CN117247519A - Organosilicon isocyanate curing agent and preparation method and application thereof - Google Patents
Organosilicon isocyanate curing agent and preparation method and application thereof Download PDFInfo
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- CN117247519A CN117247519A CN202311341041.2A CN202311341041A CN117247519A CN 117247519 A CN117247519 A CN 117247519A CN 202311341041 A CN202311341041 A CN 202311341041A CN 117247519 A CN117247519 A CN 117247519A
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- Prior art keywords
- curing agent
- isocyanate
- hydroxyl
- isocyanate curing
- polysiloxane
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 130
- 239000012948 isocyanate Substances 0.000 title claims abstract description 54
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 60
- -1 polysiloxane Polymers 0.000 claims abstract description 44
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 11
- UVVUGWBBCDFNSD-UHFFFAOYSA-N tetraisocyanatosilane Chemical compound O=C=N[Si](N=C=O)(N=C=O)N=C=O UVVUGWBBCDFNSD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000011342 resin composition Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002981 blocking agent Substances 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 6
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- ASUUYDBHVNPPRZ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)octanoic acid Chemical compound CCCCCCC(CO)(CO)C(O)=O ASUUYDBHVNPPRZ-UHFFFAOYSA-N 0.000 claims description 2
- UHAMPPWFPNXLIU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)(CO)C(O)=O UHAMPPWFPNXLIU-UHFFFAOYSA-N 0.000 claims description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical class CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 12
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 239000005028 tinplate Substances 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229920000805 Polyaspartic acid Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 108010064470 polyaspartate Proteins 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 101100112111 Caenorhabditis elegans cand-1 gene Proteins 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000283070 Equus zebra Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- WIOHBOKEUIHYIC-UHFFFAOYSA-N diethyl 2,2-bis(hydroxymethyl)propanedioate Chemical compound CCOC(=O)C(CO)(CO)C(=O)OCC WIOHBOKEUIHYIC-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides an organosilicon isocyanate curing agent, a preparation method and application thereof, wherein the preparation raw materials of the organosilicon isocyanate curing agent comprise isocyanate-terminated polysiloxane and hydroxyl-containing compounds; the molecular structure of the hydroxyl-containing compound also comprises carboxyl. In the invention, the organic silicon isocyanate curing agent adopts specific preparation raw materials, and organic silicon, carboxyl and the like are introduced into the molecular structure of the curing agent, so that the curing agent has self-emulsifying property, can be dissolved in various solvents, has good compatibility with matrix resin, has good dispersion effect in the resin, and is beneficial to improving the flexibility and the anti-graffiti performance of the coating; and the organosilicon isocyanate curing agent can also solve the problem of poor compatibility and dispersibility of the high molecular weight curing agent with other resins.
Description
Technical Field
The invention belongs to the technical field of curing agent materials, and particularly relates to an organosilicon isocyanate curing agent, and a preparation method and application thereof.
Background
At present, isocyanate curing agents comprise HDI trimer, MDI trimer, HDI trimer, TDI trimer and the like, and are widely applied to the fields of coating, adhesives, plastics and the like. However, the curing agent has high curing speed and poor flexibility, dispersibility and other properties, and limits the application of the curing agent. In addition, in the application scenario of using the macromolecular curing agent, the macromolecular curing agent often has problems of poor compatibility and dispersibility due to overlarge molecular weight, thereby influencing the performance of the macromolecular curing agent. Therefore, it is a trend of research to improve the performance of isocyanate curing agents and to solve the dispersion performance and compatibility of high molecular weight curing agents.
For example, CN 106632947a discloses a method for synthesizing an isocyanate curing agent, which comprises the following steps: 1) Synthesis of organosilicon modified polyaspartic acid ester prepolymer: taking aminosiloxane, dropwise adding maleic acid ester with the same molar weight as the aminosiloxane, and carrying out heat preservation treatment after the dropwise adding to obtain the synthesis of the polyaspartic acid ester prepolymer 2) isocyanate curing agent: and (3) dropwise adding the obtained prepolymer into isocyanate trimer with the equivalent molar weight of the prepolymer, and preserving heat after the completion of dropwise adding to obtain the organosilicon modified isocyanate curing agent. The reaction temperature of the process is not increased severely, the speed is controllable, and the synthesized polyisocyanate has low viscosity and can be directly applied to the two-component polyurethane coating industry; the silicon-oxygen bond and aspartic acid ester structure are introduced into polyurethane, so that the adhesive force of a polyurethane coating film can be effectively improved, and the performances of high temperature resistance, ageing resistance, salt fog resistance and the like are improved; has great market prospect and economic value; however, the curing agent is poor in self-emulsifying property and color developing property.
Therefore, the development of an isocyanate curing agent which has good dispersibility and color development and can solve the problems of poor compatibility with other resins and poor dispersibility of a high-molecular-weight curing agent due to excessive molecular weight is a problem to be solved urgently by those skilled in the art.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an organosilicon isocyanate curing agent, and a preparation method and application thereof. The organosilicon isocyanate curing agent has good dispersibility, color development and curing speed, has good curing effect, can solve the problem of poor compatibility and dispersibility of the large molecular weight curing agent with other resins, and can improve the curing effect of the large molecular weight curing agent in an application scene requiring the large molecular weight curing agent, so that the obtained coating has good flexibility and anti-graffiti performance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a silicone isocyanate curing agent, wherein the silicone isocyanate curing agent is prepared from isocyanate-terminated polysiloxane and hydroxyl-containing compound; the molecular structure of the hydroxyl-containing compound also comprises carboxyl.
In the invention, the organic silicon isocyanate curing agent adopts specific preparation raw materials, and organic silicon, carboxyl and the like are introduced into the molecular structure of the curing agent, so that the curing agent has self-emulsifying property, can be dissolved in various solvents, has good compatibility with matrix resin, has good dispersion effect in the resin, and is beneficial to improving the flexibility and the anti-graffiti performance of the coating; and the problem of poor compatibility and dispersibility of the macromolecular curing agent with other resins can be solved, and a coating with good flexibility and graffiti resistance can be obtained in an application scene requiring the macromolecular curing agent.
Preferably, the isocyanate-terminated polysiloxane is prepared from a raw material comprising hydroxyl-containing polysiloxane and polyisocyanate.
Preferably, the hydroxyl-containing polysiloxane has a functionality of 4 or more, for example, 4, 5, 6, 7, 8, 9, etc. Preferably, the molar ratio of hydroxyl groups in the hydroxyl-containing polysiloxane to isocyanate groups in the polyisocyanate is 1 (2-2.1), wherein the specific value in (2-2.1) can be, for example, 2, 2.01, 2.02, 2.03, 2.04, 2.05, 2.06, 2.08, 2.1 and the like.
Preferably, the polyisocyanate comprises at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate.
Preferably, the molar ratio of the isocyanate groups in the isocyanate-terminated polysiloxane to the hydroxyl groups in the hydroxyl-containing compound is 1 (0.125-0.5), wherein the specific value in (0.125-0.5) can be, for example, 0.125, 0.13, 0.135, 0.14, 0.145, 0.15, 0.155, 0.16, 0.165, 0.17, 0.18, 0.19, 0.2, 0.22, 0.24, 0.26, 0.28, 0.3, 0.32, 0.34, 0.36, 0.38, 0.4, 0.42, 0.44, 0.46, 0.48, 0.5, etc.
Preferably, the hydroxyl functionality of the hydroxyl-containing compound is more than or equal to 2, and can be 2, 3, 4, 5, 6 and the like.
Preferably, the hydroxyl-containing compound comprises at least one of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolvaleric acid or dimethyloloctanoic acid.
Preferably, the preparation raw materials of the organosilicon isocyanate curing agent further comprise a sealing agent.
Preferably, the blocking agent comprises at least one of methyl ethyl ketoxime, acetone oxime, imidazoles, 3, 5-dimethylpyrazole, isopropanol, caprolactam, sodium bisulphite, diethyl malonate, phenol, substituted phenol, ethyl acetoacetate, acetylacetone, or ethanol.
In the present invention, the imidazoles include methylimidazole.
Preferably, the molar amount of active hydrogen in the blocking agent is 1 to 1.5mol, for example, 1mol, 1.1mol, 1.2mol, 1.3mol, 1.4mol, 1.5mol, and the like, based on 1mol of isocyanate groups of the product obtained by reacting the isocyanate-terminated polysiloxane and the hydroxyl group-containing compound.
Preferably, the silicone isocyanate curing agent has a number average molecular weight of 500 to 5000g/mol, and may be, for example, 500g/mol, 600g/mol, 800g/mol, 1000g/mol, 1200g/mol, 1400g/mol, 1600g/mol, 1800g/mol, 2000g/mol, 2200g/mol, 2400g/mol, 2600g/mol, 2800g/mol, 3000g/mol, 3200g/mol, 3400g/mol, 3600g/mol, 3800g/mol, 4000g/mol, 4200g/mol, 4400g/mol, 4600g/mol, 4800g/mol, 5000g/mol, and the like.
In a second aspect, the present invention provides a method for preparing the silicone isocyanate curing agent according to the first aspect, the method comprising the steps of:
(1) Reacting a hydroxyl-containing polysiloxane with a polyisocyanate to obtain an isocyanate-terminated polysiloxane;
(2) And reacting the isocyanate-terminated polysiloxane with a hydroxyl-containing compound to obtain the organosilicon isocyanate curing agent.
Preferably, the temperature of the reaction in the step (1) is 70 to 90 ℃, for example, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃ and the like; the reaction time is 1 to 8 hours, and may be, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or the like.
Preferably, the reaction of step (1) is carried out in the presence of a catalyst; the catalyst includes, but is not limited to, organobismuth; the catalyst may be used in an amount of 1 to 2g, for example, 1g, 1.2g, 1.4g, 1.6g, 1.8g, 2g, etc., based on 100g of the hydroxyl group-containing polysiloxane.
Preferably, the temperature of the reaction in the step (2) is 70 to 90 ℃, for example, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃ and the like, and the reaction time is 1 to 8 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours and the like.
Preferably, the reaction in the step (2) further comprises the step of adding a blocking agent for reaction.
In the present invention, the reaction temperature at which the blocking agent is added may be 70 to 90℃and the reaction time may be 1 to 8 hours, such as 70℃72℃74℃76℃78℃80℃82℃84℃86℃88℃90℃and 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, etc.
Preferably, the addition of the blocking agent is carried out until the NCO content of the system is 0.
In a third aspect, the present invention provides a hardener composition comprising a hardener a and a hardener B; the curing agent a comprises the silicone isocyanate curing agent according to the first aspect.
Preferably, the curing agent B comprises a high molecular weight blocked isocyanate-terminated silicone polysiloxane.
The number average molecular weight of the curing agent B is preferably 1 to 10 ten thousand, and may be 1 ten thousand, 2 ten thousand, 3 ten thousand, 4 ten thousand, 5 ten thousand, 6 ten thousand, 7 ten thousand, 8 ten thousand, 9 ten thousand, 10 ten thousand, or the like, for example.
Preferably, the mass ratio of the curing agent A to the curing agent B is (1-100): 5-100, wherein the specific value in (1-100) can be 1, 2, 4, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 and the like; the specific value of (5-100) may be, for example, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, etc., and further preferably (5-10): 100.
In the invention, the organosilicon isocyanate curing agent can improve the compatibility and dispersibility of the large molecular weight closed isocyanate-terminated organosilicon polysiloxane and the matrix resin.
In a fourth aspect, the present invention provides a resin composition comprising a silicone isocyanate curing agent as described in the first aspect or a curing agent composition as described in the third aspect.
In the invention, the resin composition can be used in the fields of coating, adhesives, plastics and the like.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the beneficial effects that:
the organic silicon isocyanate curing agent provided by the invention adopts specific preparation raw materials, and introduces organic silicon and carboxyl into the molecular structure of the curing agent, so that the curing agent has self-emulsifying property, good dispersibility, color development property and curing speed, has a good curing effect, can be used in both aqueous systems and oily systems, and can solve the problem of poor compatibility and dispersibility of a large molecular weight curing agent with other resins; a coating film excellent in flexibility and graffiti resistance is obtained.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The hydroxyl-containing polysiloxanes used in the examples below were all from the molecular polymer company, st.Luo Ke Gao, guangzhou.
Example 1
The embodiment provides an organosilicon isocyanate curing agent, and the preparation method specifically comprises the following steps:
(1) 100g of hydroxyl-containing polysiloxane (silok 8844F1, double tetrahydroxy, molecular weight 850, n) OH =0.47 mol) and 108.8g isophorone diisocyanate (n NCO =0.97mol) was charged into a reaction kettle, and 2g of an organobismuth catalyst (DY-20) was added to react at 75 ℃ for 3 hours to obtain isocyanate-terminated polysiloxane;
(2) The isocyanate-terminated polysiloxane was reacted with 32.8g of dimethylolpropionic acid (n OH After the reaction for 3 hours at 75 ℃, 25.8g of 3, 5-dimethylpyrazole is added and mixed uniformly, the reaction is carried out for 3 hours at 75 ℃ in a heat preservation mode until the content of-NCO groups in a detection system is close to 0, and the organosilicon isocyanate curing agent (the content of NCO% after deblocking is about 3.7%) is obtained.
Example 2
The embodiment provides a preparation method of an organosilicon isocyanate curing agent, which specifically comprises the following steps:
(1) 100g of hydroxyl-containing polysiloxane (silok 8844F2, double tetrahydroxy, molecular weight 1500, n OH =0.26 mol) and 44.8g hexamethylene diisocyanate (n NCO Adding 0.52mol into a reaction kettle, adding 1g of organic bismuth catalyst (DY-20) and reacting at 80 ℃ for 2h to obtain isocyanideAcid ester terminated polysiloxanes;
(2) The isocyanate-terminated polysiloxane was reacted with 19.24 dimethylolbutyric acid (n OH =0.13 mol) at 80 ℃ for 2 h; then adding 11.3g butanone oxime, mixing uniformly, preserving heat at 80 ℃ for sealing reaction for 2 hours until the content of-NCO groups in a detection system is 0, and obtaining the organosilicon isocyanate curing agent (the content of NCO percent after deblocking is about 3.1%).
Example 3
The embodiment provides a preparation method of an organosilicon isocyanate curing agent, which specifically comprises the following steps:
(1) 100g of hydroxyl-containing polysiloxane (silok 8844F2, double-end tetrahydroxy, molecular weight 3700) and 29.8g of dicyclohexylmethane diisocyanate are put into a reaction kettle, and 0.5g of organic bismuth catalyst (DY-20) is added to react for 2 hours at 90 ℃ to obtain isocyanate-terminated polysiloxane;
(2) Reacting the isocyanate-terminated polysiloxane with 7.4g dimethylolpropionic acid at 80 ℃ for a period of 2 hours; then adding 5.29g of 3, 5-dimethylpyrazole, uniformly mixing, and preserving heat at 75 ℃ for carrying out a sealing reaction for 3 hours until the content of-NCO groups in a detection system is 0, thus obtaining the organosilicon isocyanate curing agent (the content of NCO percent after deblocking is about 1.7%).
Example 4
This example provides a silicone isocyanate curing agent which differs from example 1 only in that the molar ratio of isocyanate groups in the hexamethylene diisocyanate to hydroxyl groups in the hydroxyl-containing polysiloxane is 2:1; the molar ratio of isocyanate groups in the isocyanate-terminated polysiloxane to hydroxyl groups in the hydroxyl-containing compound was 1:0.125, and other components, amounts and preparation methods were the same as in example 1.
Example 5
This example provides a silicone isocyanate curing agent which differs from example 1 only in that the hexamethylene diisocyanate is replaced by an equimolar amount of HDI trimer (Desmodur N3390 BA), and the other components, amounts and preparation methods are the same as in example 1, resulting in a gelled product.
Comparative example 1
This comparative example provides a silicone isocyanate curing agent which differs from example 1 only in that dimethylolpropionic acid is replaced with an equimolar amount of diethyl dimethylolmalonate, and the other components, amounts and preparation methods are the same as in example 1.
Comparative example 2
This comparative example provides a silicone isocyanate curing agent which differs from example 1 only in that in the preparation process, no dimethylolpropionic acid is added, and the isocyanate-terminated polysiloxane is reacted directly with 3, 5-dimethylpyrazole, with the other raw materials, amounts and step parameters being the same as in example 1.
Application examples 1 to 5, comparative application examples 1 to 2
A curative composition comprising curative a and curative B; the curing agent A is the organic silicon isocyanate curing agent provided in the examples 1-5 and the comparative examples 1-2 respectively; the mass ratio of the curing agent A to the curing agent B is 5:50.
The preparation method of the large molecular weight blocked isocyanate blocked organosilicon polysiloxane comprises the following steps:
50g of dihydroxyl-terminated silicone oil (silok 8824F4, average molecular weight 15000), 1.7g of IPDI and 20g of acetone are uniformly mixed and heated to 80 ℃ for reaction for 4 hours; continuing to add 0.7g of 3, 5-dimethylpyrazole, carrying out a sealing reaction at 80 ℃ for 3 hours, and discharging to obtain the curing agent B (the NCO content is about 0.42%).
Application example 6
The curing agent composition is different from the application example 1 only in that the total amount of the curing agent A and the curing agent B is unchanged, the mass ratio is 2.5:50, and other components, the use amount and the preparation method are the same as those of the application example 1.
Application example 7
The curing agent composition is different from the curing agent composition in application example 1 only in that the total amount of the curing agent A and the curing agent B is unchanged, the mass ratio is 1:80, and other components, the use amount and the preparation method are the same as those of application example 1.
Application example 8
The curing agent composition is different from the application example 1 only in that the total amount of the curing agent A and the curing agent B is unchanged, the mass ratio is 15:100, and other components, the use amount and the preparation method are the same as those of the application example 1.
Comparative application example 3
A curing agent composition was different from application example 1 only in that the curing agent A was replaced with an equal mass of HDI trimer (Desmodur N3390 BA), and the other components, amounts and preparation methods were the same as those of application example 1.
Test example 1
The performance of the organosilicon isocyanate curing agent provided by the invention is tested
1. Solubility test
The organosilicon isocyanate curing agents provided in examples 1-5 and comparative examples 1-2 are respectively diluted with water, toluene, butyl acetate and dipropylene glycol dimethyl ether according to a volume ratio of 1:1, wherein ammonia water is added to adjust the pH to 7-8 when the dilution is performed with water, and the obtained results are shown in Table 1; the organic silicon isocyanate curing agent is divided into good, general and bad according to the solubility of the organic silicon isocyanate curing agent in different solvents, wherein good represents that the organic silicon isocyanate curing agent and the solvent can form a mixed solution in a uniform state, and the organic silicon isocyanate curing agent and the solvent are kept stand and are not layered; "generally" means that the above-mentioned organosilicon isocyanate curing agent is partially soluble in a solvent, and is layered after standing for 24 hours; "poor" means that the above-mentioned silicone isocyanate curing agent is substantially insoluble in the solvent, and is allowed to stand for 0.5 hours to delaminate.
TABLE 1
As can be seen from Table 1, the organosilicon isocyanate curing agent provided by the invention has good solubility in different solvents.
2. Curing Performance test
An aqueous resin composition comprising 80 parts of an aqueous hydroxy acrylic resin (DissmannXK-540, a hydroxyl value of 4.2, a solids content of 40%,0.006 mol) and 12.6 parts of curing agent a, the curing agents being the silicone isocyanate curing agents provided in examples 1 to 5, comparative examples 1 to 2, respectively. (NCO: oh=1.5:1);
and (3) uniformly mixing the resin composition, adding deionized water, diluting to 20s (coating 4 cups), spraying on a tinplate test plate, and drying at 130-150 ℃ for 20min to obtain a coating film. The coating film was tested according to the following test method, and the results obtained are shown in table 2.
Compatibility: and observing whether the resin composition has phase separation after being uniformly mixed, coating the resin composition on a tinplate, and observing whether the resin composition has shrinkage cavity phenomenon, if the resin composition has no phase separation or shrinkage cavity phenomenon, the resin composition is qualified, and if the resin composition has phase separation or shrinkage cavity phenomenon, the resin composition is unqualified.
Flexibility: the test was carried out according to the test method prescribed in GB/T1731-2020.
Anti-graffiti performance: adding 10 parts of titanium pigment and 2 parts of pigment dispersing agent into the resin composition, uniformly mixing, diluting to 20 seconds (coating 4 cups), spraying on a tin plate test board, respectively coating and marking on the surface of a coating film by using an oil ball pen of Mitsubishi corporation and an oil marking pen of zebra brand, then wiping cleanly by using dry cotton cloth, repeatedly coating and wiping for 10 times, observing residual marks of stains, and classifying the residual marks into 1-5 grades according to the residual degree of the marks, wherein the grade 1 is no marks, and the anti-graffiti performance is optimal; grade 5 is the most visible mark remaining, and the worst anti-graffiti performance.
TABLE 2
As can be seen from Table 2, the organosilicon isocyanate curing agent provided by the invention has good compatibility with matrix resin, and the obtained paint film has good flexibility and excellent graffiti resistance after curing.
Test example 2
The organosilicon isocyanate curing agent can be tested for improving the dispersion performance and the curing performance of the high molecular weight curing agent.
A resin composition comprising 80 parts of an aqueous hydroxy acrylic resin (DissmannXK-540, hydroxyl value 4.2, solid content 40%) of grease and a curing agent, wherein the curing agent is the curing agent composition provided in application examples 1-8 and comparative application examples 1-3, and the resin composition containing only the curing agent B without adding the curing agent A is used as a control group.
The test was conducted in the same manner as in test example 1, and the results obtained are shown in Table 3.
TABLE 3 Table 3
As can be seen from Table 3, the organosilicon isocyanate curing agent provided by the invention adopts specific preparation raw materials, so that the curing agent not only can realize excellent curing effect, but also can emulsify and disperse a macromolecular curing agent, solves the problems of poor compatibility with other resins and poor dispersibility of the macromolecular curing agent due to overlarge molecular weight, can be suitable for application scenes needing to use the macromolecular curing agent, and improves the curing effect of the macromolecular curing agent.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (10)
1. The organic silicon isocyanate curing agent is characterized in that the preparation raw materials of the organic silicon isocyanate curing agent comprise isocyanate-terminated polysiloxane and hydroxyl-containing compounds;
the molecular structure of the hydroxyl-containing compound also comprises carboxyl.
2. The silicone isocyanate curing agent according to claim 1, wherein the isocyanate-terminated polysiloxane is prepared from a raw material comprising a hydroxyl-containing polysiloxane and a polyisocyanate;
preferably, the functionality of the hydroxyl-containing polysiloxane is greater than or equal to 4;
preferably, the molar ratio of hydroxyl groups in the hydroxyl-containing polysiloxane to isocyanate groups in the polyisocyanate is 1 (2-2.1).
3. The silicone isocyanate curing agent of claim 2, wherein the polyisocyanate comprises at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, or hexamethylene diisocyanate;
preferably, the molar ratio of isocyanate groups in the isocyanate-terminated polysiloxane to hydroxyl groups in the hydroxyl-containing compound is 1 (0.125-0.5).
4. The organosilicon isocyanate curing agent according to any one of claims 1 to 3, wherein the hydroxyl functionality of the hydroxyl-containing compound is not less than 2;
preferably, the hydroxyl-containing compound comprises at least one of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolvaleric acid or dimethyloloctanoic acid;
preferably, the preparation raw materials of the organosilicon isocyanate curing agent further comprise a sealing agent;
preferably, the blocking agent comprises at least one of methyl ethyl ketoxime, acetone oxime, imidazoles, 3, 5-dimethylpyrazole, isopropanol, caprolactam, sodium bisulphite, diethyl malonate, phenol, substituted phenol, ethyl acetoacetate, acetylacetone, or ethanol;
preferably, the molar amount of active hydrogen in the blocking agent is 1 to 1.5mol based on 1mol of isocyanate group of the product obtained by reacting the isocyanate-terminated polysiloxane and the hydroxyl-containing compound.
5. The silicone isocyanate curing agent according to any one of claims 1 to 4, wherein the silicone isocyanate curing agent has a number average molecular weight of 500 to 5000g/mol.
6. A method for preparing the silicone isocyanate curing agent according to any one of claims 1 to 5, characterized in that the preparation method comprises the steps of:
(1) Reacting a hydroxyl-containing polysiloxane with a polyisocyanate to obtain an isocyanate-terminated polysiloxane;
(2) And reacting the isocyanate-terminated polysiloxane with a hydroxyl-containing compound to obtain the organosilicon isocyanate curing agent.
7. The preparation method according to claim 6, wherein the reaction temperature in the step (1) is 70-90 ℃ and the reaction time is 1-8 hours;
preferably, the reaction of step (1) is carried out in the presence of a catalyst;
preferably, the temperature of the reaction in the step (2) is 70-90 ℃, and the reaction time is 1-8 hours;
preferably, the reaction in the step (2) further comprises the step of adding a blocking agent for reaction;
preferably, the addition of the blocking agent is carried out until the NCO content of the system is 0.
8. A curing agent composition, characterized in that the curing agent composition comprises a curing agent a and a curing agent B;
the curing agent a comprises the silicone isocyanate curing agent according to any one of claims 1 to 5.
9. The curative composition of claim 8 wherein curative B comprises a high molecular weight blocked isocyanate-terminated silicone polysiloxane;
preferably, the number average molecular weight of the curing agent B is 1 to 10 ten thousand;
preferably, the mass ratio of the curing agent A to the curing agent B is (1-100): 5-100, more preferably (5-10): 100.
10. A resin composition comprising the silicone isocyanate curing agent according to any one of claims 1 to 5 or the curing agent composition according to claim 8 or 9.
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