CN116790076B - Yellowing-resistant and oxidation-resistant PVC film - Google Patents
Yellowing-resistant and oxidation-resistant PVC film Download PDFInfo
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- CN116790076B CN116790076B CN202310746828.0A CN202310746828A CN116790076B CN 116790076 B CN116790076 B CN 116790076B CN 202310746828 A CN202310746828 A CN 202310746828A CN 116790076 B CN116790076 B CN 116790076B
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- 238000004383 yellowing Methods 0.000 title claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 title claims description 27
- 230000003647 oxidation Effects 0.000 title claims description 26
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 40
- 238000012545 processing Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 91
- 239000013067 intermediate product Substances 0.000 claims description 66
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 43
- 238000001816 cooling Methods 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- 239000003112 inhibitor Substances 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 16
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000000314 lubricant Substances 0.000 claims description 15
- RNVYCHNNRVFSDL-UHFFFAOYSA-N 4-(2-aminoethyl)-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(CCN)=CC(C(C)(C)C)=C1O RNVYCHNNRVFSDL-UHFFFAOYSA-N 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 14
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000012745 toughening agent Substances 0.000 claims description 11
- 239000012265 solid product Substances 0.000 claims description 9
- 239000004609 Impact Modifier Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000003490 calendering Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- -1 polypropylene Polymers 0.000 abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000004611 light stabiliser Substances 0.000 abstract description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000004743 Polypropylene Substances 0.000 abstract 1
- 229920001155 polypropylene Polymers 0.000 abstract 1
- 239000004800 polyvinyl chloride Substances 0.000 description 72
- 229920000915 polyvinyl chloride Polymers 0.000 description 71
- 150000001408 amides Chemical class 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000005096 rolling process Methods 0.000 description 10
- 230000032683 aging Effects 0.000 description 8
- 150000007942 carboxylates Chemical class 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 101100322245 Caenorhabditis elegans des-2 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- HQYUWCXFCCIKPT-UHFFFAOYSA-J dizinc octadecanoate Chemical compound [Zn++].[Zn++].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQYUWCXFCCIKPT-UHFFFAOYSA-J 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 102200046998 rs62645894 Human genes 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000004394 yellowing prevention Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a method for improving the processing fluidity of polypropylene. PVC is subject to the action of light, heat and oxygen, and is easy to yellow. According to the invention, the self-made heat stabilizer is added in the formula, and the molecular structure of the heat stabilizer contains carboxyl, hydroxyl, ester amide and acryloyloxy, and also contains rare earth lanthanum and phthalate, so that the self-made heat stabilizer has the effects of heat stabilizer, light stabilizer and antioxidant, the use of light stabilizer and antioxidant can be avoided, and the obtained PVC has stable performance and better yellowing resistance and weather resistance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a yellowing-resistant and oxidation-resistant PVC film.
Background
Polyvinyl chloride (PVC) is one of five general plastics in the world. PVC is widely used in various fields such as chemical industry, construction, light industry, packaging, and cables due to its excellent properties such as good mechanical properties, flame retardancy, corrosion resistance, and low price.
The molecular structure of PVC is not simply the combination of secondary carbon atoms and chlorine atoms, but an unstable structure is also contained in the structure, so that PVC starts to decompose and release HCl at the temperature of more than 100 ℃, and researches show that the unstable structure in PVC possibly comprises the following structures:
the unstable structure contains secondary and tertiary chlorine at one end, beta unstable group at one end, and oxygen at the structure. The reason for this is probably that some of them are formed by the peroxidation of the initiator, and that the oxygen-containing structure is formed by polymerization in the presence of a trace amount of oxygen or by post-oxidation of the polymer.
The processing temperature (more than 160 ℃) of PVC is higher than the decomposition temperature (120-130 ℃), besides thermal degradation and thermal oxidative aging reaction (one of the reasons for yellowing of PVC products) occur in the PVC processing and molding process, intramolecular dehydrochlorination can cause formation of conjugated structures or peroxide in PVC molecular chains, and the color of the PVC products is also yellowing, so that a heat stabilizer is required to be added in the PVC processing and molding process to delay or prevent the thermal degradation of PVC in order to change the PVC into the PVC products.
In the use process, light and heat can aggravate the oxidation process of PVC, and oxidation leads to material yellowing, so that the problems of PVC yellowing prevention, light receiving of PVC and easy oxidation due to heat are also needed to be solved.
In summary, to solve the yellowing problem of PVC, it is required to improve the thermal stability, oxidation resistance and uv resistance of PVC.
Disclosure of Invention
The problems in the prior art are: PVC is subject to the action of light, heat and oxygen, and is easy to yellow. Aiming at the problems, the invention provides a yellowing-resistant and oxidation-resistant PVC film which comprises the following raw materials in parts by weight:
100 parts of PVC;
4-10 parts of a toughening agent;
2 parts of processing modifier ACR;
2-3 parts of a heat stabilizer;
0.5-1 part of zinc stearate;
0.4-0.7 parts of lubricant.
Specifically, the toughening agent includes at least one of impact modifiers ACR, CPE.
Specifically, the preparation method of the heat stabilizer comprises the following steps:
(1) Adding trimellitic anhydride, 4- (2-aminoethyl) -2, 6-di-tert-butylphenol and ethyl acetate into a flask, stirring at room temperature for reaction for 15-20h, removing ethyl acetate in reactants by reduced pressure distillation after the reaction is finished, and then drying at 60 ℃ in vacuum for 4h to obtain an intermediate product I;
the dosage ratio of the trimellitic anhydride to the 4- (2-aminoethyl) -2, 6-di-tert-butylphenol to the ethyl acetate is as follows: 0.1mol:0.1mol:400mL;
(2) Placing an intermediate product I, a catalyst, a polymerization inhibitor and N, N-dimethylformamide B in a three-neck flask, wherein the dosage ratio of the intermediate product I to the N, N-dimethylformamide B is 0.1mol:800mL, the dosage ratio of the intermediate product I to the catalyst is 1g:0.001-0.005g, the dosage ratio of the glycidyl acrylate to the polymerization inhibitor is 1g:0.01g, raising the temperature of a reaction system to 100-105 ℃, simultaneously dissolving the glycidyl acrylate in the N, N-dimethylformamide A, placing the N-dimethylformamide A in a constant-pressure dropping funnel, adding the N-dimethylformamide A into the three-neck flask in a dropwise manner while stirring, reacting for 12-15h at 100-105 ℃, reducing the temperature of the reaction system to room temperature after the reaction is finished, then carrying out reduced pressure distillation on the reaction system to remove the N, N-dimethylformamide, and then placing the reaction product in a vacuum at 60 ℃ for 4h to obtain an intermediate product II;
(3) Adding an intermediate product II, a polymerization inhibitor and absolute ethyl alcohol into a three-neck flask, heating to 60-80 ℃, then adding lanthanum nitrate, fully and uniformly stirring, then dropwise adding an alkaline solution with the mass concentration of 30wt% while stirring by using a dropping funnel, adjusting the pH value of a reaction system to be 6-7, stirring at constant temperature for reaction for 6 hours, standing, cooling the reaction system to room temperature, then adopting a vacuum pump to carry out suction filtration on a reaction product, washing the obtained solid product with deionized water for 3 times, putting the obtained solid product into a constant temperature drying box, and carrying out vacuum drying at 40 ℃ for 8 hours to obtain a target product III;
the dosage ratio of the intermediate product II to the absolute ethyl alcohol to the lanthanum nitrate to the deionized water is 1.2mol:500mL:1mol:1000mL;
the dosage ratio of the intermediate product II to the polymerization inhibitor is 1g to 0.005g.
Specifically, the alkaline solution includes an aqueous sodium hydroxide solution or a dilute aqueous ammonia solution.
Specifically, the catalyst in the step (2) comprises at least one of triphenylphosphine, tetrabutylammonium bromide or N, N-dimethylbenzylamine.
Specifically, the preparation method comprises the following steps:
s1: weighing PVC, a toughening agent, a processing ACR, a heat stabilizer, zinc stearate and a lubricant according to the formula amount, uniformly mixing to obtain a mixed material, heating the mixed material to 110-115 ℃ from room temperature within 10-12min, cooling to 45-50 ℃, and standing for 24h to obtain a pretreated material;
s2: extruding the pretreated material through a screw extruder, calendaring, stretching, cooling and coiling to obtain the PVC film.
Specifically, in the extrusion process of the screw extruder, the temperature of the first region is 175-190 ℃, the temperature of the second region is 140-155 ℃, and the temperature of the third region is 160-170 ℃.
Specifically, the yellowing-resistant and oxidation-resistant PVC film has the following reaction process:
the invention has the following beneficial effects:
(1) The invention provides a yellowing-resistant and oxidation-resistant PVC film, wherein the self-made heat stabilizer is added in the formula, and the molecular structure of the heat stabilizer contains carboxyl, hydroxyl, ester-based amide, acryloyloxy and rare earth lanthanum and phthalate;
the phthalate long-chain structure can effectively promote PVC plasticization and reduce the processing temperature of PVC; the rare earth lanthanum provides an empty orbit for complexing of chlorine free radicals and capturing chloride ions and HCl;
o, N element in the ester amide group and rare earth lanthanum form a coordination bond, so that HCl can be adsorbed;
the structural characteristics of the heat stabilizer, namely polyhydroxy, can avoid the phenomenon of zinc stearate zinc burning, and can ensure that the PV has excellent initial coloring resistance, so that the apparent color of the PV is kept better;
the double bond in the acryloyloxy can react with the double bond formed in the thermal decomposition process of PVC to terminate the degradation of PVC molecular chains, inhibit the color change of PVC and prevent the migration of heat stabilizer to the surface of the material;
(2) The self-made heat stabilizer structure contains rare earth element lanthanum, and the rare earth element lanthanum can absorb ultraviolet rays of 230-320mm, so that the ageing of PVC can be slowed down, and the weather resistance and the light stability of the PVC can be improved;
(3) The self-made heat stabilizer structure also contains a hindered phenol structure, and the hindered phenol structure and the acryloyloxy structure endow PVC with excellent oxidation and aging resistance;
(4) The self-made heat stabilizer has the effects of heat stabilizer, light stabilizer and antioxidant, can avoid the use of the light stabilizer and the antioxidant, and has stable PVC performance and better yellowing resistance and weather resistance.
The specific embodiment is as follows:
the present invention will be described in detail with reference to examples. It is to be understood that the following examples are illustrative of embodiments of the present invention and are not intended to limit the scope of the invention.
In the invention, the PVC in the following embodiment is TG-800, and is purchased from the trade company of Innovative diamond (Guangzhou);
the impact modifier ACR in the following examples of the present invention is ACR ZB-50A;
the CPE in the following embodiment of the invention is CPE-135A;
the processing modifier ACR in the following examples of the present invention is Japanese Brillouin chemical PA-20;
the lubricant in the following examples in the present invention is G70S;
the polymerization inhibitor in the following examples in the present invention is hydroquinone.
Example 1
The yellowing-resistant and oxidation-resistant PVC film comprises the following raw materials in parts by weight:
100 parts of PVC;
5 parts of an impact modifier ACR;
2 parts of processing modifier ACR;
2.5 parts of a heat stabilizer;
0.8 parts of zinc stearate;
0.6 parts of lubricant.
The heat stabilizer is prepared according to the following steps:
(1) Adding trimellitic anhydride, 4- (2-aminoethyl) -2, 6-di-tert-butylphenol and ethyl acetate into a flask, stirring at room temperature for reaction for 15h, removing ethyl acetate in reactants by reduced pressure distillation after the reaction is finished, and then drying in vacuum at 60 ℃ for 4h to obtain an intermediate product I, wherein the infrared data of the intermediate product I are as follows:
3511cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 : -c=o present; 1250cm -1 : the anhydride disappears; 1485cm -1 、1580cm -1 : the amide N-H is present.
The dosage ratio of the trimellitic anhydride to the 4- (2-aminoethyl) -2, 6-di-tert-butylphenol and ethyl acetate is 0.1mol:0.1mol:400mL;
(2) Placing an intermediate product I, a catalyst, a polymerization inhibitor and N, N-dimethylformamide B in a three-neck flask, wherein the dosage ratio of the intermediate product I to the N, N-dimethylformamide B is 0.1mol:800mL, the dosage ratio of the intermediate product I to the catalyst is 1g:0.001g, the dosage ratio of glycidyl acrylate to the polymerization inhibitor is 1g:0.01g, raising the temperature of a reaction system to 105 ℃, simultaneously dissolving the glycidyl acrylate in the N, N-dimethylformamide A, placing the mixture in a constant-pressure dropping funnel, adding the mixture into the three-neck flask in a dropwise manner while stirring, stirring and reacting at 105 ℃ for 12h, after the reaction, reducing the temperature of the reaction system to room temperature, then carrying out reduced pressure distillation on the reaction system to remove the N, N-dimethylformamide, and then placing the reaction product in a vacuum at 60 ℃ for 4h to obtain an intermediate product II, wherein the infrared data of the intermediate product II are as follows:
3468cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 、1735cm -1 : -c=o present; 1614cm -1 、811cm -1 : -c=c-present; 1485cm -1 、1580cm -1 : amide N-H is present; 943cm -1 、824cm -1 : the epoxy group is absent;
(3) Adding an intermediate product II, a polymerization inhibitor and absolute ethyl alcohol into a three-neck flask, heating to 70 ℃, then adding lanthanum nitrate, fully and uniformly stirring, then dropwise adding a 30wt% sodium hydroxide aqueous solution with a dropping funnel while stirring, adjusting the pH=7 of a reaction system, standing after stirring at constant temperature for 6 hours, cooling the temperature of the reaction system to room temperature, then adopting a vacuum pump to carry out suction filtration on the reaction product, washing the obtained solid product with deionized water for 3 times, putting the obtained product into a constant temperature drying oven, and carrying out vacuum drying at 40 ℃ for 8 hours to obtain a target product III, wherein the infrared data of the product III are as follows:
3468cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 、1735cm -1 : -c=o present; 1614cm -1 、811cm -1 : -c=c-present; 1485cm -1 、1580cm -1 : amide N-H is present; 1382cm -1 、1428cm -1 : the presence of a carboxylate; 793cm -1 : O-La is present;
the dosage ratio of the intermediate product II to the absolute ethyl alcohol to the lanthanum nitrate to the deionized water is 1.2mol:500mL:1mol:1000mL;
the dosage ratio of the intermediate product II to the polymerization inhibitor is 1g to 0.005g.
The preparation method of the yellowing-resistant and oxidation-resistant PVC film comprises the following steps:
s1: weighing PVC, a toughening agent, a processing ACR, a heat stabilizer, zinc stearate and a lubricant according to the formula amount, uniformly mixing to obtain a mixed material, heating the mixed material to 115 ℃ from room temperature within 12min, then cooling to 45 ℃, and standing for 24h to obtain a pretreated material;
s2: extruding the pretreated material through a screw extruder, calendaring, stretching, cooling and coiling to obtain the PVC film.
In the extrusion process of the screw extruder, the temperature of the first area is 185 ℃, the temperature of the second area is 155 ℃, and the temperature of the third area is 170 ℃.
The rolling is five-roller rolling: the temperature of the No. 1 roller is 191 ℃, and the linear speed is 9.7m/min; the temperature of the No. 2 roller is 190 ℃, and the linear speed is 10.9m/min; the temperature of the 3# roller is 193 ℃, and the linear speed is 12.8m/min; the temperature of the No. 4 roller is 204 ℃, and the linear speed is 14.3m/min; the 5# roll temperature was 200deg.C and the line speed was 15.8m/min.
The cooling is four-stage cooling, and the cooling temperature is 55 ℃, 50 ℃, 45 ℃ and 36 ℃ in sequence.
Example 2
The yellowing-resistant and oxidation-resistant PVC film comprises the following raw materials in parts by weight:
100 parts of PVC;
impact modifier ACR 4 parts;
2 parts of processing modifier ACR;
2 parts of a heat stabilizer;
0.5 parts of zinc stearate;
0.7 parts of lubricant.
The preparation method of the heat stabilizer comprises the following steps:
(1) Adding trimellitic anhydride, 4- (2-aminoethyl) -2, 6-di-tert-butylphenol and ethyl acetate into a flask, stirring at room temperature for reaction for 15h, removing ethyl acetate in reactants by reduced pressure distillation after the reaction is finished, and then drying in vacuum at 60 ℃ for 4h to obtain an intermediate product I, wherein the infrared data of the intermediate product I are as follows:
3511cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 : -c=o present; 1250cm -1 : the anhydride disappears; 1485cm -1 、1580cm -1 : amide N-H is present;
the dosage ratio of the trimellitic anhydride to the 4- (2-aminoethyl) -2, 6-di-tert-butylphenol to the ethyl acetate is as follows: 0.1mol:0.1mol:400mL;
(2) Placing an intermediate product I, a catalyst, a polymerization inhibitor and N, N-dimethylformamide B in a three-neck flask, wherein the dosage ratio of the intermediate product I to the N, N-dimethylformamide B is 0.1mol:800mL, the dosage ratio of the intermediate product I to the catalyst is 1g:0.001g, the dosage ratio of glycidyl acrylate to the polymerization inhibitor is 1g:0.01g, raising the temperature of a reaction system to 105 ℃, simultaneously dissolving the glycidyl acrylate in the N, N-dimethylformamide A, placing the mixture in a constant-pressure dropping funnel, adding the mixture into the three-neck flask in a dropwise manner while stirring, stirring and reacting at 105 ℃ for 12h, after the reaction, reducing the temperature of the reaction system to room temperature, then carrying out reduced pressure distillation on the reaction system to remove the N, N-dimethylformamide, and then placing the reaction product in a vacuum at 60 ℃ for 4h to obtain an intermediate product II, wherein the infrared data of the intermediate product II are as follows:
3468cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 、1735cm -1 : -c=o present; 1614cm -1 、811cm -1 : -c=c-present; 1485cm -1 、1580cm -1 : amide N-H is present; 943cm -1 、824cm -1 : the epoxy group is absent;
(3) Adding an intermediate product II, a polymerization inhibitor and absolute ethyl alcohol into a three-neck flask, heating to 70 ℃, then adding lanthanum nitrate, fully and uniformly stirring, then dropwise adding a 30wt% sodium hydroxide aqueous solution with a dropping funnel while stirring, adjusting the pH=7 of a reaction system, standing after stirring at constant temperature for 6 hours, cooling the temperature of the reaction system to room temperature, then adopting a vacuum pump to carry out suction filtration on the reaction product, washing the obtained solid product with deionized water for 3 times, putting the obtained product into a constant temperature drying oven, and carrying out vacuum drying at 40 ℃ for 8 hours to obtain a target product III, wherein the infrared data of the product III are as follows:
3468cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 、1735cm -1 : -c=o present; 1614cm -1 、811cm -1 : -c=c-present; 1485cm -1 、1580cm -1 : amide N-H is present; 1382cm -1 、1428cm -1 : the presence of a carboxylate; 793cm -1 : O-La is present;
the dosage ratio of the intermediate product II to the absolute ethyl alcohol to the lanthanum nitrate to the deionized water is 1.2mol:500mL:1mol:1000mL;
the dosage ratio of the intermediate product II to the polymerization inhibitor is 1g to 0.005g.
The preparation method of the yellowing-resistant and oxidation-resistant PVC film comprises the following steps:
s1: weighing PVC, a toughening agent, a processing ACR, a heat stabilizer, zinc stearate and a lubricant according to the formula amount, uniformly mixing to obtain a mixed material, heating the mixed material to 115 ℃ from room temperature within 12min, then cooling to 50 ℃, and standing for 24h to obtain a pretreated material;
s2: extruding the pretreated material through a screw extruder, calendaring, stretching, cooling and coiling to obtain the PVC film.
Specifically, in the extrusion process of the screw extruder, the temperature of the first region is 190 ℃, the temperature of the second region is 140 ℃, and the temperature of the third region is 160 ℃.
The rolling is five-roller rolling: the temperature of the No. 1 roller is 185 ℃, and the linear speed is 9.7m/min; the temperature of the No. 2 roller is 190 ℃, and the linear speed is 10.9m/min; the temperature of the No. 3 roller is 195 ℃ and the linear speed is 12.8m/min; the temperature of the No. 4 roller is 205 ℃, and the linear speed is 14.3m/min; the 5# roll temperature was 200deg.C and the line speed was 15.8m/min.
The cooling is four-stage cooling, and the cooling temperature is 55 ℃, 50 ℃, 45 ℃ and 36 ℃ in sequence.
Example 3
The yellowing-resistant and oxidation-resistant PVC film comprises the following raw materials in parts by weight:
100 parts of PVC;
impact modifier CPE 9 parts;
2 parts of processing modifier ACR;
2 parts of a heat stabilizer;
1 part of zinc stearate;
0.4 parts of lubricant.
The heat stabilizer is prepared according to the following steps:
(1) Adding trimellitic anhydride, 4- (2-aminoethyl) -2, 6-di-tert-butylphenol and ethyl acetate into a flask, stirring at room temperature for reaction for 20 hours, removing ethyl acetate in reactants by reduced pressure distillation after the reaction is finished, and then drying in vacuum at 60 ℃ for 4 hours to obtain an intermediate product I, wherein the infrared data of the intermediate product I are as follows:
3511cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 : -c=o present; 1250cm -1 : acid(s)The anhydride disappeared; 1485cm -1 、1580cm -1 : amide N-H is present;
the dosage ratio of the trimellitic anhydride to the 4- (2-aminoethyl) -2, 6-di-tert-butylphenol to the ethyl acetate is as follows: 0.1mol:0.1mol:400mL;
(2) Placing an intermediate product I, a catalyst, a polymerization inhibitor and N, N-dimethylformamide B in a three-neck flask, wherein the dosage ratio of the intermediate product I to the N, N-dimethylformamide B is 0.1mol:800mL, the dosage ratio of the intermediate product I to the catalyst is 1g:0.005g, the dosage ratio of glycidyl acrylate to the polymerization inhibitor is 1g:0.01g, heating the reaction system to 100 ℃, simultaneously dissolving the glycidyl acrylate in the N, N-dimethylformamide A, placing the mixture in a constant-pressure dropping funnel, adding the mixture into the three-neck flask in a dropwise manner while stirring, stirring and reacting at 100 ℃ for 12h, after the reaction, reducing the temperature of the reaction system to room temperature, then carrying out reduced pressure distillation on the reaction system to remove the N, N-dimethylformamide, and then placing the reaction product in a vacuum at 60 ℃ for 4h to obtain an intermediate product II, wherein the infrared data of the intermediate product II are as follows:
3468cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 、1735cm -1 : -c=o present; 1614cm -1 、811cm -1 : -c=c-present; 1485cm -1 、1580cm -1 : amide N-H is present; 943cm -1 、824cm -1 : the epoxy group is absent;
(3) Adding an intermediate product II, a polymerization inhibitor and absolute ethyl alcohol into a three-neck flask, heating to 80 ℃, then adding lanthanum nitrate, fully and uniformly stirring, then dropwise adding ammonia water with the mass concentration of 30wt% while stirring by using a dropping funnel, adjusting the pH=6 of a reaction system, stirring at constant temperature for reaction for 6 hours, standing, cooling the temperature of the reaction system to room temperature, then adopting a vacuum pump to carry out suction filtration on the reaction product, washing the obtained solid product with deionized water for 3 times, putting the obtained product into a constant temperature drying oven, and carrying out vacuum drying at 40 ℃ for 8 hours to obtain a target product III, wherein the infrared data of the product III are as follows:
3468cm -1 : -OH PresenceIn the process of; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 、1735cm -1 : -c=o present; 1614cm -1 、811cm -1 : -c=c-present; 1485cm -1 、1580cm -1 : amide N-H is present; 1382cm -1 、1428cm -1 : the presence of a carboxylate; 793cm -1 : O-La is present;
the dosage ratio of the intermediate product II to the absolute ethyl alcohol to the lanthanum nitrate to the deionized water is 1.2mol:500mL:1mol:1000mL;
the dosage ratio of the intermediate product II to the polymerization inhibitor is 1g to 0.005g.
The preparation method of the yellowing-resistant and oxidation-resistant PVC film comprises the following steps:
s1: weighing PVC, a toughening agent, a processing ACR, a heat stabilizer, zinc stearate and a lubricant according to the formula amount, uniformly mixing to obtain a mixed material, heating the mixed material to 110 ℃ from room temperature within 10min, then cooling to 50 ℃, and standing for 24h to obtain a pretreated material;
s2: extruding the pretreated material through a screw extruder, calendaring, stretching, cooling and coiling to obtain the PVC film.
Specifically, in the extrusion process of the screw extruder, the temperature of the first region is 175 ℃, the temperature of the second region is 150 ℃, and the temperature of the third region is 165 ℃.
The rolling is five-roller rolling: the temperature of the No. 1 roller is 195 ℃ and the linear speed is 9.7m/min; the temperature of the No. 2 roller is 195 ℃ and the linear speed is 10.9m/min; the temperature of the No. 3 roller is 200 ℃, and the linear speed is 12.8m/min; the temperature of the No. 4 roller is 210 ℃, and the linear speed is 14.3m/min; the 5# roll temperature was 205℃and the linear velocity was 15.8m/min.
The cooling is four-stage cooling, and the cooling temperature is 55 ℃, 50 ℃, 45 ℃ and 36 ℃ in sequence.
Example 4
The yellowing-resistant and oxidation-resistant PVC film comprises the following raw materials in parts by weight:
100 parts of PVC;
10 parts of impact modifier CPE;
2 parts of processing modifier ACR;
3 parts of a heat stabilizer;
1 part of zinc stearate;
0.6 parts of lubricant.
The preparation method of the heat stabilizer comprises the following steps:
(1) Adding trimellitic anhydride, 4- (2-aminoethyl) -2, 6-di-tert-butylphenol and ethyl acetate into a flask, stirring at room temperature for reaction for 18 hours, removing ethyl acetate in reactants by reduced pressure distillation after the reaction is finished, and then drying in vacuum at 60 ℃ for 4 hours to obtain an intermediate product I, wherein the infrared data of the intermediate product I are as follows:
3511cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 : -c=o present; 1250cm -1 : the anhydride disappears; 1485cm -1 、1580cm -1 : amide N-H is present;
the dosage ratio of the trimellitic anhydride to the 4- (2-aminoethyl) -2, 6-di-tert-butylphenol to the ethyl acetate is as follows: 0.1mol:0.1mol:400mL;
(2) Placing an intermediate product I, a catalyst, a polymerization inhibitor and N, N-dimethylformamide B in a three-neck flask, wherein the dosage ratio of the intermediate product I to the N, N-dimethylformamide B is 0.1mol:800mL, the dosage ratio of the intermediate product I to the catalyst is 1g:0.005g, the dosage ratio of glycidyl acrylate to the polymerization inhibitor is 1g:0.01g, heating the reaction system to 105 ℃, simultaneously dissolving the glycidyl acrylate in the N, N-dimethylformamide A, placing the mixture in a constant-pressure dropping funnel, adding the mixture into the three-neck flask in a dropwise manner while stirring, stirring and reacting at 105 ℃ for 15h, after the reaction, reducing the temperature of the reaction system to room temperature, then carrying out reduced pressure distillation on the reaction system to remove the N, N-dimethylformamide, and then placing the reaction product in a vacuum at 60 ℃ for 4h to obtain an intermediate product II, wherein the infrared data of the intermediate product II are as follows:
3468cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 、1735cm -1 : -c=o present; 1614cm -1 、811cm -1 : -c=c-present; 1485cm -1 、1580cm -1 : amide N-H is present; 943cm -1 、824cm -1 : the epoxy group is absent;
(3) Adding an intermediate product II, a polymerization inhibitor and absolute ethyl alcohol into a three-neck flask, heating to 60 ℃, then adding lanthanum nitrate, fully and uniformly stirring, then dropwise adding a 30wt% sodium hydroxide aqueous solution with a dropping funnel while stirring, adjusting the pH=6 of a reaction system, standing after stirring at constant temperature for 6 hours, cooling the temperature of the reaction system to room temperature, then adopting a vacuum pump to carry out suction filtration on the reaction product, washing the obtained solid product with deionized water for 3 times, putting the obtained product into a constant temperature drying oven, and carrying out vacuum drying at 40 ℃ for 8 hours to obtain a target product III, wherein the infrared data of the product III are as follows:
3468cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 、1735cm -1 : -c=o present; 1614cm -1 、811cm -1 : -c=c-present; 1485cm -1 、1580cm -1 : amide N-H is present; 1382cm -1 、1428cm -1 : the presence of a carboxylate; 793cm -1 : O-La is present;
the dosage ratio of the intermediate product II to the absolute ethyl alcohol to the lanthanum nitrate to the deionized water is 1.2mol:500mL:1mol:1000mL;
the dosage ratio of the intermediate product II to the polymerization inhibitor is 1g to 0.005g.
The preparation method of the yellowing-resistant and oxidation-resistant PVC film comprises the following steps:
s1: weighing PVC, a toughening agent, a processing ACR, a heat stabilizer, zinc stearate and a lubricant according to the formula amount, uniformly mixing to obtain a mixed material, heating the mixed material to 110 ℃ from room temperature within 10min, then cooling to 45 ℃, and standing for 24h to obtain a pretreated material;
s2: extruding the pretreated material through a screw extruder, calendaring, stretching, cooling and coiling to obtain the PVC film.
Specifically, in the extrusion process of the screw extruder, the temperature of the first region is 180 ℃, the temperature of the second region is 145 ℃, and the temperature of the third region is 160 ℃.
The rolling is five-roller rolling: the temperature of the No. 1 roller is 185 ℃, and the linear speed is 9.7m/min; the temperature of the No. 2 roller is 185 ℃, and the linear speed is 10.9m/min; the temperature of the No. 3 roller is 190 ℃, and the linear speed is 12.8m/min; the temperature of the No. 4 roller is 200 ℃, and the linear speed is 14.3m/min; the 5# roll temperature was 190℃and the linear velocity was 15.8m/min.
The cooling is four-stage cooling, and the cooling temperature is 55 ℃, 50 ℃, 45 ℃ and 36 ℃ in sequence.
Example 5
The yellowing-resistant and oxidation-resistant PVC film comprises the following raw materials in parts by weight:
100 parts of PVC;
impact modifier CPE 8 parts;
2 parts of processing modifier ACR;
3 parts of a heat stabilizer;
0.7 parts of zinc stearate;
0.6 parts of lubricant.
The preparation method of the heat stabilizer comprises the following steps:
(1) Adding trimellitic anhydride, 4- (2-aminoethyl) -2, 6-di-tert-butylphenol and ethyl acetate into a flask, stirring at room temperature for reaction for 18 hours, removing ethyl acetate in reactants by reduced pressure distillation after the reaction is finished, and then drying in vacuum at 60 ℃ for 4 hours to obtain an intermediate product I, wherein the infrared data of the intermediate product I are as follows:
3511cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 : -c=o present; 1250cm -1 : the anhydride disappears; 1485cm -1 、1580cm -1 : amide N-H is present;
the dosage ratio of the trimellitic anhydride to the 4- (2-aminoethyl) -2, 6-di-tert-butylphenol to the ethyl acetate is as follows: 0.1mol:0.1mol:400mL;
(2) Placing an intermediate product I, a catalyst, a polymerization inhibitor and N, N-dimethylformamide B in a three-neck flask, wherein the dosage ratio of the intermediate product I to the N, N-dimethylformamide B is 0.1mol:800mL, the dosage ratio of the intermediate product I to the catalyst is 1g:0.001-0.005g, the dosage ratio of the glycidyl acrylate to the polymerization inhibitor is 1g:0.01g, heating the reaction system to 100 ℃, simultaneously dissolving the glycidyl acrylate in the N, N-dimethylformamide A, placing the N, N-dimethylformamide A in a constant-pressure dropping funnel, adding the mixture into the three-neck flask in a dropwise manner while stirring, reacting for 15h at 100 ℃, after the reaction, cooling the temperature of the reaction system to room temperature, then carrying out reduced pressure distillation on the reaction system to remove the N, N-dimethylformamide, and then placing the reaction product in a vacuum at 60 ℃ for 4h to obtain an intermediate product II, wherein the infrared data of the intermediate product II are as follows:
3468cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 、1735cm -1 : -c=o present; 1614cm -1 、811cm -1 : -c=c-present; 1485cm -1 、1580cm -1 : amide N-H is present; 943cm -1 、824cm -1 : the epoxy group is absent;
(3) Adding an intermediate product II, a polymerization inhibitor and absolute ethyl alcohol into a three-neck flask, heating to 65 ℃, then adding lanthanum nitrate, fully and uniformly stirring, then dropwise adding a sodium hydroxide aqueous solution with the mass concentration of 30wt% while stirring by using a dropping funnel, adjusting the pH=7 of a reaction system, standing after stirring at constant temperature for 6 hours, cooling the temperature of the reaction system to room temperature, then adopting a vacuum pump to carry out suction filtration on a reaction product, washing the obtained solid product with deionized water for 3 times, putting the obtained product into a constant temperature drying oven, and carrying out vacuum drying at 40 ℃ for 8 hours to obtain a target product III, wherein the infrared data of the product III are as follows:
3468cm -1 : -OH is present; 3122cm -1 : -NH-present; 3024cm -1 : benzene ring C-H exists; 1761cm -1 、1735cm -1 : -c=o present; 1614cm -1 、811cm -1 : -c=c-present; 1485cm -1 、1580cm -1 : amide N-H is present; 1382cm -1 、1428cm -1 : the presence of a carboxylate; 793cm -1 : O-La is present;
the dosage ratio of the intermediate product II to the absolute ethyl alcohol to the lanthanum nitrate to the deionized water is 1.2mol:500mL:1mol:1000mL;
the dosage ratio of the intermediate product II to the polymerization inhibitor is 1g to 0.005g.
The preparation method of the yellowing-resistant and oxidation-resistant PVC film comprises the following steps:
s1: weighing PVC, a toughening agent, a processing ACR, a heat stabilizer, zinc stearate and a lubricant according to the formula amount, uniformly mixing to obtain a mixed material, heating the mixed material to 115 ℃ from room temperature within 12min, then cooling to 50 ℃, and standing for 24h to obtain a pretreated material;
s2: extruding the pretreated material through a screw extruder, calendaring, stretching, cooling and coiling to obtain the PVC film.
Specifically, in the extrusion process of the screw extruder, the temperature of the first region is 185 ℃, the temperature of the second region is 150 ℃, and the temperature of the third region is 170 ℃.
The rolling is five-roller rolling: the temperature of the No. 1 roller is 190 ℃, and the linear speed is 9.7m/min; the temperature of the No. 2 roller is 190 ℃, and the linear speed is 10.9m/min; the temperature of the No. 3 roller is 195 ℃ and the linear speed is 12.8m/min; the temperature of the No. 4 roller is 200 ℃, and the linear speed is 14.3m/min; the 5# roll temperature was 200deg.C and the line speed was 15.8m/min.
The cooling is four-stage cooling, and the cooling temperature is 55 ℃, 50 ℃, 45 ℃ and 36 ℃ in sequence.
Comparative example 1 the same as example 1 was carried out, except that comparative example 1 replaced the heat stabilizer of example 1 with an equivalent weight part of calcium zinc stabilizer.
Comparative example 2 the same as example 1 except that comparative example 2 uses the same weight part of the calcium zinc stabilizer as the heat stabilizer in example 1, and 0.7 weight part of the antioxidant 264 is additionally added.
Comparative example 3 the same as example 1, except that the heat stabilizer of comparative example 3 was prepared as follows:
adding trimellitic anhydride and absolute ethyl alcohol into a three-neck flask, placing the three-neck flask into a constant temperature tank, heating to 80 ℃, then adding lanthanum nitrate, fully and uniformly stirring, dropwise adding 30wt% of dilute ammonia water solution while stirring by a dropping funnel, slowly dropwise adding, adjusting pH=6, stirring at constant temperature for reaction for 6 hours, standing, cooling to room temperature, carrying out suction filtration by a vacuum pump, washing 3 times by deionized water, placing the obtained product into a constant temperature drying oven, and carrying out vacuum drying at 40 ℃ for 8 hours to obtain a target product, wherein the infrared data are as follows:
3024cm -1 : benzene ring C-H exists; 1382cm -1 、1428cm -1 : the presence of a carboxylate; 793cm -1 : O-La is present;
the dosage ratio of the trimellitic anhydride to the absolute ethyl alcohol to the lanthanum nitrate to the deionized water is as follows: 1.2mol:500mL:1mol:1000mL.
Comparative example 4 the same as in example 1 except that the heat stabilizer of comparative example 4 was prepared in the same manner as in comparative example 3, 0.7 parts by weight of antioxidant 264 was further added to comparative example 4.
Comparative example 5 the same as example 1, except that zinc stearate was not added in comparative example 5.
The PVC films obtained in examples 1 to 5 and comparative examples 1 to 5 of the present invention were subjected to the relevant performance test, the test results are shown in Table 1, wherein the test method is as follows:
(1) Plasticizing time: and testing the thermal stability of the PVC mixed material by adopting a torque rheometer. The preheating temperature of the mixing chamber is 180 ℃ and the rotating speed is 35r/min.
(2) Static thermal stability: the Congo red method is used for testing PVC blends with reference to GB/T2917.1-2002.
(3) Apparent color: the final color of the sample piece after the PVC film sample was detached from the roll was visually inspected. Apparent color representation method: 5 is the lightest color, namely the optimal color; 1 is the darkest, i.e. worst, color.
(4) Yellowing resistance (yellowness index): the tristimulus values X, Y, Z of the different samples before and after aging were tested by using a YI-48A whiteness colorimeter according to the GB2409 standard, and the yellow indexes of the film samples before and after aging were calculated by the following formula:
YI＝[100×(1.28X-1.06Z)]/Y
(ΔYI n ＝YI n －YI 0 wherein: ΔYI n The change amount of yellow index after the sample is aged for n days; YI (YI) 0 And YI n Yellow index values before and after n days of aging, respectively) of the film samples were tested for n=20 days in this test.
(5) Migration resistance: placing the PVC film in an ultraviolet aging test box for 20 days, taking out, eluting the PVC film with acetonitrile, taking out the eluting solution, measuring ultraviolet-visible spectrum, and setting the wavelength to be in the range of 200-500 nm. The migration effect is expressed by the following steps: 5 is the lowest molar absorption coefficient, namely the optimal mobility; 1 is the molar absorption coefficient that is the largest, i.e. the worst mobility.
TABLE 1
As can be seen from Table 1, compared with the PVC film obtained by adopting the conventional calcium zinc heat stabilizer, the yellowing-resistant and antioxidant PVC film obtained by the invention has obvious advantages in thermal stability, yellowing resistance and oxidation aging resistance, and also has better migration resistance.
Through the formula optimization design, when the weight ratio of the self-made heat stabilizer to the zinc stearate is 3:1, the yellowing-resistant and antioxidant PVC film obtained by the invention has optimal heat stability and yellowing-resistant effect.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (6)
1. The yellowing-resistant and oxidation-resistant PVC film is characterized by comprising the following raw materials in parts by weight:
100 parts of PVC;
4-10 parts of a toughening agent;
2 parts of processing modifier ACR;
2-3 parts of a heat stabilizer;
0.5-1 part of zinc stearate;
0.4-0.7 parts of lubricant;
the preparation method of the heat stabilizer comprises the following steps:
(1) Adding trimellitic anhydride, 4- (2-aminoethyl) -2, 6-di-tert-butylphenol and ethyl acetate into a flask, stirring at room temperature for reaction for 15-20h, removing ethyl acetate in reactants by reduced pressure distillation after the reaction is finished, and then drying at 60 ℃ in vacuum for 4h to obtain an intermediate product I;
the dosage ratio of the trimellitic anhydride to the 4- (2-aminoethyl) -2, 6-di-tert-butylphenol to the ethyl acetate is as follows: 0.1mol:0.1mol:400mL;
(2) Placing an intermediate product I, a catalyst, a polymerization inhibitor and N, N-dimethylformamide B in a three-neck flask, wherein the dosage ratio of the intermediate product I to the N, N-dimethylformamide B is 0.1mol:800mL, the dosage ratio of the intermediate product I to the catalyst is 1g:0.001-0.005g, the dosage ratio of glycidyl acrylate to the polymerization inhibitor is 1g:0.01g, raising the temperature of a reaction system to 100-105 ℃, simultaneously dissolving the glycidyl acrylate in the N, N-dimethylformamide A, placing the N-dimethylformamide A in a constant-pressure dropping funnel, adding the N-dimethylformamide A into the three-neck flask in a dropwise manner while stirring, stirring at 100-105 ℃ for reacting for 12-15h, reducing the temperature of the reaction system to room temperature after the reaction is finished, performing reduced pressure distillation on the reaction system to remove the N, N-dimethylformamide, and then placing the reaction product in a vacuum at 60 ℃ for 4h to obtain an intermediate product II;
(3) Adding an intermediate product II, a polymerization inhibitor and absolute ethyl alcohol into a three-neck flask, heating to 60-80 ℃, then adding lanthanum nitrate, fully and uniformly stirring, then dropwise adding an alkaline solution with the mass concentration of 30wt% while stirring by using a dropping funnel, adjusting the pH value of a reaction system to be 6-7, stirring at constant temperature for reaction for 6 hours, standing, cooling the reaction system to room temperature, then adopting a vacuum pump to carry out suction filtration on a reaction product, washing the obtained solid product with deionized water for 3 times, putting the obtained solid product into a constant temperature drying box, and carrying out vacuum drying at 40 ℃ for 8 hours to obtain a target product III;
the dosage ratio of the intermediate product II to the absolute ethyl alcohol to the lanthanum nitrate to the deionized water is 1.2mol:500mL:1mol:1000mL;
the dosage ratio of the intermediate product II to the polymerization inhibitor is 1g to 0.005g.
2. A yellowing-resistant, antioxidant PVC film according to claim 1, wherein the toughening agent comprises at least one of impact modifiers ACR, CPE.
3. A yellowing-resistant and oxidation-resistant PVC film according to claim 1, wherein the alkaline solution comprises aqueous sodium hydroxide or dilute aqueous ammonia.
4. The yellowing-resistant and oxidation-resistant PVC film according to claim 1, wherein the catalyst of step (2) comprises at least one of triphenylphosphine, tetrabutylammonium bromide or N, N-dimethylbenzylamine.
5. A yellowing resistant and antioxidant PVC film according to any one of claims 1 to 4, wherein the method of preparation comprises the steps of:
s1: weighing PVC, a toughening agent, a processing ACR, a heat stabilizer, zinc stearate and a lubricant according to the formula amount, uniformly mixing to obtain a mixed material, heating the mixed material to 110-115 ℃ from room temperature within 10-12min, cooling to 45-50 ℃, and standing for 24h to obtain a pretreated material; s2: extruding the pretreated material through a screw extruder, calendaring, stretching, cooling and coiling to obtain the PVC film.
6. The yellowing-resistant and oxidation-resistant PVC film according to claim 5, wherein the first region temperature is 175-190 ℃, the second region temperature is 140-155 ℃ and the third region temperature is 160-170 ℃ during extrusion by a screw extruder.
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| CN112915810A (en) * | 2021-01-26 | 2021-06-08 | 廖威明 | Pollution-resistant oxygen-permeable film material and preparation method thereof |
| CN116080222A (en) * | 2022-12-30 | 2023-05-09 | 江苏佳饰家新材料集团股份有限公司 | Color film imitating solid wood floor |
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| CN112915810A (en) * | 2021-01-26 | 2021-06-08 | 廖威明 | Pollution-resistant oxygen-permeable film material and preparation method thereof |
| CN116080222A (en) * | 2022-12-30 | 2023-05-09 | 江苏佳饰家新材料集团股份有限公司 | Color film imitating solid wood floor |
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| "Synthesis of lanthanum tris (mono-i-octyl phthalate) and its thermal stability for polyvinyl chloride";《Journal of central south university of technology》;第8卷(第3期);161-163 * |
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