CN117866298A - Nitrocotton liquid and preparation method and application thereof - Google Patents
Nitrocotton liquid and preparation method and application thereof Download PDFInfo
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- CN117866298A CN117866298A CN202311819008.6A CN202311819008A CN117866298A CN 117866298 A CN117866298 A CN 117866298A CN 202311819008 A CN202311819008 A CN 202311819008A CN 117866298 A CN117866298 A CN 117866298A
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- 229920001220 nitrocellulos Polymers 0.000 title claims abstract description 139
- 239000007788 liquid Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 94
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 85
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000000020 Nitrocellulose Substances 0.000 claims abstract description 19
- 239000003973 paint Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 229920002160 Celluloid Polymers 0.000 claims abstract description 6
- 239000002537 cosmetic Substances 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 57
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 17
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 9
- 239000003759 ester based solvent Substances 0.000 claims description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 5
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- CFXCGWWYIDZIMU-UHFFFAOYSA-N Octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate Chemical compound CCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 CFXCGWWYIDZIMU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 claims description 2
- 239000002964 rayon Substances 0.000 claims description 2
- 238000004383 yellowing Methods 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000000576 coating method Methods 0.000 abstract description 13
- 238000005336 cracking Methods 0.000 abstract description 9
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 4
- 229920002994 synthetic fiber Polymers 0.000 abstract description 4
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- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 39
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- 238000012360 testing method Methods 0.000 description 21
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- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 229930182556 Polyacetal Natural products 0.000 description 12
- 230000008859 change Effects 0.000 description 12
- 229920006324 polyoxymethylene Polymers 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical group CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 description 2
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 241001508399 Elaeagnus Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
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- 229920002678 cellulose Polymers 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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Landscapes
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
The invention discloses a nitrocotton liquid and a preparation method and application thereof, and belongs to the technical field of high polymer materials. The nitrocotton liquid provided by the invention comprises the following preparation raw materials in parts by mass: 20 to 40 parts of nitrocotton, 5 to 15 parts of formaldehyde resin, 0.5 to 5 parts of antioxidant and 40 to 70 parts of organic solvent. The nitrocellulose liquid disclosed by the invention is matched with the formaldehyde resin and the antioxidant, has good storage stability and excellent yellowing resistance, can well inhibit yellowing of the nitrocellulose liquid and rust of a paint can, can enhance the oxidation resistance and flexibility of a coating film, prevents the coating film from cracking after long-term outdoor exposure, prolongs the life of the coating film and improves the quality of a product. The nitrocotton liquid has wide application in the fields of paint, celluloid, artificial fiber, printing ink, film or cosmetics.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to nitrocotton liquid, a preparation method and application thereof.
Background
Nitrocotton is nitrocellulose, also called cellulose nitrate, is an important raw material for manufacturing gunpowder and explosive, and is widely used in various fields such as military fields, paint, celluloid, artificial fiber, printing ink, film, cosmetics and the like.
Nitrocotton is obtained by esterifying defatted cotton with mixed acid of nitric acid and sulfuric acid, and has precipitated-NO 2 The formation of free acid is possible, so that there is a certain residual free acid in the nitrocotton liquid, and the nitrocotton liquid easily causes rust of an iron can during storage due to the characteristics of the nitrocotton liquid, and the color of the nitrocotton liquid is darkened, and even blackened in severe cases. Further, the dissolution of cellulose resin results in powdering and cracking of the paint film after the nitrocotton liquid is solidified into a film.
Therefore, there is a need for a nitrocotton solution which is environmentally friendly, has good storage stability, flexibility and yellowing resistance, and meets the market demands for the comprehensive performance of the nitrocotton solution.
Disclosure of Invention
In order to overcome the problems of the prior art, one of the purposes of the invention is to provide a nitrocotton liquid which has good storage stability and excellent yellowing resistance and can well inhibit yellowing of the nitrocotton liquid and corrosion of paint cans.
The second purpose of the invention is to provide a preparation method of the nitrocotton liquid.
The invention also aims to provide an application of the nitrocotton liquid.
The fourth object of the present invention is to provide a coated nitrocellulose film produced from a liquid comprising the above-mentioned nitrocellulose.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a nitrocotton liquid, which comprises the following preparation raw materials in parts by mass: 20 to 40 parts of nitrocotton, 5 to 15 parts of formaldehyde resin, 0.5 to 5 parts of antioxidant and 40 to 70 parts of organic solvent.
Preferably, in the nitrocotton solution, the organic solvent is selected from ester solvents; further preferably, in the nitrocotton solution, the ester solvent is selected from acetate; still more preferably, in the nitrocotton solution, the ester solvent includes at least one of ethyl acetate, n-propyl acetate or n-butyl acetate; more preferably, in the nitrocotton solution, the ester solvent is selected from a mixed solution of ethyl acetate and n-propyl acetate.
The nitrocotton liquid is a material obtained by dissolving nitrocotton in an organic solvent, and is generally dissolved by using solvents such as ethanol, isopropanol, diethyl ether, acetone, methyl ethyl ketone and the like. Wherein diethyl ether, acetone and methyl ethyl ketone are toxic substances, and long-term breathing of diethyl ether gas can cause irritation, inflammation, memory weakening, and Elaeagnus injury emotion and the like of respiratory organs; direct contact with acetone can have stimulatory effect on skin and mucosa of human body, anesthetize nervous system, inhibit respiration, cause dyspnea, and contact with high concentration acetone can also cause damage to liver, kidney and pancreas; methyl ethyl ketone has a certain anesthetic property, can reduce the central nervous function, is inhaled too much, and can stimulate the skin, eyes, respiratory system and other parts of a human body. According to the invention, the ester solvents ethyl acetate and n-propyl acetate are preferably selected to dissolve the nitrocotton, and the prepared nitrocotton liquid has the advantages of environmental protection, environmental friendliness and the like.
Preferably, in the nitrocotton liquid, the ester solvent is selected from the group consisting of the following components in mass ratio of 1: (0.5-2) a mixed solution of ethyl acetate and n-propyl acetate. In a specific embodiment of the present invention, in the nitrocotton solution, the ester solvent is selected from the group consisting of 1: (1.3 to 1.6) a mixed solution of ethyl acetate and n-propyl acetate.
Preferably, in the nitrocotton liquid, the mass part of the organic solvent is 45-65 parts; more preferably 50 to 60 parts.
Preferably, in the nitrocotton liquid, the nitrocotton comprises at least one of 1/4 second nitrocellulose, 1/8 second nitrocellulose, 1/16 second nitrocellulose or 30 second nitrocellulose; further preferably, the nitrocotton is selected from the group consisting of 1/16 second nitrocelluloses.
The nitrocotton component is nitrocellulose, is an organic high molecular compound, is a product of esterification reaction of cellulose and nitric acid, is white or yellowish cotton flocculent, is insoluble in water, and is soluble in organic solvents such as esters, acetone and the like.
Preferably, in the nitrocotton liquid, the mass part of the nitrocotton is 22-38 parts; more preferably 25 to 35 parts.
Preferably, in the nitrocotton solution, the antioxidant comprises a phosphite antioxidant, a hindered phenol antioxidant, or a combination thereof; further preferably, the antioxidant is selected from the group consisting of phosphite antioxidants and hindered phenol antioxidants.
Preferably, in the antioxidant, the mass ratio of the phosphite antioxidant to the hindered phenol antioxidant is 1: (0.5-1.5); further preferably 1: (0.8-1.2).
Preferably, among the antioxidants, the phosphite antioxidant includes at least one of antioxidant 168, antioxidant 626 or antioxidant 618; further preferably, the phosphite antioxidant is selected from the group consisting of antioxidants 168.
Preferably, among the antioxidants, the hindered phenol antioxidant includes at least one of antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant 1135 or antioxidant 1098; further preferably, the hindered phenol antioxidant comprises at least one of antioxidant 1010, antioxidant 1076 or antioxidant 264; still more preferably, the hindered phenol antioxidant is selected from the group consisting of antioxidants 1010.
Preferably, in the nitrocotton liquid, the antioxidant comprises at least one of an antioxidant 168, an antioxidant 1010, an antioxidant 1076 or an antioxidant 264; further preferably, the antioxidants include antioxidant 168 and at least one of antioxidant 1010, antioxidant 1076, or antioxidant 264; still more preferably, the antioxidant is selected from the group consisting of antioxidant 168 and antioxidant 1010.
The antioxidant 168, the chemical name of which is tris (2, 4-di-tert-butylphenyl) phosphite, is white crystalline powder, is an antioxidant with good performance, has strong extraction resistance, is stable to hydrolysis, can remarkably improve the photostability of the product, and can prevent the molecular weight change and the color change caused by oxidative degradation of the polymer in the processing process.
The antioxidant 1010 is a hindered phenol antioxidant, the chemical name of which is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and white powder, is an antioxidant with good performance, has stable chemical properties, good compatibility with polymers, and good light stability and anti-color change performance.
Preferably, in the nitrocotton liquid, the antioxidant is used as one of the preparation raw materials of the nitrocotton liquid in a solution form.
Preferably, in the nitrocotton solution, the solvent of the antioxidant solution comprises an ester solvent, a hydrocarbon solvent, or a combination thereof.
Preferably, when the antioxidant is selected from phosphite antioxidants, the solvent of the antioxidant solution is selected from hydrocarbon solvents; further preferably, the hydrocarbon solvent is selected from methylcyclohexane.
Preferably, when the antioxidant is selected from hindered phenol antioxidants, the solvent of the antioxidant solution is selected from ester solvents; further preferably, in the antioxidant solution, the ester solvent is selected from acetate; still more preferably, in the antioxidant solution, the ester solvent includes at least one of ethyl acetate, n-propyl acetate, or n-butyl acetate; still more preferably, in the antioxidant solution, the ester solvent is selected from a mixed solution of ethyl acetate and n-propyl acetate;
preferably, in the antioxidant solution, the ester solvent is selected from the group consisting of 1: (0.8-1.2) a mixed solution of ethyl acetate and n-propyl acetate.
Preferably, in the nitrocotton liquid, the concentration of the antioxidant solution is 10-30wt%; further preferably 15 to 25wt%.
Preferably, in the nitrocotton liquid, the antioxidant is 1-4.5 parts by weight; more preferably 2 to 4 parts.
Preferably, in the nitrocotton liquid, the polyacetal resin is used as one of the preparation raw materials of the nitrocotton liquid in the form of a solution.
The formaldehyde resin solution is a material obtained by dissolving formaldehyde resin in an organic solvent.
In a specific embodiment of the present invention, the type of the polyacetal resin is BASF Basf Laropal A81 polyacetal resin, which is a colorless or yellowish transparent solid powder or granule.
Preferably, in the nitrocotton solution, the solvent of the aldehyde resin solution is selected from ester solvents; further preferably, in the aldehyde resin solution, the ester solvent is selected from acetate; still more preferably, in the aldehyde resin solution, the ester-based solvent includes at least one of ethyl acetate, n-propyl acetate, or n-butyl acetate; more preferably, in the aldehyde resin solution, the ester solvent is selected from a mixed solution of ethyl acetate and n-propyl acetate;
preferably, in the aldehyde resin solution, the ester solvent is selected from the group consisting of 1: (0.8-1.2) a mixed solution of ethyl acetate and n-propyl acetate.
Preferably, the concentration of the aldehyde resin solution in the nitrocotton liquid is 30-50wt%; further preferably 35 to 45wt%.
Preferably, in the nitrocotton liquid, the mass part of the formaldehyde resin is 6-13 parts; more preferably 8 to 12 parts.
Preferably, the nitrocotton liquid comprises the following preparation raw materials in parts by mass: 22 to 38 parts of nitrocotton, 6 to 13 parts of formaldehyde resin, 1 to 4.5 parts of antioxidant and 45 to 65 parts of organic solvent.
Further preferably, the nitrocotton liquid comprises the following preparation raw materials in parts by mass: 25-35 parts of nitrocotton, 8-12 parts of formaldehyde resin, 2-4 parts of antioxidant and 50-60 parts of organic solvent.
Still more preferably, the nitrocotton liquid comprises the following preparation raw materials in parts by weight: 25-35 parts of nitrocotton, 8-12 parts of formaldehyde resin, 1-2 parts of phosphite ester antioxidant, 1-2 parts of hindered phenol antioxidant and 50-60 parts of organic solvent.
In a specific embodiment of the invention, the antioxidant and the aldehyde resin are used as one of the preparation raw materials of the nitrocotton liquid in the form of a solution.
The second aspect of the invention provides a method for preparing the nitrocotton liquid according to the first aspect of the invention, which comprises the following steps: and mixing the preparation raw materials to obtain the nitrocotton liquid.
Preferably, in the preparation method of the nitrocotton liquid, nitrocotton and an organic solvent are firstly mixed for the first time, and then formaldehyde resin and an antioxidant are added for the second time to obtain the nitrocotton liquid.
Preferably, in the preparation method of the nitrocotton liquid, the polyacetal resin and the antioxidant are prepared into a solution and then mixed.
In a specific embodiment of the invention, the preparation method of the nitrocotton liquid comprises the following steps: firstly, mixing nitrocotton with an organic solvent, and then, adding an aldehyde resin solution and an antioxidant solution for second mixing to obtain the nitrocotton liquid.
Preferably, in the preparation method of the nitrocotton liquid, the first mixing mode and the second mixing mode are independently selected from stirring.
Preferably, in the preparation method of the nitrocotton liquid, the stirring speed of the first mixing is 750-1100 rpm; further preferably 800 to 1000rpm.
Preferably, in the preparation method of the nitrocotton liquid, the stirring temperature of the first mixing is 35-40 ℃.
Preferably, in the preparation method of the nitrocotton liquid, the stirring time of the first mixing is 30-60 min.
Preferably, in the preparation method of the nitrocotton liquid, the stirring speed of the second mixing is 300-650 rpm; further preferably 400 to 600rpm.
Preferably, in the preparation method of the nitrocotton liquid, the stirring temperature of the first mixing is 35-40 ℃.
Preferably, in the preparation method of the nitrocotton liquid, the stirring time of the first mixing is 10-15 min. A third aspect of the invention provides the use of the nitrocotton liquor of the first aspect of the invention in the fields of paint, celluloid, rayon, ink, motion picture film or cosmetics.
In a fourth aspect the present invention provides a coated nitrocotton film prepared from a nitrocotton solution comprising the first aspect of the invention.
The beneficial effects of the invention are as follows:
the nitrocellulose liquid disclosed by the invention is matched with the formaldehyde resin and the antioxidant, has good storage stability and excellent yellowing resistance, can well inhibit yellowing of the nitrocellulose liquid and rust of a paint can, can enhance the oxidation resistance and flexibility of a coating film, prevents the coating film from cracking after long-term outdoor exposure, prolongs the life of the coating film and improves the quality of a product. The nitrocotton liquid has wide application in the fields of paint, celluloid, artificial fiber, printing ink, film or cosmetics.
Specifically, compared with the prior art, the invention has the following advantages:
1. according to the invention, the ester solvents ethyl acetate and n-propyl acetate are preferably selected to dissolve the nitrocotton, and the prepared nitrocotton liquid has the advantages of environmental protection, environmental friendliness and the like.
2. The invention can produce excellent synergistic effect by matching the triphosphite antioxidant and the hindered phenol antioxidant, and can better improve the yellowing resistance of the nitrocotton liquid.
3. The added formaldehyde resin can effectively improve the flexibility of the nitrocotton coating film, prevent the coating film from cracking when exposed outdoors for a long time, prolong the life of the coating film, improve the quality of products, and can obtain nitrocotton liquid with good weather resistance, storage stability and yellowing resistance and the coating film with complete appearance and long service life by matching with the triphosphite antioxidant and the hindered phenol antioxidant.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, since various modifications and adaptations may be made by those skilled in the art in light of the teachings herein. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a selection within the suitable ranges by the description herein and are not intended to be limited to the specific data described below. The starting materials, reagents or apparatus used in the following examples and comparative examples were obtained from conventional commercial sources or by known methods unless otherwise specified.
In the embodiment of the present invention, the nitrocotton is purchased from Henan brand-created chemical product manufacturing company, and the model is: 1/16 second nitrocellulose;
the model of the formaldehyde resin is BASF Barnofal A81 formaldehyde resin;
antioxidant-1 is purchased from Shanghai Feng Rui chemical Co., ltd, and has the model number: an antioxidant 168;
antioxidant-2 is purchased from Shanghai Feng Rui chemical Co., ltd, model number is: and an antioxidant 1010.
In the embodiment of the invention, the preparation method of the aldehyde resin liquid comprises the following steps:
(1) Weighing the following components in percentage by weight: 30% ethyl acetate, 30% n-propyl acetate, 40% formaldehyde resin;
(2) Mixing ethyl acetate and n-propyl acetate, adding formaldehyde resin, and stirring to dissolve completely to obtain formaldehyde resin solution.
In the embodiment of the invention, the preparation method of the antioxidant liquid-1 comprises the following steps:
(1) Weighing the following components in percentage by weight: 80% of methylcyclohexane and 20% of an antioxidant-1;
(2) Adding methylcyclohexane into a jar, adding antioxidant-1, and stirring to dissolve completely to obtain antioxidant liquid-1.
In the embodiment of the invention, the preparation method of the antioxidant liquid-2 comprises the following steps:
(1) Weighing the following components in percentage by weight: 40% of ethyl acetate, 40% of n-propyl acetate and 20% of antioxidant-2;
(2) Mixing ethyl acetate and n-propyl acetate uniformly, adding antioxidant-2, and stirring until completely dissolving to obtain antioxidant liquid-2.
Examples 1 to 3 and comparative examples 1 to 5
Examples 1 to 3 and comparative examples 1 to 5 of the present invention provide a method for preparing a nitrocotton liquid, comprising the steps of:
(1) Mixing ethyl acetate and n-propyl acetate, adding nitrocotton, regulating the stirring speed to 800-1000 rpm, keeping the constant temperature at 35-40 ℃, and stirring for 30-60 minutes until the mixture is completely dissolved;
(2) Adding the formaldehyde resin solution and/or the antioxidant solution, adjusting the stirring speed to 400-600 rpm, keeping the constant temperature to 35-40 ℃, and stirring for 10-15 minutes until the mixture is completely uniform to obtain nitrocotton solution;
the raw material components and amounts of examples 1 to 3 and comparative examples 1 to 5 are shown in Table 1.
TABLE 1 raw material components and amounts (wt%) of nitrocotton solutions of examples 1 to 3 and comparative examples 1 to 5
Performance testing
The nitrocotton solutions described in examples 1 to 3 and comparative examples 1 to 5 were prepared into print samples on an OPP film substrate using a color development instrument, and then the nitrocotton solutions were stored in an iron can. The printed sample and the nitrocotton liquid stored in the iron tank are placed in an electrothermal blowing drying oven together for heat storage test, and the heat storage test temperature is 30 ℃. The paint film appearance, the chromaticity of the nitrocotton liquid in the iron can (measured with an iron-cobalt colorimeter) and the color appearance of the printed samples at different times were recorded.
The test results are shown in tables 2 and 3.
Table 2 results of heat storage tests of examples 1 to 3
Table 3 results of thermal storage tests of comparative examples 1 to 5
From the results in tables 2 and 3, it can be seen that:
comparison of the results of example 1 and comparative example 3 shows that comparative example 3, in which no polyacetal resin liquid was added but antioxidant liquid-1 was added, exhibited cracking of the paint film after being subjected to a heat storage test at 15 days/30 ℃; whereas example 1, with the addition of the polyacetal resin liquid and the antioxidant liquid-1, remained intact after being subjected to the heat storage test at 90 days/30 ℃. In addition, although the color change of both comparative example 3 and example 1 was from pale yellow to pale yellow after being subjected to the heat storage test at 90 days/30 ℃, the color change of example 1 was smaller with respect to the color value of comparative example 3 from 2 to 8, and the color value of example 1 from 1 to 6. The antioxidant liquid-1 is matched with the formaldehyde resin liquid, so that the nitrocotton liquid has better weather resistance and yellowing resistance.
Comparison of the results of example 2 and comparative example 4 shows that comparative example 4, in which no polyacetal resin liquid was added but antioxidant liquid-2 was added, exhibited cracking of the paint film after being subjected to a heat storage test at 15 days/30 ℃; whereas example 2, with the addition of the polyacetal resin liquid and the antioxidant liquid-2, remained intact after being subjected to the heat storage test at 90 days/30 ℃. In addition, although the color change of both comparative example 4 and example 2 was from pale yellow to pale yellow after being subjected to the heat storage test for 90 days/30 ℃, the color change of example 2 was smaller with respect to the color value of comparative example 4 from 2 to 9, and the color value of example 2 from 1 to 7. The antioxidant liquid-2 is matched with the formaldehyde resin liquid, so that the nitrocotton liquid has better weather resistance and yellowing resistance.
Comparison of the results of example 3 and comparative example 5 shows that the comparative example 5, which did not add the polyacetal resin liquid but was added with the antioxidant liquid-1 and the antioxidant liquid-2, exhibited a cracking phenomenon in the paint film after being subjected to a heat storage test at 15 days/30 ℃; while the paint film of example 3, with the addition of antioxidant liquid-1, antioxidant liquid-2 and polyacetal liquid, remained intact. In addition, although both comparative example 5 and example 3 remained pale yellow after being subjected to the heat storage test for 90 days/30 ℃, the chromaticity value of example 3 was from 1 to 4 with respect to the chromaticity value of comparative example 5, and the color change was smaller. The antioxidant liquid-1 and the antioxidant liquid-2 are matched with the formaldehyde resin liquid, so that the nitrocotton liquid has good weather resistance and yellowing resistance.
The comparative results of comparative examples 1 to 2 show that the paint film of comparative example 1 without addition of the polyacetal resin liquid is cracked after being subjected to a heat storage test at 15 days/30 ℃; whereas comparative example 2 with the addition of the polyacetal resin liquid remained intact after being subjected to the heat storage test at 90 days/30 ℃. In addition, after being subjected to the heat storage test for 90 days/30 ℃, the color change from pale yellow, to brown, to red brown, and finally to red brown with respect to comparative example 1, the chromaticity value was from 3 to 14; the color of example 2 varied from pale yellow, to brown yellow, and the chromaticity value from 3 to 11, with less color variation. The formaldehyde resin liquid can improve the weather resistance and yellowing resistance of the nitrocotton liquid.
Comparison of the results of comparative example 1 and comparative examples 3 to 4 shows that the comparative example 3 and comparative example 4, to which the antioxidant liquid-1 and the antioxidant liquid-2 were added, respectively, and the comparative example 1, to which the antioxidant liquid was not added, all exhibited cracking phenomena when subjected to a heat storage test at 90 days/30 ℃. In addition, after being subjected to the heat storage test for 90 days/30 ℃, the color change from pale yellow, to brown, to red brown, and finally to red brown with respect to comparative example 1, the chromaticity value was from 3 to 14; the color changes of comparative example 3 and comparative example 4 were all from pale yellow to pale yellow, the chromaticity values were 2 to 8, and 2 to 9, respectively, and the color changes were smaller. The antioxidant liquid can improve the yellowing resistance of the nitrocotton liquid.
Comparison of the results of comparative examples 3 to 5 shows that the paint films are cracked after being subjected to a heat storage test at 15 days/30 ℃ by matching the comparative example 5 added with the antioxidant liquid-1 and the antioxidant liquid-2 with the comparative example 3 and the comparative example 4 added with the antioxidant liquid-1 and the antioxidant liquid-2 respectively. In addition, after being subjected to the heat storage test for 90 days/30 ℃, the color change was from pale yellow to pale yellow, the chromaticity values were respectively from 2 to 8, from 2 to 9, and the comparative example 5 remained pale yellow, the chromaticity values were from 1 to 5, and the color change was smaller, with respect to the comparative example 3 and comparative example 4. It is shown that the antioxidant-1 and the antioxidant-2 can lead the nitrocotton liquid to have better yellowing resistance, because the triphosphite antioxidant (antioxidant 168) can generate excellent synergistic effect in the synergistic effect with the hindered phenol antioxidant (antioxidant 1010) and better improve the yellowing resistance of the nitrocotton liquid.
In addition, the invention prefers the ester solvents of ethyl acetate and n-propyl acetate to dissolve the nitrocotton, and the prepared nitrocotton liquid has the advantages of environmental protection, environmental protection and the like.
In conclusion, the nitrocellulose liquid is matched with the formaldehyde resin and the antioxidant, has good storage stability and excellent yellowing resistance, can well inhibit yellowing of the nitrocellulose liquid and rust of paint cans, can enhance oxidation resistance and flexibility of a coating film, prevents the coating film from cracking after long-term outdoor exposure, prolongs the life of the coating film and improves the quality of products. The nitrocotton liquid has wide application in the fields of paint, celluloid, artificial fiber, printing ink, film or cosmetics.
Claims (10)
1. The nitrocotton liquid is characterized by comprising the following preparation raw materials in parts by weight: 20 to 40 parts of nitrocotton, 5 to 15 parts of formaldehyde resin, 0.5 to 5 parts of antioxidant and 40 to 70 parts of organic solvent.
2. The nitrocotton solution of claim 1, wherein the organic solvent is selected from the group consisting of ester solvents; preferably, the ester solvent is selected from acetate; further preferably at least one of ethyl acetate, n-propyl acetate or n-butyl acetate is included.
3. The liquid of claim 1, wherein the nitrocotton comprises at least one of 1/4 second nitrocellulose, 1/8 second nitrocellulose, 1/16 second nitrocellulose, or 30 second nitrocellulose.
4. The nitrocotton solution of claim 1, wherein the antioxidant comprises a phosphite antioxidant, a hindered phenol antioxidant, or a combination thereof.
5. The nitrocotton solution of claim 4, wherein the phosphite antioxidant comprises at least one of an antioxidant 168, an antioxidant 626, or an antioxidant 618;
and/or the hindered phenol antioxidant comprises at least one of antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant 1135 or antioxidant 1098.
6. The nitrocotton solution according to claim 1, wherein the antioxidant is in the form of a solution as one of the raw materials for preparing the nitrocotton solution; preferably, the solvent of the antioxidant solution comprises an ester solvent, a hydrocarbon solvent, or a combination thereof;
preferably, the concentration of the antioxidant solution is 10-30wt%;
and/or, the formaldehyde resin is used as one of the preparation raw materials of the nitrocotton liquid in the form of a solution; preferably, the solvent of the aldehyde resin solution is selected from ester solvents; preferably, the concentration of the formaldehyde resin solution is 30 to 50wt%.
7. The method for preparing the nitrocotton liquid according to any one of claims 1 to 6, comprising the steps of: and mixing the preparation raw materials to obtain the nitrocotton liquid.
8. The method of claim 7, wherein the nitrocotton liquid is obtained by first mixing nitrocotton with an organic solvent and then adding an aldehyde resin and an antioxidant for second mixing.
9. Use of the nitrocotton liquid of any one of claims 1-6 in the fields of paint, celluloid, rayon, ink, motion picture film or cosmetics.
10. A coated film of nitrocotton, characterized in that it is produced from a nitrocotton liquid comprising the one of claims 1 to 6.
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| CN202311819008.6A CN117866298A (en) | 2023-12-27 | 2023-12-27 | Nitrocotton liquid and preparation method and application thereof |
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| CN202311819008.6A CN117866298A (en) | 2023-12-27 | 2023-12-27 | Nitrocotton liquid and preparation method and application thereof |
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