuum degassing for 1h, poured into a tetrafluoroethylene mold for curing for 7d at 60 ℃, and the mixture is dried for 7d at normal temperature, so as to obtain the polyurethane film.
And (3) testing: yellowness index test: the test piece was cut into a rectangle with a size of 30X 10mm according to HG/T3689-2014A, and measured by a 3nh spectrocolorimeter. The irradiation time was 300 hours, and the sample was tested for yellowness, as shown in the following table.
TABLE 1 yellowness index test results
Conclusion: when dimethyl carbonate: the mass ratio of the 1, 5-pentanediol is 10:1, when the catalyst addition amount is 1%, the prepared polyurethane film has the best yellowing resistance. In comparative example 1, the replacement of 1, 4-cyclohexanedimethanol with 1, 6-hexanediol resulted in a decrease in the viscosity properties of the prepared polyurethane film; comparative example 2 the catalyst content of the prepared carbonate monomer is too low, so that the glycol conversion is reduced, resulting in the performance of the prepared polyurethane film being reduced; comparative example 3 the too much amount of purified phosphoric acid added resulted in partial decomposition of the polyol with reduced stability, resulting in reduced properties of the polyurethane film produced.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a yellowing-resistant polyurethane film for laminated glass is characterized by comprising the following steps: the method comprises the following steps:
s1: adding acrylic polyol and lauramide into N, N-dimethylformamide, uniformly mixing, adding modified silicon dioxide nano particles, uniformly stirring, and sieving to obtain a nano particle mixture;
s2: and uniformly mixing polycarbonate polyol and tetrahydrofuran-ethylene oxide copolyether, adding isophorone diisocyanate, a nanoparticle mixture and triphenylbismuth, uniformly mixing, vacuum degassing, pouring into a tetrafluoroethylene mold, curing, and drying to obtain the polyurethane film.
2. The method for preparing the yellowing-resistant polyurethane film for laminated glass according to claim 1, wherein the method comprises the following steps: in step S1, the modified silica nanoparticles are prepared as follows:
adding cerium nitrate and titanium sulfate into a polyvinyl alcohol solution, adding acetic acid and ammonium hydroxide to adjust the pH of the solution to 4, adding silicon dioxide nano particles, heating and stirring, drying, calcining and grinding to obtain modified silicon dioxide nano particles.
3. The method for producing a yellowing-resistant polyurethane film for laminated glass according to claim 2, characterized by comprising the steps of: the cerium nitrate: titanium sulfate: the mass ratio of the silicon dioxide is 1: (0.8-1): 7.5; the heating and stirring temperature is 75-80 ℃, the drying temperature is 100-105 ℃, and the calcining temperature is 540-550 ℃; the particle size of the modified nano-particles is 20-50nm.
4. The method for preparing the yellowing-resistant polyurethane film for laminated glass according to claim 1, wherein the method comprises the following steps: in step S2, the polycarbonate polyol is prepared as follows:
uniformly mixing dimethyl carbonate, 1, 5-pentanediol and a catalyst, heating for reaction, filtering, and evaporating under reduced pressure to obtain a carbonate monomer; and uniformly mixing the carbonate monomer, 1, 4-cyclohexanedimethanol and a catalyst, heating for reaction, filtering, and refining to obtain the polycarbonate polyol.
5. The method for producing a yellowing-resistant polyurethane film for laminated glass according to claim 4, wherein: the reaction process is carried out under the atmosphere of nitrogen; the dimethyl carbonate: the mass ratio of the 1, 5-pentanediol is (6-10): 1, a step of; the carbonate monomer: the mass ratio of the 1, 4-cyclohexanedimethanol is (1-1.25): 1, a step of; the adding amount of the catalyst in the carbonic ester monomer is 1% of the total mass of the dimethyl carbonate and the 1, 5-pentanediol; the catalyst is added into the polycarbonate polyol, wherein the addition amount of the catalyst is 1% of the total mass of the carbonate monomer and the 1, 4-cyclohexanedimethanol.
6. The method for producing a yellowing-resistant polyurethane film for laminated glass according to claim 4, wherein: the catalyst is a Mg-Fe/Ti LDHS dual-function catalyst.
7. The method for producing a yellowing-resistant polyurethane film for laminated glass according to claim 4, wherein: adding phosphoric acid into the precipitate, mixing uniformly, adding magnesium silicate, stirring, filtering, and vacuum drying; the adding amount of the phosphoric acid is 0.7-0.8% of the mass of the precipitate; the adding amount of the magnesium silicate is 0.5-0.6% of the mass of the precipitate; the refining process is carried out at 85-90deg.C for 30-45min.
8. The method for preparing the yellowing-resistant polyurethane film for laminated glass according to claim 1, wherein the method comprises the following steps: in step S1, the acrylic polyol: lauramide: the mass ratio of the modified silicon dioxide nano particles is 75:1: (100-125); in the step S2, 5-10 parts of polycarbonate polyol, 40-60 parts of tetrahydrofuran-ethylene oxide copolyether, 20-30 parts of isophorone diisocyanate, 1-2 parts of nanoparticle mixture and 0.1-0.5 part of triphenylbismuth in parts by weight.
9. The method for producing a yellowing resistant polyurethane film for laminated glass according to any one of claims 1 to 8.
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|---|---|---|---|---|
| CN118046639A (en) * | 2023-12-28 | 2024-05-17 | 上海赫雷斯化工有限公司 | Sun-proof laminated glass for vehicle window and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583825A (en) * | 2004-05-28 | 2005-02-23 | 泰兴市金龙绿色化学有限责任公司 | Refining process for fatty polycarbonate resin |
| CN103097424A (en) * | 2010-04-14 | 2013-05-08 | 陶氏环球技术有限责任公司 | Polycarbonate polyols and polyurethanes made therefrom |
| CN106977906A (en) * | 2017-04-13 | 2017-07-25 | 东南大学 | A kind of nano combined flexible pipe of high performance polyurethane and preparation method thereof |
| CN110099943A (en) * | 2016-12-22 | 2019-08-06 | 三菱化学株式会社 | Polycarbonate polyol and polyurethane |
-
2022
- 2022-11-29 CN CN202211507906.3A patent/CN116004170A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583825A (en) * | 2004-05-28 | 2005-02-23 | 泰兴市金龙绿色化学有限责任公司 | Refining process for fatty polycarbonate resin |
| CN103097424A (en) * | 2010-04-14 | 2013-05-08 | 陶氏环球技术有限责任公司 | Polycarbonate polyols and polyurethanes made therefrom |
| CN110099943A (en) * | 2016-12-22 | 2019-08-06 | 三菱化学株式会社 | Polycarbonate polyol and polyurethane |
| CN106977906A (en) * | 2017-04-13 | 2017-07-25 | 东南大学 | A kind of nano combined flexible pipe of high performance polyurethane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王一良: "透明功能化聚碳酸酯基聚氨酯薄膜的分子结构设计与性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, vol. 1, no. 01, pages 016 - 207 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118046639A (en) * | 2023-12-28 | 2024-05-17 | 上海赫雷斯化工有限公司 | Sun-proof laminated glass for vehicle window and preparation method thereof |
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