CN111349041A - High-molecular material light stabilizer with antioxidant function and preparation method thereof - Google Patents
High-molecular material light stabilizer with antioxidant function and preparation method thereof Download PDFInfo
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- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
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Abstract
The invention relates to a high molecular material light stabilizer with an antioxidant function, which belongs to the field of high molecular material stabilizers, and has a structural general formula of simultaneously bonding a steric hindrance phenol group and an alkoxy steric hindrance amine group, so that the stabilizer has the functions of antioxidant and light stabilization; according to the method for preparing the stabilizer, malonic diester, alkoxy hindered amine piperidinol and N- (3, 5-di-tert-butyl-4-hydroxybenzyl) dimethylamine are used as raw materials, and two steps of ester exchange and hindered phenol introduction are carried out to obtain the high polymer material stabilizer which is simultaneously bonded with alkoxy hindered amine and hindered phenol on molecules.
Description
Technical Field
The invention relates to a high polymer material light stabilizer with an antioxidant function and a preparation method thereof, belonging to the technical field of high polymer material stabilizers.
Background
In order to improve the performance and prolong the service life of the polymer material, various stabilizing aids need to be added into the polymer material. Light stabilizers and antioxidants are two important components of polymeric material stabilizers. The light stabilizer can inhibit or slow down the degradation of the high molecular material caused by photo-oxidation. The hindered amine light stabilizer is the most commonly used type in high molecular material light stabilizers, and has become the mainstream of the light stabilizer due to the excellent performance of the hindered amine and the good synergistic effect of the hindered amine, the ultraviolet light absorber and the antioxidant, and the hindered amine light stabilizer accounts for more than half of the consumption of the light stabilizers all over the world. The antioxidant can delay or inhibit thermal oxidation of high molecular material compounds in air, and the most widely used antioxidant is a hindered phenol antioxidant. In the use process of various high polymer materials such as plastics, synthetic fibers, rubber and the like, in order to slow down the photodegradation and thermal oxidation of the high polymer materials and prolong the service life of the high polymer materials, a light stabilizer and an antioxidant are indispensable parts in an addition auxiliary agent of the high polymer materials.
Generally, the polymer material additives need to be compounded or added in the polymer material processing process in batches, and the whole process is very complex. It has been shown that different stabilizers may show good synergistic effects under appropriate conditions. Therefore, the research and development of multifunctional and efficient polymer material stabilizer are receiving more and more attention. In the research process, researchers pay more attention to the development of compound auxiliaries, and relatively few research and development of multifunctional high-efficiency auxiliaries formed by bonding different functional groups in the same molecule are performed. Different functional groups are bonded into the same molecule, and the effect of one dose and multiple functions can be achieved. Thus, the use complexity of the high polymer material stabilizer can be greatly reduced. An example of a successful multifunctional polymer stabilizer is Tinuvin144 developed by Ciba-Geigy, in which the unit hindered phenol group and the pentamethylpiperidine hindered amine group in the molecule show good synergistic effect, so that Tinuvin144 becomes a famous brand name of Ciba-Geigy. Meanwhile, in order to improve the service life of the hindered amine light stabilizer in an acidic environment and to improve the compatibility with a high molecular material (such as polyvinyl chloride) which may decompose an acidic substance in the using process, the low-alkalinity alkoxy hindered amine also develops into an important trend of the hindered amine.
Therefore, bonding different functional groups in the same molecule to form multifunctional stabilizers with different stabilizing effects is an important research direction in the art. The hindered amine and hindered phenol are used as the most commonly used light stabilizer and antioxidant auxiliary agent of the high polymer material, two groups of light stabilization and antioxidation are bonded on one compound, if the two groups can show positive synergistic effect, the auxiliary agent can have the functions of light stabilization and antioxidation simultaneously, and the complexity of the addition operation of the high polymer material auxiliary agent can be reduced.
Disclosure of Invention
Aiming at the complexity of the use of the conventional high polymer material stabilizer, the invention provides a high polymer material light stabilizer which is simultaneously bonded with hindered phenol and alkoxy hindered amine groups and has an antioxidant function and a preparation method thereof.
The technical scheme for solving the technical problems is as follows: a high molecular material light stabilizer with an antioxidant function is characterized in that the structural general formula (I) is as follows:
wherein R is1Is any one of C1-C18 straight-chain alkyl, branched-chain alkyl or cyclic alkyl; r2Is benzyl or phenyl; r3Is any one of H, C1-C18 alkyl or C1-C18 alkenyl.
On the basis of the technical scheme, the invention can also make the following improvements:
further, the structural general formula (II) of the benzyl is as follows:
wherein: r4、R5、R6、R7Is any one of linear chain or branched chain alkyl of H, C1-C12, R8Is H, OH OR-OR9Any one of the above; said R9Is any one of C1-C18 straight chain or branched alkyl or alkenyl.
Further, in the present invention,the structural general formula (III) of the phenyl is as follows:
wherein: r10、R11、R12、R13、R14Any one of linear chain or branched chain alkyl or alkenyl of H, C1-C18.
The invention also discloses a preparation method of the high polymer material light stabilizer with the antioxidant function, which is characterized by comprising the following steps:
1) adding malonic diester and alkoxy hindered amine piperidinol into a reactor, wherein the molar ratio of the malonic diester to the alkoxy hindered amine piperidinol is 1: 0.20-4.0; adding a catalyst A, wherein the addition amount of the catalyst A is 0.01-10.0% of the total mass of the malonic diester and the alkoxy hindered amine piperidinol, and reacting for 4-24 hours at the temperature of 50-150 ℃ and under normal pressure to obtain an ester exchange product A;
2) adding the product A obtained in the step 1) and N- (3, 5-di-tert-butyl-4-hydroxybenzyl) dimethylamine into a reactor, wherein the molar ratio of the product A to the N- (3, 5-di-tert-butyl-4-hydroxybenzyl) dimethylamine is 1: 1.0-10.0; adding a catalyst B, wherein the addition amount of the catalyst B is 0.01-5.0% of the total mass of the product A and the N- (3, 5-di-tert-butyl-4-hydroxybenzyl) dimethylamine; adding an organic solvent, and reacting at the temperature of 30-150 ℃ and under normal pressure for 6-72 hours to obtain the high polymer material light stabilizer compound with the antioxidant function;
the structural general formula (IV) of the malonic diester is as follows:
the general structural formula (V) of the alkoxy hindered amine piperidinol is as follows:
wherein R is15Is H, benzyl or phenyl; r1Is C1-C18 straight chain alkyl, branched chain alkyl or cycloalkyl; r3Is H, C1-C18 alkyl or C1Any of C18 alkylene groups.
The invention designs a high molecular material light stabilizer with an antioxidant function, which is a multifunctional high molecular material stabilizer simultaneously bonded with alkoxy hindered amine and hindered phenol on molecules by taking malonic diester, alkoxy hindered amine piperidinol and N- (3, 5-di-tert-butyl-4-hydroxybenzyl) dimethylamine as raw materials and introducing ester exchange and hindered phenol.
The reaction general formula of the invention is as follows:
on the basis of the technical scheme, the invention can also make the following improvements:
further, in the step 1), before adding the catalyst a, a reaction solvent is added into the reactor, wherein the reaction solvent is any one or a combination of several of C4-C12 straight-chain or branched-chain alkane, toluene, xylene, tetrahydrofuran, N-dimethylformamide or methyl tert-butyl ether.
Further, in the step 1), the catalyst a is any one or a combination of several of metal amide, alkali metal alkoxide, alkali metal hydroxide, tetrabutyl titanate, tetraisopropyl titanate, dibutyltin oxide and basic ionic liquid.
Further, in the step 2), the catalyst B is any one or a combination of several of alkali metal amide, alkali metal alkoxide or alkali metal hydroxide and basic ionic liquid.
The alkaline catalyst is adopted, which is beneficial to the recycling of the solvent in the preparation process.
Further, in the step 2), the organic solvent is any one or a combination of several of petroleum ether, cyclohexane, N-heptane, N-octane, tetrahydrofuran, N-dimethylformamide and methyl tert-butyl ether.
The invention has the advantages that: through two steps of ester exchange and introduction of hindered phenol groups, two functional groups of alkoxy hindered amine and hindered phenol are bonded on one molecule, so that one stabilizer has the functions of oxidation resistance and light stability, the addition process of the auxiliary agent of the high polymer material is simplified, and two stabilizing effects can be achieved by adding one auxiliary agent; meanwhile, the introduction of the alkoxy hindered amine group improves the service life of the stabilizer in an acidic environment and improves the compatibility of the stabilizer and a high polymer material which can decompose acidic substances in the using process.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
A high molecular material light stabilizer with an antioxidant function has the following structural formula:
it can be prepared by the following steps:
(1) 100ml of n-heptane, 3.31g of dimethyl malonate, 10.78g of 1-propoxy-2, 2,6, 6-tetramethylpiperidinol and 3ml of 1-butyl-3-methylimidazole hydrogen hydroxide ([ BMIM ] OH) are added into a 250 ml four-mouth bottle, the temperature is increased, reflux reaction is carried out, methanol generated in the reaction is separated out by a water separator, and the reaction is stopped when TLC monitors that the reaction is finished. Washing the reaction system with 50ml deionized water, evaporating the obtained water phase to remove water, recovering, decompressing, evaporating to remove the solvent, and recovering the 1-butyl-3-methylimidazole hydroxide for recycling. The organic phase was distilled off to recover n-heptane, which was washed successively with petroleum ether and ethyl acetate and then dried, to give 10.94g of bis (1-propoxy-2, 2,6, 6-tetramethylpiperidine) malonate in 87.9% yield.
(2) 150ml of N-heptane, 10.52g of N- (3, 5-di-tert-butyl-4-hydroxybenzyl) dimethylamine, 9.96g of bis (1-propoxy-2, 2,6, 6-tetramethylpiperidine) malonate, 0.8 g of sodium methoxide and reaction at 90 ℃ were put into a 250 ml four-necked flask, and after the reaction was monitored by TLC, the solvent was distilled off from the reaction system, washed with water, dried and concentrated. The white powdery product bis [3, 5-di-tert-butyl-4-hydroxyphenyl ] methylmalonic acid di (1-propoxy-2, 2,6, 6-tetramethyl-4-piperidyl) ester is obtained by recrystallization from a mixed solvent of petroleum ether and isopropanol (volume ratio is 3:1), and the yield is 69.1%.
1HNMR(500MHz,CDCl3),&ppm:7.01～7.04(s，4H),5.02(s,2H),4.02～3.96 (t,2H),3.61～3.74(m,4H),3.23～3.29(m,4H),1.94～1.78(m,8H),1.37(s,18H),1.31 (s,18H),1.25(s,12H),1.17(s,12H),0.96(t,6H)；MS(ESI):[M+1]945.71；
The results of nuclear magnetic resonance and mass spectrometry prove that the obtained product has a correct structure.
Example 2
A high molecular material light stabilizer with an antioxidant function has the following structural formula:
it can be prepared by the following steps:
(1) 150ml of n-octane, 3.32g of dimethyl malonate, 12.83g of 1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidinol and 5ml of 1-butyl-3-methylimidazole hydrogen hydroxide ([ BMIM ] OH) are added into a 250 ml four-neck bottle, the temperature is increased, reflux reaction is carried out, methanol generated in the reaction is separated out by a water separator, and the reaction is stopped when TLC monitors that the reaction is finished. Washing the reaction system with 50ml deionized water, evaporating the obtained water phase to remove water, recovering, decompressing, evaporating to remove the solvent, and recovering the 1-butyl-3-methylimidazole hydroxide for recycling. After the organic phase was distilled off n-octane, the organic phase was washed with a small amount of diethyl ether several times and dried to obtain 12.17g of bis (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidine) malonate in 83.7% yield.
(2) 200ml of xylene, 7.89g of N- (3, 5-di-tert-butyl-4-hydroxybenzyl) dimethylamine, 8.67g of bis (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidine) malonate, 0.6g of sodium methoxide and reaction at 90 ℃ are added into a 500ml four-neck flask, and after the reaction is monitored by TLC, the reaction system is washed by water, dried and concentrated. The mixed solvent of xylene and isopropanol (volume ratio is 4:1) is recrystallized to obtain a white powdery product, namely 10.02g of bis [3, 5-di-tert-butyl-4-hydroxyphenyl ] methyl malonic acid bis (1-cyclohexyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) ester is prepared, and the yield is 65.9%.
1HNMR(500MHz,CDCl3)，&ppm:7.01～7.04(s，4H),5.02(s,2H),4.03～3.94 (t,2H),3.52～3.44(m,4H),3.23～3.17(m,2H),1.47～1.39(m,20H),1.38(s,18H), 1.31(s,18H),1.23(s,12H),1.15(s,12H)；MS(ESI):[M+1]1015.75，
The results of nuclear magnetic resonance and mass spectrometry prove that the obtained product has a correct structure.
Example 3
A high molecular material light stabilizer with an antioxidant function has the following structural formula:
it can be prepared by the following steps:
(1) 6.31g of dimethyl 2- (4-methoxy) benzylmalonate, 10.77g of 1-propoxy-2, 2,6, 6-tetramethylpiperidinol, 180ml of n-heptane and 0.5g of sodium methoxide are added into a 500ml four-neck flask, reflux reaction is carried out, TLC is carried out until all dimethyl benzylmalonate is reacted, the solvent is evaporated under reduced pressure, washing with water and drying are carried out, and column chromatography is carried out, so that 9.47g of bis (1-propoxy-2, 2,6, 6-tetramethylpiperidine) 2- (4-methoxy) benzylmalonate is obtained, and the yield is 61.3%.
(2) Into a 500ml four-necked flask were charged 300ml of N, N-dimethylformamide, 2.65g of N- (3, 5-di-t-butyl-4-hydroxybenzyl) dimethylamine, 6.18g of bis (1-propoxy-2, 2,6, 6-tetramethylpiperidine) 2- (4-methoxy) benzylmalonate, and 0.2g of lithium amide, and after reacting at 80 ℃ for 12 hours, the reaction system was washed with water, dried, and concentrated. The product 2- (4-methoxy) benzyl-2- [ [3, 5-di-tert-butyl-4-hydroxy ] benzyl ] malonic acid bis (1-propoxy-2, 2,6, 6-tetramethylpiperidine) ester is obtained by recrystallization from a mixed solvent of petroleum ether and dichloromethane (volume ratio 6:1), and the yield is 53.4%.
1HNMR(500MHz,CDCl3),&ppm:7.01(d,2H),6.91(s,2H),6.72(s,2H), 4.02～3.96(t,2H),3.82(s,2H),3.61～3.74(m,4H),3.23～3.29(m,4H),1.92～1.80 (m,8H),1.55(s,4H),1.35(s,18H),1.27(s,12H),1.21(s,12H),0.97(t,6H)； MS(ESI):[M+1]651.3。
The results of nuclear magnetic resonance and mass spectrometry prove that the obtained product has a correct structure.
Example 4
A high molecular material light stabilizer with an antioxidant function has the following structural formula:
it can be prepared by the following steps:
(1) 5.05g of dimethyl 2- (4-methoxy) benzylmalonate, 10.22g of 1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidinol, 200ml of n-heptane and 0.5g of tetraisopropyl titanate are added into a 500ml four-neck flask, reflux reaction is carried out, methanol generated is separated out by a water separator, TLC is used for monitoring until all reactions are finished, the solvent is evaporated under reduced pressure, and after washing by water and petroleum ether, 9.85g of bis (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidine) 2- (4-methoxy) benzylmalonate is obtained by drying, and the yield is 70.4%.
(2) 300ml of N, N-dimethylformamide, 7.01g of bis (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidine) 2- (4-methoxy) benzylmalonate, 2.65g of N- (3, 5-di-tert-butyl-4-hydroxybenzyl) dimethylamine and 0.3g of lithium amide are added into a 500ml four-necked flask, and after the reaction is carried out at 75 ℃ for 10 hours, the reaction system is evaporated to remove the solvent, washed with water, dried and separated by column chromatography, 5.28g of bis (1-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidine) 2- (4-methoxy) benzyl-2- [ [3, 5-di-tert-butyl-4-hydroxy ] benzyl ] malonate as a solid powder product is obtained, wherein the yield is 57.4%.
1HNMR(500MHz,CDCl3),&ppm:7.03(d,2H),6.94(s,2H),6.83(s,2H), 4.02～3.96(t,2H),3.82(s,2H),3.61～3.74(m,4H),3.23～3.29(m,4H),1.92～1.80 (m,8H),1.55(s,4H),1.45～1.37(m,20H),1.35(s,18H),1.24(s,12H),1.15(s,12H)； MS(ESI):[M+1]916.73；
The results of nuclear magnetic resonance and mass spectrometry prove that the obtained product has a correct structure.
Testing the performance of the compound:
the results of comparing the performance evaluation of the PE and PP samples obtained by adding 0.2% of compounds 1, 2, 3 and 4 to the PE and PP samples respectively and setting blank samples and Tinuvin144 added with the products obtained in examples 1, 2, 3 and 4 respectively are as follows:
1. oxidative induction period test: according to GB/T17391-1998 test method for thermal stability of polyethylene pipes and tubes, the test is carried out on a Pyris1DSC differential scanning calorimetry analyzer of Perkinelmer company in USA, and the test results are as follows:
2. and (4) ultraviolet lamp aging test: is developed according to GB/T16422.1-2006 operating standard, and has the power of 200W and the wavelength range
The fluorescent ultraviolet lamp is used for illuminating for 24 hours, and the test results are as follows:
| adding | PE elongation at Break Retention (%) | PP elongation at Break Retention (%) |
| Compound 1 | 51 | 45 |
| Compound 2 | 43 | 49 |
| Compound 3 | 34 | 37 |
| Compound 4 | 33 | 36 |
| Tinuvin144 | 20 | 24 |
Experimental results show that the compounds 1, 2, 3 and 4 obtained in the embodiment of the invention can obviously prolong the oxidation induction period of PE and PP, and the anti-ultraviolet light aging effect is also obviously superior to Tinuvin 144; especially, the compounds 1 and 2 containing the double-hindered phenol and the double-alkoxy hindered amine in the molecular structure have excellent effects in oxidation induction experiments and ultraviolet light aging experiments. According to the experimental comparison results, the steric phenol and the alkoxy steric amine group of the designed compound show excellent positive synergistic effect, and the oxidation resistance and the light stability of the high molecular material can be obviously improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A high molecular material light stabilizer with an antioxidant function is characterized in that the structural general formula (I) is as follows:
wherein R is1Is any one of C1-C18 straight-chain alkyl, branched-chain alkyl or cyclic alkyl; r2Is benzyl or phenyl; r3Is any one of H, C1-C18 alkyl or C1-C18 alkenyl.
2. According to the claimsThe polymer material light stabilizer with antioxidant function in claim 1 is characterized in that the structural general formula (ii) of the benzyl group is:
wherein: r4、R5、R6、R7Is any one of linear chain or branched chain alkyl of H, C1-C12, R8Is H, OH OR-OR9Any one of the above; said R9Is any one of C1-C18 straight chain or branched alkyl or alkenyl.
3. The light stabilizer with antioxidant function for polymer material as claimed in claim 1, wherein the general structural formula (iii) of said phenyl group is:
wherein: r10、R11、R12、R13、R14Is any one of H, C1-C18 straight chain or branched chain alkyl or alkenyl.
4. A method for preparing the high molecular material light stabilizer with the antioxidant function according to claim 1, which comprises the following steps:
1) adding malonic diester and alkoxy hindered amine piperidinol into a reactor, wherein the molar ratio of the malonic diester to the alkoxy hindered amine piperidinol is 1: 0.20-4.0; adding a catalyst A, wherein the addition amount of the catalyst A is 0.01-10.0% of the total mass of the malonic diester and the alkoxy hindered amine piperidinol; reacting for 4-24 hours at the temperature of 50-150 ℃ and under normal pressure to obtain an ester exchange product A;
2) adding the product A obtained in the step 1) and N- (3, 5-di-tert-butyl-4-hydroxybenzyl) dimethylamine into a reactor, wherein the molar ratio of the product A to the N- (3, 5-di-tert-butyl-4-hydroxybenzyl) dimethylamine is 1: 1.0-10.0; adding a catalyst B, wherein the addition amount of the catalyst B is 0.01-5.0% of the total mass of the product A and the N- (3, 5-di-tert-butyl-4-hydroxybenzyl) dimethylamine; adding an organic solvent, and reacting at the temperature of 30-150 ℃ and under normal pressure for 6-72 hours to obtain the high polymer material light stabilizer compound with the antioxidant function;
wherein, the structural general formula (IV) of the malonic diester is as follows:
the general structural formula (V) of the alkoxy hindered amine piperidinol is as follows:
wherein R is15Is H, benzyl or phenyl; r1Is C1-C18 straight chain alkyl, branched chain alkyl or cycloalkyl; r3Is any one of H, C1-C18 alkyl or C1-C18 alkenyl.
5. The preparation method according to claim 4, wherein in the step 1), before adding the catalyst A, a reaction solvent is further added into the reactor, wherein the reaction solvent is any one or more of C4-C12 straight-chain or branched alkane, toluene, xylene, tetrahydrofuran, N-dimethylformamide or methyl tert-butyl ether.
6. The preparation method according to claim 4, wherein in the step 1), the catalyst A is any one or a combination of several of metal amide, alkali metal alkoxide, alkali metal hydroxide, tetrabutyl titanate, tetraisopropyl titanate, dibutyltin oxide and basic ionic liquid.
7. The preparation method according to claim 4, wherein in the step 2), the catalyst B is any one or a combination of several of alkali metal amide, alkali metal alkoxide or alkali metal hydroxide and basic ionic liquid.
8. The method according to claim 4, wherein in the step 2), the organic solvent is any one or a combination of several of petroleum ether, cyclohexane, N-heptane, N-octane, tetrahydrofuran, N-dimethylformamide and methyl tert-butyl ether.
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Cited By (3)
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|---|---|---|---|---|
| CN112010800A (en) * | 2020-09-08 | 2020-12-01 | 宿迁联盛科技股份有限公司 | Hindered phenol-containing hindered amine light stabilizer and preparation method and application thereof |
| CN112010799A (en) * | 2020-09-08 | 2020-12-01 | 宿迁联盛科技股份有限公司 | Hindered amine light stabilizer intermediate, and preparation method and application thereof |
| CN117106294A (en) * | 2023-09-25 | 2023-11-24 | 沧州维康食品药品包装有限公司 | Medical packaging bottle plastic material and preparation method thereof |
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| CN101885701A (en) * | 2010-06-28 | 2010-11-17 | 北京天罡助剂有限责任公司 | Hindered amine compound having double-hindered phenol structure for light stabilizer and preparation method thereof |
| CN102617450A (en) * | 2012-03-07 | 2012-08-01 | 烟台大学 | Polymer material stabilizer and preparation method thereof |
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| CN101885701A (en) * | 2010-06-28 | 2010-11-17 | 北京天罡助剂有限责任公司 | Hindered amine compound having double-hindered phenol structure for light stabilizer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112010800A (en) * | 2020-09-08 | 2020-12-01 | 宿迁联盛科技股份有限公司 | Hindered phenol-containing hindered amine light stabilizer and preparation method and application thereof |
| CN112010799A (en) * | 2020-09-08 | 2020-12-01 | 宿迁联盛科技股份有限公司 | Hindered amine light stabilizer intermediate, and preparation method and application thereof |
| CN112010800B (en) * | 2020-09-08 | 2021-11-16 | 宿迁联盛科技股份有限公司 | Hindered phenol-containing hindered amine light stabilizer and preparation method and application thereof |
| CN117106294A (en) * | 2023-09-25 | 2023-11-24 | 沧州维康食品药品包装有限公司 | Medical packaging bottle plastic material and preparation method thereof |
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