CN1715272A - Macro molecular triazine series carbon forming foaming agent and its synthetic method - Google Patents
Macro molecular triazine series carbon forming foaming agent and its synthetic method Download PDFInfo
- Publication number
- CN1715272A CN1715272A CN200510010243.4A CN200510010243A CN1715272A CN 1715272 A CN1715272 A CN 1715272A CN 200510010243 A CN200510010243 A CN 200510010243A CN 1715272 A CN1715272 A CN 1715272A
- Authority
- CN
- China
- Prior art keywords
- reaction
- carbon forming
- foaming agent
- synthetic method
- cyanuric chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention belongs to the field of organic chemistry. The synthesis process of macro molecular triazine carbon forming and foaming agents with the structural general expression includes the following steps: adding solvent to cyanuric chloride and dropping alcohol amine and acid binding agent to generate the first substituent of cyanuric chloride; raising the temperature, dropping diamine and acid binding agent and raising the reaction temperature to generate the second substituent of cyanuric chloride; adding diamine and acid binding agent into the reaction solution and raising temperature for further reaction; and suction filtering, water washing and stoving to obtain macro molecular carbon forming and foaming agent. The present invention has the advantages of continuous reaction process, short reaction period, simple synthesis, low organic solvent consumption and easy recovering of organic solvent.
Description
Technical field:
The invention belongs to organic chemistry filed, be specifically related to a kind of pyrrolotriazine derivatives and synthesis technique thereof.
Background technology:
Expansion type flame retardant (IFR) has overcome that the halogen containing flame-retardant combustion fumes is big, the shortcoming of many molten drops and inorganics fire retardant be because the detrimentally affect that addition brings the mechanics of materials, processibility the subject of knowledge and the object of knowledge greatly, being a kind of very rising BACN, also is one of fire retardant research and development most active fields.Because in traditional IFR system based on polyphosphoric acid amine (APP), the char-forming agent tetramethylolmethane has the shortcoming that easy migration and work in-process can generate phosphoric acid ester etc. with the APP reaction, so the exploitation of present IFR mainly concentrates in the development of novel char-forming agent.In recent years, pyrrolotriazine derivatives has caused people's attention as the novel char-forming agent among the IFR.Pyrrolotriazine derivatives is that a big class is rich in the compound of uncle's N structure, and the compound that contains uncle's N structure has good charing effect.Based on the nitrogenous compound of pyrrolotriazine derivatives as the novel char-forming agent in the IFR system, verified it the fire retardation that improves IFR is had the obvious synergistic effect, be present IFR architectural study and hot of research and development therefore.
Three chlorine atoms have unique response characteristic in the cyanuric chloride, the reactive behavior of three chlorine atoms is all than higher (activity that is equivalent to acyl chlorides), nucleophilic substitution reaction takes place easily, but active degree difference, three chlorine atoms can be activated under different temperature condition.Substitution reaction at room temperature just can take place in first chlorine atom, and substitution reaction need could take place about 40～70 ℃ second chlorine atom, and the 3rd the chlorine atom of staying on the ring requires just can be substituted about 100 ℃.Utilize this characteristic, control reaction temperature can be introduced different active nucleophilic reagents by substep on the molecule of cyanuric chloride, connect specific group, thereby reach the purpose of the molecule of synthetic desired design.
Japanese Patent JP.Pat.No.0,583,065, disclosing the employing cyanuric chloride among the A1 (1994) is starting raw material, with acetone is solvent, sodium hydroxide is acid binding agent, with two amine materials one substitution reaction takes place earlier down at 0～5 ℃, and the reaction times is about 3 hours, temperature of reaction is brought up to 50 ℃, with two amine materials two substitution reactions take place, the reaction times is about 10 hours, and reaction finishes after-filtration, dry under 70 ℃ of conditions in vacuum drying oven the washing back.With dimethylbenzene is solvent, and two replace intermediates with two amine materials three substitution reactions takes place under the condition that refluxes, and return time is more than 16 hours, and after filtration, must final product after washing and the drying, productive rate be about 91%, and total reaction time is more than 29 hours.
Also have some triazine series carbon forming agent synthetic articles to deliver in addition, (J.OrganicChemistry 49 referring to Anelli.Pl etc., 4197-4203,1984), (Journal of Applied PolymerScience 94 such as Xiao-Ping Hu, 1556-1561,2004) be 9%, with the weightlessness of this method synthetic char-forming agent 100 ℃ the time, weightlessness in the time of 300 ℃ has reached 21%, and the charcoal residual volume in the time of 600 ℃ only is 5%.
All there are following shortcoming in these patented technologies and synthetic method: reaction process is discontinuous, long reaction time, and consumption of organic solvent is big, difficulty is reclaimed in the distillation of solvent, product thermally-stabilised poor, neat coal amout is low, and the flame retardant effect of expandable flame retardant system also needs further to improve.
Summary of the invention:
The objective of the invention is at prior art have that reaction process is discontinuous, long reaction time, consumption of organic solvent are big, difficulty, product poor heat stability and the low shortcoming of neat coal amout are reclaimed in the solvent distillation, a kind of macro molecular triazine series carbon forming foaming agent and synthetic method thereof are provided, it have reaction process continuously, shorten the reaction times, simplify synthesis technique, reduce the recovery organic solvent of consumption of organic solvent, convenient and efficient or do not need organic solvent, acquisition has the advantage of the high-quality product of good thermal stability and carbon-forming performance.The general structure of macro molecular triazine series carbon forming foaming agent of the present invention is:
Or
In the formula: m
1=0 or 1, m
2=2 or 1; R=(CH
2)
N1, n
1=2～6, or R=C
6H
4
The synthetic method of macro molecular triazine series carbon forming foaming agent is: a, be starting raw material with the cyanuric chloride, with mineral alkali as acid binding agent, cyanuric chloride is added in the reaction vessel, in reaction vessel, add solvent, cyanuric chloride is uniformly dispersed, under-5～10 ℃ condition, drip hydramine and acid binding agent, the rate of addition of control alkaline solution, the pH value that makes solution is 5～8, reacts after 2～4 hours, and the first step substitution reaction finishes, generate a substituent 2-hydroxyl alkylamino-4 of cyanuric chloride, 6-two chloro-1,3,5-triazines; B, elevated temperature to 30～45 ℃, drip diamines and acid binding agent, the pH value is controlled at 5～8, dropwise the afterreaction temperature and be increased to 50～60 ℃, react after 5～7 hours, the second step substitution reaction finishes, generate the di-substituted N of cyanuric chloride, N-two (2-chloro-4-hydroxyl alkylamino-1,3,5-triazines) diamines; C, will be used for the 3rd the step substitution reaction diamines and acid binding agent join reaction soln together, continue the rising temperature of reaction, under the solvent refluxing temperature, reacted 6～8 hours, and after suction filtration, washing, oven dry, obtained macromolecular carbon forming-whipping agent, be i.e. hydroxyl alkylamino diamines triazine oligopolymer.
Content of the present invention is the triazine series oligomer of synthetic class hydroxyl of design and two amidos, and product is a white powder, and productive rate is more than 88%, softening temperature is at 225～250 ℃, 1% thermal weight loss decomposition temperature is all more than 270 ℃, and under the high pure nitrogen atmosphere, the neat coal amout in the time of 800 ℃ is more than 35%.Product fusion when heating, the expansion that reduces foaming, the final charcoal layer that generates expand loose and good strength, expansion multiple is at 30～50 times, and it has into charcoal and swelling capacity is strong, and the advantage of Heat stability is good.
The present invention adopts the mixture of water or water and acetone to make solvent, and reaction process is a continuous reaction, and intermediate need not take out processing separately, just organic solvent is reclaimed in the process that improves temperature of reaction simultaneously.And the traditional synthesis process complexity generally all with synthetic intermediate individual curing, influences the synthetic process; Consumption of organic solvent is big and use the disagreeableness organic solvent of some environment such as dimethylbenzene as reaction solvent, and aftertreatment extremely bothers, and reclaims difficulty.Synthesis technique of the present invention is simple, and consumption of organic solvent is few or without organic solvent, and solvent recuperation handle convenient, and the reaction times is short, only need 16～18 hours usually, and the prior art reaction times is more than 29 hours, save energy consumption greatly, improved production efficiency, reduced production cost.
Embodiment:
Embodiment one: the general structure of the macro molecular triazine series carbon forming foaming agent of present embodiment is:
Embodiment two: present embodiment is according to following step synthetic macromolecule triazine series carbon forming foaming agent: a, with the cyanuric chloride is starting raw material, with mineral alkali as acid binding agent, cyanuric chloride is added in the reaction vessel, in reaction vessel, add solvent, cyanuric chloride is uniformly dispersed, drip hydramine and acid binding agent under-5～10 ℃ condition, the rate of addition of control alkaline solution makes the pH value of solution 5～8, cyanuric chloride reacts with hydramine earlier, generate a substituent 2-hydroxyl alkylamino-4 of cyanuric chloride, 6-two chloro-1,3, the 5-triazine, react after 2～4 hours, the pH value of reaction solution is near neutral, and reaction finishes; B, elevated temperature to 30～45 ℃, drip diamines and acid binding agent, the pH value is controlled at 5～8, dropwises the afterreaction temperature and is increased to 50～60 ℃, reacts after 5～7 hours, the pH value of reaction solution is when neutral, the second step substitution reaction finishes, and generates the di-substituted N of cyanuric chloride, N-two (2-chloro-4-hydroxyl alkylamino-1,3, the 5-triazine) diamines; C, will be used for the 3rd the step substitution reaction diamines and acid binding agent join reaction soln together, continue the rising temperature of reaction (in containing the acetone system, separator steams acetone, make that reaction solvent all is a water), under the solvent refluxing temperature, reacted 6～8 hours, after suction filtration, washing, oven dry, obtain macromolecular carbon forming-whipping agent, i.e. hydroxyl alkylamino diamines triazine oligopolymer.The reaction that is taken place in the present embodiment can be carried out continuously without separating, and also every intermediate can be separated, and reacts respectively.
Present embodiment adopts the mixture of water or acetone and water as solvent.
Acid binding agent described in the present embodiment is alkali metal hydroxide, alkaline carbonate or alkali metal hydrocarbonate.
The general formula of the hydramine that present embodiment adopts is NH (ROH)
2Or NH
2ROH, the R=(CH in the formula
2)
N1, n1=2～6 are as Monoethanolamine MEA BASF, diethanolamine or monopropylene glycol amine etc.
The general formula of the diamines that present embodiment adopts is H
2NRNH
2, the R=(CH in the formula
2)
N1, n1=2～6, as quadrol, butanediamine, hexanediamine or two quadrols etc., perhaps diamines is a piperidines.
The building-up reactions equation is:
Or
In the formula: m
1=0 or 1, m
2=2 or 1; R=(CH
2)
N1, n
1=2～6, or R=C
6H
4
Embodiment three: in the 2000ml four-hole bottle of reflux exchanger, thermometer, agitator is housed, add the cyanuric chloride of 184.5g, add 600ml distilled water then, four-hole bottle is put into ice-water bath, fully stir, make the cyanuric chloride homodisperse.Drip the 61g Monoethanolamine MEA BASF in four-hole bottle, 40g sodium hydroxide drips in four-hole bottle with constant pressure funnel after adding the dissolved in distilled water of 100ml, the control rate of addition, make that the pH value of solution is 5～8, temperature of reaction is controlled at-5～10 ℃, and the reaction times is 3～4 hours.
After Monoethanolamine MEA BASF dropwises, drip the 30g quadrol earlier in four-hole bottle, 40g sodium hydroxide drips in four-hole bottle with constant pressure funnel after using the 100ml dissolved in distilled water, temperature of reaction is brought up to 30～45 ℃, the control rate of addition makes that the pH value of solution is 5～8, and the dropping time is 4～6 hours, temperature of reaction is brought up to 50～60 ℃ continue reaction for some time, when solution reached near neutrality, two substitution reactions finished, and the reaction times is about 5～7 hours altogether.
30g quadrol and 40g sodium hydroxide are joined in the four-hole bottle together, improve temperature of reaction, back flow reaction is after 6～8 hours, and reaction finishes.Filter, wash, 120 ℃ of oven dry down, obtain the carbon forming foaming agent of 172.5g white powder, productive rate is 88.04%.By FTIR and
1The test analysis of HNMR has been determined the structure of this product, and the test analysis of TGA shows that this product 1% thermal weight loss decomposition temperature is 273.2 ℃, and under the high pure nitrogen atmosphere, the neat coal amout in the time of 800 ℃ is 35.7%, and softening temperature is 230～245 ℃.
Embodiment four: the cyanuric chloride that in the 2000ml four-hole bottle of reflux exchanger, thermometer, agitator is housed, adds 184.5g, add 250ml acetone and 250ml distilled water then, four-hole bottle is put into ice-water bath, fully stir, make the cyanuric chloride homodisperse.Drip the thanomin of 61g in the four-hole bottle, 40g sodium hydroxide drips in four-hole bottle with constant pressure funnel after adding the dissolved in distilled water of 100ml, the control rate of addition, make that the pH value of solution is 5～8, temperature of reaction is controlled at-5～10 ℃, and the reaction times is 2～4 hours.
After thanomin dropwises, drip the 30g quadrol earlier in four-hole bottle, 40g sodium hydroxide drips in four-hole bottle with constant pressure funnel after using the 100ml dissolved in distilled water, temperature of reaction is brought up to 30～45 ℃, the control rate of addition makes that the pH value of solution is 5～8, and the dropping time is 4～6 hours, temperature of reaction is brought up to 50～60 ℃ continue reaction for some time, when solution reached near neutrality, two substitution reactions finished, and the reaction times is about 5～7 hours altogether.
30g quadrol and 40g sodium hydroxide are joined in the four-hole bottle together, improve temperature of reaction, acetone separation is reclaimed, replenish 200ml distilled water simultaneously and be heated to backflow with water separator.After the back flow reaction 6～8 hours, reaction finishes.Filter, wash, 120 ℃ of oven dry down, obtain the carbon forming foaming agent of 178.4g white powder, productive rate is 91.04%.By FTIR and
1The test analysis of HNMR has been determined the structure of this product, and the test analysis of TGA shows that this product 1% thermal weight loss decomposition temperature is 290 ℃, and under the high pure nitrogen atmosphere, the neat coal amout in the time of 800 ℃ is 37.2%, and softening temperature is 235～250 ℃.
Embodiment five: the cyanuric chloride that in the 2000ml four-hole bottle of reflux exchanger, thermometer, agitator is housed, adds 184.5g, add 250ml acetone and 250ml distilled water then, four-hole bottle is put into ice-water bath, fully stir, make the cyanuric chloride homodisperse.Drip the Monoethanolamine MEA BASF of 61g in the four-hole bottle, 40g sodium hydroxide drips in four-hole bottle with constant pressure funnel after adding the dissolved in distilled water of 100ml, the control rate of addition, make that the pH value of solution is 5～8, temperature of reaction is controlled at-5～10 ℃, and the reaction times is 2～4 hours.
After Monoethanolamine MEA BASF dropwises, drip the 44g butanediamine earlier in four-hole bottle, 40g sodium hydroxide drips in four-hole bottle with constant pressure funnel after using the 100ml dissolved in distilled water, temperature of reaction is brought up to 30～45 ℃, the control rate of addition makes that the pH value of solution is 5～8, and the dropping time is 4～6 hours, temperature of reaction is brought up to 50～60 ℃ continue reaction for some time, when solution reached near neutrality, two substitution reactions finished, and the reaction times is about 5～7 hours altogether.
44g butanediamine and 40g sodium hydroxide are joined in the four-hole bottle together, improve temperature of reaction, acetone separation is reclaimed, replenish 200ml distilled water simultaneously and be heated to backflow with water separator.After the back flow reaction 6～8 hours, reaction finishes.Filter, wash, 120 ℃ of oven dry down, obtain the carbon forming foaming agent of 205.0g white powder, productive rate is 91.52%.By FTIR and
1The test analysis of HNMR has been determined the structure of this product, and the test analysis of TGA shows that this product 1% thermal weight loss decomposition temperature is 285 ℃, and under the high pure nitrogen atmosphere, the neat coal amout in the time of 800 ℃ is 36.1%, and softening temperature is 230～245 ℃.
Embodiment six: the cyanuric chloride that in the 2000ml four-hole bottle of reflux exchanger, thermometer, agitator is housed, adds 184.5g, add 250ml acetone and 250ml distilled water then, four-hole bottle is put into ice-water bath, fully stir, make the cyanuric chloride homodisperse.Drip the monopropylene glycol amine of 61g in the four-hole bottle, the 84g sodium bicarbonate drips in four-hole bottle with constant pressure funnel after adding the dissolved in distilled water of 200ml, the control rate of addition, make that the pH value of solution is 5～8, temperature of reaction is controlled at-5～10 ℃, and the reaction times is 2～4 hours.
After monopropylene glycol amine dropwises, drip the 30g quadrol earlier in four-hole bottle, the 484g sodium bicarbonate drips in four-hole bottle with constant pressure funnel after adding the dissolved in distilled water of 200ml, temperature of reaction is brought up to 30～45 ℃, the control rate of addition makes that the pH value of solution is 5～8, and the dropping time is 4～6 hours, temperature of reaction is brought up to 50～60 ℃ continue reaction for some time, when solution reached near neutrality, two substitution reactions finished, and the reaction times is about 5～7 hours altogether.
30g quadrol and 40g sodium hydroxide are joined in the four-hole bottle together, improve temperature of reaction, acetone separation is reclaimed, replenish 300ml distilled water simultaneously and be heated to backflow with water separator.After the back flow reaction 6～8 hours, reaction finishes.Filter, wash, 120 ℃ of oven dry down, obtain the carbon forming foaming agent of 176.4g white powder, productive rate is 90.1%.By FTIR and
1The test analysis of HNMR has been determined the structure of this product, and the test analysis of TGA shows that this product 1% thermal weight loss decomposition temperature is 283 ℃, and under the high pure nitrogen atmosphere, the neat coal amout in the time of 800 ℃ is 36.0%, and softening temperature is 225～240 ℃.
Embodiment seven: the cyanuric chloride that in the 2000ml four-hole bottle of reflux exchanger, thermometer, agitator is housed, adds 184.5g, add 250ml acetone and 250ml distilled water then, four-hole bottle is put into ice-water bath, fully stir, make the cyanuric chloride homodisperse.Drip the diethanolamine of 105g in the four-hole bottle, 40g sodium hydroxide drips in four-hole bottle with constant pressure funnel after adding the dissolved in distilled water of 100ml, the control rate of addition, make that the pH value of solution is 5～8, temperature of reaction is controlled at-5～10 ℃, and the dropping time is 2～4 hours.
After diethanolamine dropwises, first Dropwise 5 8g hexanediamine in the four-hole bottle, 40g sodium hydroxide with the 100ml dissolved in distilled water after, drip in four-hole bottle with constant pressure funnel, temperature of reaction is brought up to 30～45 ℃, the control rate of addition makes that the pH value of solution is 5～8, and the dropping time is 4～6 hours, temperature of reaction is brought up to 50～60 ℃ continue reaction for some time, when solution reached near neutrality, two substitution reactions finished, and the reaction times is about 7～8 hours altogether.
58g hexanediamine and 40g sodium hydroxide are joined in the four-hole bottle together, improve temperature of reaction, acetone separation is reclaimed, replenish 200ml distilled water simultaneously and be heated to backflow with water separator.After the back flow reaction 6～8 hours, reaction finishes.Filter, wash, 120 ℃ of oven dry down, obtain the carbon forming foaming agent of 268.06g white powder, productive rate is 90.65%.By FTIR and
1The test analysis of HNMR has been determined the structure of this product, and the test analysis of TGA shows that this product 1% thermal weight loss decomposition temperature is 280 ℃, and under the high pure nitrogen atmosphere, the neat coal amout in the time of 800 ℃ is 33%, and softening temperature is 228～240 ℃.
Embodiment eight: the cyanuric chloride that in the 2000ml four-hole bottle of reflux exchanger, thermometer, agitator is housed, adds 184.5g, add 250ml acetone and 250ml distilled water then, four-hole bottle is put into ice-water bath, fully stir, make the cyanuric chloride homodisperse.Drip the Monoethanolamine MEA BASF of 61g in the four-hole bottle, 40g sodium hydroxide drips in four-hole bottle with constant pressure funnel after adding the dissolved in distilled water of 100ml, the control rate of addition, make that the pH value of solution is 5～8, temperature of reaction is controlled at-5～10 ℃, and the reaction times is 2～4 hours.
After Monoethanolamine MEA BASF dropwises, drip the 43g piperidines earlier in four-hole bottle, 40g sodium hydroxide drips in four-hole bottle with constant pressure funnel after using the 100ml dissolved in distilled water, temperature of reaction is brought up to 30～45 ℃, the control rate of addition makes that the pH value of solution is 5～8, and the dropping time is 4～6 hours, temperature of reaction is brought up to 50～60 ℃ continue reaction for some time, when solution reached near neutrality, two substitution reactions finished, and the reaction times is about 5～7 hours altogether.
43g piperidines and 40g sodium hydroxide are joined in the four-hole bottle together, improve temperature of reaction, acetone separation is reclaimed, replenish 200ml distilled water simultaneously and be heated to backflow with water separator.After the back flow reaction 6～8 hours, reaction finishes.Filter, wash, 120 ℃ of oven dry down, obtain the carbon forming foaming agent of 203.06g white powder, productive rate is 91.47%.By FTIR and
1The test analysis of HNMR has been determined the structure of this product, and the test analysis of TGA shows that this product 1% thermal weight loss decomposition temperature is 281 ℃, and under the high pure nitrogen atmosphere, the neat coal amout in the time of 800 ℃ is 36.0%, and softening temperature is 236～240 ℃.
Claims (9)
1, macro molecular triazine series carbon forming foaming agent is characterized in that its general structure is:
Or
In the formula: m
1=0 or 1, m
2=2 or 1; R=(CH
2)
N1, n
1=2～6, or R=C
6H
4
2, the synthetic method of the described macro molecular triazine series carbon forming foaming agent of claim 1, it is characterized in that it synthesizes according to following steps: a, with the cyanuric chloride is starting raw material, with mineral alkali as acid binding agent, cyanuric chloride is added in the reaction vessel, in reaction vessel, add solvent, cyanuric chloride is uniformly dispersed, under-5～10 ℃ condition, drip hydramine and acid binding agent, the rate of addition of control alkaline solution, the pH value that makes solution is 5～8, react after 2～4 hours, the first step substitution reaction finishes, and generates a substituent 2-hydroxyl alkylamino-4 of cyanuric chloride, 6-two chloro-1,3, the 5-triazine; B, elevated temperature to 30～45 ℃, drip diamines and acid binding agent, the pH value is controlled at 5～8, dropwise the afterreaction temperature and be increased to 50～60 ℃, react after 5～7 hours, the second step substitution reaction finishes, generate the di-substituted N of cyanuric chloride, N-two (2-chloro-4-hydroxyl alkylamino-1,3,5-triazines) diamines; C, will be used for the 3rd the step substitution reaction diamines and acid binding agent join reaction soln together, continue the rising temperature of reaction, under the solvent refluxing temperature, reacted 6～8 hours, and after suction filtration, washing, oven dry, obtained macromolecular carbon forming-whipping agent, be i.e. hydroxyl alkylamino diamines triazine oligopolymer.
3, the synthetic method of macro molecular triazine series carbon forming foaming agent according to claim 2 is characterized in that described acid binding agent is alkali metal hydroxide, alkaline carbonate or alkali metal hydrocarbonate.
4, the synthetic method of macro molecular triazine series carbon forming foaming agent according to claim 2, the general formula that it is characterized in that described hydramine are NH (ROH)
2Or NH
2ROH, the R=(CH in the formula
2)
N1, n1=2～6.
5, the synthetic method of macro molecular triazine series carbon forming foaming agent according to claim 4 is characterized in that described hydramine is Monoethanolamine MEA BASF, diethanolamine or monopropylene glycol amine.
6, the synthetic method of macro molecular triazine series carbon forming foaming agent according to claim 2, the general formula that it is characterized in that described diamines is H
2NRNH
2, the R=(CH in the formula
2)
N1, n1=2～6.
7, the synthetic method of macro molecular triazine series carbon forming foaming agent according to claim 6 is characterized in that described diamines is quadrol, butanediamine, hexanediamine or two quadrols.
8, the synthetic method of macro molecular triazine series carbon forming foaming agent according to claim 2 is characterized in that described diamines is a piperidines.
9, the synthetic method of macro molecular triazine series carbon forming foaming agent according to claim 2 is characterized in that adopting the mixture of water or acetone and water as solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510010243.4A CN1288140C (en) | 2005-08-03 | 2005-08-03 | Macro molecular triazine series carbon forming foaming agent and its synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510010243.4A CN1288140C (en) | 2005-08-03 | 2005-08-03 | Macro molecular triazine series carbon forming foaming agent and its synthetic method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1715272A true CN1715272A (en) | 2006-01-04 |
| CN1288140C CN1288140C (en) | 2006-12-06 |
Family
ID=35821469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200510010243.4A Expired - Fee Related CN1288140C (en) | 2005-08-03 | 2005-08-03 | Macro molecular triazine series carbon forming foaming agent and its synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1288140C (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161763A (en) * | 2011-02-25 | 2011-08-24 | 中山大学 | Novel expansion-type charring agent for flame-retardant polyolefine material and synthesis method thereof |
| CN101220185B (en) * | 2008-01-29 | 2011-08-31 | 北京理工大学 | Expansion type flame-proof ethylene propylene terpolymer for fire resistant flame |
| CN102181073A (en) * | 2011-02-14 | 2011-09-14 | 福建师范大学 | Triazine compound coordination crosslinking synergistic agent for elastomer and preparation method thereof |
| CN102234516A (en) * | 2010-05-06 | 2011-11-09 | 中国科学院宁波材料技术与工程研究所 | Long-chain triazine macromolecular flame retardant with bicyclic phosphate structure and preparation method thereof |
| CN102352036A (en) * | 2011-06-16 | 2012-02-15 | 东北林业大学 | Triazine carbon forming-foaming agent, synthesis method of the triazine carbon forming-foaming agent, and flame-retardant polymer composite material prepared from the triazine carbon forming-foaming agent |
| CN101712840B (en) * | 2008-10-07 | 2012-03-21 | 北京理工大学 | Ultrathin water-based epoxy resin expandable fireproof paint and preparation method thereof |
| CN101586033B (en) * | 2009-06-10 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Triazine carbonific containing aromatic chain structure and preparation method |
| CN102702522A (en) * | 2012-06-25 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Macromolecule triazine charring agent and preparation method thereof |
| CN102702521A (en) * | 2012-06-25 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Macromolecule triazine charring agent with main chain containing piperazidine structure, and preparation method thereof |
| CN104650441A (en) * | 2015-03-16 | 2015-05-27 | 四川大学 | Ceramic bovine flame retardant polymer composite material and application thereof |
| CN106905609A (en) * | 2017-03-09 | 2017-06-30 | 江苏启蓝新材料有限公司 | The halogen-free flame-retardant polypropylene composition of the expanding fire retardant of system containing triazine and its preparation |
| CN105418675B (en) * | 2015-12-23 | 2017-09-19 | 山东艾孚特科技有限公司 | A kind of triazines carbon forming agent and its preparation method and application |
| CN108384001A (en) * | 2018-03-17 | 2018-08-10 | 山东兄弟科技股份有限公司 | Primary amine blocking modification macro molecular triazine carbon forming agent and preparation method thereof |
| CN112608485A (en) * | 2020-11-25 | 2021-04-06 | 华东理工大学 | Organic-inorganic hybrid efficient synergistic flame-retardant char-forming agent and preparation method thereof |
-
2005
- 2005-08-03 CN CN200510010243.4A patent/CN1288140C/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220185B (en) * | 2008-01-29 | 2011-08-31 | 北京理工大学 | Expansion type flame-proof ethylene propylene terpolymer for fire resistant flame |
| CN101712840B (en) * | 2008-10-07 | 2012-03-21 | 北京理工大学 | Ultrathin water-based epoxy resin expandable fireproof paint and preparation method thereof |
| CN101586033B (en) * | 2009-06-10 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Triazine carbonific containing aromatic chain structure and preparation method |
| CN102234516A (en) * | 2010-05-06 | 2011-11-09 | 中国科学院宁波材料技术与工程研究所 | Long-chain triazine macromolecular flame retardant with bicyclic phosphate structure and preparation method thereof |
| CN102234516B (en) * | 2010-05-06 | 2014-06-04 | 中国科学院宁波材料技术与工程研究所 | Long-chain triazine macromolecular flame retardant with bicyclic phosphate structure and preparation method thereof |
| CN102181073A (en) * | 2011-02-14 | 2011-09-14 | 福建师范大学 | Triazine compound coordination crosslinking synergistic agent for elastomer and preparation method thereof |
| CN102161763B (en) * | 2011-02-25 | 2013-11-06 | 中山大学 | Novel expansion-type charring agent for flame-retardant polyolefine material and synthesis method thereof |
| CN102161763A (en) * | 2011-02-25 | 2011-08-24 | 中山大学 | Novel expansion-type charring agent for flame-retardant polyolefine material and synthesis method thereof |
| CN102352036A (en) * | 2011-06-16 | 2012-02-15 | 东北林业大学 | Triazine carbon forming-foaming agent, synthesis method of the triazine carbon forming-foaming agent, and flame-retardant polymer composite material prepared from the triazine carbon forming-foaming agent |
| CN102702521A (en) * | 2012-06-25 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Macromolecule triazine charring agent with main chain containing piperazidine structure, and preparation method thereof |
| CN102702521B (en) * | 2012-06-25 | 2014-04-09 | 中国科学院宁波材料技术与工程研究所 | Macromolecule triazine charring agent with main chain containing piperazidine structure, and preparation method thereof |
| CN102702522B (en) * | 2012-06-25 | 2014-04-09 | 中国科学院宁波材料技术与工程研究所 | Macromolecule triazine charring agent and preparation method thereof |
| CN102702522A (en) * | 2012-06-25 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Macromolecule triazine charring agent and preparation method thereof |
| CN104650441A (en) * | 2015-03-16 | 2015-05-27 | 四川大学 | Ceramic bovine flame retardant polymer composite material and application thereof |
| CN105418675B (en) * | 2015-12-23 | 2017-09-19 | 山东艾孚特科技有限公司 | A kind of triazines carbon forming agent and its preparation method and application |
| CN106905609A (en) * | 2017-03-09 | 2017-06-30 | 江苏启蓝新材料有限公司 | The halogen-free flame-retardant polypropylene composition of the expanding fire retardant of system containing triazine and its preparation |
| CN108384001A (en) * | 2018-03-17 | 2018-08-10 | 山东兄弟科技股份有限公司 | Primary amine blocking modification macro molecular triazine carbon forming agent and preparation method thereof |
| CN108384001B (en) * | 2018-03-17 | 2020-05-22 | 山东兄弟科技股份有限公司 | Primary amine end-capped modified macromolecule triazine charring agent and preparation method thereof |
| CN112608485A (en) * | 2020-11-25 | 2021-04-06 | 华东理工大学 | Organic-inorganic hybrid efficient synergistic flame-retardant char-forming agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1288140C (en) | 2006-12-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1288140C (en) | Macro molecular triazine series carbon forming foaming agent and its synthetic method | |
| CN100500657C (en) | Triazine series oligomer and its synthesizing method | |
| CN103319483B (en) | A kind of preparation method of important intermediate of linagliptin | |
| CN102161763B (en) | Novel expansion-type charring agent for flame-retardant polyolefine material and synthesis method thereof | |
| CN102234516B (en) | Long-chain triazine macromolecular flame retardant with bicyclic phosphate structure and preparation method thereof | |
| CN103113619A (en) | Triazine ring containing caged organic phosphate flame retardant and preparation method thereof | |
| CN111440357A (en) | All-bio-based flame retardant, flame-retardant P L A composite material and preparation method thereof | |
| CN105924672A (en) | Dual-cage structure contained triazine-ring flame retardant with anti-oxidation function and preparation method | |
| CN1681796A (en) | Process for the preparation of 4- (3'-chloro-4'-fluoroanilino) -7-methoxy-6- (3-morpholinopropoxy) quinazoline | |
| CN114044777B (en) | Preparation method of tricitabinib phosphate | |
| CN105367604A (en) | Phosphorus-nitrogen-containing star-type charring agent and preparation method thereof | |
| WO2023236938A1 (en) | Process for separating and purifying by-product 2-chloroethyl n-butyl ether in production process of tris(2-butoxyethyl)phosphate | |
| CN105801845B (en) | A kind of biradical polyamide synergistic carbon forming agent of ferrocene-triazine ring and its preparation method and application | |
| CN102389744A (en) | First class s-triazine amphoteric betaine surfactant and synthesizing method thereof | |
| CN102515121B (en) | Preparation method of linear polyhalophosphazene with high relative molecular mass | |
| CN106892943B (en) | A kind of compound in triazine class, preparation method and applications | |
| CN108794448A (en) | The preparation method of one koji Ge Lieting and its salt | |
| CN108484919A (en) | A kind of phosphorous macromolecular fire retardant and preparation method thereof | |
| CN1733736A (en) | Nitrogenous fragrant heterocyclic diamine and preparation method thereof | |
| CN111303045A (en) | Production process of 2-ethoxy-4, 6-difluoropyrimidine | |
| CN102757394A (en) | Preparation method of 2,4,6-tri(N,N-diethoxyl)amino-1,3,5-triazine | |
| CN1077193A (en) | N-5 position-protected 2,5-diamino-4,6-dichloro pyrimidine and production method thereof | |
| CN104558039A (en) | Phosphorus-nitrogen intumescent flame retardant and preparation method thereof | |
| CN108373486A (en) | O-phenylenediamine phosphoryl melamine flame retardants and preparation method thereof | |
| CN114539081B (en) | Method for separating and purifying glycine by utilizing N, N-dibutyl ethanolamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061206 Termination date: 20170803 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |