CN103073466B - Cardanol trithiocarbonate and synthesis method and application thereof - Google Patents
Cardanol trithiocarbonate and synthesis method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of chemical synthesis, and discloses cardanol trithiocarbonate and a preparation method thereof, wherein the preparation method comprises the following steps: cardanol is etherified with dihalide, and then reacts with carbon disulfide and a mercaptan compound to obtain a final product. The cardanol trithiocarbonate can be used as reversible addition-fragmentation chain transfer reagent, and can be used for preparing light-cured resins.
Description
Technical field
The present invention relates to chemical field, the reversible addition-fracture of especially a kind of cashew nut phenolic group chain shifts the synthetic of (RAFT) reagent and the application in the resin of preparation thereof.
Background technology
In recent years, along with the day by day scarcity of fossil resource and the energy, the research of other substitutable resources of people's pay attention to day by day.Wherein come from vegeto-animal renewable resources, become one of focus of research.Cashew nut shell oil (CNSL) is the liquid component extracting from cashew nut shell, is a kind of byproduct in cashew nut processing, and wherein cardanol content accounts for 90%, is discharged in environment if these byproducts are not used, will be to environment.Approximately 500,000 tons of world's cashew nut shell oil annual production are at present a kind of abundant, inexpensive renewable resourcess.At present, the purposes of cardanol only limits to paint, friction material field, therefore, to its research and application need further to be strengthened (Cheng Chuanjie, looks into Ji Wei, Liu Zhongbin, etc. applied chemistry, 2012,29 (04), 392-396.).
Since the reversible addition-fracture of discovered in recent years chain transfer polymerization (RAFT), this method has obtained extensive and deep research.Compared with other living polymerization, the outstanding advantages of RAFT shows as: 1) suitable monomers kind is wide; 2) made molecular weight distribution is narrow; 3) monomer conversion and initiator efficiency of initiation are high; 4) can prepare multipolymer and the homopolymer of multiple topological structure; 5) can in different systems such as water base grade, carry out (G.Moad, E.Rizzardo, S.Thang.Acc.Chem.Res., 2008,41,1133-1142.).
Letex polymerization is the important method of preparing water color ink, coating, tackiness agent and other polymer materials.Compared with other method, letex polymerization has the following advantages: the one, and taking water as medium, viscosity is low, is easy to realize continuous operation, operational safety, not fire hazardous etc.; The 2nd, production cost is low, has avoided using more expensive organic solvent and reclaiming the trouble of solvent; The 3rd, due to the blanketing effect of system, can effectively reduce double-basis stop, make polymerization rate and molecular weight be improved simultaneously (Zhang Hongtao, yellow rose-tinted clouds. letex polymerization new technology and application .2007, Beijing: Chemical Industry Press .).Traditional letex polymerization is often used small-molecular emulsifier, and these small-molecular emulsifiers finally can enter into polymeric articles, bring disadvantageous effect to product, for example, small-molecular emulsifier can be to surface transport, makes polymkeric substance water tolerance variation, and affect (the M.Save such as optics, electricity and the surface property of product, Y.Guillaneuf andR.G.Gilbert.Aust.J.Chem.2006,59,693-711.).
The shortcoming of simple linear polymer is that physical strength is low, and anti-scratch property is poor, a little less than resistance to chemical attack, easily aging etc., and the polymkeric substance that therefore people often make cross-linking type uses.But, if directly make cross-linked polymer, because it belongs to the undissolved thermosetting resin of a swelling, cannot be used for coating, ink, tackiness agent.So, first prepare the prepolymer with active group by suitable method, after use construction, there is again crosslinking curing, have very important significance.
Summary of the invention
The object of this invention is to provide and a kind ofly prepare cashew nut phenolic group trithiocarbonate and carry out as chain transfer agents the method that active free radical polymerization is prepared light-cured resin.
Cashew nut phenolic group trithiocarbonate provided by the invention is as shown in structural formula (I):
wherein, m=2-10; Q=1-11;
T can be C
1-C
7alkyl, carboxyl, the one in phenyl.The structure of T does not affect cashew nut phenolic group trithiocarbonate (I) and prepares corresponding resin as RAFT chain transfer agents herein.
The present invention also provides the preparation method of the compound of a kind of structural formula (I), and described method steps is as follows:
(1) by the dihalide of structural formula (II)
wherein X represents Cl, Br, and the one in I, m, as defined in compound (I), carries out etherification reaction with cardanol (III) under alkaline condition,
obtain the compound of structural formula (IV)
wherein m, X is as defined in compound (II).
(2) structure formula V
sulfur alcohol compound react under alkaline condition with dithiocarbonic anhydride, and then react with the compound of structural formula (IV), obtain the product of structural formula (I).Wherein, in the sulfur alcohol compound of structure formula V T and q as shown in structural formula (I).
In the time preparing the compound of structural formula (IV), alkali used is sodium bicarbonate, sodium carbonate, salt of wormwood, cesium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, diisopropyl ethyl amine, pyridine, N, N-dimethyl lauryl amine, Tetramethyl Ethylene Diamine, N, N-dimethylethanolamine.These alkali as acid binding agent, for neutralizing the hydrogen halide by product of generation, therefore there is no impact with above-mentioned which kind of alkali to reaction in reaction in reaction.Reaction solvent for use is acetone, methylene dichloride, 1,2-ethylene dichloride, chloroform, tetracol phenixin, acetonitrile, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, benzene,toluene,xylene.Temperature of reaction can be from-10 ° of C to solvent reflux temperature, preferably room temperature.
In the time that step (2) is prepared the compound of structural formula (I), it is sodium carbonate, salt of wormwood, cesium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, diisopropyl ethyl amine, pyridine, N that described alkaline condition reacts alkali used, N-dimethyl lauryl amine, Tetramethyl Ethylene Diamine, N, N-dimethylethanolamine.Reaction solvent for use is acetone, methylene dichloride, 1,2-ethylene dichloride, chloroform, tetracol phenixin, acetonitrile, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, or the mixed solvent of above solvent composition.React again the reflux temperature that temperature of reaction can be from 0 ° of C to solvent, preferably room temperature with the compound of structural formula (IV).
The present invention also provides compound application in radical polymerization as RAFT chain transfer agents of structural formula (I).Described polyreaction monomer used can be selected from one or more in acrylic compounds, methacrylic compounds, styrene compound.Described acrylic monomer comprises sodium acrylate, acrylate, and wherein ester is that methyl esters, ethyl ester, allyl ester etc. have cycloalkyl substituted or there is no the C of cycloalkyl substituted
1-C
20alkyl monocarbon alcohol, dibasic alcohol and polyol ester.Described methacrylic monomer, comprises sodium methacrylate, methacrylic ester, and wherein ester is that methyl esters, ethyl ester, allyl ester etc. have cycloalkyl substituted or there is no the C of cycloalkyl substituted
1-C
20alkyl monocarbon alcohol, dibasic alcohol and polyol ester; Styrene monomer comprises vinylbenzene, substituted phenylethylene, wherein substituting group position can be at ortho position, contraposition and a position monobasic or polynary replacement, substituting group is C
1-C
18alkyl, cycloalkyl, carboxyl or sulfonic group.All can there is living free radical polymerization and prepare corresponding resin in above-mentioned vinyl monomer, different monomers only have certain influence to speed of response principle.
Initiator in Raolical polymerizable of the present invention initiator system used is one or more in Sodium Persulfate, Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate; The effect of above-mentioned initiator is to produce free radical, which kind of initiator there is no essential difference with.Reductive agent used is S-WAT, sodium bisulfite, DMA, N, N, N ', one or more in N '-Tetramethyl Ethylene Diamine (TMEDA), vulkacit H (HMTA).
Raolical polymerizable of the present invention can carry out mass polymerization, solution polymerization, letex polymerization.In the time carrying out solution polymerization, solvent for use is tetrahydrofuran (THF), benzene, toluene, acetonitrile, methyl-phenoxide, dimethyl sulfoxide (DMSO), DMF.In the time carrying out letex polymerization, emulsifying agent used is cationic emulsifier, nonionic emulsifying agent or anionic emulsifier.Wherein cationic emulsifier is octadecyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, two dodecyl dimethyl ammonium chloride, palmityl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride; Nonionic emulsifying agent is polyoxyethylene octylphenol ether (OP-10), anhydrous sorbitol laurate, polyoxyethylene sorbitan laurate, stearylamine polyoxyethylene (8) ether; Anionic emulsifier is 3-(cashew nut phenolic group) propanesulfonate that sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Aerosol OT, structural formula are (VI).Mentioned emulsifier is only for stabilized emulsion system, adopts different emulsifying agents to there is no impact to polyreaction.
While utilizing the compound of structural formula (I) to carry out reversible addition-fragmentation chain transfer free radical polymerization, can obtain having the polymkeric substance of structural formula (VII); And in this living free radical polymerization system, the unsaturated terminal chain of cardanol is less or crosslinking reaction does not occur, and these carbon carbon unsaturated link(age)s can carry out later photocuring or thermofixation crosslinking reaction, thereby can be applicable in photo-cured coating or ink.
Wherein m, q, T is as the definition in structural formula (I); A
1represent the one in phenyl, carboxylic acid sodium or carboxylicesters, and ester group part to be wherein methyl esters, ethyl ester etc. have cycloalkyl substituted or there is no the C of cycloalkyl substituted
1-C
18alkyl monocarbon alcohol, dibasic alcohol and polyol ester; A
2represent the one in phenyl, carboxylic acid sodium or carboxylicesters, and ester group part to be wherein methyl esters, ethyl ester etc. have cycloalkyl substituted or there is no the C of cycloalkyl substituted
1-C
18alkyl monocarbon alcohol, dibasic alcohol and polyol ester; A
3represent the one in phenyl, carboxylic acid sodium or carboxylicesters, and ester group part to be wherein methyl esters, ethyl ester etc. have cycloalkyl substituted or there is no the C of cycloalkyl substituted
1-C
18alkyl monocarbon alcohol, dibasic alcohol and polyol ester; A
1, A
2with A
3for identical group can be also different group; E
1represent methyl or hydrogen; E
2represent methyl or hydrogen; E
3represent methyl or hydrogen; E
1, E
2with E
3can be that identical group can be also different group.R=0-1000; U=0-1000; V=0-1000; Y=0-1000; But r, u, y can not be zero simultaneously.
The reinforced molar ratio of Raolical polymerizable of the present invention is the compound of structural formula (I): monomer: initiator: reductive agent: emulsifying agent=1:(1-1000): (0.2-10): (0.2-10): (0-20), be preferably the compound of structural formula (I): monomer: initiator: reductive agent: emulsifying agent=1:(5-200): (0.5-5): (0.5-5): (0-5), can regulate polymer molecular weight size by changing proportioning, molecular structure composition.The temperature of Raolical polymerizable of the present invention is the reflux temperature of 0 ° of C to solvent, and in order to reach suitable speed of response conserve energy, temperature of reaction is preferably 40 ° of C-70 ° of C.
The application of resin is prepared in radical polymerization of the present invention, in the time carrying out photocuring, light trigger used is dimethoxybenzoin, benzophenone, 4-methyldiphenyl ketone, 4,4 '-dimethyl benzophenone, 4-dihydroxy benaophenonel, michaelis ketone, isopropyl thioxanthone, diethoxy acetophenone.Above-mentioned radical photoinitiator is only to cause radical polymerization under illumination condition, adopts different light triggers to there is no impact to reaction.
Reversible addition-the fracture of the cashew nut phenolic group chain transfer agents that the present invention is designed, making full use of on the basis of this cheap renewable resources of cardanol, both can be used as reversible addition-fracture chain transfer agents, while gained simple linear polymer after living polymerization can be used as again the prepolymer of light-cured resin.By regulating cashew nut phenolic group reversible addition-fracture chain transfer agents and the ratio of monomer and the order of addition of monomer, can obtain the crosslinkable multipolymer that molecular weight is controlled, molecular structure is controlled.Reversible addition-the fracture of cashew nut phenolic group chain transfer agents (I) synthetic method is simple, easy and simple to handle, mild condition, during for polymerization, suitable monomers scope is wide, the polymkeric substance that prepared photocurable is crosslinked has broad application prospects in photo-cured coating, ink, tackiness agent and other thermosetting resin synthetic.
Embodiment
Further set forth the present invention below in conjunction with embodiment.Should be appreciated that, these embodiment only, for the present invention is described, limit the scope of the invention and be not used in.The experimental technique of the unreceipted actual conditions of the following example, conventionally according to normal condition, or the condition that provides or advise according to manufacturer.Unless otherwise indicated, the same meaning that all specialties used herein and scientific terminology and those skilled in the art are familiar.In addition any method similar or impartial to present method and material all can be used in the inventive method.
The preparation of embodiment 1 4-brombutyl cashew nut phenolic ether (IVa)
Prepare target compound taking cardanol, Isosorbide-5-Nitrae-dibromobutane, alkali as raw material.
By Isosorbide-5-Nitrae-dibromobutane (2.70g, 12.5mmol), sodium bicarbonate (8.4g, 100mmol) and tetrahydrofuran (THF) (5mL) add in reaction flask, then cardanol (1.21g, 4mmol) is slowly added drop-wise in reaction mixture.Add after material, at room temperature react 24h.In system, add 100mL water, separatory, organic phase adds anhydrous sodium sulfate drying, and last solvent evaporated obtains yellow oil.Crude product is purified after (eluent: ether/methylene dichloride=1/1, volume ratio) with silicagel column, obtains sterling (1.25g, 71%).
1H?NMR(400MHz,CDCl
3):δ7.24-7.15(m,1H),6.83-6.71(m,3H),5.89-5.82(m,0.3H),5.49-5.34(m,3H),5.12-5.00(m,0.6H),4.02(t,2H,J=6.0Hz),3.54-3.44(m,5H),2.88-2.81(m,2H),2.63(m,2H),2.16-2.00(m,8H),1.99-1.92(2H),1.66-1.57(m,2H),1.43-1.26(m,12H),0.97-0.89(2H);
13C?NMR(100MHz,CDCl
3):δ158.8,144.6,136.8,130.4,129.9,129.8,129.3,129.1,127.6,126.8,120.9,114.7,111.3,66.6,36.0,33.6,32.6,31.4,31.0,29.8,29.6,29.5,29.4,29.3,28.0,27.2,25.6,22.7,14.2.
Embodiment 2 utilizes the synthetic compound IV a of embodiment 1 to prepare the reversible addition-fracture of cashew nut phenolic group chain transfer agents (Ia)
Prepare target compound taking compound IV a, dithiocarbonic anhydride, 3-thiohydracrylic acid, alkali as raw material.
Sodium carbonate (0.74g, 7mmol), 3-thiohydracrylic acid (0.75g, 7mmol), acetone (30mL) are added in reaction flask, mixture stirs after 30min under reflux temperature, cooling, add 2mL dithiocarbonic anhydride, then mixture at room temperature stirs 1h again.Compound IV a (3.0g, 7mmol) slowly adds in reaction system, then at room temperature reacts 2h.After reaction finishes, concentrating under reduced pressure obtains yellow oil.This oily matter is dissolved in after methylene dichloride, washes with water 5 times, anhydrous sodium sulfate drying, finally filters, concentrates to obtain crude product.Crude product is purified after (eluent: ether/ethyl acetate=3/1, volume ratio) with silicagel column, obtains sterling (3.03g, 80.6%).
IR(KBr)ν:3438(broad),3060,3028,2962,2921,1725,1637,1602,1492,1454,1238,1184,1064,853,801,701cm
-1;
1H?NMR(400MHz,CDCl
3):δ7.19-7.12(m,1H),6.79-6.64(m,3H),5.86-5.75(m,0.3H),5.44-5.26(m,2.8H),5.13-4.94(0.7H),3.99-3.90(m,2H),3.66-3.52(m,2H),3.49-3.35(m,2H),2.88-2.71(m,4H),2.56(t,2H,J=7.60Hz),2.09-1.95(m,4H),1.92-1.83(4H),1.41-1.17(m,12H),0.91-0.79(m,3H);
13C?NMR(100MHz,CDCl
3):δ222.6,178.0,157.9,143.6,135.8,129.4,128.9,128.8,128.1,126.6,125.8,119.9,113.8,110.4,66.0,35.6,35.0,30.3,28.7,28.3,28.2,27.5,26.2,23.9,21.6,13.1.
Embodiment 3 utilizes the reversible addition-fracture of cashew nut phenolic group chain transfer agents (Ia) prepared by embodiment 2 to carry out reversible addition-fracture chain transfer polymerization of methyl methacrylate (MMA)
By methyl methacrylate (3.00g, 30mmol), the reversible addition-fracture of cashew nut phenolic group chain transfer agents (Ia) (0.54g, 1.0mmol), Potassium Persulphate (0.13g, 0.57mmol) is dissolved in acetonitrile (25mL).Reaction flask, under frozen water is cooling, first vacuumizes, then inflated with nitrogen, in triplicate.Reaction solution is heated to 70 ° of C and keeps constant, then add S-WAT (0.15g, 1.25mmol) to react.After 4 hours, stop heating, add water or lower alcohol as methyl alcohol, ethanol in reaction flask, have throw out to generate, filter out solid, solid is dry 24h in the vacuum drying oven of 65 ° of C.Monomer conversion is by gravimetric determination; Molecular weight and for molecular weight distribution gel permeation chromatography (GPC) measure.If no special instructions, the aftertreatment of other radical polymerization, is also all undertaken by this step.
Theoretical molecular M
n, th=3210; Gel permeation chromatography (GPC) determining molecular weight M
n, GPC=5160; Molecular weight distribution PDI=1.46.
Embodiment 4 utilizes the reversible addition-fracture of cashew nut phenolic group chain transfer agents (Ia) prepared by embodiment 2 to carry out reversible addition-fracture chain transfer letex polymerization of methyl methacrylate (MMA)
Under argon shield; in reaction flask, add successively methyl methacrylate (3.04g; 30.4mmol), the reversible addition-fracture of cashew nut phenolic group chain transfer agents (Ia) (0.54g; 1.0mmol), Potassium Persulphate (0.39g; 1.71mmol), sodium laurylsulfonate (0.30g, 1.04mmol) and deionized water (25mL).Mixed solution is pre-emulsification 30min under room temperature and high-speed stirring condition first, then in water-bath, is heated to 60 ° of C and keeps constant temperature.S-WAT (0.15g, 1.25mmol) is dissolved in to deionized water (5mL) afterwards and adds in above-mentioned pre-emulsion with initiation reaction.After 5h, stopped reaction, adds methyl alcohol to carry out precipitation process after emulsion is cooling.
Theoretical molecular M
n, th=3285; Gel permeation chromatography (GPC) determining molecular weight M
n, GPC=2810; Molecular weight distribution PDI=1.34.
Reversible addition-fracture chain that embodiment 5 utilizes the reversible addition-fracture of cashew nut phenolic group chain transfer agents (Ia) prepared by embodiment 2 to carry out methyl methacrylate (MMA) and allyl methacrylate(AMA) shifts emulsion copolymerization
Under nitrogen protection; in reaction flask, add successively methyl methacrylate (1.50g; 15mmol), allyl methacrylate(AMA) (1.89g; 15mmol), the reversible addition-fracture of cashew nut phenolic group chain transfer agents (Ia) (0.54g; 1.0mmol), Sodium Persulfate (0.238g; 1.0mmol), palmityl trimethyl ammonium chloride (0.32g, 1.0mmol) and deionized water (30mL).Mixed solution is pre-emulsification 30min under room temperature and high-speed stirring condition first, then in water-bath, is heated to 50 ° of C and keeps constant temperature.Sodium bisulfite (0.104g, 1.0mmol) is dissolved in to deionized water (5mL) afterwards and adds in above-mentioned pre-emulsion with initiation reaction.After 6h, stopped reaction, adds ethanol to carry out precipitation process after emulsion is cooling.
Gel permeation chromatography (GPC) determining molecular weight M
n, GPC=2260; Molecular weight distribution PDI=1.57.
The preparation of embodiment 6 3-(cashew nut phenolic group) propanesulfonates (VI) aqueous solution
In a reaction flask, add 1.5 grams of (5mmol) cardanols and acetone (20mL), then add 0.28g (5mmol) potassium hydroxide, under normal temperature, stir 30min.Measure again 0.3 gram of (2.5mmol) PS and use 10ml acetone solution.Under frozen water is cooling, be added drop-wise in aforementioned solution.Under normal temperature, stir 10h.After reaction finishes, boil off acetone, resistates is dissolved in methylene dichloride, washes three times with deionized water.Organic phase anhydrous sodium sulfate drying, filters, and last solvent evaporated obtains product (1.03g, 93.1%).This product is dissolved in to 9mL deionized water, and to obtain concentration be 10% 3-(cashew nut phenolic group) propanesulfonate (VI) aqueous solution, can be directly used in letex polymerization below.
Reversible addition-the fracture of cashew nut phenolic group chain transfer agents (Ia) and 3-(cashew nut phenolic group) propanesulfonate (VI) aqueous solution prepared by embodiment 6 that embodiment 7 utilizes embodiment 2 to prepare carry out reversible addition-fracture chain transfer letex polymerization of methyl methacrylate (MMA)
Under argon shield; in reaction flask, add successively methyl methacrylate (3.0g; 30mmol), the reversible addition-fracture of cashew nut phenolic group chain transfer agents (Ia) (0.54g; 1.0mmol), Potassium Persulphate (0.39g; 1.71mmol), 3-(cashew nut phenolic group) propanesulfonate (VI) aqueous solution 4.5mL (approximately containing sterling 0.45g, 1.01mmol) and deionized water (20mL).Mixed solution is pre-emulsification 30min under room temperature and high-speed stirring condition first, then in water-bath, is heated to 65 ° of C and keeps constant temperature.S-WAT (0.15g, 1.25mmol) is dissolved in to deionized water (5mL) afterwards and adds in above-mentioned pre-emulsion with initiation reaction.After 4h, stopped reaction, adds methyl alcohol to carry out precipitation process after emulsion is cooling.
Theoretical molecular M
n, th=2467; Gel permeation chromatography (GPC) determining molecular weight M
n, GPC=3780; Molecular weight distribution PDI=1.46.
Embodiment 8 utilizes emulsion prepared by embodiment 7 to carry out UV to solidify
To in emulsion that utilize the method for embodiment 7 to prepare, add 4,4 '-dihydroxy benaophenonel 0.214g, reactive thinner ethylene glycol diacrylate 0.212g, N, N-dimethyl lauryl amine 0.217g, after stirring, uniform spreading, on sheet glass, obtains polymeric film 3.21g after then drying.This polymeric film is carried out to irradiation under the UV of 365nm light, after 20min, determine that with fingers-touch method sample has reached finger tactile dry, stop illumination, obtain cardanol methyl methacrylate light-cured resin.
Claims (12)
1. the compound of a structural formula (I)
Wherein, m=2-10; Q=1-11; T is C
1-C
7alkyl, carboxyl, the one in phenyl.
2. the preparation method of structural formula claimed in claim 1 (I) compound, comprises the steps:
(1) by structural formula be
dihalide, under alkaline condition, carry out etherification reaction with cardanol, obtain the compound of structural formula IV; Wherein X represents Cl, Br, the one in I, m=2-10;
(2) structural formula
sulfur alcohol compound react under alkaline condition with dithiocarbonic anhydride, and then the compound of the structural formula (IV) of preparing with step (1) reacts, and obtains the product of structural formula (I); Wherein structural formula
sulfur alcohol compound q=1-11; T is C
1-C
7alkyl, carboxyl, the one in phenyl.
3. preparation method according to claim 2, it is characterized in that: it is 1,2-ethylene dichloride, glycol dibromide, 1 that step (1) is reacted described dihalide, 3-propylene dichloride, 1,3-dibromopropane, 1,3-diiodo propane, Isosorbide-5-Nitrae-dibromobutane, 1, pentamethylene bromide, 1,5-bis-iodopentanes, 1,6-dibromo-hexane or 1,10-dibromo-decane; It is sodium bicarbonate, sodium carbonate, salt of wormwood, cesium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, diisopropyl ethyl amine, pyridine, N that step (1) is reacted described alkaline condition alkali used, N-dimethyl lauryl amine, Tetramethyl Ethylene Diamine or N, N-dimethylethanolamine; Described etherification reaction solvent for use is acetone, methylene dichloride, 1,2-ethylene dichloride, chloroform, tetracol phenixin, acetonitrile, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, benzene, toluene or dimethylbenzene; Described etherification reaction temperature of reaction is-10 DEG C of reflux temperatures to solvent.
4. preparation method according to claim 2, it is characterized in that: under the described alkaline condition of step (2), reacting alkali used is sodium carbonate, salt of wormwood, cesium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, diisopropyl ethyl amine, pyridine, N, N-dimethyl lauryl amine, Tetramethyl Ethylene Diamine or N, N-dimethylethanolamine, reaction solvent for use is acetone, methylene dichloride, 1,2-ethylene dichloride, chloroform, tetracol phenixin, acetonitrile, tetrahydrofuran (THF) or 1,4-dioxane, or the mixed solvent of above solvent composition; With the temperature of reaction of the compound of structural formula IV can be from 0 DEG C to solvent reflux temperature.
5. the compound of structural formula (I) application in photocureable polymer preparation as RAFT chain transfer agents described in claim 1.
6. application according to claim 5, is characterized in that: in the time that the compound of structural formula (I) carries out RAFT polymerization, monomer used is one or more in acrylic compounds, methacrylic compounds, styrene compound; Described acrylic compounds is sodium acrylate, acrylate, and wherein ester is the C that has cycloalkyl substituted or there is no cycloalkyl substituted
1-C
20alkyl monocarbon alcohol, dibasic alcohol and polyol ester; Described methacrylic compounds is sodium methacrylate, methacrylic ester, and wherein ester is the C that has cycloalkyl substituted or there is no cycloalkyl substituted
1-C
20alkyl monocarbon alcohol, dibasic alcohol; Described styrene monomer is vinylbenzene, substituted phenylethylene, and wherein substituting group position is ortho position, contraposition and a position monobasic or polynary replacement, substituting group is C
1-C
18alkyl, cycloalkyl, carboxyl or sulfonic group.
7. application according to claim 5, is characterized in that: in the time that the compound of structural formula (I) carries out RAFT polymerization, initiator is one or more in Sodium Persulfate, Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate; Reductive agent used is S-WAT, sodium bisulfite, DMA, N, N, N ', one or more in N '-Tetramethyl Ethylene Diamine TMEDA, vulkacit H HMTA.
8. application according to claim 5, is characterized in that: in the time that the compound of structural formula (I) carries out RAFT polymerization, emulsifying agent used is cationic emulsifier, nonionic emulsifying agent or anionic emulsifier.
9. application according to claim 8, wherein cationic emulsifier is octadecyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, two dodecyl dimethyl ammonium chloride, palmityl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride; Nonionic emulsifying agent is polyoxyethylene octylphenol ether OP-10, anhydrous sorbitol laurate, polyoxyethylene sorbitan laurate, stearylamine Soxylat A 25-7; Anionic emulsifier is 3-(cashew nut phenolic group) propanesulfonate that sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Aerosol OT or structural formula are (VI):
10. application according to claim 5, it is characterized in that: in the time that the compound of structural formula (I) carries out RAFT polymerization, reinforced molar ratio is the compound of structural formula (I): monomer: initiator: reductive agent: emulsifying agent=1:(1-1000): (0.2-10): (0.2-10): (0-20).
11. application according to claim 10, it is characterized in that: in the time that the compound of structural formula (I) carries out RAFT polymerization, reinforced molar ratio is the compound of structural formula (I): monomer: initiator: reductive agent: emulsifying agent=1:(5-200): (0.5-5): (0.5-5): (0-5).
12. application according to claim 5, it is characterized in that: in the time carrying out photocuring, light trigger used is dimethoxybenzoin, benzophenone, 4-methyldiphenyl ketone, 4,4 '-dimethyl benzophenone, 4-dihydroxy benaophenonel, michaelis ketone, isopropyl thioxanthone, diethoxy acetophenone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210563694.0A CN103073466B (en) | 2012-12-21 | 2012-12-21 | Cardanol trithiocarbonate and synthesis method and application thereof |
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