CN113355661A - High-activity high-stability colloidal palladium catalyst and preparation process thereof - Google Patents
High-activity high-stability colloidal palladium catalyst and preparation process thereof Download PDFInfo
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- CN113355661A CN113355661A CN202110604284.5A CN202110604284A CN113355661A CN 113355661 A CN113355661 A CN 113355661A CN 202110604284 A CN202110604284 A CN 202110604284A CN 113355661 A CN113355661 A CN 113355661A
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- palladium catalyst
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 337
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 173
- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- 230000000694 effects Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 73
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 46
- 238000001914 filtration Methods 0.000 claims abstract description 45
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 23
- 235000012141 vanillin Nutrition 0.000 claims abstract description 21
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims abstract description 21
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 20
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims abstract description 19
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001630 malic acid Substances 0.000 claims abstract description 19
- 235000011090 malic acid Nutrition 0.000 claims abstract description 19
- 239000002211 L-ascorbic acid Substances 0.000 claims abstract description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 claims abstract description 3
- LZCLXQDLBQLTDK-BYPYZUCNSA-N ethyl (2S)-lactate Chemical compound CCOC(=O)[C@H](C)O LZCLXQDLBQLTDK-BYPYZUCNSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 41
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 38
- 238000001816 cooling Methods 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 24
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 24
- 229940116333 ethyl lactate Drugs 0.000 claims description 19
- 229940099690 malic acid Drugs 0.000 claims description 18
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000009833 condensation Methods 0.000 claims description 14
- 230000005494 condensation Effects 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims description 11
- VHJLVAABSRFDPM-QWWZWVQMSA-N dithiothreitol Chemical compound SC[C@@H](O)[C@H](O)CS VHJLVAABSRFDPM-QWWZWVQMSA-N 0.000 claims description 10
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229940116298 l- malic acid Drugs 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052802 copper Inorganic materials 0.000 abstract description 28
- 239000010949 copper Substances 0.000 abstract description 28
- 239000000084 colloidal system Substances 0.000 abstract description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 11
- 238000009835 boiling Methods 0.000 abstract description 10
- -1 palladium ions Chemical class 0.000 abstract description 10
- 230000002776 aggregation Effects 0.000 abstract description 9
- 238000004220 aggregation Methods 0.000 abstract description 6
- 238000009825 accumulation Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 16
- 229940117960 vanillin Drugs 0.000 description 15
- 239000000758 substrate Substances 0.000 description 14
- 238000007747 plating Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 238000007772 electroless plating Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/23—
Abstract
The invention discloses a high-activity high-stability colloidal palladium catalyst and a preparation process thereof, wherein the catalyst comprises the following components in parts by mass: 2-5 g/L palladium source, 100-200 ml/L ethyl lactate, 1-5 g/L vanillin, 1-5 g/L ascorbic acid and 0.5-1 g/L dispersing agent. According to the invention, a palladium source is reduced by ascorbic acid, nano palladium particles are formed by filtering, particle accumulation is reduced, a nano palladium colloid is generated by controlling the temperature, a gradual step heating mode is adopted until the temperature is raised to boiling of a system, the sudden temperature increase can be prevented, the aggregation of the palladium colloid is caused, the nano particles of the palladium colloid can be better and more stably dispersed by keeping the temperature at a lower temperature for a period of time, the uniformity of the system of the palladium colloid is ensured, the colloid aggregation is avoided by filtering, the size of the colloid is reduced, malic acid is added to complex palladium ions, the condition that the state of the prepared palladium catalyst is influenced by the existence of free palladium ions in the system is avoided, the high nano activity and high stability of the palladium catalyst are ensured, and the quality of the prepared metal copper layer is improved.
Description
Technical Field
The invention relates to the technical field of metal grids, in particular to a high-activity high-stability colloidal palladium catalyst and a preparation process thereof.
Background
We will refer to a metal plating technique, called electroless plating, also called electroless plating, in which metal ions in a plating solution are deposited on an activated substrate surface by a redox reaction with the aid of a certain reducing agent in the absence of an external electric current. In conventional production, the substrate for electroless plating is mostly non-conductive, and before electroless plating, the surface of the substrate must be pretreated and activated to adsorb certain active centers on the non-metallic substrate, so as to induce the subsequent electroless plating. The activation determines not only the quality of the electroless plating but also the quality of the plating layer.
In the process of metalizing the non-metallic material, the performance of the palladium catalyst is one of the key factors related to metalizing the non-metallic material, the activity of the existing palladium catalyst is general at present, the continuous stability of the palladium catalyst solution can be ensured only by increasing the palladium content in the catalyst solution to 50-100ppm, otherwise, the subsequent chemical plating is influenced; at present, a palladium catalyst is usually directly prepared into a solution, when the solution is prepared into a concentrated solution, instability is easy to occur, palladium chloride is separated out in the production process, great waste is caused, and the cost of the palladium chloride accounts for the most part of the whole cost. Therefore, we propose a high activity and high stability colloidal palladium catalyst and its preparation process.
Disclosure of Invention
The invention aims to provide a high-activity high-stability colloidal palladium catalyst and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a high-activity high-stability colloidal palladium catalyst comprises the following components in parts by mass: 2-5 g/L palladium source, 100-200 ml/L ethyl lactate, 1-5 g/L vanillin, 1-5 g/L ascorbic acid and 0.5-1 g/L dispersing agent.
Further, the palladium catalyst also comprises 1-2 g/L malic acid.
Furthermore, the mass ratio of the palladium source to the ethyl lactate is 1 (10-20).
Further, the palladium source is one or more of palladium acetate, palladium chloride and palladium sulfate.
Further, the palladium catalyst also comprises 11-15 g/L of water-based polymer, and the water-based polymer comprises the following components in parts by mass: 38-62 parts of polyvinyl alcohol, 1.2-1.6 parts of acryloyl chloride, 1.0-1.5 parts of dithiothreitol, 16-22 parts of isophorone diisocyanate and 4-20 parts of polypropylene glycol.
A preparation process of a high-activity high-stability colloidal palladium catalyst comprises the following steps:
(1) uniformly mixing a palladium source with ethyl lactate and ascorbic acid, and stirring for 4-6 h;
(2) adding vanillin, heating to 70-90 ℃, keeping the temperature for 2-3 hours, and heating until the solution boils;
(3) cooling to room temperature, adding malic acid and a dispersant, and filtering to obtain a palladium catalyst concentrated solution;
(4) and adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1 (8-13), so as to prepare the palladium catalyst.
Further, the method comprises the following steps:
(1) uniformly mixing a palladium source with ethyl lactate and ascorbic acid, and stirring for 4-6 h;
(2) adding vanillin, heating to 60-80 ℃ under the condition of heating reflux condensation, preserving heat for 0.5-1 h, heating to 70-90 ℃, preserving heat for 2-3 h, and heating until the solution is boiled;
(3) cooling to room temperature, adding malic acid and a dispersant, and filtering to obtain a palladium catalyst concentrated solution;
(4) and adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1 (8-13), so as to prepare the palladium catalyst.
Further, the method comprises the following steps:
(1) slowly adding palladium chloride into ethyl lactate and ascorbic acid under the condition of strong stirring, continuously stirring for 4-6 h, and filtering by adopting a 400-800 nm microporous filter element; reducing palladium chloride into metal palladium particles by using ascorbic acid as a reducing agent and ethyl lactate as a solvent, and filtering the metal palladium particles through a 400-800 nm microporous filter element to reduce particle accumulation and facilitate subsequent operation;
(2) adding vanillin, stirring and heating to 60-80 ℃ under the condition of heating reflux condensation, preserving heat for 0.5-1 h, heating to 70-90 ℃ and preserving heat for 2-3 h, and heating until the solution is boiled; under the action of temperature, the metal palladium particles form palladium colloid; when the palladium sol is generated, a gradual step heating mode is adopted until the temperature is raised to the boiling state of the system, so that the temperature sudden increase can be prevented, the aggregation of the palladium colloid is caused, the nano particles of the palladium colloid can be better and more stably dispersed after the temperature is kept for a period of time at a lower temperature, and the uniformity of the system of the palladium colloid is ensured; the added vanillin plays the role of a dispersant and a protective agent, reduces collision and agglomeration caused by Brownian motion among metal palladium particles and is beneficial to generating the metal palladium particles with smaller size;
(3) cooling to room temperature, filtering by adopting a 400-800 nm microporous filter element, adding malic acid and a dispersing agent, and filtering to obtain a palladium catalyst concentrated solution; the prepared palladium colloid passes through a 400-800 nm microporous filter element, colloid aggregation is avoided, the size of the colloid is reduced, malic acid is added, palladium ions can be complexed, free palladium ions in a system are avoided, the state of the prepared palladium catalyst is prevented from being influenced, and high nano activity and high stability of the palladium catalyst are ensured;
(4) and adding water to dilute the palladium catalyst concentrated solution, and adding a surfactant, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1 (8-13), so as to prepare the palladium catalyst.
Further, the method comprises the following steps:
(1) slowly adding palladium chloride into ethyl lactate and ascorbic acid under the condition of strong stirring, continuously stirring for 4-6 h, and filtering by adopting a 400-800 nm microporous filter element;
(2) adding vanillin, stirring and heating to 60-80 ℃ under the condition of heating reflux condensation, preserving heat for 0.5-1 h, heating to 70-90 ℃ and preserving heat for 2-3 h;
(3) cooling to room temperature, filtering by adopting a 400-800 nm microporous filter element, adding malic acid and a dispersing agent, and filtering to obtain a palladium catalyst concentrated solution;
(4) dissolving polyvinyl alcohol in water, adding an ethanol solution of triethylamine and acryloyl chloride, reacting at room temperature for 22-26 h in a nitrogen atmosphere, drying, dissolving in a methanol-water mixed solution, slowly adding dithiothreitol, reacting at room temperature for 22-26 h, and drying to obtain modified polyvinyl alcohol;
mixing isophorone diisocyanate, polypropylene glycol and dibutyltin dilaurate, heating to 80-85 ℃ in a nitrogen atmosphere, reacting for 100-140 min, cooling to 70-80 ℃, adding modified polyvinyl alcohol and diethanolamine, reacting for 5-7 h, cooling to room temperature after the reaction is finished, adding triethylamine, slowly adding deionized water, and dispersing at a high speed to obtain a water-based polymer; under the action of triethylamine, polyvinyl alcohol reacts with acrylamide to generate polyvinyl alcohol-acrylate, then reacts with dithiothreitol to generate copolymer, and has hydroxyl and sulfydryl simultaneously; under the action of dibutyltin dilaurate, reacting isophorone diisocyanate and polypropylene glycol, then reacting with the copolymer, adding deionized water, and performing high-speed shearing to generate aqueous modified polyvinyl alcohol end-capped polyurethane;
(5) adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to deionized water is 1 (8-13), and adding water-based polymer to prepare the palladium catalyst.
The dispersion of the palladium catalyst concentrated solution in deionized water is promoted by adding the aqueous polymer, and the palladium colloid is protected, so that the collision and agglomeration among palladium are reduced, the stability of the palladium catalyst concentrated solution is improved, and the quality reduction of the palladium catalyst is prevented; meanwhile, the waterborne polymer contains polyurethane, so that the bonding strength between a metal copper layer and a substrate PET can be improved in the subsequent copper melting process, the waterborne polymer is in a nanometer level, and the thickness of a film body formed after the prepared palladium catalyst coating liquid is coated is thinner, the thickness of a product cannot be influenced, and the flexibility of the product can be improved; the water-based polymer also has hydroxyl, sulfydryl, diethylamine and other groups, so that the oxidation of the palladium catalyst can be avoided, the reduction of oxidized palladium ions is promoted, the palladium ions in the system are reduced, and the quality of the prepared palladium catalyst is ensured;
meanwhile, after the water-based polymer contained in the prepared palladium catalyst is used, sulfydryl and hydroxyl are introduced to the surface of the substrate, so that the wettability of the substrate and the copper solution can be improved, a catalytic active center is formed by cooperation of the substrate and the palladium catalyst, the starting time of copper is shortened, the efficiency of electroless copper plating is improved, and the prepared metal copper layer is uniform and compact and has good quality; the aqueous polymer in the palladium catalyst can also modify a metal copper layer, promote charge movement and improve the sensitivity of the prepared product.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the high-activity high-stability colloidal palladium catalyst and the preparation process thereof, a palladium source is reduced by ascorbic acid, nano palladium particles are formed by filtering, particle accumulation is reduced, a temperature is controlled to generate nano palladium colloid, a gradual step heating mode is adopted until the temperature is raised to boiling of a system, the temperature increase can be prevented, the aggregation of the palladium colloid is caused, the nano particles of the palladium colloid can be better and more stably dispersed after the temperature is kept for a period of time at a lower temperature, the uniformity of the system of the palladium colloid is ensured, the colloid aggregation is avoided by filtering, the size of the colloid is reduced, malic acid is added to complex palladium ions, the condition of the prepared palladium catalyst is prevented from being influenced by free palladium ions in the system, the high nano activity and high stability of the prepared palladium catalyst are ensured, and the quality of a metal copper layer is improved.
2. According to the high-activity high-stability colloid palladium catalyst and the preparation process thereof, modified polyvinyl alcohol containing sulfydryl is prepared from polyvinyl alcohol, acryloyl chloride and dithiothreitol, and reacts with isophorone diisocyanate and polypropylene glycol to generate aqueous macromolecules, and after the aqueous macromolecules are added into a preparation system of the palladium catalyst, particle agglomeration can be reduced, the quality of a palladium colloid is improved, and polyurethane is contained in the aqueous macromolecules, so that the bonding strength between a metal copper layer and a substrate PET (polyethylene terephthalate) and the flexibility of a prepared final product are improved; the aqueous polymer also has hydroxyl, sulfydryl, diethylamine and other groups, so that the content of palladium ions in the system is reduced, and the quality of the palladium catalyst is improved; sulfydryl and hydroxyl are introduced to the surface of the substrate by the water-based polymer, so that the wettability of the substrate and the copper melting liquid is improved, a catalytic active center is formed by the substrate and a palladium catalyst in a synergistic manner, the starting time of copper melting is shortened, the efficiency of chemical copper plating is improved, and the prepared metal copper layer is uniform and compact and has good quality; the aqueous polymer in the palladium catalyst can also modify a metal copper layer, promote charge movement and improve the sensitivity of a prepared final product.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Slowly adding palladium chloride into ethyl lactate and ascorbic acid under the condition of strong stirring, continuously stirring for 4 hours, and filtering by adopting a 400-800 nm microporous filter element;
(2) adding vanillin, stirring and heating to 60 deg.C under heating reflux condensation condition, maintaining the temperature for 0.5h, heating to 70 deg.C, maintaining the temperature for 2h, and heating until the solution is boiling;
(3) cooling to room temperature, filtering by adopting a 400-800 nm microporous filter element, adding malic acid and a dispersing agent, and filtering to obtain a palladium catalyst concentrated solution;
(4) and (3) adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1:8, so as to obtain the palladium catalyst.
Example 2
(1) Slowly adding palladium chloride into ethyl lactate and ascorbic acid under the condition of strong stirring, continuously stirring for 5 hours, and filtering by adopting a 400-800 nm microporous filter element;
(2) adding vanillin, stirring and heating to 70 ℃ under the condition of heating reflux and condensation, preserving heat for 45mn, heating to 80 ℃ and preserving heat for 2.5h, and heating until the solution is boiled;
(3) cooling to room temperature, filtering by adopting a 400-800 nm microporous filter element, adding malic acid and a dispersing agent, and filtering to obtain a palladium catalyst concentrated solution;
(4) and (3) adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1:10, so as to obtain the palladium catalyst.
Example 3
(1) Slowly adding palladium chloride into ethyl lactate and ascorbic acid under the condition of strong stirring, continuously stirring for 6 hours, and filtering by adopting a 400-800 nm microporous filter element;
(2) adding vanillin, stirring and heating to 80 deg.C under heating reflux condensation condition, maintaining for 1h, heating to 90 deg.C, maintaining for 3h, and heating until the solution is boiling;
(3) cooling to room temperature, filtering by adopting a 400-800 nm microporous filter element, adding malic acid and a dispersing agent, and filtering to obtain a palladium catalyst concentrated solution;
(4) and (3) adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1:13, so as to obtain the palladium catalyst.
Example 4
(1) Slowly adding palladium chloride into ethyl lactate and ascorbic acid under the condition of strong stirring, continuously stirring for 4 hours, and filtering by adopting a 400-800 nm microporous filter element;
(2) adding vanillin, stirring and heating to 60 deg.C under heating reflux condensation condition, maintaining the temperature for 0.5h, heating to 70 deg.C, maintaining the temperature for 2h, and heating until the solution is boiling;
(3) cooling to room temperature, filtering by adopting a 400-800 nm microporous filter element, adding malic acid and a dispersing agent, and filtering to obtain a palladium catalyst concentrated solution;
(4) dissolving polyvinyl alcohol in water, adding ethanol solution of triethylamine and acryloyl chloride, reacting at room temperature for 22h in nitrogen atmosphere, drying, dissolving in methanol-water mixed solution, slowly adding dithiothreitol, reacting at room temperature for 22h, and drying to obtain modified polyvinyl alcohol;
mixing isophorone diisocyanate, polypropylene glycol and dibutyltin dilaurate, heating to 80 ℃ in a nitrogen atmosphere, reacting for 100min, cooling to 70 ℃, adding modified polyvinyl alcohol, reacting for 5h, cooling to room temperature after the reaction is finished, adding triethylamine, slowly adding deionized water, and dispersing at a high speed to obtain a water-based polymer;
(5) and (3) adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1:10, and adding a water-based polymer to prepare the palladium catalyst.
Example 5
(1) Adding ethyl lactate and ascorbic acid, slowly adding palladium chloride under the condition of strong stirring, continuously stirring for 5 hours, and filtering by adopting a 400-800 nm microporous filter element;
(2) adding vanillin, stirring and heating to 70 deg.C under heating reflux condensation condition, maintaining the temperature for 45min, heating to 80 deg.C, maintaining the temperature for 2.5h, and heating until the solution is boiling;
(3) cooling to room temperature, filtering by adopting a 400-800 nm microporous filter element, adding malic acid and a dispersing agent, and filtering to obtain a palladium catalyst concentrated solution;
(4) dissolving polyvinyl alcohol in water, adding ethanol solution of triethylamine and acryloyl chloride, reacting at room temperature for 24h in nitrogen atmosphere, drying, dissolving in methanol-water mixed solution, slowly adding dithiothreitol, reacting at room temperature for 24h, and drying to obtain modified polyvinyl alcohol;
mixing isophorone diisocyanate, polypropylene glycol and dibutyltin dilaurate, heating to 82 ℃ in a nitrogen atmosphere, reacting for 120min, cooling to 75 ℃, adding modified polyvinyl alcohol, reacting for 6h, cooling to room temperature after the reaction is finished, adding triethylamine, slowly adding deionized water, and dispersing at a high speed to obtain a water-based polymer;
(5) and (3) adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1:10, and adding a water-based polymer to prepare the palladium catalyst.
Example 6
(1) Adding ethyl lactate and ascorbic acid, slowly adding palladium chloride under the condition of strong stirring, continuously stirring for 6 hours, and filtering by adopting a 400-800 nm microporous filter element;
(2) adding vanillin, stirring and heating to 80 deg.C under heating reflux condensation condition, maintaining for 1h, heating to 90 deg.C, maintaining for 3h, and heating until the solution is boiling;
(3) cooling to room temperature, filtering by adopting a 400-800 nm microporous filter element, adding malic acid and a dispersing agent, and filtering to obtain a palladium catalyst concentrated solution;
(4) dissolving polyvinyl alcohol in water, adding ethanol solution of triethylamine and acryloyl chloride, reacting at room temperature for 26h in nitrogen atmosphere, drying, dissolving in methanol-water mixed solution, slowly adding dithiothreitol, reacting at room temperature for 26h, and drying to obtain modified polyvinyl alcohol;
mixing isophorone diisocyanate, polypropylene glycol and dibutyltin dilaurate, heating to 85 ℃ in a nitrogen atmosphere, reacting for 140min, cooling to 80 ℃, adding modified polyvinyl alcohol, reacting for 7h, cooling to room temperature after the reaction is finished, adding triethylamine, slowly adding deionized water, and dispersing at a high speed to obtain a water-based polymer;
(5) and (3) adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1:10, and adding a water-based polymer to prepare the palladium catalyst.
Comparative example 1
(1) Adding hydrochloric acid into a sodium chloride solution, heating to 40 ℃, and slowly adding palladium chloride to prepare a solution A;
(2) dissolving stannous chloride in a sodium chloride solution, and sequentially adding sodium stannate, vanillin and ascorbic acid to prepare a solution B;
(3) slowly adding the solution A into the solution B under the stirring state, heating to 60 ℃, and preserving heat for 1 h; then, continuously heating to 90 ℃, and preserving heat for 1 h; continuing to heat until the solution is boiled, immediately stopping heating, and preserving the heat at 65 ℃ for more than 8 hours to prepare the palladium catalyst;
(4) and (3) adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1:10, so as to obtain the palladium catalyst.
Comparative example 2
(1) Slowly adding palladium chloride into ethyl lactate and ascorbic acid under the condition of strong stirring, continuously stirring for 5 hours, and filtering by adopting a 400-800 nm microporous filter element;
(2) adding vanillin, stirring and heating to 70 deg.C under heating reflux condensation condition, maintaining the temperature for 45min, heating to 80 deg.C, maintaining the temperature for 2.5h, and heating until the solution is boiling;
(3) cooling to room temperature, filtering by adopting a 400-800 nm microporous filter element, adding malic acid and a dispersing agent, and filtering to obtain a palladium catalyst concentrated solution;
(4) dissolving polyethylene glycol in water, adding ethanol solution of triethylamine and acryloyl chloride, reacting at room temperature for 24h in nitrogen atmosphere, drying, dissolving in methanol-water mixed solution, slowly adding dithiothreitol, reacting at room temperature for 24h, and drying to obtain modified polyvinyl alcohol;
mixing isophorone diisocyanate, polypropylene glycol and dibutyltin dilaurate, heating to 82 ℃ in a nitrogen atmosphere, reacting for 120min, cooling to 75 ℃, adding modified polyvinyl alcohol, reacting for 6h, cooling to room temperature after the reaction is finished, adding triethylamine, slowly adding deionized water, and dispersing at a high speed to obtain a water-based polymer;
(5) and (3) adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1:10, and adding a water-based polymer to prepare the palladium catalyst.
Comparative example 3
(1) Slowly adding palladium chloride into ethyl lactate and ascorbic acid under the condition of strong stirring, continuously stirring for 5 hours, and filtering by adopting a 400-800 nm microporous filter element;
(2) adding vanillin, stirring and heating to 70 deg.C under heating reflux condensation condition, maintaining the temperature for 45min, heating to 80 deg.C, maintaining the temperature for 2.5h, and heating until the solution is boiling;
(3) cooling to room temperature, filtering by adopting a 400-800 nm microporous filter element, adding malic acid and a dispersing agent, and filtering to obtain a palladium catalyst concentrated solution;
(4) mixing isophorone diisocyanate, polypropylene glycol and dibutyltin dilaurate, heating to 82 ℃ in a nitrogen atmosphere, reacting for 120min, cooling to 75 ℃, adding polyvinyl alcohol, reacting for 6h, cooling to room temperature after the reaction is finished, adding triethylamine, slowly adding deionized water, and dispersing at a high speed to obtain a water-based polymer;
(5) and (3) adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1:10, and adding a water-based polymer to prepare the palladium catalyst.
Experiment of
Coating a photoresist on a substrate PET film, coating the surface of the photoresist on a coating liquid of the palladium catalyst obtained in examples 1-6 and comparative examples 1-3, coating a protective layer, developing and exposing, preparing a copper plating solution from a copper salt, a complexing agent, a pH regulator, a reducing agent and a stabilizing agent in the copper plating solution, immersing the substrate in the copper plating solution, carrying out copper plating treatment at the temperature of 28 ℃ for 10min to form a metal copper layer, preparing a sample, respectively detecting the copper plating starting time, the deposition rate, the sensitivity, the sheet resistance and the electric conductivity of the prepared metal copper layer, and recording the detection result:
from the data in the table above, it is clear that the following conclusions can be drawn:
the coating liquids of the palladium catalysts obtained in examples 1 to 6 and comparative examples 1 to 3 and the metallic copper layers produced therefrom were compared, and the results of the measurements were found to be:
the coating liquids of the palladium catalysts obtained in examples 1 to 6 and the prepared metallic copper layers thereof have the advantages that the copper-dissolving start time data is obviously shortened, the deposition rate data is obviously improved, the sensitivity and sheet resistance data of the prepared metallic copper layers are obviously reduced, and the conductivity data is increased, so that the palladium catalysts obtained in examples 1 to 6 and the prepared metallic copper layers have higher quality;
after the palladium catalyst obtained in examples 1 to 6 is placed for 10 days, the experimental data of the palladium catalyst is not changed obviously, while after the palladium catalyst obtained in comparative example 1 is placed for 10 days, the experimental data of the palladium catalyst is degraded obviously, and after the palladium catalyst obtained in comparative examples 2 to 3 is placed for 10 days, the experimental data of the palladium catalyst is slightly degraded, which fully shows that the invention realizes high activity and high stability of the prepared palladium catalyst;
in comparison with the coating solutions of palladium catalysts and the metallic copper layers prepared in examples 1 to 3 and 4 to 6, the data in examples 4 to 6 are significantly optimized, and it is known that the quality of the palladium catalyst and the metallic copper layers prepared can be improved and the effect is stable by setting the aqueous polymer component and the preparation process thereof.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Furthermore, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The high-activity high-stability colloidal palladium catalyst is characterized by comprising the following components in parts by mass: 2-5 g/L palladium source, 100-200 ml/L ethyl lactate, 1-5 g/L vanillin, 1-5 g/L ascorbic acid and 0.5-1 g/L dispersing agent.
2. The high activity high stability colloidal palladium catalyst of claim 1 wherein: the palladium catalyst also comprises 1-2 g/L malic acid.
3. The high activity high stability colloidal palladium catalyst of claim 1 wherein: the mass ratio of the palladium source to the ethyl lactate is 1 (10-20).
4. The high activity high stability colloidal palladium catalyst of claim 1 wherein: the palladium source is one or more of palladium acetate, palladium chloride and palladium sulfate.
5. The high activity high stability colloidal palladium catalyst of claim 1 wherein: the palladium catalyst further comprises 11-15 g/L of water-based polymer, and the water-based polymer comprises the following components in parts by mass: 38-62 parts of polyvinyl alcohol, 1.2-1.6 parts of acryloyl chloride, 1.0-1.5 parts of dithiothreitol, 16-22 parts of isophorone diisocyanate and 4-20 parts of polypropylene glycol.
6. A preparation process of a high-activity high-stability colloidal palladium catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing a palladium source with ethyl lactate and ascorbic acid, and stirring for 4-6 h;
(2) adding vanillin, heating to 70-90 ℃, keeping the temperature for 2-3 hours, and heating until the solution boils;
(3) cooling to room temperature, adding malic acid and a dispersant, and filtering to obtain a palladium catalyst concentrated solution;
(4) and adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1 (8-13), so as to prepare the palladium catalyst.
7. The process according to claim 6, wherein the catalyst is prepared by the following steps: the method comprises the following steps:
(1) uniformly mixing a palladium source with ethyl lactate and ascorbic acid, and stirring for 4-6 h;
(2) adding vanillin, heating to 60-80 ℃ under the condition of heating reflux condensation, preserving heat for 0.5-1 h, heating to 70-90 ℃, preserving heat for 2-3 h, and heating until the solution is boiled;
(3) cooling to room temperature, adding malic acid and a dispersant, and filtering to obtain a palladium catalyst concentrated solution;
(4) and adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1 (8-13), so as to prepare the palladium catalyst.
8. The process according to claim 7, wherein the catalyst is prepared by the following steps: the method comprises the following steps:
(1) slowly adding palladium chloride into ethyl lactate and ascorbic acid under the condition of strong stirring, continuously stirring for 4-6 h, and filtering by adopting a 400-800 nm microporous filter element;
(2) adding vanillin, stirring and heating to 60-80 ℃ under the condition of heating reflux condensation, preserving heat for 0.5-1 h, heating to 70-90 ℃ and preserving heat for 2-3 h, and heating until the solution is boiled;
(3) cooling to room temperature, filtering by adopting a 400-800 nm microporous filter element, adding malic acid and a dispersing agent, and filtering to obtain a palladium catalyst concentrated solution;
(4) and adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to the deionized water is 1 (8-13), so as to prepare the palladium catalyst.
9. The process according to claim 8, wherein the catalyst is prepared by the following steps: the method comprises the following steps:
(1) slowly adding palladium chloride into ethyl lactate and ascorbic acid under the condition of strong stirring, continuously stirring for 4-6 h, and filtering by adopting a 400-800 nm microporous filter element;
(2) adding vanillin, stirring and heating to 60-80 ℃ under the condition of heating reflux condensation, preserving heat for 0.5-1 h, heating to 70-90 ℃ and preserving heat for 2-3 h, and heating until the solution is boiled;
(3) cooling to room temperature, filtering by adopting a 400-800 nm microporous filter element, adding malic acid and a dispersing agent, and filtering to obtain a palladium catalyst concentrated solution;
(4) dissolving polyvinyl alcohol in water, adding an ethanol solution of triethylamine and acryloyl chloride, reacting at room temperature for 22-26 h in a nitrogen atmosphere, drying, dissolving in a methanol-water mixed solution, slowly adding dithiothreitol, reacting at room temperature for 22-26 h, and drying to obtain modified polyvinyl alcohol;
mixing isophorone diisocyanate, polypropylene glycol and dibutyltin dilaurate, heating to 80-85 ℃ in a nitrogen atmosphere, reacting for 100-140 min, cooling to 70-80 ℃, adding modified polyvinyl alcohol, reacting for 5-7 h, cooling to room temperature after the reaction is finished, adding triethylamine, slowly adding deionized water, and dispersing at a high speed to obtain a water-based polymer;
(5) adding water to dilute the palladium catalyst concentrated solution, wherein the mass ratio of the palladium catalyst concentrated solution to deionized water is 1 (8-13), and adding water-based polymer to prepare the palladium catalyst.
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