CN115724828A - Preparation method of low-distribution light stabilizer 944 - Google Patents
Preparation method of low-distribution light stabilizer 944 Download PDFInfo
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- CN115724828A CN115724828A CN202211472841.3A CN202211472841A CN115724828A CN 115724828 A CN115724828 A CN 115724828A CN 202211472841 A CN202211472841 A CN 202211472841A CN 115724828 A CN115724828 A CN 115724828A
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- 239000004611 light stabiliser Substances 0.000 title claims abstract description 27
- 238000009826 distribution Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 15
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- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- HPFWYRKGZUGGPB-UHFFFAOYSA-N 4,6-dichloro-n-(2,4,4-trimethylpentan-2-yl)-1,3,5-triazin-2-amine Chemical compound CC(C)(C)CC(C)(C)NC1=NC(Cl)=NC(Cl)=N1 HPFWYRKGZUGGPB-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000007530 organic bases Chemical class 0.000 claims abstract description 9
- 239000012074 organic phase Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000012295 chemical reaction liquid Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002516 radical scavenger Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000005292 vacuum distillation Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
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- 230000004580 weight loss Effects 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
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- 238000004821 distillation Methods 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
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- UCQQHIZRIQSXEM-UHFFFAOYSA-N hexane-1,6-diamine piperidine Chemical compound N1CCCCC1.NCCCCCCN UCQQHIZRIQSXEM-UHFFFAOYSA-N 0.000 description 1
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- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of a low-distribution light stabilizer 944, which comprises the following steps: in the presence of an organic solvent, 4, 6-dichloro-2-tert-octylamino-1, 3, 5-triazine, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine and an organic base are used as raw materials to synthesize an intermediate II, the intermediate II reacts with the N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine at high temperature and high pressure, after the reaction is finished, the organic solvent is added for dissolving after cooling, the mixture is filtered, a certain amount of water is added, the temperature is reduced for crystallization, the mixture is filtered, and the organic phase is subjected to vacuum distillation to obtain a finished product; the light stabilizer 944 obtained by the method has the characteristics of moderate molecular weight, narrow molecular weight distribution, less micromolecules, small environmental pollution, low cost, simple operation and high product yield, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of high polymer material modification aids, and particularly relates to a preparation method of a low-distribution light stabilizer 944.
Background
<xnotran> Chimassorb 944 Ciba-Geigy 20 80 ,90 , HALS , - { [6- [ (1,1,3,3- ) - ] -1,3,5- -2,4- ] [2- (2,2,6,6- ) - - - [4- (2,2,6,6- ) - ] ] }, 2000, , , , , FDA HALS . </xnotran>
In the currently disclosed synthesis method of hindered amine light stabilizer 944, a direct polymerization method of 4, 6-dichloro-2-tert-octylamino-1, 3, 5-triazine and N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine is mostly adopted, the method mainly has the defects of wide molecular weight distribution and more small molecules, and further influences the compatibility with high molecular materials, and the existing process mainly adopts a solvent method for synthesis and adds an inorganic alkaline aqueous solution as an acid-binding agent, the used solvent is mostly benzene which is a toxic chemical substance, the benzene substance is difficult to be removed cleanly in post-treatment due to high boiling point, the light stabilizer 944 is not favorable for being added into food packaging, the inorganic alkali is used as the acid-binding agent, and the generation of a large amount of high-salinity wastewater is inevitable, and the treatment cost is increased.
Disclosure of Invention
In order to solve the problems, the invention discloses a preparation method of a low-distribution light stabilizer 944.
The technical scheme of the invention is as follows:
a process for the preparation of a low profile light stabilizer 944, said process comprising the steps of:
step (1): dissolving the intermediate I and N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine in an organic solvent, adding an organic base acid-binding agent, heating to 60 to 80 ℃, keeping the temperature for 5 to 12h to obtain an intermediate reaction liquid, filtering the reaction liquid, cooling and crystallizing under stirring, filtering, and drying to obtain an intermediate II solid;
step (2): putting the intermediate II solid, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine and an organic alkali acid-binding agent into a high-pressure reaction kettle in the step (1), reacting at high temperature and high pressure for 6 to 12h, cooling to 50 to 60 ℃, adding an organic solvent for dissolving, filtering, transferring into a flask, adding water, stirring, cooling for crystallization, filtering, and distilling an organic phase to obtain a low-distribution light stabilizer 944; the intermediate I is 4, 6-dichloro-2-tert-octylamino-1, 3, 5-triazine.
Further, the organic base acid-binding agent is any one of triethylamine, pyridine, diisopropylethylamine, dimethylaminopyridine and hexamethylenetetramine.
Further, in step (1), the molar ratio of the N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine to the intermediate I to the organic base is 1:1.95 to 2.3:2 to 4; the dosage of the organic solvent is 4 to 10 times of N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine;
further, the organic solvent in the step (1) is any one of acetone, ethyl acetate, petroleum ether, acetonitrile, n-heptane, n-octane, cyclohexane and n-hexane, and the organic solvent in the step (2) is any one of acetone, ethyl acetate, petroleum ether, acetonitrile, ethanol, isopropanol and n-butanol.
Further, in the step (1), the temperature of the cooling crystallization is 0 to 20 ℃, and the crystallization time is 1 to 5 hours.
Further, the molar ratio of the intermediate II to the N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine to the organic base in step (2) is 1:1 to 3:2 to 4; the dosage of the organic solvent is 1 to 5 times of that of the intermediate II.
Further, the water adding amount in the step (2) is 5% -30% of the total mass of the solution.
Further, in the step (2), the temperature for cooling and crystallization is 0 to 20 ℃, and the crystallization time is 1 to 5 hours.
Further, in the step (2), the reaction temperature is 120 to 200 ℃, and the initial pressure of the reaction is 0.1 to 0.5 MPa.
The invention relates to a reaction chemical formula as follows:
the invention has the beneficial effects that:
(1): the synthesis method of the light stabilizer 944 adopts a mode of pre-polymerizing 4, 6-dichloro-2-tert-octylamino-1, 3, 5-triazine and N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine to synthesize an intermediate II, so that the problem that the second chlorine is easy to hydrolyze under the high-temperature condition of the 4, 6-dichloro-2-tert-octylamino-1, 3, 5-triazine can be reduced, the proportion of the intermediate II and the N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine can be adjusted, and the defect of wide molecular weight distribution existing in the synthesis method of the light stabilizer 944 at the present stage can be effectively solved;
(2): according to the invention, an organic alkali acid-binding agent is used as an acid-binding agent, so that the problem of high-salinity wastewater caused by adopting inorganic alkaline water in the prior art is effectively solved;
(3): the final polymerization adopts a melting method for polymerization, so that the concentration of the reaction liquid is improved, the collision probability among molecules in a system is further increased, and the generation of cyclics can be reduced;
(4) In the later stage of the reaction, a micromolecular solvent with a low boiling point is added into the system to dissolve the product, and a certain amount of cooling crystallization is added, so that most micromolecular impurities can be removed, no solvent residue in the product can be ensured, and benzene toxic and harmful solvent residue is avoided;
(5) The light stabilizer 944 obtained by the invention finally obtains a qualified product with the molecular weight of 2000-3100, the molecular weight of 1-1.5 and the light transmittance of more than or equal to 95%, and the product can improve the compatibility with a high polymer material, the migration resistance, the extraction resistance and the aging resistance, reduce the toxicity and the volatility of the product and show excellent effects in processing and use.
Drawings
FIG. 1 is a GPC chart of a light stabilizer 944 in example 1 of the present invention;
FIG. 2 is a TGA spectrum of light stabilizer 944 of example 1 of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
Example 1
50g of 4, 6-dichloro-2-tert-octylamino-1, 3, 5-triazine, 35.62 g of N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine, 21.90g of triethylamine and 200g of petroleum ether are added into a reaction bottle, the temperature is raised to 70 ℃, the reaction is kept for 7 hours to obtain intermediate reaction liquid, the reaction liquid is cooled to 40 ℃, filtered, salts generated in the reaction are removed, then the temperature is reduced to 5 ℃, stirred for 2 hours, filtered and dried to obtain intermediate II solid, the solid content of the intermediate II is 96.23%, and the yield is 94.05%.
74.31g of intermediate II, 60.31g of N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine and 10.20 g of triethylamine are put into a high-pressure reaction kettle, the initial pressure is 0.3MPa, the temperature is increased to 180 ℃, the heat preservation reaction is carried out for 12 hours, the temperature is reduced to 60 ℃, 150g of petroleum ether is added, the stirring is carried out for 60 minutes, the feed liquid is contained, the system is milky turbid liquid, the salt and part of small molecular impurities generated in the reaction are removed by filtration, colorless transparent liquid is obtained, the colorless transparent liquid is transferred into a flask, 20g of water is added into the system, the temperature is reduced to 3 ℃, the stirring is carried out for 3 hours, the milky liquid is obtained by multiple times of filtration, clear transparent liquid is obtained, the organic phase is subjected to pressure distillation to obtain a pale yellow solid, namely a low-distribution light stabilizer 944, the yield is 95.35%, mn =2859, mz/Mn =1.07, the light transmittance (425 nm) 98.01%, the softening point is 121 ℃, and the weight loss 5% temperature is 390.02 ℃.
Example 2
100 g of 4, 6-dichloro-2-tert-octylamino-1, 3, 5-triazine, 71.25 g of N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine, 38.33g of triethylamine and 400g of cyclohexane are added into a reaction bottle, the mixture is heated to 60 ℃ and reacted for 10 hours to obtain intermediate reaction liquid, the reaction liquid is cooled to 30 ℃ and filtered, salts generated by the reaction are removed, then the temperature is reduced to 0 ℃ and stirred for 2 hours, and the intermediate II solid is obtained by filtering and drying, the solid content of the intermediate II is 93.89%, and the yield is 92.16%.
145.65g of intermediate II, 118.20gN, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexamethylenediamine and 35.32 g of triethylamine are put into a high-pressure reaction kettle, the initial pressure is 0.5MPa, the temperature is increased to 160 ℃, the heat preservation reaction is carried out for 10 hours, the temperature is reduced to 60 ℃, 200g of ethanol is added into the system, the system is milky turbid liquid, colorless transparent liquid is obtained by filtration, the colorless transparent liquid is transferred into a flask, 50g of water is added into the system, the temperature is reduced to 2 ℃, the stirring is carried out for 2 hours, clear transparent liquid is obtained by multiple filtration, organic phase pressure distillation is carried out to obtain a light yellow product, namely the low-distribution light stabilizer 944, the yield is 93.35%, mn =2725, mz/Mn =1.25, the light transmittance (425 nm) is 97.9%, the softening point is 113 ℃, and the weight loss 5% temperature is 395.45 ℃.
Example 3
Adding 88.42 g of 4, 6-dichloro-2-tert-octylamino-1, 3, 5-triazine and 60 g of N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine, 24.03g of pyridine and 240g of acetonitrile into a reaction bottle, heating to 60 ℃, keeping the temperature, reacting for 8 hours to obtain intermediate reaction liquid, cooling the reaction liquid to 30 ℃, filtering, removing salts generated by the reaction, cooling to 10 ℃, stirring for 3 hours, filtering, and drying to obtain an intermediate II solid, wherein the solid content of the intermediate II is 92.12%, and the yield is 90.11%.
119.92g of intermediate II, 86.50g of N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine and 21.65g of triethylamine are put into a high-pressure reaction kettle, the initial pressure is 0.2MPa, the temperature is increased to 160 ℃, the heat preservation reaction is carried out for 14 hours, the temperature is reduced to 60 ℃, 200g of acetonitrile is added, the system is milky turbid liquid, colorless transparent liquid is obtained by filtration, the colorless transparent liquid is transferred into a flask, 25g of water is added into the system, the temperature is reduced to 0 ℃, the stirring is carried out for 2 hours, clear transparent liquid is obtained by multiple filtration, and organic phase is subjected to pressure distillation to obtain a light yellow product, namely a low-distribution light stabilizer 944, wherein the product yield is 93.01%, the Mn =2599, the Mz/Mn =1.30, the light transmittance (425 nm) is 98.5%, the softening point is 115 ℃, and the weight loss 5% temperature is 385.78 ℃.
Example 4
Adding 69.10 g of 4, 6-dichloro-2-tert-octylamino-1, 3, 5-triazine, 49.24g of N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine, 33.83g of diisopropylethylamine and 200g of n-heptane into a reaction bottle, heating to 70 ℃, keeping the temperature, reacting for 8 hours to obtain an intermediate reaction liquid, cooling the reaction liquid to 30 ℃, filtering, removing salts generated by the reaction, cooling to 0 ℃, stirring for 3 hours, filtering, drying to obtain an intermediate II solid, filtering, wherein the solid content of the intermediate II is 93.05%, and the yield is 91.43%.
99.84g of the intermediate II, 90.04g of N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine and 30.19g of diisopropylethylamine are put into a high-pressure reaction kettle, the initial pressure is 0.5MPa, the temperature is raised to 200 ℃, the reaction is kept for 12 hours, the temperature is reduced to 60 ℃, 200g of isopropanol is added, the system is milky turbid liquid, colorless transparent liquid is obtained by filtration, the colorless transparent liquid is transferred into a flask, 30 g of water is added, the temperature is reduced to 0 ℃, the stirring is carried out for 2 hours, clear transparent liquid is obtained by multiple filtration, and organic phase vacuum distillation is carried out to obtain a light yellow product, namely a low-distribution light stabilizer 944, the product yield is 90.21%, mn =2317, mz/Mn =1.05, the light transmittance (425 nm) is 97.01%, the softening point is 111 ℃, and the weight loss 5% temperature is 380.20 ℃.
Example 5
271.75g of 4, 6-dichloro-2-tert-octylamino-1, 3, 5-triazine, 193.63g of hexamethylenediamine piperidine, 81.42g of pyridine and 1000g of petroleum ether are added into a reaction bottle, the mixture is heated to 70 ℃ and kept warm to react for 10 hours to obtain intermediate reaction liquid, the reaction liquid is cooled to 30 ℃ and filtered to remove salts generated by the reaction, then the temperature is reduced to 0 ℃ and stirred for 5 hours, and the intermediate II is filtered and dried to obtain intermediate II solid, the content of the intermediate II is 95.21 percent, and the yield is 93.05 percent.
399.57g of intermediate II, 360.34g of N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine and 75.77g of pyridine are put into a high-pressure reaction kettle, the initial pressure is 0.5MPa, the temperature is increased to 200 ℃, the heat preservation reaction is carried out for 12 hours, the temperature is reduced to 60 ℃, 600 g of isopropanol is added, the system is milky turbid liquid, colorless transparent liquid is obtained by filtration, the colorless transparent liquid is transferred into a flask, 120 g of water is added, the temperature is reduced to 5 ℃, the stirring is carried out for 4 hours, clear transparent liquid is obtained by multiple filtration, organic phase vacuum distillation is carried out to obtain a light yellow product, namely the light stabilizer 944 with low distribution is obtained, the product yield is 92.14%, mn =2630 and Mz/Mn =1.10. 98.7 percent of light transmittance (425 nm), 113 percent of softening point and 386.3 percent of temperature of 5 percent of weight loss.
Example 6
And (3) fully mixing the product obtained in the embodiment 1-5 with PE in a 50 ℃ high-speed mixer according to the proportion that the addition amount is 0.5%, and then feeding the mixture into a film blowing machine for film blowing, wherein the film blowing temperature is 180 ℃, so that the modified PE sample is obtained.
Putting the prepared modified PE sample into a fluorescent ultraviolet lamp with the standard ISO 4892-2, wherein the aging time is 2000h, the illumination time is 8h, the temperature is 60 ℃, the condensation time is 4h, the temperature is 50 ℃, the wavelength is 320nm to 400nm, and the radiation intensity is 0.76W/m 2 。
And (3) testing mechanical properties: the tensile properties are according to GB/T1040-2006, tensile rate 200 mm/min. The results are shown in Table 1:
as can be seen from the table, after aging for 2000h, the pure PE sample is directly pulverized without tensile strength, and the tensile strength retention rate of the modified PP sample added with the product can be improved to be more than 80%. Therefore, the product contributes to the improvement of the aging resistance of the PE material.
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it will be apparent to those skilled in the art that several modifications and embellishments can be made without departing from the principle of the present invention, and these modifications and embellishments fall within the protection scope of the claims of the present invention.
Claims (9)
1. A method of making a low profile light stabilizer 944, the method comprising the steps of:
step (1): dissolving the intermediate I and N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine in an organic solvent, adding an organic base acid-binding agent, heating to 60 to 80 ℃, keeping the temperature for 5 to 12h to obtain an intermediate reaction liquid, filtering the intermediate reaction liquid, cooling and crystallizing under stirring, filtering, and drying to obtain an intermediate II solid;
step (2): putting the intermediate II solid obtained in the step (1), N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine and an organic alkali acid-binding agent into a high-pressure reaction kettle, reacting at high temperature and high pressure for 6 to 12h, cooling to 50 to 60 ℃, adding an organic solvent for dissolving, filtering, transferring into a flask, adding water, stirring, cooling for crystallization, filtering, and distilling an organic phase to obtain a low-distribution light stabilizer 944; the intermediate I is 4, 6-dichloro-2-tert-octylamino-1, 3, 5-triazine.
2. The method of claim 1, wherein the organic base acid-binding agent is any one of triethylamine, pyridine, diisopropylethylamine, dimethylaminopyridine, and hexamethylenetetramine.
3. The method of claim 1, wherein the molar ratio of the N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine to the intermediate I to the organic base acid scavenger in step (1) is 1:1.95 to 2.3:2 to 4; the dosage of the organic solvent is 4 to 10 times of that of the N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine.
4. The method for preparing a low distribution light stabilizer 944 according to claim 1, wherein the organic solvent in step (1) is any one of acetone, ethyl acetate, petroleum ether, acetonitrile, n-heptane, n-octane, cyclohexane and n-hexane, and the organic solvent in step (2) is any one of acetone, ethyl acetate, petroleum ether, acetonitrile, ethanol, isopropanol and n-butanol.
5. The method for preparing a low-profile light stabilizer 944 in accordance with claim 2, wherein the crystallization temperature in the step (1) and the crystallization time in the step (2) are from 0 to 20 ℃ and from 1 to 5 hours.
6. The method of claim 1, wherein the molar ratio of the intermediate II to the N, N-bis (2, 6-tetramethyl-4-piperidyl) 1, 6-hexanediamine to the organic base in step (2) is 1:1 to 3:2 to 4; the dosage of the organic solvent is 1 to 5 times of that of the intermediate II.
7. The method for preparing the low-distribution light stabilizer 944 of claim 1, wherein the water addition amount in the step (2) is 5% to 30% of the total mass of the solution.
8. The method for preparing a low-distribution light stabilizer 944 according to claim 1, wherein the temperature for cooling and crystallization in step (2) is from 0 ℃ to 20 ℃ and the crystallization time is from 1 h to 5h.
9. The method for preparing a low-profile light stabilizer 944 as claimed in claim 1, wherein the reaction temperature in step (2) is from 120 to 200 ℃ and the initial pressure of the reaction is from 0.1 to 0.5 MPa.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0881222A1 (en) * | 1997-05-30 | 1998-12-02 | Ciba SC Holding AG | A process for the preparation of polytriazine products containing 2,2,6,6-tetramethyl-4-piperidyl groups |
| CN101591331A (en) * | 2009-06-25 | 2009-12-02 | 中国乐凯胶片集团公司 | A kind of preparation method of hindered amine as light stabilizer |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0881222A1 (en) * | 1997-05-30 | 1998-12-02 | Ciba SC Holding AG | A process for the preparation of polytriazine products containing 2,2,6,6-tetramethyl-4-piperidyl groups |
| CN101591331A (en) * | 2009-06-25 | 2009-12-02 | 中国乐凯胶片集团公司 | A kind of preparation method of hindered amine as light stabilizer |
Non-Patent Citations (2)
| Title |
|---|
| 孟祎: "受阻胺类光稳定剂GW-944的合成", 精细化工, vol. 20, no. 9, pages 564 - 574 * |
| 葛凤燕: "受阻胺光稳定剂GW-944合成方法改进", 精细化工, vol. 22, no. 1, pages 56 - 58 * |
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