CN104876822A - Pentaerythritol tetraacrylate preparation method - Google Patents
Pentaerythritol tetraacrylate preparation method Download PDFInfo
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- CN104876822A CN104876822A CN201410070354.3A CN201410070354A CN104876822A CN 104876822 A CN104876822 A CN 104876822A CN 201410070354 A CN201410070354 A CN 201410070354A CN 104876822 A CN104876822 A CN 104876822A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 135
- 239000012074 organic phase Substances 0.000 claims abstract description 129
- 239000002904 solvent Substances 0.000 claims abstract description 43
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 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 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000004821 distillation Methods 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 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 5
- 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 claims description 106
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
- 229940059574 pentaerithrityl Drugs 0.000 claims description 39
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 36
- 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 description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- -1 thiourea peroxide Chemical class 0.000 claims description 24
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 20
- 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 18
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 16
- 230000002829 reductive effect Effects 0.000 claims description 15
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 13
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 13
- 229940045803 cuprous chloride Drugs 0.000 claims description 13
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 13
- UIICPZFWHBJNIG-UHFFFAOYSA-N sodium;2-methoxyethanolate Chemical compound [Na+].COCC[O-] UIICPZFWHBJNIG-UHFFFAOYSA-N 0.000 claims description 13
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 8
- 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 8
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 30
- 238000010992 reflux Methods 0.000 abstract description 16
- 238000005406 washing Methods 0.000 abstract description 13
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 238000005886 esterification reaction Methods 0.000 abstract description 7
- 239000003112 inhibitor Substances 0.000 abstract description 6
- 230000032050 esterification Effects 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 58
- 238000013517 stratification Methods 0.000 description 58
- 239000000243 solution Substances 0.000 description 54
- 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
- 239000012670 alkaline solution Substances 0.000 description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 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 15
- 238000009835 boiling Methods 0.000 description 15
- 238000004128 high performance liquid chromatography Methods 0.000 description 15
- 238000007664 blowing Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 238000011085 pressure filtration Methods 0.000 description 14
- 238000010926 purge Methods 0.000 description 14
- 238000005292 vacuum distillation Methods 0.000 description 14
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 8
- 230000008901 benefit Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 150000004053 quinones Chemical class 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 241001550224 Apha Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000006223 plastic coating Substances 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
- 230000004044 response Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035939 shock Effects 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
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a pentaerythritol tetraacrylate preparation method, and belongs to the technical field of esterification product preparation. The method comprises: adding pentaerythrotol, acrylic acid, a solvent, a catalyst and a first polymerization inhibitor to a reactor; carrying out a reflux reaction of the reaction system at a preset temperature, and stopping the reaction when tracking a molar ratio of the pentaerythritol triacrylate to pentaerythritol tetraacrylate at 1:3-10; after cooling the reaction system, carrying out waster washing and alkali washing, and taking a first organic phase; washing the first organic phase with a reducing agent, carrying out water washing until achieving a neutral state, and taking a second organic phase; and adding a second polymerization inhibitor to the second organic phase, and carrying out pressure reducing distillation and filtering to obtain the pentaerythritol tetraacrylate. According to the present invention, the reducing agent reacting with the oxidized polymerization inhibitor is adopted as the decoloration agent to prepare the pentaerythritol tetraacrylate with characteristics of low hydroxyl value and low chrominance; and the method of the present invention is simple, is easy to control, and is suitable for scale industrial production.
Description
Technical field
The present invention relates to carboxylate preparing technical field, particularly a kind of preparation method of pentaerythritol acrylate.
Background technology
Pentaerythritol acrylate is a kind of polyfunctionality polymerization single polymerization monomer, comprises pentaerythritol triacrylate and tetramethylol methane tetraacrylate.Pentaerythritol acrylate contains highdensity carbon-to-carbon double bond structure, there is excellent laser curing velocity and high crosslink density, the fields such as photo-cured coating, photocuring sizing agent, liquid photoresist material, optical thin film and adhesion promoter can be widely used in.
At present, prepare pentaerythritol acrylate usually through following methods: add in reactor by toluene, tosic acid, phenolic inhibitor, tetramethylolmethane and vinylformic acid, at a certain temperature, make reaction system reflux dewatering carry out esterification.After esterification terminates, repeatedly alkali cleaning and washing are carried out to reaction system, gets organic phase, and underpressure distillation is carried out to this organic phase slough toluene, namely obtain pentaerythritol acrylate.Due in esterification reaction process, phenolic inhibitor is easily oxidized to quinones, makes the color of prepared pentaerythritol acrylate comparatively dark, is unfavorable for the application of pentaerythritol acrylate.So prior art adsorbs quinones by adding activated carbon in reaction system, thus decolours to pentaerythritol acrylate.
Realizing in process of the present invention, contriver finds that prior art at least exists following problem:
For the pentaerythritol acrylate (color problem of especially low hydroxyl value pentaerythritol acrylate is even more serious) that color is darker, prior art uses activated carbon to decolour, due to the limited sorption capacity of activated carbon, the effect of its decolouring is poor, the colourity of the pentaerythritol acrylate after decolouring is still higher, seriously limits the application of pentaerythritol acrylate.
Summary of the invention
In order to solve prior art to the poor problem of pentaerythritol acrylate decolorizing effect, embodiments provide a kind of preparation method of pentaerythritol acrylate.Described technical scheme is as follows:
Embodiments provide a kind of preparation method of pentaerythritol acrylate, described method comprises: in reactor, add tetramethylolmethane, vinylformic acid, solvent, catalyzer and the first stopper, and described reactor is heated to preset temp;
Make reaction system back flow reaction under described preset temp, follow the tracks of the mol ratio of pentaerythritol triacrylate and tetramethylol methane tetraacrylate in described reaction system, when the mol ratio of described pentaerythritol triacrylate and described tetramethylol methane tetraacrylate is 1:3-10, terminate described back flow reaction;
After the cooling of described reaction system, respectively described reaction system to be washed, alkali cleaning, get the first organic phase;
Use reductive agent to wash described first organic phase, and then neutrality is washed to described first organic phase, get Second Organic Phase;
In described Second Organic Phase, add the second stopper, underpressure distillation, filtration are carried out to described Second Organic Phase, obtain described pentaerythritol acrylate.
Particularly, as preferably, described reductive agent is selected from least one in thiourea peroxide, two (2-methoxyethoxy) sodium aluminate of dihydro, S-WAT, hypo solution.
Particularly, as preferably, the mass concentration of two (2-methoxyethoxy) sodium aluminate of described thiourea peroxide, dihydro, S-WAT, hypo solution is 5%-10%.
As preferably, described tetramethylolmethane and described acrylic acid mol ratio are 1:4-8.
Particularly, described solvent is selected from least one in hexanaphthene, toluene, ethyl acetate, and the quality of described solvent is the 40%-80% of described tetramethylolmethane and described vinylformic acid total mass.
Particularly, described catalyzer is selected from least one in tosic acid, methylsulphonic acid, solid super-strong acid, and the quality of described catalyzer is the 1.0%-4.0% of described tetramethylolmethane and described vinylformic acid total mass.
Particularly, described first stopper is selected from least one in MEHQ, Resorcinol, Salzburg vitriol, cuprous chloride, p-tert-butylphenol, p-ten.-butylcatechol, and the quality of described first stopper is the 0.05%-0.5% of described tetramethylolmethane and described vinylformic acid total mass.
As preferably, described second stopper is selected from least one in MEHQ, Resorcinol, p-tert-butylphenol, p-ten.-butylcatechol, and the quality of described second stopper is the 0.05%-0.5% of described Second Organic Phase quality.
As preferably, described preset temp is 80-100 DEG C.
As preferably, described temperature when carrying out underpressure distillation to described Second Organic Phase controls at 40 DEG C-80 DEG C.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
Embodiments provide a kind of preparation method of pentaerythritol acrylate, by existing for prerequisite with solvent, catalyzer and the first stopper, tetramethylolmethane and vinylformic acid is made to carry out back flow reaction under preset temp, obtain pentaerythritol triacrylate and tetramethylol methane tetraacrylate, and to control its mol ratio be 1:3-10, thus low hydroxyl value pentaerythritol acrylate can be obtained, its hydroxyl value can reach lower than 30mgKOH/g; In order to obtain the pentaerythritol acrylate of hydroxyl value lower than 30mgKOH/g, the reaction times will be partially long, causes its colourity to be greater than 50APHA, even 100APHA, add decolouring difficulty.And the present invention is by using the reductive agent being merely able to react with the stopper that is oxidized in reaction system as discoloring agent, thus the stopper of oxidation is reduced, low hydroxyl value pentaerythritol acrylate is decoloured, its decolorizing effect so can be made very obvious, colourity can reach the level lower than 30APHA, thus preparing the pentaerythritol acrylate having low hydroxyl value and low colourity concurrently, practical application is with the obvious advantage; In addition, the method that the embodiment of the present invention provides is easy and simple to handle, easy to control, is convenient to large-scale industrial and produces.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is preparation method's schema of a kind of pentaerythritol acrylate that the embodiment of the present invention provides;
Fig. 2 is preparation method's schema of a kind of pentaerythritol acrylate that further embodiment of this invention provides.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
Embodiment 1
As shown in Figure 1, embodiments provide a kind of preparation method of pentaerythritol acrylate, the method comprises:
Step 101: add tetramethylolmethane, vinylformic acid, solvent, catalyzer and the first stopper in reactor, and this reactor is heated to preset temp.
Step 102: make reaction system back flow reaction under this preset temp, follow the tracks of the mol ratio of pentaerythritol triacrylate and tetramethylol methane tetraacrylate in reaction system, when the mol ratio of pentaerythritol triacrylate and tetramethylol methane tetraacrylate is 1:3-10, terminate back flow reaction.
Step 103: after the cooling of this reaction system, respectively this reaction system to be washed, alkali cleaning, get the first organic phase.
Step 104: use reductive agent to wash this first organic phase, and then neutrality is washed to this first organic phase, get Second Organic Phase.
Step 105: add the second stopper in this Second Organic Phase, underpressure distillation, filtration are carried out to this Second Organic Phase, obtains pentaerythritol acrylate.
Embodiments provide a kind of preparation method of pentaerythritol acrylate, by existing for prerequisite with solvent, catalyzer and the first stopper, tetramethylolmethane and vinylformic acid is made to carry out back flow reaction under preset temp, obtain pentaerythritol triacrylate and tetramethylol methane tetraacrylate, and to control its mol ratio be 1:3-10, thus low hydroxyl value pentaerythritol acrylate can be obtained, its hydroxyl value can reach lower than 30mgKOH/g; In order to obtain the pentaerythritol acrylate of hydroxyl value lower than 30mgKOH/g, the reaction times will be partially long, causes its colourity to be greater than 50APHA, even 100APHA, add decolouring difficulty.And the present invention is led to and is used the reductive agent being merely able to react with the stopper that is oxidized in reaction system as discoloring agent, thus the stopper of oxidation is reduced, low hydroxyl value pentaerythritol acrylate is decoloured, its decolorizing effect so can be made very obvious, colourity can reach the level lower than 30APHA, thus preparing the pentaerythritol acrylate having low hydroxyl value and low colourity concurrently, practical application is with the obvious advantage; In addition, the method that the embodiment of the present invention provides is easy and simple to handle, easy to control, is convenient to large-scale industrial and produces.
Embodiment 2
As shown in Figure 2, embodiments provide a kind of preparation method of pentaerythritol acrylate, the method comprises:
Step 201: add tetramethylolmethane, vinylformic acid, solvent, catalyzer and the first stopper in the four-hole boiling flask that thermometer, water trap, serpentine condenser, stirring rake be housed, and this reactor is heated to 80-100 DEG C.
Particularly, tetramethylolmethane and acrylic acid mol ratio are 1:4-8, preferred 1:4-6.5.In the embodiment of the present invention, be 1:3-10 in the mol ratio ensureing pentaerythritol triacrylate and tetramethylol methane tetraacrylate, and ensure tetramethylolmethane and the higher transformation efficiency of vinylformic acid, tetramethylolmethane and acrylic acid mol ratio are defined as 1:4-8, preferred 1:4-6.5.The low hydroxyl value pentaerythritol acrylate of expectation is prepared by the tetramethylolmethane of said ratio and vinylformic acid.
Wherein, the first stopper is selected from least one in MEHQ, Resorcinol, Salzburg vitriol, cuprous chloride, p-tert-butylphenol, p-ten.-butylcatechol, preferred Salzburg vitriol, cuprous chloride; The quality of this first stopper is the 0.05%-0.5% of tetramethylolmethane and vinylformic acid total mass.
In reaction process, the amount of stopper crosses that I haven't seen you for ages causes polymerization inhibition effect not obvious, and cause reactant partial polymerization, the amount of stopper too much can affect product color further.Consider from the factor such as polymerization inhibition effect, product color, the preferred p-ten.-butylcatechol of the embodiment of the present invention, p-tert-butylphenol, MEHQ, Salzburg vitriol and cuprous chloride.Above-mentioned first stopper is controlled, when the 0.05%-0.5% of tetramethylolmethane and vinylformic acid total mass, good polymerization inhibition effect can be reached.For the ease of in follow-up water-washing step, part first stopper can be removed, Salzburg vitriol, cuprous chloride are as further preferred.
Solvent is selected from least one in hexanaphthene, toluene, ethyl acetate; The quality of this solvent is the 40%-80% of tetramethylolmethane and vinylformic acid total mass, preferred 50%-70%.
Catalyzer is selected from least one in tosic acid, methylsulphonic acid, solid super-strong acid; The quality of this catalyzer is the 1.0%-4.0% of tetramethylolmethane and vinylformic acid total mass.Consider from factors such as catalytic effect, product color, production costs, embodiment of the present invention catalyzer preferable methyl sulfonic acid and tosic acid, its consumption is preferably the 1.5%-3.0% of tetramethylolmethane and vinylformic acid total mass.
Step 202: make reaction system back flow reaction at 80-100 DEG C, follow the tracks of the mol ratio of pentaerythritol triacrylate and tetramethylol methane tetraacrylate in this reaction system, when the mol ratio of pentaerythritol triacrylate and tetramethylol methane tetraacrylate is 1:3-10, terminate back flow reaction.
Tetramethylolmethane in reaction system and vinylformic acid carry out esterification in reaction medium solvent, generate pentaerythritol triacrylate and tetramethylol methane tetraacrylate simultaneously.Because the generated time of tetramethylol methane tetraacrylate is longer, in order to improve the speed of reaction of esterification, the preferred 80-100 DEG C of embodiment of the present invention temperature of reaction.And under this temperature of reaction, make reaction system backflow 15-20 hour, to ensure reaction fully and completely.Particularly, by using high performance liquid chromatography, both mol ratios are followed the tracks of in reaction system according to the peak area size ratio of pentaerythritol triacrylate and tetramethylol methane tetraacrylate, when the mol ratio of pentaerythritol triacrylate and described tetramethylol methane tetraacrylate is 1:3-10, terminate back flow reaction.
Step 203: after the cooling of question response system, to wash respectively this reaction system, alkali cleaning 2-5 time, gets the first organic phase.
In the embodiment of the present invention, this washing, alkali cleaning are specially: in reaction system, add the sodium chloride solution that mass concentration is 5% ~ 10%, stratification after rapid stirring.Get upper solution and organic phase, repeat above step 2-5 time; The sodium hydroxide solution that mass concentration is 5% ~ 10% is added, stratification after rapid stirring in reaction system.Get organic phase, repeat above step 2-5 time.Washing, alkali cleaning can the acidity of neutralization reaction system, removed by catalyzer, and can remove part mineral-type stopper, improve product purity from reaction system.
Step 204: functional quality concentration is at least one in the thiourea peroxide of 5%-10%, two (2-methoxyethoxy) sodium aluminate of dihydro, S-WAT, hypo solution to this first organic phase washing 1-5 time, and then neutrality is washed to this first organic phase, get Second Organic Phase.
Because the embodiment of the present invention is in order to prepare the tetramethylol methane tetraacrylate of low hydroxyl value, the mol ratio that need control pentaerythritol triacrylate and tetramethylol methane tetraacrylate is 1:3-10, and the time of the building-up reactions of tetramethylol methane tetraacrylate is longer, nearly 15-20 hour.In so long esterification reaction process, phenolic inhibitor is easy to be oxidized to quinones, thus cause the colourity of reaction system higher, and then make the colourity of pentaerythritol acrylate remain on higher level, have a strong impact on the application of pentaerythritol acrylate.Based on this, the embodiment of the present invention selects mass concentration to be at least one in the reductive agent thiourea peroxide of 5%-10%, two (2-methoxyethoxy) sodium aluminate of dihydro, S-WAT, hypo solution as discoloring agent, repeatedly washs the first organic phase containing stopper and pentaerythritol acrylate.Because above-mentioned reductive agent only can react with oxidized stopper in reaction system, and other reactant and reaction product can not be affected, so this reductive agent can make stopper oxidized in reaction system be reduced, thus slough oxidated stopper and cause the color of the organic phase darkened, and then the colourity of pentaerythritol acrylate is reduced.The decolorizing effect of the pentaerythritol acrylate after decolouring is better, and its colourity can be down to below 30APHA, is beneficial to its application as photo-cured coating, photocuring sizing agent, liquid photoresist material, optical thin film etc.Be understandable that, on the basis of the present invention's discoloring agent used, the decolorizing effect of pentaerythritol acrylate can also be strengthened further with the use of Typical physical discoloring agents such as activated carbon.After decolouring, the mode of washing is adopted to remove above-mentioned discoloring agent.
For the problem that the color how solving the acrylate comprising pentaerythritol acrylate is darker, at home and abroad there is no solution effectively at present, cause large batch of acrylate comparatively deeply cannot be utilized effectively due to color, cause resource serious waste.And the present invention washs pentaerythritol acrylate by using the solution containing reductive agent, not only efficiently solve this difficult problem, and ensure that prepared pentaerythritol acrylate hydroxyl value is lower simultaneously, the recycling for pentaerythritol acrylate has great importance.
Step 205: add the second stopper in this Second Organic Phase, at 40 DEG C-80 DEG C, underpressure distillation, filtration are carried out to this Second Organic Phase, obtains pentaerythritol acrylate.
In order to remove the impurity in organic phase further, the embodiment of the present invention carries out underpressure distillation and filtration step successively to the organic phase after decolouring.Wherein, the operating parameters of underpressure distillation step is: vacuum degree control is at-0.1MPa, and temperature controls at 40 ~ 80 DEG C, and time controling was at 4 hours.Control underpressure distillation under higher vacuum tightness and relatively low temperature, the solvent in organic phase can be eliminated and be not easy to cause solidification.In order to avoid pentaerythritol acrylate generation copolymerization in the process of underpressure distillation, need to add the second stopper in this Second Organic Phase.For avoiding the colourity of the pentaerythritol acrylate after decolouring again to improve, the preferred organic stopper of this second stopper: at least one in MEHQ, Resorcinol, p-tert-butylphenol, p-ten.-butylcatechol.At guarantee pentaerythritol acrylate polymerization inhibition effect and under not affecting the prerequisite of its quality, the usage quantity of this second stopper is preferably the 0.05%-0.5% of Second Organic Phase quality.
In sum, the embodiment of the present invention uses decoloring agent to decolour to product, and than adopting, the decolorizing effect of the physical decolorization agent such as activated carbon is more remarkable.And being raw materials usedly technical grade, technique is simple, easy to operate, and reaction is easy to control, and can produce in batches in a kettle..Prepared pentaerythritol acrylate has low hydroxyl value (lower than 30mgKOH/g) and low colourity (APHA color value is lower than 30) concurrently, and there is water-fast, resistance toization, wear-resisting, shock-resistant, thermotolerance, high rigidity, low-shrinkage and the advantage good to low-pole substrate adhesion, be applicable to the fields such as photocuring sizing agent, adhesion promoter, plastic coating, metallic coating, woodenware coating, liquid photoresist material, optical thin film, ink for screen printing.
Embodiment 3
Successively 28.87g tetramethylolmethane, 61.13g vinylformic acid, 49.5g toluene, 48.7g hexanaphthene, 1.35g methylsulphonic acid, 1.35g HND-6 solid super-strong acid, 0.3g Salzburg vitriol, 0.045g MEHQ are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed, and add 13.2g toluene and 12.4g hexanaphthene at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 90 DEG C, reflux 15 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1:3 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 35 DEG C, then utilize the sodium chloride solution of 10% to wash 2 times to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 10% of excessive 10% weight part to wash this reaction system 1 time, stratification, gets upper organic phase; The thiourea peroxide alkaline solution re-using 10% washs this organic phase 2 times, stratification, then washs 2 times, stratification with the sodium chloride solution of 10%, gets upper organic phase.
In this organic phase, add 0.015g MEHQ and 0.015g Resorcinol, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 55 DEG C, and time controling was at 3 hours.Last pressure filtration at 55 DEG C, obtain pentaerythritol acrylate finished product, its purity is 98%, and yield is 86%.Recording this pentaerythritol acrylate colourity is 10APHA, and hydroxyl value is 25.06mg KOH/g, and the viscosity 25 DEG C time is 650mPa.s.
Under same conditional operation condition, use the activated carbon of same quality proportioning to replace thiourea peroxide alkaline solution as discoloring agent, prepare pentaerythritol acrylate.The colourity recording this pentaerythritol acrylate is 55APHA, and it is far above the colourity using thiourea peroxide alkaline solution as pentaerythritol acrylate prepared during discoloring agent.Visible, the embodiment of the present invention, by adopting thiourea peroxide alkaline solution as discoloring agent, reaches good decolorizing effect.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, has wider application prospect.
Embodiment 4
Successively 24.69g tetramethylolmethane, 65.31g vinylformic acid, 46.6g toluene, 3.74g methylsulphonic acid, 0.07g Salzburg vitriol, 0.01g cuprous chloride, 0.045g p-ten.-butylcatechol are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed, and add 26.5g toluene at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 100 DEG C, reflux 18 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1:6.5 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then utilize the sodium chloride solution of 5% to wash 1 time to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 5% of excessive 10% weight part to wash this reaction system 2 times, stratification, gets upper organic phase; Re-use two this organic phase of (2-methoxy ethoxy) sodium aluminate alkali solution washing of 5% dihydro 2 times, stratification, then wash 2 times, stratification with the sodium chloride solution of 5%, get upper organic phase.
In this organic phase, add 0.035g MEHQ and 0.035g p-ten.-butylcatechol, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 80 DEG C, and time controling was at 3 hours.Last pressure filtration at 50 DEG C, obtain pentaerythritol acrylate finished product, its purity is 97%, and yield is 87%.Recording this pentaerythritol acrylate colourity is 20APHA, and hydroxyl value is 18.27mg KOH/g, and the viscosity 25 DEG C time is 680mPa.s.Visible, the embodiment of the present invention, by adopting thiourea peroxide alkaline solution as discoloring agent, reaches good decolorizing effect.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, has wider application prospect.
Embodiment 5
Successively 33.02g tetramethylolmethane, 66.98g vinylformic acid, 47.9g hexanaphthene, 3.23g methylsulphonic acid, 0.055g Salzburg vitriol, 0.035g p-ten.-butylcatechol are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed, and add 25.7g hexanaphthene at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 100 DEG C, reflux 15 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1:10 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then utilize the sodium chloride solution of 10% to wash 2 times to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 10% of excessive 10% weight part to wash this reaction system 1 time, stratification, gets upper organic phase; Re-use the S-WAT alkaline solution of 10% and the Sulfothiorine alkaline solution of 5% washs this organic phase 2 times, stratification, then wash 2 times, stratification with the sodium chloride solution of 10%, get upper organic phase.
In this organic phase, add 0.045g MEHQ and 0.045g p-ten.-butylcatechol, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 80 DEG C, and time controling was at 3 hours.Last pressure filtration at 55 DEG C, obtain pentaerythritol acrylate finished product, its purity is 96%, and yield is 88%.Recording this pentaerythritol acrylate colourity is 21APHA, and hydroxyl value is 12.8mg KOH/g, and the viscosity 25 DEG C time is 650mPa.s.Visible, the embodiment of the present invention, by adopting thiourea peroxide alkaline solution as discoloring agent, reaches good decolorizing effect.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, has wider application prospect.
Embodiment 6
Successively 21.56g tetramethylolmethane, 68.44g vinylformic acid, 48.5g hexanaphthene, 46.8g ethyl acetate, 2.83g methylsulphonic acid, 1.14g HND-6 solid super-strong acid, 0.16g Salzburg vitriol, 0.025g MEHQ are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed, and add 11.17g hexanaphthene and 10.6g ethyl acetate at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 100 DEG C, reflux 17 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1:6 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then utilize the sodium chloride solution of 10% to wash 2 times to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 10% of excessive 10% weight part to wash this reaction system 1 time, stratification, gets upper organic phase; Re-use 10% S-WAT alkaline solution washing and 10% Sulfothiorine alkaline solution washs this organic phase 2 times, stratification, then wash 2 times, stratification with the sodium chloride solution of 10%, get upper organic phase.
In this organic phase, add 0.06g MEHQ, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 80 DEG C, and time controling was at 3 hours.Last pressure filtration at 50 DEG C, obtain pentaerythritol acrylate finished product, its purity is 97%, and yield is 87%.Recording this pentaerythritol acrylate colourity is 15APHA, and hydroxyl value is 19.75mg KOH/g, and the viscosity 25 DEG C time is 720mPa.s.Visible, the embodiment of the present invention, by adopting thiourea peroxide alkaline solution as discoloring agent, reaches good decolorizing effect.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, has wider application prospect.
Embodiment 7
By 2,20.27g tetramethylolmethane, 69.73g vinylformic acid, 48.0g toluene, 49.6g ethyl acetate, 2.12g methylsulphonic acid, 0.98g tosic acid, 0.076g cuprous chloride, 0.055g p-ten.-butylcatechol are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed successively, and add 11.17g hexanaphthene and 10.6g ethyl acetate at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 100 DEG C, reflux 18 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1:5.5 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then utilize the sodium chloride solution of 10% to wash 3 times to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 10% of excessive 10% weight part to wash this reaction system 5 times, stratification, gets upper organic phase; Re-use two (2-methoxy ethoxy) sodium aluminate of 10% dihydro and 10% Sulfothiorine alkaline solution washs this organic phase 3 times, stratification, then wash 2 times, stratification with the sodium chloride solution of 10%, get upper organic phase.
In this organic phase, add 0.075g p-ten.-butylcatechol, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 40 DEG C, and time controling was at 3 hours.Last pressure filtration at 50 DEG C, obtain pentaerythritol acrylate finished product, its purity is 95%, and yield is 86%.Recording this pentaerythritol acrylate colourity is 15APHA, and hydroxyl value is 22.16mg KOH/g, and the viscosity 25 DEG C time is 700mPa.s.Visible, the embodiment of the present invention, by adopting thiourea peroxide alkaline solution as discoloring agent, reaches good decolorizing effect.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, has wider application prospect.
Embodiment 8
Successively 26.62g tetramethylolmethane, 63.38g vinylformic acid, 49.1g toluene, 49.5g hexanaphthene, 3.62g methylsulphonic acid, 0.036g cuprous chloride, 0.027g Salzburg vitriol, 0.038g p-ten.-butylcatechol, 0.043g MEHQ are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed, and add 12.66g toluene and 12.31g hexanaphthene at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 100 DEG C, reflux 18 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1:6.5 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then utilize the sodium chloride solution of 10% to wash 3 times to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 10% of excessive 10% weight part to wash this reaction system 5 times, stratification, gets upper organic phase; Re-use this organic phase of thiourea peroxide solution washing 2 times of 10%, stratification, then wash 2 times, stratification with the sodium chloride solution of 10%, get upper organic phase.
In this organic phase, add 0.065g p-ten.-butylcatechol and 0.035g MEHQ, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 60 DEG C, and time controling was at 3 hours.Last pressure filtration at 50 DEG C, obtain pentaerythritol acrylate finished product, its purity is 97%, and yield is 88%.Recording this pentaerythritol acrylate colourity is 20APHA, and hydroxyl value is 18.95mg KOH/g, and the viscosity 25 DEG C time is 690mPa.s.Visible, the embodiment of the present invention, by adopting thiourea peroxide alkaline solution as discoloring agent, reaches good decolorizing effect.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, has wider application prospect.
Embodiment 9
Successively 23.99g tetramethylolmethane, 66.01g vinylformic acid, 48.9g hexanaphthene, 47.3g ethyl acetate, 2.26g tosic acid, 1.21g HND-6 solid super-strong acid, 0.073g Salzburg vitriol, 0.026g p-ten.-butylcatechol, 0.024g MEHQ are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed, and add 12.81g hexanaphthene and 11.39g ethyl acetate at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 100 DEG C, reflux 20 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1:8 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then utilize the sodium chloride solution of 10% to wash 2 times to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 10% of excessive 10% weight part to wash this reaction system 2 times, stratification, gets upper organic phase; Re-use two (2-methoxy ethoxy) sodium aluminate 10% S-WAT alkaline solution of 5% dihydro and wash this organic phase 2 times, stratification, then wash 2 times, stratification with the sodium chloride solution of 10%, get upper organic phase.
In this organic phase, add 0.065g p-ten.-butylcatechol and 0.035g MEHQ, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 80 DEG C, and time controling was at 3 hours.Last pressure filtration at 50 DEG C, obtain pentaerythritol acrylate finished product, its purity is 98%, and yield is 89%.Recording this pentaerythritol acrylate colourity is 25APHA, and hydroxyl value is 16.35mg KOH/g, and the viscosity 25 DEG C time is 710mPa.s.Visible, the embodiment of the present invention, by adopting thiourea peroxide alkaline solution as discoloring agent, reaches good decolorizing effect.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, has wider application prospect.
Embodiment 10
Successively 22.41g tetramethylolmethane, 67.59g vinylformic acid, 49.9g toluene, 2.81g methylsulphonic acid, 0.9gHND-6 solid super-strong acid, 0.088g Salzburg vitriol, 0.053g p-ten.-butylcatechol, 0.032g MEHQ are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed, and add 24.4g toluene at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 100 DEG C, reflux 18 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1:6.5 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then utilize the sodium chloride solution of 10% to wash 2 times to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 10% of excessive 10% weight part to wash this reaction system 2 times, stratification, gets upper organic phase; The Sulfothiorine re-using 10% washs this organic phase 2 times, stratification, then washs 2 times, stratification with the sodium chloride solution of 10%, gets upper organic phase.
In this organic phase, add 0.077g p-ten.-butylcatechol and 0.045g MEHQ, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 80 DEG C, and time controling was at 3 hours.Last pressure filtration at 50 DEG C, obtain pentaerythritol acrylate finished product, its purity is 97%, and yield is 86%.Recording this pentaerythritol acrylate colourity is 15APHA, and hydroxyl value is 19.11mg KOH/g, and the viscosity 25 DEG C time is 630mPa.s.Visible, the embodiment of the present invention, by adopting thiourea peroxide alkaline solution as discoloring agent, reaches good decolorizing effect.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, has wider application prospect.
Embodiment 11
Successively 21.02g tetramethylolmethane, 68.98g vinylformic acid, 47.8g hexanaphthene, 3.26g methylsulphonic acid, 0.065g cuprous chloride, 0.046g p-ten.-butylcatechol, 0.011g MEHQ are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed, and add 22.64g hexanaphthene at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 100 DEG C, reflux 17 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1:7 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then utilize the sodium chloride solution of 10% to wash 3 times to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 10% of excessive 10% weight part to wash this reaction system 1 time, stratification, gets upper organic phase; The Sulfothiorine re-using 10% washs this organic phase 2 times, stratification, then washs 2 times, stratification with the sodium chloride solution of 10%, gets upper organic phase.
In this organic phase, add 0.054g p-ten.-butylcatechol and 0.072g MEHQ, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 80 DEG C, and time controling was at 3 hours.Last pressure filtration at 50 DEG C, obtain pentaerythritol acrylate finished product, its purity is 97%, and yield is 88%.Recording this pentaerythritol acrylate colourity is 15APHA, and hydroxyl value is 17.97mg KOH/g, and the viscosity 25 DEG C time is 660mPa.s.Visible, the embodiment of the present invention, by adopting thiourea peroxide alkaline solution as discoloring agent, reaches good decolorizing effect.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, has wider application prospect.
Embodiment 12
Successively 27.93g tetramethylolmethane, 62.07g vinylformic acid, 47.9g toluene, 3.88g methylsulphonic acid, 0.08g Salzburg vitriol, 0.005g cuprous chloride, 0.055g p-ten.-butylcatechol are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed, and add 27.5g toluene at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 100 DEG C, reflux 16 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1:5.5 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then utilize the sodium chloride solution of 8% to wash 2 times to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 8% of excessive 10% weight part to wash this reaction system 2 times, stratification, gets upper organic phase; Re-use the thiourea peroxide of 5% and the S-WAT alkaline solution of 5% washs this organic phase 2 times, stratification, then wash 2 times, stratification with the sodium chloride solution of 10%, get upper organic phase.
In this organic phase, add 0.045g MEHQ and 0.045g p-ten.-butylcatechol, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 80 DEG C, and time controling was at 3 hours.Last pressure filtration at 50 DEG C, obtain pentaerythritol acrylate finished product, its purity is 98%, and yield is 88%.Recording this pentaerythritol acrylate colourity is 15APHA, and hydroxyl value is 21.84mg KOH/g, and the viscosity 25 DEG C time is 700mPa.s.Visible, the embodiment of the present invention, by adopting thiourea peroxide alkaline solution as discoloring agent, reaches good decolorizing effect.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, has wider application prospect.
Embodiment 13
Successively 22.41g tetramethylolmethane, 67.59g vinylformic acid, 46.9g hexanaphthene, 47.3g ethyl acetate, 3.21g tosic acid, 0.27g HND-6 solid super-strong acid, 0.068g Salzburg vitriol, 0.031g p-ten.-butylcatechol, 0.014g MEHQ are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed, and add 11.93g hexanaphthene and 12.14g ethyl acetate at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 100 DEG C, reflux 16 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1:7 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then utilize the sodium chloride solution of 5% to wash 2 times to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 5% of excessive 10% weight part to wash this reaction system 2 times, stratification, gets upper organic phase; Re-use the thiourea peroxide of 5%, two (2-methoxy ethoxy) sodium aluminate of dihydro of 5% and the S-WAT alkaline solution of 5% and wash this organic phase 2 times, stratification, then wash 2 times, stratification with the sodium chloride solution of 10%, get upper organic phase.
In this organic phase, add 0.045g MEHQ and 0.045g p-ten.-butylcatechol, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 80 DEG C, and time controling was at 3 hours.Last pressure filtration at 50 DEG C, obtain pentaerythritol acrylate finished product, its purity is 97%, and yield is 89%.Recording this pentaerythritol acrylate colourity is 20APHA, and hydroxyl value is 17.16mg KOH/g, and the viscosity 25 DEG C time is 690mPa.s.Visible, the embodiment of the present invention, by adopting thiourea peroxide alkaline solution as discoloring agent, reaches good decolorizing effect.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, has wider application prospect.
Embodiment 14
Successively 21.83g tetramethylolmethane, 68.16g vinylformic acid, 48.4g hexanaphthene, 3.77g methylsulphonic acid, 0.045g Salzburg vitriol, 0.045g p-ten.-butylcatechol are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed, and add 26.8g hexanaphthene at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 100 DEG C, reflux 16 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1:5.5 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then utilize the sodium chloride solution of 10% to wash 2 times to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 10% of excessive 10% weight part to wash this reaction system 2 times, stratification, gets upper organic phase; Re-use two (2-methoxy ethoxy) sodium aluminate of dihydro of 10% and the Sulfothiorine alkaline solution of 10% washs this organic phase 2 times, stratification, then wash 2 times, stratification with the sodium chloride solution of 10%, get upper organic phase.
In this organic phase, add 0.055g MEHQ and 0.035g p-ten.-butylcatechol, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 80 DEG C, and time controling was at 3 hours.Last pressure filtration at 50 DEG C, obtain pentaerythritol acrylate finished product, its purity is 97%, and yield is 89%.Recording this pentaerythritol acrylate colourity is 10APHA, and hydroxyl value is 21.55mg KOH/g, and the viscosity 25 DEG C time is 700mPa.s.Visible, the embodiment of the present invention, by adopting thiourea peroxide alkaline solution as discoloring agent, reaches good decolorizing effect.Prepared pentaerythritol acrylate has low hydroxyl value and low colourity concurrently, has wider application prospect.
Embodiment 15
Successively 27.04g tetramethylolmethane, 62.96g vinylformic acid, 49.9g toluene, 3.25g methylsulphonic acid, 0.08g Salzburg vitriol, 0.02g cuprous chloride, 0.033g p-ten.-butylcatechol are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed, and add 28.6g toluene at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 100 DEG C, reflux 16 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 1:6.5 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then utilize the sodium chloride solution of 5% to wash 2 times to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 5% of excessive 10% weight part to wash this reaction system 2 times, stratification, gets upper organic phase; Re-use two (2-methoxy ethoxy) sodium aluminate of dihydro of 10% and the Sulfothiorine alkaline solution of 10% washs this organic phase 2 times, stratification, then wash 2 times, stratification with the sodium chloride solution of 10%, get upper organic phase.
Activated carbon is adopted to decolour to this organic phase, then in this organic phase, 0.045g MEHQ and 0.045g p-ten.-butylcatechol is added, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 80 DEG C, and time controling was at 3 hours.Last pressure filtration at 50 DEG C, obtain pentaerythritol acrylate finished product, its purity is 96%, and yield is 87%.Recording this pentaerythritol acrylate colourity is 90APHA, and hydroxyl value is 19.73mg KOH/g.
Although the embodiment of the present invention is by obtaining the pentaerythritol acrylate of low hydroxyl value, but due to the activated carbon that discoloring agent is selected, its decolorizing effect is poor, and pentaerythritol acrylate colourity, up to 90APHA, has had a strong impact on the quality of this pentaerythritol acrylate.Visible, compare activated carbon, the discoloring agent that the embodiment of the present invention provides has more excellent decolorizing effect.
Embodiment 16
Successively 25g tetramethylolmethane, 70.37g vinylformic acid, 49.9g toluene, 3.25g methylsulphonic acid, 0.08g Salzburg vitriol, 0.02g cuprous chloride, 0.033g p-ten.-butylcatechol are put into the four-hole boiling flask of the 500ml that thermometer, water trap, serpentine condenser and stirring rake are housed, and add 28.6g toluene at water trap.
Open oil bath heating unit, being heated to temperature to reaction system is 100 DEG C, reflux 16 hours.When pentaerythritol triacrylate and tetramethylol methane tetraacrylate ratio reach 2:1 in employing high performance liquid chromatography tracking reaction system, terminate back flow reaction.
By reaction system cooling down to 30 DEG C, then utilize the sodium chloride solution of 5% to wash 2 times to this reaction system, stratification, get upper organic phase and measure acid number; According to surveyed acid number, use the sodium hydroxide solution of 5% of excessive 10% weight part to wash this reaction system 2 times, stratification, gets upper organic phase; Re-use two (2-methoxy ethoxy) sodium aluminate of dihydro of 10% and the Sulfothiorine alkaline solution of 10% washs this organic phase 2 times, stratification, then wash 2 times, stratification with the sodium chloride solution of 10%, get upper organic phase.
Activated carbon is adopted to decolour to this organic phase, then in this organic phase, 0.045g MEHQ and 0.045g p-ten.-butylcatechol is added, underpressure distillation is carried out to it, and blowing air purges to solvent <0.1%, sloughs the solvent in organic phase.In this vacuum distillation process: vacuum degree control is at-0.1Mpa, and temperature controls at 80 DEG C, and time controling was at 3 hours.Last pressure filtration at 50 DEG C, obtain pentaerythritol acrylate finished product, its purity is 96%, and yield is 87%.Recording this pentaerythritol acrylate colourity is 35APHA, and hydroxyl value is 106.5mg KOH/g.
The embodiment of the present invention is decoloured by adopting the pentaerythritol acrylate of activated carbon to high hydroxyl value, when the colourity of the pentaerythritol acrylate of high hydroxyl value itself is less (about 43APHA), also its colourity cannot be down to below 30APHA, its decolorizing effect is poor.Visible, compared with activated carbon, the discoloring agent that the embodiment of the present invention provides has more excellent decolorizing effect.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for pentaerythritol acrylate, is characterized in that, described method comprises:
In reactor, add tetramethylolmethane, vinylformic acid, solvent, catalyzer and the first stopper, and described reactor is heated to preset temp;
Make reaction system back flow reaction under described preset temp, follow the tracks of the mol ratio of pentaerythritol triacrylate and tetramethylol methane tetraacrylate in described reaction system, when the mol ratio of described pentaerythritol triacrylate and described tetramethylol methane tetraacrylate is 1:3-10, terminate described back flow reaction;
After the cooling of described reaction system, respectively described reaction system to be washed, alkali cleaning, get the first organic phase;
Use reductive agent to wash described first organic phase, and then neutrality is washed to described first organic phase, get Second Organic Phase;
In described Second Organic Phase, add the second stopper, underpressure distillation, filtration are carried out to described Second Organic Phase, obtain described pentaerythritol acrylate.
2. the preparation method of pentaerythritol acrylate according to claim 1, it is characterized in that, described reductive agent is selected from least one in thiourea peroxide, two (2-methoxyethoxy) sodium aluminate of dihydro, S-WAT, hypo solution.
3. the preparation method of pentaerythritol acrylate according to claim 2, is characterized in that, the mass concentration of two (2-methoxyethoxy) sodium aluminate of described thiourea peroxide, dihydro, S-WAT, hypo solution is 5%-10%.
4. the preparation method of pentaerythritol acrylate according to claim 1, is characterized in that, described tetramethylolmethane and described acrylic acid mol ratio are 1:4-8.
5. the preparation method of pentaerythritol acrylate according to claim 1, it is characterized in that, described solvent is selected from least one in hexanaphthene, toluene, ethyl acetate, and the quality of described solvent is the 40%-80% of described tetramethylolmethane and described vinylformic acid total mass.
6. the preparation method of pentaerythritol acrylate according to claim 1, it is characterized in that, described catalyzer is selected from least one in tosic acid, methylsulphonic acid, solid super-strong acid, and the quality of described catalyzer is the 1.0%-4.0% of described tetramethylolmethane and described vinylformic acid total mass.
7. the preparation method of pentaerythritol acrylate according to claim 1, it is characterized in that, described first stopper is selected from least one in MEHQ, Resorcinol, Salzburg vitriol, cuprous chloride, p-tert-butylphenol, p-ten.-butylcatechol, and the quality of described first stopper is the 0.05%-0.5% of described tetramethylolmethane and described vinylformic acid total mass.
8. the preparation method of pentaerythritol acrylate according to claim 1, it is characterized in that, described second stopper is selected from least one in MEHQ, Resorcinol, p-tert-butylphenol, p-ten.-butylcatechol, and the quality of described second stopper is the 0.05%-0.5% of described Second Organic Phase quality.
9. the preparation method of pentaerythritol acrylate according to claim 1, is characterized in that, described preset temp is 80-100 DEG C.
10. the preparation method of pentaerythritol acrylate according to claim 1, is characterized in that, described temperature when carrying out underpressure distillation to described Second Organic Phase controls at 40 DEG C-80 DEG C.
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Denomination of invention: A preparation method of pentaerythritol acrylate Effective date of registration: 20231120 Granted publication date: 20170905 Pledgee: Bank of Shanghai Limited by Share Ltd. Pudong branch Pledgor: Shanghai FeiKai Material Technology Co.,Ltd. Registration number: Y2023310000759 |