CN101066914B - Method of preparing mixture of alpha-hydroxycarbonyl group derivative of alpha-methylstyrene derivative - Google Patents
Method of preparing mixture of alpha-hydroxycarbonyl group derivative of alpha-methylstyrene derivative Download PDFInfo
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- CN101066914B CN101066914B CN2007101025025A CN200710102502A CN101066914B CN 101066914 B CN101066914 B CN 101066914B CN 2007101025025 A CN2007101025025 A CN 2007101025025A CN 200710102502 A CN200710102502 A CN 200710102502A CN 101066914 B CN101066914 B CN 101066914B
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- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 26
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- -1 alpha-brominated isobutyl acylbromide Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000539 dimer Substances 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 230000031709 bromination Effects 0.000 claims description 7
- 238000005893 bromination reaction Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 238000006384 oligomerization reaction Methods 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 230000036571 hydration Effects 0.000 claims description 5
- 238000006703 hydration reaction Methods 0.000 claims description 5
- 150000007517 lewis acids Chemical class 0.000 claims description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 238000007171 acid catalysis Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- 241001597008 Nomeidae Species 0.000 abstract 1
- XJZFXLYIKVRQLA-UHFFFAOYSA-N [Br].BrC(C(=O)O)(C)C Chemical compound [Br].BrC(C(=O)O)(C)C XJZFXLYIKVRQLA-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/16—Halogens
- C08F12/21—Bromine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/12—Separation of polymers from solutions
Abstract
A process for preparing a mixture of alpha-hydroxy carbonyl derivant of oligomer of alpha-methylstyrene includes Friedel-Crafts reaction between alpha-methylstyrene oligomer and alpha-bromoisobutyric acid bromine.
Description
Technical field
The present invention relates to a kind of method of mixture of the alpha-hydroxy carbonyl derivative for preparing the alpha-methyl styrene derivative.
Background technology
In photopolymerization, use oligomeric light trigger and use the monomer light trigger to compare to have some advantages, from formulation, move reductions, by the amount minimizing of the volatile compound of photolysis generation such as light trigger.These features are extremely important for industrial application, because these features can reduce finished product by undesirable compound polluted risk.
In oligomeric light trigger, the alpha-hydroxy carbonyl derivative of the oligopolymer of alpha-methyl styrene is known.
For example, US4987159 has described these light triggers.
These light triggers mainly are made up of dimer and tripolymer mixture of isomers.At room temperature, mixture is the very high product of viscosity, and this product is difficult for being used for industrial application like this.
In the present invention, the word of " the alpha-hydroxy carbonyl derivative of the oligopolymer of alpha-methyl styrene " is meant the compound of general formula I, and wherein n is equal to or greater than 0 numeral:
In patent US 4987159, the applicant described the dimer of a-Methylstyrene Low-Polymer and trimerical alpha-hydroxy carbonyl derivative preparation process of mixture, comprising: make the alpha-methyl styrene oligomerization, and cyclisation simultaneously; Then by being reflected at carbonylate on the aromatic ring with isobutyryl chloride; The alpha-position generation chlorination of carbonyl; Last hydrolysis obtains required mixture.
The mixture that the International Application No. WO of being submitted to by same applicant 02/085832 has been described by the alpha-hydroxy carbonyl derivative of the oligopolymer of the alpha-methyl styrene of the dimer isomer that contains 60 weight % at least begins, the method of the solid mixture of the alpha-hydroxy carbonyl derivative of the oligopolymer of preparation alpha-methyl styrene, described solid mixture contains at least 90% dimer isomer, and wherein active higher dimer isomer is main.
In WO 02/085832, the preparation of the intermediate blend of the dimer isomer that oligomerization and the cyclization by alpha-methyl styrene contains at least 60 weight %, by being reflected at carbonylate on the aromatic ring, make the alpha-position chlorination of carbonyl, hydrolysis then with isobutyryl chloride.
In the patent application WO 2004/099111 that submits to by CIBA subsequently, the preparation process of mixed crystal of alpha-hydroxy carbonyl derivative of the cyclic dimer of alpha-methyl styrene has been described; This preparation process is by phenyl 1, and 2-indane (indane) beginning is by carrying out with isobutyryl chloride reaction and chlorination.
Know that when no matter being to use chlorine also to be to use SULPHURYL CHLORIDE or other chlorizating agent to carry out, chlorination reaction all relates to the danger of safe and ecological aspect, this is that then a kind of situation can discharge sulfurous gas because the previous case is dangerous.
According to basic sides of the present invention, the method for mixture of alpha-hydroxy carbonyl derivative of the oligopolymer of preparation alpha-methyl styrene has been described, this method does not comprise chlorinating step.
Other advantage of the present invention is that the required step of the entire method that begun by alpha-methyl styrene is than the some steps of minimizing required in the art methods.
Summary of the invention
The method of mixture that the purpose of this invention is to provide a kind of alpha-hydroxy carbonyl derivative of the oligopolymer for preparing alpha-methyl styrene, described method comprises: a) make the alpha-methyl styrene oligomerization, and cyclisation simultaneously obtains the mixture of a-Methylstyrene Low-Polymer; B) under Louis acid catalysis, Friedel-Crafts reaction takes place between a-Methylstyrene Low-Polymer that step a) obtains and the alpha-brominated isobutyl acylbromide, obtain the mixture of bromination intermediate; C) mixture of bromination intermediate and hydration alkali (hydratebase) solution, carbonate or supercarbonate reaction obtains the mixture of alpha-hydroxy carbonyl derivative of the oligopolymer of alpha-methyl styrene.
Embodiment
In the literature the oligomerization and the cyclisation simultaneously of alpha-methyl styrene are described in detail.
This is reflected under the condition of no any solvent and carries out, and in the presence of acid catalyst, carries out 0.5-8 hour-10 ℃ to 150 ℃ temperature.
The mixture of the oligopolymer of the alpha-methyl styrene that is obtained by step a) mainly is made up of cyclic dimer and tripolymer, but also can have a small amount of non-cyclized oligomer.
Acid catalyst can be acid clay, ion exchange resin, carboxylic acid or aryl sulfonic acid, mineral acid.
The preferred use is insoluble to the acid catalyst of alpha-methyl styrene and oligopolymer thereof, thereby can when step a) finishes this catalyst separating be come out; Preferred acid catalyst is an ion exchange resin.
In realizing a preferred form of the present invention, generally carry out simple process by the mixture that filters the oligopolymer of the alpha-methyl styrene of step a), remove catalyzer.
Can also after step a), carry out other distilation steps a '); Step a ') the alpha-methyl styrene dimer is separated.
When finishing, method of the present invention when people wish the crystalline mixture of alpha-hydroxy carbonyl derivative of oligopolymer of alpha-methyl styrene, preferably carries out step a ').
The sulfonic ion exchange resin that comprises sour form is especially preferably as an acidic catalyst.
The characterization step of the inventive method is a step b), and wherein alpha-brominated isobutyl acylbromide is an acylating agent.
Solution by preparation acylating agent and a-Methylstyrene Low-Polymer carries out Friedel-Crafts reaction; the solvent of described solution is aliphatic chlorinated solvent; for example methylene dichloride or other suitable solvent; such as other chlorinated derivatives of the suitable aliphatic hydrocarbon of chlorobenzene or benzene, heptane, hexane or other volatility, the aromatic ring of oligopolymer and the mol ratio of acylating agent are 1.0-1.1.
With Lewis acid (preferred AlCl
3) join in the solution that obtains like this, temperature is remained on-20 ℃ to 20 ℃, be preferably-5 ℃ to 15 ℃. in batchesPerhaps, can also prepare a kind of solution, this solution comprises the title complex that is formed by acylating agent and Lewis acid, and this drips of solution is added in the a-Methylstyrene Low-Polymer.
Reaction times is depended on the heat release and the cooling system of reaction; Usually the reaction times is 0.5-10 hour.
The mixture of the bromination intermediate that obtains when step b) finishes mainly is made up of the dimer of general formula I Ia and IIb:
They account for more than the 90 weight % of mixture usually.
Alpha-brominated isobutyl acylbromide is commercially available, and has the appropriate technology feature as Industrial products, can not carry out any extra process and use like this.
Alpha-brominated isobutyl acylbromide is a fluid cpds, is stable under working conditions, and metering easily in industrial environment.
The Friedel-Crafts reaction of step b) is generally comprised within the final decomposition phase of the title complex that forms under the Lewis acid effect, by using the sour water reaction mixture, the organic phase that contains the bromination intermediate that each phase of separation and water further wash gained makes mutually for this.
In realizing preferred form of the present invention, organic phase can be used in the step c) like this, perhaps when step b) finishes, before carrying out step c), desolvates by evaporating to remove.
Usually, in step c), with an organic solvent, such as methylene dichloride, ethylene dichloride, chlorobenzene, Virahol, methyl alcohol, ethanol, isopropylcarbinol.
According to the solvent that uses, the mixture of step c) can be single-phase or two-phase, and this is inessential; When mixture is two phase times, preferably in reaction process, add phase-transfer catalyst, for example, benzyltriethylammonium chloride (BTEAC).
When before carrying out step c), removing the solvent of step b) earlier, with the reaction product of step b) be dissolved in the miscible fatty alcohol of water in, be preferably dissolved in the Virahol.
Usually used hydration alkali is NaOH or KOH in step c), and form is the aqueous solution of 20-50%, but also can use basic carbonate and supercarbonate; Preferred hydration alkali is NaOH.
The reaction of step c) is heat release, in the process of step c), with temperature maintenance at 15-70 ℃.
When step c) finishes, after water phase separated, after the organic phase and remove of mixture of alpha-hydroxy carbonyl derivative that washing contains the oligopolymer of alpha-methyl styrene is desolvated, obtain the mixture of alpha-hydroxy carbonyl derivative of the oligopolymer of alpha-methyl styrene.
Method of the present invention has very big advantage, does not relate to the use and the control corresponding of gaseous reagent, and these gaseous reagents for example chlorine or other can produce the reagent of sulfur-bearing gaseous by-product.
The mixture of the alpha-hydroxy carbonyl derivative of the oligopolymer of the alpha-methyl styrene that obtains according to the inventive method is used as light trigger in the energy-curable technology, be used in particular for containing the photocuring of prescription of the mixture of the unsaturated compound of vinylformic acid and/or methacrylic acid type or unsaturated compound.
In the advantageous applications of mixture of the present invention, the inventor point out mixture of the present invention at low yellowing lacquer and varnish, tackiness agent, patterned artistic, industrial coating, fibre coating, be used for the Photocurable composition of printing plate as light trigger.
Embodiment 1
A) oligomerization of alpha-methyl styrene and cyclisation:
Under mechanical stirring, 10 gram Amberlyst 15 are joined in 1 liter of reaction flask, drip 400 gram (3.38 moles) alpha-methyl styrenes according to the following stated then.
After adding about 50 milliliters of alpha-methyl styrenes, temperature reaches 50 ℃ naturally; Stop to feed in raw material, reaction mixture is heated to 70 ℃.
Continue to add alpha-methyl styrene, regulate reinforced flow, internal temperature is remained on 80 ℃.After 2 hours, in 30 ', reaction mixture is heated to 120-125 ℃, stir more than 2 hours.
After filtering resin, obtain 370 gram products, mainly by 1,1,3-trimethylammonium-3-phenyl 1, the 2-indane is formed.
1H-NMR：CDCl
3，300MHz，.ppm：7.05-7.30，m，9H；2.43，d，1H；2.2，d，2H；1.67，s，3H；1.32，s，3H；1.05，s，3H
B) preparation of the mixture of brominated derivative:
Under agitation, under 0 ℃ to 5 ℃ temperature, in about 45 minutes, 24.81 gram (0.186 mole) aluminum chlorides are joined product that 20 grams that form obtain in (0.0846 mole) step a) (mainly by 1 in 200 milliliters of methylene dichloride, 1,3-trimethylammonium-3-phenyl 1, the 2-indane is formed) and 41.06 restrain in the solution of 97.5% alpha-brominated isobutyl acylbromide.
Behind reinforced the end, mixture was stirred 1.5 hours at 5 ℃, be poured into then in 200 ml solns of water and ice and 10 milliliters of concentrated hydrochloric acids.Separate organic phase, water washs, and uses dried over sodium sulfate.
1H-NMR(200MHz，CDCl
3，(ppm)：7.9-8.2，m，4H；7.15-7.31，m，3H；4.2，m，2H；2.48，m，1H；2.23，d，1H；1.9-2.01，m，12H；1.71，m，3H；1.3-1.4；m，3H；1.05，m，3H
C) preparation of the mixture of the alpha-hydroxy carbonyl derivative of the oligopolymer of alpha-methyl styrene:
The BTEAC aqueous solution of 200 gram 20% NaOH and 0.6 gram 50% is joined in the solution of being made by the product that obtains in the 147 gram step b) and 250 milliliters of methylene dichloride.
Methylene dichloride is removed in distillation, reaches 50 ℃ up to temperature, and this reaction mixture is remained on this temperature, solvent cycle under vigorous stirring.Every interval 20 ' adds 0.6 gram BTEAC.After 2 hours, make the solution cooling, separate organic phase, wash twice with water, use dried over sodium sulfate, vaporising under vacuum; Obtain 103.8 gram products.
1H-NMR(200MHz，CDCl
3，(ppm)：7.8-8.05，m，4H；7.15-7.31，m，3H；2.45，m，1H；2.26，d，1H；1.6-1.75，m，15H；1.38，m，3H；1.05，m，3H。
Claims (9)
1. the method for the mixture of the alpha-hydroxy carbonyl derivative of an oligopolymer for preparing alpha-methyl styrene shown in the general formula I, n=0 in the general formula I, this method comprises: a) make alpha-methyl styrene oligomerization in the presence of acid catalyst, and cyclisation simultaneously obtains the mixture of a-Methylstyrene Low-Polymer; B) under Louis acid catalysis, Friedel-Crafts reaction takes place between a-Methylstyrene Low-Polymer that step a) obtains and the alpha-brominated isobutyl acylbromide, obtain the mixture of bromination intermediate; C) mixture of bromination intermediate and hydration alkaline solution, carbonate or supercarbonate reaction obtains the mixture of alpha-hydroxy carbonyl derivative of the oligopolymer of alpha-methyl styrene
2. the method for claim 1 is characterized in that, the mixture of described bromination intermediate mainly is made up of the dimer of general formula I Ia and IIb:
3. method as claimed in claim 2 is characterized in that, step a) was being carried out 0.5-8 hour under the condition of no any solvent, under-10 ℃ to 150 ℃ temperature, uses to comprise the sulfonic ion exchange resin of sour form as acid catalyst.
4. method as claimed in claim 3, it is characterized in that, described Friedel-Crafts reaction is undertaken by following steps: the alpha-brominated isobutyl acylbromide of preparation in suitable solvent and the solution of a-Methylstyrene Low-Polymer, and the mol ratio of the aromatic ring of oligopolymer and alpha-brominated isobutyl acylbromide is 1.0-1.1; In the solution that obtains like this, add Lewis acid, temperature is remained on-20 ℃ to 20 ℃ in batches; By with sour water reaction mixture and wash organic phase with water, make the title complex decomposition that forms by the Louis.
5. method as claimed in claim 4 is characterized in that described Lewis acid is AlCl
3
6. method as claimed in claim 4 is characterized in that the organic phase that obtains is used for step c) like this when step b) finishes, the reaction mixture of step c) is two-phase and comprises phase-transfer catalyst.
7. method as claimed in claim 4 is characterized in that, before carrying out step c), the solvent in the organic phase that obtains when step b) is finished is removed, with the reaction product of step b) be dissolved in the miscible fatty alcohol of water in, to carry out step c).
8. method as claimed in claim 7 is characterized in that described alcohol is Virahol.
9. the method for claim 1 is characterized in that, being used in hydration alkali used in the step c) is NaOH.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITVA2006A000021 | 2006-05-02 | ||
| IT000021A ITVA20060021A1 (en) | 2006-05-02 | 2006-05-02 | PROCESS FOR THE PREPARATION OF MIXTURES OF ALPHA-HYDROXICARBONYL DERIVATIVES OF ALPHA-METHYSTIRENE OLIGOMERS |
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| Publication Number | Publication Date |
|---|---|
| CN101066914A CN101066914A (en) | 2007-11-07 |
| CN101066914B true CN101066914B (en) | 2011-12-07 |
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| CN2007101025025A Active CN101066914B (en) | 2006-05-02 | 2007-04-27 | Method of preparing mixture of alpha-hydroxycarbonyl group derivative of alpha-methylstyrene derivative |
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| Country | Link |
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| KR (1) | KR20070107604A (en) |
| CN (1) | CN101066914B (en) |
| IT (1) | ITVA20060021A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| IT1393223B1 (en) | 2009-03-11 | 2012-04-11 | Lamberti Spa | PROCEDURE FOR THE PREPARATION OF CRYSTAL MIXTURES OF ALPHA-HYDROXICARBONYL DERIVATIVES OF ALPHA-METHYSTIRENE DIMERS |
| CN112698547B (en) * | 2019-10-23 | 2022-02-22 | 常州强力电子新材料股份有限公司 | Photo-curing composition and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4987159A (en) * | 1990-04-11 | 1991-01-22 | Fratelli Lamberti S.P.A. | Carbonyl derivatives of 1-phenylindan suitable for use as polymerization photoinitiators, their preparation and use |
| CN1529688A (en) * | 2001-04-24 | 2004-09-15 | Solid mixtures of alpha-hydroxycarbonyl derivatives of alpha-methylstyrene oligomers and theire use |
-
2006
- 2006-05-02 IT IT000021A patent/ITVA20060021A1/en unknown
-
2007
- 2007-04-27 CN CN2007101025025A patent/CN101066914B/en active Active
- 2007-05-02 KR KR1020070042563A patent/KR20070107604A/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4987159A (en) * | 1990-04-11 | 1991-01-22 | Fratelli Lamberti S.P.A. | Carbonyl derivatives of 1-phenylindan suitable for use as polymerization photoinitiators, their preparation and use |
| CN1529688A (en) * | 2001-04-24 | 2004-09-15 | Solid mixtures of alpha-hydroxycarbonyl derivatives of alpha-methylstyrene oligomers and theire use |
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| Publication number | Publication date |
|---|---|
| KR20070107604A (en) | 2007-11-07 |
| CN101066914A (en) | 2007-11-07 |
| ITVA20060021A1 (en) | 2007-11-03 |
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