CN111646901A - Preparation method of ditrimethylolpropane tetraacrylate - Google Patents
Preparation method of ditrimethylolpropane tetraacrylate Download PDFInfo
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- CN111646901A CN111646901A CN202010570333.3A CN202010570333A CN111646901A CN 111646901 A CN111646901 A CN 111646901A CN 202010570333 A CN202010570333 A CN 202010570333A CN 111646901 A CN111646901 A CN 111646901A
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- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 25
- 239000003112 inhibitor Substances 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 25
- 239000002351 wastewater Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010992 reflux Methods 0.000 claims abstract description 17
- 238000007599 discharging Methods 0.000 claims abstract description 16
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 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 13
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000005886 esterification reaction Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- 229950000688 phenothiazine Drugs 0.000 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- -1 polyol acrylates Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process 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
- 230000035484 reaction time Effects 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
-
- 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
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of ditrimethylolpropane tetraacrylate, which comprises the following steps: (1) putting a part of solvent, main materials of ditrimethylolpropane and acrylic acid, an antioxidant, a catalyst and a part of polymerization inhibitor into a reaction kettle; (2) heating the reaction kettle to carry out reflux reaction, keeping the temperature until no water is brought out of reflux liquid or the acid value of reaction liquid is controlled to be 20-40mgKOH/g, and cooling to room temperature; (3) putting the second part of solvent into a reaction kettle, adding alkali liquor for washing, controlling the pH, standing until the reaction materials are layered, and discharging the wastewater at the lower layer; (4) adding water into the material subjected to alkaline washing for washing, adding a second part of polymerization inhibitor, standing for layering of the reaction material, and discharging the wastewater on the lower layer; (5) and transferring the reaction material without the wastewater into an evaporator, vacuumizing, and removing the solvent and the water to obtain the product. The invention can reduce the generation of polymers in the product, and ensure that the product has low color number, low acid value and high ester content.
Description
Technical Field
The invention relates to preparation of acrylate in the field of fine chemical preparation, in particular to a preparation method of ditrimethylolpropane tetraacrylate.
Background
Di-trimethylolpropane tetraacrylate (Di-TMPTA for short) is an important variety in polyol acrylates, and is a high-activity dilution monomer with ideal cost performance, wide application and large using amount in polyol acrylate series products. Four hydroxymethyl groups on a main chain of ditrimethylolpropane and acrylic acid are subjected to acid-alcohol reaction to generate ester, the structure of the ester is mainly trans, the ester is relatively stable and has a large molecular structure, and a flexible ether bond exists, so that the material can have better elasticity and toughness after being cured, and the brittleness is greatly improved. It also has the characteristics of high boiling point, high reaction activity, low volatility, high curing speed, high gloss, low irritation and low viscosity, has good intermiscibility with acrylic prepolymer, can be used as an active diluent, is mainly used as a reactive diluent of ultraviolet curing coating and printing ink, plays a role of dilution before ultraviolet irradiation, and reacts after irradiation to form a part of a curing film.
The existing production method of ditrimethylolpropane tetraacrylate mostly adopts a method of directly esterifying acid and alcohol, takes excessive acrylic acid, toluene or benzene as a solvent with water and sulfuric acid as a catalyst, but the quality of a finished product prepared by the method has the following defects: 1. turbidity of different degrees is easy to occur; 2. the chroma is higher; 3. the acid value is higher; 4. the ester content is low.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of ditrimethylolpropane tetraacrylate, which can reduce the generation of polymers in products and ensure that the products have low color number, low acid value and high ester content.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing ditrimethylolpropane tetraacrylate comprises the following steps:
(1) putting a part of solvent into an esterification reaction kettle, then adding main materials of ditrimethylolpropane and acrylic acid, and then adding an antioxidant, a catalyst and a part of polymerization inhibitor;
(2) heating the esterification reaction kettle to 60-110 ℃ for reflux reaction, preserving heat for 4-12h until no moisture is brought out of reflux liquid or the acid value of reaction liquid is controlled at 20-40mgKOH/g, and cooling to room temperature;
(3) putting the second part of solvent into an esterification reaction kettle, adding alkali liquor for washing, controlling the pH of reaction materials to be 7-9, standing, and discharging the wastewater on the lower layer after the reaction materials are layered;
(4) adding water into the material subjected to alkaline washing, washing until the pH value of an eluate is 7-8, adding a second part of polymerization inhibitor, standing until the reaction materials are layered, and discharging the wastewater on the lower layer;
(5) transferring the reaction material without the wastewater into an evaporator, vacuumizing, and removing the solvent and water to obtain a ditrimethylolpropane tetraacrylic acid product;
wherein the esterification reaction system comprises the following components in parts by weight: 10-20% of a first part of solvent, 10-20% of a second part of solvent, 25-45% of ditrimethylolpropane, 30-50% of acrylic acid, 0.01-0.5% of antioxidant, 0.5-5% of catalyst, 100-400 ppm of a first part of polymerization inhibitor and 10-200 ppm of a second part of polymerization inhibitor.
Further, the solvent in the step (1) and the step (3) is one or more of benzene, toluene, xylene, n-hexane and cyclohexane.
Further, the antioxidant in the step (1) is one or more of hypophosphorous acid, phosphorous acid and phosphoric acid.
Further, the catalyst in the step (1) is one or more of methane sulfonic acid, p-toluenesulfonic acid and dodecylbenzene sulfonic acid.
Further, the polymerization inhibitor in the step (1) and the step (4) is one or more of hydroquinone, p-benzoquinone, phenothiazine and p-hydroxyanisole.
Further, the alkali liquor in the step (3) is one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate.
Further, the alkali liquor in the step (3) is 2-20% by mass.
Further, the adding amount of water in the step (4) is 5-20% of the total feeding amount.
Further, the vacuum degree in the step (5) is less than 4000Pa, the removing temperature is 40-90 ℃, and the removing time is 0.5-1.5 h.
The ditrimethylolpropane tetraacrylate (Di-TMPTA) product is prepared according to the preparation method of the ditrimethylolpropane tetraacrylate.
Di-TMPTA reaction equation:
the invention has the beneficial effects that:
the invention is mainly embodied in the preparation method of the ditrimethylolpropane tetraacrylate, the solvent is added in two times of reaction and post-treatment in the reaction process, the reaction concentration is improved while the water-carrying effect is ensured, the reaction time is shortened, the loss of the solvent is reduced, the reaction esterification rate can be improved, and the ester content of the product is more than 98.0 percent; a low-boiling point and low-toxicity solvent is adopted, and the reaction reflux temperature is lower, so that the color number of the obtained product is less than 15 (a platinum-cobalt colorimetric method); in the post-treatment alkali washing process, the product phase is washed to be alkalescent, so that the acid value of the product is less than or equal to 0.05 mgKOH/g. The invention can reduce the generation of polymers in the product, and ensure that the product has low color number, low acid value and high ester content.
Detailed Description
The following describes the specific embodiments of the present invention with reference to examples, so that the technical solutions and the advantages thereof are more clear and clear. The following described embodiments are exemplary and are intended to be illustrative of the invention, but are not to be construed as limiting the invention.
In the specific embodiment of the invention, the preparation method of ditrimethylolpropane tetraacrylate is specifically disclosed, and the specific steps are as follows:
(1) putting a part of solvent into an esterification reaction kettle, then adding main materials of ditrimethylolpropane and acrylic acid, and then adding an antioxidant, a catalyst and a part of polymerization inhibitor;
(2) heating the esterification reaction kettle to 60-110 ℃ for reflux reaction, preserving heat for 4-12h until no moisture is brought out of reflux liquid or the acid value of reaction liquid is controlled at 20-40mgKOH/g, and cooling to room temperature;
(3) putting the second part of solvent into an esterification reaction kettle, adding alkali liquor for washing, controlling the pH of reaction materials to be 7-9, standing, and discharging the wastewater on the lower layer after the reaction materials are layered;
(4) adding water into the material subjected to alkaline washing, washing until the pH value of an eluate is 7-8, adding a second part of polymerization inhibitor, standing until the reaction materials are layered, and discharging the wastewater on the lower layer;
(5) transferring the reaction material without the wastewater into an evaporator, vacuumizing, and removing the solvent and water to obtain a ditrimethylolpropane tetraacrylic acid product;
wherein the esterification reaction system comprises the following components in parts by weight: 10-20% of a first part of solvent, 10-20% of a second part of solvent, 25-45% of ditrimethylolpropane, 30-50% of acrylic acid, 0.01-0.5% of antioxidant, 0.5-5% of catalyst, 100-400 ppm of a first part of polymerization inhibitor and 10-200 ppm of a second part of polymerization inhibitor;
the solvent in the step (1) and the step (3) is one or more of benzene, toluene, xylene, n-hexane and cyclohexane;
the antioxidant in the step (1) is one or more of hypophosphorous acid, phosphorous acid and phosphoric acid;
the catalyst in the step (1) is one or more of methane sulfonic acid, p-toluenesulfonic acid and dodecylbenzene sulfonic acid;
the polymerization inhibitor in the step (1) and the step (4) is one or more of hydroquinone, p-benzoquinone, phenothiazine and p-hydroxyanisole;
the alkali liquor in the step (3) is one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate;
selecting the alkali liquor with the mass percentage concentration of 2-20% as the alkali liquor in the step (3);
the adding amount of water in the step (4) is 5-20% of the total amount of fed materials;
the vacuum degree in the step (5) is less than 4000Pa, the removing temperature is 40-90 ℃, and the removing time is 0.5-1.5 h.
Di-TMPTA reaction equation:
example 1:
the preparation method of ditrimethylolpropane tetraacrylate of this example includes the following steps:
(1) putting 440.0g of solvent toluene into an esterification reaction kettle, adding 692.2g of main material ditrimethylolpropane and 816.9g of acrylic acid, and then adding 0.3g of polymerization inhibitor phenothiazine, 5.1g of antioxidant 50% hypophosphorous acid solution and 31.0g of catalyst p-toluenesulfonic acid;
(2) heating the esterification reaction kettle to 105 ℃ for reflux reaction, preserving the heat for 6 hours until no moisture is brought out of the reflux liquid, measuring the acid value of the reaction liquid to be 28mgKOH/g, and beginning to cool to room temperature;
(3) putting 440g of solvent n-hexane into an esterification reaction kettle, adding a mixed solution of 5% of sodium hydroxide and 10% of sodium carbonate, washing, controlling the pH of reaction materials to be 7.6, standing, and discharging the wastewater on the lower layer after the reaction materials are layered;
(4) adding 300g of water into the material subjected to alkaline washing, washing until the pH value of an eluate is 7, adding 0.1g of phenothiazine serving as a polymerization inhibitor, standing until the reaction material is layered, and discharging the wastewater at the lower layer;
(5) the reaction material without wastewater is transferred to an evaporator to remove the solvent, the removal temperature is 80 ℃, the removal time is 0.5h, the vacuum degree is less than 4000Pa, and the target product ditrimethylolpropane tetraacrylate 1225.5g, the acid value is 0.04mgKOH/g (the acid value detection method is determined according to the method of GB 1668-2008), the color number 15 (determined according to the regulation of GB 1664-.
Example 2:
the preparation method of ditrimethylolpropane tetraacrylate of this example includes the following steps:
(1) putting 480.0g of solvent cyclohexane into an esterification reaction kettle, adding 692.2g of main material ditrimethylolpropane and 876.7g of acrylic acid, adding 0.5g of polymerization inhibitor hydroquinone, 6.8g of antioxidant 50% hypophosphorous acid solution and 28.0g of catalyst methane sulfonic acid;
(2) heating the esterification reaction kettle to 89 ℃ for reflux reaction, preserving the temperature for 9 hours until no water is separated from the reflux liquid, measuring the acid value of the reaction liquid to be 20mgKOH/g, and cooling to room temperature;
(3) putting 400g of solvent cyclohexane into an esterification reaction kettle, adding 10% sodium carbonate solution for washing, controlling the pH of reaction materials to be 7.5, standing, and discharging the wastewater on the lower layer after the reaction materials are layered;
(4) adding 300g of water into the material subjected to alkaline washing, washing until the pH value of an eluate is 7, adding 0.1g of hydroquinone serving as a polymerization inhibitor, standing until the reaction material is layered, and discharging the wastewater on the lower layer;
(5) the reaction material without wastewater is transferred to an evaporator to remove the solvent, the removal temperature is 60 ℃, the removal time is 1.0h, the vacuum degree is less than 1000Pa, and 1251.3g of the target product ditrimethylolpropane tetraacrylate, the acid value is 0.04mgKOH/g (the acid value detection method is determined according to the method of GB 1668-2008), the color number is 10 (determined according to the regulation of GB 1664-.
Example 3:
the preparation method of ditrimethylolpropane tetraacrylate of this example includes the following steps:
(1) putting 500.0kg of solvent benzene into an esterification reaction kettle, adding 692.2kg of main materials of ditrimethylolpropane and 844.8kg of acrylic acid, and then adding 0.5kg of polymerization inhibitor p-benzoquinone, 5.0kg of antioxidant phosphorous acid and 34.0kg of catalyst dodecyl benzene sulfonic acid;
(2) heating the esterification reaction kettle to 80 ℃ for reflux reaction, preserving the heat for 12 hours until no moisture is brought out of the reflux liquid, measuring the acid value of the reaction liquid to be 40mgKOH/g, and beginning to cool to room temperature;
(3) putting 380kg of solvent benzene into an esterification reaction kettle, adding a mixed solution of 5% of sodium hydroxide and 10% of sodium carbonate for washing, controlling the pH of reaction materials to be 8.0, standing, and discharging the wastewater on the lower layer after the reaction materials are layered;
(4) adding 250kg of water into the material subjected to alkaline washing, washing until the pH value of an eluate is 7.5, adding 0.1kg of polymerization inhibitor p-benzoquinone, standing until the reaction material is layered, and discharging the lower-layer wastewater;
(5) the reaction material without wastewater is transferred to an evaporator to remove the solvent, the removal temperature is 50 ℃, the removal time is 1h, the vacuum degree is less than 500Pa, and 1230.5kg of the target product ditrimethylolpropane tetraacrylate, the acid value is 0.03mgKOH/g (the acid value detection method is determined according to the method of GB 1668-2008), the color number is No. 10 (determined according to the regulation of GB 1664-.
Example 4:
the preparation method of ditrimethylolpropane tetraacrylate of this example includes the following steps:
(1) putting 565.0kg of solvent n-hexane into an esterification reaction kettle, adding 692.2kg of main materials of ditrimethylolpropane and 916.5kg of acrylic acid, and then adding 0.4kg of polymerization inhibitor p-hydroxyanisole, 4.0kg of antioxidant phosphoric acid and 33.0kg of catalyst p-toluenesulfonic acid;
(2) heating the esterification reaction kettle to 79 ℃ for reflux reaction, preserving the heat for 10 hours until no moisture is brought out of the reflux liquid, measuring the acid value of the reaction liquid to be 34mgKOH/g, and beginning to cool to room temperature;
(3) putting 315kg of solvent n-hexane into an esterification reaction kettle, adding 12% sodium hydroxide solution for washing, controlling the pH of reaction materials to be 8.5, standing, and discharging the wastewater on the lower layer after the reaction materials are layered;
(4) adding 200kg of water into the material subjected to alkaline washing, washing until the pH value of an eluate is 8, adding 0.1kg of p-hydroxyanisole serving as a polymerization inhibitor, standing until the reaction material is layered, and discharging the lower-layer wastewater;
(5) the reaction material without wastewater is transferred to an evaporator to remove the solvent, the removal temperature is 50 ℃, the removal time is 1h, the vacuum degree is less than 500Pa, and 1280.5kg of the target product ditrimethylolpropane tetraacrylate, the acid value is 0.01mgKOH/g (the acid value detection method is determined according to the method of GB 1668-2008), the color number 15 (determined according to the regulation of GB 1664-.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A method for preparing ditrimethylolpropane tetraacrylate is characterized in that: the preparation method comprises the following steps:
(1) putting a part of solvent into an esterification reaction kettle, then adding main materials of ditrimethylolpropane and acrylic acid, and then adding an antioxidant, a catalyst and a part of polymerization inhibitor;
(2) heating the esterification reaction kettle to 60-110 ℃ for reflux reaction, preserving heat for 4-12h until no moisture is brought out of reflux liquid or the acid value of reaction liquid is controlled at 20-40mgKOH/g, and cooling to room temperature;
(3) putting the second part of solvent into an esterification reaction kettle, adding alkali liquor for washing, controlling the pH of reaction materials to be 7-9, standing, and discharging the wastewater on the lower layer after the reaction materials are layered;
(4) adding water into the material subjected to alkaline washing, washing until the pH value of an eluate is 7-8, adding a second part of polymerization inhibitor, standing until the reaction materials are layered, and discharging the wastewater on the lower layer;
(5) transferring the reaction material without the wastewater into an evaporator, vacuumizing, and removing the solvent and water to obtain a ditrimethylolpropane tetraacrylic acid product;
wherein the esterification reaction system comprises the following components in parts by weight: 10-20% of a first part of solvent, 10-20% of a second part of solvent, 25-45% of ditrimethylolpropane, 30-50% of acrylic acid, 0.01-0.5% of antioxidant, 0.5-5% of catalyst, 100-400 ppm of a first part of polymerization inhibitor and 10-200 ppm of a second part of polymerization inhibitor.
2. The method for preparing ditrimethylolpropane tetraacrylate according to claim 1, wherein the solvent in step (1) and step (3) is one or more of benzene, toluene, xylene, n-hexane and cyclohexane.
3. The method for preparing ditrimethylolpropane tetraacrylate according to claim 1, wherein the antioxidant in step (1) is one or more of hypophosphorous acid, phosphorous acid and phosphoric acid.
4. The method for preparing ditrimethylolpropane tetraacrylate according to claim 1, wherein the catalyst in step (1) is one or more of methane sulfonic acid, p-toluenesulfonic acid and dodecylbenzene sulfonic acid.
5. The method for preparing ditrimethylolpropane tetraacrylate according to claim 1, wherein the polymerization inhibitor in step (1) and step (4) is one or more of hydroquinone, p-benzoquinone, phenothiazine and p-hydroxyanisole.
6. The method for preparing ditrimethylolpropane tetraacrylate according to claim 1, wherein the alkaline solution in step (3) is one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate.
7. The method for preparing ditrimethylolpropane tetraacrylate according to claim 6, wherein 2-20% by mass of lye is selected as the lye in step (3).
8. The method for preparing ditrimethylolpropane tetraacrylate according to claim 1, wherein the amount of water added in step (4) is 5-20% of the total amount of the raw materials.
9. The method for preparing ditrimethylolpropane tetraacrylate according to claim 1, wherein the degree of vacuum in step (5) is less than 4000Pa, the removal temperature is 40-90 ℃, and the removal time is 0.5-1.5 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114230480A (en) * | 2021-12-13 | 2022-03-25 | 山东省海洋化工科学研究院 | Polymerization inhibitor for purifying diacetone acrylamide and method for purifying diacetone acrylamide |
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| CN102146038A (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 ditrimethylolpropane tetraacrylate |
| CN102643197A (en) * | 2012-03-31 | 2012-08-22 | 江苏利田科技股份有限公司 | Cleaning production method for di-trimethylolpropane tetra-acrylic ester or pentaerythritol tetra-acrylic ester |
| CN103342644A (en) * | 2013-07-23 | 2013-10-09 | 天津市天骄化工有限公司 | Preparation method of polyhydric alcohol acrylate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102146038A (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 ditrimethylolpropane tetraacrylate |
| CN102643197A (en) * | 2012-03-31 | 2012-08-22 | 江苏利田科技股份有限公司 | Cleaning production method for di-trimethylolpropane tetra-acrylic ester or pentaerythritol tetra-acrylic ester |
| CN103342644A (en) * | 2013-07-23 | 2013-10-09 | 天津市天骄化工有限公司 | Preparation method of polyhydric alcohol acrylate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114230480A (en) * | 2021-12-13 | 2022-03-25 | 山东省海洋化工科学研究院 | Polymerization inhibitor for purifying diacetone acrylamide and method for purifying diacetone acrylamide |
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