CN116656006A - Reactive light stabilizer and preparation method and application thereof - Google Patents
Reactive light stabilizer and preparation method and application thereof Download PDFInfo
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- CN116656006A CN116656006A CN202310241678.8A CN202310241678A CN116656006A CN 116656006 A CN116656006 A CN 116656006A CN 202310241678 A CN202310241678 A CN 202310241678A CN 116656006 A CN116656006 A CN 116656006A
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- 239000004611 light stabiliser Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 78
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 22
- 239000012295 chemical reaction liquid Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- 238000004090 dissolution Methods 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000005022 packaging material Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229920001634 Copolyester Polymers 0.000 claims description 2
- 229920002732 Polyanhydride Polymers 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- RPDJEKMSFIRVII-UHFFFAOYSA-N oxomethylidenehydrazine Chemical compound NN=C=O RPDJEKMSFIRVII-UHFFFAOYSA-N 0.000 claims description 2
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 abstract description 5
- 238000011105 stabilization Methods 0.000 abstract description 5
- 239000004597 plastic additive Substances 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 48
- 239000011246 composite particle Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 20
- 238000007731 hot pressing Methods 0.000 description 18
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 14
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 239000003513 alkali Substances 0.000 description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920001896 polybutyrate Polymers 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- VGHVJQXWDXRTRJ-UHFFFAOYSA-N 1-(2-hydroxyphenyl)-2-phenylethanone Chemical compound OC1=CC=CC=C1C(=O)CC1=CC=CC=C1 VGHVJQXWDXRTRJ-UHFFFAOYSA-N 0.000 description 6
- 238000007872 degassing Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 4
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical compound OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- 206010051246 Photodermatosis Diseases 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008845 photoaging Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- 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
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application relates to the field of plastic additives, and discloses a reactive light stabilizer, a preparation method and application thereof. The stress type light stabilizer is prepared by reacting a UVS monomer containing an ultraviolet light stabilizing group and a reactive monomer containing a reactive group, wherein the reactive monomer contains at least two reactive groups. The application constructs the light stabilizer which simultaneously contains the ultraviolet light stable group inner core and the reactive group outer arm, so that the light stabilizer can be compounded with the polymer matrix through chemical reaction in the subsequent processing process, has good compatibility with the polymer matrix while playing a role in light stabilization, and is not easy to run off from the matrix in the use process.
Description
Technical Field
The application relates to the field of plastic additives, in particular to a reactive light stabilizer, a preparation method and application thereof.
Background
After the ultraviolet rays are absorbed by the high polymer product, the polymer can be triggered to be oxidized and degraded, chemical bonds of the polymer are broken, the polymer is broken and crosslinked, and the appearance, such as color, and the physical and mechanical properties of the high polymer product are changed, so that the strength is reduced, and the service life is shortened; this process is known as photoredox or photoaging.
The most common method of preventing or retarding photoaging of polymers is to incorporate stabilizers such as ultraviolet absorbers, radical scavengers, quenchers, ultraviolet light screening agents, and the like into the polymer. However, the following problems are caused by the method of adding the stabilizer: 1. the light stabilizer or the ultraviolet light shielding agent has poor compatibility with the polymer matrix, especially the inorganic ultraviolet light shielding agent, so that the uniform dispersion in the polymer matrix is difficult to realize, and the polymer matrix often contains an agglomerated stabilizer, thereby influencing the physical and mechanical properties of the material; 2. the high-volatility small-molecule light stabilizer is easy to volatilize and lose in the high-temperature processing process; 3. in the use process, the problem that the micromolecular light stabilizer migrates from the polymer matrix under the influence of water, oil and the like exists. Therefore, designing and constructing a stabilizer that is compatible and well-bonded with the polymer matrix is advantageous for improving the polymer properties.
Disclosure of Invention
The application aims to overcome the problems of the light stabilizer in the prior art, and provides a reactive light stabilizer, a preparation method and application thereof, wherein the light stabilizer is constructed to contain an ultraviolet light stabilizing group inner core and a reactive group outer arm, so that the light stabilizer can be compounded with a polymer matrix through chemical reaction in the subsequent processing process, has good compatibility with the polymer matrix while playing a role in light stabilization, and is not easy to run off from the matrix in the use process.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a reactive light stabilizer is prepared by reacting a UVS monomer containing an ultraviolet light stabilizing group with a reactive monomer containing a reactive group;
the UVS monomer is selected from one or more of the following compounds and corresponding derivatives thereof:
wherein R is 1 Is H or alkyl;
the reactive monomer comprises at least two reactive groups, and the reactive groups are selected from one or more of amino, isocyanate, hydroxyl, carboxyl, acyl chloride and anhydride.
In order to construct the light stabilizer simultaneously containing the ultraviolet light stable group inner core and the reactive group outer arm, a UVS monomer with a specific structure and a reactive monomer are selected for reaction. The ultraviolet light stabilizing group in the UVS monomer can lead the obtained light stabilizer to have good ultraviolet light shielding effect, and one part of the reactive group in the reactive monomer can carry out esterification reaction, halogenation reaction, addition reaction and other chemical reactions with active groups such as hydroxyl and the like in the UVS monomer, so that the UVS monomer and the reactive monomer are connected through chemical bonds; the other part of reactive groups can react with hydroxyl-terminated groups or carboxyl-terminated groups in the polymer matrix, so that the light stabilizer can be added into the polymer matrix and can be connected with the polymer matrix through chemical bonds through subsequent processing reaction, the compatibility of the light stabilizer and the polymer matrix is improved, and the problem that the small molecular light stabilizer migrates and runs off from the polymer matrix under the influence of water, oil and the like is avoided. Therefore, the reactive light stabilizer of the application can play the dual roles of light stabilization and material compatibility.
The application also provides a preparation method of the reactive light stabilizer, which comprises the following steps:
(1) Adding a UVS monomer and a reactive monomer into a solvent, and uniformly mixing;
(2) Heating to 50-150 ℃, then dripping NaOH aqueous solution, and then heating to 60-180 ℃ for reaction;
(3) And extracting the reaction liquid with water after the reaction is finished, performing rotary evaporation on the obtained organic phase, dissolving the obtained solid sample in anhydrous diethyl ether, purifying by a dissolution precipitation method, and drying to obtain the reactive light stabilizer.
Preferably, the mass ratio of UVS monomer to reactive monomer in step (1) is 0.2-0.6:1-10.
Preferably, the mass concentration of the NaOH aqueous solution added in the step (2) is 5-50%, and the mol ratio of NaOH in the added NaOH aqueous solution to UVS monomer is 1-4:1; after the temperature is raised to 50-150 ℃, dropwise adding the NaOH aqueous solution within 0.5-2 h; and after the temperature is raised to 60-180 ℃, the reaction is continued for 0.5-2 h.
Preferably, in the step (3), deionized water is used for extracting the reaction liquid, and the volume ratio of the deionized water to the reaction liquid is 5-20: 1 to 5; the temperature during rotary steaming is 20-120 ℃; the mass ratio of the solid sample to the anhydrous diethyl ether in the purification process by the dissolution precipitation method is 20-50: 1 to 5, and the dissolution and precipitation times are 3 to 5 times; the temperature during drying is 40-100 ℃ and the drying time is 10-48 h.
The application also provides an ultraviolet-resistant polymer, which comprises a polymer matrix and the reactive light stabilizer.
Preferably, the polymer matrix is selected from one or more of aromatic polyesters, aliphatic aromatic copolyesters, polycarbonates, polyesteramides, polyanhydrides, polyphosphazenes, amino acid polymers, polysaccharides, polyhydroxyalkanoates, and polyvinyl alcohols.
Preferably, the mass of the reactive light stabilizer is 0.1 to 30.0% of the mass of the polymer matrix.
The application also provides a preparation method of the ultraviolet-resistant polymer, which is selected from one of in-situ copolymerization or melt blending.
The application also provides application of the ultraviolet-resistant polymer in packaging materials, powder coatings, agricultural films, building boards and electronic devices.
When the ultraviolet-resistant polymer is prepared into a product, the preparation method is selected from one or more of a casting method, a film blowing method, a spin coating method, a calendaring method, a solution casting method, a biaxial stretching method, a laminating method and a multilayer coextrusion method.
Therefore, the application has the following beneficial effects:
(1) The light stabilizer provided by the application contains the ultraviolet light stable group inner core and the reactive group outer arm, can be compounded with the polymer matrix through chemical reaction in the subsequent processing process, has good compatibility with the polymer matrix while playing a role in light stabilization, and is not easy to run off from the matrix in the use process;
(2) The polymer is suitable for various polymer systems such as polyester, polycarbonate, polyesteramide, amino acid polymer and the like, can be applied to ultraviolet protection or ultraviolet-resistant weather-resistant films, sheets and plates, and has wide application range in manufacturing packaging materials, powder coatings, agricultural films, building plates, electronic devices and the like.
Detailed Description
The application is further described below in connection with the following detailed description.
Example 1:
1. preparation of the reactive light stabilizer:
adding 0.58g of UVS monomer 2-hydroxybenzophenone, 9.90g of reactive monomer N-methylethanolamine and 19.9g of DMSO into a three-neck flask, mixing, gradually increasing the temperature to 149 ℃, then gradually adding 49wt% of NaOH aqueous solution according to the mol ratio of NaOH to 2-hydroxybenzophenone being 3.99:1 in 1.9h, and then continuously reacting for 2.0h at 178 ℃; after the reaction is finished, extracting the reaction liquid with deionized water for three times, wherein the volume ratio of the deionized water to the reaction liquid is 5:1, removing salt, residual alkali and DMSO, and performing rotary evaporation on the obtained organic phase at 115 ℃ to remove excessive N-methylethanolamine; purifying the obtained solid in anhydrous diethyl ether by a dissolution precipitation method, wherein the mass ratio of a solid sample to the anhydrous diethyl ether is 20:1, the dissolution and precipitation times are 3 times, and then the reaction type light stabilizer is obtained by vacuum drying at 98 ℃ for 48 hours.
2. Preparation of light stabilizer composite film:
melt mixing the PBAT resin with the prepared reactive light stabilizer in HAAKE MiniLab II at 150 ℃ and 100rpm, wherein the mass of the reactive light stabilizer is 28.5wt% of that of the PBAT resin; the feeding amount is 8.0g each time, the mixing time is 7min, an internal circulation mode is adopted to prepare a flaky compound with the width of 5mm and the thickness of 1mm, and the flaky compound is cut into compound particles with the thickness of about 2mm for standby; hot-pressing the composite particles on a GT-7014-A50C tablet press at 140 ℃ to form the composite particles, wherein the composite particles are firstly melted between plates for 5min, then degassing operation is carried out for 2-3 times to discharge gas among the particles, then hot-pressing for 5min at 300bar, finally pressure maintaining is carried out, and the obtained film sample is cooled to room temperature by using circulating condensate water, wherein the thickness of the obtained film sample is 50 mu m; meanwhile, pure PBAT particles are subjected to the extrusion and hot-pressing film forming operations as well, and the blank control is used.
Example 2:
1. preparation of the reactive light stabilizer:
adding 0.21g of UVS monomer 2 '-hydroxy-2-phenyl acetophenone, 1.10g of reactive monomer octadecanedioic acid and 1.2g of DMSO into a three-neck flask, mixing, gradually increasing the temperature to 52 ℃, then gradually adding 5.5wt% NaOH aqueous solution according to the mol ratio of NaOH to 2' -hydroxy-2-phenyl acetophenone of 1.01:1 in 0.5h, and then continuously reacting for 0.5h at 61 ℃; after the reaction is finished, extracting the reaction liquid with deionized water for three times, wherein the volume ratio of the deionized water to the reaction liquid is 5:5, removing salt, residual alkali and DMSO, and spin-evaporating the obtained organic phase at 21 ℃ to remove excessive octadecanedioic acid; purifying the obtained solid in anhydrous diethyl ether by a dissolution precipitation method, wherein the mass ratio of a solid sample to the anhydrous diethyl ether is 20:5, dissolving and precipitating for 4 times, and then drying in vacuum at 41 ℃ for 10 hours to obtain the reactive light stabilizer.
2. Preparation of light stabilizer composite film:
melt mixing the PLA resin with the above-prepared reactive light stabilizer in HAAKE MiniLab II at 190℃and 100rpm, the mass of the reactive light stabilizer being 0.11% by weight of the mass of the PLA resin; the feeding amount is 8.0g each time, the mixing time is 7min, an internal circulation mode is adopted to prepare a flaky compound with the width of 5mm and the thickness of 1mm, and the flaky compound is cut into compound particles with the thickness of about 2mm for standby; hot-pressing the composite particles on a GT-7014-A50C tablet press at 180 ℃ to form the composite particles, wherein the composite particles are firstly melted between plates for 5min, then degassing operation is carried out for 2-3 times to discharge gas among the particles, then hot-pressing for 5min at 300bar, finally pressure maintaining is carried out, and the obtained film sample is cooled to room temperature by using circulating condensate water, wherein the thickness of the obtained film sample is 50 mu m; meanwhile, pure PLA particles are subjected to the extrusion and hot-pressing film forming operation as well, and the blank control is used.
Example 3:
1. preparation of the reactive light stabilizer:
0.30g of UVS monomer 1-methyl-2, 6-tetramethylpiperidine, 5.56g of Hexamethylene Diisocyanate (HDI) and 6.5g of DMSO are added into a three-neck flask, the mixture is gradually raised to 70 ℃ after mixing, then 10wt% of NaOH aqueous solution is gradually added according to the mol ratio of NaOH to 1.5:1 of 1-methyl-2, 6-tetramethylpiperidine in 0.8h, and then the mixture is raised to 95 ℃ to continue the reaction for 0.7h; after the reaction is finished, extracting the reaction liquid with deionized water for three times, wherein the volume ratio of the deionized water to the reaction liquid is 20:1, removing salt, residual alkali and DMSO, and spin-evaporating the obtained organic phase at 89 ℃ to remove excessive HDI; purifying the obtained solid in anhydrous diethyl ether by a dissolution precipitation method, wherein the mass ratio of a solid sample to the anhydrous diethyl ether is 50:1, dissolving and precipitating for 5 times, and then vacuum drying at 60 ℃ for 22 hours to obtain the reactive light stabilizer.
2. Preparation of light stabilizer composite film:
melt mixing PET/PLA blend resin (mass ratio 3:2) with the prepared reactive light stabilizer at 270 ℃ and 100rpm in HAAKE MiniLab II, wherein the mass of the reactive light stabilizer is 10.5wt% of the total mass of the blend resin; the feeding amount is 8.0g each time, the mixing time is 7min, an internal circulation mode is adopted to prepare a flaky compound with the width of 5mm and the thickness of 1mm, and the flaky compound is cut into compound particles with the thickness of about 2mm for standby; hot-pressing the composite particles on a GT-7014-A50C tablet press at 260 ℃ to form the composite particles, wherein the composite particles are firstly melted between plates for 5min, then degassing operation is carried out for 2-3 times to discharge gas among the particles, then hot-pressing is carried out for 5min at 300bar, finally pressure is maintained, and the composite particles are cooled to room temperature by using circulating condensate water, so that the thickness of the obtained film sample is 50 mu m; meanwhile, the pure PET/PLA sample is subjected to the operations of extrusion and hot-pressing film forming as a blank control.
Example 4:
preparation of the reactive light stabilizer:
0.45g of UVS monomer 2- (2-hydroxyphenyl) -2H-benzotriazole, 6.90g of reactive monomer maleic anhydride and 14.9g of DMSO are added into a three-neck flask, the mixture is gradually raised to 85 ℃ after mixing, then in 1.2H, 39.6wt% NaOH aqueous solution is gradually added according to the mol ratio of NaOH to 2- (2-hydroxyphenyl) -2H-benzotriazole being 2.5:1, and then the mixture is raised to 110 ℃ to continue the reaction for 1.2H; after the reaction is finished, extracting the reaction liquid with deionized water for three times, wherein the volume ratio of the deionized water to the reaction liquid is 20:5, removing salt, residual alkali and DMSO, and spin-evaporating the obtained organic phase at the temperature of 51 ℃ to remove excessive maleic anhydride; purifying the obtained solid in anhydrous diethyl ether by a dissolution precipitation method, wherein the mass ratio of a solid sample to the anhydrous diethyl ether is 50:5, dissolving and precipitating for 4 times, and then drying in vacuum at 55 ℃ for 18 hours to obtain the reactive light stabilizer.
2. Preparation of light stabilizer composite film:
in HAAKE MiniLab II, the PBAT/PLA blend resin (mass ratio 9:1) and the prepared reactive light stabilizer are melt mixed at 190 ℃ and 100rpm, wherein the mass of the reactive light stabilizer is 0.6wt% of the mass of the blend resin; the feeding amount is 8.0g each time, the mixing time is 7min, an internal circulation mode is adopted to prepare a flaky compound with the width of 5mm and the thickness of 1mm, and the flaky compound is cut into compound particles with the thickness of about 2mm for standby; hot-pressing the composite particles on a GT-7014-A50C tablet press at 180 ℃ to form the composite particles, wherein the composite particles are firstly melted between plates for 5min, then degassing operation is carried out for 2-3 times to discharge gas among the particles, then hot-pressing for 5min at 300bar, finally pressure maintaining is carried out, and the obtained film sample is cooled to room temperature by using circulating condensate water, wherein the thickness of the obtained film sample is 50 mu m; meanwhile, pure PBAT/PLA is subjected to the extrusion and hot-pressing film forming operation as a blank control.
Example 5:
preparation of the reactive light stabilizer:
0.59g of UVS monomer 2- (2-hydroxyphenyl) -2H-benzotriazole and 1-methyl-2, 6-tetramethylpiperidine mixture (mass ratio 2:1), 9.89g of reactive monomer octadecanedioic acid and 11.7g of DMSO were added into a three-necked flask, the mixture was gradually raised to 98℃after mixing, then 15wt% aqueous NaOH solution was gradually added to the mixture of 2- (2-hydroxyphenyl) -2H-benzotriazole and 1-methyl-2, 6-tetramethylpiperidine at a molar ratio of NaOH to the mixture of 1-methyl-2, 6-tetramethylpiperidine of 2:1 in 0.6 hour, and then the reaction was continued at 150℃for 1.5 hours; after the reaction is finished, extracting the reaction liquid with deionized water for three times, wherein the volume ratio of the deionized water to the reaction liquid is 10:3, removing salt, residual alkali and DMSO, and performing rotary evaporation on the obtained organic phase at 80 ℃ to remove excessive octadecanedioic acid; purifying the obtained solid in anhydrous diethyl ether by a dissolution precipitation method, wherein the mass ratio of a solid sample to the anhydrous diethyl ether is 40:1, dissolving and precipitating for 5 times, and then drying in vacuum at 80 ℃ for 10.1h to obtain the reactive light stabilizer.
Preparation of light stabilizer composite film:
melt mixing the PBAT/Polyhydroxyalkanoate (PHA) blend resin (mass ratio 7:3) with the above-prepared reactive light stabilizer in HAAKE MiniLab II at 200℃and 100rpm, the mass of the reactive light stabilizer being 8.0wt% of the total mass of the blend resin; the feeding amount is 8.0g each time, the mixing time is 7min, an internal circulation mode is adopted to prepare a flaky compound with the width of 5mm and the thickness of 1mm, and the flaky compound is cut into compound particles with the thickness of about 2mm for standby; hot-pressing the composite particles on a GT-7014-A50C tablet press at 190 ℃ to form the composite particles, wherein the composite particles are firstly melted between plates for 5min, then degassing operation is carried out for 2-3 times to discharge gas among the particles, then hot-pressing is carried out for 5min at 300bar, finally pressure is maintained, and the composite particles are cooled to room temperature by using circulating condensate water, so that the thickness of the obtained film sample is 50 mu m; meanwhile, the pure PBAT/PHA sample is subjected to the extrusion and hot-pressing film forming operations as well, and the blank control is used.
Example 6:
preparation of the reactive light stabilizer:
0.50g of UVS monomer 2 '-hydroxy-2-phenyl acetophenone, 7.69g of a mixture of reactive monomer maleic anhydride and octadecanedioic acid (mass ratio of 1:1) and 8.0g of DMSO are added into a three-neck flask, the mixture is gradually heated to 120 ℃ after being mixed, then 25wt% of NaOH aqueous solution is gradually added within 1.6h according to the mol ratio of NaOH to 2' -hydroxy-2-phenyl acetophenone of 2.99, and then the mixture is heated to 178 ℃ to continue the reaction for 0.9h; after the reaction is finished, extracting the reaction liquid with deionized water for three times, wherein the volume ratio of the deionized water to the reaction liquid is 15:2, removing the salt, residual alkali and DMSO, and spin-evaporating the obtained organic phase at 70 ℃ to remove excessive maleic anhydride and octadecanedioic acid; purifying the obtained solid in anhydrous diethyl ether by a dissolution precipitation method, wherein the mass ratio of a solid sample to the anhydrous diethyl ether is 40:3, dissolving and precipitating for 3 times, and then drying in vacuum at 99 ℃ for 15 hours to obtain the reactive light stabilizer.
Preparation of light stabilizer composite film:
melt mixing PLA/Polyhydroxyalkanoate (PHA) blend resin (mass ratio 7:3) with the above-prepared reactive light stabilizer at 200℃and 100rpm in HAAKE MiniLab II, the mass of the reactive light stabilizer being 12.0wt% of the mass of the blend resin; the feeding amount is 8.0g each time, the mixing time is 7min, an internal circulation mode is adopted to prepare a flaky compound with the width of 5mm and the thickness of 1mm, and the flaky compound is cut into compound particles with the thickness of about 2mm for standby; hot-pressing the composite particles on a GT-7014-A50C tablet press at 190 ℃ to form the composite particles, wherein the composite particles are firstly melted between plates for 5min, then degassing operation is carried out for 2-3 times to discharge gas among the particles, then hot-pressing is carried out for 5min at 300bar, finally pressure is maintained, and the composite particles are cooled to room temperature by using circulating condensate water, so that the thickness of the obtained film sample is 50 mu m; meanwhile, the pure PLA/PHA sample is subjected to the operations of extrusion and hot-pressing film forming as a blank control.
Comparative example 1:
the preparation method of the reactive light stabilizer in comparative example 1 is:
adding 0.50g of UVS monomer 2 '-hydroxy-2-phenyl acetophenone and 8.0g of DMSO into a three-neck flask, mixing, gradually heating to 120 ℃, then gradually adding 25wt% of NaOH aqueous solution according to the mol ratio of NaOH to 2' -hydroxy-2-phenyl acetophenone of 2.99 in 1.6h, and then heating to 178 ℃ for continuous reaction for 0.9h; after the reaction is finished, extracting the reaction liquid with deionized water for three times, wherein the volume ratio of the deionized water to the reaction liquid is 15:2, removing the salt, residual alkali and DMSO, and spin-evaporating the obtained organic phase at 70 ℃ to remove excessive maleic anhydride and octadecanedioic acid; purifying the obtained solid in anhydrous diethyl ether by a dissolution precipitation method, wherein the mass ratio of a solid sample to the anhydrous diethyl ether is 40:3, dissolving and precipitating for 3 times, and then vacuum drying at 99 ℃ for 15 hours to obtain the reactive light stabilizer;
the preparation method of the light stabilizer composite film was the same as in example 6.
Comparative example 2:
the preparation method of the reactive light stabilizer in comparative example 2 is:
7.69g of a mixture of reactive monomer maleic anhydride and octadecanedioic acid (mass ratio of 1:1) and 8.0g of DMSO are added into a three-neck flask, the temperature is gradually raised to 120 ℃ after mixing, then 25wt% of NaOH aqueous solution is gradually added according to the mol ratio of NaOH to maleic anhydride of 2.99 in 1.6h, and the temperature is raised to 178 ℃ to continue the reaction for 0.9h; after the reaction is finished, extracting the reaction liquid with deionized water for three times, wherein the volume ratio of the deionized water to the reaction liquid is 15:2, removing the salt, residual alkali and DMSO, and spin-evaporating the obtained organic phase at 70 ℃ to remove excessive maleic anhydride and octadecanedioic acid; purifying the obtained solid in anhydrous diethyl ether by a dissolution precipitation method, wherein the mass ratio of a solid sample to the anhydrous diethyl ether is 40:3, dissolving and precipitating for 3 times, and then vacuum drying at 99 ℃ for 15 hours to obtain the reactive light stabilizer;
the preparation method of the light stabilizer composite film was the same as in example 6.
The light stabilizer composite films prepared in the above examples and comparative examples were subjected to ultraviolet accelerated aging in a xenon lamp experimental box simulating the irradiation spectrum of sunlight using a xenon arc lamp and a solar filter; the cycling conditions included 102min light (0.51W/(m) at 340nm 2 Nm), then 18min of light (0.51W/(m) 2 Nm), 340 nm) and spraying, the blackboard temperature is 63+/-3 ℃. The mechanical properties after accelerated aging for 250 hours are shown in Table 1. The test method of the mechanical property is referred to GB/T1040.3-2006.
Table 1: results of performance testing after accelerated aging of the polymer films.
As can be seen from Table 1, the composite films prepared by compounding the reactive light stabilizer and the polymer in examples 1 to 6 have good long-acting ultraviolet resistance. Compared with example 6, the light stabilizer prepared in comparative example 1 has no grafting reaction group, which results in poor compatibility of the light stabilizer with the polymer and uneven dispersion of the light stabilizer in the polymer film, and the light stabilizer is easy to migrate, volatilize and withdraw in the film, causes weakening of anti-aging capability, and does not have long-acting light stabilization effect. Compared with example 6, the composite film prepared in comparative example 2 contains only reactive groups, and the mechanical properties of the polymer film after accelerated aging are greatly reduced and the aging resistance is remarkably reduced due to the lack of the light stabilizer.
Claims (10)
1. A reactive light stabilizer is characterized by being prepared by reacting a UVS monomer containing an ultraviolet light stabilizing group and a reactive monomer containing a reactive group;
the UVS monomer is selected from one or more of the following compounds and corresponding derivatives thereof:
wherein R is 1 Is H or alkyl;
the reactive monomer comprises at least two reactive groups, and the reactive groups are selected from one or more of amino, isocyanate, hydroxyl, carboxyl, acyl chloride and anhydride.
2. A process for the preparation of a reactive light stabilizer as claimed in claim 1, comprising the steps of:
(1) Adding a UVS monomer and a reactive monomer into a solvent, and uniformly mixing;
(2) Heating to 50-150 ℃, then dripping NaOH aqueous solution, and then heating to 60-180 ℃ for reaction;
(3) And extracting the reaction liquid with water after the reaction is finished, performing rotary evaporation on the obtained organic phase, dissolving the obtained solid sample in anhydrous diethyl ether, purifying by a dissolution precipitation method, and drying to obtain the reactive light stabilizer.
3. The method for producing a reactive light stabilizer according to claim 2, wherein the mass ratio of the UVS monomer to the reactive monomer in the step (1) is 0.2 to 0.6:1 to 10.
4. The method for preparing a reactive light stabilizer according to claim 2, wherein the mass concentration of the aqueous NaOH solution added in the step (2) is 5-50%, and the molar ratio of NaOH to UVS monomer in the aqueous NaOH solution added is 1-4:1; after the temperature is raised to 50-150 ℃, dropwise adding the NaOH aqueous solution within 0.5-2 h; and after the temperature is raised to 60-180 ℃, the reaction is continued for 0.5-2 h.
5. The method for preparing a reactive light stabilizer according to claim 2, wherein the step (3) comprises the steps of extracting the reaction solution with deionized water, wherein the volume ratio of the deionized water to the reaction solution is 5-20: 1 to 5; the rotary steaming temperature is 20-120 ℃; the mass ratio of the solid sample to the anhydrous diethyl ether in the purification process by the dissolution precipitation method is 20-50: 1 to 5, and the dissolution and precipitation times are 3 to 5 times; the drying temperature is 40-100 ℃ and the drying time is 10-48 h.
6. An ultraviolet-resistant polymer comprising a polymer matrix and a reactive light stabilizer as defined in claim 1.
7. The uv resistant polymer of claim 6 wherein the polymer matrix is selected from one or more of aromatic polyesters, aliphatic aromatic copolyesters, polycarbonates, polyesteramides, polyanhydrides, polyphosphazenes, amino acid polymers, polysaccharides, polyhydroxyalkanoates, polyvinyl alcohols.
8. The ultraviolet-resistant polymer according to claim 6 or 7, wherein the mass of the reactive light stabilizer is 0.1 to 30.0% of the mass of the polymer matrix.
9. A method of preparing an ultraviolet-resistant polymer according to any one of claims 6 to 8, wherein the polymer is selected from one of in situ copolymerization and melt blending.
10. Use of the uv-resistant polymer according to any one of claims 6 to 8 in packaging materials, powder coatings, agricultural films, building boards, electronic devices.
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