CN106543156A - It is a kind of to reduce epoxychloropropane residue in triglycidyl isocyanurate (TGIC) - Google Patents
It is a kind of to reduce epoxychloropropane residue in triglycidyl isocyanurate (TGIC) Download PDFInfo
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- CN106543156A CN106543156A CN201610830129.4A CN201610830129A CN106543156A CN 106543156 A CN106543156 A CN 106543156A CN 201610830129 A CN201610830129 A CN 201610830129A CN 106543156 A CN106543156 A CN 106543156A
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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Abstract
It is a kind of to reduce epoxychloropropane residue in triglycidyl isocyanurate (TGIC), it is related to a kind of chemical separation and purification process, the present invention discloses a kind of new technology for reducing epoxychloropropane residual quantity in triglycidyl isocyanurate (TGIC).The technique is refined to TGIC crude products using solvent pairs crystallisation, using the good solvent big to TGIC dissolubilities, TGIC crude products are dissolved, then add poor solvent less to TGIC dissolubilities again by a certain percentage, TGIC crude products are made to crystallize in mixed solvent, the technique can efficiently remove the epoxychloropropane in TGIC crude products, and highly purified TGIC products are obtained, and in TGIC, epichlorohydrin content is in below 50ppm.
Description
Technical field
The present invention relates to a kind of chemical separation and purification process, more particularly to one kind reduce isocyanuric acid three and shrink sweet
Epoxychloropropane residue in grease (TGIC).
Background technology
The curing agent that triglycidyl isocyanurate (TGIC) is commonly used as polyester powder class coating, it is excellent due to which
Cementability, electrical properties in high temperatures and crosslinking curing performance and become one of most important curing agent of base-material containing carboxyl functional group.
Using two step synthetic method triglycidyl isocyanurate (TGIC), its synthetic route is for current factory：Isocyanide urea
Acid and epichlorohydrin reaction, generate intermediate product-three (chloro- 2 hydroxypropyls of 3-) isocyanuric acid ester, intermediate product again with hydroxide
There is cyclization in sodium, generate triglycidyl isocyanurate, and its reaction equation is as follows：
The production process of TGIC is：Quantitative isocyanuric acid, epoxychloropropane and catalyst are put in reactor, is warming up to
110 DEG C, reaction is cooled to 45 DEG C after terminating, and adds quantitative NaOH, is cyclized, is added a certain amount of in reactor
Water, static layering, by organic layer vacuum distillation, recycling design epoxychloropropane, obtain TGIC crude products.Crude product Jing methyl alcohol is tied
TGIC commodity are obtained after brilliant, granulation, drying.
In the refined TGIC of current country's methanol crystallization technique, epichlorohydrin content is in the range of 300 ~ 500 ppm.
The epoxychloropropane of high residue can have a strong impact on the electrical property of TGIC commodity, and in electrostatic spraying operation can also damage operation
People's is healthy and safe.In the TGIC commodity that the state such as Japan, America and Europe uses at present, epichlorohydrin content is within 100ppm.The U.S.
Patent（US4395542A）Report the method that vaporizing extract process removes traces of ethylene chloropropane in TGIC, the method 159 DEG C of temperature,
N2Under conditions of being 0.144 with the mass ratio of product, the TGIC of heating is flowed down from the top of stripper, N is passed through at bottom of towe end2
The epoxychloropropane of vaporization is taken away, the content of epoxychloropropane is reduced to 7 ppm by 447 original ppm in TGIC after stripping,
The technique needs stripper apparatus, and operating condition is harsher.
The content of the invention
It is an object of the invention to provide epoxychloropropane is residual in a kind of reduction triglycidyl isocyanurate (TGIC)
Allowance method, the method are a kind of epoxy chloropropionates suitable for industrial reduction isocyanuric acid three-glycidyl ester (TGIC)
The new technology of alkane residual quantity, it is higher by epoxychloropropane residual quantity in the TGIC obtained by methanol crystallization technique at present to solve
Problem.
The purpose of the present invention is achieved through the following technical solutions：
A kind of to reduce epoxychloropropane residue in triglycidyl isocyanurate (TGIC), methods described is using double molten
Agent crystallisation is refined to TGIC crude products, and TGIC crude products are dissolved in good solvent, adds poor solvent so as to mixed
Crystallize in bonding solvent, so as to efficiently remove the epoxychloropropane in TGIC crude products, obtain highly purified TGIC products；
Its specific operating process is as follows：
TGIC crude products and good solvent are added in the conical flask equipped with condensation reflux unit, is stirred at 40 ~ 80 DEG C, to TGIC
Crude product is completely dissolved, and adds poor solvent, and then natural cooling in -5 ~ 0 DEG C of environment separates out TGIC crystal, filter,
Filter cake is placed in vacuum drying chamber, 3h is vacuum dried at 60-80 DEG C, is obtained product.
Epoxychloropropane residue in a kind of described reduction triglycidyl isocyanurate (TGIC), it is described
Good solvent is DMF or acetone, dichloromethane, 1,2- dichloroethanes, and poor solvent is methyl alcohol or ethanol；
The ratio of TGIC crude products and good solvent is 1:The volume ratio of 1 ~ 3 (w/v), good solvent and poor solvent is 1: 1~4.
Epoxychloropropane residue in a kind of described reduction triglycidyl isocyanurate (TGIC), using N,
Dinethylformamide as good solvent, methyl alcohol or ethanol as poor solvent when, be improve TGIC yields, add it is bad molten
Water is added while agent, is then crystallized.
Epoxychloropropane residue in a kind of described reduction triglycidyl isocyanurate (TGIC), uses third
Ketone, dichloromethane or 1,2- dichloroethanes as good solvent, methyl alcohol or ethanol as poor solvent when, after primary crystallization is filtered
Mother liquor concentrations, carry out secondary crystallization, filter, will the filter cake that filtered twice merge after be dried, obtain TGIC products.
Advantages of the present invention with effect is：
Solvent pairs crystallization processes of the present invention, device are simple, easy to operate, it is easy to industrialize.Work is crystallized using solvent pairs of the present invention
Skill, in the TGIC after refining, epichlorohydrin content is less than 50 ppm, better than methanol crystallization technique.
Specific embodiment
With reference to embodiment, the present invention is described in detail.
The technical solution adopted in the present invention is the residual quantity that epoxychloropropane in TGIC is reduced using solvent pairs crystallisation,
Using the good solvent big to TGIC solubility, at a certain temperature TGIC is dissolved in the proper ratio, these good solvents can be with
It is N,N-dimethylformamide, acetone, dichloromethane, 1,2- dichloroethanes；Then add it is appropriate to TGIC solubility compared with
Little poor solvent, poor solvent can be methyl alcohol, ethanol, and the TGIC crystallizations under low temperature are separated out, and epoxychloropropane then dissolves
Do not separate out in mixed solvent, so as to reduce the purpose of epoxychloropropane residual quantity in TGIC.
In the crystallization processes that the present invention is provided, made using DMF as good solvent, methyl alcohol or ethanol
For poor solvent when, can add poor solvent while add appropriate water, to increase the polarity of mixed solvent, make TGIC more
Easily separate out, improve yield；Using acetone, dichloromethane, 1,2- dichloroethanes, used as good solvent, methyl alcohol or ethanol are used as bad
During solvent, yield can be improved using the method for the mother liquor concentrations-recrystallization after filtering to primary crystallization.
Described technical scheme is operated by procedure below：
1st, the concrete operations crystallized by N,N-dimethylformamide/methyl alcohol (ethanol) dual-solvent system are adopted for：To equipped with cold
A certain amount of TGIC crude products and appropriate DMF are added in the conical flask of solidifying reflux, is stirred at 80 DEG C
Mix, be completely dissolved to TGIC crude products, add a certain amount of methyl alcohol or ethanol, and add appropriate water, natural cooling, in -5 ~ 0
DEG C environment in separate out TGIC crystal, filter, filter cake is placed in vacuum drying chamber, 3h is vacuum dried at 80 DEG C.
2nd, using acetone (dichloromethane, 1,2- dichloroethanes)/methyl alcohol (ethanol) dual-solvent system crystallized it is concrete
Operate and be：A certain amount of TGIC crude products and appropriate acetone (dichloromethane are added in the conical flask equipped with condensation reflux unit
Alkane, 1,2- dichloroethanes), stir at 40 ~ 80 DEG C, be completely dissolved to TGIC crude products, add a certain amount of methyl alcohol or ethanol,
Natural cooling, separates out TGIC crystal in -5 ~ 0 DEG C of environment, filters, and concentrates the filtrate to the 1/2 ~ 1/3 of original volume, nature
Cooling, separates out TGIC crystal in -5 ~ 0 DEG C of environment, filters, be placed in vacuum drying chamber after filter cake twice is merged,
3h is vacuum dried at 60-80 DEG C.
It is heretofore described it is refined after TGIC in the content of epoxychloropropane be to be determined by gas chromatography analysis, with outer
Mark method is calculated, and analytical conditions for gas chromatography is as follows：
Chromatographic column：SE-54 capillary columns；Initial temperature：90℃；Heating rate：10℃/min；Temperature of vaporization chamber：250℃；Inspection
Survey room temperature：280℃；Detector：FID.
Embodiment 1
5.00 g TGIC crude products, 5ml N, N- dimethyl methyls are added in the 100 ml conical flasks equipped with condensation reflux unit
Acid amides, is heated to 80 DEG C, and stirring is completely dissolved TGIC crude products, is subsequently adding 10ml methyl alcohol and 2ml water, by mixed liquor nature
Cooling, after be transferred in 0 DEG C of environment and separate out TGIC crystal, filter, filter cake be placed in vacuum drying chamber, the vacuum at 80 DEG C
3h is dried, 3.51 g TGIC are obtained.Jing gas chromatographic analysis, in TGIC, epichlorohydrin content is 35ppm.
Embodiment 2
Concrete steps add 15 ml 1,2- dichloroethanes to be heated to 80 in 10.00g TGIC crude products with reference to embodiment 1
DEG C, stirring is completely dissolved TGIC, adds 15ml methyl alcohol, by mixed liquor natural cooling, after be transferred in 0 DEG C of environment and separate out
TGIC crystal, filters, and concentrates the filtrate to 15ml, and natural cooling separates out TGIC crystal in being transferred to 0 DEG C of environment, filters, will
Filter cake twice is placed in vacuum drying chamber after merging, and is vacuum dried 3 h, obtains 7.01g TGIC at 80 DEG C.Jing gas phase colors
Spectrum detection, the epichlorohydrin content in TGIC are 40ppm.
Claims (4)
- It is 1. a kind of to reduce epoxychloropropane residue in triglycidyl isocyanurate (TGIC), it is characterised in that：Institute State method to refine TGIC crude products using solvent pairs crystallisation, TGIC crude products are dissolved in good solvent, add not Good solvent so as to crystallize in mixed solvent, so as to efficiently remove the epoxychloropropane in TGIC crude products, obtain highly purified TGIC products；Its specific operating process is as follows：TGIC crude products and good solvent are added in the conical flask equipped with condensation reflux unit, is stirred at 40 ~ 80 DEG C, to TGIC Crude product is completely dissolved, and adds poor solvent, and then natural cooling in -5 ~ 0 DEG C of environment separates out TGIC crystal, filter, Filter cake is placed in vacuum drying chamber, 3h is vacuum dried at 60-80 DEG C, is obtained product.
- 2. in a kind of reduction triglycidyl isocyanurate (TGIC) according to claim 1, epoxychloropropane is remained Amount method, it is characterised in that：Described good solvent is N,N-dimethylformamide or acetone, dichloromethane, bis- chloroethenes of 1,2- Alkane, poor solvent are methyl alcohol or ethanol；The ratio of TGIC crude products and good solvent is 1:1 ~ 3 (w/v), good solvent and bad molten The volume ratio of agent is 1: 1~4.
- 3. one kind according to claim 1 reduces epoxychloropropane residual quantity in triglycidyl isocyanurate (TGIC) Method, it is characterised in that：Using DMF as good solvent, methyl alcohol or ethanol as poor solvent when, to carry High TGIC yields, while poor solvent is added add water, are then crystallized.
- 4. one kind according to claim 1 reduces epoxychloropropane residual quantity in triglycidyl isocyanurate (TGIC) Method, it is characterised in that：Using acetone, dichloromethane or 1,2- dichloroethanes as good solvent, methyl alcohol or ethanol as bad During solvent, the mother liquor concentrations after primary crystallization is filtered carry out secondary crystallization, filter, and the filter cake for filtering twice is merged laggard Row drying, obtains TGIC products.
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| CN201610830129.4A CN106543156A (en) | 2016-09-19 | 2016-09-19 | It is a kind of to reduce epoxychloropropane residue in triglycidyl isocyanurate (TGIC) |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457302A (en) * | 2020-12-15 | 2021-03-09 | 黄山市德邦粉体材料有限公司 | Crystallization process in synthesis of triglycidyl isocyanurate |
| CN113244854A (en) * | 2021-06-10 | 2021-08-13 | 黄山友谊南海新材料有限公司 | High-purity TGIC system of processing |
| CN114195981A (en) * | 2021-12-24 | 2022-03-18 | 广东省科学院化工研究所 | Biphenyl epoxy resin and synthetic method and application thereof |
| CN114315809A (en) * | 2020-09-29 | 2022-04-12 | 湖南云科化工有限公司 | Preparation method of triglycidyl isocyanurate |
| CN114805248A (en) * | 2022-06-05 | 2022-07-29 | 黄山学院 | Comprehensive utilization method of industrial low-concentration acetic acid |
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| CN103319469A (en) * | 2013-06-06 | 2013-09-25 | 黄山华惠科技有限公司 | Triglycidyl isocyanurate production method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114315809A (en) * | 2020-09-29 | 2022-04-12 | 湖南云科化工有限公司 | Preparation method of triglycidyl isocyanurate |
| CN114315809B (en) * | 2020-09-29 | 2023-12-15 | 湖南云科化工有限公司 | Preparation method of triglycidyl isocyanurate |
| CN112457302A (en) * | 2020-12-15 | 2021-03-09 | 黄山市德邦粉体材料有限公司 | Crystallization process in synthesis of triglycidyl isocyanurate |
| CN113244854A (en) * | 2021-06-10 | 2021-08-13 | 黄山友谊南海新材料有限公司 | High-purity TGIC system of processing |
| CN114195981A (en) * | 2021-12-24 | 2022-03-18 | 广东省科学院化工研究所 | Biphenyl epoxy resin and synthetic method and application thereof |
| CN114195981B (en) * | 2021-12-24 | 2023-10-13 | 广东省科学院化工研究所 | Biphenyl epoxy resin and synthetic method and application thereof |
| CN114805248A (en) * | 2022-06-05 | 2022-07-29 | 黄山学院 | Comprehensive utilization method of industrial low-concentration acetic acid |
| CN114805248B (en) * | 2022-06-05 | 2023-10-17 | 黄山学院 | Comprehensive utilization method of industrial low-concentration acetic acid |
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Application publication date: 20170329 |