CN114702533A - Benzoate monomer containing ferrocene unit and preparation method thereof - Google Patents
Benzoate monomer containing ferrocene unit and preparation method thereof Download PDFInfo
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- CN114702533A CN114702533A CN202210329981.9A CN202210329981A CN114702533A CN 114702533 A CN114702533 A CN 114702533A CN 202210329981 A CN202210329981 A CN 202210329981A CN 114702533 A CN114702533 A CN 114702533A
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- metal
- pigment
- ferrocene
- benzoate
- effect pigment
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- 239000000178 monomer Substances 0.000 title claims abstract description 84
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title claims abstract description 63
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000049 pigment Substances 0.000 claims abstract description 73
- 230000000694 effects Effects 0.000 claims abstract description 58
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 239000002798 polar solvent Substances 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 125000003172 aldehyde group Chemical group 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 5
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 230000005389 magnetism Effects 0.000 abstract description 5
- 230000000007 visual effect Effects 0.000 abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- -1 sorbitan fatty acid Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- QKJHNPXSYSFZMJ-UHFFFAOYSA-N 4-ethenyl-2-methylphenol Chemical compound CC1=CC(C=C)=CC=C1O QKJHNPXSYSFZMJ-UHFFFAOYSA-N 0.000 description 1
- WYVMDJWLFVQZAL-UHFFFAOYSA-N 4-propan-2-ylbenzene-1,2-diol Chemical compound CC(C)C1=CC=C(O)C(O)=C1 WYVMDJWLFVQZAL-UHFFFAOYSA-N 0.000 description 1
- UHIWSJXHUHEAMG-UHFFFAOYSA-N 5-ethenyl-2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC(C=C)=CC=C1O UHIWSJXHUHEAMG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
Abstract
The invention discloses a benzoate monomer containing a ferrocene unit and a preparation method thereof, relating to the technical field of polymer composite materials. The invention uses in-situ polymerization method to coat a layer of magnetic polymer on the outer layer of the metal-like effect pigment. The magnetic polymer is a benzoate monomer containing ferrocene units, can be magnetized under the action of a magnetic field, so that the metal-like pigment has magnetism, the orientation of the metal-like pigment is changed under the action of the magnetic field, the flow pattern problem of the material is greatly reduced, and the surface of the composite material is endowed with an excellent visual effect of metallic color texture.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a benzoate monomer containing a ferrocene unit and a preparation method thereof.
Background
The imitation metal texture plastic has unique aesthetic effect and is very popular with people. Spraying-free metal texture plastics, achieving the appearance of metal by directly adding metal powder in the plastic particle granulation process, being capable of being formed at one time, simple in process, high in yield, environment-friendly, energy-saving, recyclable and reusable, good in color durability, not easy to fade in the transportation and use processes and the like. In recent years, spraying-free metal-texture plastics are gradually applied to small household appliances such as air conditioners, refrigerators, electric cookers and the like and automobile bumpers to replace traditional spraying products. In general, spraying-free metal-texture plastics are products which accord with the design concept of customers, conform to the development trend of the industry, have market space and can create economic benefits.
On the other hand, since the metallic pigment has a flake structure, when the melt encounters a grid, hole structure in the mold, the melt is divided into two streams, which then join at the other end to form a flow pattern. The flow pattern problem becomes a main problem which hinders the large-area popularization and application of the non-spraying aesthetic material at present. In order to solve this problem, researchers have devised many methods, such as optimizing the design and structure of a mold, a three-dimensional pigment technology, a surface treatment technology, and a high-temperature steam mold technology (also called a rapid cooling and rapid heating technology). Optimizing a mould and design, and enabling flow marks to appear on a non-appearance surface by optimizing structures such as a glue opening, a rib position and the like; the stereo pigment technology mainly reduces the length-diameter ratio of the pigment and lightens the flow marks; the surface treatment is to carry out surface treatment on effect pigments such as aluminum pigment, pearlescent pigment and the like to optimize the dispersion of the effect pigments; the high-temperature steam mold technology leads the polymer melt to flow and fuse better by increasing the molding temperature of the mold, thereby lightening the appearance defects. The technology alleviates the flow pattern phenomenon to a certain extent, and the research for improving the flow pattern problem from the angle of a magnetic field is not available at present.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide a benzoate monomer containing a ferrocene unit and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a benzoate monomer containing a ferrocene unit is a compound shown in a formula (I), and the structural formula of the compound shown in the formula (I) is as follows:
r1 is a side group containing double bonds, and R1 is at least one of vinyl, propenyl and butenyl; r2 is a side group, and R2 is at least one of aldehyde group, carboxyl group, hydroxyl group, methyl, ethyl, propyl and butyl.
The invention provides a magnetic polymer, which is a benzoate monomer containing a ferrocene unit and can be magnetized under the action of a magnetic field.
Preferably, in the structural formula of the benzoate monomer containing ferrocene unit, R1 is vinyl; r2 is at least one of aldehyde group and carboxyl group. After a great deal of experimental exploration, the inventor finds that R1 is vinyl; when R2 is at least one of aldehyde group and carboxyl, the prepared benzoate monomer containing ferrocene unit can be better coated on the outer layer of the effect pigment in the subsequent in-situ polymerization process with the effect pigment, and the compound has better magnetism under the action of an external magnetic field.
In addition, the invention provides a preparation method of the benzoate monomer containing the ferrocene unit, which comprises the following steps:
(1) synthesizing ferrocenecarbonyl chloride, wherein the structural formula of the ferrocenecarbonyl chloride is shown as a formula (II);
(2) synthesizing a benzoate monomer containing a ferrocene unit, dissolving ferrocene formyl chloride in a dry polar solvent, dripping the polar solvent for dissolving a phenol monomer while stirring, wherein the stirring time is 10-12h, the stirring temperature is 25-30 ℃, and performing rotary evaporation drying to obtain the benzoate monomer containing the ferrocene unit; wherein the structural formula of the phenol monomer is shown as the formula (III)
R1 is a side group containing double bonds, and R1 is at least one of vinyl, propenyl and butenyl; r2 is a side group, and R2 is at least one of aldehyde group, carboxyl group, hydroxyl group, methyl, ethyl, propyl and butyl.
Preferably, the synthesis method of ferrocenecarbonyl chloride in the step (1) comprises the following steps: dissolving ferrocenecarboxylic acid in a dry polar solvent, stirring uniformly, slowly dropwise adding the polar solvent for dissolving oxalyl chloride, and extracting and distilling under reduced pressure to obtain the ferrocenecarboxylic acid chloride; wherein the stirring speed is 450-550rpm, the stirring time is 7-9h, and the dripping speed of oxalyl chloride is 4-6 ml/min.
Preferably, in the preparation method of the benzoate monomer containing ferrocene units, the polar solvent is at least one of pyridine, tetrahydrofuran, dichloromethane and N, N-dimethylformamide.
Further, the invention provides a magnetic metal-like effect pigment, which is obtained by in-situ polymerization of a benzoate monomer containing a ferrocene unit and a metal-like effect pigment.
The invention uses in-situ polymerization method to coat a layer of magnetic polymer on the outer layer of the metal-like effect pigment. The magnetic polymer is a benzoate monomer containing ferrocene units, can be magnetized under the action of a magnetic field, so that the imitation metal pigment has magnetism, the orientation of the imitation metal pigment is changed under the action of the magnetic field, the flow pattern problem of the material is greatly reduced, and the surface of the composite material is endowed with an excellent visual effect of metal color texture.
Preferably, the preparation method of the magnetic metal-like effect pigment comprises the following steps of carrying out in-situ polymerization reaction on a benzoate monomer containing a ferrocene unit and the metal-like effect pigment: uniformly mixing a benzoate monomer containing ferrocene units, an initiator, a metal-like effect pigment and an emulsifier, adding the mixture into a reactor, slowly adding water, replacing air in the reactor with nitrogen, and stirring and polymerizing for 22-26 hours at 75-85 ℃ to obtain the magnetic metal-like effect pigment.
Preferably, the initiator is at least one of azodiisobutyronitrile, lauric peroxide and dibenzoyl peroxide; the emulsifier is at least one of sodium dodecyl benzene sulfonate and sorbitan fatty acid (span 80); the weight ratio of the benzoate monomer containing ferrocene unit, the initiator, the metal effect imitating pigment and the emulsifier is as follows: benzoate monomer containing ferrocene unit: initiator: imitation metal effect pigment: emulsifier ═ (10-25): (0.2-0.5): (40-60): (0.5-1).
Preferably, the metal effect imitating pigment is at least one of aluminum pigment, pearlescent pigment, gold powder, silver powder, copper powder and mica powder; preferably, the metal effect imitating pigment has an average particle diameter of 1 to 20 μm and an aspect ratio of 1.5 to 10.
Further preferably, the invention provides application of the magnetic metal-like effect pigment in thermoplastic plastics such as polypropylene (PP), acrylonitrile-butadiene-styrene (ABS), polymethyl methacrylate (PMMA), terpolymer ASA consisting of acrylonitrile, styrene and acrylic rubber, Polycarbonate (PC), Polyamide (PA) and the like. Furthermore, the invention provides the application of the magnetic metal-like effect pigment in automobiles, household appliances, air conditioners and toys.
Compared with the prior art, the invention has the beneficial effects that: the invention uses in-situ polymerization method to coat a layer of magnetic polymer on the outer layer of the metal effect imitating pigment. The magnetic polymer is a benzoate monomer containing ferrocene units, can be magnetized under the action of a magnetic field, so that the metal-like pigment has magnetism, the orientation of the metal-like pigment is changed under the action of the magnetic field, the flow pattern problem of the material is greatly reduced, and the surface of the composite material is endowed with an excellent visual effect of metallic color texture.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a benzoate monomer 1 containing a ferrocene unit;
FIG. 2 is a nuclear magnetic spectrum of a benzoate monomer 2 containing a ferrocene unit;
FIG. 3 is a nuclear magnetic spectrum of a benzoate monomer 3 containing a ferrocene unit;
FIG. 4 is a nuclear magnetic spectrum of benzoate monomer 4 containing a ferrocene unit.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific examples.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
The preparation method of the magnetic metal-like effect pigment comprises the following steps:
(1) synthesizing ferrocenecarbonyl chloride; the synthesis method comprises the following steps: dissolving ferrocenecarboxylic acid in dry pyridine, stirring uniformly, slowly dropwise adding oxalyl chloride in pyridine solution, extracting, and distilling under reduced pressure to obtain the ferrocenecarboxylic acid chloride; wherein the stirring speed is 500rpm, the stirring time is 8h, and the dripping speed of oxalyl chloride is 5 ml/min; the synthesis modes of the ferrocene formyl chloride in the embodiment and the comparative example are the same;
(2) synthesizing a benzoate monomer containing a ferrocene unit; dissolving ferroceneformyl chloride in a dry tetrahydrofuran solution, dripping a pyridine solution of a phenol monomer while stirring, wherein the stirring time is 10 hours, the stirring temperature is 25 ℃, and performing rotary evaporation drying to obtain a benzoate monomer containing a ferrocene unit; the polar solvent, the stirring temperature and the time used in the embodiment and the comparative example are the same, and only the selection of the phenol monomer is different;
(3) in-situ polymerization is carried out on a benzoate monomer containing ferrocene units and a metal-like effect pigment to obtain the magnetic metal-like effect pigment; the preparation method comprises the following steps: uniformly mixing a benzoate monomer containing a ferrocene unit, an initiator, a metal-like effect pigment and an emulsifier, adding the mixture into a reactor, slowly adding water, replacing air in the reactor with nitrogen, and stirring and polymerizing for 24 hours at 80 ℃ to obtain a magnetic metal-like effect pigment; the initiator, the emulsifier and the metal-like effect pigment used in the embodiment and the comparative example are the same in stirring temperature and time, the initiator is lauric peroxide, the emulsifier is span 80, the metal-like effect pigment is a pearlescent pigment, the particle size is 10 microns, the length-diameter ratio is 5, and the weight ratio of the benzoate monomer containing ferrocene units, the initiator, the metal-like effect pigment and the emulsifier is as follows: benzoate monomer containing ferrocene unit: initiator: imitation metal effect pigment: emulsifier 10:0.3:50: 0.5;
benzoate monomer containing ferrocene unit
Benzoate monomer containing ferrocene unit 1: adopting a phenol monomer 1 (purchased from Sigma-Aldrich and named 4-vinyl-2-aldehyde phenol, and the structural formula is shown as follows); the phenol monomer R1 is vinyl; r2 is an aldehyde group; phenol monomer 1, and junction of benzoate monomer 1 containing ferrocene unit
Benzoate monomer containing ferrocene unit 2: phenol monomer 2 (purchased from Sigma-Aldrich under the name of 4-vinyl-2-carboxyphenol and having the following structural formula) is adopted; the phenol monomer R1 is vinyl; r2 is carboxy; phenol monomer 2, and junction of benzoate monomer 2 containing ferrocene unit
Benzoate monomer containing ferrocene unit 3: adopting a phenol monomer 3 (purchased from Sigma-Aldrich and named 4-isopropyl-2-hydroxyphenol with the structural formula shown in the specification); the phenol monomer R1 is propenyl; r2 is hydroxy; phenol monomer 3, and structure of benzoate monomer 3 containing ferrocene unit
Benzoate monomer containing ferrocene unit 4: phenol monomer 4 (purchased from Sigma-Aldrich under the name of 4-vinyl-2-methylphenol, with the structural formula shown below) is adopted; the phenol monomer R1 is vinyl; r2 is methyl; phenol monomer 4, and junction of benzoate monomer 4 containing ferrocene unit
The magnetic metal-like effect pigment of example 1 is prepared by the above preparation method, wherein a phenol monomer 1 is used to obtain a benzoate monomer 1 containing a ferrocene unit, a nuclear magnetic spectrum of the benzoate monomer 1 containing the ferrocene unit is shown in fig. 1, and the magnetic metal-like effect pigment 1 is obtained after polymerization;
the magnetic metal-like effect pigment of example 2 is prepared by the above preparation method, wherein the phenol monomer 2 is used to obtain the benzoate monomer 2 containing ferrocene unit, the nuclear magnetic spectrum of the benzoate monomer 2 containing ferrocene unit is shown in fig. 2, and the magnetic metal-like effect pigment 2 is obtained after polymerization;
the magnetic metal-like effect pigment of example 3 is prepared by the above preparation method, and the phenol monomer 3 is used to obtain the benzoate monomer 3 containing ferrocene unit, and the nuclear magnetic spectrum of the benzoate monomer 3 containing ferrocene unit is shown in fig. 3, and the magnetic metal-like effect pigment 3 is obtained after polymerization;
the magnetic metal-like effect pigment of example 4 is prepared by the above preparation method, and the phenol monomer 4 is used to obtain the benzoate monomer 4 containing ferrocene unit, and the nuclear magnetic spectrum of the benzoate monomer 4 containing ferrocene unit is shown in fig. 4, and the magnetic metal-like effect pigment 4 is obtained after polymerization;
comparative example 1
In-situ polymerizing a benzoate monomer and a metal-like effect pigment to obtain the magnetic metal-like effect pigment; the preparation method comprises the following steps: uniformly mixing the benzoate monomer, the initiator, the metal-like effect pigment and the emulsifier, adding the mixture into a reactor, slowly adding water, replacing air in the reactor with nitrogen, and stirring and polymerizing for 24 hours at 80 ℃ to obtain the magnetic metal-like effect pigment.
Performance testing
Adding 1% of magnetic metal effect imitation pigment into an ABS substrate, uniformly mixing, manufacturing a smooth colored plate by using an injection molding machine, testing the surface glossiness of the colored plate and evaluating the appearance at the injection molding temperature of 230 ℃.
(1) Surface gloss: the test standard is GB/T8807-1988 plastic mirror surface gloss test method, and the reflection data of the angle of 60 ℃ is tested under the test condition of normal temperature.
(2) Appearance evaluation: the appearance evaluation was based on visual observation, and the following evaluation criteria were used, with 5 samples evaluated separately, and the average was taken:
9-10 minutes-good surface metal effect and no flow marks; 7-8 min-the surface metal effect is better, and no flow lines exist; 5-6 minutes, the surface metal effect is better, and slight flow lines are allowed to exist; less than 5 minutes, the surface metal effect is weak, and obvious flow lines can be seen visually;
the test data are shown in table 1;
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | |
| Degree of gloss | 92 | 90 | 88 | 87 | 70 |
| Appearance of the product | 9 | 9 | 7 | 8 | 4 |
The invention uses in-situ polymerization method to coat a layer of magnetic polymer on the outer layer of the metal-like effect pigment. The magnetic polymer is a benzoate monomer containing a ferrocene unit, can be magnetized under the action of a magnetic field, so that the metal-like pigment has magnetism, the orientation of the metal-like pigment is changed under the action of the magnetic field, the problem of flow marks of the material is greatly reduced, the surface of the composite material is endowed with an excellent visual effect of metal color texture, and the final glossiness is more than or equal to 87.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The ferrocene unit-containing benzoate monomer is characterized in that the ferrocene unit-containing benzoate monomer is shown in formula (I)A compound of formula (I) having the formula:
r1 is a side group containing double bonds, and R1 is at least one of vinyl, propenyl and butenyl; r2 is a side group, and R2 is at least one of aldehyde group, carboxyl group, hydroxyl group, methyl, ethyl, propyl and butyl.
2. The ferrocene unit-containing benzoate monomer according to claim 1, wherein in the structural formula of the ferrocene unit-containing benzoate monomer, R1 is vinyl; r2 is at least one of aldehyde group and carboxyl group.
3. A method for preparing a benzoate monomer containing a ferrocene unit as defined in claim 1, comprising the steps of:
(1) synthesizing ferrocenecarbonyl chloride, wherein the structural formula of the ferrocenecarbonyl chloride is shown as a formula (II);
(2) synthesizing a benzoate monomer containing a ferrocene unit, dissolving ferrocene formyl chloride in a dry polar solvent, dripping the polar solvent for dissolving a phenol monomer while stirring, wherein the stirring time is 10-12h, the stirring temperature is 25-30 ℃, and performing rotary evaporation drying to obtain the benzoate monomer containing the ferrocene unit; wherein the structural formula of the phenol monomer is shown as the formula (III)
R1 is a side group containing double bonds, and R1 is at least one of vinyl, propenyl and butenyl; r2 is a side group, and R2 is at least one of aldehyde group, carboxyl group, hydroxyl group, methyl, ethyl, propyl and butyl.
4. The method for preparing a benzoate monomer containing a ferrocene unit according to claim 3, wherein the synthesis method of the ferrocenecarbonyl chloride in the step (1) comprises the following steps: dissolving ferrocenecarboxylic acid in a dry polar solvent, stirring uniformly, slowly dropwise adding the polar solvent for dissolving oxalyl chloride, and extracting and distilling under reduced pressure to obtain the ferrocenecarboxylic acid chloride; wherein the stirring speed is 450-550rpm, the stirring time is 7-9h, and the dripping speed of oxalyl chloride is 4-6 ml/min.
5. A magnetic metal-like effect pigment, which is characterized in that the magnetic metal-like effect pigment is obtained by in-situ polymerization of the ferrocene unit-containing benzoate monomer and the metal-like effect pigment according to claim 1 or 2.
6. The magnetic metal-like effect pigment of claim 5, wherein the preparation method of the magnetic metal-like effect pigment comprises the following steps of carrying out in-situ polymerization reaction on a benzoate monomer containing a ferrocene unit and the metal-like effect pigment: uniformly mixing a benzoate monomer containing ferrocene units, an initiator, a metal-like effect pigment and an emulsifier, adding the mixture into a reactor, slowly adding water, replacing air in the reactor with nitrogen, and stirring and polymerizing for 22-26 hours at 75-85 ℃ to obtain the magnetic metal-like effect pigment.
7. The magnetic metal-like effect pigment of claim 5, wherein the metal-like effect pigment is at least one of an aluminum pigment, a pearlescent pigment, gold powder, silver powder, copper powder, mica powder; preferably, the average particle size of the metal effect imitating pigment is 1-20 microns, and the length-diameter ratio is 1.5-10.
8. Use of the magnetic metal effect-imitating pigment according to any one of claims 5 to 7 in automobiles, home appliances, air conditioners, toys.
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Citations (2)
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| CN109735061A (en) * | 2019-01-11 | 2019-05-10 | 深圳市金志成塑胶科技有限公司 | A kind of PET polyester material exempts from coating manufacturing process |
| CN115477810A (en) * | 2022-09-15 | 2022-12-16 | 广州汽车集团股份有限公司 | Spraying-free polypropylene material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109735061A (en) * | 2019-01-11 | 2019-05-10 | 深圳市金志成塑胶科技有限公司 | A kind of PET polyester material exempts from coating manufacturing process |
| CN115477810A (en) * | 2022-09-15 | 2022-12-16 | 广州汽车集团股份有限公司 | Spraying-free polypropylene material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MAO SHI ET AL.,: "Reversible Addition-Fragmentation Transfer Polymerization of a Novel Monomer Containing Both Aldehyde and Ferrocene Functional Groups", MACROMOLECULES, vol. 40, pages 1891 - 1896 * |
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