CN105037158A - Dihydric alcohol hyperbranched monomer based on maleic anhydride and preparation method thereof - Google Patents
Dihydric alcohol hyperbranched monomer based on maleic anhydride and preparation method thereof Download PDFInfo
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- CN105037158A CN105037158A CN201510463781.2A CN201510463781A CN105037158A CN 105037158 A CN105037158 A CN 105037158A CN 201510463781 A CN201510463781 A CN 201510463781A CN 105037158 A CN105037158 A CN 105037158A
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- maleic anhydride
- warming
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- dibasic alcohol
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000000178 monomer Substances 0.000 title claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 128
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 108
- 239000000047 product Substances 0.000 claims description 89
- 238000010792 warming Methods 0.000 claims description 72
- 238000003756 stirring Methods 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 30
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 20
- 239000013067 intermediate product Substances 0.000 claims description 20
- 239000000155 melt Substances 0.000 claims description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 13
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000003973 paint Substances 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 28
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 28
- 238000004821 distillation Methods 0.000 description 26
- 239000000203 mixture Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 13
- 238000000016 photochemical curing Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 241001550224 Apha Species 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 3
- 241000723346 Cinnamomum camphora Species 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 229960000846 camphor Drugs 0.000 description 3
- 229930008380 camphor Natural products 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- GHVHDYYKJYXFGU-UHFFFAOYSA-N Beta-Orcinol Chemical compound CC1=CC(O)=C(C)C(O)=C1 GHVHDYYKJYXFGU-UHFFFAOYSA-N 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 150000008065 acid anhydrides Chemical group 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GNBCKKSGQPLTRW-UHFFFAOYSA-N C(C=C)(=O)OC.C(N)(O)=O Chemical compound C(C=C)(=O)OC.C(N)(O)=O GNBCKKSGQPLTRW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004851 dental resin Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/60—Maleic acid esters; Fumaric acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- 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
- C08F122/00—Homopolymers 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/12—Esters of phenols or saturated alcohols
- C08F122/20—Esters containing oxygen in addition to the carboxy oxygen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention relates to a dihydric alcohol hyperbranched monomer based on maleic anhydride. The structural formula of the monomer is shown in the description, wherein HO-(CH2)n-OH is divalent alcohol, and n is not smaller than 4. The dihydric alcohol hyperbranched monomer has the advantages as follows: (1) the monomer has four degree of functionality, is high in double bond conversion rate, and good in thermal stability; (2) the monomer is better in adhesive force and better in hardness, and can be applied to the field of paint; other advantages are also achieved. The invention also relates to a preparation method of the dihydric alcohol hyperbranched monomer based on maleic anhydride, and the preparation method has the advantages of being few in reaction steps, short in preparation cycle, simple and convenient to operate, easy to control and the like.
Description
Technical field
The present invention relates to photosensitive macromolecular material technical field, particularly relate to a kind of over-expense branched acrylic fat based on maleic anhydride as photo polymerization monomer.
Background technology
Photopolymerization (also known as photocuring) technology utilizes light (UV-light or visible ray) to cause the fluent meterial fast transition with chemical reactivity to be the process of solid matter, to be the novel green technology of coming out the sixties in 20th century.Nineteen forty-six, American I nmont company has delivered unsaturated polyester/vinylbenzene UV curing inks patent first, and to the end of the eighties, UV curing technology remains the rate of increase of average annual more than 15% always.Since entering the mid-90 in 20th century, still increase fast with the annual speed close to 10%, also had rising tendency in some field.The features such as photocuring technology has efficiently, wide adaptability, economy, energy-conservation, environmental friendliness, these features meet world to environmental protection, energy-conservation requirement, are widely used in the fields such as coating, ink, tackiness agent, imaging, microelectronics, gear division reparation and biomaterial.
Photocuring technology is with traditional heat curing techniques difference: photocuring reaction essence be by UV-light cause be polymerized, crosslinking reaction, any one photocuring system at least comprises following three parts: (1) oligopolymer (or claiming prepolymer, resin), gives material with basic physical and chemical performance; (2) monomer, also known as reactive thinner, is mainly used in the viscosity of regulation system, but also has impact to the performance of solidification rate and material; (3) light trigger, for generation of the spike (free radical or positively charged ion) of initiated polymerization.
Reactive thinner is generally the small molecules containing polymerizable functional group, is thus in the field of businessly also referred to as traditionally " monomer ".Reactive thinner can participate in polymerization crosslinking process usually, evaporate in air unlike the organic solvent in traditional solvent based coating, ink, and therefore, this advantage imparts the environmental protection characteristic of photocuring system.Reactive thinner by reactive group contained by its each molecule number, mono-functional reactive's thinner and polyfunctional group reactive thinner can be divided into.The group of curing reaction only can be participated in containing one, as methacrylic acid-β-hydroxyl ethyl ester (HEMA) in each molecule of mono-functional reactive's thinner.Polyfunctional group reactive thinner refers to the reactive thinner that can participate in curing reaction group in each molecule containing two or more, as 1,6 hexanediol diacrylate (HDDA).Adopt containing more multi-functional monomer, except increasing reactive behavior, cured film crosslinking structure can also be given.
In radiation curing composition, monomer plays a part key.Except the viscosity of regulation system, it can also have influence on cure kinetics, extent of polymerization and the physicomechanical properties generating polymkeric substance etc.Although the character of solidify material is determined by used oligopolymer substantially, main technology and safety problem but must consider the character of monomer used.
By curing mechanism, reactive thinner can be divided into free radical type and cationic two classes.(methyl) esters of acrylic acid is typical free radical type reactive thinner, and curing reaction is undertaken by radical photopolymerization.Epoxies then belongs to cationic reactive thinner, and its curing kinetics is then cationic polymerization.And vinyl ethers both can participate in radical polymerization, also can carry out cationoid polymerisation, therefore can be used as the reactive thinner of two kinds of photocuring systems.
In photocurable formulation system, reactive thinner accounts for more than 90% of whole prescription quality together with oligopolymer, and determines the physical and chemical performance that shaping rear material is basic.Desirable monomer has following characteristics: (1) polymerization shrinkage is little, state of cure is high (namely double bond conversion rate is high) and the mechanical property of material after can not reducing solidification; (2) hydrophobicity is good; (3) cheap, synthesis is simple; (4) good stability, is convenient to long-time preservation.
In the monofunctional monomer of early application, as n-butyl acrylate (n-BA), isobutyl acrylate (i-BA) are high volatile volatile thinner, be mainly used in early days preparing wood lacquer, there is the defects such as inflammable, smell is large, curing speed is low, therefore seldom adopt now.And difunctionality monomer contains two photoactive (methyl) acrylate-functional groups.Curing speed is faster than Monofunctional monomers, and the cross-linking density of film forming increases with the increase of cross-linking set thereupon, but still keeps good dilution effect.In addition, increase with monomer functionality, molecule quantitative change is large, and its volatility reduces gradually, and smell also reduces.DuyguAvci etc. with EHMA, HEA and HEMA for raw material, with C
18two acrylate chloride is obtained by reacting bifunctional (methyl) acrylic ester monomer of a series of band methylol.With DSC, its photopolymerization behavior is studied simultaneously.This kind of monomer contains pliable and tough backbone, can the shock-resistance of strongthener and toughness, has widened its Application Areas.(DuyguA, JenniferN, LonJM.Synthesisandphotopolymerizationkineticsofnewflexib lediacrylatecrosslinkersbasedonC18diacid [J] .Polymer, 2003,44:963-968) in general acrylic ester monomer photocuring post-shrinkage ratio is large, thermotolerance is poor, and the Application Areas of photo-curing material is affected.Therefore, design and development of new functional acrylic ester photoactive monomer are to expanding the Application Areas of photo-curing material and preparing high performance photo-curing material and have great importance.Traditional carbamate (methyl) acrylate is all generally carried out addition reaction preparation by isocyanic ester and hydroxyl compound and obtained.But the irritant smell of isocyanic ester, have strong impulse effect to skin, eyes and respiratory tract, toxic side effect is larger.
Summary of the invention
The object of the present invention is to provide a kind of dibasic alcohol branched monomer based on maleic anhydride, there is following advantage:
(1) this monomer is four functionality, and double bond turnover ratio is high, thermally-stabilised good;
(2) sticking power of this monomer is better, and hardness is better, can be used for paint field;
The object of the present invention is to provide a kind of preparation method of the dibasic alcohol branched monomer based on maleic anhydride, there is following advantage:
(1) reactions steps is few, and preparation cycle is short, easy and simple to handle, is easy to control.
The technical solution adopted for the present invention to solve the technical problems is: the hyperbranched monomer of a kind of dibasic alcohol based on maleic anhydride, and its structural formula is as follows:
Wherein
for dibasic alcohol, n>=4.
Particularly, described dibasic alcohol is ethylene glycol, the one in propylene glycol, butyleneglycol, pentanediol, hexylene glycol, polyoxyethylene glycol.
As above based on a preparation method for the hyperbranched monomer of dibasic alcohol of maleic anhydride, comprise the steps:
Step one: with dibasic alcohol, maleic anhydride and glyceral methacrylate for first-generation product prepared by raw material, its structural formula is:
Step 2: with first-generation product, maleic anhydride and glyceral methacrylate for s-generation product prepared by raw material, be target product: the hyperbranched monomer of the dibasic alcohol based on maleic anhydride, its structural formula is:
As preferably, the concrete steps of described step one are:
(1) by 1 part of dibasic alcohol, 3-4 part maleic anhydride joins in reaction vessel, mixes, be warming up to 60-70 DEG C, and add catalyzer and stopper, after maleic anhydride melts, be warming up to 80-85 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, dry, remove solvent, obtain intermediate product;
(2) by 2-3 part glycidyl methacrylate, catalysts and solvents joins in reaction vessel, is warming up to 70 DEG C, intermediate product in 1 part of step (1) is dropwise instilled in reactor, drips off in 0.5-1h, then reaction system is warming up to 85 DEG C, after continuing to stir 5h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times, filter, drying, removes solvent, obtains first-generation product.
As preferably, the concrete steps of described step 2 are:
(1) by 1 part of first-generation product G1,3-4 part maleic anhydride joins in reaction vessel, mixes, be warming up to 60-70 DEG C, and add catalyzer and stopper, after maleic anhydride melts, be warming up to 80-85 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, dry, remove solvent, obtain intermediate product;
(2) by 2-3 part glycidyl methacrylate, catalysts and solvents joins in reaction vessel, is warming up to 70 DEG C, intermediate product in 1 part of step (3) is dropwise instilled in reactor, drips off in 0.5-1h, then reaction system is warming up to 85 DEG C, after continuing to stir 5h, be cooled to room temperature, be extracted with ethyl acetate product, then wash 2 ~ 3 times with water, filter, drying, removes solvent, obtains s-generation product.
Particularly, the catalyzer in described step (1) is the one in the vitriol oil, concentrated hydrochloric acid, tosic acid, methanesulfonic and sulfur oxychloride, and its weight added is the 2-5wt% of reaction system.
Particularly, described step (1) stopper is the one in MEHQ, cuprous chloride, Resorcinol, para benzoquinone and 2,5-dimethyl Resorcinol, and its weight added is the 1-5wt ‰ of reaction system.
Particularly, the catalyzer in described step (2) is the one in Tetrabutyl amonium bromide, tetramethyl ammonium chloride, triethylamine, DMA and triphenyl phosphorus, and its weight added is the 2-5wt% of reaction system.
The present invention is from Molecular Structure Design, (for butyleneglycol) two hydroxyls first on dibasic alcohol open the acid anhydride structure on maleic anhydride, generate intermediate product G0.5, then opened the epoxy construction on GMA by the carboxyl of two on G0.5, obtain generation product G1, two hydroxyls then on G1 open the acid anhydride structure on maleic anhydride, generate intermediate product G1.5, then two carboxyls on G1.5 open the epoxy construction on GMA, obtain two generation product, i.e. final product G2.
Prepared by the present invention, a kind of whole reaction equation of the dibasic alcohol branched monomer based on maleic anhydride can be expressed as: (for BDO)
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is photopolymerization double bond conversion rate-time diagram that cracking type initiator 184 causes the G2 that embodiment 1 obtains;
Fig. 2 is that each formula is along with temperature rising thermogravimetric curve figure.
Embodiment
In conjunction with the accompanying drawings, the present invention is further detailed explanation.These accompanying drawings are the schematic diagram of simplification, only basic structure of the present invention are described in a schematic way, and therefore it only shows the formation relevant with the present invention.
Embodiment 1
(1) by 0.1mol (9.1g) butyleneglycol, 0.3mol (29.4g) maleic anhydride joins in reaction vessel, mix, stirring is warming up to 60 DEG C, and add catalyzer tosic acid (0.77g, the 2wt% of reaction system) and stopper MEHQ (0.19g, the 5wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be extracted with ethyl acetate product, then wash 2 ~ 3 times with water, filter, anhydrous sodium sulfate drying, underpressure distillation, except desolventizing, obtains generation product G0.5.
(2) by the glycidyl methacrylate (GMA) of 0.2mol (28.4g), catalyzer tetrabutylammonium chloride (1.14g, the 2wt% of reaction system) and stopper MEHQ (0.29g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by 1 part of G0.5 (0.1mol, 28.8g) dropwise instill in reactor, drip off in 0.5h, then reaction system is warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times, filter, and with anhydrous sodium sulfate drying, revolve steaming, obtain first-generation product G1.
(3) by the first-generation product G1 of 0.1mol (57.05g), the maleic anhydride of 0.3mol (29.4g) joins in reaction vessel, mix, stirring is warming up to 60 DEG C, and add catalyzer tosic acid (1.73g, the 2wt% of reaction system) and stopper MEHQ (0.43g, the 5wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain intermediate product G1.5.
(4) by the glycidyl methacrylate (GMA) of 0.2mol (28.4g), catalyzer tetrabutylammonium chloride (1.98g, the 2wt% of reaction system) and stopper MEHQ (0.49g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by 1 part of G1.5 (0.1mol, 70.6g) dropwise instill in reactor, drip off in 0.5h, then reaction system is warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain s-generation product G2, i.e. target product 105.1g.
The basic physical properties test of product: viscosity (cps25 DEG C) 1010, colourity (APHA/Gardner) 380, specific refractory power 1.517, surface tension (Dynes/cm20 DEG C) 82.3.
Embodiment 2
(1) by 0.1mol (9.1g) butyleneglycol, 0.3mol (29.4g) maleic anhydride joins in reaction vessel, mix, stirring is warming up to 60 DEG C, and add catalyzer tosic acid (0.77g, the 2wt% of reaction system) and stopper MEHQ (0.19g, the 5wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be extracted with ethyl acetate product, then wash 2 ~ 3 times with water, filter, anhydrous sodium sulfate drying, underpressure distillation, except desolventizing, obtains generation product G0.5.。
(2) by the glycidyl methacrylate (GMA) of 0.21mol (29.9g), catalyzer tetrabutylammonium chloride (1.17g, the 2wt% of reaction system) and stopper MEHQ (0.29g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by the reaction product (0.1mol in 1 part of step (1), 28.8g) dropwise instill in reactor, drip off in 0.5h, then reaction system is warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain first-generation product G1.
(3) by the first-generation product G1 of 0.1mol (50.05g), the maleic anhydride of 0.3mol (29.4g) joins in reaction vessel, mix, stirring is warming up to 60 DEG C, and add catalyzer tosic acid (1.59g, the 2wt% of reaction system) and stopper MEHQ (0.39g, the 5wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain intermediate product G1.5.
(4) by the glycidyl methacrylate (GMA) of 0.21mol (29.9), catalyzer tetrabutylammonium chloride (2.04g, the 2wt% of reaction system) and stopper MEHQ (0.51g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by 1 part of G1.5 (0.1mol, 72.2g) dropwise instill in reactor, drip off in 0.5h, then reaction system is warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain s-generation product G2, i.e. target product 103.2g.
The basic physical properties test of product: viscosity (cps25 DEG C) 1005, colourity (APHA/Gardner) 374, specific refractory power 1.613, surface tension (Dynes/cm20 DEG C) 81.3.
Embodiment 3
(1) by 0.1mol (9.1g) butyleneglycol, 0.3mol (29.4g) maleic anhydride joins in reaction vessel, mix, stirring is warming up to 60 DEG C, and add catalyzer tosic acid (0.77g, the 2wt% of reaction system) and stopper MEHQ (0.19g, the 5wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be extracted with ethyl acetate product, then wash 2 ~ 3 times with water, filter, anhydrous sodium sulfate drying, underpressure distillation, except desolventizing, obtains generation product G0.5.。
(2) by the glycidyl methacrylate (GMA) of 0.22mol (31.28g), catalyzer tetrabutylammonium chloride (1.21g, the 2wt% of reaction system) and stopper MEHQ (0.30g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by the reaction product (0.1mol in 1 part of step (1), 28.8g) dropwise instill in reactor, drip off in 0.5h, then reaction system is warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain first-generation product G1.
(3) by the first-generation product G1 of 0.1mol (48.01g), the maleic anhydride of 0.3mol (29.4g) joins in reaction vessel, mix, stirring is warming up to 60 DEG C, and add catalyzer tosic acid (1.55g, the 2wt% of reaction system) and stopper MEHQ (0.39g, the 5wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain intermediate product G1.5.
(4) by the glycidyl methacrylate (GMA) of 0.22mol (31.28g), catalyzer tetrabutylammonium chloride (2.03g, the 2wt% of reaction system) and stopper MEHQ (0.51g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by 1 part of G1.5 (0.1mol, 70.6g) dropwise instill in reactor, drip off in 0.5h, then reaction system is warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain s-generation product G2, i.e. target product 104.9g.
The basic physical properties test of product: viscosity (cps25 DEG C) 1003, colourity (APHA/Gardner) 372, specific refractory power 1.601, surface tension (Dynes/cm20 DEG C) 80.3.
Embodiment 4
(1) by 0.1mol (9.1g) butyleneglycol, 0.3mol (29.4g) maleic anhydride joins in reaction vessel, mix, stirring is warming up to 70 DEG C, and add catalyzer tosic acid (0.77g, the 2wt% of reaction system) and stopper MEHQ (0.19g, the 5wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain intermediate product G0.5.
(2) by the glycidyl methacrylate (GMA) of 0.22mol (31.28g), catalyzer tetrabutylammonium chloride (2.03g, the 2wt% of reaction system) and stopper MEHQ (0.51g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by the reaction product (0.1mol in 1 part of step (1), 28.8g) dropwise instill in reactor, drip off in 0.5h, then reaction system is warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain first-generation product G1.
(3) by the first-generation product G1 of 0.1mol (48.01g), the maleic anhydride of 0.3mol (29.4g) joins in reaction vessel, mix, stirring is warming up to 70 DEG C, and add catalyzer tosic acid (1.55g, the 2wt% of reaction system) and stopper MEHQ (0.39g, the 5wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain intermediate product G1.5.
(4) by the glycidyl methacrylate (GMA) of 0.22mol (31.28g), catalyzer tetrabutylammonium chloride (2.03g, the 2wt% of reaction system) and stopper MEHQ (0.51g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by 1 part of G1.5 (0.1mol, 70.6g) dropwise instill in reactor, drip off in 0.5h, then reaction system is warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain s-generation product G2, i.e. target product 104.1g.
The basic physical properties test of product: viscosity (cps25 DEG C) 1008, colourity (APHA/Gardner) 381, specific refractory power 1.589, surface tension (Dynes/cm20 DEG C) 84.3.
Embodiment 5
(1) by 0.1mol (9.1g) butyleneglycol, 0.33mol (32.34g) maleic anhydride joins in reaction vessel, mix, stirring is warming up to 70 DEG C, and add catalyzer tosic acid (1.24g, the 3wt% of reaction system) and stopper MEHQ (0.17g, the 4wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain intermediate product G0.5.
(2) by the glycidyl methacrylate (GMA) of 0.22mol (31.28g), catalyzer tetrabutylammonium chloride (2.03g, the 2wt% of reaction system) and stopper MEHQ (0.51g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by the reaction product (0.1mol in 1 part of step (1), 28.8g) dropwise instill in reactor, drip off in 0.5h, then reaction system is warming up to 85 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain first-generation product G1.
(3) by the first-generation product G1 of 0.1mol (48.01g), the maleic anhydride of 0.33mol (32.34g) joins in reaction vessel, mix, stirring is warming up to 70 DEG C, and add catalyzer tosic acid (2.41g, the 3wt% of reaction system) and stopper MEHQ (0.32g, the 4wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing G1.5.
(4) by the glycidyl methacrylate (GMA) of 0.22mol (31.28g), catalyzer tetrabutylammonium chloride (2.03g, the 2wt% of reaction system) and stopper MEHQ (0.51g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by 1 part of G1.5 (0.1mol, 70.6g) dropwise instill in reactor, drip off in 0.5h, then reaction system is warming up to 85 DEG C, after continuing to stir 4h, be cooled to room temperature and be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain s-generation product G2, i.e. target product 100.4g.
The basic physical properties test of product: viscosity (cps25 DEG C) 1008, colourity (APHA/Gardner) 381, specific refractory power 1.589, surface tension (Dynes/cm20 DEG C) 84.3.
Embodiment 6
(1) by 0.1mol (9.1g) butyleneglycol, 0.35mol (34.3g) maleic anhydride joins in reaction vessel, mix, stirring is warming up to 70 DEG C, and add catalyzer tosic acid (1.74g, the 4wt% of reaction system) and stopper MEHQ (0.22g, the 5wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain intermediate product G0.5.
(2) by the glycidyl methacrylate (GMA) of 0.25mol (35.55g), catalyzer tetrabutylammonium chloride (1.29g, the 2wt% of reaction system) and stopper MEHQ (0.32g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by the reaction product (0.1mol in 1 part of step (1), 28.8g), drip off in 0.5h, then reaction system is warming up to 85 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain first-generation product G1.
(3) by the first-generation product G1 of 0.1mol (48.01g), the maleic anhydride of 0.35mol (34.3g) joins in reaction vessel, mix, stirring is warming up to 70 DEG C, and add catalyzer tosic acid (3.29g, the 4wt% of reaction system) and stopper MEHQ (0.41g, the 5wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain intermediate product G1.5.
(4) by the glycidyl methacrylate (GMA) of 0.25mol (31.28g), catalyzer tetrabutylammonium chloride (2.04g, the 2wt% of reaction system) and stopper MEHQ (0.51g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by 1 part of G1.5 (0.1mol, 70.6g) dropwise instill in reactor, drip off in 0.5h, then reaction system is warming up to 85 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain s-generation product G2, i.e. target product 101.8g.
The basic physical properties test of product: viscosity (cps25 DEG C) 1001, colourity (APHA/Gardner) 376, specific refractory power 1.591, surface tension (Dynes/cm20 DEG C) 85.1.
Embodiment 7
(1) by 0.1mol (9.1g) butyleneglycol, 0.4mol (39.2g) maleic anhydride joins in reaction vessel, mix, stirring is warming up to 70 DEG C, and add catalyzer tosic acid (0.97g, the 2wt% of reaction system) and stopper MEHQ (0.24g, the 5wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain intermediate product G0.5.
(2) by the glycidyl methacrylate (GMA) of 0.3mol (42.66g), catalyzer tetrabutylammonium chloride (1.43g, the 2wt% of reaction system) and stopper MEHQ (0.36g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by the reaction product (0.1mol in 1 part of step (1), 28.8g), drip off in 0.5h, then reaction system is warming up to 85 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times, filter, and with anhydrous sodium sulfate drying, revolve steaming, obtain first-generation product G1.
(3) by the first-generation product G1 of 0.1mol (48.01g), the maleic anhydride of 0.4mol (39.2g) joins in reaction vessel, mix, stirring is warming up to 70 DEG C, and add catalyzer tosic acid (1.74g, the 2wt% of reaction system) and stopper MEHQ (0.16g, the 5wt ‰ of reaction system), after maleic anhydride melts, be warming up to 80 DEG C, after continuing to stir 4h, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain intermediate product G1.5.
(4) by the glycidyl methacrylate (GMA) of 0.3mol (42.66g), catalyzer tetrabutylammonium chloride (2.27g, the 2wt% of reaction system) and stopper MEHQ (0.57g, the 5wt ‰ of reaction system) join in reaction vessel, be warming up to 70 DEG C, by 1 part of G1.5 (0.1mol, 70.6g) dropwise instill in reactor, dropwise instill in reactor, drip off in 0.5h, then reaction system is warming up to 85 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, anhydrous sodium sulfate drying, underpressure distillation is except desolventizing, obtain s-generation product G2, i.e. target product 102.6g.
The basic physical properties test of product: viscosity (cps25 DEG C) 418, colourity (APHA/Gardner) 169, specific refractory power 1.3208, surface tension (Dynes/cm20 DEG C) 44.8.
Application Example:
Solidification rate:
The hyperbranched monomer of the s-generation obtained with embodiment 1, the crack type photoinitiator 184 of hyperbranched for butyleneglycol s-generation monomer and different concns is mixed with polymerization system (initiator concentration: 0.5%, 1%, 2%, 3%, 4%), ultrasonic vibration 2 minutes guarantee systems mix, then, getting micro-example spreads upon on pressing potassium bromide troche, at room temperature with being with the EFOSLite pointolite of 400-500nm wave band filter plate with 500mW/cm
2light intensity irradiate sample 5 minutes, be furnished with the RTIR of horizontal sample platform by monitoring 800-850cm
-1the change of acrylic double bond charateristic avsorption band peak area reflects the degree of polymerization system intuitively.Specifically formula is as follows for it:
| Formula | Two generation hyperbranched monomer | Initiator 184 |
| 1 | 4.0g | 0.5％ |
| 2 | 4.0g | 1％ |
| 3 | 4.0g | 2％ |
| 4 | 4.0g | 3％ |
| 5 | 4.0g | 4％ |
Its result as shown in Figure 1, as can be seen from Figure 1, can be polymerized for 300 seconds completely, and when initiator concentration 4%, acrylate double bond conversion rate is close to 72.5% by hyperbranched s-generation monomer G2 UV illumination.
Thermomechanical property:
The formula system that the present invention prepares G3, carries out thermogravimetic analysis (TGA), adopts general dental resin formula system (Guangzhou Chen Fa Medical Devices Co., Ltd.-resin CN1005,60 parts; Sartomer Guangdong Chemical Co., Ltd.-thinner PETTA, 40 parts; Jining Ming Da novel material company limited-female CQ of initiator camphor, 1.5 parts; System Qi chemical industry (Shanghai) Co., Ltd.-mineral filler SiO
2, 50 parts), change integral part and the content of monomer (PETTA) wherein and G2, the thermostability of observe system.As shown in Figure 2, when G2 substitutes monomer PETTA, the better heat stability of whole system, starts to decompose about 330 DEG C greatly its result.
The formula system that the present invention prepares G3, carries out adhesion performance test, and the formula system of employing is:
System formulation is as follows: (Guangzhou Chen Fa Medical Devices Co., Ltd.-resin CN1005,60 parts; Thinner G2,40 parts; Jining Ming Da novel material company limited-female CQ of initiator camphor, 1.5 parts; System Qi chemical industry (Shanghai) Co., Ltd.-mineral filler SiO2,50 parts)
Unlike material sticking power is tested: (iso standard-T9999358)
| Sample material | Grade |
| PP | 4 |
| Iron plate | 0 |
| 100mmPET | 0 |
| 200mmPET | 0 |
| 50mmPET | 0 |
| Tinplate | 2 |
| Simple glass | 1 |
Pencil hardness test:
The formula system that the present invention prepares G3, carries out pencil hardness test, and the formula system of employing is:
System formulation is as follows: (Guangzhou Chen Fa Medical Devices Co., Ltd.-resin CN1005,60 parts; Thinner G2,40 parts; Jining Ming Da novel material company limited-female CQ of initiator camphor, 1.5 parts; System Qi chemical industry (Shanghai) Co., Ltd.-mineral filler SiO2,50 parts)
| Pencil specification | Test result |
| 6H | Broken |
| 5H | Broken |
| 4H | Do not break |
| 3H | Do not break |
| 2H | Do not break |
| H | Do not break |
| B | Do not break |
| HB | Do not break |
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to right.
Claims (8)
1., based on the hyperbranched monomer of dibasic alcohol of maleic anhydride, its structural formula is as follows:
Wherein
for dibasic alcohol, n>=4.
2. the hyperbranched monomer of a kind of dibasic alcohol based on maleic anhydride as claimed in claim 1, is characterized in that: described dibasic alcohol is ethylene glycol, the one in propylene glycol, butyleneglycol, pentanediol, hexylene glycol, polyoxyethylene glycol.
3., as claimed in claim 1 or 2 based on a preparation method for the hyperbranched monomer of dibasic alcohol of maleic anhydride, comprise the steps:
Step one: with dibasic alcohol, maleic anhydride and glyceral methacrylate for first-generation product prepared by raw material, its structural formula is:
Step 2: with first-generation product, maleic anhydride and glyceral methacrylate for s-generation product prepared by raw material, its structural formula is:
4. the preparation method of the hyperbranched monomer of a kind of dibasic alcohol based on maleic anhydride as claimed in claim 3, is characterized in that: the concrete steps of described step one are:
(1) by 1 part of dibasic alcohol, 3-4 part maleic anhydride joins in reaction vessel, mixes, be warming up to 60-70 DEG C, and add catalyzer and stopper, after maleic anhydride melts, be warming up to 80-85 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, dry, remove solvent, obtain intermediate product;
(2) by 2-3 part glycidyl methacrylate, catalysts and solvents joins in reaction vessel, is warming up to 70 DEG C, intermediate product in 1 part of step (1) is dropwise instilled in reactor, drips off in 0.5-1h, then reaction system is warming up to 85 DEG C, after continuing to stir 5h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times, filter, drying, removes solvent, obtains first-generation product.
5. the preparation method of the hyperbranched monomer of a kind of dibasic alcohol based on maleic anhydride as claimed in claim 3, is characterized in that: the concrete steps of described step 2 are:
(1) by 1 part of first-generation product, 3-4 part maleic anhydride joins in reaction vessel, mixes, be warming up to 60-70 DEG C, and add catalyzer and stopper, after maleic anhydride melts, be warming up to 80-85 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, wash 2 ~ 3 times again with water, filter, dry, remove solvent, obtain intermediate product;
(2) by 2-3 part glycidyl methacrylate, catalysts and solvents joins in reaction vessel, is warming up to 70 DEG C, intermediate product in 1 part of step (3) is dropwise instilled in reactor, drips off in 0.5-1h, then reaction system is warming up to 85 DEG C, after continuing to stir 4h, be cooled to room temperature, be extracted with ethyl acetate product, then wash 2 ~ 3 times with water, filter, drying, removes solvent, obtains s-generation product.
6. the preparation method of the hyperbranched monomer of a kind of dibasic alcohol based on maleic anhydride as described in any one of claim 4-5, it is characterized in that: the catalyzer in described step (1) is the one in the vitriol oil, concentrated hydrochloric acid, tosic acid, methanesulfonic and sulfur oxychloride, and its weight added is the 2-5wt% of reaction system.
7. the preparation method of the hyperbranched monomer of a kind of dibasic alcohol based on maleic anhydride as described in any one of claim 4-5, it is characterized in that: described step (1) stopper is MEHQ, cuprous chloride, Resorcinol, para benzoquinone and 2, one in 5-dimethyl Resorcinol, its weight added is the 1-5wt ‰ of reaction system.
8. the preparation method of the hyperbranched monomer of a kind of dibasic alcohol based on maleic anhydride as described in any one of claim 4-5, it is characterized in that: the catalyzer in described step (2) is Tetrabutyl amonium bromide, tetramethyl ammonium chloride, triethylamine, N, one in accelerine and triphenyl phosphorus, its weight added is the 2-5wt% of reaction system.
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