CN118185228A - Preparation method of rare earth coupling agent - Google Patents
Preparation method of rare earth coupling agent Download PDFInfo
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- CN118185228A CN118185228A CN202410288141.1A CN202410288141A CN118185228A CN 118185228 A CN118185228 A CN 118185228A CN 202410288141 A CN202410288141 A CN 202410288141A CN 118185228 A CN118185228 A CN 118185228A
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- 239000007822 coupling agent Substances 0.000 title claims abstract description 86
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 59
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 52
- 239000005011 phenolic resin Substances 0.000 claims abstract description 52
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 45
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 36
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 60
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 52
- -1 alkenyl phenolic resin Chemical compound 0.000 claims description 47
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 46
- 239000002904 solvent Substances 0.000 claims description 36
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 33
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- OOIBFPKQHULHSQ-UHFFFAOYSA-N (3-hydroxy-1-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2(O)CC1(OC(=O)C(=C)C)C3 OOIBFPKQHULHSQ-UHFFFAOYSA-N 0.000 claims description 17
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 17
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 17
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 235000017281 sodium acetate Nutrition 0.000 claims description 17
- 239000001632 sodium acetate Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- GJOWSEBTWQNKPC-UHFFFAOYSA-N 3-methyloxiran-2-ol Chemical compound CC1OC1O GJOWSEBTWQNKPC-UHFFFAOYSA-N 0.000 claims description 14
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 7
- 150000004756 silanes Chemical class 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 17
- 239000004033 plastic Substances 0.000 abstract description 17
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000004743 Polypropylene Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of rare earth coupling agents and discloses a preparation method of a rare earth coupling agent, which comprises the steps of adding water into lanthanum oxide to prepare slurry, stirring, adding an aqueous solution of polyvinyl alcohol, heating, then adding a sulfuric acid solution, and stirring to obtain a rare earth coupling agent A; then continuously adding the coupling agent B into the mixture to obtain a rare earth coupling agent; the rare earth element in the rare earth coupling agent can improve the heat resistance and tensile strength of the plastic, and greatly improve the mechanical properties of the plastic, wherein the phenolic resin and cyanuric chloride in the coupling agent B have better high temperature resistance, and the isocyanate and epoxy groups react to obtain the oxazolidone which has high temperature resistance effect, and the oxazolidone is applied to the plastic, so that the high temperature resistance of the plastic is improved; and the adamantyl group in the rare earth coupling agent has better rigidity and the synergistic effect of rare earth elements, so that the mechanical property of the plastic is improved.
Description
Technical Field
The invention relates to the technical field of rare earth coupling agents, in particular to a preparation method of a rare earth coupling agent.
Background
The coupling agent is used as a key auxiliary material for improving the performance of the polymer composite material and reducing the cost of the polymer composite material, is widely applied to industries such as plastics, rubber, glass fiber reinforced plastics, paint, pigment, papermaking, adhesives and the like, and rare earth elements are added into the coupling agent to prepare the rare earth coupling agent; for example, the document 'application of rare earth coupling agent in inorganic rigid particle toughening polypropylene system' reports that the notch impact strength of the composite of CaCO3 treated by WOT and polypropylene (PP) can reach 2 times of pure PP and the elongation at break can reach about 3 times of pure PP under certain conditions, and the composite shows remarkable inorganic particle toughening effect; how to improve the performance of plastic products is therefore the key to solving the problem.
Disclosure of Invention
(One) solving the technical problems
Aiming at the defects of the prior art, the invention provides a preparation method of a rare earth coupling agent, which improves the mechanical property and the high temperature resistance of plastic products.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: a preparation method of a rare earth coupling agent, which comprises the following steps: adding water into lanthanum oxide to prepare slurry, heating to 30-45 ℃, stirring, adding aqueous solution of polyvinyl alcohol, heating to 50-60 ℃, then adding sulfuric acid solution with mass concentration of 20-30%, and stirring for 15-35min to obtain rare earth coupling agent A; and then continuously adding the coupling agent B into the mixture, and stirring and mixing the mixture to obtain the rare earth coupling agent.
Preferably, the mass ratio of the lanthanum oxide to the polyvinyl alcohol to the sulfuric acid is 1:1.2-1.4:1.1-1.6.
Preferably, the mass ratio of the rare earth coupling agent A to the coupling agent B is 1.1-1.3:0.8-1.
Preferably, the preparation method of the coupling agent B comprises the following steps:
(1) Uniformly mixing phenolic resin and epoxy chloropropane, and reacting for 6-10h at 60-90 ℃; then continuously adding 3-hydroxy-1-methacryloxy adamantane and boron trifluoride diethyl etherate catalyst, reacting for 6-12h at 75-100 ℃, concentrating under reduced pressure after finishing, washing and drying to obtain the alkenylation phenolic resin;
(2) Adding alkenyl phenolic resin and hydrogen peroxide into N, N-dimethylformamide solvent, and reacting for 3-6h at 60-100 ℃; then continuously adding a silane coupling agent JH-M920, reacting for 6-8 hours at 70-80 ℃, washing with anhydrous diethyl ether after finishing, drying and concentrating to obtain a hydroxyl modified silane coupling agent;
(3) Adding cyanuric chloride and epoxypropanol into butanone solvent for dissolution, introducing nitrogen for protection, stirring for 20-40min, then adding aqueous solution of sodium acetate, refluxing for 3-5h at 80-100 ℃, cooling, concentrating to remove butanone, washing, and recrystallizing ethyl acetate to obtain epoxidized cyanuric chloride;
(4) Adding hexamethylene diisocyanate, epoxy cyanuric chloride and hydroxyl modified silane coupling agent into N, N-dimethylformamide solvent for reaction, reacting at 90-110 ℃ for 8-12h, distilling under reduced pressure to remove the solvent after the reaction, filtering and drying to obtain the coupling agent B.
Preferably, the mass ratio of the phenolic resin to the epichlorohydrin to the 3-hydroxy-1-methacryloxy adamantane to the boron trifluoride diethyl etherate catalyst in the step (1) is 0.8-1.2:1:1.1-1.3:0.01-0.02.
Preferably, the mass ratio of the alkenyl phenolic resin to the hydrogen peroxide to the silane coupling agent JH-M920 in the step (2) is 1.2-1.4:1.3-1.5:1.5-2.1.
Preferably, the mass ratio of the cyanuric chloride, the glycidol and the sodium acetate in the step (3) is 1:1.5-2.3:0.02-0.1.
Preferably, the mass ratio of the hexamethylene diisocyanate, the epoxidized cyanuric chloride and the hydroxyl modified silane coupling agent in the step (4) is 1.2-1.5:1:0.8-1.6.
(III) beneficial technical effects
Adding water into lanthanum oxide to prepare slurry, stirring, adding an aqueous solution of polyvinyl alcohol, heating, then adding a sulfuric acid solution, and stirring to obtain a rare earth coupling agent A; and then continuously adding the coupling agent B into the mixture to obtain the rare earth coupling agent.
Uniformly mixing phenolic resin and epoxy chloropropane, continuously adding 3-hydroxy-1-methacryloxy adamantane and boron trifluoride diethyl etherate catalyst after reaction to obtain alkenyl phenolic resin, adding hydrogen peroxide to carry out double bond epoxidation, and introducing a silane coupling agent JH-M920 to obtain a hydroxy modified silane coupling agent; reacting cyanuric chloride with glycidol in aqueous solution of sodium acetate to obtain epoxidized cyanuric chloride; and adding hexamethylene diisocyanate, epoxidized cyanuric chloride and a hydroxyl modified silane coupling agent into an N, N-dimethylformamide solvent for reaction to obtain a coupling agent B.
The rare earth element in the rare earth coupling agent can improve the heat resistance and tensile strength of the plastic, greatly improve the mechanical property of the plastic, the rare earth coupling agent can be uniformly distributed in the plastic, the property of the plastic is further improved, the rare earth coupling agent can also improve the compatibility between inorganic powder and organic resin, the rare earth coupling agent contains phenolic resin and inorganic rare earth element, the compatibility between the phenolic resin and the inorganic rare earth element is good, and the plastic is further improved when the rare earth coupling agent is applied to the plastic; the phenolic resin and cyanuric chloride in the coupling agent B have good high temperature resistance, and isocyanate and epoxy groups react to obtain oxazolidone which has high temperature resistance, and the oxazolidone is applied to plastics to improve the high temperature resistance of the plastics; and the adamantyl group in the rare earth coupling agent has better rigidity and the synergistic effect of rare earth elements, so that the mechanical property of the plastic is improved.
Detailed Description
Example 1
(1) Uniformly mixing phenolic resin and epichlorohydrin, and reacting for 6 hours at 60 ℃; then continuously adding 3-hydroxy-1-methacryloxy-adamantane and boron trifluoride diethyl etherate catalyst, reacting for 6 hours at 75 ℃, wherein the mass ratio of the phenolic resin to the epichlorohydrin to the 3-hydroxy-1-methacryloxy-adamantane to the boron trifluoride diethyl etherate catalyst is 0.8:1:1.1:0.01, concentrating under reduced pressure after finishing, washing and drying to obtain the alkenylation phenolic resin;
(2) Adding alkenyl phenolic resin and hydrogen peroxide into N, N-dimethylformamide solvent, and reacting for 3h at 60 ℃; then continuously adding a silane coupling agent JH-M920, wherein the mass ratio of the alkenylation phenolic resin to the hydrogen peroxide to the silane coupling agent JH-M920 is 1.2:1.3:1.5, reacting for 6 hours at 70 ℃, washing with anhydrous diethyl ether after the reaction is finished, drying, and concentrating to obtain the hydroxyl modified silane coupling agent;
(3) Adding cyanuric chloride and epoxypropanol into butanone solvent for dissolution, introducing nitrogen for protection, stirring for 20min, then adding aqueous solution of sodium acetate, wherein the mass ratio of cyanuric chloride to epoxypropanol to sodium acetate is 1:1.5:0.02, refluxing for 3h at 80 ℃, cooling, concentrating to remove butanone, washing, and recrystallizing ethyl acetate to obtain epoxidized cyanuric chloride;
(4) Adding hexamethylene diisocyanate, epoxidized cyanuric chloride and a hydroxyl modified silane coupling agent into an N, N-dimethylformamide solvent for reaction, wherein the mass ratio of the hexamethylene diisocyanate to the epoxidized cyanuric chloride to the hydroxyl modified silane coupling agent is 1.2:1:0.8, reacting for 8 hours at 90 ℃, distilling the solvent under reduced pressure after the reaction, filtering and drying to obtain a coupling agent B;
(5) Adding water into lanthanum oxide to prepare slurry, heating to 30 ℃, stirring, adding an aqueous solution of polyvinyl alcohol, heating to 50 ℃, then adding a sulfuric acid solution with the mass concentration of 20%, wherein the mass ratio of the lanthanum oxide to the polyvinyl alcohol to the sulfuric acid is 1:1.2:1.1, and stirring for 15min to obtain a rare earth coupling agent A; and then continuously adding the coupling agent B into the mixture, wherein the mass ratio of the rare earth coupling agent A to the coupling agent B is 1.1:0.8, and stirring and mixing the mixture to obtain the rare earth coupling agent.
Example 2
(1) Uniformly mixing phenolic resin and epichlorohydrin, and reacting for 10 hours at 90 ℃; then continuously adding 3-hydroxy-1-methacryloxy-adamantane and boron trifluoride diethyl etherate catalyst, reacting for 12 hours at 100 ℃, wherein the mass ratio of the phenolic resin to the epichlorohydrin to the 3-hydroxy-1-methacryloxy-adamantane to the boron trifluoride diethyl etherate catalyst is 1.2:1:1.3:0.02, concentrating under reduced pressure after finishing, washing and drying to obtain the alkenylation phenolic resin;
(2) Adding alkenyl phenolic resin and hydrogen peroxide into N, N-dimethylformamide solvent, and reacting for 6 hours at 100 ℃; then continuously adding a silane coupling agent JH-M920, wherein the mass ratio of the alkenylation phenolic resin to the hydrogen peroxide to the silane coupling agent JH-M920 is 1.4:1.5:2.1, reacting for 8 hours at 80 ℃, washing with anhydrous diethyl ether after the reaction is finished, drying, and concentrating to obtain the hydroxyl modified silane coupling agent;
(3) Adding cyanuric chloride and epoxypropanol into butanone solvent for dissolution, introducing nitrogen for protection, stirring for 40min, then adding aqueous solution of sodium acetate, wherein the mass ratio of cyanuric chloride to epoxypropanol to sodium acetate is 1:2.3:0.1, refluxing for 5h at 100 ℃, cooling, concentrating to remove butanone, washing, and recrystallizing ethyl acetate to obtain epoxidized cyanuric chloride;
(4) Adding hexamethylene diisocyanate, epoxidized cyanuric chloride and a hydroxyl modified silane coupling agent into an N, N-dimethylformamide solvent for reaction, wherein the mass ratio of the hexamethylene diisocyanate to the epoxidized cyanuric chloride to the hydroxyl modified silane coupling agent is 1.5:1:1.6, reacting for 12 hours at 110 ℃, distilling the solvent under reduced pressure after the reaction, filtering and drying to obtain a coupling agent B;
(5) Adding water into lanthanum oxide to prepare slurry, heating to 45 ℃, stirring, adding an aqueous solution of polyvinyl alcohol, heating to 60 ℃, then adding a sulfuric acid solution with the mass concentration of 30%, wherein the mass ratio of the lanthanum oxide to the polyvinyl alcohol to the sulfuric acid is 1:1.4:1.6, and stirring for 35min to obtain a rare earth coupling agent A; and then continuously adding the coupling agent B into the mixture, wherein the mass ratio of the rare earth coupling agent A to the coupling agent B is 1.3:1, and stirring and mixing the mixture to obtain the rare earth coupling agent.
Example 3
(1) Uniformly mixing phenolic resin and epichlorohydrin, and reacting for 8 hours at 75 ℃; then continuously adding 3-hydroxy-1-methacryloxy-adamantane and boron trifluoride diethyl etherate catalyst, reacting for 9 hours at 87.5 ℃, wherein the mass ratio of the phenolic resin to the epichlorohydrin to the 3-hydroxy-1-methacryloxy-adamantane to the boron trifluoride diethyl etherate catalyst is 1.0:1:1.2:0.015, concentrating under reduced pressure after finishing, washing and drying to obtain the alkenylation phenolic resin;
(2) Adding alkenyl phenolic resin and hydrogen peroxide into N, N-dimethylformamide solvent, and reacting for 4.5 hours at 80 ℃; then continuously adding a silane coupling agent JH-M920, wherein the mass ratio of the alkenylation phenolic resin to the hydrogen peroxide to the silane coupling agent JH-M920 is 1.3:1.4:1.8, reacting for 7 hours at 75 ℃, washing with anhydrous diethyl ether after finishing, drying and concentrating to obtain the hydroxyl modified silane coupling agent;
(3) Adding cyanuric chloride and epoxypropanol into butanone solvent for dissolution, introducing nitrogen for protection, stirring for 30min, then adding aqueous solution of sodium acetate, wherein the mass ratio of cyanuric chloride to epoxypropanol to sodium acetate is 1:1.9:0.06, refluxing for 4h at 90 ℃, cooling, concentrating to remove butanone, washing, and recrystallizing ethyl acetate to obtain epoxidized cyanuric chloride;
(4) Adding hexamethylene diisocyanate, epoxidized cyanuric chloride and a hydroxyl modified silane coupling agent into an N, N-dimethylformamide solvent for reaction, wherein the mass ratio of the hexamethylene diisocyanate to the epoxidized cyanuric chloride to the hydroxyl modified silane coupling agent is 1.35:1:1.2, reacting for 10 hours at 105 ℃, distilling under reduced pressure to remove the solvent after the reaction, filtering and drying to obtain a coupling agent B;
(5) Adding water into lanthanum oxide to prepare slurry, heating to 37.5 ℃, stirring, adding an aqueous solution of polyvinyl alcohol, heating to 55 ℃, then adding a sulfuric acid solution with the mass concentration of 25%, wherein the mass ratio of the lanthanum oxide to the polyvinyl alcohol to the sulfuric acid is 1:1.3:1.35, and stirring for 25min to obtain a rare earth coupling agent A; and then continuously adding the coupling agent B into the mixture, wherein the mass ratio of the rare earth coupling agent A to the coupling agent B is 1.2:0.9, and stirring and mixing the mixture to obtain the rare earth coupling agent.
Example 4
(1) Uniformly mixing phenolic resin and epichlorohydrin, and reacting for 6 hours at 60 ℃; then continuously adding 3-hydroxy-1-methacryloxy-adamantane and boron trifluoride diethyl etherate catalyst, reacting for 6 hours at 75 ℃, wherein the mass ratio of the phenolic resin to the epichlorohydrin to the 3-hydroxy-1-methacryloxy-adamantane to the boron trifluoride diethyl etherate catalyst is 0.8:1:1.1:0.01, concentrating under reduced pressure after finishing, washing and drying to obtain the alkenylation phenolic resin;
(2) Adding alkenyl phenolic resin and hydrogen peroxide into N, N-dimethylformamide solvent, and reacting for 3h at 60 ℃; then continuously adding a silane coupling agent JH-M920, wherein the mass ratio of the alkenylation phenolic resin to the hydrogen peroxide to the silane coupling agent JH-M920 is 1.2:1.3:1.5, reacting for 6 hours at 70 ℃, washing with anhydrous diethyl ether after the reaction is finished, drying, and concentrating to obtain the hydroxyl modified silane coupling agent;
(2) Adding alkenyl phenolic resin and hydrogen peroxide into N, N-dimethylformamide solvent, and reacting for 6 hours at 100 ℃; then continuously adding a silane coupling agent JH-M920, wherein the mass ratio of the alkenylation phenolic resin to the hydrogen peroxide to the silane coupling agent JH-M920 is 1.4:1.5:2.1, reacting for 8 hours at 80 ℃, washing with anhydrous diethyl ether after the reaction is finished, drying, and concentrating to obtain the hydroxyl modified silane coupling agent;
(3) Adding cyanuric chloride and epoxypropanol into butanone solvent for dissolution, introducing nitrogen for protection, stirring for 40min, then adding aqueous solution of sodium acetate, wherein the mass ratio of cyanuric chloride to epoxypropanol to sodium acetate is 1:2.3:0.1, refluxing for 5h at 100 ℃, cooling, concentrating to remove butanone, washing, and recrystallizing ethyl acetate to obtain epoxidized cyanuric chloride;
(4) Adding hexamethylene diisocyanate, epoxidized cyanuric chloride and a hydroxyl modified silane coupling agent into an N, N-dimethylformamide solvent for reaction, wherein the mass ratio of the hexamethylene diisocyanate to the epoxidized cyanuric chloride to the hydroxyl modified silane coupling agent is 1.35:1:1.2, reacting for 10 hours at 105 ℃, distilling under reduced pressure to remove the solvent after the reaction, filtering and drying to obtain a coupling agent B;
(5) Adding water into lanthanum oxide to prepare slurry, heating to 37.5 ℃, stirring, adding an aqueous solution of polyvinyl alcohol, heating to 55 ℃, then adding a sulfuric acid solution with the mass concentration of 25%, wherein the mass ratio of the lanthanum oxide to the polyvinyl alcohol to the sulfuric acid is 1:1.3:1.35, and stirring for 25min to obtain a rare earth coupling agent A; and then continuously adding the coupling agent B into the mixture, wherein the mass ratio of the rare earth coupling agent A to the coupling agent B is 1.2:0.9, and stirring and mixing the mixture to obtain the rare earth coupling agent.
Example 5
(1) Uniformly mixing phenolic resin and epichlorohydrin, and reacting for 10 hours at 90 ℃; then continuously adding 3-hydroxy-1-methacryloxy-adamantane and boron trifluoride diethyl etherate catalyst, reacting for 12 hours at 100 ℃, wherein the mass ratio of the phenolic resin to the epichlorohydrin to the 3-hydroxy-1-methacryloxy-adamantane to the boron trifluoride diethyl etherate catalyst is 1.2:1:1.3:0.02, concentrating under reduced pressure after finishing, washing and drying to obtain the alkenylation phenolic resin;
(2) Adding alkenyl phenolic resin and hydrogen peroxide into N, N-dimethylformamide solvent, and reacting for 6 hours at 100 ℃; then continuously adding a silane coupling agent JH-M920, wherein the mass ratio of the alkenylation phenolic resin to the hydrogen peroxide to the silane coupling agent JH-M920 is 1.4:1.5:2.1, reacting for 8 hours at 80 ℃, washing with anhydrous diethyl ether after the reaction is finished, drying, and concentrating to obtain the hydroxyl modified silane coupling agent;
(2) Adding alkenyl phenolic resin and hydrogen peroxide into N, N-dimethylformamide solvent, and reacting for 4.5 hours at 80 ℃; then continuously adding a silane coupling agent JH-M920, wherein the mass ratio of the alkenylation phenolic resin to the hydrogen peroxide to the silane coupling agent JH-M920 is 1.3:1.4:1.8, reacting for 7 hours at 75 ℃, washing with anhydrous diethyl ether after finishing, drying and concentrating to obtain the hydroxyl modified silane coupling agent;
(3) Adding cyanuric chloride and epoxypropanol into butanone solvent for dissolution, introducing nitrogen for protection, stirring for 30min, then adding aqueous solution of sodium acetate, wherein the mass ratio of cyanuric chloride to epoxypropanol to sodium acetate is 1:1.9:0.06, refluxing for 4h at 90 ℃, cooling, concentrating to remove butanone, washing, and recrystallizing ethyl acetate to obtain epoxidized cyanuric chloride;
(4) Adding hexamethylene diisocyanate, epoxidized cyanuric chloride and a hydroxyl modified silane coupling agent into an N, N-dimethylformamide solvent for reaction, wherein the mass ratio of the hexamethylene diisocyanate to the epoxidized cyanuric chloride to the hydroxyl modified silane coupling agent is 1.2:1:0.8, reacting for 8 hours at 90 ℃, distilling the solvent under reduced pressure after the reaction, filtering and drying to obtain a coupling agent B;
(5) Adding water into lanthanum oxide to prepare slurry, heating to 30 ℃, stirring, adding an aqueous solution of polyvinyl alcohol, heating to 50 ℃, then adding a sulfuric acid solution with the mass concentration of 20%, wherein the mass ratio of the lanthanum oxide to the polyvinyl alcohol to the sulfuric acid is 1:1.2:1.1, and stirring for 15min to obtain a rare earth coupling agent A; and then continuously adding the coupling agent B into the mixture, wherein the mass ratio of the rare earth coupling agent A to the coupling agent B is 1.1:0.8, and stirring and mixing the mixture to obtain the rare earth coupling agent.
Comparative example 1
Adding water into lanthanum oxide to prepare slurry, heating to 30 ℃, stirring, adding an aqueous solution of polyvinyl alcohol, heating to 50 ℃, then adding a sulfuric acid solution with the mass concentration of 20%, wherein the mass ratio of the lanthanum oxide to the polyvinyl alcohol to the sulfuric acid is 1:1.2:1.1, and stirring for 15min to obtain the rare earth coupling agent.
Comparative example 2
(1) Uniformly mixing phenolic resin and epichlorohydrin, and reacting for 10 hours at 90 ℃; then continuously adding 3-hydroxy-1-methacryloxy-adamantane and boron trifluoride diethyl etherate catalyst, reacting for 12 hours at 100 ℃, wherein the mass ratio of the phenolic resin to the epichlorohydrin to the 3-hydroxy-1-methacryloxy-adamantane to the boron trifluoride diethyl etherate catalyst is 1.2:1:1.3:0.02, concentrating under reduced pressure after finishing, washing and drying to obtain the alkenylation phenolic resin;
(2) Adding alkenyl phenolic resin and hydrogen peroxide into N, N-dimethylformamide solvent, and reacting for 6 hours at 100 ℃; then continuously adding a silane coupling agent JH-M920, wherein the mass ratio of the alkenylation phenolic resin to the hydrogen peroxide to the silane coupling agent JH-M920 is 1.4:1.5:2.1, reacting for 8 hours at 80 ℃, washing with anhydrous diethyl ether after the reaction is finished, drying, and concentrating to obtain the hydroxyl modified silane coupling agent;
(2) Adding alkenyl phenolic resin and hydrogen peroxide into N, N-dimethylformamide solvent, and reacting for 4.5 hours at 80 ℃; then continuously adding a silane coupling agent JH-M920, wherein the mass ratio of the alkenylation phenolic resin to the hydrogen peroxide to the silane coupling agent JH-M920 is 1.3:1.4:1.8, reacting for 7 hours at 75 ℃, washing with anhydrous diethyl ether after finishing, drying and concentrating to obtain the hydroxyl modified silane coupling agent;
(3) Adding cyanuric chloride and epoxypropanol into butanone solvent for dissolution, introducing nitrogen for protection, stirring for 30min, then adding aqueous solution of sodium acetate, wherein the mass ratio of cyanuric chloride to epoxypropanol to sodium acetate is 1:1.9:0.06, refluxing for 4h at 90 ℃, cooling, concentrating to remove butanone, washing, and recrystallizing ethyl acetate to obtain epoxidized cyanuric chloride;
(4) Adding hexamethylene diisocyanate, epoxidized cyanuric chloride and a hydroxyl modified silane coupling agent into an N, N-dimethylformamide solvent for reaction, wherein the mass ratio of the hexamethylene diisocyanate to the epoxidized cyanuric chloride to the hydroxyl modified silane coupling agent is 1.2:1:0.8, reacting for 8 hours at 90 ℃, distilling the solvent under reduced pressure after the reaction, filtering and drying to obtain a coupling agent B;
Test examples
The coupling agents obtained in examples 1-5 and comparative examples 1-2 were added to 1000 parts by weight of polyethylene by taking 100 parts by weight of the coupling agent, stirred and mixed, and added to a twin-screw extruder at a blending temperature of 180-190℃and an extrusion temperature of 170-180℃to modify the polyethylene by the coupling agent.
The thermal performance of the coupling agent modified polyethylene is tested by a thermogravimetric analyzer, and the maximum temperature is 800 ℃ under the nitrogen atmosphere at the heating rate of 20 ℃/min.
The tensile properties were tested by a tensile tester at a tensile rate of 10mm/min with a sample of 100mm by 5mm and the test results are shown in Table 1.
As is clear from Table 1, in examples 1 to 5 of the present invention, the mass loss temperature was at most 462.8 ℃at 10%, the mass loss temperature was at most 507.9℃at 50%, and the mass retention rate was at most 29.6 at 800 ℃; the tensile strength reaches 39.4-44.7MPa, and the elongation at break reaches 142.8-150.6%.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (8)
1. The preparation method of the rare earth coupling agent is characterized by comprising the following steps of: adding water into lanthanum oxide to prepare slurry, heating to 30-45 ℃, stirring, adding aqueous solution of polyvinyl alcohol, heating to 50-60 ℃, then adding sulfuric acid solution with mass concentration of 20-30%, and stirring for 15-35min to obtain rare earth coupling agent A; and then continuously adding the coupling agent B into the mixture, and stirring and mixing the mixture to obtain the rare earth coupling agent.
2. The method for preparing a rare earth coupling agent according to claim 1, wherein the mass ratio of lanthanum oxide, polyvinyl alcohol and sulfuric acid is 1:1.2-1.4:1.1-1.6.
3. The preparation method of the rare earth coupling agent according to claim 1, wherein the mass ratio of the rare earth coupling agent A to the rare earth coupling agent B is 1.1-1.3:0.8-1.
4. The method for preparing a rare earth coupling agent according to claim 1, wherein the method for preparing the coupling agent B comprises the steps of:
(1) Uniformly mixing phenolic resin and epoxy chloropropane, and reacting for 6-10h at 60-90 ℃; then continuously adding 3-hydroxy-1-methacryloxy adamantane and boron trifluoride diethyl etherate catalyst, reacting for 6-12h at 75-100 ℃, concentrating under reduced pressure after finishing, washing and drying to obtain the alkenylation phenolic resin;
(2) Adding alkenyl phenolic resin and hydrogen peroxide into N, N-dimethylformamide solvent, and reacting for 3-6h at 60-100 ℃; then continuously adding a silane coupling agent JH-M920, reacting for 6-8 hours at 70-80 ℃, washing with anhydrous diethyl ether after finishing, drying and concentrating to obtain a hydroxyl modified silane coupling agent;
(3) Adding cyanuric chloride and epoxypropanol into butanone solvent for dissolution, introducing nitrogen for protection, stirring for 20-40min, then adding aqueous solution of sodium acetate, refluxing for 3-5h at 80-100 ℃, cooling, concentrating to remove butanone, washing, and recrystallizing ethyl acetate to obtain epoxidized cyanuric chloride;
(4) Adding hexamethylene diisocyanate, epoxy cyanuric chloride and hydroxyl modified silane coupling agent into N, N-dimethylformamide solvent for reaction, reacting at 90-110 ℃ for 8-12h, distilling under reduced pressure to remove the solvent after the reaction, filtering and drying to obtain the coupling agent B.
5. The method according to claim 4, wherein the mass ratio of the phenolic resin, epichlorohydrin, 3-hydroxy-1-methacryloxy adamantane, boron trifluoride diethyl etherate catalyst in (1) is 0.8-1.2:1:1.1-1.3:0.01-0.02.
6. The method for preparing rare earth coupling agent according to claim 4, wherein the mass ratio of the alkenylated phenolic resin, the hydrogen peroxide and the silane coupling agent JH-M920 in (2) is 1.2-1.4:1.3-1.5:1.5-2.1.
7. The method for preparing rare earth coupling agent according to claim 4, wherein the mass ratio of cyanuric chloride, glycidol and sodium acetate in (3) is 1:1.5-2.3:0.02-0.1.
8. The method for preparing rare earth coupling agent according to claim 4, wherein the mass ratio of hexamethylene diisocyanate, epoxidized cyanuric chloride and hydroxyl-modified silane coupling agent in (4) is 1.2-1.5:1:0.8-1.6.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002084402A2 (en) * | 2001-04-11 | 2002-10-24 | Clariant International Ltd | Process for producing film forming resins for photoresist compositions |
| US20070248913A1 (en) * | 2006-04-24 | 2007-10-25 | Rahman M Dalil | Process for producing film forming resins for photoresist compositions |
| CN101193928A (en) * | 2005-06-09 | 2008-06-04 | 东曹株式会社 | Novel packing material with excellent hydrophilicity and process for producing the same |
| CN102127324A (en) * | 2011-01-13 | 2011-07-20 | 中国科学技术大学 | Preparation method of modified graphene oxide and preparation method of composite material containing modified graphene oxide |
| CN102675787A (en) * | 2012-05-30 | 2012-09-19 | 兖矿鲁南化肥厂 | Rare earth coupling agent, preparation method and application thereof in treatment of glass fiber reinforced polyformaldehyde composite material |
| JP2017095444A (en) * | 2015-11-16 | 2017-06-01 | 住友化学株式会社 | Compound, resin, resist composition and method for producing resist pattern |
| CN113302223A (en) * | 2019-01-11 | 2021-08-24 | 三菱瓦斯化学株式会社 | Film-forming composition, resist composition, radiation-sensitive composition, method for producing amorphous film, method for forming resist pattern, composition for forming underlayer film for lithography, method for producing underlayer film for lithography, and method for forming circuit pattern |
| CN115968391A (en) * | 2020-07-08 | 2023-04-14 | 三菱瓦斯化学株式会社 | Composition, resin, method for producing amorphous film, method for forming resist pattern, method for producing underlayer film for lithography, and method for forming circuit pattern |
| US20230324801A1 (en) * | 2020-08-14 | 2023-10-12 | Mitsubishi Gas Chemical Company, Inc. | Underlayer film forming composition for lithography, underlayer film, and pattern formation method |
-
2024
- 2024-03-14 CN CN202410288141.1A patent/CN118185228B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002084402A2 (en) * | 2001-04-11 | 2002-10-24 | Clariant International Ltd | Process for producing film forming resins for photoresist compositions |
| CN101193928A (en) * | 2005-06-09 | 2008-06-04 | 东曹株式会社 | Novel packing material with excellent hydrophilicity and process for producing the same |
| US20070248913A1 (en) * | 2006-04-24 | 2007-10-25 | Rahman M Dalil | Process for producing film forming resins for photoresist compositions |
| CN102127324A (en) * | 2011-01-13 | 2011-07-20 | 中国科学技术大学 | Preparation method of modified graphene oxide and preparation method of composite material containing modified graphene oxide |
| CN102675787A (en) * | 2012-05-30 | 2012-09-19 | 兖矿鲁南化肥厂 | Rare earth coupling agent, preparation method and application thereof in treatment of glass fiber reinforced polyformaldehyde composite material |
| JP2017095444A (en) * | 2015-11-16 | 2017-06-01 | 住友化学株式会社 | Compound, resin, resist composition and method for producing resist pattern |
| CN113302223A (en) * | 2019-01-11 | 2021-08-24 | 三菱瓦斯化学株式会社 | Film-forming composition, resist composition, radiation-sensitive composition, method for producing amorphous film, method for forming resist pattern, composition for forming underlayer film for lithography, method for producing underlayer film for lithography, and method for forming circuit pattern |
| CN115968391A (en) * | 2020-07-08 | 2023-04-14 | 三菱瓦斯化学株式会社 | Composition, resin, method for producing amorphous film, method for forming resist pattern, method for producing underlayer film for lithography, and method for forming circuit pattern |
| US20230324801A1 (en) * | 2020-08-14 | 2023-10-12 | Mitsubishi Gas Chemical Company, Inc. | Underlayer film forming composition for lithography, underlayer film, and pattern formation method |
Non-Patent Citations (2)
| Title |
|---|
| CHIOU-CHANG WU，等: "Curing and thermal properties of copolymer epoxy resins prepared by copolymerized bisphenol-A and epichlorohydrin with liquefied Dendrocalamus latiflorus", 《POLYMER JOURNAL》, vol. 42, 4 August 2010 (2010-08-04), pages 711 - 715 * |
| 孙嘉彦，等: "钦酸斓烧结物中未化合氧化斓含量的测定", 《理化检验-化学分册》, vol. 33, no. 4, 31 December 1997 (1997-12-31), pages 174 - 175 * |
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