CN117986532A - Preparation method of dual-curing prepolymer based on castor oil - Google Patents
Preparation method of dual-curing prepolymer based on castor oil Download PDFInfo
- Publication number
- CN117986532A CN117986532A CN202410150097.8A CN202410150097A CN117986532A CN 117986532 A CN117986532 A CN 117986532A CN 202410150097 A CN202410150097 A CN 202410150097A CN 117986532 A CN117986532 A CN 117986532A
- Authority
- CN
- China
- Prior art keywords
- prepolymer
- epoxy
- isocyanate
- castor oil
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004359 castor oil Substances 0.000 title claims abstract description 39
- 235000019438 castor oil Nutrition 0.000 title claims abstract description 39
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000004593 Epoxy Substances 0.000 claims abstract description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 34
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 31
- DLMVDBDHOIWEJZ-UHFFFAOYSA-N isocyanatooxyimino(oxo)methane Chemical compound O=C=NON=C=O DLMVDBDHOIWEJZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 13
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 10
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000012948 isocyanate Substances 0.000 claims description 37
- 150000002513 isocyanates Chemical class 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 25
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 23
- 230000009977 dual effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- -1 3, 4-epoxycyclohexylmethyl Chemical group 0.000 claims description 6
- 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 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- 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 claims description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001723 curing Methods 0.000 description 36
- 238000000016 photochemical curing Methods 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- 238000000576 coating method Methods 0.000 description 8
- 239000002966 varnish Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- NWOALVZUPHRBJV-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl formate Chemical compound C1C(COC=O)CCC2OC21 NWOALVZUPHRBJV-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012952 cationic photoinitiator Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000013008 moisture curing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- OXQXGKNECHBVMO-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1C(C(=O)O)CCC2OC21 OXQXGKNECHBVMO-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- TZIHFWKZFHZASV-UHFFFAOYSA-N anhydrous methyl formate Natural products COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/2845—Monohydroxy epoxy compounds
-
- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of a dual-curing prepolymer based on castor oil, which comprises the steps of firstly reacting alicyclic epoxy resin and polyisocyanate with acrylic acid and hydroxyl epoxy monomers respectively to obtain alicyclic epoxy acrylic acid prepolymer and epoxy isocyanate prepolymer, then mixing the alicyclic epoxy acrylic acid prepolymer and the epoxy isocyanate prepolymer with castor oil according to a certain proportion, reacting again, and connecting an acrylic ester double bond and an epoxy group to the same molecular chain through chemical bonds to ensure good compatibility. After ultraviolet irradiation, the cured film shows higher gloss and fullness, good toughness, adhesive force and hardness, and good technical effect is obtained.
Description
Technical Field
The invention belongs to the technical field of photo-curing materials, and particularly relates to a preparation method of a dual-curing prepolymer based on castor oil.
Background
With the attention of people to the exhaustion of petrochemical energy and the change of climate, a low-carbon, environment-friendly and sustainable economic development mode becomes a future development trend. Most of the traditional organic polymer materials are petroleum-based products, which utilize non-renewable resources, and the used waste has little degradability, thus causing a series of environmental problems. The renewable biomass raw materials are used for manufacturing environment-friendly functional coatings, inks and adhesives, so that carbon emission can be effectively reduced, petroleum crisis is relieved, and the environment-friendly functional coatings, inks and adhesives become research hotspots of countries around the world. Vegetable oils, which were the first biobased material used to synthesize a variety of coating resins, including alkyd resins, alkyd urethane oils, have found little application in the field of photocuring.
The photo-curing technology has the advantages of high efficiency, energy saving, economy, environmental protection, wide adaptability and the like, and is a new material technology with wide application prospect. The photocuring production line can form an automatic production line together with coating equipment and drying equipment, so that the production efficiency is greatly improved. In recent decades, free radical photo-curing technology has been widely used in the fields of wood lacquer coating, paper gloss oil, plastic finishing coating, etc. However, due to the defects of the photo-curing technology (serious oxygen polymerization inhibition, difficult curing of thick coating, etc.), the application field is limited to a certain extent. Dual curing can effectively overcome this disadvantage, and common ways include "free radical photo-curing-thermosetting", "free radical photo-curing-moisture curing", "free radical photo-curing-cationic photo-curing", and the like. The dual curing can effectively combine the advantages of two curing modes, make up the defect of a single curing mode, and development is more and more paid attention in recent years, for example: thermal curing or moisture curing can effectively increase the crosslink density of the insufficiently illuminated areas, thereby increasing overall performance.
Chinese patent application nos. 201710412597.4 and 202010577464.4 disclose a dual curing mode of photo-curing-thermosetting and a radical curing-cationic curing, respectively, the main principle being to physically mix the components of the two curing modes and then to sequentially perform photo-curing-thermosetting and radical curing-cationic curing. The method can utilize the existing raw materials to the greatest extent, is simple to operate and low in use cost, but has certain defects in stability and transparency of the cured film because two components are not chemically crosslinked and compatibility between different components is different.
Chinese patent application No. 201010150600.8 discloses a preparation method of a dual-curing group resin containing acrylate double bond and epoxy group and application thereof, wherein excessive bisphenol A epoxy resin and polyisocyanate are firstly used to react with acrylic acid, polyether polyol and hydroxyacrylic acid respectively, and then the reaction is carried out between the two to obtain polyurethane resin simultaneously containing acrylate double bond and epoxy group. However, during the actual synthesis operation, the viscosity increases sharply as the chain extension reaction proceeds, so that stirring and mixing are difficult and gelation tends to occur.
Disclosure of Invention
The invention aims at the defects in the prior art and provides a preparation method of a dual-curing prepolymer based on castor oil. In the prepolymer, the acrylate double bond for free radical photo-curing and the epoxy group for cationic photo-curing are connected through a chemical chain, so that the prepolymer has good stability and compatibility, and a cured film has high gloss and fullness, good toughness, adhesive force and hardness, and good technical effect.
The preparation method of the castor oil-based dual-curing prepolymer comprises the following steps:
Step 1: mixing alicyclic epoxy resin, acrylic acid and a catalyst A in proportion, and heating for reaction to obtain alicyclic epoxy acrylic acid prepolymer;
step 2: mixing polyisocyanate, hydroxyl epoxy monomer and catalyst B in proportion, and heating for reaction to obtain epoxy isocyanate prepolymer;
Step 3: mixing the alicyclic epoxy acrylic prepolymer obtained in the step 1, the epoxy isocyanate prepolymer obtained in the step 2, castor oil and the catalyst B according to a certain proportion, and heating for reaction to obtain the castor oil-based dual-curing prepolymer.
The alicyclic epoxy resin is selected from one or more of 3, 4-epoxycyclohexyl methyl formate, bis ((3, 4-epoxycyclohexyl) methyl) adipate and 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexane carboxylic acid) ester.
The catalyst A is one or more selected from tetrabutylammonium chloride, tetrabutylammonium bromide, tetraethylammonium chloride and tetraethylammonium bromide.
The polyisocyanate is selected from one or more of Xudio compound TMA-100, TLA-100, TUL-100, 24A-100, TPA-100 and TKA-100.
The hydroxy epoxy monomer is selected from one or more of 3-ethyl-3-hydroxymethyl oxetane and glycidol.
And the catalyst B is one or more of dibutyl tin dilaurate, stannous chloride and stannous octoate.
In the step 1, a certain mass of alicyclic epoxy resin, acrylic acid, a catalyst A and a polymerization inhibitor are weighed and placed in a reactor, the molar ratio of epoxy groups to acrylic acid is 1.00:1-1.04:1, the catalyst A accounts for 0.2-0.5% of the total mass, and the para-hydroxyanisole accounts for 0.05-0.3% of the total mass, and the reaction is slowly carried out until the acid value is reduced to below 3mgKOH/g, so that the alicyclic epoxy acrylic acid prepolymer is obtained.
The "total mass" herein is the sum of the mass of the epoxy resin, acrylic acid, catalyst A.
The polymerization inhibitor is p-hydroxyanisole, and is used for reducing side reactions and preventing reaction failure.
In the step 2, a certain mass of polyisocyanate, hydroxyl epoxy monomer and catalyst B are weighed and placed in a reactor, the molar ratio of isocyanate to hydroxyl is 1.5:1-3:1, the catalyst B accounts for 0.01-0.04% of the total mass, and the reaction is carried out after the catalyst B is slowly heated to 60-90 ℃ until the content of isocyanate reaches a theoretical value.
The "total mass" here is the sum of the masses of polyisocyanate, hydroxy epoxy monomer and catalyst B.
In this reaction, the molar ratio of isocyanate to hydroxyl groups is from 1.5:1 to 3:1, i.e. the isocyanate is in excess relative to the hydroxyl groups. From the feed ratio, the theoretical content of isocyanate, i.e. "theoretical value", theoretical value= (molar amount of isocyanate-molar amount of hydroxyl group) ×42/(mass of polyisocyanate+mass of hydroxyl epoxy monomer+mass of catalyst B) can be calculated. When the actual content of isocyanate reaches a theoretical value, the reaction is completely carried out (the content of isocyanate can be measured by a di-n-butylamine method: national standard GB/T12009.4-2016);
In the preferred scheme, in the step 3, the alicyclic epoxy acrylic prepolymer (containing B mol of hydroxyl groups) obtained in the step 1, the epoxy isocyanate prepolymer (containing a mol of isocyanate) obtained in the step 2 and castor oil (containing c mol of hydroxyl groups) are weighed and placed in a reaction flask, the mol ratio of a, B and c is controlled to be a (b+c) =1:1.01-1:1.04, b:c=0.25:1-4:1, and simultaneously, a catalyst B accounting for 0.01-0.04 percent of the total mass and a polymerization inhibitor accounting for 0.05-0.3 percent of the total mass are added, and the mixture is slowly heated to 60-90 ℃ for reaction until the content of isocyanate is lower than 0.4 percent.
The "total mass" herein is the sum of the masses of the alicyclic epoxy acrylic prepolymer obtained in step 1, the epoxy isocyanate prepolymer obtained in step 2, castor oil, catalyst B and polymerization inhibitor.
The polymerization inhibitor is p-hydroxyanisole, and is used for reducing side reactions and preventing reaction failure.
The beneficial effects of the invention are as follows:
the castor oil-based dual-curing prepolymer synthesized by the invention contains the free radical photo-curing acrylate group and the cation curing epoxy group in the molecular chain, which are connected by chemical bonds, and has good stability and compatibility. After ultraviolet light curing, the cured film shows higher gloss and fullness, good toughness, adhesive force and hardness due to the existence of castor oil chain segments and a dual-curing cross-linked network, and a better technical effect is obtained.
Detailed Description
Example 1:
The preparation method of the castor oil-based dual-curing prepolymer in the embodiment comprises the following steps:
1. Weighing 133.9g of 3',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate (containing 1.03 mol of epoxy groups), 72g of acrylic acid (containing 1 mol of acrylic acid), 0.82g of tetrabutylammonium chloride and 0.31g of p-hydroxyanisole, placing the materials into a four-neck flask, stirring uniformly, slowly heating to 115 ℃ for reaction until the acid value is lower than 3mg KOH/g, cooling and discharging to obtain the alicyclic epoxy acrylic prepolymer.
2. 547G of TMA-100 (Asahi chemical) containing 3 mol of isocyanate, 116g of 3-ethyl-3-hydroxymethyl oxetane containing 1 mol of hydroxyl and 0.13g of dibutyl tin dilaurate are weighed, placed in a four-neck flask, stirred uniformly, heated slowly to 70 ℃ for reaction until the isocyanate content is lower than 12.7%, cooled and discharged to obtain the epoxy isocyanate prepolymer.
3. 206G of the alicyclic epoxy acrylic prepolymer (containing 1 mole of hydroxyl groups) obtained in the step 1, 660g of the epoxy isocyanate prepolymer (containing 2 moles of isocyanate) obtained in the step 2, 354.5g of castor oil (containing 1.03 moles of hydroxyl groups), 1.22g of para-hydroxyanisole and 0.37g of dibutyl tin dilaurate were weighed, placed in a four-necked flask, stirred uniformly, heated slowly to 75 ℃ for reaction until the isocyanate content is lower than 0.4%, cooled and discharged to obtain the castor oil-based dual-curing prepolymer 1.
Example 2:
The preparation method of the castor oil-based dual-curing prepolymer in the embodiment comprises the following steps:
1. 204g of bis ((3, 4-epoxycyclohexyl) methyl) adipate (containing 1.02 mol of epoxy groups), 72g of acrylic acid (containing 1 mol of acrylic acid), 1.24g of tetrabutylammonium bromide and 0.33g of p-hydroxyanisole are weighed, placed in a four-neck flask, stirred uniformly, heated slowly to 120 ℃ for reaction until the acid value is below 3mg KOH/g, cooled and discharged to obtain the alicyclic epoxy acrylic acid prepolymer.
2. TUL-100 (Asahi chemical) 547.8g (containing 3 mol of isocyanate), glycidol 111.15g (containing 1.5 mol of hydroxyl) and stannous octoate 0.13g are weighed, placed in a four-neck flask, stirred uniformly, heated slowly to 70 ℃ for reaction until the isocyanate content is lower than 9.6%, cooled and discharged to obtain the epoxy isocyanate prepolymer.
3. 276G of the alicyclic epoxy acrylic prepolymer (containing 1 mol of hydroxyl) obtained in the step 1, 655g of the epoxy isocyanate prepolymer (containing 1.5 mol of isocyanate) obtained in the step 2, 177.3g of castor oil (containing 0.515 mol of hydroxyl), 1.11g of para-hydroxyanisole and 0.33g of stannous octoate are weighed, placed in a four-necked flask, stirred uniformly, heated slowly to 75 ℃ for reaction until the isocyanate content is lower than 0.4%, cooled and discharged, and the dual-curing prepolymer 2 based on castor oil is obtained.
Example 3:
The preparation method of the castor oil-based dual-curing prepolymer in the embodiment comprises the following steps:
1. 214g of 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexane carboxylic acid) ester (containing 1.02 mol of epoxy groups), 72g of acrylic acid (containing 1 mol of acrylic acid), 0.86g of tetraethylammonium bromide and 0.46g of p-hydroxyanisole are weighed, placed in a four-neck flask, stirred uniformly, heated slowly to 120 ℃ for reaction until the acid value reaches below 3mg KOH/g, cooled and discharged, and the alicyclic epoxy acrylic acid prepolymer is obtained.
2. 545.4G of TPA-100 (Asahi chemical) containing 3mol of isocyanate, 139.2g of 3-ethyl-3-hydroxymethyl oxetane containing 1.2 mol of hydroxyl and 0.14g of stannous chloride are weighed, placed in a four-mouth flask, stirred uniformly, heated slowly to 70 ℃ for reaction until the isocyanate content is lower than 11.1%, cooled and discharged to obtain the epoxy isocyanate prepolymer.
3. 286G of the cycloaliphatic epoxy acrylic prepolymer (containing 1 mole of hydroxyl groups) obtained in the step 1, 681g of the epoxy isocyanate prepolymer (containing 1.8 mole of isocyanate) obtained in the step 2, 283.6g of castor oil (containing 0.824 mole of hydroxyl groups), 1.25g of para-hydroxyanisole and 0.38g of stannous octoate are weighed, placed in a four-necked flask, stirred uniformly, heated slowly to 75 ℃ for reaction until the isocyanate content is lower than 0.4%, cooled and discharged, and the dual-curing prepolymer 3 based on castor oil is obtained.
Example 4:
The preparation method of the castor oil-based dual-curing prepolymer in the embodiment comprises the following steps:
1. 132.6g of 3, 4-epoxycyclohexylmethyl formate (containing 1.02 mol of epoxy groups), 72g of acrylic acid (containing 1mol of acrylic acid), 0.61g of tetraethylammonium chloride and 0.33g of p-hydroxyanisole are weighed, placed in a four-neck flask, stirred uniformly, heated slowly to 115 ℃ for reaction until the acid value reaches below 3mg KOH/g, cooled and discharged, and the alicyclic epoxy acrylic acid prepolymer is obtained.
2. 537G of 24A-100 (Asahi chemical) containing 3mol of isocyanate, 150.8g of 3-ethyl-3-hydroxymethyl oxetane containing 1.3 mol of hydroxyl and 0.14g of stannous octoate are weighed and placed in a four-mouth flask, stirred uniformly, heated slowly to 70 ℃ for reaction until the isocyanate content is lower than 10.4%, cooled and discharged to obtain the epoxy isocyanate prepolymer.
3. 205G of the alicyclic epoxy acrylic prepolymer (containing 1 mol of hydroxyl) obtained in the step 1, 684g of the epoxy isocyanate prepolymer (containing 1.7 mol of isocyanate) obtained in the step 2, 248.2g of castor oil (containing 0.72 mol of hydroxyl), 1.14g of para-hydroxyanisole and 0.34g of stannous octoate are weighed, placed in a four-mouth bottle, stirred uniformly, heated slowly to 70 ℃ for reaction until the isocyanate content is lower than 0.4%, cooled and discharged, and the dual-curing prepolymer 4 based on castor oil is obtained.
Comparative example 1:
1. 137.9g of 3, 4-epoxycyclohexylmethyl formate (containing 1.06 mol of epoxy groups), 74g of acrylic acid (containing 1.03 mol of acrylic acid), 0.85g of tetrabutylammonium chloride and 0.32g of p-hydroxyanisole are weighed, placed in a four-neck flask, stirred uniformly, heated slowly to 115 ℃ for reaction until the acid value reaches below 3mg KOH/g, cooled and discharged, and the alicyclic epoxy acrylic acid prepolymer is obtained.
2. 548G of TMA-100 (Asahi chemical) containing 3 mol of isocyanate, 232g of 3-ethyl-3-hydroxymethyl oxetane containing 2 mol of hydroxyl and 0.16g of dibutyl tin dilaurate are weighed, placed in a four-neck flask, stirred uniformly, heated slowly to 70 ℃ for reaction until the isocyanate content is lower than 5.4%, cooled and discharged to obtain the epoxy isocyanate prepolymer.
3. 212.2G of the alicyclic epoxy acrylic prepolymer (containing 1.03 mol of hydroxyl) obtained in the step 1, 776g of the epoxy isocyanate prepolymer (containing 1 mol of isocyanate) obtained in the step 2 and 1.0g of p-hydroxyanisole and 0.3g of dibutyl tin dilaurate are weighed, placed in a four-mouth bottle, stirred uniformly, heated slowly to 75 ℃ for reaction until the isocyanate content is lower than 0.4%, cooled and discharged to obtain the dual-curing prepolymer 1.
Comparative example 2:
1. 210g of bis ((3, 4-epoxycyclohexyl) methyl) adipate (containing 1.05 mol of epoxy groups), 74g of acrylic acid (containing 1.03 mol of acrylic acid), 1.28g of tetrabutylammonium bromide and 0.34g of p-hydroxyanisole are weighed, placed in a four-neck flask, stirred uniformly, heated slowly to 120 ℃ for reaction until the acid value is below 3mg KOH/g, cooled and discharged to obtain the alicyclic epoxy acrylic acid prepolymer.
2. TUL-100 (Asahi chemical) 547.8g (containing 3 mol isocyanate), 3-ethyl-3-hydroxymethyl oxetane 232g (containing 2 mol hydroxyl) and stannous octoate 0.16g are weighed, placed in a four-mouth flask, stirred uniformly, heated slowly to 70 ℃ for reaction until the isocyanate content is lower than 5.4%, cooled and discharged to obtain the epoxy isocyanate prepolymer.
3. 284G of the alicyclic epoxy acrylic prepolymer (containing 1.03 mol of hydroxyl) obtained in the step 1, 776g of the epoxy isocyanate prepolymer (containing 1 mol of isocyanate) obtained in the step 2 and 1.06g of para-hydroxyanisole and 0.32g of stannous octoate are weighed, placed in a four-mouth bottle, stirred uniformly, heated slowly to 70 ℃ for reaction until the isocyanate content is lower than 0.4%, cooled and discharged, and dual-curing prepolymer 2 is obtained.
Performance test:
The above-synthesized castor oil-based dual-curing prepolymer 1 to 4, the dual-curing prepolymer 1 to 2,1, 6-hexanediol diacrylate HDDA (Jiangsu Sanmu chemical Co., ltd.), and the radical photoinitiator 1173 (Jiangsu Sanmu chemical Co., ltd.), and the cationic photoinitiator TTAUV to 692 (Jiangsu Taier) were formulated according to the following Table 1 to obtain a photocurable varnish.
TABLE 1 photo-curable varnish formulations
| 1# | 2# | 3# | 4# | 5# | 6# | |
| Castor oil-based dual cure prepolymer 1 | 80 | |||||
| Castor oil-based dual cure prepolymer 2 | 80 | |||||
| Castor oil-based dual cure prepolymer 3 | 80 | |||||
| Castor oil-based dual cure prepolymer 4 | 80 | |||||
| Comparative example Dual curing prepolymer 1 | 80 | |||||
| Comparative example Dual curing prepolymer 2 | 80 | |||||
| HDDA | 16 | 16 | 16 | 16 | 16 | 16 |
| Radical photoinitiator 1173 | 2 | 2 | 2 | 2 | 2 | 2 |
| Cationic photoinitiator TTAUV-692 | 2 | 2 | 2 | 2 | 2 | 2 |
The varnish samples prepared in Table 1 were scraped with a bar to give coating films having a thickness of about 25. Mu.m. Irradiating with mercury lamp light source for 20 seconds, standing in oven at 90deg.C for 30min, and measuring gloss, hardness, flexibility and adhesion of the cured film.
TABLE 2 comparative results of the film properties of photo-curable varnishes
As can be seen from Table 2, the castor oil-based dual-curing prepolymers 1 to 4 exhibit a strong round feel, a high fullness and a good balance of hardness, flexibility and adhesion, and good overall properties, due to the unsaturated double bonds and the long branched structure, compared with the dual-curing prepolymers (comparative examples 1 to 2) without castor oil added.
Gloss was tested according to the method described in national standard GB/T9754-2007 determination of specular gloss at 20 °, 60 ° and 85 ° for paint films of paints and varnishes free of metallic pigments.
The hardness was tested according to the method described in national Standard GB/T6739-2006 "paint film hardness measured by the paint and varnish pencil method".
Flexibility was tested according to the method described in national Standard GB/T1731-1993 paint film flexibility determination.
The adhesion was tested according to the method described in national standard GB/T9286-1998, cross-hatch test for paints and varnishes.
The experimental results show that the castor oil-based dual-curing prepolymer prepared by synthesizing the various reaction raw material compositions through a large number of experiments has higher hardness (not less than H), and has good fullness, luster, flexibility and adhesive force, and a better technical effect is achieved.
Claims (8)
1. A method for preparing a castor oil-based dual cure prepolymer, comprising the steps of:
Step 1: mixing alicyclic epoxy resin, acrylic acid and a catalyst A in proportion, and heating for reaction to obtain alicyclic epoxy acrylic acid prepolymer;
step 2: mixing polyisocyanate, hydroxyl epoxy monomer and catalyst B in proportion, and heating for reaction to obtain epoxy isocyanate prepolymer;
Step 3: mixing the alicyclic epoxy acrylic prepolymer obtained in the step 1, the epoxy isocyanate prepolymer obtained in the step 2, castor oil and the catalyst B according to a certain proportion, and heating for reaction to obtain the castor oil-based dual-curing prepolymer.
2. The method of manufacturing according to claim 1, characterized in that:
The alicyclic epoxy resin is selected from one or more of 3, 4-epoxycyclohexylmethyl formate-3 ',4' -epoxycyclohexylmethyl ester, bis ((3, 4-epoxycyclohexyl) methyl) adipate and 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexane carboxylic acid) ester;
the catalyst A is one or more selected from tetrabutylammonium chloride, tetrabutylammonium bromide, tetraethylammonium chloride and tetraethylammonium bromide;
The polyisocyanate is selected from one or more of Xudio compound TMA-100, TLA-100, TUL-100, 24A-100, TPA-100 and TKA-100;
The hydroxy epoxy monomer is selected from one or more of 3-ethyl-3-hydroxymethyl oxetane and glycidol;
And the catalyst B is one or more of dibutyl tin dilaurate, stannous chloride and stannous octoate.
3. The preparation method according to claim 1 or 2, characterized in that:
In the step 1, a certain mass of alicyclic epoxy resin, acrylic acid, a catalyst A and a polymerization inhibitor are weighed and placed in a reactor, and the reaction is carried out after the reaction is slowly heated to 110-140 ℃ until the acid value is reduced to below 3mgKOH/g, thus obtaining the alicyclic epoxy acrylic acid prepolymer.
4. A method of preparation according to claim 3, characterized in that:
In the step 1, the molar ratio of the epoxy group to the acrylic acid is 1.00:1-1.04:1, the catalyst A accounts for 0.2-0.5% of the total mass, and the para-hydroxyanisole accounts for 0.05-0.3% of the total mass.
5. The preparation method according to claim 1 or 2, characterized in that:
In the step 2, the polyisocyanate, the hydroxyl epoxy monomer and the catalyst B with certain mass are weighed and placed in a reactor, and the reactor is slowly heated to 60-90 ℃ for reaction until the content of the isocyanate reaches a theoretical value.
6. The method of manufacturing according to claim 5, wherein:
in the step 2, the mol ratio of isocyanate to hydroxyl is 1.5:1-3:1, and the catalyst B accounts for 0.01-0.04% of the total mass.
7. The preparation method according to claim 1 or 2, characterized in that:
In the step 3, the alicyclic epoxy acrylic prepolymer obtained in the step 1, the epoxy isocyanate prepolymer obtained in the step 2 and castor oil are weighed and placed in a reaction flask, and a catalyst B and a polymerization inhibitor are added at the same time, and the mixture is slowly heated to 60-90 ℃ for reaction until the content of isocyanate is lower than 0.4%.
8. The method of manufacturing according to claim 7, wherein:
In the step 3, the ratio of the mole number of isocyanate contained in the epoxy isocyanate prepolymer to the total mole number of hydroxyl contained in the alicyclic epoxy acrylic prepolymer and castor oil is 1:1.01-1:1.04; the molar ratio of the hydroxyl groups contained in the alicyclic epoxy acrylic prepolymer to the castor oil is 0.25:1-4:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410150097.8A CN117986532A (en) | 2024-02-02 | 2024-02-02 | Preparation method of dual-curing prepolymer based on castor oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410150097.8A CN117986532A (en) | 2024-02-02 | 2024-02-02 | Preparation method of dual-curing prepolymer based on castor oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117986532A true CN117986532A (en) | 2024-05-07 |
Family
ID=90890210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410150097.8A Pending CN117986532A (en) | 2024-02-02 | 2024-02-02 | Preparation method of dual-curing prepolymer based on castor oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117986532A (en) |
-
2024
- 2024-02-02 CN CN202410150097.8A patent/CN117986532A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105859584B (en) | One kind being based on the 3 degree of functionality urethane acrylates and its preparation method and application of trihydroxy methyl second (third) alkane | |
| CN103274967B (en) | Tri-functional polyurethane acrylate, and preparation method and application thereof | |
| CN103214649B (en) | 9-functionality-degree polyurethane acrylate as well as preparation method and application thereof | |
| CN103242508B (en) | A kind of 4 functionality urethane acrylates and its preparation method and application | |
| CN105859585B (en) | A kind of 3 degree of functionality urethane acrylates based on glycerine and its preparation method and application | |
| CN115677997A (en) | Low-viscosity UV (ultraviolet) photocuring hyperbranched polyester acrylate resin as well as preparation method and application thereof | |
| CN113667106B (en) | Ultraviolet light curing itaconic acid-based polyester resin and preparation method thereof | |
| CN111978512A (en) | High-functionality epoxy acrylate and preparation method thereof | |
| CN105859587B (en) | A kind of 4 degree of functionality urethane acrylates based on pentaerythrite and its preparation method and application | |
| CN103193953B (en) | Urethane acrylate with functionality of 12 as well as preparation method and application thereof | |
| CN113897082A (en) | All-bio-based photocuring material and preparation method and application thereof | |
| CN105860028A (en) | Tri-functionality urethane acrylate based on 2, 2-dimethylolpropionic acid/2, 2-dimethylolbutanoic acid and preparation method and application of tri-functionality urethane acrylate | |
| CN105820063B (en) | A kind of 4 degree of functionality urethane acrylates based on anhydrous citric acid and its preparation method and application | |
| US3991024A (en) | Novel curable resin and preparation thereof | |
| CN110498813B (en) | Chlorine-containing phosphorus-containing acrylate oligomer and preparation method thereof | |
| CN105860026A (en) | Hexa-functionality urethane acrylate based on dipentaerythritol and preparation method and application of hexa-functionality urethane acrylate | |
| CN117986532A (en) | Preparation method of dual-curing prepolymer based on castor oil | |
| CN103242507B (en) | Eight-functionality urethane acrylate as well as preparation method and application thereof | |
| CN107418298B (en) | Interpenetrating network structure-based mercapto-modified acrylate prepolymer UV (ultraviolet) ink and preparation method thereof | |
| CN105884655B (en) | A kind of 4 degree of functionality urethane acrylates based on double trimethylolpropane and its preparation method and application | |
| KR20210031726A (en) | Epoxy-modified acrylic resin, its manufacturing method, energy curable composition and application containing epoxy-modified acrylic resin | |
| CN113354954B (en) | Cationic photocuring epoxy vegetable oil-based flame-retardant material and preparation method and application thereof | |
| CN110922603B (en) | Photocuring resin modified by different chain segments and preparation method and application thereof | |
| Zhou et al. | Preparation of high-performance epoxy soybean oil-based UV-curable oligomers and coatings | |
| CN114213626A (en) | Preparation method of vegetable oil-based photocuring urethane acrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |