CN104876822B - A kind of preparation method of pentaerythritol acrylate - Google Patents
A kind of preparation method of pentaerythritol acrylate Download PDFInfo
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- CN104876822B CN104876822B CN201410070354.3A CN201410070354A CN104876822B CN 104876822 B CN104876822 B CN 104876822B CN 201410070354 A CN201410070354 A CN 201410070354A CN 104876822 B CN104876822 B CN 104876822B
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- organic phase
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- pentaerythritol acrylate
- polymerization inhibitor
- pentaerythritol
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- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 135
- 239000012074 organic phase Substances 0.000 claims abstract description 126
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 43
- 239000003112 inhibitor Substances 0.000 claims abstract description 40
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 39
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 35
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 63
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 29
- 150000007513 acids Chemical class 0.000 claims description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 18
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 claims description 13
- 235000011150 stannous chloride Nutrition 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 6
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001119 stannous chloride Substances 0.000 claims description 6
- 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 6
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 44
- 239000003795 chemical substances by application Substances 0.000 abstract description 29
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 150000007942 carboxylates Chemical class 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 58
- 238000013517 stratification Methods 0.000 description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 239000011780 sodium chloride Substances 0.000 description 29
- 230000000694 effects Effects 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 18
- 230000008569 process Effects 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- 238000009835 boiling Methods 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 14
- 238000007664 blowing Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 238000011085 pressure filtration Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 238000004811 liquid chromatography Methods 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 7
- 235000019345 sodium thiosulphate Nutrition 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- LKMPHZSEWBUEPW-UHFFFAOYSA-N sulfur dioxide;urea Chemical compound O=S=O.NC(N)=O LKMPHZSEWBUEPW-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 150000004053 quinones Chemical class 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- -1 sodium aluminates Chemical class 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000255964 Pieridae Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229960003742 phenol Drugs 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- SNDJGKIVHKOEHY-UHFFFAOYSA-M S(=S)(=O)(O)O.S[Na] Chemical compound S(=S)(=O)(O)O.S[Na] SNDJGKIVHKOEHY-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
Abstract
The invention discloses a kind of preparation method of pentaerythritol acrylate, belong to carboxylate preparing technical field.Methods described includes：Pentaerythrite, acrylic acid, solvent, catalyst and the first polymerization inhibitor are added into reactor；Make reaction system back flow reaction under preset temperature, the mol ratio of tracking pentaerythritol triacrylate and tetramethylol methane tetraacrylate to 1:When 3 10, terminate reaction；After the cooling of question response system, it is washed, alkali cleaning, take the first organic phase；The first organic phase is washed using reducing agent, neutrality is then washed to, takes Second Organic Phase；The second polymerization inhibitor is added into Second Organic Phase, vacuum distillation, filtering are carried out to it, pentaerythritol acrylate is obtained.The present invention, as decolorising agent, prepares the pentaerythritol acrylate for having low hydroxyl value and low colourity concurrently by using the reducing agent with the reaction of the polymerization inhibitor of oxidation.The method that the present invention is provided is simple, easy to control, is easy to scale industrial production.
Description
Technical field
The present invention relates to carboxylate preparing technical field, more particularly to a kind of preparation method of pentaerythritol acrylate.
Background technology
Pentaerythritol acrylate is a kind of polyfunctionality polymerized monomer, including pentaerythritol triacrylate and season penta 4
Alcohol tetraacrylate.Pentaerythritol acrylate contains highdensity carbon-to-carbon double bond structure, with excellent laser curing velocity and
High crosslink density, can be widely used in photocureable coating, photocuring adhesive, liquid photoresist, optical thin film and attachment
The fields such as power accelerator.
At present, pentaerythritol acrylate is prepared usually through following methods：By toluene, p-methyl benzenesulfonic acid, phenols inhibition
Agent, pentaerythrite and acrylic acid are added in reactor, at a certain temperature, reaction system reflux dewatering is carried out esterification.
After esterification terminates, multiple alkali cleaning and washing are carried out to reaction system, organic phase is taken, and vacuum distillation is carried out to the organic phase
Toluene is sloughed, that is, obtains pentaerythritol acrylate.Because in esterification reaction process, phenolic inhibitor is easily oxidized to quinone
Class, makes the color of prepared pentaerythritol acrylate deeper, is unfavorable for the application of pentaerythritol acrylate.So, it is existing
There is technology by adding activated carbon into reaction system to adsorb quinones, so as to decolourize to pentaerythritol acrylate.
During the present invention is realized, inventor has found that prior art at least has problems with：
For the pentaerythritol acrylate that color is deeper（The color problem of especially low hydroxyl value pentaerythritol acrylate
It is even more serious）, prior art decolourized using activated carbon, due to the limited sorption capacity of activated carbon, its effect decolourized compared with
Difference, the colourity of the pentaerythritol acrylate after decolouring is still higher, seriously limits the application of pentaerythritol acrylate.
The content of the invention
In order to solve the problem of prior art is poor to pentaerythritol acrylate decolorizing effect, the embodiment of the present invention is provided
A kind of preparation method of pentaerythritol acrylate.The technical scheme is as follows：
The embodiments of the invention provide a kind of preparation method of pentaerythritol acrylate, methods described includes：To reaction
Pentaerythrite, acrylic acid, solvent, catalyst and the first polymerization inhibitor are added in device, and the reactor is heated to preset temperature；
Make reaction system back flow reaction under the preset temperature, track the acrylic acid of pentaerythrite three in the reaction system
The mol ratio of ester and tetramethylol methane tetraacrylate, when the pentaerythritol triacrylate and pentaerythrite tetrapropylene acid
The mol ratio of ester is 1:During 3-10, terminate the back flow reaction；
After after reaction system cooling, the reaction system is washed respectively, alkali cleaning, take the first organic phase；
First organic phase is washed using reducing agent, neutrality then is washed to first organic phase again,
Take Second Organic Phase；
The second polymerization inhibitor is added into the Second Organic Phase, vacuum distillation, filtering are carried out to the Second Organic Phase, is obtained
To the pentaerythritol acrylate.
Specifically, preferably, the reducing agent be selected from double (2- methoxyethoxies) sodium aluminates of thiourea dioxide, dihydro,
At least one of sodium sulfite, hypo solution.
Specifically, preferably, the thiourea dioxide, dihydro double (2- methoxyethoxies) sodium aluminate, sodium sulfite, sulphur
The mass concentration of sodium thiosulfate solution is 5%-10%.
Preferably, the mol ratio of the pentaerythrite and the acrylic acid is 1:4-8.
Specifically, the solvent is selected from least one of hexamethylene, toluene, ethyl acetate, and the quality of the solvent is
The pentaerythrite and the 40%-80% of the acrylic acid gross mass.
Specifically, the catalyst is selected from least one of p-methyl benzenesulfonic acid, pyrovinic acid, solid super-strong acid, described
The quality of catalyst is the pentaerythrite and the 1.0%-4.0% of the acrylic acid gross mass.
Specifically, first polymerization inhibitor be selected from MEHQ, hydroquinones, Salzburg vitriol, stannous chloride,
At least one of p-t-butyl phenol, p-tert-Butylcatechol, the quality of first polymerization inhibitor is the pentaerythrite
With the 0.05%-0.5% of the acrylic acid gross mass.
Preferably, second polymerization inhibitor be selected from MEHQ, hydroquinones, p-t-butyl phenol, to tertiary fourth
At least one of base catechol, the quality of second polymerization inhibitor is the 0.05%-0.5% of the Second Organic Phase quality.
Preferably, the preset temperature is 80-100 DEG C.
Preferably, the temperature control during progress vacuum distillation to the Second Organic Phase is at 40 DEG C -80 DEG C.
The beneficial effect that technical scheme provided in an embodiment of the present invention is brought is：
The embodiments of the invention provide a kind of preparation method of pentaerythritol acrylate, by with solvent, catalyst and
Premised on first polymerization inhibitor is present, pentaerythrite and acrylic acid is carried out back flow reaction under preset temperature, obtain pentaerythrite
Triacrylate and tetramethylol methane tetraacrylate, and control its mol ratio to be 1:3-10, so as to obtain low hydroxyl value season penta
Tetrol acrylate, its hydroxyl value can reach less than 30mgKOH/g；In order to obtain the pentaerythrite third that hydroxyl value is less than 30mgKOH/g
Olefin(e) acid ester, the reaction time will be partially long, causes its colourity to be more than 50APHA, or even 100APHA, adds decolouring difficulty.And this
The reducing agent that invention is reacted by using the polymerization inhibitor being merely able to being aoxidized in reaction system is as decolorising agent, so as to oxidation
Polymerization inhibitor is reduced, and low hydroxyl value pentaerythritol acrylate is decolourized, so its decolorizing effect can be made extremely obvious,
Colourity can reach the level less than 30APHA, so that the pentaerythritol acrylate for having low hydroxyl value and low colourity concurrently is prepared,
Practical application is with the obvious advantage；In addition, method provided in an embodiment of the present invention is easy to operate, and it is easy to control, it is easy to large-scale industrial to give birth to
Production.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, makes required in being described below to embodiment
Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for
For those of ordinary skill in the art, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is a kind of preparation method flow chart of pentaerythritol acrylate provided in an embodiment of the present invention；
Fig. 2 is a kind of preparation method flow chart for pentaerythritol acrylate that further embodiment of this invention is provided.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing to embodiment party of the present invention
Formula is described in further detail.
Embodiment 1
As shown in Figure 1, the embodiments of the invention provide a kind of preparation method of pentaerythritol acrylate, this method bag
Include：
Step 101：Pentaerythrite, acrylic acid, solvent, catalyst and the first polymerization inhibitor are added into reactor, and should
Reactor is heated to preset temperature.
Step 102：Make the propylene of pentaerythrite three in reaction system back flow reaction under the preset temperature, tracking reaction system
The mol ratio of acid esters and tetramethylol methane tetraacrylate, when rubbing for pentaerythritol triacrylate and tetramethylol methane tetraacrylate
You are than being 1:During 3-10, terminate back flow reaction.
Step 103：After after reaction system cooling, the reaction system is washed respectively, alkali cleaning, taken first organic
Phase.
Step 104：First organic phase is washed using reducing agent, in being then washed to again to first organic phase
Property, take Second Organic Phase.
Step 105：The second polymerization inhibitor is added into the Second Organic Phase, vacuum distillation, mistake are carried out to the Second Organic Phase
Filter, obtains pentaerythritol acrylate.
The embodiments of the invention provide a kind of preparation method of pentaerythritol acrylate, by with solvent, catalyst and
Premised on first polymerization inhibitor is present, pentaerythrite and acrylic acid is carried out back flow reaction under preset temperature, obtain pentaerythrite
Triacrylate and tetramethylol methane tetraacrylate, and control its mol ratio to be 1:3-10, so as to obtain low hydroxyl value season penta
Tetrol acrylate, its hydroxyl value can reach less than 30mgKOH/g；In order to obtain the pentaerythrite third that hydroxyl value is less than 30mgKOH/g
Olefin(e) acid ester, the reaction time will be partially long, causes its colourity to be more than 50APHA, or even 100APHA, adds decolouring difficulty.And this
Invention is logical use and is merely able to reducing agent that the polymerization inhibitor with being aoxidized in reaction system reacts as decolorising agent, so that the resistance to oxidation
Poly- agent is reduced, and low hydroxyl value pentaerythritol acrylate is decolourized, so its decolorizing effect can be made extremely obvious, color
Degree can reach the level less than 30APHA, so that the pentaerythritol acrylate for having low hydroxyl value and low colourity concurrently is prepared, it is real
Border application advantage is obvious；In addition, method provided in an embodiment of the present invention is easy to operate, and it is easy to control, it is easy to scale industrial production.
Embodiment 2
As shown in Figure 2, the embodiments of the invention provide a kind of preparation method of pentaerythritol acrylate, this method bag
Include：
Step 201：Ji Wusi is added in equipped with thermometer, water knockout drum, serpentine condenser, the four-hole boiling flask of agitating paddle
Alcohol, acrylic acid, solvent, catalyst and the first polymerization inhibitor, and the reactor is heated to 80-100 DEG C.
Specifically, the mol ratio of pentaerythrite and acrylic acid is 1:4-8, preferably 1:4-6.5.In the embodiment of the present invention,
The mol ratio for ensureing pentaerythritol triacrylate and tetramethylol methane tetraacrylate is 1:3-10, and ensure pentaerythrite and third
The higher conversion ratio of olefin(e) acid, 1 is defined as by the mol ratio of pentaerythrite and acrylic acid:4-8, preferably 1:4-6.5.Matched somebody with somebody by above-mentioned
The pentaerythrite and acrylic acid of ratio prepare desired low hydroxyl value pentaerythritol acrylate.
Wherein, the first polymerization inhibitor be selected from MEHQ, hydroquinones, Salzburg vitriol, stannous chloride, to tertiary fourth
At least one of base phenol, p-tert-Butylcatechol, preferably Salzburg vitriol, stannous chloride；First polymerization inhibitor
Quality is pentaerythrite and the 0.05%-0.5% of acrylic acid gross mass.
During the course of the reaction, the amount of polymerization inhibitor is very few to cause polymerization inhibition effect unobvious, cause reactant partial polymerization, resistance
The amount of poly- agent excessively can further influence product color.Consider from factors such as polymerization inhibition effect, product colors, the embodiment of the present invention is excellent
Select p-tert-Butylcatechol, p-t-butyl phenol, MEHQ, Salzburg vitriol and stannous chloride.By above-mentioned
The control of one polymerization inhibitor can reach preferable polymerization inhibition effect in pentaerythrite and the 0.05%-0.5% of acrylic acid gross mass.For
It is easy in follow-up water-washing step, the polymerization inhibitor of part first can be removed, Salzburg vitriol, stannous chloride is as entering one
What is walked is preferred.
Solvent is selected from least one of hexamethylene, toluene, ethyl acetate；The quality of the solvent is pentaerythrite and propylene
The 40%-80% of sour gross mass, preferably 50%-70%.
Catalyst is selected from least one of p-methyl benzenesulfonic acid, pyrovinic acid, solid super-strong acid；The quality of the catalyst is
Pentaerythrite and the 1.0%-4.0% of acrylic acid gross mass.Consider from factors such as catalytic effect, product color, production costs, this hair
The bright preferred pyrovinic acid of embodiment catalyst and p-methyl benzenesulfonic acid, its consumption is preferably pentaerythrite and acrylic acid gross mass
1.5%-3.0%。
Step 202：Make reaction system back flow reaction at 80-100 DEG C, track the propylene of pentaerythrite three in the reaction system
The mol ratio of acid esters and tetramethylol methane tetraacrylate, when rubbing for pentaerythritol triacrylate and tetramethylol methane tetraacrylate
You are than being 1:During 3-10, terminate back flow reaction.
Pentaerythrite and acrylic acid in reaction system carry out esterification in reaction medium solvent, while generating season penta
Tetrol triacrylate and tetramethylol methane tetraacrylate.Because the generated time of tetramethylol methane tetraacrylate is longer, in order to
Improve the reaction rate of esterification, preferred 80-100 DEG C of reaction temperature of the embodiment of the present invention.And under the reaction temperature, make anti-
System is answered to flow back 15-20 hours, to ensure reaction fully and completely.Specifically, by using high performance liquid chromatography, according to season penta
The peak area size ratio of tetrol triacrylate and tetramethylol methane tetraacrylate tracks in reaction system both moles
Than when the mol ratio of pentaerythritol triacrylate and the tetramethylol methane tetraacrylate is 1:During 3-10, terminate backflow anti-
Should.
Step 203：After the cooling of question response system, the reaction system is washed respectively, alkali cleaning 2-5 times, take first to have
Machine phase.
In the embodiment of the present invention, the washing, alkali cleaning are specially：It is 5%~10% that mass concentration is added into reaction system
Sodium chloride solution, stratification after quick stirring.Upper solution i.e. organic phase is taken, above step is repeated 2-5 times；To reaction system
It is middle to add the sodium hydroxide solution that mass concentration is 5%~10%, stratification after quick stirring.Organic phase is taken, repeats to walk above
It is rapid 2-5 times.The acidity of neutralization reaction system is capable of in washing, alkali cleaning, catalyst is removed from reaction system, and can remove part
Inorganic polymerization inhibitor, improves product purity.
Step 204：Use quality concentration is 5%-10% thiourea dioxide, double (2- methoxyethoxies) aluminic acids of dihydro
At least one of sodium, sodium sulfite, hypo solution to first organic phase wash 1-5 times, then again to this first
Organic phase is washed to neutrality, takes Second Organic Phase.
Due to the embodiment of the present invention in order to prepare the tetramethylol methane tetraacrylate of low hydroxyl value, pentaerythrite need to be controlled
The mol ratio of triacrylate and tetramethylol methane tetraacrylate is 1:3-10, and the synthetic reaction of tetramethylol methane tetraacrylate
Time it is longer, up to 15-20 hours.In such prolonged esterification reaction process, phenolic inhibitor is easily oxidized
Into quinones, so as to cause the colourity of reaction system higher, and then the colourity of pentaerythritol acrylate is caused to be maintained at higher
Level, has had a strong impact on the application of pentaerythritol acrylate.Based on this, selection mass concentration of the embodiment of the present invention is 5%-
In 10% reducing agent thiourea dioxide, dihydro double (2- methoxyethoxies) sodium aluminate, sodium sulfite, hypo solutions
At least one is as decolorising agent, repeatedly to be washed to the first organic phase containing polymerization inhibitor and pentaerythritol acrylate.
Because above-mentioned reducing agent is merely capable of reacting with the polymerization inhibitor being oxidized in reaction system, without influenceing other reactants
And reaction product, so the reducing agent can be reduced the polymerization inhibitor being oxidized in reaction system, aoxidized so as to slough
Polymerization inhibitor and cause the color of organic phase darkened, and then reduce the colourity of pentaerythritol acrylate.After decolouring
Pentaerythritol acrylate decolorizing effect preferably, its colourity can be down to below 30APHA, be applied beneficial to it as photocuring
The application of material, photocuring adhesive, liquid photoresist, optical thin film etc..It is understood that in decolorising agent used in the present invention
On the basis of, it can also further strengthen the decolouring of pentaerythritol acrylate with the use of Typical physical decolorising agents such as activated carbon
Effect.After decolouring is finished, above-mentioned decolorising agent is removed by the way of washing.
For how to solve the problem of the color of the acrylate including pentaerythritol acrylate is deeper, current state
It is inside and outside not yet to efficiently solve method, cause large batch of acrylate because color is relatively deep and can not be utilized effectively,
Cause resource serious waste.And by the present invention in that washed with the solution containing reducing agent to pentaerythritol acrylate,
The problem is not only efficiently solved, and ensure that prepared pentaerythritol acrylate hydroxyl value is relatively low simultaneously, for Ji Wusi
The recycling of alcohol acrylate has great importance.
Step 205：The second polymerization inhibitor is added into the Second Organic Phase, the Second Organic Phase is entered at 40 DEG C -80 DEG C
Row vacuum distillation, filtering, obtain pentaerythritol acrylate.
In order to further remove the impurity in organic phase, the embodiment of the present invention is depressurized successively to the organic phase after decolouring
Distillation and filtration step.Wherein, the operating parameter of vacuum distillation step is：Vacuum degree control is in -0.1MPa, and temperature control is 40
~80 DEG C, time control was at 4 hours.Control vacuum distillation under higher vacuum and relatively low temperature, will can have
Solvent in machine phase eliminates and is not easy to cause solidification.In order to avoid pentaerythritol acrylate is sent out during vacuum distillation
Raw copolymerization in the Second Organic Phase, it is necessary to add the second polymerization inhibitor.To avoid the color of the pentaerythritol acrylate after decolourizing
Degree is improved again, the preferred organic polymerization inhibitor of second polymerization inhibitor：It is MEHQ, hydroquinones, p-t-butyl phenol, right
At least one of tert-butyl catechol.Ensure pentaerythritol acrylate polymerization inhibition effect and do not influence the premise of its quality
Under, the usage amount of second polymerization inhibitor is preferably the 0.05%-0.5% of Second Organic Phase quality.
In summary, the embodiment of the present invention is decolourized using decoloring agent to product, than using things such as activated carbon
The decolorizing effect for managing decolorising agent is more notable.And raw materials used is technical grade, technique is simple, easy to operate, and reaction is easy to control
System, can be produced in batches in a kettle..Prepared pentaerythritol acrylate has low hydroxyl value concurrently（Less than 30mgKOH/g）And it is low
Colourity（APHA color value is less than 30）, and with water-fast, resistance toization, wear-resisting, impact resistance, heat resistance, high rigidity, low-shrinkage and
The advantage good to low pole substrate adhesion, it is adaptable to photocuring adhesive, adhesion promoter, plastic coating, metal coating,
The fields such as woodenware coating, liquid photoresist, optical thin film, ink for screen printing.
Embodiment 3
Successively by 28.87g pentaerythrites, 61.13g acrylic acid, 49.5g toluene, 48.7g hexamethylenes, 1.35g methyl sulphurs
Acid, 1.35g HND-6 solid super-strong acids, 0.3g Salzburg vitriols, 0.045g MEHQs are put into equipped with thermometer, divided
In the 500ml of hydrophone, serpentine condenser and agitating paddle four-hole boiling flask, and 13.2g toluene and 12.4g rings are added in water knockout drum
Hexane.
Oil bath heating device is opened, temperature is heated to reaction system for 90 DEG C, is heated to reflux 15 hours.Using efficient liquid
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1 in phase chromatography tracking reaction system:When 3, knot
Beam back flow reaction.
By reaction system cooling down to 35 DEG C, then the reaction system is washed 2 times using 10% sodium chloride solution,
Stratification, takes upper organic phase to determine acid number；According to surveyed acid number, 10% sodium hydroxide using excessive 10% parts by weight is molten
Liquid washs the reaction system 1 time, and stratification takes upper organic phase；The thiourea dioxide aqueous slkali for reusing 10% washs this and had
Machine phase 2 times, stratification, then washed 2 times with 10% sodium chloride solution, stratification takes upper organic phase.
0.015g MEHQs and 0.015g hydroquinones are added into the organic phase, vacuum distillation is carried out to it,
And blowing air is purged to solvent<0.1%, to slough the solvent in organic phase.In the vacuum distillation process：Vacuum degree control
In -0.1Mpa, temperature control is at 55 DEG C, and time control was at 3 hours.The last pressure filtration at 55 DEG C, obtains pentaerythrite third
Olefin(e) acid ester finished product, its purity is 98%, and yield is 86%.The pentaerythritol acrylate colourity is measured for 10APHA, hydroxyl value is
25.06mg KOH/g, the viscosity at 25 DEG C is 650mPa.s.
Under the conditions of same conditional operation, thiourea dioxide aqueous slkali is replaced using the activated carbon of same quality proportioning
As decolorising agent, to prepare pentaerythritol acrylate.The colourity for measuring the pentaerythritol acrylate is 55APHA, its
Far above the colourity of pentaerythritol acrylate prepared when using thiourea dioxide aqueous slkali as decolorising agent.It can be seen that, this
Inventive embodiments, as decolorising agent, have reached good decolorizing effect by using thiourea dioxide aqueous slkali.Prepared season
Penta tetrol acrylate has low hydroxyl value and low colourity concurrently, with wider application prospect.
Embodiment 4
24.69g pentaerythrites, 65.31g acrylic acid, 46.6g toluene, 3.74g pyrovinic acids, 0.07g five are hydrated successively
Copper sulphate, 0.01g stannous chlorides, 0.045g p-tert-Butylcatechols be put into equipped with thermometer, water knockout drum, serpentine condenser and
In the 500ml of agitating paddle four-hole boiling flask, and 26.5g toluene is added in water knockout drum.
Oil bath heating device is opened, temperature is heated to reaction system for 100 DEG C, is heated to reflux 18 hours.Using efficient
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1 in liquid chromatography tracking reaction system:6.5
When, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then the reaction system is washed 1 time using 5% sodium chloride solution, it is quiet
Layering is put, takes upper organic phase to determine acid number；According to surveyed acid number, 5% sodium hydroxide solution of excessive 10% parts by weight is used
Wash the reaction system 2 times, stratification takes upper organic phase；Reuse double (2- methoxy ethoxies) sodium aluminates of 5% dihydro
Aqueous slkali washs the organic phase 2 times, stratification, then is washed 2 times with 5% sodium chloride solution, and stratification takes upper strata organic
Phase.
0.035g MEHQs and 0.035g p-tert-Butylcatechols are added into the organic phase, it is carried out
Vacuum distillation, and blowing air purged to solvent<0.1%, to slough the solvent in organic phase.In the vacuum distillation process：Very
Reciprocal of duty cycle is controlled in -0.1Mpa, and temperature control is at 80 DEG C, and time control was at 3 hours.The last pressure filtration at 50 DEG C, obtains season
Penta tetrol acrylate finished product, its purity is 97%, and yield is 87%.The pentaerythritol acrylate colourity is measured for 20APHA,
Hydroxyl value is 18.27mg KOH/g, and the viscosity at 25 DEG C is 680mPa.s.It can be seen that, the embodiment of the present invention is by using titanium dioxide
Thiocarbamide aqueous slkali has reached good decolorizing effect as decolorising agent.Prepared pentaerythritol acrylate has low hydroxyl value concurrently
And low colourity, with wider application prospect.
Embodiment 5
Successively by 33.02g pentaerythrites, 66.98g acrylic acid, 47.9g hexamethylenes, 3.23g pyrovinic acids, 0.055g five
Hydrated copper sulfate, 0.035g p-tert-Butylcatechols are put into equipped with thermometer, water knockout drum, serpentine condenser and agitating paddle
In 500ml four-hole boiling flask, and 25.7g hexamethylenes are added in water knockout drum.
Oil bath heating device is opened, temperature is heated to reaction system for 100 DEG C, is heated to reflux 15 hours.Using efficient
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1 in liquid chromatography tracking reaction system:When 10,
Terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then the reaction system is washed 2 times using 10% sodium chloride solution,
Stratification, takes upper organic phase to determine acid number；According to surveyed acid number, 10% sodium hydroxide using excessive 10% parts by weight is molten
Liquid washs the reaction system 1 time, and stratification takes upper organic phase；Reuse 10% sodium sulfite aqueous slkali and 5% it is thio
Sodium sulphate aqueous slkali washs the organic phase 2 times, stratification, then is washed 2 times with 10% sodium chloride solution, and stratification takes
Layer organic phase.
0.045g MEHQs and 0.045g p-tert-Butylcatechols are added into the organic phase, it is carried out
Vacuum distillation, and blowing air purged to solvent<0.1%, to slough the solvent in organic phase.In the vacuum distillation process：Very
Reciprocal of duty cycle is controlled in -0.1Mpa, and temperature control is at 80 DEG C, and time control was at 3 hours.The last pressure filtration at 55 DEG C, obtains season
Penta tetrol acrylate finished product, its purity is 96%, and yield is 88%.The pentaerythritol acrylate colourity is measured for 21APHA,
Hydroxyl value is 12.8mg KOH/g, and the viscosity at 25 DEG C is 650mPa.s.It can be seen that, the embodiment of the present invention is by using sulfur dioxide
Urea aqueous slkali has reached good decolorizing effect as decolorising agent.Prepared pentaerythritol acrylate have concurrently low hydroxyl value and
Low colourity, with wider application prospect.
Embodiment 6
Successively by 21.56g pentaerythrites, 68.44g acrylic acid, 48.5g hexamethylenes, 46.8g ethyl acetate, 2.83g methyl
Sulfonic acid, 1.14g HND-6 solid super-strong acids, 0.16g Salzburg vitriols, 0.025g MEHQs are put into equipped with temperature
In meter, water knockout drum, the 500ml of serpentine condenser and agitating paddle four-hole boiling flask, and water knockout drum add 11.17g hexamethylenes and
10.6g ethyl acetate.
Oil bath heating device is opened, temperature is heated to reaction system for 100 DEG C, is heated to reflux 17 hours.Using efficient
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1 in liquid chromatography tracking reaction system:When 6,
Terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then the reaction system is washed 2 times using 10% sodium chloride solution,
Stratification, takes upper organic phase to determine acid number；According to surveyed acid number, 10% sodium hydroxide using excessive 10% parts by weight is molten
Liquid washs the reaction system 1 time, and stratification takes upper organic phase；Reuse the washing of 10% sodium sulfite aqueous slkali and 10% sulphur
Sodium thiosulfate aqueous slkali washs the organic phase 2 times, stratification, then is washed 2 times with 10% sodium chloride solution, and stratification takes
Upper organic phase.
0.06g MEHQs are added into the organic phase, vacuum distillation is carried out to it, and blowing air is purged to solvent
Content<0.1%, to slough the solvent in organic phase.In the vacuum distillation process：Vacuum degree control is in -0.1Mpa, temperature control
At 80 DEG C, time control was at 3 hours.The last pressure filtration at 50 DEG C, obtains pentaerythritol acrylate finished product, its purity is
97%, yield is 87%.The pentaerythritol acrylate colourity is measured for 15APHA, hydroxyl value is 19.75mg KOH/g, at 25 DEG C
Viscosity be 720mPa.s.It can be seen that, the embodiment of the present invention, as decolorising agent, has reached good by using thiourea dioxide aqueous slkali
Good decolorizing effect.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, with wider application prospect.
Embodiment 7
Successively by 2 by 20.27g pentaerythrites, 69.73g acrylic acid, 48.0g toluene, 49.6g ethyl acetate, 2.12g first
Base sulfonic acid, 0.98g p-methyl benzenesulfonic acid, 0.076g stannous chlorides, 0.055g p-tert-Butylcatechols are put into equipped with thermometer, divided
In the 500ml of hydrophone, serpentine condenser and agitating paddle four-hole boiling flask, and 11.17g hexamethylenes and 10.6g are added in water knockout drum
Ethyl acetate.
Oil bath heating device is opened, temperature is heated to reaction system for 100 DEG C, is heated to reflux 18 hours.Using efficient
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1 in liquid chromatography tracking reaction system:5.5
When, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then the reaction system is washed 3 times using 10% sodium chloride solution,
Stratification, takes upper organic phase to determine acid number；According to surveyed acid number, 10% sodium hydroxide using excessive 10% parts by weight is molten
Liquid washs the reaction system 5 times, and stratification takes upper organic phase；Reuse double (2- methoxy ethoxies) aluminic acids of 10% dihydro
Sodium and 10% sodium thiosulfate aqueous slkali wash the organic phase 3 times, stratification, then are washed 2 times with 10% sodium chloride solution, quiet
Layering is put, upper organic phase is taken.
0.075g p-tert-Butylcatechols are added into the organic phase, vacuum distillation is carried out to it, and blowing air is purged
To solvent<0.1%, to slough the solvent in organic phase.In the vacuum distillation process：Vacuum degree control is in -0.1Mpa, temperature
Degree control is at 40 DEG C, and time control was at 3 hours.The last pressure filtration at 50 DEG C, obtains pentaerythritol acrylate finished product, its
Purity is 95%, and yield is 86%.The pentaerythritol acrylate colourity is measured for 15APHA, hydroxyl value is 22.16mg KOH/g,
Viscosity at 25 DEG C is 700mPa.s.It can be seen that, the embodiment of the present invention, as decolorising agent, reaches by using thiourea dioxide aqueous slkali
Good decolorizing effect is arrived.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, with wider application
Prospect.
Embodiment 8
Successively by 26.62g pentaerythrites, 63.38g acrylic acid, 49.1g toluene, 49.5g hexamethylenes, 3.62g methyl sulphurs
Acid, 0.036g stannous chlorides, 0.027g Salzburg vitriols, 0.038g p-tert-Butylcatechols, 0.043g para hydroxybenzene first
Ether is put into the four-hole boiling flask of the 500ml equipped with thermometer, water knockout drum, serpentine condenser and agitating paddle, and is added in water knockout drum
12.66g toluene and 12.31g hexamethylenes.
Oil bath heating device is opened, temperature is heated to reaction system for 100 DEG C, is heated to reflux 18 hours.Using efficient
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1 in liquid chromatography tracking reaction system:6.5
When, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then the reaction system is washed 3 times using 10% sodium chloride solution,
Stratification, takes upper organic phase to determine acid number；According to surveyed acid number, 10% sodium hydroxide using excessive 10% parts by weight is molten
Liquid washs the reaction system 5 times, and stratification takes upper organic phase；Reusing 10% sulfur dioxide urea solution, to wash this organic
Phase 2 times, stratification, then washed 2 times with 10% sodium chloride solution, stratification takes upper organic phase.
0.065g p-tert-Butylcatechols and 0.035g MEHQs are added into the organic phase, it is subtracted
Pressure is distilled, and blowing air is purged to solvent<0.1%, to slough the solvent in organic phase.In the vacuum distillation process：Vacuum
Degree control is in -0.1Mpa, and temperature control is at 60 DEG C, and time control was at 3 hours.The last pressure filtration at 50 DEG C, obtains season penta
Tetrol acrylate finished product, its purity is 97%, and yield is 88%.The pentaerythritol acrylate colourity is measured for 20APHA, hydroxyl
It is worth for 18.95mg KOH/g, the viscosity at 25 DEG C is 690mPa.s.It can be seen that, the embodiment of the present invention is by using sulfur dioxide
Urea aqueous slkali has reached good decolorizing effect as decolorising agent.Prepared pentaerythritol acrylate have concurrently low hydroxyl value and
Low colourity, with wider application prospect.
Embodiment 9
Successively by 23.99g pentaerythrites, 66.01g acrylic acid, 48.9g hexamethylenes, 47.3g ethyl acetate, 2.26g to first
Benzene sulfonic acid, 1.21g HND-6 solid super-strong acids, 0.073g Salzburg vitriols, 0.026g p-tert-Butylcatechols, 0.024g
MEHQ is put into the four-hole boiling flask of the 500ml equipped with thermometer, water knockout drum, serpentine condenser and agitating paddle, and
Water knockout drum adds 12.81g hexamethylenes and 11.39g ethyl acetate.
Oil bath heating device is opened, temperature is heated to reaction system for 100 DEG C, is heated to reflux 20 hours.Using efficient
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1 in liquid chromatography tracking reaction system：When 8,
Terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then the reaction system is washed 2 times using 10% sodium chloride solution,
Stratification, takes upper organic phase to determine acid number；According to surveyed acid number, 10% sodium hydroxide using excessive 10% parts by weight is molten
Liquid washs the reaction system 2 times, and stratification takes upper organic phase；Reuse double (2- methoxy ethoxies) aluminic acids of 5% dihydro
The sodium sulfite aqueous slkali of sodium 10% washs the organic phase 2 times, stratification, then is washed 2 times with 10% sodium chloride solution, stands and divides
Layer, takes upper organic phase.
0.065g p-tert-Butylcatechols and 0.035g MEHQs are added into the organic phase, it is subtracted
Pressure is distilled, and blowing air is purged to solvent<0.1%, to slough the solvent in organic phase.In the vacuum distillation process：Vacuum
Degree control is in -0.1Mpa, and temperature control is at 80 DEG C, and time control was at 3 hours.The last pressure filtration at 50 DEG C, obtains season penta
Tetrol acrylate finished product, its purity is 98%, and yield is 89%.The pentaerythritol acrylate colourity is measured for 25APHA, hydroxyl
It is worth for 16.35mg KOH/g, the viscosity at 25 DEG C is 710mPa.s.It can be seen that, the embodiment of the present invention is by using sulfur dioxide
Urea aqueous slkali has reached good decolorizing effect as decolorising agent.Prepared pentaerythritol acrylate have concurrently low hydroxyl value and
Low colourity, with wider application prospect.
Embodiment 10
It is successively that 22.41g pentaerythrites, 67.59g acrylic acid, 49.9g toluene, 2.81g pyrovinic acids, 0.9gHND-6 is solid
Body super acids, 0.088g Salzburg vitriols, 0.053g p-tert-Butylcatechols, 0.032g MEHQs are put into and are equipped with
In thermometer, water knockout drum, the 500ml of serpentine condenser and agitating paddle four-hole boiling flask, and 24.4g toluene is added in water knockout drum.
Oil bath heating device is opened, temperature is heated to reaction system for 100 DEG C, is heated to reflux 18 hours.Using efficient
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1 in liquid chromatography tracking reaction system：6.5
When, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then the reaction system is washed 2 times using 10% sodium chloride solution,
Stratification, takes upper organic phase to determine acid number；According to surveyed acid number, 10% sodium hydroxide using excessive 10% parts by weight is molten
Liquid washs the reaction system 2 times, and stratification takes upper organic phase；The sodium thiosulfate for reusing 10% washs the organic phase 2
It is secondary, stratification, then washed 2 times with 10% sodium chloride solution, stratification takes upper organic phase.
0.077g p-tert-Butylcatechols and 0.045g MEHQs are added into the organic phase, it is subtracted
Pressure is distilled, and blowing air is purged to solvent<0.1%, to slough the solvent in organic phase.In the vacuum distillation process：Vacuum
Degree control is in -0.1Mpa, and temperature control is at 80 DEG C, and time control was at 3 hours.The last pressure filtration at 50 DEG C, obtains season penta
Tetrol acrylate finished product, its purity is 97%, and yield is 86%.The pentaerythritol acrylate colourity is measured for 15APHA, hydroxyl
It is worth for 19.11mg KOH/g, the viscosity at 25 DEG C is 630mPa.s.It can be seen that, the embodiment of the present invention is by using sulfur dioxide
Urea aqueous slkali has reached good decolorizing effect as decolorising agent.Prepared pentaerythritol acrylate have concurrently low hydroxyl value and
Low colourity, with wider application prospect.
Embodiment 11
Successively by 21.02g pentaerythrites, 68.98g acrylic acid, 47.8g hexamethylenes, 3.26g pyrovinic acids, 0.065g chlorine
Change cuprous, 0.046g p-tert-Butylcatechols, 0.011g MEHQs to be put into equipped with thermometer, water knockout drum, snakelike cold
In the 500ml of solidifying pipe and agitating paddle four-hole boiling flask, and 22.64g hexamethylenes are added in water knockout drum.
Oil bath heating device is opened, temperature is heated to reaction system for 100 DEG C, is heated to reflux 17 hours.Using efficient
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1 in liquid chromatography tracking reaction system：When 7,
Terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then the reaction system is washed 3 times using 10% sodium chloride solution,
Stratification, takes upper organic phase to determine acid number；According to surveyed acid number, 10% sodium hydroxide using excessive 10% parts by weight is molten
Liquid washs the reaction system 1 time, and stratification takes upper organic phase；The sodium thiosulfate for reusing 10% washs the organic phase 2
It is secondary, stratification, then washed 2 times with 10% sodium chloride solution, stratification takes upper organic phase.
0.054g p-tert-Butylcatechols and 0.072g MEHQs are added into the organic phase, it is subtracted
Pressure is distilled, and blowing air is purged to solvent<0.1%, to slough the solvent in organic phase.In the vacuum distillation process：Vacuum
Degree control is in -0.1Mpa, and temperature control is at 80 DEG C, and time control was at 3 hours.The last pressure filtration at 50 DEG C, obtains season penta
Tetrol acrylate finished product, its purity is 97%, and yield is 88%.The pentaerythritol acrylate colourity is measured for 15APHA, hydroxyl
It is worth for 17.97mg KOH/g, the viscosity at 25 DEG C is 660mPa.s.It can be seen that, the embodiment of the present invention is by using sulfur dioxide
Urea aqueous slkali has reached good decolorizing effect as decolorising agent.Prepared pentaerythritol acrylate have concurrently low hydroxyl value and
Low colourity, with wider application prospect.
Embodiment 12
27.93g pentaerythrites, 62.07g acrylic acid, 47.9g toluene, 3.88g pyrovinic acids, 0.08g five are hydrated successively
Copper sulphate, 0.005g stannous chlorides, 0.055g p-tert-Butylcatechols are put into equipped with thermometer, water knockout drum, serpentine condenser
27.5g toluene is added in the 500ml of agitating paddle four-hole boiling flask, and in water knockout drum.
Oil bath heating device is opened, temperature is heated to reaction system for 100 DEG C, is heated to reflux 16 hours.Using efficient
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1 in liquid chromatography tracking reaction system：5.5
When, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then the reaction system is washed 2 times using 8% sodium chloride solution, it is quiet
Layering is put, takes upper organic phase to determine acid number；According to surveyed acid number, 8% sodium hydroxide solution of excessive 10% parts by weight is used
Wash the reaction system 2 times, stratification takes upper organic phase；Reuse 5% thiourea dioxide and 5% sulfurous acid soda
Solution washs the organic phase 2 times, stratification, then is washed 2 times with 10% sodium chloride solution, and stratification takes upper strata organic
Phase.
0.045g MEHQs and 0.045g p-tert-Butylcatechols are added into the organic phase, it is carried out
Vacuum distillation, and blowing air purged to solvent<0.1%, to slough the solvent in organic phase.In the vacuum distillation process：Very
Reciprocal of duty cycle is controlled in -0.1Mpa, and temperature control is at 80 DEG C, and time control was at 3 hours.The last pressure filtration at 50 DEG C, obtains season
Penta tetrol acrylate finished product, its purity is 98%, and yield is 88%.The pentaerythritol acrylate colourity is measured for 15APHA,
Hydroxyl value is 21.84mg KOH/g, and the viscosity at 25 DEG C is 700mPa.s.It can be seen that, the embodiment of the present invention is by using titanium dioxide
Thiocarbamide aqueous slkali has reached good decolorizing effect as decolorising agent.Prepared pentaerythritol acrylate has low hydroxyl value concurrently
And low colourity, with wider application prospect.
Embodiment 13
Successively by 22.41g pentaerythrites, 67.59g acrylic acid, 46.9g hexamethylenes, 47.3g ethyl acetate, 3.21g to first
Benzene sulfonic acid, 0.27g HND-6 solid super-strong acids, 0.068g Salzburg vitriols, 0.031g p-tert-Butylcatechols, 0.014g
MEHQ is put into the four-hole boiling flask of the 500ml equipped with thermometer, water knockout drum, serpentine condenser and agitating paddle, and
Water knockout drum adds 11.93g hexamethylenes and 12.14g ethyl acetate.
Oil bath heating device is opened, temperature is heated to reaction system for 100 DEG C, is heated to reflux 16 hours.Using efficient
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1 in liquid chromatography tracking reaction system：When 7,
Terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then the reaction system is washed 2 times using 5% sodium chloride solution, it is quiet
Layering is put, takes upper organic phase to determine acid number；According to surveyed acid number, 5% sodium hydroxide solution of excessive 10% parts by weight is used
Wash the reaction system 2 times, stratification takes upper organic phase；Reuse 5% thiourea dioxide, double (the 2- first of 5% dihydro
Epoxide ethyoxyl) sodium aluminate and 5% sodium sulfite aqueous slkali wash the organic phase 2 times, stratification, then with 10% sodium chloride
Solution is washed 2 times, and stratification takes upper organic phase.
0.045g MEHQs and 0.045g p-tert-Butylcatechols are added into the organic phase, it is carried out
Vacuum distillation, and blowing air purged to solvent<0.1%, to slough the solvent in organic phase.In the vacuum distillation process：Very
Reciprocal of duty cycle is controlled in -0.1Mpa, and temperature control is at 80 DEG C, and time control was at 3 hours.The last pressure filtration at 50 DEG C, obtains season
Penta tetrol acrylate finished product, its purity is 97%, and yield is 89%.The pentaerythritol acrylate colourity is measured for 20APHA,
Hydroxyl value is 17.16mg KOH/g, and the viscosity at 25 DEG C is 690mPa.s.It can be seen that, the embodiment of the present invention is by using titanium dioxide
Thiocarbamide aqueous slkali has reached good decolorizing effect as decolorising agent.Prepared pentaerythritol acrylate has low hydroxyl value concurrently
And low colourity, with wider application prospect.
Embodiment 14
Successively by 21.83g pentaerythrites, 68.16g acrylic acid, 48.4g hexamethylenes, 3.77g pyrovinic acids, 0.045g five
Hydrated copper sulfate, 0.045g p-tert-Butylcatechols are put into equipped with thermometer, water knockout drum, serpentine condenser and agitating paddle
In 500ml four-hole boiling flask, and 26.8g hexamethylenes are added in water knockout drum.
Oil bath heating device is opened, temperature is heated to reaction system for 100 DEG C, is heated to reflux 16 hours.Using efficient
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1 in liquid chromatography tracking reaction system:5.5
When, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then the reaction system is washed 2 times using 10% sodium chloride solution,
Stratification, takes upper organic phase to determine acid number；According to surveyed acid number, 10% sodium hydroxide using excessive 10% parts by weight is molten
Liquid washs the reaction system 2 times, and stratification takes upper organic phase；Reuse 10% double (2- methoxy ethoxies) aluminium of dihydro
Sour sodium and 10% sodium thiosulfate aqueous slkali wash the organic phase 2 times, stratification, then wash 2 with 10% sodium chloride solution
Secondary, stratification takes upper organic phase.
0.055g MEHQs and 0.035g p-tert-Butylcatechols are added into the organic phase, it is carried out
Vacuum distillation, and blowing air purged to solvent<0.1%, to slough the solvent in organic phase.In the vacuum distillation process：Very
Reciprocal of duty cycle is controlled in -0.1Mpa, and temperature control is at 80 DEG C, and time control was at 3 hours.The last pressure filtration at 50 DEG C, obtains season
Penta tetrol acrylate finished product, its purity is 97%, and yield is 89%.The pentaerythritol acrylate colourity is measured for 10APHA,
Hydroxyl value is 21.55mg KOH/g, and the viscosity at 25 DEG C is 700mPa.s.It can be seen that, the embodiment of the present invention is by using titanium dioxide
Thiocarbamide aqueous slkali has reached good decolorizing effect as decolorising agent.Prepared pentaerythritol acrylate has low hydroxyl value concurrently
And low colourity, with wider application prospect.
Embodiment 15
27.04g pentaerythrites, 62.96g acrylic acid, 49.9g toluene, 3.25g pyrovinic acids, 0.08g five are hydrated successively
Copper sulphate, 0.02g stannous chlorides, 0.033g p-tert-Butylcatechols be put into equipped with thermometer, water knockout drum, serpentine condenser and
In the 500ml of agitating paddle four-hole boiling flask, and 28.6g toluene is added in water knockout drum.
Oil bath heating device is opened, temperature is heated to reaction system for 100 DEG C, is heated to reflux 16 hours.Using efficient
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1 in liquid chromatography tracking reaction system:6.5
When, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then the reaction system is washed 2 times using 5% sodium chloride solution, it is quiet
Layering is put, takes upper organic phase to determine acid number；According to surveyed acid number, 5% sodium hydroxide solution of excessive 10% parts by weight is used
Wash the reaction system 2 times, stratification takes upper organic phase；Reuse 10% double (2- methoxy ethoxies) aluminic acids of dihydro
Sodium and 10% sodium thiosulfate aqueous slkali wash the organic phase 2 times, stratification, then are washed 2 times with 10% sodium chloride solution,
Stratification, takes upper organic phase.
The organic phase is decolourized using activated carbon, then into the organic phase add 0.045g MEHQs with
And 0.045g p-tert-Butylcatechols, vacuum distillation is carried out to it, and blowing air is purged to solvent<0.1%, to slough
Solvent in organic phase.In the vacuum distillation process：Vacuum degree control is in -0.1Mpa, and temperature control is at 80 DEG C, and time control exists
3 hours.The last pressure filtration at 50 DEG C, obtains pentaerythritol acrylate finished product, and its purity is 96%, and yield is 87%.Survey
The pentaerythritol acrylate colourity is obtained for 90APHA, hydroxyl value is 19.73mg KOH/g.
It is due to that decolorising agent is selected although the embodiment of the present invention is by having obtained the pentaerythritol acrylate of low hydroxyl value
Activated carbon, its decolorizing effect is poor, and pentaerythritol acrylate colourity is up to 90APHA, has had a strong impact on the pentaerythrite third
The quality of olefin(e) acid ester.It can be seen that, compared to activated carbon, decolorising agent provided in an embodiment of the present invention has more excellent decolorizing effect.
Embodiment 16
25g pentaerythrites, 70.37g acrylic acid, 49.9g toluene, 3.25g pyrovinic acids, 0.08g five are hydrated sulphur successively
Sour copper, 0.02g stannous chlorides, 0.033g p-tert-Butylcatechols are put into equipped with thermometer, water knockout drum, serpentine condenser and stirred
In the four-hole boiling flask for the 500ml for mixing oar, and 28.6g toluene is added in water knockout drum.
Oil bath heating device is opened, temperature is heated to reaction system for 100 DEG C, is heated to reflux 16 hours.Using efficient
Pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 2 in liquid chromatography tracking reaction system:When 1,
Terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then the reaction system is washed 2 times using 5% sodium chloride solution, it is quiet
Layering is put, takes upper organic phase to determine acid number；According to surveyed acid number, 5% sodium hydroxide solution of excessive 10% parts by weight is used
Wash the reaction system 2 times, stratification takes upper organic phase；Reuse 10% double (2- methoxy ethoxies) aluminic acids of dihydro
Sodium and 10% sodium thiosulfate aqueous slkali wash the organic phase 2 times, stratification, then are washed 2 times with 10% sodium chloride solution,
Stratification, takes upper organic phase.
The organic phase is decolourized using activated carbon, then into the organic phase add 0.045g MEHQs with
And 0.045g p-tert-Butylcatechols, vacuum distillation is carried out to it, and blowing air is purged to solvent<0.1%, to slough
Solvent in organic phase.In the vacuum distillation process：Vacuum degree control is in -0.1Mpa, and temperature control is at 80 DEG C, and time control exists
3 hours.The last pressure filtration at 50 DEG C, obtains pentaerythritol acrylate finished product, and its purity is 96%, and yield is 87%.Survey
The pentaerythritol acrylate colourity is obtained for 35APHA, hydroxyl value is 106.5mg KOH/g.
The embodiment of the present invention is decolourized by using activated carbon come the pentaerythritol acrylate to high hydroxyl value, in high hydroxyl
In the case of the colourity of the pentaerythritol acrylate of value in itself is less（About in 43APHA）, its colourity can not be also down to
Below 30APHA, its decolorizing effect is poor.It can be seen that, compared with activated carbon, decolorising agent provided in an embodiment of the present invention has more excellent
Decolorizing effect.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (7)
1. a kind of preparation method of pentaerythritol acrylate, it is characterised in that methods described includes：
Pentaerythrite, acrylic acid, solvent, catalyst and the first polymerization inhibitor are added into reactor, and the reactor is heated
To preset temperature；
Make reaction system back flow reaction under the preset temperature, season penta in the reaction system is tracked using high performance liquid chromatography
The mol ratio of tetrol triacrylate and tetramethylol methane tetraacrylate, when the pentaerythritol triacrylate and the season penta
The mol ratio of tetra-acrylate is 1:During 3-10, terminate the back flow reaction；
After after reaction system cooling, the reaction system is washed respectively, alkali cleaning, take the first organic phase；
First organic phase is washed using reducing agent, neutrality then is washed to first organic phase again, is taken
Two organic phases；
The second polymerization inhibitor is added into the Second Organic Phase, vacuum distillation, filtering are carried out to the Second Organic Phase, institute is obtained
State pentaerythritol acrylate；
The reducing agent is 5%-10% thiourea dioxide, double (2- methoxyethoxies) aluminic acids of dihydro selected from mass concentration
At least one of sodium, sodium sulfite, hypo solution；
First polymerization inhibitor is in Salzburg vitriol, stannous chloride, p-t-butyl phenol, p-tert-Butylcatechol
It is at least one；
Second polymerization inhibitor is in MEHQ, hydroquinones, p-t-butyl phenol, p-tert-Butylcatechol
At least one, the quality of second polymerization inhibitor is the 0.05%-0.5% of the Second Organic Phase quality.
2. the preparation method of pentaerythritol acrylate according to claim 1, it is characterised in that the pentaerythrite with
The mol ratio of the acrylic acid is 1:4-8.
3. the preparation method of pentaerythritol acrylate according to claim 1, it is characterised in that the solvent is selected from ring
At least one of hexane, toluene, ethyl acetate, the quality of the solvent is the pentaerythrite and the acrylic acid gross mass
40%-80%.
4. the preparation method of pentaerythritol acrylate according to claim 1, it is characterised in that the catalyst is selected from
At least one of p-methyl benzenesulfonic acid, pyrovinic acid, solid super-strong acid, the quality of the catalyst is the pentaerythrite and institute
State the 1.0%-4.0% of acrylic acid gross mass.
5. the preparation method of pentaerythritol acrylate according to claim 1, it is characterised in that first polymerization inhibitor
Quality for the pentaerythrite and the acrylic acid gross mass 0.05%-0.5%.
6. the preparation method of pentaerythritol acrylate according to claim 1, it is characterised in that the preset temperature is
80-100℃。
7. the preparation method of pentaerythritol acrylate according to claim 1, it is characterised in that described to described second
Temperature control during organic phase progress vacuum distillation is at 40 DEG C -80 DEG C.
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| US4187383A (en) * | 1976-12-28 | 1980-02-05 | Union Carbide Corporation | Process for producing low color residue acrylate esters |
| CN102146034A (en) * | 2010-11-24 | 2011-08-10 | 天津市天骄辐射固化材料有限公司 | Method for preparing dipentaerythritol pentaacrylate |
| CN103274940A (en) * | 2013-05-14 | 2013-09-04 | 常州大学 | Environment-friendly preparation method of pentaerythritol acrylic ester and derivate |
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| TW200940500A (en) * | 2008-01-24 | 2009-10-01 | Toagosei Co Ltd | Process for production of (meth)acrylate composition |
| CN103553920A (en) * | 2013-09-26 | 2014-02-05 | 上海维凯化学品有限公司 | Preparation method of phenoxy benzyl acrylic ester |
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| US4187383A (en) * | 1976-12-28 | 1980-02-05 | Union Carbide Corporation | Process for producing low color residue acrylate esters |
| CN102146034A (en) * | 2010-11-24 | 2011-08-10 | 天津市天骄辐射固化材料有限公司 | Method for preparing dipentaerythritol pentaacrylate |
| CN103274940A (en) * | 2013-05-14 | 2013-09-04 | 常州大学 | Environment-friendly preparation method of pentaerythritol acrylic ester and derivate |
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