CN116102739A - Copper-based multifunctional auxiliary agent for nylon and preparation method and application thereof - Google Patents
Copper-based multifunctional auxiliary agent for nylon and preparation method and application thereof Download PDFInfo
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- CN116102739A CN116102739A CN202310098811.9A CN202310098811A CN116102739A CN 116102739 A CN116102739 A CN 116102739A CN 202310098811 A CN202310098811 A CN 202310098811A CN 116102739 A CN116102739 A CN 116102739A
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- 239000004677 Nylon Substances 0.000 title claims abstract description 102
- 229920001778 nylon Polymers 0.000 title claims abstract description 102
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 66
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 64
- 239000010949 copper Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000013110 organic ligand Substances 0.000 claims abstract description 39
- 150000001879 copper Chemical class 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000002667 nucleating agent Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012965 benzophenone Substances 0.000 claims description 6
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- LFEWXDOYPCWFHR-UHFFFAOYSA-N 4-(4-carboxybenzoyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C=C1 LFEWXDOYPCWFHR-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 27
- 238000002425 crystallisation Methods 0.000 abstract description 22
- 230000008025 crystallization Effects 0.000 abstract description 22
- 230000006750 UV protection Effects 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 15
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- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
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- 239000002105 nanoparticle Substances 0.000 abstract description 2
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- 239000000047 product Substances 0.000 description 18
- 229920006118 nylon 56 Polymers 0.000 description 17
- 238000001125 extrusion Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 12
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- 239000004952 Polyamide Substances 0.000 description 10
- 229920002647 polyamide Polymers 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
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- 238000010586 diagram Methods 0.000 description 4
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- 238000009396 hybridization Methods 0.000 description 4
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- 239000002131 composite material Substances 0.000 description 3
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- 239000006096 absorbing agent Substances 0.000 description 2
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- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
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- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention belongs to the technical field of polymer modification and functional auxiliary agent preparation, and particularly discloses a copper-based multifunctional auxiliary agent for nylon, and a preparation method and application thereof. The copper-based multifunctional auxiliary agent for nylon is prepared by mixing copper salt, nonfunctional organic ligand (and functional organic ligand) and solvent and then performing hydrothermal reaction. The copper-based multifunctional auxiliary agent for nylon prepared by the invention can exert the scattering effect of nano particles on ultraviolet light and the absorption effect of semiconductor characteristics on ultraviolet light, and can exert the absorption effect of organic ligands on ultraviolet light, so that the nylon has excellent ultraviolet protection performance; meanwhile, the nylon material can be used as a heterogeneous nucleation point to improve the crystallization rate of the nylon material, so that the crystallization performance is improved, and the problems of poor nylon performance and low service life are solved.
Description
Technical Field
The invention relates to the technical field of polymer modification and functional auxiliary agent preparation, in particular to a copper-based multifunctional auxiliary agent for nylon and a preparation method and application thereof.
Background
Nylon (polyamide) has very wide application, but has poor ultraviolet resistance and easy aging, especially in the special fields of outdoor and the like, and has no ultraviolet protection function, which can lead to the change of the structure and the performance of polyamide fiber and seriously affect the service life of polyamide. In addition, severe damage to the skin of the wearer can occur, which places greater demands on the uv resistance of nylon. Therefore, the development of functional aids for improving the uv resistance of polyamide substrates is a problem that has been urgently addressed in the industry.
Nylon is a semi-crystalline polymeric material that, after molding, contains crystalline and amorphous regions. The existence of a large number of amorphous regions can influence the mechanical property, optical property, thermal property, solvent resistance and other properties of nylon, so that the crystallization property of nylon has a great room for improvement. In conclusion, the nylon nucleating agent is an important functional auxiliary agent.
The anti-ultraviolet agent is also a common means for improving the use performance of the polymer, and aims to solve the problem that the polyamide is broken due to ultraviolet light, namely high-energy electromagnetic waves. The anti-ultraviolet agent specifically comprises: light shielding agent: the ultraviolet resistant agent has wide sources and low price, has poor compatibility with a nylon matrix, and can influence the crystallization property, mechanical property and the like of polyamide if being added excessively; if the amount of the additive is small, the ultraviolet-resistant effect is poor. Light absorber: can generate structural interconversion under the irradiation of ultraviolet rays, thereby transferring the ultraviolet energy. Because most of the ultraviolet resistant agents are small molecules and have good compatibility with a matrix, the performance of the ultraviolet resistant agents is not affected in the nylon master batch. However, the light absorber has the defects of poor stability, toxicity and the like. The nucleating agent is a functional auxiliary agent which is suitable for polymer materials with incomplete crystallinity, and can accelerate the crystallization rate, increase the crystallinity and promote the grain size to be refined by changing the crystallization behavior of the polymer, thereby shortening the molding cycle and improving the mechanical property. Mainly comprises the following steps: inorganic nucleating agent: such nucleating agents are inexpensive and practical to develop and utilize, but their use in high performance polyamide materials is limited due to poor transparency and surface gloss. Organic nucleating agent: the problems of poor transparency and glossiness of the inorganic nucleating agent are overcome, and the processability of the product can be obviously improved, but due to poor compatibility with the polymer, many properties of the polymer material cannot be exerted.
The conventional polyamide auxiliary agent has single performance, and can even produce side effects on other performances while improving certain performances. Therefore, how to provide a copper-based multifunctional assistant for nylon, which has low cost, no toxicity, environmental protection, no negative effect on other properties (mechanical properties, etc.), and excellent anti-ultraviolet effect and nucleation effect, is a problem to be solved in the art.
Disclosure of Invention
In view of the above, the invention provides a copper-based multifunctional auxiliary agent for nylon, and a preparation method and application thereof, so as to solve the problems of low service life of nylon materials, poor ultraviolet light resistance, high amorphous area ratio, single function of the existing auxiliary agent and influence on other properties of the materials.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the copper-based multifunctional auxiliary agent for nylon comprises the following steps: mixing copper salt, nonfunctional organic ligand and solvent, and carrying out hydrothermal reaction to obtain copper-based multifunctional auxiliary agent for nylon;
the nonfunctional organic ligand comprises one or more of terephthalic acid, trimesic acid, pyridine, 2 '-bipyridine and 4,4' -bipyridine.
Preferably, the hydrothermal reaction raw material further comprises a functional organic ligand, wherein the functional organic ligand comprises one or more of 2-aminobenzophenone-2-carboxylic acid, benzophenone-4, 4-dicarboxylic acid and 3,3', 4' -tetracarboxylic acid benzophenone.
Preferably, the temperature of the hydrothermal reaction is 100-180 ℃ and the time is 12-72 h.
Preferably, the copper salt comprises one or more of copper sulfate pentahydrate, copper nitrate trihydrate, copper chloride dihydrate and copper acetate monohydrate; the solvent comprises one or more of water, methanol, ethanol, acetone, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, when no functional organic ligand is added, the mass ratio of copper salt to nonfunctional organic ligand is 1: 0.1-1, wherein the mass volume ratio of the copper salt to the solvent is 1g:25 mL-100 mL;
when the functional organic ligand is added, the mass ratio of the copper salt to the nonfunctional organic ligand to the functional organic ligand is 1:0.1 to 1: 0.1-1, wherein the mass volume ratio of the copper salt to the solvent is 1g:25 mL-100 mL.
Preferably, after finishing the hydrothermal reaction, a post-treatment step is further included;
the post-treatment steps are as follows: and centrifugally washing the hydrothermal reaction product, and then drying in vacuum to obtain the copper-based multifunctional auxiliary agent for nylon.
Preferably, the times of centrifugal washing are 2-6 times, the temperature of vacuum drying is 60-95 ℃ and the time is 6-24 hours.
The invention further aims to provide the copper-based multifunctional auxiliary agent for nylon, which is prepared by the preparation method.
It is still another object of the present invention to provide the use of a copper-based multifunctional adjuvant for nylon as a nylon uv-blocking agent and nucleating agent.
Preferably, the mass ratio of the nylon to the copper-based multifunctional auxiliary agent for nylon is 95-99.99: 0.01 to 5.
Compared with the prior art, the invention has the following beneficial effects:
1. the copper-based multifunctional auxiliary agent for nylon is prepared by creatively combining the functional characteristics of the ultraviolet-resistant auxiliary agent and the nucleating agent by utilizing an organic metal hybridization technology. The composite material has the advantages of stable structure, good compatibility with a matrix, obvious effect, no toxicity and the like;
2. the copper-based multifunctional auxiliary agent for nylon disclosed by the invention not only utilizes the scattering effect of MOF (metal-organic framework) nano particles on ultraviolet light and the absorption effect of semiconductor characteristics on ultraviolet light, but also plays the absorption effect of an organic ligand part diphenyl ketone structure on ultraviolet light, so that the excellent ultraviolet protection performance is endowed to nylon, and the copper-based multifunctional auxiliary agent has the characteristics of small addition amount, good ultraviolet resistance effect and the like; in addition, the copper-based multifunctional auxiliary agent for nylon prepared by the invention can not only improve the ultraviolet resistance of the nylon material, thereby enhancing the light aging resistance and preventing the wearer from being hurt by ultraviolet light; but also can be used as heterogeneous nucleation points to improve the crystallization rate of the nylon material, thereby improving the crystallization performance;
3. the copper-based multifunctional auxiliary agent for nylon prepared by the invention has better ultraviolet resistance to biological-based nylon materials than the conventional copper MOF materials (HKUST-1 and the like) and the pure benzophenone ultraviolet light absorber; the invention improves the crystallization performance of the bio-based nylon material more than the traditional nucleating agent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction pattern of a copper-based multifunctional adjuvant for nylon prepared in example 1;
FIG. 2 is a scanning electron microscope image of the copper-based multifunctional auxiliary agent for nylon prepared in example 1;
FIG. 3 is an X-ray diffraction pattern of the copper-based multifunctional auxiliary agent for nylon prepared in example 2;
FIG. 4 is a scanning electron microscope image of the copper-based multifunctional auxiliary agent for nylon prepared in example 2.
Detailed Description
The preparation method of the copper-based multifunctional auxiliary agent for nylon comprises the following steps: mixing copper salt, nonfunctional organic ligand and solvent, and carrying out hydrothermal reaction to obtain copper-based multifunctional auxiliary agent for nylon;
the nonfunctional organic ligand comprises one or more of terephthalic acid, trimesic acid, pyridine, 2 '-bipyridine and 4,4' -bipyridine.
In the invention, the hydrothermal reaction raw material also comprises a functional organic ligand, wherein the functional organic ligand comprises one or more of 2-aminobenzophenone-2-carboxylic acid, benzophenone-4, 4-dicarboxylic acid and 3,3', 4' -tetracarboxylic benzophenone.
In the present invention, the nonfunctional organic ligand is capable of facilitating the coordination of the functional organic ligand and the metal ion.
In the invention, the temperature of the hydrothermal reaction is 100-180 ℃, and can be specifically 110 ℃, 120 ℃, 140 ℃, 150 ℃ and 160 ℃; the time is 12-72 h, and can be specifically 18h, 24h, 30h, 36h, 45h, 48h, 55h, 60h and 66h.
In the present invention, the copper salt includes one or more of copper sulfate pentahydrate, copper nitrate trihydrate, copper chloride dihydrate and copper acetate monohydrate.
In the present invention, a portion of the water in the hydrated salt acts as a ligand and coordinates to the metal ion, which results in a more active metal site on the copper ion that coordinates more readily to the ligand to form the MOF.
In the present invention, the solvent includes one or more of water, methanol, ethanol, acetone, N-dimethylformamide and N, N-dimethylacetamide.
In the present invention, when no functional organic ligand is added, the mass ratio of copper salt to nonfunctional organic ligand is 1: 0.1-1, wherein the mass volume ratio of the copper salt to the solvent is 1g:25 mL-100 mL; preferably, the mass ratio of the copper salt to the nonfunctional organic ligand is 1: 0.2-0.8, wherein the mass volume ratio of the copper salt to the solvent is 1g:30 mL-80 mL; it is further preferred that the mass ratio of copper salt to nonfunctional organic ligand is 1: 0.4-0.6, wherein the mass volume ratio of the copper salt to the solvent is 1g:40 mL-60 mL; a further step is preferably that the mass ratio of copper salt to nonfunctional organic ligand is 1:0.5, wherein the mass volume ratio of the copper salt to the solvent is 1g:55mL;
when the functional organic ligand is added, the mass ratio of the copper salt to the nonfunctional organic ligand to the functional organic ligand is 1:0.1 to 1: 0.1-1, wherein the mass volume ratio of the copper salt to the solvent is as follows: 1g:25 mL-100 mL; preferably, the mass ratio of the copper salt to the nonfunctional organic ligand is 1:0.2 to 0.8: 0.2-0.8, wherein the mass volume ratio of the copper salt to the solvent is 1g:30 mL-80 mL; it is further preferable that the mass ratio of the copper salt to the nonfunctional organic ligand is 1:0.4 to 0.6: 0.4-0.6, wherein the mass volume ratio of the copper salt to the solvent is 1g:40 mL-60 mL; a further step is preferably that the mass ratio of copper salt to nonfunctional organic ligand is 1:0.5:0.5, wherein the mass volume ratio of the copper salt to the solvent is 1g:55mL.
In the invention, after the hydrothermal reaction is completed, the method further comprises a post-treatment step;
the post-treatment steps are as follows: and centrifugally washing the hydrothermal reaction product, and then drying in vacuum to obtain the copper-based multifunctional auxiliary agent for nylon.
In the invention, the times of centrifugal washing are 2-6 times, and can be 3, 4 and 5 times specifically; the vacuum drying temperature is 60-95 ℃, specifically 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ and 90 ℃; the time is 6-24 h, and can be specifically 8h, 10h, 12h, 15h, 18h, 20h and 22h.
The invention also provides a copper-based multifunctional auxiliary agent for nylon prepared by the preparation method.
The invention also provides application of the copper-based multifunctional auxiliary agent for nylon as a nylon anti-ultraviolet agent and a nucleating agent.
In the invention, the mass ratio of the nylon to the copper-based multifunctional auxiliary agent for nylon is 95-99.99: 0.01 to 5, preferably 96 to 98:2 to 4, more preferably 97:3.
the application method specifically comprises the following steps: and (3) drying and blending the copper-based multifunctional auxiliary agent for nylon and the nylon, and extruding and granulating in an extruder to obtain the nylon master batch with excellent high ultraviolet protection performance and crystallization performance.
The extrusion temperature of the extruder is preferably 265 ℃, and the extrusion rotating speed is preferably 100r/min.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
S1, weighing 1.0g of copper acetate monohydrate and 0.90g of trimesic acid, dissolving the copper acetate monohydrate and the trimesic acid in 70mLN, N-dimethylformamide without adding a functional ligand benzophenone substance, and uniformly mixing;
s2, taking out the precipitate (namely the product) after the mixed solution reacts in a hydrothermal kettle at the temperature of 100 ℃ for 60 hours;
and S3, centrifugally washing the product by methanol for 4 times, and vacuum drying at 80 ℃ for 12 hours to obtain the copper-based multifunctional assistant for nylon.
The X-ray diffraction diagram of the copper-based multifunctional auxiliary agent for nylon prepared by the embodiment is shown in figure 1, the scanning electron microscope diagram is shown in figure 2, and the heights of the synthesized crystal characteristic peaks of the embodiment 1 are consistent with the heights of the fitting characteristic peaks, so that the copper-based multifunctional auxiliary agent for nylon is proved to be successfully prepared; as can be seen from FIG. 2, the obtained copper-based multifunctional assistant for nylon has a uniform and regular hexagonal structure of crystals due to the existence of non-functional ligands.
Example 2
S1, weighing 1.0g of copper acetate monohydrate, 0.39g of 4,4' -bipyridine and 0.90g of 3,3', 4' -tetracarboxylic benzophenone, dissolving in 70mL of deionized water, and uniformly mixing;
s2, taking out the precipitate after the mixed solution reacts in a hydrothermal kettle at 140 ℃ for 60 hours;
and S3, centrifugally washing the product by deionized water for 4 times, and vacuum drying at 80 ℃ for 12 hours to obtain the copper-based metal organic hybridization multifunctional auxiliary agent.
The X-ray diffraction diagram of the copper-based multifunctional auxiliary agent for nylon prepared by the embodiment is shown in fig. 3, the scanning electron microscope diagram is shown in fig. 4, and the height of the synthesized crystal characteristic peak of the embodiment 2 is consistent with that of the fitting characteristic peak, so that the copper-based multifunctional auxiliary agent for nylon is proved to be successfully prepared; as can be seen from FIG. 4, the copper-based multifunctional assistant for nylon obtained is generally a flake-like crystal of different sizes due to the presence of both functional ligands and nonfunctional ligands.
Example 3
S1, weighing 1.0g of copper sulfate pentahydrate and 1.0g of trimesic acid, dissolving in 30mL of deionized water, and uniformly mixing;
s2, taking out the precipitate after the mixed solution reacts in a hydrothermal kettle at 160 ℃ for 20 hours;
and S3, centrifugally washing the product by deionized water for 4 times, and vacuum drying at 60 ℃ for 12 hours to obtain the copper-based metal organic hybridization multifunctional auxiliary agent.
Example 4
S1, weighing 1.0g of copper nitrate trihydrate, 0.1g of pyridine and 0.3g of 2-aminobenzophenone-2-carboxylic acid, dissolving in 100mL of deionized water, and uniformly mixing;
s2, reacting the mixed solution in a hydrothermal kettle at 110 ℃ for 68 hours, and taking out the precipitate;
and S3, centrifugally washing the product by deionized water for 4 times, and vacuum drying at 80 ℃ for 10 hours to obtain the copper-based metal organic hybridization multifunctional auxiliary agent.
Application example 1
The copper-based multifunctional auxiliary agent for nylon prepared in the example 1 is applied to the nylon processing process, and the specific processing process is as follows:
1) The biobased nylon 56 and the product from example 1 were dried in a vacuum oven at 80 ℃ for 12 hours for later use;
2) Blending 1000g of bio-based nylon 56 and 1g of the product obtained in the example 1 in the pretreatment material obtained in the step 1), and extruding and granulating in an extruder; the extrusion temperature is 265 ℃, the extrusion speed is 100r/min, and the nylon material with improved ultraviolet protection performance and excellent crystallization performance can be obtained.
Application example 2
The copper-based multifunctional auxiliary agent for nylon prepared in the example 1 is applied to the nylon processing process, and the specific processing process is as follows:
1) The biobased nylon 56 and the product from example 1 were dried in a vacuum oven at 80 ℃ for 12 hours for later use;
2) Blending 1000g of bio-based nylon 56 and 2g of the product obtained in the example 1 in the pretreatment material obtained in the step 1), and extruding and granulating in an extruder; the extrusion temperature is 265 ℃, the extrusion speed is 100r/min, and the nylon material with high ultraviolet protection performance and excellent crystallization performance can be obtained.
Application example 3
The copper-based multifunctional auxiliary agent for nylon prepared in the example 1 is applied to the nylon processing process, and the specific processing process is as follows:
1) The biobased nylon 56 and the product from example 1 were dried in a vacuum oven at 80 ℃ for 12 hours for later use;
2) Blending 1000g of bio-based nylon 56 and 4g of the product obtained in the example 1 in the pretreatment material obtained in the step 1), and extruding and granulating in an extruder; the extrusion temperature is 265 ℃, the extrusion speed is 100r/min, and the nylon material with high ultraviolet protection performance and excellent crystallization performance can be obtained.
Application example 4
The copper-based multifunctional auxiliary agent for nylon prepared in example 2 is applied to the nylon processing process, and the specific processing process is as follows:
1) The biobased nylon 56 and the product from example 2 were dried in a vacuum oven at 80 ℃ for 12 hours for later use;
2) Blending 1000g of bio-based nylon 56 and 1g of the product obtained in the example 2 in the pretreatment material obtained in the step 1), and extruding and granulating in an extruder; the extrusion temperature is 265 ℃, the extrusion speed is 100r/min, and the nylon material with high ultraviolet protection performance and excellent crystallization performance can be obtained.
Application example 5
The copper-based multifunctional auxiliary agent for nylon prepared in example 2 is applied to the nylon processing process, and the specific processing process is as follows:
1) The biobased nylon 56 and the product from example 2 were dried in a vacuum oven at 80 ℃ for 12 hours for later use;
2) Blending 1000g of bio-based nylon 56 and 2g of the product obtained in the example 2 in the pretreatment material obtained in the step 1), and extruding and granulating in an extruder; the extrusion temperature is 265 ℃, the extrusion speed is 100r/min, and the nylon material with high ultraviolet protection performance and excellent crystallization performance can be obtained.
Application example 6
The copper-based multifunctional auxiliary agent for nylon prepared in example 2 is applied to the nylon processing process, and the specific processing process is as follows:
1) The biobased nylon 56 and the product from example 2 were dried in a vacuum oven at 80 ℃ for 12 hours for later use;
2) Blending 1000g of bio-based nylon 56 and 4g of the product obtained in the example 2 in the pretreatment material obtained in the step 1), and extruding and granulating in an extruder; the extrusion temperature is 265 ℃, the extrusion speed is 100r/min, and the nylon material with high ultraviolet protection performance and excellent crystallization performance can be obtained.
Comparative example 1
1) The bio-based nylon 56 is placed in a vacuum oven at 80 ℃ for drying for 12 hours for subsequent use;
2) Extruding and granulating 1000g of the biological nylon 56 which is the pretreated material obtained in the step 1) in an extruder; the extrusion temperature was 265℃and the extrusion speed was 100r/min.
Experimental example 1
The samples prepared in comparative example 1 and application examples 1 to 6 were respectively subjected to ultraviolet protection factor, crystallization property and mechanical property test, and the test results are shown in table 1.
Wherein, the Ultraviolet Protection Factor (UPF) represents the ultraviolet protection capability of the sample, and the higher the UPF value is, the better the ultraviolet shielding performance of the material is;
where E (λ) is the solar spectral emissivity, ε (λ) is the relative erythema effect spectral value, T (λ) is the ultraviolet spectral transmittance at wavelength λ, and Δλ is the wavelength interval of the measurement.
The crystallization performance was tested as follows:
step one, weighing 7mg of a sample, heating to 300 ℃ at a heating rate of 50 ℃/min, and keeping the temperature for 3 minutes to eliminate heat history;
step two, cooling the sample to room temperature again at a cooling rate of 20 ℃/min and preserving the temperature for 1 minute;
and thirdly, heating the sample to 300 ℃ at a heating rate of 20 ℃/min, recording the change of heat flow with time, and calculating the crystallization rate.
The crystallinity is calculated from the melting enthalpy in step three and the theoretical melting enthalpy of nylon 56:
in DeltaH m Is the secondary melting enthalpy value of the composite nylon 56 material, and delta H 0 Is the theoretical enthalpy value (here 188.7J/g) of pure nylon material when it is fully crystallized.
Mechanical property test, tensile strength detection is carried out according to GB/T1040-92; impact strength detection is in accordance with GB/T1843-2008.
Table 1 application performance test results
From table 1, it can be seen that the copper-based multifunctional auxiliary agents for nylon obtained in example 1 and example 2 can strengthen the ultraviolet protection performance of the nylon master batch under the condition of different addition mass ratios, which indicates that the copper-based metal organic hybrid multifunctional auxiliary agent disclosed by the invention can be used as an ultraviolet resistant agent of polyamide. In addition, the UPF values of application examples 4 to 6 are far higher than application examples 1 to 3 due to the presence of the benzophenone structure in the organic framework at the same additive mass ratio.
Table 1 also shows that the copper-based multifunctional auxiliary agent for nylon can accelerate the crystallization rate of the nylon master batch and improve the crystallinity of the nylon master batch, which shows that the copper-based multifunctional auxiliary agent for nylon disclosed by the invention can be used as a nucleating agent for polyamide. Furthermore, example 1 is more effective in increasing crystallinity; in contrast, example 2 is more effective in accelerating the crystallization rate.
In addition, the invention can enhance the ultraviolet resistance and crystallization performance of nylon, and can not influence the mechanical property of nylon and generate side effects, which indicates that the copper-based multifunctional auxiliary agent for nylon prepared by the invention is a multifunctional composite auxiliary agent suitable for polyamide matrix.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the copper-based multifunctional auxiliary agent for nylon is characterized by comprising the following steps of: mixing copper salt, nonfunctional organic ligand and solvent, and carrying out hydrothermal reaction to obtain copper-based multifunctional auxiliary agent for nylon;
the nonfunctional organic ligand comprises one or more of terephthalic acid, trimesic acid, pyridine, 2 '-bipyridine and 4,4' -bipyridine.
2. The method for preparing the copper-based multifunctional auxiliary agent for nylon according to claim 1, wherein the hydrothermal reaction raw material further comprises a functional organic ligand, and the functional organic ligand comprises one or more of 2-aminobenzophenone-2-carboxylic acid, benzophenone-4, 4-dicarboxylic acid and 3,3', 4' -tetracarboxylic benzophenone.
3. The method for preparing the copper-based multifunctional auxiliary agent for nylon according to claim 1 or 2, wherein the hydrothermal reaction is carried out at a temperature of 100-180 ℃ for 12-72 h.
4. The method for preparing the copper-based multifunctional auxiliary agent for nylon according to claim 3, wherein the copper salt comprises one or more of copper sulfate pentahydrate, copper nitrate trihydrate, copper chloride dihydrate and copper acetate monohydrate; the solvent comprises one or more of water, methanol, ethanol, acetone, N-dimethylformamide and N, N-dimethylacetamide.
5. The method for preparing the copper-based multifunctional auxiliary agent for nylon according to claim 4, wherein when no functional organic ligand is added, the mass ratio of the copper salt to the nonfunctional organic ligand is 1: 0.1-1, wherein the mass volume ratio of the copper salt to the solvent is 1g:25 mL-100 mL;
when the functional organic ligand is added, the mass ratio of the copper salt to the nonfunctional organic ligand to the functional organic ligand is 1:0.1 to 1: 0.1-1, wherein the mass volume ratio of the copper salt to the solvent is 1g:25 mL-100 mL.
6. The method for preparing the copper-based multifunctional auxiliary agent for nylon according to claim 5, wherein the method further comprises a post-treatment step after finishing the hydrothermal reaction;
the post-treatment steps are as follows: and centrifugally washing the hydrothermal reaction product, and then drying in vacuum to obtain the copper-based multifunctional auxiliary agent for nylon.
7. The method for preparing the copper-based multifunctional auxiliary agent for nylon according to claim 6, wherein the centrifugal washing is performed for 2-6 times, the vacuum drying is performed at 60-95 ℃ for 6-24 hours.
8. The copper-based multifunctional auxiliary agent for nylon prepared by the preparation method of any one of claims 1 to 7.
9. The use of the copper-based multifunctional auxiliary agent for nylon as claimed in claim 8 as an anti-ultraviolet agent and a nucleating agent for nylon.
10. The use of the copper-based multifunctional auxiliary agent for nylon according to claim 9, wherein the mass ratio of the copper-based multifunctional auxiliary agent for nylon to the nylon is 95-99.99: 0.01 to 5.
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