CN102086176A - Synthetic method of triazine derivative - Google Patents
Synthetic method of triazine derivative Download PDFInfo
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- CN102086176A CN102086176A CN2009102165544A CN200910216554A CN102086176A CN 102086176 A CN102086176 A CN 102086176A CN 2009102165544 A CN2009102165544 A CN 2009102165544A CN 200910216554 A CN200910216554 A CN 200910216554A CN 102086176 A CN102086176 A CN 102086176A
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Abstract
The invention relates to a synthetic method of a triazine derivative. Two triazine compounds cyanuric chloride and melamine, and one aminoalcohol compound are heated together in a molar ratio of 0.01-1:1:0.2-6 in nitrogen atmosphere to synthesize the triazine derivative. The synthetic method of triazine derivative disclosed in the invention requires low reaction temperature, short time, and no addition of catalyst. In addition, the synthesized triazine derivative possesses low impurity content, high stability, and is suitable for modification of amino resin.
Description
One, technical field
The invention belongs to chemical field, relate to a kind of production process of chemical product, the synthetic method of pyrrolotriazine derivatives specifically, this pyrrolotriazine derivatives can be used as aminoresin properties-correcting agent.
Two, background technology
In the application of aminoresin especially for fiber and foamy high solids content terpolycyantoamino-formaldehyde resin, need to regulate the viscosity of resin usually, improve the plasticity of resin, improve particularly its derived product flexible purpose of its processing characteristics.In recent years, raising is awfully hot research direction based on the snappiness of the goods of terpolycyantoamino-formaldehyde resin, also has lot of documents to report the method for the simplification compound of pyrrolotriazine derivatives such as single replacements of trimeric cyanamide and alkamine compound prepared in reaction, two replacement, three replacement hydroxyl alkoxyl group trimeric cyanamides, two or three mixture.
The forties in last century, US 2228161, US 2393755, US 2467523, US 2723244 have reported that with trimeric cyanamide and alkamine compound be the method for starting raw material production of melamine derivative, but industrial value is not high.Nineteen eighty-two, US4312988 has reported with trimeric cyanamide and the synthetic substituent of alkamine compound reaction, but byproduct of reaction is many, yield is low, when the trimeric cyanamide transformation efficiency is 82%, the amount of the isomer of non-activity is 20%, and the trimeric cyanamide transformation efficiency is higher to 99% o'clock, all is not have active isomer substantially.1989, US 4886882 has reported with the cyanuric chloride to be the synthetic substituted monomer of starting raw material, and is the method for the synthetic pyrrolotriazine derivatives mixture of starting raw material with the trimeric cyanamide: 1. need add other solvent during synthon, and long reaction time, postprocessing working procedures is many, and yield is not high; 2. trimeric cyanamide is the synthetic pyrrolotriazine derivatives mixture of starting raw material, and it is long to synthesize the high replacement mixture reaction time of three substitute proportions; 3. need add catalyzer.1998, US5792867 reported the method for synthetic pyrrolotriazine derivatives, but the temperature of reaction height, long reaction time, and reaction-ure conversion-age is not high, and yield is low.2007, CN200510090795 has reported a kind of method for preparing the aminoresin reactive plasticizer, what mainly contain is single substituted melamine, and according to document and molecular structure, when modified aminoresin, methylol oxyethyl group side chain ratio height in three replacements, effective when modified aminoresin, and have a small amount of single replacement that enough-NH can be provided in the mixture with two replacements
2The isoreactivity group.
Three, summary of the invention
According to the present invention, be starting raw material jointly with cyanuric chloride and trimeric cyanamide, preparation is used for the properties-correcting agent pyrrolotriazine derivatives of aminoresin, has overcome above-mentioned shortcoming.Synthetic method of the present invention does not need to add an acidic catalyst, and has taken into account well that synthetic method is simple, reaction conditions is gentle and improve its derived product flexible advantage, and production technique is easy to reach, applied range.
The pyrrolotriazine derivatives main component that the present invention is used for the aminoresin modification be single replacement, two replacement, three replace hydroxyl alkoxyl group trimeric cyanamides a kind of, two kinds or three kinds.The preparation method of this pyrrolotriazine derivatives is as follows: in reactor; with weak nitrogen gas stream is protection gas; the mixture of heating initial reactant cyanuric chloride, trimeric cyanamide and amino alcohol carries out building-up reactions, neutralizes then, concentrates, discharging obtains faint yellow pyrrolotriazine derivatives.The main component of this pyrrolotriazine derivatives be single replacement, two replacement, three substituted melamines a kind of, two kinds or three kinds.
Single replacement is two to be replaced
Three replace
Wherein R is a kind of of following substituting group:
This reaction does not need extra catalyst, and by one of generation product of reaction itself as catalyzer, simultaneously, the consumption of catalyzer can promote the carrying out that react again, thereby better reaches the purpose of catalyzed reaction.And the inorganic salt that generate during neutralization reaction do not need to remove by filter, and can be used as inorganic salt and are added into aminoresin.
The preparation method of a kind of pyrrolotriazine derivatives of the present invention, make according to the following steps:
(1) solid material cyanuric chloride, trimeric cyanamide are put in the reactor by metered proportions earlier, weak nitrogen gas stream protection is added to the alkamine compound of metered proportions in the reactor down, the mol ratio of cyanuric chloride, trimeric cyanamide and alkamine compound is 0.01～1: 1: 2～6, during reheat to 100～120 ℃, reaction is 30 minutes under the protection of weak nitrogen gas stream;
(2) be warming up to 150～160 ℃, under weak nitrogen gas stream protection, reacted 2～5 hours;
(3) alkali lye that drops into metering carries out neutralization reaction, concentrates again, and the concentrated product that obtains in the still is pyrrolotriazine derivatives.
Wherein alkamine compound comprises: the 2-monoethanolamine, 3-aminopropanol, 2-aminopropanol, 1-amino-2-propyl alcohol, 2-aminoisobutanol, 2-amino butanol, 2-amino-2-methyl-1-propanol, 4-amino butanol, N-(2-amino-ethyl) thanomin, 2-(2-amino ethoxy) ethanol, p-benzoyl monoethanolamine a kind of; Hydramine be preferably the 2-monoethanolamine, a kind of in the 3-aminopropanol, 4-amino butanol, 2-(2-amino ethoxy) ethanol.
The mol ratio of cyanuric chloride, trimeric cyanamide and alkamine compound is preferably 0.1～1: 1: 3～5; Temperature of reaction is preferably 120～160 ℃; Reaction times is preferably 3～5 hours.
After reaction finishes, keep temperature, add the solution neutralization reactions such as sodium hydroxide, potassium hydroxide, yellow soda ash of 50% concentration, the mode by underpressure distillation concentrates then, and vacuum gauge pressure is 0.06Mp a～0.09Mp a.Cooling then, 100 ℃ with bottom discharge, and the product pyrrolotriazine derivatives is faint yellow, can be used for the aminoresin modification.For example, in the production process of melamine fiber, add the spinning property that this derivative can well improve resin; In the production process of melamine foamed plastic, the interpolation of this derivative also can well improve the snappiness of foam article, improves foamy tear strength and tensile property.Simultaneously, this derivative has the triazine ring identical with trimeric cyanamide, also have simultaneously part-NH2 ,-NH and-OH, this makes the interpolation of this properties-correcting agent enter in the curing cross-linked process of aminoresin to have activity, can not be present in the goods with the form of free monomer as other softening agent and causes product performance to be affected.
Carry out under the protection of nitrogen gas stream a little less than this is reflected at, can better replace ammonia and promote reaction, simultaneously, can well weaken the color of resultant.
Needs according to the aminoresin product properties, control reaction mass proportioning and reaction times, can obtain single replacement of different ratios, two replacement, three replacement pyrrolotriazine derivatives, be used for the modification of aminoresin, be particularly suitable for the modification of terpolycyantoamino-formaldehyde resins such as fiber, foam.
Four, embodiment
Introduce implementation process of the present invention in detail below by example, only limit to the understanding of the present invention, but the present invention is not limited thereto or be so limited.
Embodiment 1
In reactor, add 1 mole of 184 gram cyanuric chloride, 10 mole of 1260 gram trimeric cyanamide and 30 mole of 1832 gram 2-monoethanolamine, feed weak nitrogen gas stream simultaneously, be warming up to 100～120 ℃, under agitation reacted 30 minutes, be warming up to 150～160 ℃ of reactions 3 hours then.Entire reaction course is protected with weak nitrogen gas stream; behind the end of synthesis; the sodium hydroxide solution that adds 3 mole 50% stirred about 15 minutes; opening the vacuum decompression distillation then concentrates; temperature maintenance is 150～160; cooling is lower than 100 until the reaction product temperature then, and product is the light yellow resin shape.
Detect through HPL C, single replacement, two replacement, trisubstituted molar percentage are 15mol%: 40mol%: 45mol% in the mixture of this pyrrolotriazine derivatives.
Embodiment 2
Add 3 mole of 552 gram cyanuric chloride, 10 mole of 1260 gram trimeric cyanamide and 30 mole of 2670 gram 4-amino butanol in synthesis reaction vessel, reaction process is identical with embodiment 1 with the reaction times.
Detect through HPL C, single replacement in the mixture of this pyrrolotriazine derivatives, two replacement, three replace the molar percentage of pyrrolotriazine derivatives for being: 5mol%: 40mol%: 55mol%.
Embodiment 3
In synthesis reaction vessel, add 3 mole of 552 gram cyanuric chloride, 10 mole of 1260 gram trimeric cyanamide and 50 mole of 5257 gram 2-(2-amino ethoxy) ethanol, reaction process is identical with embodiment 1, synthesising reacting time is 5 hours, and neutralization reaction is with 4.5 moles sodium carbonate solution.
Detect through HPLC, the molar percentage of two replacements in the mixture of this pyrrolotriazine derivatives, three replacement pyrrolotriazine derivatives is for being: 30mol%: 70mol%.
Embodiment 4
Be added in the synthesis reaction vessel and add 1 mole of 184 gram cyanuric chloride, 10 mole of 1260 gram trimeric cyanamide and 30 mole of 1832 gram 2-monoethanolamine in the reactor, feed weak nitrogen gas stream simultaneously, be warming up to 100～120 ℃, under agitation reacted 30 minutes, be warming up to 130 ℃ of reactions 3 hours then.Entire reaction course is protected with weak nitrogen gas stream; behind the end of synthesis; the sodium hydroxide solution that adds 3 mole 50% stirred about 15 minutes; opening the vacuum decompression distillation then concentrates; temperature maintenance is at 150～160 ℃; cooling is lower than 100 ℃ until the reaction product temperature then, and product is the light yellow resin shape.
Detect through HP L C, single replacement, two replacement, trisubstituted molar percentage are 55mol%: 35mol%: 10mol% in the mixture of this pyrrolotriazine derivatives.
Claims (8)
1. the preparation method of a pyrrolotriazine derivatives is characterized in that making according to the following steps:
(1) solid material cyanuric chloride, trimeric cyanamide are put in the reactor by metered proportions earlier, weak nitrogen gas stream protection is added to the alkamine compound of metered proportions in the reactor down, the mol ratio of cyanuric chloride, trimeric cyanamide and alkamine compound is 0.01～1: 1: 2～6, during reheat to 100～120 ℃, reaction is 30 minutes under the protection of weak nitrogen gas stream;
(2) be warming up to 150～160 ℃, under weak nitrogen gas stream protection, reacted 2～5 hours;
(3) alkali lye that drops into metering carries out neutralization reaction, concentrates again, and the concentrated product that obtains in the still is pyrrolotriazine derivatives.
2. preparation method according to claim 1 is characterized in that alkamine compound comprises: the 2-monoethanolamine, 3-aminopropanol, 2-aminopropanol, 1-amino-2-propyl alcohol, 2-aminoisobutanol, 2-amino butanol, 2-amino-2-methyl-1-propanol, 4-amino butanol, N-(2-amino-ethyl) thanomin, 2-(2-amino ethoxy) ethanol, p-benzoyl monoethanolamine a kind of.
3. production method according to claim 2, it is characterized in that alkamine compound be preferably the 2-monoethanolamine, 3-aminopropanol, 4-amino butanol, 2-(2-amino ethoxy) ethanol a kind of.
4. production method according to claim 1 is characterized in that the mol ratio of cyanuric chloride, trimeric cyanamide and alkamine compound is preferably 0.1～1: 1: 3～5.
5. production method according to claim 1 is characterized in that temperature of reaction is preferably 120～160 ℃.
6. production method according to claim 1 is characterized in that the reaction times is preferably 3～5 hours.
7. production method according to claim 1 is characterized in that the concentrated employing underpressure distillation mode in the step (3), and vacuum is collected the cut condensation by condenser to 0.06Mpa～0.09Mpa again in the reactor.
8. the pyrrolotriazine derivatives of preparing according to the described preparation method of claim 1 is characterized in that:
Main component be single replacement, two replacement, three substituted melamines a kind of, two kinds or three kinds:
Single replacement is two to be replaced
Three replace
Wherein R is a kind of of following substituting group:
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| CN2009102165544A CN102086176A (en) | 2009-12-04 | 2009-12-04 | Synthetic method of triazine derivative |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151272A (en) * | 2017-05-15 | 2017-09-12 | 江南大学 | A kind of preparation method of pyrrolotriazine derivatives modified cellulose nanocrystal |
| CN114890960A (en) * | 2022-05-17 | 2022-08-12 | 淮阴师范学院 | Preparation method and application of hydroxyl modified melamine |
| CN116874266A (en) * | 2023-09-08 | 2023-10-13 | 宝都国际新材料有限公司 | Detachable acoustic insulation board and manufacturing method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4312988A (en) * | 1980-11-10 | 1982-01-26 | American Cyanamid Company | Synthesis of hydroxy functional melamine derivatives |
| US4886882A (en) * | 1985-09-07 | 1989-12-12 | Basf Aktiengesellschaft | Hydroxyoxaalkylmelamines |
| CN1127506A (en) * | 1993-07-20 | 1996-07-24 | 日产化学工业株式会社 | Method of alkylating triazine derivative |
| CN1916061A (en) * | 2005-08-16 | 2007-02-21 | 北京绿寰宇化工有限公司 | Active plasticization modifier in use for amino resin |
-
2009
- 2009-12-04 CN CN2009102165544A patent/CN102086176A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4312988A (en) * | 1980-11-10 | 1982-01-26 | American Cyanamid Company | Synthesis of hydroxy functional melamine derivatives |
| US4886882A (en) * | 1985-09-07 | 1989-12-12 | Basf Aktiengesellschaft | Hydroxyoxaalkylmelamines |
| CN1127506A (en) * | 1993-07-20 | 1996-07-24 | 日产化学工业株式会社 | Method of alkylating triazine derivative |
| CN1916061A (en) * | 2005-08-16 | 2007-02-21 | 北京绿寰宇化工有限公司 | Active plasticization modifier in use for amino resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151272A (en) * | 2017-05-15 | 2017-09-12 | 江南大学 | A kind of preparation method of pyrrolotriazine derivatives modified cellulose nanocrystal |
| CN114890960A (en) * | 2022-05-17 | 2022-08-12 | 淮阴师范学院 | Preparation method and application of hydroxyl modified melamine |
| CN114890960B (en) * | 2022-05-17 | 2023-09-15 | 淮阴师范学院 | Preparation method and application of hydroxyl modified melamine |
| CN116874266A (en) * | 2023-09-08 | 2023-10-13 | 宝都国际新材料有限公司 | Detachable acoustic insulation board and manufacturing method thereof |
| CN116874266B (en) * | 2023-09-08 | 2023-12-12 | 宝都国际新材料有限公司 | Detachable acoustic insulation board and manufacturing method thereof |
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Application publication date: 20110608 |