CN112608516A - Multifunctional light-stable composition and preparation method thereof - Google Patents
Multifunctional light-stable composition and preparation method thereof Download PDFInfo
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
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- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
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- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08K5/3492—Triazines
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- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
The invention belongs to the field of high polymer material additives, and particularly relates to a multifunctional light-stable composition and a preparation method thereof. The light stabilizer is a polymer shown in a formula I, wherein n is 2-10. The light stabilizer of the light stabilizing composition shown in the formula I and other assistantsThe light stabilizer shown in the formula I has multiple functional groups, so that the application range of the light stabilizer can be greatly enlarged, the light stabilizer has good ageing resistance on multiple materials, and the light stabilizer has good synergistic effect with other substances mixed with the components, so that the compounded composition has good compatibility with most high molecular materials, volatilization and migration in the using process can be effectively prevented, the lasting and stable effect is kept, and the ageing resistance of the polymer is effectively improved.
Description
Technical Field
The invention belongs to the field of high polymer material additives, and particularly relates to a multifunctional light-stable composition and a preparation method thereof.
Background
With the development of science and technology, the use of high polymer materials such as plastics, rubber, resin and fiber is becoming more and more widespread. These high molecular materials are highly irreplaceable in many fields, and people rely on the high molecular materials to a higher degree. However, a series of new problems also arise, and these materials are easily yellowed, embrittled, cracked and sticky under the action of oxygen, water and ultraviolet rays in the air during the production, transportation, storage and use of the materials, which leads to the reduction of the appearance and mechanical properties of the materials, influences the use, and causes the degradation and aging of the polymer materials.
With the destruction of atmospheric ozone layer, the ultraviolet radiation irradiated to the ground is greatly increased, which causes the degradation of the polymer material by photo-oxidation, thermal oxidation and other reactions under the conditions of light, oxygen, heat and the like, and also causes the aging degradation of the polymer material. Based on this, people pay more and more attention to what method can prevent or delay the aging of high polymer materials and prolong the service life of the materials. Researches find that the materials can be added with some additives with specific functions to delay the aging of the materials and prolong the service life, and the additives are light stabilizers.
There are four main classes of light stabilizers discovered today: a radical scavenger, an ultraviolet absorber, a light-shielding agent and a quencher. Among them, radical scavengers, particularly hindered amine light stabilizers and ultraviolet absorbers, are most widely used. The hindered amine light stabilizer belongs to aliphatic amines, has no absorption effect on ultraviolet rays, has a different action mechanism with an ultraviolet absorbent, but has a better synergistic effect with an antioxidant or the ultraviolet absorbent and the like, so that the anti-aging capability of the material is enhanced; meanwhile, the complex use of the compounds is found to have better compatibility with most polymers, and the application range of the compounds can be greatly increased. In addition, the molecular weight, alkalinity and molecular weight distribution of the light stabilizer have great influence on the migration resistance, extraction resistance, precipitation resistance, heat resistance and other properties of the light stabilizer.
Disclosure of Invention
The invention aims to provide a multifunctional light-stable composition and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a light stabilizer characterized by: the light stabilizer is a polymer shown in a formula I:
wherein n is 2-10.
A preparation method of a light stabilizer is characterized in that the polymer shown in the formula I is synthesized by a light stabilizer 3346 and 2- (2-hydroxy-5-bromomethyl-3-methylphenyl) -benzotriazole.
Further, adding the light stabilizer 3346 and the 2- (2-hydroxy-5-bromomethyl-3-methylphenyl) -benzotriazole into the autoclave in sequence, wherein the molar ratio of the light stabilizer 3346 to the 2- (2-hydroxy-5-bromomethyl-3-methylphenyl) -benzotriazole is 1:2-1:8, uniformly mixing, and heating to 80-120 ℃ in an alkaline environment for reacting for 8-24 hours; standing and separating the solution after the reaction is finished, washing an organic phase, distilling under reduced pressure, and cooling the concentrated solution to separate out a light yellow solid, namely the polymer shown in the formula I, wherein the molecular weight of the polymer is between 2000-5000-.
The base is selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and disodium hydrogen phosphate.
The molecular weight of the multifunctional group light stabilizer is between 2000 and 5000, and 2500 and 3500 are preferred.
A multifunctional light-stabilizing composition, which is the polymer of the formula I and other components; wherein the polymer shown in the formula I and other components are mixed according to the mass ratio of 40-80: 20-60 parts of; the other components are one or more of hindered amine light stabilizer, benzotriazole light stabilizer, triazine light stabilizer, benzophenone light stabilizer and antioxidant.
Preferably, the composition is the polymer of formula I and other ingredients; wherein the polymer shown in the formula I and other components are mixed according to the mass ratio of 40-80: 20-60 parts of; the other components are an antioxidant and a stabilizer, the mass ratio of the antioxidant to the stabilizer is 5-10:15-50, and the stabilizer is any three of a hindered amine light stabilizer, a benzotriazole light stabilizer, a triazine light stabilizer and a benzophenone light stabilizer.
Further preferably, the composition comprises, by weight, 40-60 parts of the polymer of the formula I, 15-20 parts of hindered amine light stabilizer, 10-15 parts of benzotriazole light stabilizer, 10-15 parts of triazine light stabilizer and 5-10 parts of antioxidant.
The hindered amine light stabilizer is selected from a reaction product of N, N' -bis [ N- (2,2,6, 6-tetramethyl-4-piperidyl) ] -1, 6-hexanediamine and 4-methylamino-2, 6-dichloro-1, 3, 5-triazine; bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) -2-cyclohexyl-2- (2-hydroxy-3, 5-di-tert-butylbenzyl) malonate; a reaction product of 2,4, 6-trichloro-1, 3, 5-triazine, 1, 2-bis (3-aminopropylamino) ethane and 4-cyclohexylamino-2, 2,6, 6-tetramethylpiperidine; a reaction product of N, N' -bis [ N- (2,2,6, 6-tetramethyl-4-piperidyl) ] -1, 6-hexanediamine and 4-morpholino-2, 6-dichloro-1, 3, 5-triazine; bis (2,2,6, 6-tetramethyl-4-piperidinyl) suberate; bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate; bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate; the reaction product of 2-chloro-4, 6-bis (4-cyclohexylamino-2, 2,6, 6-tetramethyl-4-piperidinyl) -1,3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane; 2- [ (2-hydroxyethyl) amino ] -4, 6-bis [ N- (1-cyclohexyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) ] cyclohexylamino-1, 3, 5-triazine; succinic acid, [ (4-phenyl) -methylene ] -bis- (1-methoxy-2, 2,6, 6-tetramethyl-4-piperidinyl) ester; n- (1-phenoxy-2, 2,6, 6-tetramethyl-4-piperidinyl) -N' -dodecyloxamide; bis (1-cyclohexyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate; the reaction product of 1- (2-hydroxyethyl) -2,2,6, 6-tetramethyl-4-hydroxypiperidine and suberic acid; tris (2,2,6, 6-tetramethyl-4-piperidinyl) nitrilotriacetate; 1- (2-hydroxyethyl) -2,2,6, 6-tetramethyl-4-hydroxypiperidine succinate; bis (2,2,6, 6-tetramethyl-4-piperidyl) stearate; bis (2,2,6, 6-tetramethyl-4-piperidinyl) succinate; bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) succinate; 4-dodecyloxy-2, 2,6, 6-tetramethylpiperidine; tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,3, 4-butanetetracarboxylate; bis (1-dodecyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) stearate; the reaction product of N, N' -bis [ N- (2,2,6, 6-tetramethyl-4-piperidyl) ] -1, 6-hexanediamine and 4-tert-butylamino-2, 6-dichloro-1, 3, 5-triazine, 3-octyl-1- (1-acetyl-2, 2,6, 6-tetramethyl-4-piperidyl) pyrrolidin-2, 5-one; 4-benzoyl-2, 2,6, 6-tetramethylpiperidine; bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, and bis (2,2,6, 6-tetramethyl-4-piperidyl) succinate are preferable.
The benzotriazole light stabilizer is selected from 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -benzotriazole; 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chloro-benzotriazole; 2- (2-hydroxy-5-methylphenyl) -benzotriazole; 2- (2-hydroxy-5-tert-butylphenyl) -benzotriazole; 5-bromomethyl-2- (2-hydroxy-3-isopropyl-5-methylphenyl) -benzotriazole; 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -benzotriazole; 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chloro-benzotriazole; 2- (2-hydroxy-3-methoxy-5-ethylphenyl) -benzotriazole; 2- (2-hydroxy-5-octylphenyl) -benzotriazole; 2- (2-hydroxy-3-benzyl-5-methoxyphenyl) -benzotriazole; 2- (2-hydroxy-3-tert-butyl-5-sec-butylphenyl) -benzotriazole; preference is given to 2- (2-hydroxy-3-tert-butyl-5-methoxyphenyl) -benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -benzotriazole and 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -benzotriazole.
The triazine light stabilizer is selected from 2,4, 6-tri (2-hydroxy-4-octyloxyphenyl) -1,3, 5-triazine; 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine; 2, 4-bis (2-hydroxy-4-propoxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine; 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine; 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (4-methylphenyl) -1,3, 5-triazine; 2- (2-hydroxy-4-dodecyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine; 2- [ 2-hydroxy-4- (2-hydroxy-3-butoxypropoxy) phenyl ] -4, 6-bis (2, 4-dimethyl) -1,3, 5-triazine; 2- [ 2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl ] -4, 6-bis (2, 4-dimethyl) -1,3, 5-triazine; preference is given to 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and 2, 4-bis (2-hydroxy-4-propoxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine.
The benzophenone light stabilizer is selected from 2,2' -dihydroxy benzophenone; 2, 4-dihydroxybenzophenone; 2-hydroxy-4-methoxy-benzophenone; 2-hydroxy-4-octyloxy-benzophenone; 2-hydroxy-4-decyloxy-benzophenone; 2-hydroxy-4-cyclohexyloxy-benzophenone; 2-hydroxy-4-benzyloxy-benzophenone; 2,2',4,4' -tetrahydroxybenzophenone; 2,2 '-dihydroxy-4, 4' -dimethoxybenzophenone; 2,2 '-dihydroxy-4, 4' -di-tert-butyl benzophenone; preference is given to 2,2 '-dihydroxy-4, 4' -di-tert-butylbenzophenone, 2-hydroxy-4-cyclohexyloxy-benzophenone and 2-hydroxy-4-benzyloxy-benzophenone.
The antioxidant is selected from 2, 6-di-tert-butyl-4-methylphenol; 2-tert-butyl-4, 6-dimethylphenol; 2, 6-di-tert-butyl-2-ethylphenol; 2, 6-di-tert-butyl-4-methoxyphenol; 2, 4-dioctylthiomethyl-6-methoxyphenol; 2, 4-dioctylthiomethyl-6-methylphenol; 2, 4-dioctylthiomethyl-6-tert-butylphenol; 2, 5-di-tert-butylhydroquinone; 2, 6-di-tert-butylhydroquinone; 2, 6-diphenyl-4-octadecyloxyphenol; 2,2' -thiobis (6-tert-butyl-4-methylphenol); 2,2' -methylenebis (6-tert-butyl-4-methylphenol); 2,2' -methylenebis (4, 6-di-tert-butylphenol); 2, 6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol; n, N' -dipropyl-p-phenylenediamine; n, N' -di-tert-butyl-p-phenylenediamine; n, N' -dicyclohexyl-p-phenylenediamine; n, N '-diphenyl-p-phenylenediamine, preferably 2, 6-di-tert-butyl-4-methoxyphenol, 2, 4-dioctylthiomethyl-6-methylphenol and 2,2' -methylenebis (6-tert-butyl-4-methylphenol).
A method for preparing multifunctional light-stable composition comprises mixing the above components at the above ratio; or mixing the components in proportion and dissolving in other modes to obtain the composition.
Further, the following steps are carried out:
1. directly and fully mixing the compound of the formula I, other light stabilizers and an antioxidant according to a certain proportion;
2. uniformly mixing the compound of the formula I, other light stabilizers and an antioxidant in a certain proportion, heating to melt the composition, cooling and crushing to obtain a target composition;
3. after the reaction for preparing the compound shown in the formula I is finished and filtered, directly adding other light stabilizer and antioxidant into the mother liquor to obtain a target composition;
4. the compound of the formula I, other light stabilizers and an antioxidant are uniformly mixed according to a certain proportion, a solvent is added to be completely dissolved, and then the solvent is evaporated to obtain the target composition.
The other mode is heating and melting or evaporating the solvent after the mixture is dissolved by the solvent.
The solvent is selected from toluene, acetone, xylene, N-dimethylformamide and tetrahydrofuran.
The invention has the characteristics and beneficial effects that:
the light stabilizer shown in the formula I is compounded and mixed with other additives, wherein the light stabilizer shown in the formula I has multiple functional groups, the application range of the light stabilizer can be greatly enlarged, the light stabilizer has good anti-aging performance on multiple materials, and the light stabilizer has good synergistic effect with other substances mixed with the components.
Detailed Description
The preparation method and application of the multifunctional light stabilizing composition of the present invention will be described in detail by the following examples, which are only for further description of the related contents of the present invention, and are not intended to limit the scope of the present invention, and for some insubstantial modifications and optimizations, the present invention still belongs to the scope of the present invention.
Preparation of multifunctional light stabilizer Polymer I
Example i
53.0g of light stabilizer 3346 was weighed out and dissolved in 300mL of toluene, and the above solvent was added to an autoclave, then 100mL of an aqueous solution of 8g of sodium hydroxide was added, 200mL of a toluene solution in which 31.8g of 2- (2-hydroxy-5-bromomethyl-3-methylphenyl) -benzotriazole was dissolved was slowly added, the air in the autoclave was replaced with nitrogen three times, the temperature was slowly raised to 110 ℃, and the reaction was stirred for 16 hours. After the reaction is finished, the water layer is separated, the organic phase is washed for 3 times by 100mL of deionized water, the toluene is evaporated under reduced pressure, and the concentrated solution is naturally cooled to separate out a light yellow solid I. The number average molecular weight of the product is measured: 2827.
example ii
53.0g of light stabilizer 3346 was weighed out and dissolved in 300mL of toluene, and the above solvent was added to an autoclave, then 100mL of an aqueous solution of 8g of sodium hydroxide was added, 200mL of a toluene solution in which 63.6g of 2- (2-hydroxy-5-bromomethyl-3-methylphenyl) -benzotriazole was dissolved was slowly added, the air in the autoclave was replaced with nitrogen three times, the temperature was slowly raised to 90 ℃, and the reaction was stirred for 12 hours. And (3) separating a water layer after the reaction is finished, washing an organic phase for 3 times by using 100mL of deionized water, evaporating toluene under reduced pressure for concentration, and naturally cooling a concentrated solution to separate out a light yellow solid I. The number average molecular weight of the product is measured: 2336.
example iii
53.0g of light stabilizer 3346 was weighed out and dissolved in 300mL of acetone, and the above solvent was added to an autoclave, then 100mL of an aqueous solution of 12g of sodium hydroxide was added, 200mL of an acetone solution in which 63.6g of 2- (2-hydroxy-5-bromomethyl-3-methylphenyl) -benzotriazole was dissolved was slowly added, the air in the autoclave was replaced three times with nitrogen, and the mixture was heated to 105 ℃ with stirring and reacted for 20 hours. And (3) separating a water layer after the reaction is finished, washing an organic phase for 3 times by using 100mL of deionized water, evaporating acetone under reduced pressure for concentration, and naturally cooling a concentrated solution to separate out a light yellow solid I. The number average molecular weight of the product is measured: 3815.
preparation of multifunctional light stabilizing composition:
example 1:
preparation of composition (1): 50g of the polymer I in example I, 20g of bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) succinate, 15g of 2- (2-hydroxy-3-tert-butyl-5-methoxyphenyl) -benzotriazole, 12g of 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and 3g of 2, 6-di-tert-butyl-4-methoxyphenol were thoroughly mixed in a ball mill for 30 minutes to obtain a composition (1).
Example 2:
preparation of composition (2): 50g of the polymer I in example I, 20g of bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) succinate, 15g of 2- (2-hydroxy-3-tert-butyl-5-methoxyphenyl) -benzotriazole, 12g of 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and 3g of 2, 6-di-tert-butyl-4-methoxyphenol were mixed and melted, stirred for 10 minutes to mix uniformly, cooled and then ground to obtain a composition (2).
Example 3:
preparation of composition (3): 50g of the polymer I in example I, 20g of bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) succinate, 15g of 2- (2-hydroxy-3-tert-butyl-5-methoxyphenyl) -benzotriazole, 12g of 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and 3g of 2, 6-di-tert-butyl-4-methoxyphenol were taken, the above mixture was charged into a flask, xylene was added to completely dissolve the mixture, and the solvent was distilled off to obtain a composition (3).
Example 4:
preparation of composition (4): 50g of the polymer I obtained in example ii, 20g of bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) succinate, 15g of 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 12g of 2,2 '-dihydroxy-4, 4' -di-tert-butylbenzophenone and 3g of 2, 6-di-tert-butyl-4-methoxyphenol were thoroughly mixed in a ball mill for 30 minutes to obtain a composition (4).
Example 5:
preparation of composition (5): 50g of the polymer I obtained in example iii, 20g of 2- (2-hydroxy-3-tert-butyl-5-methoxyphenyl) -benzotriazole, 15g of 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 12g of 2,2 '-dihydroxy-4, 4' -di-tert-butylbenzophenone and 3g of 2, 6-di-tert-butyl-4-methoxyphenol were thoroughly mixed in a ball mill for 30 minutes to obtain a composition (5).
Example 6:
preparation of composition (6): 55g of the polymer I in example I, 25g of 2- (2-hydroxy-3-tert-butyl-5-methoxyphenyl) -benzotriazole, 15g of 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and 5g of 2, 6-di-tert-butyl-4-methoxyphenol were thoroughly mixed in a ball mill for 30 minutes to give a composition (6).
Example 7:
preparation of composition (7): 55g of the polymer I from example I, 25g of 2- (2-hydroxy-3-tert-butyl-5-methoxyphenyl) -benzotriazole, 15g of 2,2 '-dihydroxy-4, 4' -di-tert-butylbenzophenone and 5g of 2, 6-di-tert-butyl-4-methoxyphenol were thoroughly mixed in a ball mill for 30min to give a composition (7).
Example 8:
preparation of composition (8): 55g of the polymer I in example I, 25g of bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) succinate, 15g of 2,2 '-dihydroxy-4, 4' -di-tert-butylbenzophenone and 5g of 2, 6-di-tert-butyl-4-methoxyphenol were thoroughly mixed in a ball mill for 30 minutes to obtain a composition (8).
Example 9:
preparation of composition (9): 60g of the polymer I in example I, 20g of bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) succinate, 10g of 2- (2-hydroxy-3-tert-butyl-5-methoxyphenyl) -benzotriazole and 10g of 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine were thoroughly mixed in a ball mill for 30 minutes to obtain a composition (9).
Example 10:
preparation of composition (10): 60g of the polymer I in example I, 20g of bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) succinate, 10g of 2- (2-hydroxy-3-tert-butyl-5-methoxyphenyl) -benzotriazole and 10g of 2,2 '-dihydroxy-4, 4' -di-tert-butylbenzophenone were thoroughly mixed in a ball mill for 30 minutes to obtain a composition (10).
Example 11:
preparation of composition (11): 60g of the polymer I in example I, 20g of 2- (2-hydroxy-3-tert-butyl-5-methoxyphenyl) -benzotriazole, 10g of 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and 10g of 2,2 '-dihydroxy-4, 4' -di-tert-butylbenzophenone were thoroughly mixed in a ball mill for 30 minutes to obtain a composition (11).
Example 12:
preparation of composition (12): 60g of the polymer I in example I, 20g of bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) succinate and 20g of 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine were thoroughly mixed in a ball mill for 30 minutes to obtain a composition (12).
Example 13:
preparation of composition (13): 60g of the polymer I in example I, 20g of 2- (2-hydroxy-3-tert-butyl-5-methoxyphenyl) -benzotriazole and 20g of 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine were thoroughly mixed in a ball mill for 30min to obtain a composition (13).
Example 14:
preparation of composition (14): 60g of the polymer I in example I, 20g of 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and 20g of 2,2 '-dihydroxy-4, 4' -di-tert-butylbenzophenone were thoroughly mixed in a ball mill for 30min to obtain a composition (14).
Preparing the anti-aging master batch: adding the light-stable compositions 1-14 into low density polyethylene according to a ratio of 0.3%, granulating with a twin-screw extruder to obtain anti-aging master batch, and tabletting to obtain 100 μm thick sheet.
The aging apparatus was a Ci65 type aging test chamber from ATLAS, USA, with a back plate temperature of 63 deg.C, no water spray, 0.35W/m2, 340 nm. The carbonyl index of the above samples was measured using an infrared spectrophotometer and the time to reach 0.1 for the carbonyl index of 1-14 photostable compositions was recorded as shown in table 1:
table 1: the time taken for the carbonyl index of the different light-stabilizing compositions to reach 0.1
| Light stabilizing composition | Time (h) for carbonyl index to reach 0.1 |
| 1 | 3120 |
| 2 | 3080 |
| 3 | 3050 |
| 4 | 2820 |
| 5 | 2860 |
| 6 | 2580 |
| 7 | 2620 |
| 8 | 2740 |
| 9 | 2460 |
| 10 | 2320 |
| 11 | 2330 |
| 12 | 1960 |
| 13 | 2010 |
| 14 | 2030 |
The time for the 4 and 5 carbonyl indexes of the composition to reach 0.1 is shorter than that of the compositions 1-3, and the aging resistance is strongest, so that a synergistic effect is exerted between the compositions, the aging resistance of a single stabilizer is greatly improved, the aging resistance effect of the polymer I in the examples ii and iii is poorer than that of the polymer I in the example I, and the molecular weight of the polymer I has a certain influence on the aging resistance.
And (3) insolation experiment: the anti-aging master batches 1-14 are prepared into films with the thickness of 65 mu m, and the samples are analyzed for breaking elongation and tensile strength retention rate after being exposed to the sun for 18 months, and the results are shown in Table 2:
TABLE 2 Exposure experiments with photostable compositions
As can be seen from Table 2, compositions 1-5 have minimal impact on the elongation at break retention and tensile strength of the article, indicating that synergistic effects between the components are achieved, enhancing the aging resistance of the individual components after forming the composition; the retention of elongation at break and tensile strength of compositions 4 and 5 are slightly inferior to compositions 1-3, further illustrating that the molecular weight of polymer I has some effect on its aging resistance.
The invention is not limited to the combination in the above embodiments, and the combination scheme can be changed in many ways without contradiction, and the changes still fall into the protection scope of the invention.
Claims (10)
1. A light stabilizer characterized by: the light stabilizer is a polymer shown in a formula I:
wherein n is 2-10.
2. A process for the preparation of a light stabilizer according to claim 1, characterized in that: the polymer shown in the formula I is synthesized by a light stabilizer 3346 and 2- (2-hydroxy-5-bromomethyl-3-methylphenyl) -benzotriazole.
3. The process for producing a light stabilizer according to claim 2, characterized in that:
sequentially adding a light stabilizer 3346 and 2- (2-hydroxy-5-bromomethyl-3-methylphenyl) -benzotriazole into an autoclave in a molar ratio of 1:2-1:8, uniformly mixing, and heating to 80-120 ℃ in an alkaline environment to react for 8-24 hours; standing and separating the solution after the reaction is finished, washing an organic phase, distilling under reduced pressure, and cooling the concentrated solution to separate out a light yellow solid, namely the polymer shown in the formula I, wherein the molecular weight of the polymer is between 2000-5000-.
4. A multifunctional light stabilizing composition characterized by: the composition is the polymer of the formula I in claim 1 and other components; wherein the polymer of the formula I according to claim 1 and other components are present in a mass ratio of 40 to 80: 20-60 parts of; the other components are one or more of hindered amine light stabilizer, benzotriazole light stabilizer, triazine light stabilizer, benzophenone light stabilizer and antioxidant.
5. The multifunctional light stabilizing composition according to claim 4, characterized in that: the composition is a polymer of formula I according to claim 1 and other ingredients; wherein the polymer of the formula I according to claim 1 and other components are present in a mass ratio of 40 to 80: 20-60 parts of; the other components are antioxidant and stabilizer, and the mass ratio of the antioxidant to the stabilizer is 5-10:15-50, wherein the stabilizer is any three of hindered amine light stabilizer, benzotriazole light stabilizer, triazine light stabilizer and benzophenone light stabilizer.
6. The multifunctional light stabilizing composition of claim 5, wherein:
the composition comprises, by weight, 40-60 parts of a polymer of formula I as defined in claim 1, 15-20 parts of a hindered amine light stabilizer, 10-15 parts of a benzotriazole light stabilizer, 10-15 parts of a triazine light stabilizer, and 5-10 parts of an antioxidant.
7. The multifunctional light stabilizing composition according to any one of claims 4 to 6, characterized in that:
the hindered amine light stabilizer is selected from a reaction product of N, N' -bis [ N- (2,2,6, 6-tetramethyl-4-piperidyl) ] -1, 6-hexanediamine and 4-methylamino-2, 6-dichloro-1, 3, 5-triazine; bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) -2-cyclohexyl-2- (2-hydroxy-3, 5-di-tert-butylbenzyl) malonate; a reaction product of 2,4, 6-trichloro-1, 3, 5-triazine, 1, 2-bis (3-aminopropylamino) ethane and 4-cyclohexylamino-2, 2,6, 6-tetramethylpiperidine; a reaction product of N, N' -bis [ N- (2,2,6, 6-tetramethyl-4-piperidyl) ] -1, 6-hexanediamine and 4-morpholino-2, 6-dichloro-1, 3, 5-triazine; bis (2,2,6, 6-tetramethyl-4-piperidinyl) suberate; bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate; bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate; the reaction product of 2-chloro-4, 6-bis (4-cyclohexylamino-2, 2,6, 6-tetramethyl-4-piperidinyl) -1,3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane; 2- [ (2-hydroxyethyl) amino ] -4, 6-bis [ N- (1-cyclohexyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) ] cyclohexylamino-1, 3, 5-triazine; succinic acid, [ (4-phenyl) -methylene ] -bis- (1-methoxy-2, 2,6, 6-tetramethyl-4-piperidinyl) ester; n- (1-phenoxy-2, 2,6, 6-tetramethyl-4-piperidinyl) -N' -dodecyloxamide; bis (1-cyclohexyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate; the reaction product of 1- (2-hydroxyethyl) -2,2,6, 6-tetramethyl-4-hydroxypiperidine and suberic acid; tris (2,2,6, 6-tetramethyl-4-piperidinyl) nitrilotriacetate; 1- (2-hydroxyethyl) -2,2,6, 6-tetramethyl-4-hydroxypiperidine succinate; bis (2,2,6, 6-tetramethyl-4-piperidyl) stearate; bis (2,2,6, 6-tetramethyl-4-piperidinyl) succinate; bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) succinate; 4-dodecyloxy-2, 2,6, 6-tetramethylpiperidine; tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,3, 4-butanetetracarboxylate; bis (1-dodecyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) stearate; the reaction product of N, N' -bis [ N- (2,2,6, 6-tetramethyl-4-piperidyl) ] -1, 6-hexanediamine and 4-tert-butylamino-2, 6-dichloro-1, 3, 5-triazine, 3-octyl-1- (1-acetyl-2, 2,6, 6-tetramethyl-4-piperidyl) pyrrolidin-2, 5-one; 4-benzoyl-2, 2,6, 6-tetramethylpiperidine;
the benzotriazole light stabilizer is selected from 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -benzotriazole; 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chloro-benzotriazole; 2- (2-hydroxy-5-methylphenyl) -benzotriazole; 2- (2-hydroxy-5-tert-butylphenyl) -benzotriazole; 5-bromomethyl-2- (2-hydroxy-3-isopropyl-5-methylphenyl) -benzotriazole; 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -benzotriazole; 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chloro-benzotriazole; 2- (2-hydroxy-3-methoxy-5-ethylphenyl) -benzotriazole; 2- (2-hydroxy-5-octylphenyl) -benzotriazole; 2- (2-hydroxy-3-benzyl-5-methoxyphenyl) -benzotriazole; 2- (2-hydroxy-3-tert-butyl-5-sec-butylphenyl) -benzotriazole;
the triazine light stabilizer is selected from 2,4, 6-tri (2-hydroxy-4-octyloxyphenyl) -1,3, 5-triazine; 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine; 2, 4-bis (2-hydroxy-4-propoxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine; 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine; 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (4-methylphenyl) -1,3, 5-triazine; 2- (2-hydroxy-4-dodecyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine; 2- [ 2-hydroxy-4- (2-hydroxy-3-butoxypropoxy) phenyl ] -4, 6-bis (2, 4-dimethyl) -1,3, 5-triazine; 2- [ 2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl ] -4, 6-bis (2, 4-dimethyl) -1,3, 5-triazine;
the benzophenone light stabilizer is selected from 2,2' -dihydroxy benzophenone; 2, 4-dihydroxybenzophenone; 2-hydroxy-4-methoxy-benzophenone; 2-hydroxy-4-octyloxy-benzophenone; 2-hydroxy-4-decyloxy-benzophenone; 2-hydroxy-4-cyclohexyloxy-benzophenone; 2-hydroxy-4-benzyloxy-benzophenone; 2,2',4,4' -tetrahydroxybenzophenone; 2,2 '-dihydroxy-4, 4' -dimethoxybenzophenone; 2,2 '-dihydroxy-4, 4' -di-tert-butyl benzophenone.
8. The multifunctional light stabilizing composition according to any one of claims 4 to 6 characterized in that
The antioxidant is selected from 2, 6-di-tert-butyl-4-methylphenol; 2-tert-butyl-4, 6-dimethylphenol; 2, 6-di-tert-butyl-2-ethylphenol; 2, 6-di-tert-butyl-4-methoxyphenol; 2, 4-dioctylthiomethyl-6-methoxyphenol; 2, 4-dioctylthiomethyl-6-methylphenol; 2, 4-dioctylthiomethyl-6-tert-butylphenol; 2, 5-di-tert-butylhydroquinone; 2, 6-di-tert-butylhydroquinone; 2, 6-diphenyl-4-octadecyloxyphenol; 2,2' -thiobis (6-tert-butyl-4-methylphenol); 2,2' -methylenebis (6-tert-butyl-4-methylphenol); 2,2' -methylenebis (4, 6-di-tert-butylphenol); 2, 6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol; n, N' -dipropyl-p-phenylenediamine; n, N' -di-tert-butyl-p-phenylenediamine; n, N' -dicyclohexyl-p-phenylenediamine; n, N' -diphenyl-p-phenylenediamine.
9. A method of making the multifunctional light stabilizing composition of claim 4, wherein: mixing the components according to the proportion; or mixing the components in proportion and dissolving in other modes to obtain the composition.
10. The method of preparing a multifunctional light stabilizing composition according to claim 9, characterized in that: the other mode is heating and melting or evaporating the solvent after the mixture is dissolved by the solvent.
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